U.S. patent application number 15/327849 was filed with the patent office on 2017-08-10 for combination of novel nitrification inhibitors and herbicides as well as combination of (thio)phosphoric acid triamides and herbicides.
The applicant listed for this patent is BASF SE. Invention is credited to Joachim Dickhaut, Nicholas Fassler, Mark Howard, Claudia Klodwig, Barbara Nave, Gregor Pasda, Markus Schmid, Karl-Heinrich Schneider, Mihiret Tekeste Sisay, Laura Vance, Alexander Wisse-Meier, James A. Wofford, Andrew Woodyard, Wolfram Zerulla.
Application Number | 20170223964 15/327849 |
Document ID | / |
Family ID | 50486853 |
Filed Date | 2017-08-10 |
United States Patent
Application |
20170223964 |
Kind Code |
A1 |
Nave; Barbara ; et
al. |
August 10, 2017 |
Combination of Novel Nitrification Inhibitors and Herbicides as
Well as Combination of (Thio)Phosphoric Acid Triamides and
Herbicides
Abstract
A composition including (a) at least one (thio)phosphoric acid
triamide (T) according to the general formula (Ia)
R.sup.a1R.sup.a2N--P(X)(NH.sub.2).sub.2 (Ia) wherein X is oxygen or
sulfur; R.sup.a1 is a C.sub.1 to C.sub.20 alkyl, C.sub.3 to
C.sub.20 cycloalkyl, C.sub.6 to C.sub.20 aryl, or
dialkylaminocarbonyl group; R.sup.a2 is H; or R.sup.a1 and R.sup.a2
together with the nitrogen atom linking them define a 5- or
6-membered saturated or unsaturated heterocyclic radical, which
optionally comprises 1 or 2 further heteroatoms selected from the
group consisting of nitrogen, oxygen, and sulfur; and (b) at least
one specific herbicide.
Inventors: |
Nave; Barbara;
(Ruppertsberg, DE) ; Dickhaut; Joachim;
(Heidelberg, DE) ; Sisay; Mihiret Tekeste;
(Mannheim, DE) ; Wisse-Meier; Alexander; (Speyer,
DE) ; Zerulla; Wolfram; (Maikammer, DE) ;
Pasda; Gregor; (Neustadt, DE) ; Schneider;
Karl-Heinrich; (Kleinkarlbach, DE) ; Klodwig;
Claudia; (Hessheim, DE) ; Howard; Mark;
(Fuquay Varina, NC) ; Vance; Laura; (Raleigh,
NC) ; Woodyard; Andrew; (Champaign, IL) ;
Fassler; Nicholas; (Raleigh, NC) ; Schmid;
Markus; (Deidesheim, DE) ; Wofford; James A.;
(Fuquay Varina, NC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Family ID: |
50486853 |
Appl. No.: |
15/327849 |
Filed: |
April 16, 2015 |
PCT Filed: |
April 16, 2015 |
PCT NO: |
PCT/US2015/026112 |
371 Date: |
January 20, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C05G 3/60 20200201; A01N
31/14 20130101; C05G 3/90 20200201; Y02P 60/21 20151101; A01N 43/10
20130101; A01N 57/12 20130101; A01N 39/04 20130101; Y02P 60/218
20151101; C05C 1/02 20130101; A01N 57/20 20130101; A01N 43/54
20130101; A01N 31/14 20130101; A01N 37/40 20130101; A01N 37/40
20130101; A01N 39/04 20130101; A01N 43/10 20130101; A01N 43/18
20130101; A01N 43/50 20130101; A01N 43/54 20130101; A01N 43/60
20130101; A01N 43/80 20130101; A01N 47/36 20130101; A01N 47/38
20130101; A01N 57/20 20130101; A01N 57/12 20130101; A01N 37/40
20130101; A01N 37/40 20130101; A01N 39/04 20130101; A01N 43/10
20130101; A01N 43/18 20130101; A01N 43/50 20130101; A01N 43/54
20130101; A01N 43/60 20130101; A01N 43/80 20130101; A01N 47/36
20130101; A01N 47/38 20130101; A01N 57/20 20130101 |
International
Class: |
A01N 57/20 20060101
A01N057/20; A01N 43/10 20060101 A01N043/10; C05G 3/08 20060101
C05G003/08; C05C 1/02 20060101 C05C001/02; C05G 3/02 20060101
C05G003/02; A01N 43/54 20060101 A01N043/54; A01N 39/04 20060101
A01N039/04 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 17, 2014 |
EP |
14165219.8 |
Claims
1. A composition comprising: a) at least one (thio)phosphoric acid
triamide (T) according to the general formula (Ia)
R.sup.a1R.sup.a2N--P(X)(NH.sub.2).sub.2 (Ia) wherein X is oxygen or
sulfur; R.sup.a1 is a C.sub.1 to C.sub.20 alkyl, C.sub.3 to
C.sub.20 cycloalkyl, C.sub.6 to C.sub.20 aryl, or
dialkylaminocarbonyl group; R.sup.a2 is H, or R.sup.a1 and R.sup.a2
together with the nitrogen atom linking them define a 5- or
6-membered saturated or unsaturated heterocyclic radical, which
optionally comprises 1 or 2 further heteroatoms selected from the
group consisting of nitrogen, oxygen, and sulfur; and b) at least
one herbicide selected from the group consisting of: (i) amino acid
derivatives selected from the group consisting of glyphosate
(B.2.1), glufosinate (B.2.2), sulfosate (B.2.3), and bilanafos;
(ii) acetamides selected from the group consisting of acetochlor
(B.1.1), alachlor, butachlor, dimethachlor, dimethenamid (B.1.2),
flufenacet (B.1.3), mefenacet (B.1.4), metolachlor (B.1.5),
metazachlor (B.1.6), napropamide, naproanilide, pethoxamid,
pretilachlor, propachlor, and thenylchlor; (iii)
aryloxyphenoxypropionates selected from the group consisting of
clodinafop (B.3.1), cyhalofop-butyl, fenoxaprop (B.3.2), fluazifop
(B.3.3), haloxyfop (B.3.4), metamifop, propaquizafop (B.3.5),
quizalofop, and quizalofop-P-tefuryl; (iv) bipyridyls selected from
the group consisting of diquat, and paraquat (B.4.1); (v)
(thio)carbamates selected from the group consisting of asulam,
butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC),
esprocarb, molinate, orbencarb, phenmedipham (B.5.1), prosulfocarb,
pyributicarb, thiobencarb, and triallate; (vi) cyclohexanediones
selected from the group consisting of butroxydim, clethodim
(B.6.1), cycloxydim (B.6.2), profoxydim (B.6.3), sethoxydim
(B.6.4), tepraloxydim (B.6.5), and tralkoxydim; (vii)
dinitroanilines selected from the group consisting of benfluralin,
ethalfluralin, oryzalin, pendimethalin (B.7.1), prodiamine (B.7.2),
and trifluralin (B.7.3); (viii) diphenyl ethers selected from the
group consisting of acifluorfen (B.8.1), aclonifen, bifenox,
diclofop, ethoxyfen, fomesafen, lactofen, and oxyfluorfen; (ix)
hydroxybenzonitriles selected from the group consisting of
bomoxynil (B.9.1), dichlobenil, and ioxynil; (x) imidazolinones
selected from the group consisting of imazamethabenz, imazamox
(B.10.1), imazapic (B.10.2), imazapyr (B.10.3), imazaquin (B.10.4),
and imazethapyr (B.10.5); (xi) phenoxy acetic acids selected from
the group consisting of clomeprop, 2,4-dichlorophenoxyacetic acid
(2,4-D) (B.11.1), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB,
and Mecoprop; (xii) pyrazines selected from the group consisting of
chloridazon (B.11.2), flufenpyr-ethyl, fluthiacet, norflurazon, and
pyridate; (xiii) pyridines selected from the group consisting of
aminopyralid, clopyralid (B.12.1), diflufenican, dithiopyr,
fluridone, fluroxypyr (B.12.2), picloram (B.12.3), picolinafen
(B.12.4), and thiazopyr; (xiv) sulfonyl ureas selected from the
group consisting of amidosulfuron, azimsulfuron, bensulfuron
(B.13.1), chlorimuron-ethyl (B.13.2), chlorsulfuron, cinosulfuron,
cyclosulfamuron (B.13.3), ethoxysulfuron, flazasulfuron,
flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron,
imazosulfuron, iodosulfuron (B.13.4), mesosulfuron (B.13.5),
metazosulfuron, metsulfuron-methyl (B.13.6), nicosulfuron (B.13.7),
oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron,
rimsulfuron (B.13.8), sulfometuron, sulfosulfuron, thifensulfuron,
triasulfuron, tribenuron (B.13.10), trifloxysulfuron,
triflusulfuron (B.13.9), tritosulfuron, and
1-((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimet-
hoxy-pyrimidin-2-yl)urea; (xv) triazines selected from the group
consisting of ametryn, atrazine (B.14.1), cyanazine, dimethametryn,
ethiozin, hexazinone (B.14.2), metamitron, metribuzin, prometryn,
simazine, terbuthylazine, terbutryn, and triaziflam; (xvi) ureas
selected from the group consisting of chlorotoluron, daimuron,
diuron (B.15.1), fluometuron, isoproturon, linuron,
methabenzthiazuron, and tebuthiuron; (xvii) other acetolactate
synthase inhibitors selected from the group consisting of
bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam
(B.16.1), flucarbazone, flumetsulam, metosulam, ortho-sulfamuron,
penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim,
pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac,
pyroxasulfone (B.16.2), and pyroxsulam; and (xviii) amicarbazone,
aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone,
benfluresate, benzofenap, bentazone (B.17.1), benzobicyclon,
bicyclopyrone, bromacil, bromobutide, butafenacil, butamifos,
cafenstrole, carfentrazone, cinidon-ethyl (B.17.2), chlorthal,
cinmethylin (B.17.3), clomazone (B.17.4), cumyluron,
cyprosulfamide, dicamba (B.17.5), difenzoquat, diflufenzopyr
(B.17.6), Drechslera monoceras, endothal, ethofumesate,
etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl,
flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan,
isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac
(B.17.7), quinmerac (B.17.8), mesotrione (B.17.9), methyl arsonic
acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone,
pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole,
pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil (B.17.10),
sulcotrione (B.17.11), sulfentrazone, terbacil, tefuryltrione,
tembotrione, thiencarbazone, topramezone (B.17.12),
(3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-
-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl
ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid
methyl ester,
6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol,
4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic
acid,
4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carbox-
ylic acid methyl ester, and
4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2--
carboxylic acid methyl ester.
2. The composition according to claim 1, wherein in the general
formula (Ia) of (T) X is sulfur.
3. The composition according to claim 1, wherein in the general
formula (Ia) of (T) R.sup.a1 is C.sub.1-C.sub.20 alkyl and R.sup.a2
is H.
4. The composition according to claim 1, wherein the
(thio)phosphoric acid triamide (T) is one of
N-n-butylthiophosphoric acid triamide (NBPT) and
N-n-propylthiophosphoric acid triamide (NPPT).
5. The composition according to claim 1, wherein the herbicide is a
herbicide selected from the group consisting of dicamba (B.17.5),
glyphosate (B.2.1), propaquizafop (B.3.5), cycloxydim (B.6.2),
bomoxynil (B.9.1), imazamox (B.10.1), nicosulfuron (B.13.7),
tribenuron (B.13.10), saflufenacil (B.17.10), topramezone (B.17.2),
dimethenamid (B.1.2), and 2,4-dichlorophenoxyacetic acid (2,4-D)
(B.11.1).
6. A method for at least one of increasing the health of a plant
and increasing the herbicidal activity of a herbicide, the method
comprising: treating at least one of (a) a plant growing on at
least one of soil or soil substituents, and (b) and at least one of
the locus, soil, and soil substituents where the plant is at least
one of growing or intended to grow, with a) at least one
(thio)phosphoric acid triamide (T) according to the general formula
(Ia) R.sup.a1R.sup.a2N--P(X)(NH.sub.2).sub.2 (Ia) wherein X is
oxygen or sulfur; R.sup.a1 is a C.sub.1 to C.sub.20 alkyl, C.sub.3
to C.sub.20 cycloalkyl, C.sub.6 to C.sub.20 aryl, or
dialkylaminocarbonyl group; R.sup.a2 is H, or R.sup.a1 and R.sup.a2
together with the nitrogen atom linking them define a 5- or
6-membered saturated or unsaturated heterocyclic radical, which
optionally comprises 1 or 2 further heteroatoms selected from the
group consisting of nitrogen, oxygen, and sulfur and b) at least
one herbicide selected from the group consisting of (i) amino acid
derivatives selected from the group consisting of glyphosate
(B.2.1), glufosinate (B.2.2), sulfosate (B.2.3), and bilanafos;
(ii) acetamides selected from the group consisting of acetochlor
(B.1.1), alachlor, butachlor, dimethachlor, dimethenamid (B.1.2),
flufenacet (B.1.3), mefenacet (B.1.4), metolachlor (B.1.5),
metazachlor (B.1.6), napropamide, naproanilide, pethoxamid,
pretilachlor, propachlor, and thenylchlor; (iii)
aryloxyphenoxypropionates selected from the group consisting of
clodinafop (B.3.1), cyhalofop-butyl, fenoxaprop (B.3.2), fluazifop
(B.3.3), haloxyfop (B.3.4), metamifop, propaquizafop (B.3.5),
quizalofop, and quizalofop-P-tefuryl; (iv) bipyridyls selected from
the group consisting of diquat, and paraquat (B.4.1); (v)
(thio)carbamates selected from the group consisting of asulam,
butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC),
esprocarb, molinate, orbencarb, phenmedipham (B.5.1), prosulfocarb,
pyributicarb, thiobencarb, and triallate; (vi) cyclohexanediones
selected from the group consisting of butroxydim, clethodim
(B.6.1), cycloxydim (B.6.2), profoxydim (B.6.3), sethoxydim
(B.6.4), tepraloxydim (B.6.5), and tralkoxydim; (vii)
dinitroanilines selected from the group consisting of benfluralin,
ethalfluralin, oryzalin, pendimethalin (B.7.1), prodiamine (B.7.2),
and trifluralin (B.7.3); (viii) diphenyl ethers selected from the
group consisting of acifluorfen (B.8.1), aclonifen, bifenox,
diclofop, ethoxyfen, fomesafen, lactofen, and oxyfluorfen; (ix)
hydroxybenzonitriles selected from the group consisting of
bomoxynil (B.9.1), dichlobenil, and ioxynil; (x) imidazolinones
selected from the group consisting of imazamethabenz, imazamox
(B.10.1), imazapic (B.10.2), imazapyr (B.10.3), imazaquin (B.10.4),
and imazethapyr (B.10.5); (xi) phenoxy acetic acids selected from
the group consisting of clomeprop, 2,4-dichlorophenoxyacetic acid
(2,4-D) (B.11.1), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB,
and Mecoprop; (xii) pyrazines selected from the group consisting of
chloridazon (B.11.2), flufenpyr-ethyl, fluthiacet, norflurazon, and
pyridate; (xiii) pyridines selected from the group consisting of
aminopyralid, clopyralid (B.12.1), diflufenican, dithiopyr,
fluridone, fluroxypyr (B.12.2), picloram (B.12.3), picolinafen
(B.12.4), and thiazopyr; (xiv) sulfonyl ureas selected from the
group consisting of amidosulfuron, azimsulfuron, bensulfuron
(B.13.1), chlorimuron-ethyl (B.13.2), chlorsulfuron, cinosulfuron,
cyclosulfamuron (B.13.3), ethoxysulfuron, flazasulfuron,
flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron,
imazosulfuron, iodosulfuron (B.13.4), mesosulfuron (B.13.5),
metazosulfuron, metsulfuron-methyl (B.13.6), nicosulfuron (B.13.7),
oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron,
rimsulfuron (B.13.8), sulfometuron, sulfosulfuron, thifensulfuron,
triasulfuron, tribenuron (B.13.10), trifloxysulfuron,
triflusulfuron (B.13.9), tritosulfuron, and
1-((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimet-
hoxy-pyrimidin-2-yl)urea; (xv) triazines selected from the group
consisting of ametryn, atrazine (B.14.1), cyanazine, dimethametryn,
ethiozin, hexazinone (B.14.2), metamitron, metribuzin, prometryn,
simazine, terbuthylazine, terbutryn, and triaziflam; (xvi) ureas
selected from the group consisting of chlorotoluron, daimuron,
diuron (B.15.1), fluometuron, isoproturon, linuron,
methabenzthiazuron, and tebuthiuron; (xvii) other acetolactate
synthase inhibitors selected from the group consisting of
bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam
(B.16.1), flucarbazone, flumetsulam, metosulam, ortho-sulfamuron,
penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim,
pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac,
pyroxasulfone (B.16.2), and pyroxsulam; and (xviii) amicarbazone,
aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone,
benfluresate, benzofenap, bentazone (B.17.1), benzobicyclon,
bicyclopyrone, bromacil, bromobutide, butafenacil, butamifos,
cafenstrole, carfentrazone, cinidon-ethyl (B.17.2), chlorthal,
cinmethylin (B.17.3), clomazone (B.17.4), cumyluron,
cyprosulfamide, dicamba (B.17.5), difenzoquat, diflufenzopyr
(B.17.6), Drechslera monoceras, endothal, ethofumesate,
etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl,
flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan,
isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac
(B.17.7), quinmerac (B.17.8), mesotrione (B.17.9), methyl arsonic
acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone,
pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole,
pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil (B.17.10),
sulcotrione (B.17.11), sulfentrazone, terbacil, tefuryltrione,
tembotrione, thiencarbazone, topramezone (B.17.12),
(3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-
-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl
ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid
methyl ester,
6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol,
4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic
acid,
4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carbox-
ylic acid methyl ester, and
4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2--
carboxylic acid methyl ester.
7. The method according to claim 6, wherein the plant is
additionally provided with a urea-containing fertilizer selected
from the group consisting of urea, formaldehyde urea, UAN, urea
sulfur, stabilized urea, urea based NPK-fertilizers, and urea
ammonium sulfate.
8. The method according to claim 6, wherein the herbicide is
selected from the group consisting of dicamba (B.17.5), glyphosate
(B.2.1), propaquizafop (B.3.5), cycloxydim (B.6.2), bomoxynil
(B.9.1), imazamox (B.10.1), nicosulfuron (B.13.7), tribenuron
(B.13.10), saflufenacil (B.17.10), topramezone (B.17.2),
dimethenamid (B.1.2), and 2,4-dichlorophenoxyacetic acid (2,4-D)
(B.11.1).
9. The method according to claim 6, wherein the application of the
(thio)phosphoric acid triamide (T) and the herbicide is carried out
simultaneously or with a time lag.
10. A method for at least one of increasing the health of a plant
and increasing the herbicidal activity of the herbicide, the method
comprising using the composition of claim 1.
11-25. (canceled)
26. The method according to claim 9, wherein the application of the
(thio)phosphoric acid triamide (T), the herbicide, and the
urea-containing fertilizer is carried out simultaneously or with a
time lag.
27. The method according to claim 26, wherein the time lag is an
interval selected from the group consisting of 1 day, 2 days, 3
days, 1 week, 2 weeks, and 3 weeks.
28. The method according to claim 9, wherein the time lag is an
interval selected from the group consisting of 1 day, 2 days, 3
days, 1 week, 2 weeks, and 3 weeks.
Description
[0001] The present invention relates to combination of novel
nitrification inhibitors of formula I and herbicides as well as to
the combination of (thio)phosphoric acid triamides and herbicides.
Moreover, the invention relates to the use of this combination of
novel nitrification inhibitors and herbicides for increasing the
health of a plant, and to the use of the combination of
(thio)phosphoric acid triamides and herbicides for increasing the
health of a plant, as well as compositions comprising the
nitrification inhibitor and a herbicide, and compositions
comprising the (thio)phosphoric acid triamide and a herbicide.
Further encompassed by the present invention are methods for
increasing the health of a plant comprising the treatment of
plants, soils and/or loci with said combination of the novel
nitrification inhibitor and a herbicide or with said combination of
(thio)phosphoric acid triamides and a herbicide.
[0002] Nitrogen is an essential element for plant growth, plant
health and reproduction. About 25% of the plant available nitrogen
in soils (ammonium and nitrate) originate from decomposition
processes (mineralization) of organic nitrogen compounds such as
humus, plant and animal residues and organic fertilizers.
Approximately 5% derive from rainfall. On a global basis, the
biggest part (70%), however, are supplied to the plant by inorganic
nitrogen fertilizers. The mainly used nitrogen fertilizers comprise
ammonium compounds or derivatives thereof, i.e. nearly 90% of the
nitrogen fertilizers applied worldwide is in the NH.sub.4.sub.+
form (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302).
This is, inter alia, due to the fact that NH.sub.4 assimilation is
energetically more efficient than assimilation of other nitrogen
sources such as NO.sub.3.sub.-.
[0003] Moreover, being a cation, NH.sub.4 is held electrostatically
by the negatively charged clay surfaces and functional groups of
soil organic matter. This binding is strong enough to limit
NH.sub.4.sub.+-loss by leaching to groundwater. By contrast,
NO.sub.3.sub.-, being negatively charged, does not bind to the soil
and is liable to be leached out of the plants' root zone. In
addition, nitrate may be lost by denitrification which is the
microbiological conversion of nitrate and nitrite (NO.sub.2.sub.-)
to gaseous forms of nitrogen such as nitrous oxide (N.sub.2O) and
molecular nitrogen (N.sub.2).
[0004] However, ammonium (NH.sub.4.sub.+) compounds are converted
by soil microorganisms to nitrates (NO.sub.3.sub.-) in a relatively
short time in a process known as nitrification. The nitrification
is carried out primarily by two groups of chemolithotrophic
bacteria, ammonia-oxidizing bacteria (AOB) of the genus
Nitrosomonas and Nitrobacter, which are ubiquitous component of
soil bacteria populations. The enzyme, which is essentially
responsible for nitrification is ammonia monooxygenase (AMO), which
was also found in ammonia-oxidizing archaea (Subbarao et al., 2012,
Advances in Agronomy, 114, 249-302).
[0005] The nitrification process typically leads to nitrogen
leakage and environmental pollution. As a result of the various
losses, approximately 50% of the applied nitrogen fertilizers is
lost during the year following fertilizer addition (see Nelson and
Huber; Nitrification inhibitors for corn production (2001),
National Corn Handbook, Iowa State University).
[0006] As countermeasures the use of nitrification inhibitors,
mostly together with fertilizers, was suggested. Suitable
nitrification inhibitors include biological nitrification
inhibitors (BNIs) such as linoleic acid, alpha-linolenic acid,
methyl p-coumarate, methyl ferulate, MHPP, Karanjin, brachialacton
or the p-benzoquinone sorgoleone (Subbarao et al., 2012, Advances
in Agronomy, 114, 249-302). Further suitable nitrification
inhibitors are synthetic chemical inhibitors such as Nitrapyrin,
dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DMPP),
4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea
(ASU), 2-amino-4-chloro-6-methylpyrimidine (AM),
5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole), or
2-sulfanilamidothiazole (ST) (Slangen and Kerkhoff, 1984,
Fertilizer research, 5(1), 1-76).
[0007] EP 0 917 526 further mentions the use of polyacids to treat
mineral fertilizers containing a nitrification inhibitor in order
to improve the fixation of the nitrification inhibitors in the
inorganic fertilizer. Moreover, the volatility of the nitrification
inhibitor can be reduced.
[0008] However, many of these inhibitors only work sub-optimal or
have undesirable side effects.
[0009] In view of this situation there is hence a continuous need
for compositions that increase the health of plants. Healthier
plants are desirable since they result among other in better crop
yields and/or a better quality of the plants or crops. Healthier
plants also better resist to biotic and abiotic stress. A better
resistance to stress in turn allows reducing the quantity of
pesticides, which also helps avoiding the development of
resistances against the respective pesticides.
[0010] One object of the present invention is to provide a
composition containing a nitrification inhibitor which increases
the health of plants, and/or provides better crop yields and/or a
better quality of the plants or crops, and/or shows a better
resistance to stress, and/or allows the reduction of the quantity
of pesticides used, and/or helps avoiding the development of
resistances against the respective pesticides
[0011] Another object of the present invention is to provide a
composition containing the (thio)phosphoric acid triamide(s) (T)
which--each preferably through a synergistic action-- [0012] (i)
enhances the stability of the (thio)phosphoric acid triamide(s),
and/or [0013] (ii) enhances the urease inhibiting effect of the
(thio)phosphoric acid triamide(s), and/or [0014] (iii) enhances the
yield increase effect of the (thio)phosphoric acid triamide(s),
and/or [0015] (iv) has a relatively long storage life, particularly
before being applied to or coated on nitrogen-containing
fertilizers, and/or [0016] (v) reduces the emission of nitrous
oxide from soils, and/or [0017] (vi) reduces the ammonia emission
from soils, particularly when applied with urea-containing
fertilizer on the same locus, [0018] (vii) is toxicologically
unobjectionable, and/or [0019] (viii) does not adversely affect the
urease-inhibiting effect and/or activity of the (thio)phosphoric
acid triamide, and/or [0020] (ix) can be easily and safely
packaged, transported and shipped, even in large quantities, and/or
[0021] (x) can be easily and safely handled and applied for soil
treatment, even in large quantities, and/or [0022] (xi) improves
the nutrient use efficiency, and/or [0023] (xii) improves the
delivery of the herbicide to the plant, and/or [0024] (xiii)
improves the plant growth (e.g. biomass, yield, root branching and
length; compact growth in case of ornamental plants), and/or [0025]
(xiv) enables a better developed root system, a larger leaf area,
greener leaves, stronger shoots and/or [0026] (xv) improves the
plant defense of the plants, and/or [0027] (xvi) improves the plant
health of the plants, and/or [0028] (xvii) improves the quality of
the plants, and/or [0029] (xviii) improves the storage or
survivability of the herbicide and/or prolong the availability of
herbicides to the plants, and/or [0030] (xix) enhances the
herbicidal effect of the herbicide, and/or [0031] (xx) allows the
reduction of the quantity of herbicides used, and/or [0032] (xxi)
increase the survivability rate of seedlings, for example
transplanted seedlings, and/or [0033] (xxii) reduce or avoid
unfavorable environmental or toxicological effects whilst still
allowing effective pest control, and/or [0034] (xxiii) enable
earlier seed germination and/or blooming.
[0035] The objects (xiii), (xiv), (xv), (xvi), (xvii) and (xxi)
particularly pertains to such plants or seedlings wherein such
plants or seedlings were, or the soil in which the such plants or
seedlings were placed was subject to the application of composition
of the present invention.
[0036] The preferred objects of the present invention are (i),
(ii), (v), (vi), (vii), (xi), (xii), (xiii), (xiv), (xv), (xvi),
(xvii), (xviii), (xix), (xx), the more preferred objects of the
present invention are (ii), (vi), (xii), (xiii), (xv), (xvi),
(xix), and/or (xx), the most preferred objects of the present
invention are (ii), (vi), (xvi), and/or (xix), the particularly
preferred objects of the present invention are (xvi) and/or
(xix).
[0037] The term "in a synergistic way" means that the composition
comprising the (thio)phosphoric acid triamide (T) and a further
compound can fulfil the one or more of the objects (i) to (xxvii)
significantly better than the individual compounds--i.e. the
(thio)phosphoric acid triamide (T) or said further compound--alone
can do, and preferably, this better fulfilment of the objects by
said composition compared to the individual compounds is evidenced
by calculations according to Colby's formula, see Colby, S. R.
(Calculating synergistic and antagonistic responses of herbicide
Combinations", Weeds, 15, pp. 20-22, 1967).
[0038] The present invention addresses this need and relates to a
combination of a novel nitrification inhibitor of formula I
##STR00001##
[0039] or a stereoisomer, salt, tautomer or N-oxide thereof,
[0040] wherein [0041] A is aryl or hetaryl, wherein the aromatic
ring may in each case be unsubstituted or may be partially or fully
substituted by substituents, which are independently of each other
selected from R.sup.A; [0042] R.sup.1 and R.sup.2 are independently
of each other selected from H and C.sub.1-C.sub.2-alkyl; and [0043]
R.sup.3 is H, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-hydroxyalkyl, ethynylhydroxymethyl,
phenylhydroxymethyl, or aryl, wherein the aromatic ring may be
unsubstituted or may be partially or fully substituted by
substituents, which are independently of each other selected from
R.sup.B;
[0044] and wherein [0045] R.sup.A is [0046] (i) halogen, CN,
NR.sup.aR.sup.b, OR.sup.c, SR.sup.c, C(.dbd.Y.sup.1)R.sup.c,
C(.dbd.Y.sup.1)OR.sup.c, C(.dbd.Y.sup.1)SR.sup.c,
C(.dbd.Y.sup.1)NR.sup.aR.sup.b, Y.sup.2C(.dbd.Y.sup.1)R.sup.c,
Y.sup.2C(.dbd.Y.sup.1)OR.sup.c, Y.sup.2C(.dbd.Y.sup.1)SR.sup.c,
Y.sup.2C(.dbd.Y.sup.1)NR.sup.aR.sup.b,
Y.sup.3Y.sup.2C(.dbd.Y.sup.1)R.sup.c,
NR.sup.gN.dbd.C(R.sup.d)(R.sup.e), C(.dbd.N--OR.sup.c)R.sup.g,
C(.dbd.N--OR.sup.c)R.sup.g, C(.dbd.N--SR.sup.c)R.sup.g,
C(.dbd.N--NR.sup.aR.sup.b)R.sup.g, S(.dbd.O).sub.2R.sup.f,
NR.sup.gS(.dbd.O).sub.2R.sup.f,
S(.dbd.O).sub.2Y.sup.2C(.dbd.Y.sup.1)R.sup.c,
S(.dbd.O).sub.2Y.sup.2C(.dbd.Y.sup.1)OR.sup.c,
S(.dbd.O).sub.2Y.sup.2C(.dbd.Y.sup.1)SR.sup.c,
S(.dbd.O).sub.2Y.sup.2C(.dbd.Y.sup.1)NR.sup.aR.sup.b, NO.sub.2,
NON--CN, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-cyanoalkyl, C.sub.1-C.sub.4-hydroxyalkyl,
C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyl-C.sub.1-C.sub.2-hydroxyalkyl,
C.sub.2-C.sub.4-alkynyloxy; [0047] (ii)
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)R.sup.c,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)R.sup.c,
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)OR.sup.c,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)OR.sup.c,
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)SR.sup.c,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)SR.sup.c,
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)NR.sup.aNR.sup.b,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)NR.sup.aNR.sup.b,
C.sub.1-C.sub.4-alkylene-Y.sup.2--C(.dbd.Y.sup.1)R.sup.c,
C.sub.2-C.sub.4-alkenylene-Y.sup.2--C(.dbd.Y.sup.1)R.sup.c,
C.sub.1-C.sub.4-alkylene-NR.sup.aR.sup.b,
C.sub.2-C.sub.4-alkenylene-NR.sup.aR.sup.b,
C.sub.1-C.sub.4-alkylene-OR.sup.c,
C.sub.2-C.sub.4-alkenylene-OR.sup.c,
C.sub.1-C.sub.4-alkylene-SR.sup.c,
C.sub.2-C.sub.4-alkenylene-SR.sup.c, wherein the
C.sub.1-C.sub.4-alkylene or C.sub.2-C.sub.4-alkenylene chain may in
each case be unsubstituted or may be partially or fully substituted
by OR.sup.g, CN, halogen or phenyl; [0048] (iii) aryl,
aryl-C.sub.1-C.sub.2-alkyl, hetaryl or
hetaryl-C.sub.1-C.sub.2-alkyl, wherein the aromatic ring of the
aryl or hetaryl group may be unsubstituted or may be partially or
fully substituted by substituents, which are independently of each
other selected from R.sup.h; [0049] (iv) a 3- to 14-membered
saturated or unsaturated carbocycle or heterocycle, which may
contain 1, 2, or 3 heteroatoms which, independently of each other,
are selected from NR.sup.1b, O, and S, wherein S may be oxidized
and/or wherein the carbocycle or heterocycle may be unsubstituted
or may be partially or fully substituted by substituents which,
independently of each other, are selected from R.sup.i; and wherein
R.sup.1b is H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g; or [0050] (v) L-B, wherein [0051] L is --CH.sub.2--,
--CH.dbd.CH--, --C.ident.C--, --C(.dbd.O)-- or --CH.dbd., and
[0052] B is aryl or hetaryl, wherein the aromatic ring of the ary
or hetaryl group may be unsubstituted or may be partially or fully
substituted by substituents, which are independently of each other
selected from R.sup.h; [0053] or [0054] a 3- to 14-membered
saturated or unsaturated carbocycle or heterocycle, which may
contain 1, 2, or 3 heteroatoms which, independently of each other,
are selected from NR.sup.1b, O, and S, wherein S may be oxidized
and/or wherein the carbocycle or heterocycle may be unsubstituted
or may be partially or fully substituted by substituents which,
independently of each other, are selected from R.sup.i; and wherein
R.sup.1b is H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g; or [0055] (vi) two substituents R.sup.A together
represent a carbocyclic or heterocyclic ring, which is fused to A
and may contain 1, 2, or 3 heteroatoms which, independently of each
other, are selected from NR.sup.1c, O, and S, wherein S may be
oxidized and/or wherein the carbocycle or heterocycle may be
unsubstituted or may be partially or fully substituted by
substituents which, independently of each other, are selected from
R.sup.i; and wherein R.sup.1c is H, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkylmethyl, C.sub.3-C.sub.6-heterocyclyl,
C.sub.3-C.sub.6-heterocyclylmethyl or OR.sup.g;
[0056] and wherein [0057] R.sup.B is
NH--C(.dbd.O)--(C.sub.1-C.sub.4-alkyl),
NH--C(.dbd.O)--(C.sub.2-C.sub.4-alkenyl),
NH--C(.dbd.O)--(C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl),
NH--C(.dbd.O)--(C.sub.3-C.sub.6-cycloalkyl),
NH--S(.dbd.O).sub.2--(C.sub.1-C.sub.4-alkyl), or NO.sub.2;
[0058] and wherein [0059] Y.sup.1, Y.sup.2 and Y.sup.3 are
independently of each other selected from O, S and NR.sup.1a,
wherein R.sup.1a is in each case independently H,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl,
OR.sup.g, SR.sup.g or NR.sup.mR.sup.n; [0060] R.sup.a and R.sup.b
are independently of each other selected from [0061] (i) H,
NR.sup.jR.sup.k, OR.sup.l, SR.sup.l, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl,
C.sub.1-C.sub.4-hydroxyalkyl, C.sub.1-C.sub.4-alkoxy,
C(.dbd.Y.sup.1)R.sup.l, C(.dbd.Y.sup.1)OR.sup.l,
C(.dbd.Y.sup.1)SR.sup.l, C(.dbd.Y.sup.1)NR.sup.jR.sup.k,
C(.dbd.Y.sup.1)C(.dbd.Y.sup.2)R.sup.l, S(.dbd.O).sub.2R.sup.f;
[0062] (ii) aryl or hetaryl, wherein the aromatic ring of the aryl
or hetaryl group may be unsubstituted or may be partially or fully
substituted by substituents, which are independently of each other
selected from R.sup.h; or [0063] R.sup.a and R.sup.b together with
the nitrogen atom to which they are bound form [0064] (iii) a
hetaryl group which may be unsubstituted or may be partially or
fully substituted by substituents, which are independently of each
other selected from R.sup.h; or [0065] (iv) a 3- to 10-membered,
saturated or unsaturated heterocycle, which may contain 1, 2, or 3
heteroatoms which, independently of each other, are selected from
NR.sup.1b, O, and S, wherein S may be oxidized and/or wherein the
heterocycle may be unsubstituted or may be partially or fully
substituted by substituents which, independently of each other, are
selected from R.sup.i; and wherein R.sup.1b is H,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g; [0066] R.sup.c is [0067] (i) H, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl,
C(.dbd.O)OR.sup.l, C(.dbd.O)SR.sup.l, C(.dbd.O)NR.sup.jR.sup.k;
[0068] (ii) C.sub.1-C.sub.4-alkylene-C(.dbd.O)R.sup.l,
C.sub.1-C.sub.4-alkylene-C(.dbd.O)OR.sup.l, wherein the
C.sub.1-C.sub.4-alkylene chain may in each case be unsubstituted or
may be partially or fully substituted by OR.sup.g, CN, halogen, or
phenyl; [0069] (iii) aryl, aryl-C.sub.1-C.sub.2-alkyl, hetaryl, or
hetaryl-C.sub.1-C.sub.2-alkyl, wherein the aromatic ring of the
aryl or hetaryl group may be unsubstituted or may be partially or
fully substituted by substituents, which are independently of each
other selected from R.sup.h; or [0070] (iv) a 3- to 10-membered
saturated or unsaturated carbocycle or heterocycle, which may
contain 1, 2, or 3 heteroatoms which, independently of each other,
are selected from NR.sup.1b, O, and S, wherein S may be oxidized
and/or wherein the carbocycle or heterocycle may be unsubstituted
or may be partially or fully substituted by substituents which,
independently of each other, are selected from R.sup.i; and wherein
R.sup.1b is H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g; [0071] R.sup.d and R.sup.e are independently selected
from C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
NR.sup.jR.sup.k, OR.sup.l, SR.sup.l, CN, C(.dbd.Y.sup.1)R.sup.l,
C(.dbd.Y.sup.1)OR.sup.l, C(.dbd.Y.sup.1)SR.sup.l, or
C(.dbd.Y.sup.1)NR.sup.jR.sup.k; [0072] R.sup.f is
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, NR.sup.jR.sup.k,
OR.sup.l, SR.sup.l, aryl or hetaryl, wherein the aromatic ring of
the aryl or hetaryl group may be unsubstituted or may be partially
or fully substituted by substituents, which are independently of
each other selected from R.sup.h; [0073] R.sup.g is H or
C.sub.1-C.sub.4-alkyl; [0074] R.sup.h is halogen, CN, NO.sub.2,
NR.sup.jR.sup.k, OR.sup.l, SR.sup.l, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyloxy, C(.dbd.Y.sup.1)R.sup.l,
C(.dbd.Y.sup.1)OR.sup.l, C(.dbd.Y.sup.1)SR.sup.l,
C(.dbd.Y.sup.1)NR.sup.jR.sup.k, aryl, aryloxy, hetaryl and
hetaryloxy; [0075] R.sup.i is [0076] (i) halogen, CN,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.2-C.sub.4-haloalkenyl; [0077] (ii)=NR.sup.1d, wherein
R.sup.1d is H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g; [0078] (iii)=O, .dbd.S, NR.sup.jR.sup.k, OR.sup.l,
SR.sup.l, C(.dbd.Y.sup.1)R.sup.l, C(.dbd.Y.sup.1)OR.sup.l,
C(.dbd.Y.sup.1)SR.sup.l, C(.dbd.Y.sup.1)NR.sup.jR.sup.k; [0079]
(iv) aryl, aryl-C.sub.1-C.sub.2-alkyl, hetaryl, or
hetaryl-C.sub.1-C.sub.2-alkyl, wherein the aromatic ring of the
aryl or hetaryl group may be unsubstituted or may be partially or
fully substituted by substituents, which are independently of each
other selected from halogen, CN, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyloxy, OR.sup.g, and SR.sup.g; or [0080] (v)
C.sub.3-C.sub.6-cycloalkyl, or 3- to 6-membered heterocyclyl,
wherein the cycloalkyl ring or the heterocyclyl ring may be
unsubstituted or may be partially or fully substituted by
substituents, which are independently of each other selected from
halogen, CN, C.sub.1-C.sub.4-alkyl, OR.sup.g, and SR.sup.g; [0081]
R.sup.j and R.sup.k are independently selected from H, OR.sup.g,
SR.sup.g, C(.dbd.Y.sup.1)R.sup.g, C(.dbd.Y.sup.1)OR.sup.g,
C(.dbd.Y.sup.1)SR.sup.g, C(.dbd.Y.sup.1)NR.sup.mR.sup.n,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-haloalkyl, aryl or
hetaryl, wherein the aromatic ring of the aryl or hetaryl group may
be unsubstituted or may be partially or fully substituted by
substituents, which are independently selected from halogen, CN,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.2-C.sub.4-alkynyloxy, OR.sup.g, and
SR.sup.g; [0082] R.sup.l is H, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl,
C.sub.1-C.sub.4-haloalkyl, C(.dbd.Y.sup.1)R.sup.g,
C(.dbd.Y.sup.1)OR.sup.g, C(.dbd.Y.sup.1)SR.sup.g,
C(.dbd.Y.sup.1)NR.sup.mR.sup.n, aryl or hetaryl, wherein the
aromatic ring of the aryl or hetaryl group may be unsubstituted or
may be partially or fully substituted by substituents, which are
independently selected from halogen, CN, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyloxy, OR.sup.g, and SR.sup.g; and [0083]
R.sup.m and R.sup.n are independently selected from H and
C.sub.1-C.sub.4-alkyl;
[0084] and a herbicide.
[0085] The inventors surprisingly found that by applying the
compound of formula I as defined herein above and of a herbicide
the nitrification of ammonium to nitrate could significantly be
reduced, biotic stress could be reduced and in consequence the
health of a plant could be increased.
[0086] The inventors surprisingly found that by applying the
(thio)phosphoric acid triamide (T) as defined herein above and of a
herbicide the urease inhibiting effect of the (thio)phosphoric acid
triamide(s) could be enhanced, biotic stress could be reduced and
in consequence the health of a plant could be increased, also the
herbicidal activity of the herbicide could be enhanced, and other
objects as mentioned above under the list (i) to (xxviii) could be
fulfilled preferably in a synergistic way.
[0087] The present invention relates in another aspect to the
composition (Q) comprising a herbicide and a (thio)phosphoric acid
triamide according to the general formula (Ia)
R.sup.a1R.sup.a2N--P(X)(NH.sub.2).sub.2 (Ia) [0088] wherein [0089]
X is oxygen or sulfur; [0090] R.sup.a1 is a C.sub.1 to C.sub.20
alkyl, C.sub.3 to C.sub.20 cycloalkyl, C.sub.6 to C.sub.20 aryl, or
dialkylaminocarbonyl group; [0091] R.sup.a2 is H, or [0092]
R.sup.a1 and R.sup.a2 together with the nitrogen atom linking them
define a 5- or 6-membered saturated or unsaturated heterocyclic
radical, which optionally comprises 1 or 2 further heteroatoms
selected from the group consisting of nitrogen, oxygen, and
sulfur,
[0093] and the present invention preferably relates to a
composition (Q) comprising a herbicide and a (thio)phosphoric acid
triamide according to the general formula (Ia) and not comprising
any nitrification inhibitor of the compound of formula I.
[0094] The "(thio)phosphoric acid triamide according to the general
formula (Ia)" is also referred to as "(thio)phosphoric acid
triamide (T)" or "(T)" in the present patent application. "wt. %"
refers to "percent by weight".
[0095] The composition (Q) also includes kit-of-parts comprising a
herbicide and (T). Here, the term "kit-of-parts" is to be
understood to denote a kit comprising at least two separate parts
wherein each of the parts can be independently removed from the
kit. A kit includes a box, a tool, a vessel, a container, a bag or
any kit-like equipment. Also a kit whose separate parts are only
together in this one kit for a extremely short period of time are
regarded as kit-of-parts. Kit-of-parts are useful for the combined
application (of the contents) of the separate parts of the kit.
[0096] The present invention relates in another aspect to the use
of a composition (Q) comprising a herbicide and a (thio)phosphoric
acid triamide (T) for increasing the health of a plant, and the
present invention preferably relates to the use of a composition
(Q) comprising a herbicide and a (thio)phosphoric acid triamide (T)
and not comprising any nitrification inhibitor of the compound of
formula I for increasing the health of a plant.
[0097] The present invention relates in another aspect to the use
of a composition (Q) comprising a herbicide and a (thio)phosphoric
acid triamide (T) for increasing the herbicidal activity of the
herbicide, and the present invention preferably relates to the use
of a composition (Q) comprising a herbicide and a (thio)phosphoric
acid triamide (T) and not comprising any nitrification inhibitor of
the compound of formula I for increasing the herbicidal activity of
the herbicide.
[0098] X in the general formula (Ia) is preferably sulfur.
[0099] R.sup.a1 in the general formula (Ia) is preferably
C.sub.1-C.sub.20-alkyl, more preferably C.sub.1-C.sub.10-alkyl,
most preferably C.sub.2-C.sub.7 alkyl, for example C.sub.3-C.sub.4
alkyl. Examples of alkyl groups are methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl,
isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl,
octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl and isodecyl.
Examples of cycloalkyl groups are cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl and cyclooctyl, examples of aryl groups are
phenyl or naphthyl. Examples of heterocyclic radicals
R.sup.a1R.sup.a2N-- are piperazinyl, morpholinyl, pyrrolyl,
pyrazolyl, triazolyl, oxazolyl, thiazolyl or imidazolyl groups.
[0100] According to one embodiment, the (thio)phosphoric acid
triamide (T) is preferably N-n-butylthiophosphoric acid triamide
(NBPT) and/or N-n-propylthiophosphoric acid triamide (NPPT), more
preferably NBPT. According to another embodiment, (T) is preferably
NPPT. According to another embodiment, (T) is preferably LIMUS,
i.e. a mixture of NBPT and NPPT with about NBPT at 63% and NPPT at
22%, secondary compounds at 10%, further secondary compounds such
as amines below 4% and dimerease derivatives below 1%.
[0101] According to another embodiment, the composition (Q)
comprises a herbicide and at least two different (thio)phosphoric
acid triamides (T) having structures of the general formula (Ia)
and wherein said at least two different (thio)phosphoric acid
triamides differ in a of radicals R.sup.a1 or R.sup.a2, and
preferably, one of said at least two different (thio)phosphoric
acid triamides is N-n-butylthiophosphoric acid triamide (NBPT), and
more preferably, the other of said at least two different
(thio)phosphoric acid triamides is selected from the group
consisting of N-cyclohexyl-, N-pentyl-, N-isobutyl- and
N-n-propylphosphoric acid triamide and -thiophosphoric acid
triamide. More preferably, (Q) comprises a herbicide, NBPT and
NPPT. Particularly preferably, (Q) comprises a herbicide, NBPT and
NPPT, wherein NBPT is present in amounts of from 1 to 99.99 wt. %,
more preferably from 10 to 99.9 wt. %, most preferably from 20 to
99 wt. %, particularly preferably from 30 to 98 wt. %, more
particularly preferably from 40 to 95 wt. %, most particularly
preferably from 50 to 90 wt. %, especially from 60 to 85 wt. %,
especially preferably from 72 to 80 wt. %, for example from 74 to
77 wt. %, in each case based on the total weight of the
(thio)phosphoric acid triamides (T) contained in the composition
(Q).
[0102] Generally, the (thio)phosphoric acid triamides (T) can be
contained in varying amounts in the composition (Q). Preferably,
the amount of (T) is not more than 95 wt. % (wt. % stands for
"percent by weight"), more preferably not more than 90 wt. %, most
preferably not more than 85 wt. %, more particularly preferably not
more than 75 wt. %, most particularly preferably not more than 65
wt. %, particularly not more than 55 wt. %, especially not more
than 45 wt. % for example not more than 35 wt. %, based on the
total weight of the composition (Q). Preferably, the amount of (T)
is at least 1 wt. %, more preferably at least 4 wt. %, most
preferably at least 14 wt. %, more particularly preferably at least
24 wt. %, most particularly preferably at least 34 wt. %,
particularly at least 44 wt. %, especially at least 54 wt. %, for
example at least 64 wt. %, based on the total weight of the
composition (Q).
[0103] According to another embodiment, the composition (Q)
preferably does not comprise any nitrification inhibitor of the
compound of formula I.
[0104] Thus, in one aspect the present invention relates to the use
of combination of a herbicide and a nitrification inhibitor for
increasing the health of a plant, wherein said nitrification
inhibitor is a compound of formula I as defined herein above.
[0105] In a preferred embodiment of said use, in said compound of
formula I, A is phenyl or a 5- or 6-membered hetaryl, wherein the
aromatic ring may in each case be unsubstituted or may be partially
or fully substituted by substituents, which are independently of
each other selected from R.sup.A.
[0106] In another preferred embodiment of said use, in said
compound of formula I, R.sup.1 and R.sup.2 both represent
hydrogen.
[0107] In yet another preferred embodiment of said use, in said
compound of formula I, R.sup.3 is hydrogen,
C.sub.1-C.sub.4-haloalkyl or ethinylhydroxymethyl, and preferably
R.sup.3 is hydrogen.
[0108] In still another preferred embodiment of said use, in said
compound of formula I, R.sup.A, if present, is [0109] (i) halogen,
CN, NR.sup.aR.sup.b, OR.sup.c, C(.dbd.Y.sup.1)R.sup.c,
C(.dbd.Y.sup.1)OR.sup.c, C(.dbd.Y.sup.1)SR.sup.c,
C(.dbd.Y.sup.1)NR.sup.aR.sup.b, Y.sup.2C(.dbd.Y.sup.1)R.sup.c,
Y.sup.2C(.dbd.Y.sup.1)NR.sup.aR.sup.b,
NR.sup.gN.dbd.C(R.sup.d)(R.sup.e), S(.dbd.O).sub.2R.sup.f,
NO.sub.2, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyl-C.sub.1-C.sub.2-hydroxyalkyl,
C.sub.2-C.sub.4-alkynyloxy; [0110] (ii)
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)R.sup.c,
C.sub.2-C.sub.4-alkenylene-Y.sup.2--C(.dbd.Y.sup.1)R.sup.c, wherein
the C.sub.1-C.sub.4-alkylene or C.sub.2-C.sub.4-alkenylene chain
may in each case be unsubstituted or may be partially or fully
substituted by CN or halogen; [0111] (iii) aryl, wherein the
aromatic ring of the aryl group may be unsubstituted or may be
partially or fully substituted by substituents, which are
independently of each other selected from R.sup.h; or [0112] (iv) a
3- to 14-membered saturated or unsaturated heterocycle, which may
contain 1, 2, or 3 heteroatoms which, independently of each other,
are selected from NR.sup.1b, O, and S, wherein S may be oxidized
and/or wherein the heterocycle may be unsubstituted or may be
partially or fully substituted by substituents which, independently
of each other, are selected from R.sup.i; and wherein R.sup.1b is
H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g.
[0113] In a further preferred embodiment of said use, the herbicide
is at least one herbicide selected form the group of herbicides
comprising: [0114] (i) acetamides selected from acetochlor (B.1.1),
alachlor, butachlor, dimethachlor, dimethenamid (B.1.2), flufenacet
(B.1.3), mefenacet (B.1.4), metolachlor (B.1.5), metazachlor
(B.1.6), napropamide, naproanilide, pethoxamid, pretilachlor,
propachlor, thenylchlor; [0115] (ii) amino acid derivatives
selected from bilanafos, glyphosate (B.2.1), glufosinate (B.2.2),
sulfosate (B.2.3); [0116] (iii) aryloxyphenoxypropionates selected
from clodinafop (B.3.1), cyhalofop-butyl, fenoxaprop (B.3.2),
fluazifop (B.3.3), haloxyfop (B.3.4), metamifop, propaquizafop
(B.3.5), quizalofop, quizalofop-P-tefuryl; [0117] (iv) bipyridyls
selected from diquat, paraquat (B.4.1); [0118] (v) (thio)carbamates
selected from asulam, butylate, carbetamide, desmedipham,
dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb,
phenmedipham (B.5.1), prosulfocarb, pyributicarb, thiobencarb,
triallate; [0119] (vi) cyclohexanediones selected from butroxydim,
clethodim (B.6.1), cycloxydim (B.6.2), profoxydim (B.6.3),
sethoxydim (B.6.4), tepraloxydim (B.6.5), tralkoxydim; [0120] (vii)
dinitroanilines selected from benfluralin, ethalfluralin, oryzalin,
pendimethalin (B.7.1), prodiamine (B.7.2), trifluralin (B.7.3);
[0121] (viii) diphenyl ethers selected from acifluorfen (B.8.1),
aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen,
oxyfluorfen; [0122] (ix) hydroxybenzonitriles selected from
bomoxynil (B.9.1), dichlobenil, ioxynil; [0123] (x) imidazolinones
selected from imazamethabenz, imazamox (B.10.1), imazapic (B.10.2),
imazapyr (B.10.3), imazaquin (B.10.4), imazethapyr (B.10.5); [0124]
(xi) phenoxy acetic acids selected from clomeprop,
2,4-dichlorophenoxyacetic acid (2,4-D) (B.11.1), 2,4-DB,
dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop; [0125] (xii)
pyrazines selected from chloridazon (B.11.2), flufenpyr-ethyl,
fluthiacet, norflurazon, pyridate; [0126] (xiii) pyridines selected
from aminopyralid, clopyralid (B.12.1), diflufenican, dithiopyr,
fluridone, fluroxypyr (B.12.2), picloram (B.12.3), picolinafen
(B.12.4), thiazopyr; [0127] (xiv) sulfonyl ureas selected from
amidosulfuron, azimsulfuron, bensulfuron (B.13.1),
chlorimuron-ethyl (B.13.2), chlorsulfuron, cinosulfuron,
cyclosulfamuron (B.13.3), ethoxysulfuron, flazasulfuron,
flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron,
imazosulfuron, iodosulfuron (B.13.4), mesosulfuron (B.13.5),
metazosulfuron, metsulfuron-methyl (B.13.6), nicosulfuron (B.13.7),
oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron,
rimsulfuron (B.13.8), sulfometuron, sulfosulfuron, thifensulfuron,
triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron
(B.13.9), tritosulfuron,
1-((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimet-
hoxy-pyrimidin-2-yl)urea; [0128] (xv) triazines selected from
ametryn, atrazine (B.14.1), cyanazine, dimethametryn, ethiozin,
hexazinone (B.14.2), metamitron, metribuzin, prometryn, simazine,
terbuthylazine, terbutryn, triaziflam; [0129] (xvi) ureas selected
from chlorotoluron, daimuron, diuron (B.15.1), fluometuron,
isoproturon, linuron, methabenzthiazuron, tebuthiuron; [0130]
(xvii) other acetolactate synthase inhibitors selected from
bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam
(B.16.1), flucarbazone, flumetsulam, metosulam, ortho-sulfamuron,
penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim,
pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac,
pyroxasulfone (B.16.2), pyroxsulam; and [0131] (xviii)
amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin,
bencarbazone, benfluresate, benzofenap, bentazone (B.17.1),
benzobicyclon, bicyclopyrone, bromacil, bromobutide, butafenacil,
butamifos, cafenstrole, carfentrazone, cinidon-ethyl (B.17.2),
chlorthal, cinmethylin (B.17.3), clomazone (B.17.4), cumyluron,
cyprosulfamide, dicamba (B.17.5), difenzoquat, diflufenzopyr
(B.17.6), Drechslera monoceras, endothal, ethofumesate,
etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl,
flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan,
isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac
(B.17.7), quinmerac (B.17.8), mesotrione (B.17.9), methyl arsonic
acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone,
pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole,
pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil (B.17.10),
sulcotrione (B.17.11), sulfentrazone, terbacil, tefuryltrione,
tembotrione, thiencarbazone, topramezone (B.17.12),
(3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-
-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl
ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid
methyl ester,
6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol,
4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic
acid,
4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carbox-
ylic acid methyl ester, and
4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2--
carboxylic acid methyl ester.
[0132] In a particularly preferred embodiment, said herbicide is
dicamba (B.17.5), glyphosate (B.2.1), propaquizafop (B.3.5),
cycloxydim (B.6.2), bomoxynil (B.9.1), imazamox (B.10.1),
nicosulfuron (B.13.7), tribenuron (B.13.10), saflufenacil
(B.17.10), or topramezone (B.17.2).
[0133] In a further preferred embodiment, said combination of a
nitrification inhibitor or (T) and a herbicide further comprises a
fertilizer.
[0134] In a further aspect the present invention relates to a
composition for increasing the health of a plant comprising at
least one nitrification inhibitor as defined herein above and at
least one herbicide as defined herein above.
[0135] In a further aspect the present invention relates to a
composition for increasing the health of a plant comprising a
(thio)phosphoric acid triamide (T) and at least one herbicide as
defined herein above.
[0136] In a preferred embodiment said agricultural composition
additionally comprises at least one carrier.
[0137] In another aspect the present invention relates to a method
for increasing the health of a plant, comprising treating a plant
growing on soil or soil substituents and/or the locus or soil or
soil substituents where the plant is growing or is intended to grow
with a combination of at least one nitrification inhibitor and at
least one herbicide as defined herein above, or a composition as
defined herein above.
[0138] In a preferred embodiment of the method the plant and/or the
locus or soil or soil substituents where the plant is growing or is
intended to grow is additionally provided with a fertilizer.
[0139] In a further preferred embodiment of the method, the
application of said nitrification inhibitor (A) and of said
herbicide (B), and optionally of said fertilizer (C) is carried out
simultaneously or with a time lag.
[0140] In a further preferred embodiment of the method, the
application of (thio)phosphoric acid triamide (T) and of said
herbicide (B), and optionally of said fertilizer (C) is carried out
simultaneously or with a time lag.
[0141] In a particularly preferred embodiment, said time lag is an
interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.
[0142] In a further preferred embodiment of a use, composition or
method of the invention as mentioned herein above, said increase of
the health of a plant is reflected by an increase in growth of root
and shoot, an overall increase in productivity and/or a faster and
more efficient development of the plant.
[0143] In a further preferred embodiment of the use, composition or
method of the invention as mentioned herein above, said plant is an
agricultural plant such as wheat, barley, oat, rye, soybean, corn,
oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet,
rice or a vegetable such as spinach, lettuce, asparagus, or
cabbages; or sorghum; a silvicultural plant; an ornamental plant;
or a horticultural plant, each in its natural or in a genetically
modified form.
[0144] In addition, a process for treating the soil comprising
applying the compositions of the invention into the soil in-furrow
and/or as side dress and/or as broadcast was found.
[0145] The present invention relates in one aspect to the use of a
herbicide and a nitrification inhibitor for increasing the health
of a plant, wherein said nitrification inhibitor is a compound of
formula I as defined herein.
[0146] The present invention relates in another aspect to the use
of a herbicide and a (thio)phosphoric acid triamide (T) for
increasing the health of a plant.
[0147] Although the present invention will be described with
respect to particular embodiments, this description is not to be
construed in a limiting sense.
[0148] Before describing in detail exemplary embodiments of the
present invention, definitions important for understanding the
present invention are given. As used in this specification and in
the appended claims, the singular forms of "a" and "an" also
include the respective plurals unless the context clearly dictates
otherwise. In the context of the present invention, the terms
"about" and "approximately" denote an interval of accuracy that a
person skilled in the art will understand to still ensure the
technical effect of the feature in question. The term typically
indicates a deviation from the indicated numerical value of
.+-.20%, preferably .+-.15%, more preferably .+-.10%, and even more
preferably .+-.5%. It is to be understood that the term
"comprising" is not limiting. For the purposes of the present
invention the term "consisting of" is considered to be a preferred
embodiment of the term "comprising of". If hereinafter a group is
defined to comprise at least a certain number of embodiments, this
is meant to also encompass a group which preferably consists of
these embodiments only. Furthermore, the terms "first", "second",
"third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the
description and in the claims, are used for distinguishing between
similar elements and not necessarily for describing a sequential or
chronological order. It is to be understood that the terms so used
are interchangeable under appropriate circumstances and that the
embodiments of the invention described herein are capable of
operation in other sequences than described or illustrated herein.
In case the terms "first", "second", "third" or "(a)", "(b)",
"(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or
assay there is no time or time interval coherence between the
steps, i.e. the steps may be carried out simultaneously or there
may be time intervals of seconds, minutes, hours, days, weeks,
months or even years between such steps, unless otherwise indicated
in the application as set forth herein above or below. It is to be
understood that this invention is not limited to the particular
methodology, protocols, reagents etc. described herein as these may
vary. It is also to be understood that the terminology used herein
is for the purpose of describing particular embodiments only, and
is not intended to limit the scope of the present invention that
will be limited only by the appended claims. Unless defined
otherwise, all technical and scientific terms used herein have the
same meanings as commonly understood by one of ordinary skill in
the art.
[0149] The term "nitrification inhibitor" is to be understood in
this context as a chemical substance which slows down or stops the
nitrification process. Nitrification inhibitors accordingly retard
the natural transformation of ammonium into nitrate, by inhibiting
the activity of bacteria such as Nitrosomonas spp. The term
"nitrification" as used herein is to be understood as the
biological oxidation of ammonia (NH.sub.3) or ammonium
(NH.sub.4.sub.+) with oxygen into nitrite (NO.sub.2.sub.-) followed
by the oxidation of these nitrites into nitrates (NO.sub.3.sub.-)
by microorganisms. Besides nitrate (NO.sub.3.sub.-) nitrous oxide
is also produced though nitrification. Nitrification is an
important step in the nitrogen cycle in soil. The inhibition of
nitrification may thus also reduce NO.sub.2 losses.
[0150] The term "compound(s) according to the invention", or
"compounds of formula I" comprises the compound(s) as defined
herein as well as a stereoisomer, salt, tautomer or N-oxide
thereof. The term "compound(s) of the present invention" is to be
understood as equivalent to the term "compound(s) according to the
invention", therefore also comprising a stereoisomer, salt,
tautomer or N-oxide thereof.
[0151] The compounds of formula I may be amorphous or may exist in
one or more different crystalline states (polymorphs) which may
have different macroscopic properties such as stability or show
different biological properties such as activities. The present
invention relates to amorphous and crystalline compounds of formula
I, mixtures of different crystalline states of the respective
compound I, as well as amorphous or crystalline salts thereof.
[0152] Salts of the compounds of the formula I are preferably
agriculturally acceptable salts. They can be formed in a customary
manner, e.g. by reacting the compound with an acid of the anion in
question if the compound of formula I has a basic functionality.
Agriculturally useful salts of the compounds of formula I encompass
especially the acid addition salts of those acids whose cations and
anions, respectively, have no adverse effect on the mode of action
of the compounds of formula I. Anions of useful acid addition salts
are primarily chloride, bromide, fluoride, hydrogensulfate,
sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate,
nitrate, bicarbonate, carbonate, hexafluorosilicate,
hexafluorophosphate, benzoate, and the anions of
C.sub.1-C.sub.4-alkanoic acids, preferably formate, acetate,
propionate and butyrate. They can be formed by reacting compounds
of formula I with an acid of the corresponding anion, preferably of
hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid
or nitric acid.
[0153] The term "N-oxide" includes any compound of formula I which
has at least one tertiary nitrogen atom that is oxidized to an
N-oxide moiety.
[0154] The organic moieties mentioned in the above definitions of
the variables are--like the term halogen--collective terms for
individual listings of the individual group members. The prefix
C.sub.n-C.sub.m indicates in each case the possible number of
carbon atoms in the group.
[0155] The term "halogen" denotes in each case fluorine, bromine,
chlorine or iodine, in particular fluorine, chlorine or
bromine.
[0156] The term "alkyl" as used herein denotes in each case a
straight-chain or branched alkyl group having usually from 1 to 10
carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to
4 carbon atoms, more preferably from 1 to 3 carbon atoms. Examples
of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl,
2-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl,
2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl,
n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl.
[0157] The term "haloalkyl" as used herein denotes in each case a
straight-chain or branched alkyl group having usually from 1 to 10
carbon atoms, frequently from 1 to 6 carbon atoms, preferably from
1 to 4 carbon atoms, wherein the hydrogen atoms of this group are
partially or totally replaced with halogen atoms. Preferred
haloalkyl moieties are selected from C.sub.1-C.sub.4-haloalkyl,
more preferably from C.sub.1-C.sub.3-haloalkyl or
C.sub.1-C.sub.2-haloalkyl, in particular from
C.sub.1-C.sub.2-fluoroalkyl such as fluoromethyl, difluoromethyl,
trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,
2,2,2-trifluoroethyl, pentafluoroethyl, and the like.
[0158] The term "cyanoalkyl" as used herein denotes in each case a
straight-chain or branched alkyl group having usually from 1 to 10
carbon atoms, frequently from 1 to 6 carbon atoms, preferably from
1 to 4 carbon atoms, wherein the hydrogen atoms of this group are
partially or totally replaced with cyano groups. Preferred
cyanoalkyl moieties are selected from C.sub.1-C.sub.4-cyanoalkyl,
more preferably from C.sub.1-C.sub.3-cyanooalkyl or
C.sub.1-C.sub.2-cyanoalkyl.
[0159] The term "hydroxyalkyl" as used herein denotes in each case
a straight-chain or branched alkyl group having usually from 1 to
10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably
from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group
are partially or totally replaced with hydroxy groups. Preferred
hydroxyalkyl moieties are selected from
C.sub.1-C.sub.4-hydroxyalkyl, more preferably from
C.sub.1--C-hydroxyalkyl or C.sub.1-C.sub.2-hydroxyalkyl. Preferred
hydroxyalkyl moieties are selected from hydroxymethyl,
dihydroxymethyl, trihydroxymethyl, 1-hydroxyethyl and
2-hydroxyethyl. The term "ethynylhydroxymethyl" as used herein
refers to the following substituent.
##STR00002##
[0160] The term "phenylhydroxymethyl" as used herein refers to the
following substituent.
##STR00003##
[0161] The term "alkoxy" as used herein denotes in each case a
straight-chain or branched alkyl group which is bound via an oxygen
atom and has usually from 1 to 10 carbon atoms, frequently from 1
to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of an
alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy,
n-butyloxy, 2-butyloxy, iso-butyloxy, tert-butyloxy, and the
like.
[0162] The term "alkoxyalkyl" as used herein refers to alkyl
usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2
carbon atoms, wherein 1 carbon atom carries an alkoxy radical
usually comprising 1 to 4, preferably 1 or 2 carbon atoms as
defined above. Examples are CH.sub.2OCH.sub.3,
CH.sub.2--OC.sub.2H.sub.5, 2-(methoxy)ethyl, and
2-(ethoxy)ethyl.
[0163] The term "alkylene" as used herein and in the moieties of
e.g. C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)R,
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)OR,
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)SR.sup.c,
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)NR.sup.aNR.sup.b,
C.sub.1-C.sub.4-alkylene-Y.sup.2--C(.dbd.Y.sup.1)R.sup.c,
C.sub.1-C.sub.4-alkylene-NR.sup.aR.sup.b,
C.sub.1-C.sub.4-alkylene-OR.sup.c, and C.sub.1-C.sub.4-alkylene-SR
refers to a straight-chain or branched alkylene group having
usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon
atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3
carbon atoms. Preferably, said alkenylene group connects a
substituent, such as C(.dbd.Y.sup.1)R.sup.c,
C(.dbd.Y.sup.1)OR.sup.c, C(.dbd.Y.sup.1)SR.sup.c,
C(.dbd.Y.sup.1)NR.sup.aNR.sup.b, Y.sup.2--C(.dbd.Y.sup.1)R.sup.c,
NR.sup.aR.sup.b, OR.sup.c, SR.sup.c, with the remainder of the
molecule.
[0164] The term "alkenyl" as used herein denotes in each case an at
least singly unsaturated hydrocarbon radical, i.e. a hydrocarbon
radical having at least one carbon-carbon double bond, having
usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms,
e.g. vinyl, allyl (2-propen-1-yl), 1-propen-1-yl, 2-propen-2-yl,
methallyl (2-methylprop-2-en-1-yl), 2-buten-1-yl, 3-buten-1-yl,
2-penten-1-yl, 3-penten-1-yl, 4-penten-1-yl, 1-methylbut-2-en-1-yl,
2-ethylprop-2-en-1-yl and the like.
[0165] The term "haloalkenyl" as used herein refers to an alkenyl
group as defined above, wherein the hydrogen atoms are partially or
totally replaced with halogen atoms.
[0166] The term "alkenylene" as used herein and in the moieties of
e.g. C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)R.sup.c,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)OR.sup.c,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)SR.sup.c,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)NR.sup.aNR.sup.b,
C.sub.2-C.sub.4-alkenylene-Y.sup.2--C(.dbd.Y.sup.1)R.sup.c,
C.sub.2-C.sub.4-alkenylene-NR.sup.aR.sup.b,
C.sub.2-C.sub.4-alkenylene-OR.sup.c, and
C.sub.2-C.sub.4-alkenylene-SR.sup.c refers to a straight-chain or
branched alkenylene group, which is at least singly unsaturated,
and has usually from 2 to 10 carbon atoms, frequently from 2 to 6
carbon atoms, preferably 2 to 4 carbon atoms, more preferably from
2 to 3 carbon atoms. Preferably, said alkenylene group connects a
substituent, such as C(.dbd.Y.sup.1)R.sup.c,
C(.dbd.Y.sup.1)OR.sup.c, C(.dbd.Y.sup.1)SR.sup.c,
C(.dbd.Y.sup.1)NR.sup.aNR.sup.b, Y.sup.2--C(.dbd.Y.sup.1)R.sup.c,
NR.sup.aR.sup.b, OR.sup.c, SR.sup.c, with the remainder of the
molecule.
[0167] The term "alkynyl" as used herein denotes in each case a
hydrocarbon radical having at least one carbon-carbon triple bond
and having usually 2 to 10, frequently 2 to 6, preferably 2 to 4
carbon atoms, e.g. ethynyl, propargyl (2-propyn-1-yl),
1-propyn-1-yl, 1-methylprop-2-yn-1-yl), 2-butyn-1-yl, 3-butyn-1-yl,
1-pentyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbut-2-yn-1-yl,
1-ethylprop-2-yn-1-yl and the like.
[0168] The term "haloalkynyl" as used herein refers to an alkynyl
group as defined above, wherein the hydrogen atoms are partially or
totally replaced with halogen atoms.
[0169] The term "alkynylalkyl" as used herein refers to alkyl
usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2
carbon atoms, wherein 1 carbon atom carries an alkynyl radical
usually comprising 2 to 4, preferably 2 or 3 carbon atoms as
defined above.
[0170] The term "alkynylhydroxyalkyl" as used herein refers to an
hydroxyalkyl as defined above usually comprising 1 to 10,
frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon
atom carries an alkynyl radical usually comprising 2 to 4,
preferably 2 or 3 carbon atoms as defined above. An exemplary
alkynylhydroxyalkyl is ethynylhydroxymethyl.
[0171] The term "alkynyloxy" as used herein denotes in each case an
alkynyl group which is bound to the remainder of the molecule via
an oxygen atom and has usually from 2 to 6 carbon atoms, frequently
from 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms.
[0172] The term "cycloalkyl" as used herein and in the cycloalkyl
moieties of cycloalkoxy and cycloalkylmethyl denotes in each case a
monocyclic cycloaliphatic radical having usually from 3 to 10 or
from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and
cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and
cyclohexyl.
[0173] The term "cycloalkylalkyl" refers to a cycloalkyl group as
defined above which is bound via an alkyl group, such as a
C.sub.1-C.sub.5-alkyl group or a C.sub.1-C.sub.4-alkyl group, in
particular a methyl group (=cycloalkylmethyl), to the remainder of
the molecule.
[0174] The term "cycloalkenyl" as used herein denotes in each case
a monocyclic singly unsaturated non-aromatic radical having usually
from 5 to 10 or from 3 to 8 carbon atoms, including e.g.
cycloheptenyl or cyclooctenyl.
[0175] The term "heterocyclyl" or "heterocycle" includes in general
3- to 14-membered, preferably 3- to 10-membered, more preferably
5-, or 6-membered non-aromatic radicals with at least one
heteroatom. The term "heterocyclyl" or "heterocycle" refers to
monocyclic, bicyclic or tricyclic heterocyclic non-aromatic
radicals. The term "heterocyclyl" or "heterocycle" also includes
bicyclic or tricyclic radicals, which comprise a non-aromatic ring
and a fused aryl or hetaryl ring. Particularly preferred are 5- and
6-membered monocyclic heterocyclic non-aromatic radicals. The
heterocyclic radicals usually comprise 1, 2, 3, 4 or 5, preferably
1, 2 or 3 heteroatoms selected from N, O and S as ring members,
where S-atoms as ring members may be present as S, SO or SO.sub.2.
Examples of 5- or 6-membered heterocyclic radicals comprise
saturated or unsaturated, non-aromatic heterocyclic rings, such as
oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothietanyl),
thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl,
pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl,
thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl,
S-oxodihydrothienyl, S-dioxodihydro-thienyl, oxazolidinyl,
oxazolinyl, thiazolinyl, oxathiolanyl, piperidinyl, piperazinyl,
pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxanyl,
thiopyranyl, S.oxothiopyranyl, S-dioxothiopyranyl,
dihydrothiopyranyl, S-oxodihydrothiopyranyl,
S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl,
S-oxotetrahydrothiopyranyl, S-dioxotetrahydrothiopyranyl,
morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl,
S-dioxothiomorpholinyl, thiazinyl and the like. Examples for
heterocyclic rings also comprising 1 or 2 carbonyl groups as ring
members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl,
imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl and the
like. Particularly preferred are also bicyclic 8- to 10-membered
heterocyclic radicals comprising as ring members 1, 2, 3, 4 or 5,
preferably 1, 2 or 3 heteroatoms selected from N, O and S members,
where S-atoms as ring members may be present as S, SO or SO.sub.2.
Preferably, said bicyclic 8- to 10-membered heterocyclic radicals
comprise a 5- or 6-membered non-aromatic ring as defined above,
which is fused to an aryl or hetaryl ring or to another
heterocyclic ring. These fused heterocyclyl radicals may be bound
to the remainder of the molecule via any ring atom of the 5- or
6-membered ring or the fused ring.
[0176] The term "heterocyclylalkyl" refers to heterocyclyl as
defined above, which is bound via a C.sub.1-C.sub.5-alkyl group or
a C.sub.1-C.sub.4-alkyl group, in particular a methyl group
(=heterocyclylmethyl), to the remainder of the molecule.
[0177] The term "carbocyclyl" or "carbocycle" includes in general
3- to 14-membered, preferably 3- to 10-membered, more preferably 5-
or 6-membered non-aromatic radicals. The term "carbocyclyl" or
"carbocycle" may refer to monocyclic, bicyclic or tricyclic
carbocyclic non-aromatic radicals. Preferred carbocycles are
cycloalkyl and cycloalkenyl groups having from 3 to 10, preferably
5 or 6 carbon atoms.
[0178] Particularly preferred are also bicyclic 8- to 10-membered
carbocyclic radicals, wherein a 5- or 6-membered non-aromatic ring
is fused to an aryl ring or another carbocyclic ring. These fused
carbocyclyl radicals may be bonded to the remainder of the molecule
via any ring atom of the 5- or 6-membered ring or the fused
ring.
[0179] The term "carbocyclylalkyl" refers to carbocyclyl as defined
above which is bound via a C.sub.1-C.sub.5-alkyl group or a
C.sub.1-C.sub.4-alkyl group, in particular a methyl group
(=carbocyclylmethyl), to the remainder of the molecule.
[0180] The term "hetaryl" includes monocyclic 5- or 6-membered
heteroaromatic radicals comprising as ring members 1, 2, 3 or 4
heteroatoms selected from N, O and S. Examples of 5- or 6-membered
heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or 4-pyridyl,
pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, pyrazinyl, pyridazinyl,
i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl,
i.e. 2- or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e.
2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4- or 5-isoxazolyl,
thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4- or
5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4- or 5-pyrazolyl, i.e. 1-,
2-, 4- or 5-imidazolyl, oxadiazolyl, e.g. 2- or
5-[1,3,4]oxadiazolyl, 4- or 5-(1,2,3-oxadiazol)yl, 3- or
5-(1,2,4-oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, thiadiazolyl,
e.g. 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3-
or 5-(1,2,4-thiadiazol)yl, triazolyl, e.g. 1H-, 2H- or
3H-1,2,3-triazol-4-yl, 2H-triazol-3-yl, 1H-, 2H-, or
4H-1,2,4-triazolyl and tetrazolyl, i.e. 1H- or 2H-tetrazolyl. The
term "hetaryl" also includes bicyclic 8 to 13-membered, preferably
8- to 10 membered heteroaromatic radicals comprising as ring
members 1, 2 or 3 heteroatoms selected from N, O and S, wherein a
5- or 6-membered heteroaromatic ring is fused to a phenyl ring or
to a 5- or 6-membered heteroaromatic radical. Examples of a 5- or
6-membered heteroaromatic ring fused to a phenyl ring or to a 5- or
6-membered heteroaromatic radical include benzofuranyl,
benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl,
benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl,
isochinolinyl, purinyl, 1,8-naphthyridyl, pteridyl,
pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like. These
fused hetaryl radicals may be bonded to the remainder of the
molecule via any ring atom of 5- or 6-membered heteroaromatic ring
or via a carbon atom of the fused phenyl moiety.
[0181] The term "hetarylalkyl" refers to hetaryl as defined above
which is bound via a C.sub.1-C.sub.5-alkyl group or a
C.sub.1-C.sub.4-alkyl group, in particular a methyl group
(=hetarylmethyl), to the remainder of the molecule.
[0182] The term "heteraryloxy" refers to heteraryl as defined
above, which is bound via an oxygen atom to the remainder of the
molecule.
[0183] The term "aryl" includes monocyclic, bicyclic or tricyclic
aromatic radicals comprising 6 to 14 carbon atoms, preferably 6 or
10 carbon atoms, more preferably 6 carbon atoms. Exemplary aryl
radicals include anthracenyl, naphthalenyl and phenyl. A preferred
aryl radical is phenyl.
[0184] The term "arylalkyl" refers to aryl as defined above which
is bound via a C.sub.1-C.sub.5-alkyl group or a
C.sub.1-C.sub.4-alkyl group, in particular a methyl group
(=arylmethyl), to the remainder of the molecule. A preferred
arylalkyl group is phenylmethyl, i.e. benzyl.
[0185] The term "aryloxy" refers to aryl as defined above, which is
bound via an oxygen atom to the remainder of the molecule. A
preferred aryloxy group is e.g. benzyloxy.
[0186] As has been set out above, the present invention concerns in
one aspect the use of a nitrification inhibitor for reducing
nitrification, wherein said nitrification inhibitor is a compound
of formula I
##STR00004##
[0187] or a stereoisomer, salt, tautomer or N-oxide thereof,
[0188] wherein [0189] A is aryl or hetaryl, wherein the aromatic
ring may in each case be unsubstituted or may be partially or fully
substituted by substituents, which are independently of each other
selected from R.sup.A; [0190] R.sup.1 and R.sup.2 are independently
of each other selected from H and C.sub.1-C.sub.2-alkyl; and [0191]
R.sup.3 is H, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-hydroxyalkyl, ethynylhydroxymethyl,
phenylhydroxymethyl, or aryl, wherein the aromatic ring may be
unsubstituted or may be partially or fully substituted by
substituents, which are independently of each other selected from
R.sup.B;
[0192] and wherein [0193] R.sup.A is [0194] (i) halogen, CN,
NR.sup.aR.sup.b, OR.sup.c, SR.sup.c, C(.dbd.Y.sup.1)R.sup.c,
C(.dbd.Y.sup.1)OR.sup.c, C(.dbd.Y.sup.1)SR.sup.c,
C(.dbd.Y.sup.1)NR.sup.aR.sup.b, Y.sup.2C(.dbd.Y.sup.1)R.sup.c,
Y.sup.2C(.dbd.Y.sup.1)OR.sup.c, Y.sup.2C(.dbd.Y.sup.1)SR.sup.c,
Y.sup.2C(.dbd.Y.sup.1)NR.sup.aR.sup.b,
Y.sup.3Y.sup.2C(.dbd.Y.sup.1)R.sup.c,
NR.sup.gN.dbd.C(R.sup.d)(R.sup.e), C(.dbd.N--OR.sup.c)R.sup.g,
C(.dbd.N--OR.sup.c)R.sup.g, C(.dbd.N--SR.sup.c)R.sup.g,
C(.dbd.N--NR.sup.aR.sup.b)R.sup.g, S(.dbd.O).sub.2R.sup.f,
NR.sup.gS(.dbd.O).sub.2R.sup.f,
S(.dbd.O).sub.2Y.sup.2C(.dbd.Y.sup.1)R.sup.c,
S(.dbd.O).sub.2Y.sup.2C(.dbd.Y.sup.1)OR.sup.c,
S(.dbd.O).sub.2Y.sup.2C(.dbd.Y.sup.1)SR.sup.c,
S(.dbd.O).sub.2Y.sup.2C(.dbd.Y.sup.1)NR.sup.aR.sup.b, NO.sub.2,
NON--CN, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-cyanoalkyl, C.sub.1-C.sub.4-hydroxyalkyl,
C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyl-C.sub.1-C.sub.2-hydroxyalkyl,
C.sub.2-C.sub.4-alkynyloxy; [0195] (ii)
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)R,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)R.sup.c,
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)OR,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)OR.sup.c,
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)SR.sup.c,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)SR.sup.c,
C.sub.1-C.sub.4-alkylene-C(.dbd.Y.sup.1)NR.sup.aNR.sup.b,
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)NR.sup.aNR.sup.b,
C.sub.1-C.sub.4-alkylene-Y.sup.2--C(.dbd.Y.sup.1)R.sup.c,
C.sub.2-C.sub.4-alkenylene-Y.sup.2--C(.dbd.Y.sup.1)R.sup.c,
C.sub.1-C.sub.4-alkylene-NR.sup.aR.sup.b,
C.sub.2-C.sub.4-alkenylene-NR.sup.aR.sup.b,
C.sub.1-C.sub.4-alkylene-OR.sup.c,
C.sub.2-C.sub.4-alkenylene-OR.sup.c, C.sub.1-C.sub.4-alkylene-SR,
C.sub.2-C.sub.4-alkenylene-SR.sup.c, wherein the
C.sub.1-C.sub.4-alkylene or C.sub.2-C.sub.4-alkenylene chain may in
each case be unsubstituted or may be partially or fully substituted
by OR.sup.g, CN, halogen or phenyl; [0196] (iii) aryl,
aryl-C.sub.1-C.sub.2-alkyl, hetaryl or
hetaryl-C.sub.1-C.sub.2-alkyl, wherein the aromatic ring of the
aryl or hetaryl group may be unsubstituted or may be partially or
fully substituted by substituents, which are independently of each
other selected from R.sup.h; [0197] (iv) a 3- to 14-membered
saturated or unsaturated carbocycle or heterocycle, which may
contain 1, 2, or 3 heteroatoms which, independently of each other,
are selected from NR.sup.1b, O, and S, wherein S may be oxidized
and/or wherein the carbocycle or heterocycle may be unsubstituted
or may be partially or fully substituted by substituents which,
independently of each other, are selected from R.sup.i; and wherein
R.sup.1b is H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g; or [0198] (v) L-B, wherein [0199] L is --CH.sub.2--,
--CH.dbd.CH--, --C.ident.C--, --C(.dbd.O)-- or --CH.dbd., and
[0200] B is aryl or hetaryl, wherein the aromatic ring of the ary
or hetaryl group may be unsubstituted or may be partially or fully
substituted by substituents, which are independently of each other
selected from R.sup.h; [0201] or [0202] a 3- to 14-membered
saturated or unsaturated carbocycle or heterocycle, which may
contain 1, 2, or 3 heteroatoms which, independently of each other,
are selected from NR.sup.1b, O, and S, wherein S may be oxidized
and/or wherein the carbocycle or heterocycle may be unsubstituted
or may be partially or fully substituted by substituents which,
independently of each other, are selected from R.sup.i; and wherein
R.sup.1b is H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g; or [0203] (vi) two substituents R.sup.A together
represent a carbocyclic or heterocyclic ring, which is fused to A
and may contain 1, 2, or 3 heteroatoms which, independently of each
other, are selected from NR.sup.1c, O, and S, wherein S may be
oxidized and/or wherein the carbocycle or heterocycle may be
unsubstituted or may be partially or fully substituted by
substituents which, independently of each other, are selected from
R.sup.i; and wherein R.sup.1c is H, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.3-C.sub.6-cycloalkyl,
C.sub.3-C.sub.6-cycloalkylmethyl, C.sub.3-C.sub.6-heterocyclyl,
C.sub.3-C.sub.6-heterocyclylmethyl or OR.sup.g;
[0204] and wherein [0205] R.sup.B is
NH--C(.dbd.O)--(C.sub.1-C.sub.4-alkyl),
NH--C(.dbd.O)--(C.sub.2-C.sub.4-alkenyl),
NH--C(.dbd.O)--(C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl),
NH--C(.dbd.O)--(C.sub.3-C.sub.6-cycloalkyl),
NH--S(.dbd.O).sub.2--(C.sub.1-C.sub.4-alkyl), or NO.sub.2;
[0206] and wherein [0207] Y.sup.1, Y.sup.2 and Y.sup.3 are
independently of each other selected from O, S and NR.sup.1a,
wherein R.sup.1a is in each case independently H,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl,
OR.sup.g, SR.sup.g or NR.sup.mR.sup.n; [0208] R.sup.a and R.sup.b
are independently of each other selected from [0209] (i) H,
NR.sup.jR.sup.k, OR.sup.l, SR.sup.l, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl,
C.sub.1-C.sub.4-hydroxyalkyl, C.sub.1-C.sub.4-alkoxy,
C(.dbd.Y.sup.1)R.sup.l, C(.dbd.Y.sup.1)OR.sup.l,
C(.dbd.Y.sup.1)SR.sup.l, C(.dbd.Y.sup.1)NR.sup.jR.sup.k,
C(.dbd.Y.sup.1)C(.dbd.Y.sup.2)R.sup.l, S(.dbd.O).sub.2R.sup.f;
[0210] (ii) aryl or hetaryl, wherein the aromatic ring of the aryl
or hetaryl group may be unsubstituted or may be partially or fully
substituted by substituents, which are independently of each other
selected from R.sup.h; or [0211] R.sup.a and R.sup.b together with
the nitrogen atom to which they are bound form [0212] (iii) a
hetaryl group which may be unsubstituted or may be partially or
fully substituted by substituents, which are independently of each
other selected from R.sup.h; or [0213] (iv) a 3- to 10-membered,
saturated or unsaturated heterocycle, which may contain 1, 2, or 3
heteroatoms which, independently of each other, are selected from
NR.sup.1b, O, and S, wherein S may be oxidized and/or wherein the
heterocycle may be unsubstituted or may be partially or fully
substituted by substituents which, independently of each other, are
selected from R.sup.i; and wherein R.sup.1b is H,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g; [0214] R.sup.c is [0215] (i) H, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl,
C(.dbd.O)OR.sup.l, C(.dbd.O)SR.sup.l, C(.dbd.O)NR.sup.jR.sup.k;
[0216] (ii) C.sub.1-C.sub.4-alkylene-C(.dbd.O)R.sup.l,
C.sub.1-C.sub.4-alkylene-C(.dbd.O)OR.sup.l, wherein the
C.sub.1-C.sub.4-alkylene chain may in each case be unsubstituted or
may be partially or fully substituted by OR.sup.g, CN, halogen, or
phenyl; [0217] (iii) aryl, aryl-C.sub.1-C.sub.2-alkyl, hetaryl, or
hetaryl-C.sub.1-C.sub.2-alkyl, wherein the aromatic ring of the
aryl or hetaryl group may be unsubstituted or may be partially or
fully substituted by substituents, which are independently of each
other selected from R.sup.h; or [0218] (iv) a 3- to 10-membered
saturated or unsaturated carbocycle or heterocycle, which may
contain 1, 2, or 3 heteroatoms which, independently of each other,
are selected from NR.sup.1b, O, and S, wherein S may be oxidized
and/or wherein the carbocycle or heterocycle may be unsubstituted
or may be partially or fully substituted by substituents which,
independently of each other, are selected from R.sup.i; and wherein
R.sup.1b is H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g; [0219] R.sup.d and R.sup.e are independently selected
from C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
NR.sup.jR.sup.k, OR.sup.l, SR.sup.l, CN, C(.dbd.Y.sup.1)R.sup.l,
C(.dbd.Y.sup.1)OR.sup.l, C(.dbd.Y.sup.1)SR.sup.l, or
C(.dbd.Y.sup.1)NR.sup.jR.sup.k; [0220] R.sup.f is
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, NR.sup.jR.sup.k,
OR.sup.l, SR.sup.l, aryl or hetaryl, wherein the aromatic ring of
the aryl or hetaryl group may be unsubstituted or may be partially
or fully substituted by substituents, which are independently of
each other selected from R.sup.h; [0221] R.sup.g is H or
C.sub.1-C.sub.4-alkyl; [0222] R.sup.h is halogen, CN, NO.sub.2,
NR.sup.jR.sup.k, OR.sup.l, SR.sup.l, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyloxy, C(.dbd.Y.sup.1)R.sup.l,
C(.dbd.Y.sup.1)OR.sup.l, C(.dbd.Y.sup.1)SR.sup.l,
C(.dbd.Y.sup.1)NR.sup.jR.sup.k, aryl, aryloxy, hetaryl and
hetaryloxy; [0223] R.sup.i is [0224] (i) halogen, CN,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.2-C.sub.4-haloalkenyl; [0225] (ii)=NR.sup.1d, wherein
R.sup.1d is H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g; [0226] (iii)=O, .dbd.S, NR.sup.jR.sup.k, OR.sup.l,
SR.sup.l, C(.dbd.Y.sup.1)R.sup.l, C(.dbd.Y.sup.1)OR.sup.l,
C(.dbd.Y.sup.1)SR.sup.l, C(.dbd.Y.sup.1)NR.sup.jR.sup.k; [0227]
(iv) aryl, aryl-C.sub.1-C.sub.2-alkyl, hetaryl, or
hetaryl-C.sub.1-C.sub.2-alkyl, wherein the aromatic ring of the
aryl or hetaryl group may be unsubstituted or may be partially or
fully substituted by substituents, which are independently of each
other selected from halogen, CN, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyloxy, OR.sup.g, and SR.sup.g; or [0228] (v)
C.sub.3-C.sub.6-cycloalkyl, or 3- to 6-membered heterocyclyl,
wherein the cycloalkyl ring or the heterocyclyl ring may be
unsubstituted or may be partially or fully substituted by
substituents, which are independently of each other selected from
halogen, CN, C.sub.1-C.sub.4-alkyl, OR.sup.g, and SR.sup.g; [0229]
R.sup.j and R.sup.k are independently selected from H, OR.sup.g,
SR.sup.g, C(.dbd.Y.sup.1)R.sup.g, C(.dbd.Y.sup.1)OR.sup.g,
C(.dbd.Y.sup.1)SR.sup.g, C(.dbd.Y.sup.1)NR.sup.mR.sup.n,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-haloalkyl, aryl or
hetaryl, wherein the aromatic ring of the aryl or hetaryl group may
be unsubstituted or may be partially or fully substituted by
substituents, which are independently selected from halogen, CN,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl,
C.sub.1-C.sub.4-alkoxy, C.sub.2-C.sub.4-alkynyloxy, OR.sup.g, and
SR.sup.g; [0230] R.sup.l is H, C.sub.1-C.sub.4-alkyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl,
C.sub.1-C.sub.4-haloalkyl, C(.dbd.Y.sup.1)R.sup.g,
C(.dbd.Y.sup.1)OR.sup.g, C(.dbd.Y.sup.1)SR.sup.g,
C(.dbd.Y.sup.1)NR.sup.mR.sup.n, aryl or hetaryl, wherein the
aromatic ring of the aryl or hetaryl group may be unsubstituted or
may be partially or fully substituted by substituents, which are
independently selected from halogen, CN, C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyloxy, OR.sup.g, and SR.sup.g; and [0231]
R.sup.m and R.sup.n are independently selected from H and
C.sub.1-C.sub.4-alkyl.
[0232] In a preferred embodiment of said compound of formula I, A
is phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring
may in each case be unsubstituted or may be partially or fully
substituted by substituents, which are independently of each other
selected from R.sup.A. These compounds correspond to compounds of
formula I.1, wherein A' represents phenyl or a 5- or 6-membered
hetaryl, wherein the aromatic ring may in each case be
unsubstituted or may be partially or fully substituted by
substituents, which are independently of each other selected from
R.sup.A.
##STR00005##
[0233] In a further preferred embodiment of said compound of
formula I, R.sup.1 and R.sup.2 both represent hydrogen. These
compounds correspond to compounds of formula I.A.
##STR00006##
[0234] In another preferred embodiment of said compound of formula
I, R.sup.3 is hydrogen, C.sub.1-C.sub.4-haloalkyl or
ethynylhydroxymethyl. It is even more preferred that R.sup.3 is
hydrogen. These compounds correspond to compounds of formula
I.X.
##STR00007##
[0235] In a particularly preferred embodiment of said compound of
formula I, A is A', i.e. phenyl or a 5- or 6-membered hetaryl,
wherein the aromatic ring may in each case be unsubstituted or may
be partially or fully substituted by substituents, which are
independently of each other selected from R.sup.A, and R.sup.1 and
R.sup.2 are both hydrogen. These compounds correspond to compounds
of formula I.1.A.
##STR00008##
[0236] In another more preferred embodiment of said compound of
formula I, A is A', i.e. phenyl or a 5- or 6-membered hetaryl,
wherein the aromatic ring may in each case be unsubstituted or may
be partially or fully substituted by substituents, which are
independently of each other selected from R.sup.A, and R.sup.3 is
hydrogen. These compounds correspond to compounds of formula
I.1.X.
##STR00009##
[0237] In another more preferred embodiment of said compound of
formula I, R.sup.1 and R.sup.2 are both hydrogen, and R.sup.3 is
hydrogen. These compounds correspond to compounds of formula
I.A.X.
##STR00010##
[0238] In the most preferred embodiment of said compound of formula
I, A is A', i.e. phenyl or a 5- or 6-membered hetaryl, wherein the
aromatic ring may in each case be unsubstituted or may be partially
or fully substituted by substituents, which are independently of
each other selected from R.sup.A, R.sup.1 and R.sup.2 are both
hydrogen, and R.sup.3 is hydrogen.
##STR00011##
[0239] Further preferred embodiments of said compound of formula I
relate to the substituents R.sup.A, with which A may be partially
or fully substituted.
[0240] In a preferred embodiment of the compound of formula I,
R.sup.A, if present, is [0241] (i) halogen, CN, NR.sup.aR.sup.b,
OR.sup.c, C(.dbd.Y.sup.1)R.sup.c, C(.dbd.Y.sup.1)OR.sup.c,
C(.dbd.Y.sup.1)SR.sup.c, C(.dbd.Y.sup.1)NR.sup.aR.sup.b,
Y.sup.2C(.dbd.Y.sup.1)R.sup.c,
Y.sup.2C(.dbd.Y.sup.1)NR.sup.aR.sup.b,
NR.sup.gN.dbd.C(R.sup.d)(R.sup.e), S(.dbd.O).sub.2R.sup.f,
NO.sub.2, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyl-C.sub.1-C.sub.2-hydroxyalkyl,
C.sub.2-C.sub.4-alkynyloxy; [0242] (ii)
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)R.sup.c,
C.sub.2-C.sub.4-alkenylene-Y.sup.2--C(.dbd.Y.sup.1)R.sup.c, wherein
the C.sub.1-C.sub.4-alkylene or C.sub.2-C.sub.4-alkenylene chain
may in each case be unsubstituted or may be partially or fully
substituted by CN or halogen; [0243] (iii) aryl, wherein the
aromatic ring of the aryl group may be unsubstituted or may be
partially or fully substituted by substituents, which are
independently of each other selected from R.sup.h; or [0244] (iv) a
3- to 14-membered saturated or unsaturated heterocycle, which may
contain 1, 2, or 3 heteroatoms which, independently of each other,
are selected from NR.sup.1b, O, and S, wherein S may be oxidized
and/or wherein the heterocycle may be unsubstituted or may be
partially or fully substituted by substituents which, independently
of each other, are selected from R.sup.i; and wherein R.sup.1b is
H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g.
[0245] In a particularly preferred embodiment of the present
invention, the compound of formula I, is a compound of formula I.1,
I.A, I.X, I.1.A, I.1.X, I.A.X or I.1.A.X, wherein R.sup.A, if
present, is [0246] (i) halogen, CN, NR.sup.aR.sup.b, OR.sup.c,
C(.dbd.Y.sup.1)R.sup.c, C(.dbd.Y.sup.1)OR.sup.c,
C(.dbd.Y.sup.1)SR.sup.c, C(.dbd.Y.sup.1)NR.sup.aR.sup.b,
Y.sup.2C(.dbd.Y.sup.1)R.sup.c,
Y.sup.2C(.dbd.Y.sup.1)NR.sup.aR.sup.b,
NR.sup.gN.dbd.C(R.sup.d)(R.sup.e), S(.dbd.O).sub.2R.sup.f,
NO.sub.2, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy,
C.sub.2-C.sub.4-alkynyl-C.sub.1-C.sub.2-hydroxyalkyl,
C.sub.2-C.sub.4-alkynyloxy; [0247] (ii)
C.sub.2-C.sub.4-alkenylene-C(.dbd.Y.sup.1)R.sup.c,
C.sub.2-C.sub.4-alkenylene-Y.sup.2--C(.dbd.Y.sup.1)R.sup.c, wherein
the C.sub.1-C.sub.4-alkylene or C.sub.2-C.sub.4-alkenylene chain
may in each case be unsubstituted or may be partially or fully
substituted by CN or halogen; [0248] (iii) aryl, wherein the
aromatic ring of the aryl group may be unsubstituted or may be
partially or fully substituted by substituents, which are
independently of each other selected from R.sup.h; or [0249] (iv) a
3- to 14-membered saturated or unsaturated heterocycle, which may
contain 1, 2, or 3 heteroatoms which, independently of each other,
are selected from NR.sup.1b, O, and S, wherein S may be oxidized
and/or wherein the heterocycle may be unsubstituted or may be
partially or fully substituted by substituents which, independently
of each other, are selected from R.sup.i; and wherein R.sup.1b is
H, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-alkenyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or
OR.sup.g.
[0250] If R.sup.A is present in the compounds of formula I or a
compound of any one of formulae I.1, I.A, I.X, I.1.A, I.1.X, I.A.X
or I.1.A.X, and preferably if R.sup.A is selected as indicated
above, the following substituent definitions are particularly
preferred according to the present invention.
[0251] Preferably, Y.sup.1, Y.sup.2 and Y.sup.3 are independently
of each other selected from O, S and NR.sup.1a, wherein preferably
R.sup.1a is in each case independently H, C.sub.1-C.sub.4-alkyl,
OR.sup.g, or NR.sup.mR.sup.n.
[0252] Preferably, R.sup.a and R.sup.b are independently of each
other selected from [0253] (i) H, NR.sup.jR.sup.k,
C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-hydroxyalkyl,
C(.dbd.Y.sup.1)R.sup.l; or [0254] R.sup.a and R.sup.b together with
the nitrogen atom to which they are bound form [0255] (iv) a 3- to
10-membered, saturated or unsaturated heterocycle, which may
contain 1, 2, or 3 heteroatoms which, independently of each other,
are selected from NR.sup.1b, O, and S, wherein S may be oxidized
and/or wherein the heterocycle may be unsubstituted or may be
partially or fully substituted by substituents which, independently
of each other, are selected from R.sup.i; and wherein R.sup.1b is
preferably H, C.sub.1-C.sub.4-alkyl, or OR.sup.g.
[0256] Preferably, R.sup.c is [0257] (i) H, C.sub.1-C.sub.4-alkyl;
or [0258] (iv) a 3- to 10-membered saturated or unsaturated
carbocycle or heterocycle, which may contain 1, 2, or 3 heteroatoms
which, independently of each other, are selected from NR.sup.1b, O,
and S, wherein S may be oxidized and/or wherein the carbocycle or
heterocycle may be unsubstituted or may be partially or fully
substituted by substituents which, independently of each other, are
selected from R.sup.i; and wherein R.sup.1b is preferably H,
C.sub.1-C.sub.4-alkyl, or OR.sup.g.
[0259] Preferably, R.sup.d and R.sup.e are independently selected
from NR.sup.jR.sup.k and C(.dbd.Y.sup.1)OR.sup.l;
[0260] Preferably, R.sup.f is C.sub.1-C.sub.4-alkyl.
[0261] Preferably, R.sup.g is H.
[0262] Preferably, R.sup.h is halogen or
C.sub.1-C.sub.4-alkoxy.
[0263] Preferably, R.sup.i is [0264] (i) C.sub.1-C.sub.4-alkyl,
C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-haloalkenyl; or [0265]
(iii) .dbd.O.
[0266] Preferably, R.sup.j and R.sup.k are both H.
[0267] Preferably, R.sup.l is H.
[0268] Preferably, R.sup.m and R.sup.n are both H.
[0269] Preferred compounds of the present invention are listed in
the following Table 1:
TABLE-US-00001 Entry (No. comp. A) Compound structure 1
##STR00012## 2 ##STR00013## 3 ##STR00014## 4 ##STR00015## 5
##STR00016## 6 ##STR00017## 7 ##STR00018## 8 ##STR00019## 9
##STR00020## 10 ##STR00021## 11 ##STR00022## 12 ##STR00023## 13
##STR00024## 4 ##STR00025## 15 ##STR00026## 16 ##STR00027## 17
##STR00028## 18 ##STR00029## 19 ##STR00030## 20 ##STR00031## 21
##STR00032## 22 ##STR00033## 23 ##STR00034## 24 ##STR00035## 25
##STR00036## 26 ##STR00037## 27 ##STR00038## 28 ##STR00039## 29
##STR00040## 30 ##STR00041## 31 ##STR00042## 32 ##STR00043## 33
##STR00044## 34 ##STR00045## 35 ##STR00046## 36 ##STR00047## 37
##STR00048## 38 ##STR00049## 39 ##STR00050## 40 ##STR00051## 41
##STR00052## 42 ##STR00053## 43 ##STR00054## 44 ##STR00055## 45
##STR00056## 46 ##STR00057## 47 ##STR00058## 48 ##STR00059## 49
##STR00060## 50 ##STR00061## 51 ##STR00062## 52 ##STR00063## 53
##STR00064## 54 ##STR00065## 55 ##STR00066## 56 ##STR00067## 57
##STR00068## 58 ##STR00069## 59 ##STR00070## 60 ##STR00071## 61
##STR00072## 62 ##STR00073## 63 ##STR00074## 64 ##STR00075## 65
##STR00076## 66 ##STR00077## 67 ##STR00078## 68 ##STR00079## 69
##STR00080## 70 ##STR00081## 71 ##STR00082## 72 ##STR00083## 73
##STR00084## 74 ##STR00085## 75 ##STR00086## 76 ##STR00087## 77
##STR00088## 78 ##STR00089## 79 ##STR00090## 80 ##STR00091## 81
##STR00092## 82 ##STR00093## 83 ##STR00094## 84 ##STR00095## 85
##STR00096## 86 ##STR00097## 87 ##STR00098## 88 ##STR00099## 89
##STR00100## 90 ##STR00101## 91 ##STR00102## 92 ##STR00103## 93
##STR00104## 94 ##STR00105## 95 ##STR00106## 96 ##STR00107## 97
##STR00108## 98 ##STR00109## 99 ##STR00110## 100 ##STR00111## 101
##STR00112## 102 ##STR00113## 103 ##STR00114## 104 ##STR00115## 105
##STR00116## 106 ##STR00117## 107 ##STR00118## 108 ##STR00119## 109
##STR00120## 110 ##STR00121## 111 ##STR00122## 112 ##STR00123## 113
##STR00124## 114 ##STR00125## 115 ##STR00126## 116 ##STR00127## 117
##STR00128## 118 ##STR00129## 119 ##STR00130## 120 ##STR00131## 121
##STR00132## 122 ##STR00133##
123 ##STR00134## 124 ##STR00135## 125 ##STR00136## 126 ##STR00137##
127 ##STR00138## 128 ##STR00139## 129 ##STR00140## 130 ##STR00141##
131 ##STR00142## 132 ##STR00143## 133 ##STR00144## 134 ##STR00145##
135 ##STR00146## 136 ##STR00147## 137 ##STR00148## 138 ##STR00149##
139 ##STR00150## 140 ##STR00151## 141 ##STR00152## 142 ##STR00153##
143 ##STR00154## 144 ##STR00155## 145 ##STR00156## 146 ##STR00157##
147 ##STR00158## 148 ##STR00159## 149 ##STR00160## 150 ##STR00161##
151 ##STR00162## 152 ##STR00163## 153 ##STR00164## 154 ##STR00165##
155 ##STR00166## 156 ##STR00167## 157 ##STR00168## 158 ##STR00169##
159 ##STR00170## 160 ##STR00171## 161 ##STR00172## 162 ##STR00173##
163 ##STR00174## 164 ##STR00175## 165 ##STR00176## 166 ##STR00177##
167 ##STR00178## 168 ##STR00179## 169 ##STR00180## 170 ##STR00181##
171 ##STR00182## 172 ##STR00183## 173 ##STR00184## 174 ##STR00185##
175 ##STR00186## 176 ##STR00187## 177 ##STR00188## 178 ##STR00189##
179 ##STR00190## 180 ##STR00191## 181 ##STR00192## 182 ##STR00193##
183 ##STR00194## 184 ##STR00195## 185 ##STR00196## 186 ##STR00197##
187 ##STR00198## 188 ##STR00199## 189 ##STR00200## 190 ##STR00201##
191 ##STR00202## 192 ##STR00203## 193 ##STR00204## 194 ##STR00205##
195 ##STR00206## 196 ##STR00207## 197 ##STR00208## 198 ##STR00209##
199 ##STR00210## 200 ##STR00211## 201 ##STR00212## 202 ##STR00213##
203 ##STR00214## 204 ##STR00215## 205 ##STR00216## 206 ##STR00217##
207 ##STR00218## 208 ##STR00219## 209 ##STR00220## 210 ##STR00221##
211 ##STR00222## 212 ##STR00223## 213 ##STR00224## 214 ##STR00225##
215 ##STR00226##
[0270] In a central aspect the present invention thus relates to
the use of a combination of a nitrification inhibitor or (T) and a
herbicide as defined herein above, or of a composition comprising
said combination of a nitrification inhibitor or (T) and a
herbicide as defined herein for increasing the health of a plant.
The nitrification inhibitor or derivatives or salts thereof as
defined herein above in combination with a herbicide, in particular
compounds of formula I and/or salts or suitable derivatives thereof
in combination with a herbicide, as well as compositions comprising
said nitrification inhibitor or (T) and a herbicide as defined
herein may be used for increasing the health of a plant. The use
may be based on an application of the combination of the
nitrification inhibitor or (T) and a herbicide, the or the
composition as defined herein to a plant growing on soil and/or the
locus where the plant is growing or is intended to grow, or the
application of the combination of the nitrification inhibitor or
(T) and a herbicide, or the composition as defined herein to soil
where a plant is growing or is intended to grow or to soil
substituents. In specific embodiments, the combination of the
nitrification inhibitor or (T) and a herbicide may be used in the
absence of plants, e.g. as preparatory activity for subsequent
agricultural activity.
[0271] The use may further include the application of a combination
of a herbicide and (T) or the nitrification inhibitor or
derivatives or salts thereof as defined herein above, in particular
compounds of formula I and/or salts or suitable derivatives
thereof, as well as compositions comprising said combination of a
herbicide and (T) or the nitrification inhibitor, or agrochemical
mixtures comprising said nitrification inhibitor as defined herein
to environments, areas or zones, where nitrification takes place or
is assumed or expected to take place. Such environments, areas or
zones may, in specific embodiments, not comprise plants or soil,
but be planned for subsequent growth of plants. Examples of such
environments are laboratory environments or green houses or similar
indoor facilities.
[0272] The term "plant health" as used herein is intended to mean a
condition of the plant which is determined by several aspects alone
or in combination with each other. One indicator (indicator 1) for
the condition of the plant is the crop yield. "Crop" and "fruit"
are to be understood as any plant product which is further utilized
after harvesting, e.g. fruits in the proper sense, vegetables,
nuts, grains, seeds, wood (e.g. in the case of silviculture
plants), flowers (e.g. in the case of gardening plants,
ornamentals) etc., that is anything of economic value that is
produced by the plant. Another indicator (indicator 2) for the
condition of the plant is the plant vigor. The plant vigor becomes
manifest in several aspects, too, some of which are visual
appearance, e.g. leaf color, fruit color and aspect, amount of dead
basal leaves and/or extent of leaf blades, plant weight, plant
height, extent of plant verse (lodging), number, strong ness and
productivity of tillers, panicles' length, extent of root system,
strongness of roots, extent of nodulation, in particular of
rhizobial nodulation, point of time of germination, emergence,
flowering, grain maturity and/or senescence, protein content, sugar
content and the like. Another indicator (indicator 3) for an
increase of a plant's health is the reduction of biotic or abiotic
stress factors.
[0273] The three above mentioned indicators for the health
condition of a plant may be interdependent and may result from each
other. For example, a reduction of biotic or stress may lead to a
better plant vigor, e.g. to better and bigger crops, and thus to an
increased yield.
[0274] Biotic stress, especially over longer terms, can have
harmful effects on plants. The term "biotic stress" as used in the
context of the present invention refers in particular to stress
caused by living organisms, such as competing plants, especially
weeds. As a result, the quantity and the quality of the stressed
plants, their crops and fruits decrease. As far as quality is
concerned, reproductive development is usually severely affected
with consequences on the crops which are important for fruits or
seeds. Growth may be slowed by the stresses; polysaccharide
synthesis, both structural and storage, may be reduced or modified:
these effects may lead to a decrease in biomass and to changes in
the nutritional value of the product. A reduction of biotic stress
factors may, for example, be due to a herbicidal effect to
competing plants such as weeds of a herbicide as defined
herein.
[0275] Abiotic stress includes drought, cold, increased UV,
increased heat, or other changes in the environment of the plant,
that leads to sub-optimal growth conditions. A reduction of abiotic
stress factors may, for example, be due to a reduction of
nitrification and a corresponding improvement of uptake of nitrogen
nutrients.
[0276] The term "increased yield" of a plant as used herein means
that the yield of a product of the respective plant is increased by
a measurable amount over the yield of the same product of the plant
produced under the same conditions, but without the application of
the composition of the invention. According to the present
invention, it is preferred that the yield be increased by at least
0.5%, more preferred at least 1%, even more preferred at least 2%,
still more preferred at least 4%. An increased yield may, for
example, be due to a reduction of nitrification and a corresponding
improvement of uptake of nitrogen nutrients, as well as a
herbicidal effect to competing plants such as weeds of a herbicide
as defined herein.
[0277] The term "improved plant vigor" as used herein means that
certain crop characteristics are increased or improved by a
measurable or noticeable amount over the same factor of the plant
produced under the same conditions, but without the application of
the composition of the present invention. Improved plant vigor can
be characterized, among others, by following improved properties of
a plant: [0278] (a) improved vitality of the plant, [0279] (b)
improved quality of the plant and/or of the plant products, e.g.
[0280] (b) enhanced protein content, [0281] (c) improved visual
appearance, [0282] (d) delay of senescence, [0283] (e) enhanced
root growth and/or more developed root system (e.g. determined by
the dry mass of the root), [0284] (f) enhanced nodulation, in
particular rhizobial nodulation, [0285] (g) longer panicles, [0286]
(h) bigger leaf blade, [0287] (i) less dead basal leaves, [0288]
(j) increased chlorophyll content [0289] (k) prolonged
photosynthetically active period
[0290] The improvement of the plant vigor according to the present
invention particularly means that the improvement of anyone or
several or all of the above mentioned plant characteristics are
improved. It further means that if not all of the above
characteristics are improved, those which are not improved are not
worsened as compared to plants which were not treated according to
the invention or are at least not worsened to such an extent that
the negative effect exceeds the positive effect of the improved
characteristic (i.e. there is always an overall positive effect
which preferably results in an improved crop yield). An improved
plant vigor may, for example, be due to a reduction of
nitrification and a corresponding improvement of uptake of nitrogen
nutrients, as well as a herbicidal effect to competing plants such
as weeds of a herbicide as defined herein.
[0291] It is particularly preferred that said increase of the
health of a plant is reflected by an increase in growth of root and
shoot and/or an overall increase in productivity and/or a faster
and more efficient development of the plant.
[0292] The term "reducing nitrification" or "reduction of
nitrification" as used herein refers to a slowing down or stopping
of nitrification processes, e.g. by retarding or eliminating the
natural transformation of ammonium into nitrate. Such reduction may
be a complete or partial elimination of nitrification at the plant
or locus where the inhibitor or composition comprising said
inhibitor is applied. For example, a partial elimination may result
in a residual nitrification on or in the plant, or in or on the
soil or soil substituents where a plant grows or is intended to
grow of about 90% to 1%, e.g. 90%, 85%, 80%, 70%, 60%, 50%, 40%,
30%, 20%, 10% or less than 10%, e.g. 5% or less than 5% in
comparison to a control situation where the nitrification inhibitor
is not used. In certain embodiments, a partial elimination may
result in a residual nitrification on or in the plant or in or on
the soil or soil substituents where a plant grows or is intended to
grow of below 1%, e.g. at 0.5%, 0.1% or less in comparison to a
control situation where the nitrification inhibitor is not
used.
[0293] A "herbicide" as mentioned herein above may be any herbicide
known to the skilled person.
[0294] In one embodiment, the herbicide is an acetamide (B.1.0).
Suitable examples of acetamide herbicides to be used in combination
with a nitrification inhibitor and/or with a (thio)phosphoric acid
triamide (T)--preferably used in combination with (T)--according to
the present invention are acetochlor (B.1.1), alachlor (B.1.7),
butachlor (B.1.8), dimethachlor (B.1.9), dimethenamid (B.1.2),
flufenacet (B.1.3), mefenacet (B.1.4), metolachlor (B.1.5),
metazachlor (B.1.6), napropamide (B.1.10), naproanilide (B.1.11),
pethoxamid (B.1.12), pretilachlor (B.1.13), propachlor (B.1.14),
and thenylchlor (B.1.15).
[0295] In a further embodiment, the herbicide is an amino acid
derivative (B.2.0). Suitable examples of amino acid derivative
herbicides to be used in combination with a nitrification inhibitor
and/or with a (thio)phosphoric acid triamide (T)--preferably used
in combination with (T)--according to the present invention are
bilanafos (B.2.4), glyphosate (B.2.1), glufosinate (B.2.2), and
sulfosate (B.2.3).
[0296] In a further embodiment, the herbicide is an
aryloxyphenoxypropionate (B.3.0). Suitable examples of
aryloxyphenoxypropionate herbicides to be used in combination with
a nitrification inhibitor and/or with a (thio)phosphoric acid
triamide (T)--preferably used in combination with (T)--according to
the present invention are clodinafop (B.3.1), cyhalofop-butyl
(B.3.6), fenoxaprop (B.3.2), fluazifop (B.3.3), haloxyfop (B.3.4),
metamifop (B.3.7), propaquizafop (B.3.5), quizalofop (B.3.8), and
quizalofop-P-tefuryl (B.3.9).
[0297] In a further embodiment, the herbicide is a bipyridyl
(B.4.0). Suitable examples of bipyridyl herbicides to be used in
combination with a nitrification inhibitor and/or with a
(thio)phosphoric acid triamide (T)--preferably used in combination
with (T)--according to the present invention are diquat (B.4.2),
and paraquat (B.4.1).
[0298] In a further embodiment, the herbicide is a (thio)carbamate
(B.5.0). Suitable examples of (thio)carbamate herbicides to be used
in combination with a nitrification inhibitor and/or with a
(thio)phosphoric acid triamide (T)--preferably used in combination
with (T)--according to the present invention are asulam (B.5.2),
butylate (B.5.3), carbetamide (B.5.4), desmedipham (B.5.5),
dimepiperate (B.5.6), eptam (EPTC) (B.5.7), esprocarb (B.5.8),
molinate (B.5.9), orbencarb (B.5.10), phenmedipham (B.5.1),
prosulfocarb (B.5.11), pyributicarb (B.5.12), thiobencarb (B.5.13),
and triallate (B.5.14).
[0299] In a further embodiment, the herbicide is a cyclohexanedione
(B.6.0). Suitable examples of cyclohexanedione herbicides to be
used in combination with a nitrification inhibitor and/or with a
(thio)phosphoric acid triamide (T)--preferably used in combination
with (T)--according to the present invention are butroxydim
(B.6.6), clethodim (B.6.1), cycloxydim (B.6.2), profoxydim (B.6.3),
sethoxydim (B.6.4), tepraloxydim (B.6.5), and tralkoxydim
(B.6.7).
[0300] In a further embodiment, the herbicide is a dinitroaniline
(B.7.0). Suitable examples of dinitroaniline herbicides to be used
in combination with a nitrification inhibitor and/or with a
(thio)phosphoric acid triamide (T)--preferably used in combination
with (T)--according to the present invention are benfluralin
(B.7.4), ethalfluralin (B.7.5), oryzalin (B.7.6), pendimethalin
(B.7.1), prodiamine (B.7.2), and trifluralin (B.7.3).
[0301] In a further embodiment, the herbicide is a diphenyl ether
(B.8.0). Suitable examples of diphenyl ether herbicides to be used
in combination with a nitrification inhibitor and/or with a
(thio)phosphoric acid triamide (T)--preferably used in combination
with (T)--according to the present invention are acifluorfen
(B.8.1), aclonifen (B.8.2), bifenox (B.8.3), diclofop (B.8.4),
ethoxyfen (B.8.5), fomesafen (B.8.6), lactofen (B.8.7), and
oxyfluorfen (B.8.8).
[0302] In a further embodiment, the herbicide is a
hydroxybenzonitrile (B.9.0). Suitable examples of
hydroxybenzonitrile herbicides to be used in combination with a
nitrification inhibitor and/or with a (thio)phosphoric acid
triamide (T)--preferably used in combination with (T)--according to
the present invention are bomoxynil (B.9.1), dichlobenil (B.9.2),
and ioxynil (B.9.3).
[0303] In a further embodiment, the herbicide is an imidazolinone
(B.10.0). Suitable examples of imidazolinon herbicides to be used
in combination with a nitrification inhibitor and/or with a
(thio)phosphoric acid triamide (T)--preferably used in combination
with (T)--according to the present invention are imazamethabenz
(B.10.6), imazamox (B.10.1), imazapic (B.10.2), imazapyr (B.10.3),
imazaquin (B.10.4), and imazethapyr (B.10.5).
[0304] In a further embodiment, the herbicide is a phenoxy acetic
acid (B.11.0). Suitable examples of phenoxy acetic acid herbicides
to be used in combination with a nitrification inhibitor and/or
with a (thio)phosphoric acid triamide (T)--preferably used in
combination with (T)--according to the present invention are
clomeprop (B.11.3), 2,4-dichlorophenoxyacetic acid (2,4-D)
(B.11.1), 2,4-DB (B.11.4), dichlorprop (B.11.5), MCPA (B.11.6),
MCPA-thioethyl (B.11.7), MCPB (B.11.8), and Mecoprop (B.11.9). In a
further embodiment, the herbicide is a pyrazine (B.11.10). Suitable
examples of pyrazine herbicides to be used in combination with a
nitrification inhibitor and/or with a (thio)phosphoric acid
triamide (T)--preferably used in combination with (T)--according to
the present invention are chloridazon (B.11.2), flufenpyr-ethyl
(B.11.11), fluthiacet (B.11.12), norflurazon (B.11.13), and
pyridate (B.11.14).
[0305] In a further embodiment, the herbicide is a pyridine
(B.12.0). Suitable examples of pyridine herbicides to be used in
combination with a nitrification inhibitor and/or with a
(thio)phosphoric acid triamide (T)--preferably used in combination
with (T)--according to the present invention areaminopyralid
(B.12.5), clopyralid (B.12.1), diflufenican (B.12.6), dithiopyr
(B.12.7), fluridone (B.12.8), fluroxypyr (B.12.2), picloram
(B.12.3), picolinafen (B.12.4), and thiazopyr (B.12.9).
[0306] In a further embodiment, the herbicide is a sulfonyl urea
(B.13.0). Suitable examples of sulfonyl urea herbicides to be used
in combination with a nitrification inhibitor and/or with a
(thio)phosphoric acid triamide (T)--preferably used in combination
with (T)--according to the present invention are amidosulfuron
(B.13.11), azimsulfuron (B.13.12), bensulfuron (B.13.1),
chlorimuron-ethyl (B.13.2), chlorsulfuron (B.13.13), cinosulfuron
(B.13.14), cyclosulfamuron (B.13.3), ethoxysulfuron (B.13.15),
flazasulfuron (B.13.16), flucetosulfuron (B.13.17), flupyrsulfuron
(B.13.18), foramsulfuron (B.13.19), halosulfuron (B.13.20),
imazosulfuron (B.13.21), iodosulfuron (B.13.4), mesosulfuron
(B.13.5), metazosulfuron (B.13.22), metsulfuron-methyl (B.13.6),
nicosulfuron (B.13.7), oxasulfuron (B.13.23), primisulfuron
(B.13.24), prosulfuron (B.13.25), pyrazosulfuron (B.13.26),
rimsulfuron (B.13.8), sulfometuron (B.13.27), sulfosulfuron
(B.13.28), thifensulfuron (B.13.29), triasulfuron (B.13.30),
tribenuron (B.13.10), trifloxysulfuron (B.13.31), triflusulfuron
(B.13.9), tritosulfuron (B.13.32), and
1-((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimet-
hoxy-pyrimidin-2-yl)urea (B.13.33).
[0307] In a further embodiment, the herbicide is a triazine
(B.14.0). Suitable examples of triazine herbicides to be used in
combination with a nitrification inhibitor and/or with a
(thio)phosphoric acid triamide (T)--preferably used in combination
with (T)--according to the present invention are ametryn (B.14.3),
atrazine (B.14.1), cyanazine (B.14.4), dimethametryn (B.14.5),
ethiozin (B.14.6), hexazinone (B.14.2), metamitron (B.14.7),
metribuzin (B.14.8), prometryn (B.14.9), simazine (B.14.10),
terbuthylazine (B.14.11), terbutryn (B.14.12), and triaziflam
(B.14.13).
[0308] In a further embodiment, the herbicide is a urea (B.15.0).
Suitable examples of urea herbicides to be used in combination with
a nitrification inhibitor and/or with a (thio)phosphoric acid
triamide (T)--preferably used in combination with (T)--according to
the present invention are chlorotoluron (B.15.2), daimuron
(B.15.3), diuron (B.15.1), fluometuron (B.15.4), isoproturon
(B.15.5), linuron (B.15.6), methabenzthiazuron (B.15.7), and
tebuthiuron (B.15.8).
[0309] In a further embodiment, the herbicide is a acetolactate
synthase inhibitor (B.16.0). Suitable examples of acetolactate
synthase inhibitor herbicides to be used in combination with a
nitrification inhibitor and/or with a (thio)phosphoric acid
triamide (T)--preferably used in combination with (T)--according to
the present invention are bispyribac-sodium (B.16.3),
cloransulam-methyl (B.16.4), diclosulam (B.16.5), florasulam
(B.16.1), flucarbazone (B.16.6), flumetsulam (B.16.7), metosulam
(B.16.8), ortho-sulfamuron (B.16.9), penoxsulam (B.16.10),
propoxycarbazone (B.16.11), pyribambenz-propyl (B.16.12),
pyribenzoxim (B.16.13), pyriftalid (B.16.14), pyriminobac-methyl
(B.16.15), pyrimisulfan (B.16.16), pyrithiobac (B.16.17),
pyroxasulfone (B.16.2), and pyroxsulam (B.16.18).
[0310] Further envisaged herbicides to be used in combination with
a nitrification inhibitor and/or with a (thio)phosphoric acid
triamide (T)--preferably used in combination with (T)--according to
the present invention are amicarbazone (B.17.13), aminotriazole
(B.17.14), anilofos (B.17.15), beflubutamid (B.17.16), benazolin
(B.17.17), bencarbazone (B.17.18), benfluresate (B.17.19),
benzofenap (B.17.20), bentazone (B.17.1), benzobicyclon (B.17.21),
bicyclopyrone (B.17.22), bromacil (B.17.23), bromobutide (B.17.24),
butafenacil (B.17.25), butamifos (B.17.26), cafenstrole (B.17.27),
carfentrazone (B.17.28), cinidon-ethyl (B.17.2), chlorthal
(B.17.29), cinmethylin (B.17.3), clomazone (B.17.4), cumyluron
(B.17.30), cyprosulfamide (B.17.31), dicamba (B.17.5), difenzoquat
(B.17.32), diflufenzopyr (B.17.6), Drechslera monoceras (B.17.33),
endothal (B.17.34), ethofumesate (B.17.35), etobenzanid (B.17.36),
fenoxasulfone (B.17.37), fentrazamide (B.17.38), flumiclorac-pentyl
(B.17.39), flumioxazin (B.17.40), flupoxam (B.17.41),
flurochloridone (B.17.42), flurtamone (B.17.43), indanofan
(B.17.44), isoxaben (B.17.45), isoxaflutole (B.17.46), lenacil
(B.17.47), propanil (B.17.48), propyzamide (B.17.49), quinclorac
(B.17.7), quinmerac (B.17.8), mesotrione (B.17.9), methyl arsonic
acid (B.17.50), naptalam (B.17.51), oxadiargyl (B.17.52), oxadiazon
(B.17.53), oxaziclomefone (B.17.54), pentoxazone (B.17.55),
pinoxaden (B.17.56), pyraclonil (B.17.57), pyraflufen-ethyl
(B.17.58), pyrasulfotole (B.17.59), pyrazoxyfen (B.17.60),
pyrazolynate (B.17.61), quinoclamine (B.17.62), saflufenacil
(B.17.10), sulcotrione (B.17.11), sulfentrazone (B.17.63), terbacil
(B.17.64), tefuryltrione (B.17.65), tembotrione (B.17.66),
thiencarbazone (B.17.67), topramezone (B.17.12),
(3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-
-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl
ester (B.17.68),
6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl
ester (B.17.69),
6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol
(B.17.70),
4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic
acid (B.17.71),
4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carbox-
ylic acid methyl ester (B.17.72), and
4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2--
carboxylic acid methyl ester (B.17.73).
[0311] In a particularly preferred embodiment, the herbicide is
dicamba (B.17.5), glyphosate (B.2.1), propaquizafop (B.3.5),
cycloxydim (B.6.2), bomoxynil (B.9.1), imazamox (B.10.1),
nicosulfuron (B.13.7), tribenuron (B.13.10), saflufenacil
(B.17.10), or topramezone (B.17.2).
[0312] Accordingly, the present invention furthermore relates to
compositions comprising as compound I (component A) a nitrification
inhibitor as defined herein above and as compound I (component B) a
herbicide as defined herein, i.e. a combination of component A and
B. In preferred embodiments, such compositions may be selected from
the component A of Table 2 in column 2 (Com. A) and from component
B of Table 2 in column 3 (Com. B). The number of component A of
Table 2 corresponds to the number of component A as shown in Table
1, supra ("Entry"). Preferred embodiments thus include the
specified combinations or compositions comprising component A and B
as defined in Cb-1 to Cb-2150 of Table 2:
TABLE-US-00002 Comb. Com. A Com. B Comb. Com. A Com. B Comb. Com. A
Com. B Cb-1 1 B.2.1 Cb-216 1 B.3.5 Cb-431 1 B.6.2 Cb-2 2 B.2.1
Cb-217 2 B.3.5 Cb-432 2 B.6.2 Cb-3 3 B.2.1 Cb-218 3 B.3.5 Cb-433 3
B.6.2 Cb-4 4 B.2.1 Cb-219 4 B.3.5 Cb-434 4 B.6.2 Cb-5 5 B.2.1
Cb-220 5 B.3.5 Cb-435 5 B.6.2 Cb-6 6 B.2.1 Cb-221 6 B.3.5 Cb-436 6
B.6.2 Cb-7 7 B.2.1 Cb-222 7 B.3.5 Cb-437 7 B.6.2 Cb-8 8 B.2.1
Cb-223 8 B.3.5 Cb-438 8 B.6.2 Cb-9 9 B.2.1 Cb-224 9 B.3.5 Cb-439 9
B.6.2 Cb-10 10 B.2.1 Cb-225 10 B.3.5 Cb-440 10 B.6.2 Cb-11 11 B.2.1
Cb-226 11 B.3.5 Cb-441 11 B.6.2 Cb-12 12 B.2.1 Cb-227 12 B.3.5
Cb-442 12 B.6.2 Cb-13 13 B.2.1 Cb-228 13 B.3.5 Cb-443 13 B.6.2
Cb-14 14 B.2.1 Cb-229 14 B.3.5 Cb-444 14 B.6.2 Cb-15 15 B.2.1
Cb-230 15 B.3.5 Cb-445 15 B.6.2 Cb-16 16 B.2.1 Cb-231 16 B.3.5
Cb-446 16 B.6.2 Cb-17 17 B.2.1 Cb-232 17 B.3.5 Cb-447 17 B.6.2
Cb-18 18 B.2.1 Cb-233 18 B.3.5 Cb-448 18 B.6.2 Cb-19 19 B.2.1
Cb-234 19 B.3.5 Cb-449 19 B.6.2 Cb-20 20 B.2.1 Cb-235 20 B.3.5
Cb-450 20 B.6.2 Cb-21 21 B.2.1 Cb-236 21 B.3.5 Cb-451 21 B.6.2
Cb-22 22 B.2.1 Cb-237 22 B.3.5 Cb-452 22 B.6.2 Cb-23 23 B.2.1
Cb-238 23 B.3.5 Cb-453 23 B.6.2 Cb-24 24 B.2.1 Cb-239 24 B.3.5
Cb-454 24 B.6.2 Cb-25 25 B.2.1 Cb-240 25 B.3.5 Cb-455 25 B.6.2
Cb-26 26 B.2.1 Cb-241 26 B.3.5 Cb-456 26 B.6.2 Cb-27 27 B.2.1
Cb-242 27 B.3.5 Cb-457 27 B.6.2 Cb-28 28 B.2.1 Cb-243 28 B.3.5
Cb-458 28 B.6.2 Cb-29 29 B.2.1 Cb-244 29 B.3.5 Cb-459 29 B.6.2
Cb-30 30 B.2.1 Cb-245 30 B.3.5 Cb-460 30 B.6.2 Cb-31 31 B.2.1
Cb-246 31 B.3.5 Cb-461 31 B.6.2 Cb-32 32 B.2.1 Cb-247 32 B.3.5
Cb-462 32 B.6.2 Cb-33 33 B.2.1 Cb-248 33 B.3.5 Cb-463 33 B.6.2
Cb-34 34 B.2.1 Cb-249 34 B.3.5 Cb-464 34 B.6.2 Cb-35 35 B.2.1
Cb-250 35 B.3.5 Cb-465 35 B.6.2 Cb-36 36 B.2.1 Cb-251 36 B.3.5
Cb-466 36 B.6.2 Cb-37 37 B.2.1 Cb-252 37 B.3.5 Cb-467 37 B.6.2
Cb-38 38 B.2.1 Cb-253 38 B.3.5 Cb-468 38 B.6.2 Cb-39 39 B.2.1
Cb-254 39 B.3.5 Cb-469 39 B.6.2 Cb-40 40 B.2.1 Cb-255 40 B.3.5
Cb-470 40 B.6.2 Cb-41 41 B.2.1 Cb-256 41 B.3.5 Cb-471 41 B.6.2
Cb-42 42 B.2.1 Cb-257 42 B.3.5 Cb-472 42 B.6.2 Cb-43 43 B.2.1
Cb-258 43 B.3.5 Cb-473 43 B.6.2 Cb-44 44 B.2.1 Cb-259 44 B.3.5
Cb-474 44 B.6.2 Cb-45 45 B.2.1 Cb-260 45 B.3.5 Cb-475 45 B.6.2
Cb-46 46 B.2.1 Cb-261 46 B.3.5 Cb-476 46 B.6.2 Cb-47 47 B.2.1
Cb-262 47 B.3.5 Cb-477 47 B.6.2 Cb-48 48 B.2.1 Cb-263 48 B.3.5
Cb-478 48 B.6.2 Cb-49 49 B.2.1 Cb-264 49 B.3.5 Cb-479 49 B.6.2
Cb-50 50 B.2.1 Cb-265 50 B.3.5 Cb-480 50 B.6.2 Cb-51 51 B.2.1
Cb-266 51 B.3.5 Cb-481 51 B.6.2 Cb-52 52 B.2.1 Cb-267 52 B.3.5
Cb-482 52 B.6.2 Cb-53 53 B.2.1 Cb-268 53 B.3.5 Cb-483 53 B.6.2
Cb-54 54 B.2.1 Cb-269 54 B.3.5 Cb-484 54 B.6.2 Cb-55 55 B.2.1
Cb-270 55 B.3.5 Cb-485 55 B.6.2 Cb-56 56 B.2.1 Cb-271 56 B.3.5
Cb-486 56 B.6.2 Cb-57 57 B.2.1 Cb-272 57 B.3.5 Cb-487 57 B.6.2
Cb-58 58 B.2.1 Cb-273 58 B.3.5 Cb-488 58 B.6.2 Cb-59 59 B.2.1
Cb-274 59 B.3.5 Cb-489 59 B.6.2 Cb-60 60 B.2.1 Cb-275 60 B.3.5
Cb-490 60 B.6.2 Cb-61 61 B.2.1 Cb-276 61 B.3.5 Cb-491 61 B.6.2
Cb-62 62 B.2.1 Cb-277 62 B.3.5 Cb-492 62 B.6.2 Cb-63 63 B.2.1
Cb-278 63 B.3.5 Cb-493 63 B.6.2 Cb-64 64 B.2.1 Cb-279 64 B.3.5
Cb-494 64 B.6.2 Cb-65 65 B.2.1 Cb-280 65 B.3.5 Cb-495 65 B.6.2
Cb-66 66 B.2.1 Cb-281 66 B.3.5 Cb-496 66 B.6.2 Cb-67 67 B.2.1
Cb-282 67 B.3.5 Cb-497 67 B.6.2 Cb-68 68 B.2.1 Cb-283 68 B.3.5
Cb-498 68 B.6.2 Cb-69 69 B.2.1 Cb-284 69 B.3.5 Cb-499 69 B.6.2
Cb-70 70 B.2.1 Cb-285 70 B.3.5 Cb-500 70 B.6.2 Cb-71 71 B.2.1
Cb-286 71 B.3.5 Cb-501 71 B.6.2 Cb-72 72 B.2.1 Cb-287 72 B.3.5
Cb-502 72 B.6.2 Cb-73 73 B.2.1 Cb-288 73 B.3.5 Cb-503 73 B.6.2
Cb-74 74 B.2.1 Cb-289 74 B.3.5 Cb-504 74 B.6.2 Cb-75 75 B.2.1
Cb-290 75 B.3.5 Cb-505 75 B.6.2 Cb-76 76 B.2.1 Cb-291 76 B.3.5
Cb-506 76 B.6.2 Cb-77 77 B.2.1 Cb-292 77 B.3.5 Cb-507 77 B.6.2
Cb-78 78 B.2.1 Cb-293 78 B.3.5 Cb-508 78 B.6.2 Cb-79 79 B.2.1
Cb-294 79 B.3.5 Cb-509 79 B.6.2 Cb-80 80 B.2.1 Cb-295 80 B.3.5
Cb-510 80 B.6.2 Cb-81 81 B.2.1 Cb-296 81 B.3.5 Cb-511 81 B.6.2
Cb-82 82 B.2.1 Cb-297 82 B.3.5 Cb-512 82 B.6.2 Cb-83 83 B.2.1
Cb-298 83 B.3.5 Cb-513 83 B.6.2 Cb-84 84 B.2.1 Cb-299 84 B.3.5
Cb-514 84 B.6.2 Cb-85 85 B.2.1 Cb-300 85 B.3.5 Cb-515 85 B.6.2
Cb-86 86 B.2.1 Cb-301 86 B.3.5 Cb-516 86 B.6.2 Cb-87 87 B.2.1
Cb-302 87 B.3.5 Cb-517 87 B.6.2 Cb-88 88 B.2.1 Cb-303 88 B.3.5
Cb-518 88 B.6.2 Cb-89 89 B.2.1 Cb-304 89 B.3.5 Cb-519 89 B.6.2
Cb-90 90 B.2.1 Cb-305 90 B.3.5 Cb-520 90 B.6.2 Cb-91 91 B.2.1
Cb-306 91 B.3.5 Cb-521 91 B.6.2 Cb-92 92 B.2.1 Cb-307 92 B.3.5
Cb-522 92 B.6.2 Cb-93 93 B.2.1 Cb-308 93 B.3.5 Cb-523 93 B.6.2
Cb-94 94 B.2.1 Cb-309 94 B.3.5 Cb-524 94 B.6.2 Cb-95 95 B.2.1
Cb-310 95 B.3.5 Cb-525 95 B.6.2 Cb-96 96 B.2.1 Cb-311 96 B.3.5
Cb-526 96 B.6.2 Cb-97 97 B.2.1 Cb-312 97 B.3.5 Cb-527 97 B.6.2
Cb-98 98 B.2.1 Cb-313 98 B.3.5 Cb-528 98 B.6.2 Cb-99 99 B.2.1
Cb-314 99 B.3.5 Cb-529 99 B.6.2 Cb-100 100 B.2.1 Cb-315 100 B.3.5
Cb-530 100 B.6.2 Cb-101 101 B.2.1 Cb-316 101 B.3.5 Cb-531 101 B.6.2
Cb-102 102 B.2.1 Cb-317 102 B.3.5 Cb-532 102 B.6.2 Cb-103 103 B.2.1
Cb-318 103 B.3.5 Cb-533 103 B.6.2 Cb-104 104 B.2.1 Cb-319 104 B.3.5
Cb-534 104 B.6.2 Cb-105 105 B.2.1 Cb-320 105 B.3.5 Cb-535 105 B.6.2
Cb-106 106 B.2.1 Cb-321 106 B.3.5 Cb-536 106 B.6.2 Cb-107 107 B.2.1
Cb-322 107 B.3.5 Cb-537 107 B.6.2 Cb-108 108 B.2.1 Cb-323 108 B.3.5
Cb-538 108 B.6.2 Cb-109 109 B.2.1 Cb-324 109 B.3.5 Cb-539 109 B.6.2
Cb-110 110 B.2.1 Cb-325 110 B.3.5 Cb-540 110 B.6.2 Cb-111 111 B.2.1
Cb-326 111 B.3.5 Cb-541 111 B.6.2 Cb-112 112 B.2.1 Cb-327 112 B.3.5
Cb-542 112 B.6.2 Cb-113 113 B.2.1 Cb-328 113 B.3.5 Cb-543 113 B.6.2
Cb-114 114 B.2.1 Cb-329 114 B.3.5 Cb-544 114 B.6.2 Cb-115 115 B.2.1
Cb-330 115 B.3.5 Cb-545 115 B.6.2 Cb-116 116 B.2.1 Cb-331 116 B.3.5
Cb-546 116 B.6.2 Cb-117 117 B.2.1 Cb-332 117 B.3.5 Cb-547 117 B.6.2
Cb-118 118 B.2.1 Cb-333 118 B.3.5 Cb-548 118 B.6.2 Cb-119 119 B.2.1
Cb-334 119 B.3.5 Cb-549 119 B.6.2 Cb-120 120 B.2.1 Cb-335 120 B.3.5
Cb-550 120 B.6.2 Cb-121 121 B.2.1 Cb-336 121 B.3.5 Cb-551 121 B.6.2
Cb-122 122 B.2.1 Cb-337 122 B.3.5 Cb-552 122 B.6.2 Cb-123 123 B.2.1
Cb-338 123 B.3.5 Cb-553 123 B.6.2 Cb-124 124 B.2.1 Cb-339 124 B.3.5
Cb-554 124 B.6.2 Cb-125 125 B.2.1 Cb-340 125 B.3.5 Cb-555 125 B.6.2
Cb-126 126 B.2.1 Cb-341 126 B.3.5 Cb-556 126 B.6.2 Cb-127 127 B.2.1
Cb-342 127 B.3.5 Cb-557 127 B.6.2 Cb-128 128 B.2.1 Cb-343 128 B.3.5
Cb-558 128 B.6.2 Cb-129 129 B.2.1 Cb-344 129 B.3.5 Cb-559 129 B.6.2
Cb-130 130 B.2.1 Cb-345 130 B.3.5 Cb-560 130 B.6.2 Cb-131 131 B.2.1
Cb-346 131 B.3.5 Cb-561 131 B.6.2 Cb-132 132 B.2.1 Cb-347 132 B.3.5
Cb-562 132 B.6.2 Cb-133 133 B.2.1 Cb-348 133 B.3.5 Cb-563 133 B.6.2
Cb-134 134 B.2.1 Cb-349 134 B.3.5 Cb-564 134 B.6.2 Cb-135 135 B.2.1
Cb-350 135 B.3.5 Cb-565 135 B.6.2 Cb-136 136 B.2.1 Cb-351 136 B.3.5
Cb-566 136 B.6.2 Cb-137 137 B.2.1 Cb-352 137 B.3.5 Cb-567 137 B.6.2
Cb-138 138 B.2.1 Cb-353 138 B.3.5 Cb-568 138 B.6.2 Cb-139 139 B.2.1
Cb-354 139 B.3.5 Cb-569 139 B.6.2 Cb-140 140 B.2.1 Cb-355 140 B.3.5
Cb-570 140 B.6.2 Cb-141 141 B.2.1 Cb-356 141 B.3.5 Cb-571 141 B.6.2
Cb-142 142 B.2.1 Cb-357 142 B.3.5 Cb-572 142 B.6.2 Cb-143 143 B.2.1
Cb-358 143 B.3.5 Cb-573 143 B.6.2 Cb-144 144 B.2.1 Cb-359 144 B.3.5
Cb-574 144 B.6.2 Cb-145 145 B.2.1 Cb-360 145 B.3.5 Cb-575 145 B.6.2
Cb-146 146 B.2.1 Cb-361 146 B.3.5 Cb-576 146 B.6.2 Cb-147 147 B.2.1
Cb-362 147 B.3.5 Cb-577 147 B.6.2 Cb-148 148 B.2.1 Cb-363 148 B.3.5
Cb-578 148 B.6.2 Cb-149 149 B.2.1 Cb-364 149 B.3.5 Cb-579 149 B.6.2
Cb-150 150 B.2.1 Cb-365 150 B.3.5 Cb-580 150 B.6.2 Cb-151 151 B.2.1
Cb-366 151 B.3.5 Cb-581 151 B.6.2 Cb-152 152 B.2.1 Cb-367 152 B.3.5
Cb-582 152 B.6.2 Cb-153 153 B.2.1 Cb-368 153 B.3.5 Cb-583 153 B.6.2
Cb-154 154 B.2.1 Cb-369 154 B.3.5 Cb-584 154 B.6.2 Cb-155 155 B.2.1
Cb-370 155 B.3.5 Cb-585 155 B.6.2 Cb-156 156 B.2.1 Cb-371 156 B.3.5
Cb-586 156 B.6.2 Cb-157 157 B.2.1 Cb-372 157 B.3.5 Cb-587 157 B.6.2
Cb-158 158 B.2.1 Cb-373 158 B.3.5 Cb-588 158 B.6.2 Cb-159 159 B.2.1
Cb-374 159 B.3.5 Cb-589 159 B.6.2 Cb-160 160 B.2.1 Cb-375 160 B.3.5
Cb-590 160 B.6.2 Cb-161 161 B.2.1 Cb-376 161 B.3.5 Cb-591 161 B.6.2
Cb-162 162 B.2.1 Cb-377 162 B.3.5 Cb-592 162 B.6.2 Cb-163 163 B.2.1
Cb-378 163 B.3.5 Cb-593 163 B.6.2 Cb-164 164 B.2.1 Cb-379 164 B.3.5
Cb-594 164 B.6.2 Cb-165 165 B.2.1 Cb-380 165 B.3.5 Cb-595 165 B.6.2
Cb-166 166 B.2.1 Cb-381 166 B.3.5 Cb-596 166 B.6.2 Cb-167 167 B.2.1
Cb-382 167 B.3.5 Cb-597 167 B.6.2 Cb-168 168 B.2.1 Cb-383 168 B.3.5
Cb-598 168 B.6.2 Cb-169 169 B.2.1 Cb-384 169 B.3.5 Cb-599 169 B.6.2
Cb-170 170 B.2.1 Cb-385 170 B.3.5 Cb-600 170 B.6.2 Cb-171 171 B.2.1
Cb-386 171 B.3.5 Cb-601 171 B.6.2 Cb-172 172 B.2.1 Cb-387 172 B.3.5
Cb-602 172 B.6.2 Cb-173 173 B.2.1 Cb-388 173 B.3.5 Cb-603 173 B.6.2
Cb-174 174 B.2.1 Cb-389 174 B.3.5 Cb-604 174 B.6.2 Cb-175 175 B.2.1
Cb-390 175 B.3.5 Cb-605 175 B.6.2 Cb-176 176 B.2.1 Cb-391 176 B.3.5
Cb-606 176 B.6.2 Cb-177 177 B.2.1 Cb-392 177 B.3.5 Cb-607 177 B.6.2
Cb-178 178 B.2.1 Cb-393 178 B.3.5 Cb-608 178 B.6.2 Cb-179 179 B.2.1
Cb-394 179 B.3.5 Cb-609 179 B.6.2 Cb-180 180 B.2.1 Cb-395 180 B.3.5
Cb-610 180 B.6.2 Cb-181 181 B.2.1 Cb-396 181 B.3.5 Cb-611 181 B.6.2
Cb-182 182 B.2.1 Cb-397 182 B.3.5 Cb-612 182 B.6.2 Cb-183 183 B.2.1
Cb-398 183 B.3.5 Cb-613 183 B.6.2 Cb-184 184 B.2.1 Cb-399 184 B.3.5
Cb-614 184 B.6.2 Cb-185 185 B.2.1 Cb-400 185 B.3.5 Cb-615 185 B.6.2
Cb-186 186 B.2.1 Cb-401 186 B.3.5 Cb-616 186 B.6.2 Cb-187 187 B.2.1
Cb-402 187 B.3.5 Cb-617 187 B.6.2 Cb-188 188 B.2.1 Cb-403 188 B.3.5
Cb-618 188 B.6.2 Cb-189 189 B.2.1 Cb-404 189 B.3.5 Cb-619 189 B.6.2
Cb-190 190 B.2.1 Cb-405 190 B.3.5 Cb-620 190 B.6.2 Cb-191 191 B.2.1
Cb-406 191 B.3.5 Cb-621 191 B.6.2 Cb-192 192 B.2.1 Cb-407 192 B.3.5
Cb-622 192 B.6.2 Cb-193 193 B.2.1 Cb-408 193 B.3.5 Cb-623 193 B.6.2
Cb-194 194 B.2.1 Cb-409 194 B.3.5 Cb-624 194 B.6.2 Cb-195 195 B.2.1
Cb-410 195 B.3.5 Cb-625 195 B.6.2 Cb-196 196 B.2.1 Cb-411 196 B.3.5
Cb-626 196 B.6.2 Cb-197 197 B.2.1 Cb-412 197 B.3.5 Cb-627 197 B.6.2
Cb-198 198 B.2.1 Cb-413 198 B.3.5 Cb-628 198 B.6.2 Cb-199 199 B.2.1
Cb-414 199 B.3.5 Cb-629 199 B.6.2 Cb-200 200 B.2.1 Cb-415 200 B.3.5
Cb-630 200 B.6.2 Cb-201 201 B.2.1 Cb-416 201 B.3.5 Cb-631 201 B.6.2
Cb-202 202 B.2.1 Cb-417 202 B.3.5 Cb-632 202 B.6.2 Cb-203 203 B.2.1
Cb-418 203 B.3.5 Cb-633 203 B.6.2 Cb-204 204 B.2.1 Cb-419 204 B.3.5
Cb-634 204 B.6.2 Cb-205 205 B.2.1 Cb-420 205 B.3.5 Cb-635 205 B.6.2
Cb-206 206 B.2.1 Cb-421 206 B.3.5 Cb-636 206 B.6.2 Cb-207 207 B.2.1
Cb-422 207 B.3.5 Cb-637 207 B.6.2 Cb-208 208 B.2.1 Cb-423 208 B.3.5
Cb-638 208 B.6.2 Cb-209 209 B.2.1 Cb-424 209 B.3.5 Cb-639 209 B.6.2
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Cb-426 211 B.3.5 Cb-641 211 B.6.2 Cb-212 212 B.2.1 Cb-427 212 B.3.5
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Cb-214 214 B.2.1 Cb-429 214 B.3.5 Cb-644 214 B.6.2 Cb-215 215 B.2.1
Cb-430 215 B.3.5 Cb-645 215 B.6.2 Cb-646 1 B.9.1 Cb-861 1 B.10.1
Cb-1076 1 B.13.7 Cb-647 2 B.9.1 Cb-862 2 B.10.1 Cb-1077 2 B.13.7
Cb-648 3 B.9.1 Cb-863 3 B.10.1 Cb-1078 3 B.13.7 Cb-649 4 B.9.1
Cb-864 4 B.10.1 Cb-1079 4 B.13.7 Cb-650 5 B.9.1 Cb-865 5 B.10.1
Cb-1080 5 B.13.7 Cb-651 6 B.9.1 Cb-866 6 B.10.1 Cb-1081 6 B.13.7
Cb-652 7 B.9.1 Cb-867 7 B.10.1 Cb-1082 7 B.13.7 Cb-653 8 B.9.1
Cb-868 8 B.10.1 Cb-1083 8 B.13.7 Cb-654 9 B.9.1 Cb-869 9 B.10.1
Cb-1084 9 B.13.7 Cb-655 10 B.9.1 Cb-870 10 B.10.1 Cb-1085 10 B.13.7
Cb-656 11 B.9.1 Cb-871 11 B.10.1 Cb-1086 11 B.13.7 Cb-657 12 B.9.1
Cb-872 12 B.10.1 Cb-1087 12 B.13.7 Cb-658 13 B.9.1 Cb-873 13 B.10.1
Cb-1088 13 B.13.7 Cb-659 14 B.9.1 Cb-874 14 B.10.1 Cb-1089 14
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B.9.1 Cb-876 16 B.10.1 Cb-1091 16 B.13.7 Cb-662 17 B.9.1 Cb-877 17
B.10.1 Cb-1092 17 B.13.7 Cb-663 18 B.9.1 Cb-878 18 B.10.1 Cb-1093
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Cb-1097 22 B.13.7 Cb-668 23 B.9.1 Cb-883 23 B.10.1 Cb-1098 23
B.13.7 Cb-669 24 B.9.1 Cb-884 24 B.10.1 Cb-1099 24 B.13.7 Cb-670 25
B.9.1 Cb-885 25 B.10.1 Cb-1100 25 B.13.7 Cb-671 26 B.9.1 Cb-886 26
B.10.1 Cb-1101 26 B.13.7 Cb-672 27 B.9.1 Cb-887 27 B.10.1 Cb-1102
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30 B.10.1 Cb-1105 30 B.13.7 Cb-676 31 B.9.1 Cb-891 31 B.10.1
Cb-1106 31 B.13.7
Cb-677 32 B.9.1 Cb-892 32 B.10.1 Cb-1107 32 B.13.7 Cb-678 33 B.9.1
Cb-893 33 B.10.1 Cb-1108 33 B.13.7 Cb-679 34 B.9.1 Cb-894 34 B.10.1
Cb-1109 34 B.13.7 Cb-680 35 B.9.1 Cb-895 35 B.10.1 Cb-1110 35
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Cb-1118 43 B.13.7 Cb-689 44 B.9.1 Cb-904 44 B.10.1 Cb-1119 44
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B.9.1 Cb-906 46 B.10.1 Cb-1121 46 B.13.7 Cb-692 47 B.9.1 Cb-907 47
B.10.1 Cb-1122 47 B.13.7 Cb-693 48 B.9.1 Cb-908 48 B.10.1 Cb-1123
48 B.13.7 Cb-694 49 B.9.1 Cb-909 49 B.10.1 Cb-1124 49 B.13.7 Cb-695
50 B.9.1 Cb-910 50 B.10.1 Cb-1125 50 B.13.7 Cb-696 51 B.9.1 Cb-911
51 B.10.1 Cb-1126 51 B.13.7 Cb-697 52 B.9.1 Cb-912 52 B.10.1
Cb-1127 52 B.13.7 Cb-698 53 B.9.1 Cb-913 53 B.10.1 Cb-1128 53
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B.9.1 Cb-915 55 B.10.1 Cb-1130 55 B.13.7 Cb-701 56 B.9.1 Cb-916 56
B.10.1 Cb-1131 56 B.13.7 Cb-702 57 B.9.1 Cb-917 57 B.10.1 Cb-1132
57 B.13.7 Cb-703 58 B.9.1 Cb-918 58 B.10.1 Cb-1133 58 B.13.7 Cb-704
59 B.9.1 Cb-919 59 B.10.1 Cb-1134 59 B.13.7 Cb-705 60 B.9.1 Cb-920
60 B.10.1 Cb-1135 60 B.13.7 Cb-706 61 B.9.1 Cb-921 61 B.10.1
Cb-1136 61 B.13.7 Cb-707 62 B.9.1 Cb-922 62 B.10.1 Cb-1137 62
B.13.7 Cb-708 63 B.9.1 Cb-923 63 B.10.1 Cb-1138 63 B.13.7 Cb-709 64
B.9.1 Cb-924 64 B.10.1 Cb-1139 64 B.13.7 Cb-710 65 B.9.1 Cb-925 65
B.10.1 Cb-1140 65 B.13.7 Cb-711 66 B.9.1 Cb-926 66 B.10.1 Cb-1141
66 B.13.7 Cb-712 67 B.9.1 Cb-927 67 B.10.1 Cb-1142 67 B.13.7 Cb-713
68 B.9.1 Cb-928 68 B.10.1 Cb-1143 68 B.13.7 Cb-714 69 B.9.1 Cb-929
69 B.10.1 Cb-1144 69 B.13.7 Cb-715 70 B.9.1 Cb-930 70 B.10.1
Cb-1145 70 B.13.7 Cb-716 71 B.9.1 Cb-931 71 B.10.1 Cb-1146 71
B.13.7 Cb-717 72 B.9.1 Cb-932 72 B.10.1 Cb-1147 72 B.13.7 Cb-718 73
B.9.1 Cb-933 73 B.10.1 Cb-1148 73 B.13.7 Cb-719 74 B.9.1 Cb-934 74
B.10.1 Cb-1149 74 B.13.7 Cb-720 75 B.9.1 Cb-935 75 B.10.1 Cb-1150
75 B.13.7 Cb-721 76 B.9.1 Cb-936 76 B.10.1 Cb-1151 76 B.13.7 Cb-722
77 B.9.1 Cb-937 77 B.10.1 Cb-1152 77 B.13.7 Cb-723 78 B.9.1 Cb-938
78 B.10.1 Cb-1153 78 B.13.7 Cb-724 79 B.9.1 Cb-939 79 B.10.1
Cb-1154 79 B.13.7 Cb-725 80 B.9.1 Cb-940 80 B.10.1 Cb-1155 80
B.13.7 Cb-726 81 B.9.1 Cb-941 81 B.10.1 Cb-1156 81 B.13.7 Cb-727 82
B.9.1 Cb-942 82 B.10.1 Cb-1157 82 B.13.7 Cb-728 83 B.9.1 Cb-943 83
B.10.1 Cb-1158 83 B.13.7 Cb-729 84 B.9.1 Cb-944 84 B.10.1 Cb-1159
84 B.13.7 Cb-730 85 B.9.1 Cb-945 85 B.10.1 Cb-1160 85 B.13.7 Cb-731
86 B.9.1 Cb-946 86 B.10.1 Cb-1161 86 B.13.7 Cb-732 87 B.9.1 Cb-947
87 B.10.1 Cb-1162 87 B.13.7 Cb-733 88 B.9.1 Cb-948 88 B.10.1
Cb-1163 88 B.13.7 Cb-734 89 B.9.1 Cb-949 89 B.10.1 Cb-1164 89
B.13.7 Cb-735 90 B.9.1 Cb-950 90 B.10.1 Cb-1165 90 B.13.7 Cb-736 91
B.9.1 Cb-951 91 B.10.1 Cb-1166 91 B.13.7 Cb-737 92 B.9.1 Cb-952 92
B.10.1 Cb-1167 92 B.13.7 Cb-738 93 B.9.1 Cb-953 93 B.10.1 Cb-1168
93 B.13.7 Cb-739 94 B.9.1 Cb-954 94 B.10.1 Cb-1169 94 B.13.7 Cb-740
95 B.9.1 Cb-955 95 B.10.1 Cb-1170 95 B.13.7 Cb-741 96 B.9.1 Cb-956
96 B.10.1 Cb-1171 96 B.13.7 Cb-742 97 B.9.1 Cb-957 97 B.10.1
Cb-1172 97 B.13.7 Cb-743 98 B.9.1 Cb-958 98 B.10.1 Cb-1173 98
B.13.7 Cb-744 99 B.9.1 Cb-959 99 B.10.1 Cb-1174 99 B.13.7 Cb-745
100 B.9.1 Cb-960 100 B.10.1 Cb-1175 100 B.13.7 Cb-746 101 B.9.1
Cb-961 101 B.10.1 Cb-1176 101 B.13.7 Cb-747 102 B.9.1 Cb-962 102
B.10.1 Cb-1177 102 B.13.7 Cb-748 103 B.9.1 Cb-963 103 B.10.1
Cb-1178 103 B.13.7 Cb-749 104 B.9.1 Cb-964 104 B.10.1 Cb-1179 104
B.13.7 Cb-750 105 B.9.1 Cb-965 105 B.10.1 Cb-1180 105 B.13.7 Cb-751
106 B.9.1 Cb-966 106 B.10.1 Cb-1181 106 B.13.7 Cb-752 107 B.9.1
Cb-967 107 B.10.1 Cb-1182 107 B.13.7 Cb-753 108 B.9.1 Cb-968 108
B.10.1 Cb-1183 108 B.13.7 Cb-754 109 B.9.1 Cb-969 109 B.10.1
Cb-1184 109 B.13.7 Cb-755 110 B.9.1 Cb-970 110 B.10.1 Cb-1185 110
B.13.7 Cb-756 111 B.9.1 Cb-971 111 B.10.1 Cb-1186 111 B.13.7 Cb-757
112 B.9.1 Cb-972 112 B.10.1 Cb-1187 112 B.13.7 Cb-758 113 B.9.1
Cb-973 113 B.10.1 Cb-1188 113 B.13.7 Cb-759 114 B.9.1 Cb-974 114
B.10.1 Cb-1189 114 B.13.7 Cb-760 115 B.9.1 Cb-975 115 B.10.1
Cb-1190 115 B.13.7 Cb-761 116 B.9.1 Cb-976 116 B.10.1 Cb-1191 116
B.13.7 Cb-762 117 B.9.1 Cb-977 117 B.10.1 Cb-1192 117 B.13.7 Cb-763
118 B.9.1 Cb-978 118 B.10.1 Cb-1193 118 B.13.7 Cb-764 119 B.9.1
Cb-979 119 B.10.1 Cb-1194 119 B.13.7 Cb-765 120 B.9.1 Cb-980 120
B.10.1 Cb-1195 120 B.13.7 Cb-766 121 B.9.1 Cb-981 121 B.10.1
Cb-1196 121 B.13.7 Cb-767 122 B.9.1 Cb-982 122 B.10.1 Cb-1197 122
B.13.7 Cb-768 123 B.9.1 Cb-983 123 B.10.1 Cb-1198 123 B.13.7 Cb-769
124 B.9.1 Cb-984 124 B.10.1 Cb-1199 124 B.13.7 Cb-770 125 B.9.1
Cb-985 125 B.10.1 Cb-1200 125 B.13.7 Cb-771 126 B.9.1 Cb-986 126
B.10.1 Cb-1201 126 B.13.7 Cb-772 127 B.9.1 Cb-987 127 B.10.1
Cb-1202 127 B.13.7 Cb-773 128 B.9.1 Cb-988 128 B.10.1 Cb-1203 128
B.13.7 Cb-774 129 B.9.1 Cb-989 129 B.10.1 Cb-1204 129 B.13.7 Cb-775
130 B.9.1 Cb-990 130 B.10.1 Cb-1205 130 B.13.7 Cb-776 131 B.9.1
Cb-991 131 B.10.1 Cb-1206 131 B.13.7 Cb-777 132 B.9.1 Cb-992 132
B.10.1 Cb-1207 132 B.13.7 Cb-778 133 B.9.1 Cb-993 133 B.10.1
Cb-1208 133 B.13.7 Cb-779 134 B.9.1 Cb-994 134 B.10.1 Cb-1209 134
B.13.7 Cb-780 135 B.9.1 Cb-995 135 B.10.1 Cb-1210 135 B.13.7 Cb-781
136 B.9.1 Cb-996 136 B.10.1 Cb-1211 136 B.13.7 Cb-782 137 B.9.1
Cb-997 137 B.10.1 Cb-1212 137 B.13.7 Cb-783 138 B.9.1 Cb-998 138
B.10.1 Cb-1213 138 B.13.7 Cb-784 139 B.9.1 Cb-999 139 B.10.1
Cb-1214 139 B.13.7 Cb-785 140 B.9.1 Cb-1000 140 B.10.1 Cb-1215 140
B.13.7 Cb-786 141 B.9.1 Cb-1001 141 B.10.1 Cb-1216 141 B.13.7
Cb-787 142 B.9.1 Cb-1002 142 B.10.1 Cb-1217 142 B.13.7 Cb-788 143
B.9.1 Cb-1003 143 B.10.1 Cb-1218 143 B.13.7 Cb-789 144 B.9.1
Cb-1004 144 B.10.1 Cb-1219 144 B.13.7 Cb-790 145 B.9.1 Cb-1005 145
B.10.1 Cb-1220 145 B.13.7 Cb-791 146 B.9.1 Cb-1006 146 B.10.1
Cb-1221 146 B.13.7 Cb-792 147 B.9.1 Cb-1007 147 B.10.1 Cb-1222 147
B.13.7 Cb-793 148 B.9.1 Cb-1008 148 B.10.1 Cb-1223 148 B.13.7
Cb-794 149 B.9.1 Cb-1009 149 B.10.1 Cb-1224 149 B.13.7 Cb-795 150
B.9.1 Cb-1010 150 B.10.1 Cb-1225 150 B.13.7 Cb-796 151 B.9.1
Cb-1011 151 B.10.1 Cb-1226 151 B.13.7 Cb-797 152 B.9.1 Cb-1012 152
B.10.1 Cb-1227 152 B.13.7 Cb-798 153 B.9.1 Cb-1013 153 B.10.1
Cb-1228 153 B.13.7 Cb-799 154 B.9.1 Cb-1014 154 B.10.1 Cb-1229 154
B.13.7 Cb-800 155 B.9.1 Cb-1015 155 B.10.1 Cb-1230 155 B.13.7
Cb-801 156 B.9.1 Cb-1016 156 B.10.1 Cb-1231 156 B.13.7 Cb-802 157
B.9.1 Cb-1017 157 B.10.1 Cb-1232 157 B.13.7 Cb-803 158 B.9.1
Cb-1018 158 B.10.1 Cb-1233 158 B.13.7 Cb-804 159 B.9.1 Cb-1019 159
B.10.1 Cb-1234 159 B.13.7 Cb-805 160 B.9.1 Cb-1020 160 B.10.1
Cb-1235 160 B.13.7 Cb-806 161 B.9.1 Cb-1021 161 B.10.1 Cb-1236 161
B.13.7 Cb-807 162 B.9.1 Cb-1022 162 B.10.1 Cb-1237 162 B.13.7
Cb-808 163 B.9.1 Cb-1023 163 B.10.1 Cb-1238 163 B.13.7 Cb-809 164
B.9.1 Cb-1024 164 B.10.1 Cb-1239 164 B.13.7 Cb-810 165 B.9.1
Cb-1025 165 B.10.1 Cb-1240 165 B.13.7 Cb-811 166 B.9.1 Cb-1026 166
B.10.1 Cb-1241 166 B.13.7 Cb-812 167 B.9.1 Cb-1027 167 B.10.1
Cb-1242 167 B.13.7 Cb-813 168 B.9.1 Cb-1028 168 B.10.1 Cb-1243 168
B.13.7 Cb-814 169 B.9.1 Cb-1029 169 B.10.1 Cb-1244 169 B.13.7
Cb-815 170 B.9.1 Cb-1030 170 B.10.1 Cb-1245 170 B.13.7 Cb-816 171
B.9.1 Cb-1031 171 B.10.1 Cb-1246 171 B.13.7 Cb-817 172 B.9.1
Cb-1032 172 B.10.1 Cb-1247 172 B.13.7 Cb-818 173 B.9.1 Cb-1033 173
B.10.1 Cb-1248 173 B.13.7 Cb-819 174 B.9.1 Cb-1034 174 B.10.1
Cb-1249 174 B.13.7 Cb-820 175 B.9.1 Cb-1035 175 B.10.1 Cb-1250 175
B.13.7 Cb-821 176 B.9.1 Cb-1036 176 B.10.1 Cb-1251 176 B.13.7
Cb-822 177 B.9.1 Cb-1037 177 B.10.1 Cb-1252 177 B.13.7 Cb-823 178
B.9.1 Cb-1038 178 B.10.1 Cb-1253 178 B.13.7 Cb-824 179 B.9.1
Cb-1039 179 B.10.1 Cb-1254 179 B.13.7 Cb-825 180 B.9.1 Cb-1040 180
B.10.1 Cb-1255 180 B.13.7 Cb-826 181 B.9.1 Cb-1041 181 B.10.1
Cb-1256 181 B.13.7 Cb-827 182 B.9.1 Cb-1042 182 B.10.1 Cb-1257 182
B.13.7 Cb-828 183 B.9.1 Cb-1043 183 B.10.1 Cb-1258 183 B.13.7
Cb-829 184 B.9.1 Cb-1044 184 B.10.1 Cb-1259 184 B.13.7 Cb-830 185
B.9.1 Cb-1045 185 B.10.1 Cb-1260 185 B.13.7 Cb-831 186 B.9.1
Cb-1046 186 B.10.1 Cb-1261 186 B.13.7 Cb-832 187 B.9.1 Cb-1047 187
B.10.1 Cb-1262 187 B.13.7 Cb-833 188 B.9.1 Cb-1048 188 B.10.1
Cb-1263 188 B.13.7 Cb-834 189 B.9.1 Cb-1049 189 B.10.1 Cb-1264 189
B.13.7 Cb-835 190 B.9.1 Cb-1050 190 B.10.1 Cb-1265 190 B.13.7
Cb-836 191 B.9.1 Cb-1051 191 B.10.1 Cb-1266 191 B.13.7 Cb-837 192
B.9.1 Cb-1052 192 B.10.1 Cb-1267 192 B.13.7 Cb-838 193 B.9.1
Cb-1053 193 B.10.1 Cb-1268 193 B.13.7 Cb-839 194 B.9.1 Cb-1054 194
B.10.1 Cb-1269 194 B.13.7 Cb-840 195 B.9.1 Cb-1055 195 B.10.1
Cb-1270 195 B.13.7 Cb-841 196 B.9.1 Cb-1056 196 B.10.1 Cb-1271 196
B.13.7 Cb-842 197 B.9.1 Cb-1057 197 B.10.1 Cb-1272 197 B.13.7
Cb-843 198 B.9.1 Cb-1058 198 B.10.1 Cb-1273 198 B.13.7 Cb-844 199
B.9.1 Cb-1059 199 B.10.1 Cb-1274 199 B.13.7 Cb-845 200 B.9.1
Cb-1060 200 B.10.1 Cb-1275 200 B.13.7 Cb-846 201 B.9.1 Cb-1061 201
B.10.1 Cb-1276 201 B.13.7 Cb-847 202 B.9.1 Cb-1062 202 B.10.1
Cb-1277 202 B.13.7 Cb-848 203 B.9.1 Cb-1063 203 B.10.1 Cb-1278 203
B.13.7 Cb-849 204 B.9.1 Cb-1064 204 B.10.1 Cb-1279 204 B.13.7
Cb-850 205 B.9.1 Cb-1065 205 B.10.1 Cb-1280 205 B.13.7 Cb-851 206
B.9.1 Cb-1066 206 B.10.1 Cb-1281 206 B.13.7 Cb-852 207 B.9.1
Cb-1067 207 B.10.1 Cb-1282 207 B.13.7 Cb-853 208 B.9.1 Cb-1068 208
B.10.1 Cb-1283 208 B.13.7 Cb-854 209 B.9.1 Cb-1069 209 B.10.1
Cb-1284 209 B.13.7 Cb-855 210 B.9.1 Cb-1070 210 B.10.1 Cb-1285 210
B.13.7 Cb-856 211 B.9.1 Cb-1071 211 B.10.1 Cb-1286 211 B.13.7
Cb-857 212 B.9.1 Cb-1072 212 B.10.1 Cb-1287 212 B.13.7 Cb-858 213
B.9.1 Cb-1073 213 B.10.1 Cb-1288 213 B.13.7 Cb-859 214 B.9.1
Cb-1074 214 B.10.1 Cb-1289 214 B.13.7 Cb-860 215 B.9.1 Cb-1075 215
B.10.1 Cb-1290 215 B.13.7 Cb-1291 1 B.13.10 Cb-1506 1 B.17.2
Cb-1721 1 B.17.5 Cb-1292 2 B.13.10 Cb-1507 2 B.17.2 Cb-1722 2
B.17.5 Cb-1293 3 B.13.10 Cb-1508 3 B.17.2 Cb-1723 3 B.17.5 Cb-1294
4 B.13.10 Cb-1509 4 B.17.2 Cb-1724 4 B.17.5 Cb-1295 5 B.13.10
Cb-1510 5 B.17.2 Cb-1725 5 B.17.5 Cb-1296 6 B.13.10 Cb-1511 6
B.17.2 Cb-1726 6 B.17.5 Cb-1297 7 B.13.10 Cb-1512 7 B.17.2 Cb-1727
7 B.17.5 Cb-1298 8 B.13.10 Cb-1513 8 B.17.2 Cb-1728 8 B.17.5
Cb-1299 9 B.13.10 Cb-1514 9 B.17.2 Cb-1729 9 B.17.5 Cb-1300 10
B.13.10 Cb-1515 10 B.17.2 Cb-1730 10 B.17.5 Cb-1301 11 B.13.10
Cb-1516 11 B.17.2 Cb-1731 11 B.17.5 Cb-1302 12 B.13.10 Cb-1517 12
B.17.2 Cb-1732 12 B.17.5 Cb-1303 13 B.13.10 Cb-1518 13 B.17.2
Cb-1733 13 B.17.5 Cb-1304 14 B.13.10 Cb-1519 14 B.17.2 Cb-1734 14
B.17.5 Cb-1305 15 B.13.10 Cb-1520 15 B.17.2 Cb-1735 15 B.17.5
Cb-1306 16 B.13.10 Cb-1521 16 B.17.2 Cb-1736 16 B.17.5 Cb-1307 17
B.13.10 Cb-1522 17 B.17.2 Cb-1737 17 B.17.5 Cb-1308 18 B.13.10
Cb-1523 18 B.17.2 Cb-1738 18 B.17.5 Cb-1309 19 B.13.10 Cb-1524 19
B.17.2 Cb-1739 19 B.17.5 Cb-1310 20 B.13.10 Cb-1525 20 B.17.2
Cb-1740 20 B.17.5 Cb-1311 21 B.13.10 Cb-1526 21 B.17.2 Cb-1741 21
B.17.5 Cb-1312 22 B.13.10 Cb-1527 22 B.17.2 Cb-1742 22 B.17.5
Cb-1313 23 B.13.10 Cb-1528 23 B.17.2 Cb-1743 23 B.17.5 Cb-1314 24
B.13.10 Cb-1529 24 B.17.2 Cb-1744 24 B.17.5 Cb-1315 25 B.13.10
Cb-1530 25 B.17.2 Cb-1745 25 B.17.5 Cb-1316 26 B.13.10 Cb-1531 26
B.17.2 Cb-1746 26 B.17.5 Cb-1317 27 B.13.10 Cb-1532 27 B.17.2
Cb-1747 27 B.17.5 Cb-1318 28 B.13.10 Cb-1533 28 B.17.2 Cb-1748 28
B.17.5 Cb-1319 29 B.13.10 Cb-1534 29 B.17.2 Cb-1749 29 B.17.5
Cb-1320 30 B.13.10 Cb-1535 30 B.17.2 Cb-1750 30 B.17.5 Cb-1321 31
B.13.10 Cb-1536 31 B.17.2 Cb-1751 31 B.17.5 Cb-1322 32 B.13.10
Cb-1537 32 B.17.2 Cb-1752 32 B.17.5 Cb-1323 33 B.13.10 Cb-1538 33
B.17.2 Cb-1753 33 B.17.5 Cb-1324 34 B.13.10 Cb-1539 34 B.17.2
Cb-1754 34 B.17.5 Cb-1325 35 B.13.10 Cb-1540 35 B.17.2 Cb-1755 35
B.17.5 Cb-1326 36 B.13.10 Cb-1541 36 B.17.2 Cb-1756 36 B.17.5
Cb-1327 37 B.13.10 Cb-1542 37 B.17.2 Cb-1757 37 B.17.5 Cb-1328 38
B.13.10 Cb-1543 38 B.17.2 Cb-1758 38 B.17.5 Cb-1329 39 B.13.10
Cb-1544 39 B.17.2 Cb-1759 39 B.17.5 Cb-1330 40 B.13.10 Cb-1545 40
B.17.2 Cb-1760 40 B.17.5 Cb-1331 41 B.13.10 Cb-1546 41 B.17.2
Cb-1761 41 B.17.5 Cb-1332 42 B.13.10 Cb-1547 42 B.17.2 Cb-1762 42
B.17.5 Cb-1333 43 B.13.10 Cb-1548 43 B.17.2 Cb-1763 43 B.17.5
Cb-1334 44 B.13.10 Cb-1549 44 B.17.2 Cb-1764 44 B.17.5 Cb-1335 45
B.13.10 Cb-1550 45 B.17.2 Cb-1765 45 B.17.5 Cb-1336 46 B.13.10
Cb-1551 46 B.17.2 Cb-1766 46 B.17.5 Cb-1337 47 B.13.10 Cb-1552 47
B.17.2 Cb-1767 47 B.17.5 Cb-1338 48 B.13.10 Cb-1553 48 B.17.2
Cb-1768 48 B.17.5 Cb-1339 49 B.13.10 Cb-1554 49 B.17.2 Cb-1769 49
B.17.5 Cb-1340 50 B.13.10 Cb-1555 50 B.17.2 Cb-1770 50 B.17.5
Cb-1341 51 B.13.10 Cb-1556 51 B.17.2 Cb-1771 51 B.17.5 Cb-1342 52
B.13.10 Cb-1557 52 B.17.2 Cb-1772 52 B.17.5 Cb-1343 53 B.13.10
Cb-1558 53 B.17.2 Cb-1773 53 B.17.5 Cb-1344 54 B.13.10 Cb-1559 54
B.17.2 Cb-1774 54 B.17.5 Cb-1345 55 B.13.10 Cb-1560 55 B.17.2
Cb-1775 55 B.17.5 Cb-1346 56 B.13.10 Cb-1561 56 B.17.2 Cb-1776 56
B.17.5 Cb-1347 57 B.13.10 Cb-1562 57 B.17.2 Cb-1777 57 B.17.5
Cb-1348 58 B.13.10 Cb-1563 58 B.17.2 Cb-1778 58 B.17.5 Cb-1349 59
B.13.10 Cb-1564 59 B.17.2 Cb-1779 59 B.17.5 Cb-1350 60 B.13.10
Cb-1565 60 B.17.2 Cb-1780 60 B.17.5 Cb-1351 61 B.13.10 Cb-1566 61
B.17.2 Cb-1781 61 B.17.5 Cb-1352 62 B.13.10 Cb-1567 62 B.17.2
Cb-1782 62 B.17.5 Cb-1353 63 B.13.10 Cb-1568 63 B.17.2 Cb-1783 63
B.17.5 Cb-1354 64 B.13.10 Cb-1569 64 B.17.2 Cb-1784 64 B.17.5
Cb-1355 65 B.13.10 Cb-1570 65 B.17.2 Cb-1785 65 B.17.5 Cb-1356 66
B.13.10 Cb-1571 66 B.17.2 Cb-1786 66 B.17.5 Cb-1357 67 B.13.10
Cb-1572 67 B.17.2 Cb-1787 67 B.17.5
Cb-1358 68 B.13.10 Cb-1573 68 B.17.2 Cb-1788 68 B.17.5 Cb-1359 69
B.13.10 Cb-1574 69 B.17.2 Cb-1789 69 B.17.5 Cb-1360 70 B.13.10
Cb-1575 70 B.17.2 Cb-1790 70 B.17.5 Cb-1361 71 B.13.10 Cb-1576 71
B.17.2 Cb-1791 71 B.17.5 Cb-1362 72 B.13.10 Cb-1577 72 B.17.2
Cb-1792 72 B.17.5 Cb-1363 73 B.13.10 Cb-1578 73 B.17.2 Cb-1793 73
B.17.5 Cb-1364 74 B.13.10 Cb-1579 74 B.17.2 Cb-1794 74 B.17.5
Cb-1365 75 B.13.10 Cb-1580 75 B.17.2 Cb-1795 75 B.17.5 Cb-1366 76
B.13.10 Cb-1581 76 B.17.2 Cb-1796 76 B.17.5 Cb-1367 77 B.13.10
Cb-1582 77 B.17.2 Cb-1797 77 B.17.5 Cb-1368 78 B.13.10 Cb-1583 78
B.17.2 Cb-1798 78 B.17.5 Cb-1369 79 B.13.10 Cb-1584 79 B.17.2
Cb-1799 79 B.17.5 Cb-1370 80 B.13.10 Cb-1585 80 B.17.2 Cb-1800 80
B.17.5 Cb-1371 81 B.13.10 Cb-1586 81 B.17.2 Cb-1801 81 B.17.5
Cb-1372 82 B.13.10 Cb-1587 82 B.17.2 Cb-1802 82 B.17.5 Cb-1373 83
B.13.10 Cb-1588 83 B.17.2 Cb-1803 83 B.17.5 Cb-1374 84 B.13.10
Cb-1589 84 B.17.2 Cb-1804 84 B.17.5 Cb-1375 85 B.13.10 Cb-1590 85
B.17.2 Cb-1805 85 B.17.5 Cb-1376 86 B.13.10 Cb-1591 86 B.17.2
Cb-1806 86 B.17.5 Cb-1377 87 B.13.10 Cb-1592 87 B.17.2 Cb-1807 87
B.17.5 Cb-1378 88 B.13.10 Cb-1593 88 B.17.2 Cb-1808 88 B.17.5
Cb-1379 89 B.13.10 Cb-1594 89 B.17.2 Cb-1809 89 B.17.5 Cb-1380 90
B.13.10 Cb-1595 90 B.17.2 Cb-1810 90 B.17.5 Cb-1381 91 B.13.10
Cb-1596 91 B.17.2 Cb-1811 91 B.17.5 Cb-1382 92 B.13.10 Cb-1597 92
B.17.2 Cb-1812 92 B.17.5 Cb-1383 93 B.13.10 Cb-1598 93 B.17.2
Cb-1813 93 B.17.5 Cb-1384 94 B.13.10 Cb-1599 94 B.17.2 Cb-1814 94
B.17.5 Cb-1385 95 B.13.10 Cb-1600 95 B.17.2 Cb-1815 95 B.17.5
Cb-1386 96 B.13.10 Cb-1601 96 B.17.2 Cb-1816 96 B.17.5 Cb-1387 97
B.13.10 Cb-1602 97 B.17.2 Cb-1817 97 B.17.5 Cb-1388 98 B.13.10
Cb-1603 98 B.17.2 Cb-1818 98 B.17.5 Cb-1389 99 B.13.10 Cb-1604 99
B.17.2 Cb-1819 99 B.17.5 Cb-1390 100 B.13.10 Cb-1605 100 B.17.2
Cb-1820 100 B.17.5 Cb-1391 101 B.13.10 Cb-1606 101 B.17.2 Cb-1821
101 B.17.5 Cb-1392 102 B.13.10 Cb-1607 102 B.17.2 Cb-1822 102
B.17.5 Cb-1393 103 B.13.10 Cb-1608 103 B.17.2 Cb-1823 103 B.17.5
Cb-1394 104 B.13.10 Cb-1609 104 B.17.2 Cb-1824 104 B.17.5 Cb-1395
105 B.13.10 Cb-1610 105 B.17.2 Cb-1825 105 B.17.5 Cb-1396 106
B.13.10 Cb-1611 106 B.17.2 Cb-1826 106 B.17.5 Cb-1397 107 B.13.10
Cb-1612 107 B.17.2 Cb-1827 107 B.17.5 Cb-1398 108 B.13.10 Cb-1613
108 B.17.2 Cb-1828 108 B.17.5 Cb-1399 109 B.13.10 Cb-1614 109
B.17.2 Cb-1829 109 B.17.5 Cb-1400 110 B.13.10 Cb-1615 110 B.17.2
Cb-1830 110 B.17.5 Cb-1401 111 B.13.10 Cb-1616 111 B.17.2 Cb-1831
111 B.17.5 Cb-1402 112 B.13.10 Cb-1617 112 B.17.2 Cb-1832 112
B.17.5 Cb-1403 113 B.13.10 Cb-1618 113 B.17.2 Cb-1833 113 B.17.5
Cb-1404 114 B.13.10 Cb-1619 114 B.17.2 Cb-1834 114 B.17.5 Cb-1405
115 B.13.10 Cb-1620 115 B.17.2 Cb-1835 115 B.17.5 Cb-1406 116
B.13.10 Cb-1621 116 B.17.2 Cb-1836 116 B.17.5 Cb-1407 117 B.13.10
Cb-1622 117 B.17.2 Cb-1837 117 B.17.5 Cb-1408 118 B.13.10 Cb-1623
118 B.17.2 Cb-1838 118 B.17.5 Cb-1409 119 B.13.10 Cb-1624 119
B.17.2 Cb-1839 119 B.17.5 Cb-1410 120 B.13.10 Cb-1625 120 B.17.2
Cb-1840 120 B.17.5 Cb-1411 121 B.13.10 Cb-1626 121 B.17.2 Cb-1841
121 B.17.5 Cb-1412 122 B.13.10 Cb-1627 122 B.17.2 Cb-1842 122
B.17.5 Cb-1413 123 B.13.10 Cb-1628 123 B.17.2 Cb-1843 123 B.17.5
Cb-1414 124 B.13.10 Cb-1629 124 B.17.2 Cb-1844 124 B.17.5 Cb-1415
125 B.13.10 Cb-1630 125 B.17.2 Cb-1845 125 B.17.5 Cb-1416 126
B.13.10 Cb-1631 126 B.17.2 Cb-1846 126 B.17.5 Cb-1417 127 B.13.10
Cb-1632 127 B.17.2 Cb-1847 127 B.17.5 Cb-1418 128 B.13.10 Cb-1633
128 B.17.2 Cb-1848 128 B.17.5 Cb-1419 129 B.13.10 Cb-1634 129
B.17.2 Cb-1849 129 B.17.5 Cb-1420 130 B.13.10 Cb-1635 130 B.17.2
Cb-1850 130 B.17.5 Cb-1421 131 B.13.10 Cb-1636 131 B.17.2 Cb-1851
131 B.17.5 Cb-1422 132 B.13.10 Cb-1637 132 B.17.2 Cb-1852 132
B.17.5 Cb-1423 133 B.13.10 Cb-1638 133 B.17.2 Cb-1853 133 B.17.5
Cb-1424 134 B.13.10 Cb-1639 134 B.17.2 Cb-1854 134 B.17.5 Cb-1425
135 B.13.10 Cb-1640 135 B.17.2 Cb-1855 135 B.17.5 Cb-1426 136
B.13.10 Cb-1641 136 B.17.2 Cb-1856 136 B.17.5 Cb-1427 137 B.13.10
Cb-1642 137 B.17.2 Cb-1857 137 B.17.5 Cb-1428 138 B.13.10 Cb-1643
138 B.17.2 Cb-1858 138 B.17.5 Cb-1429 139 B.13.10 Cb-1644 139
B.17.2 Cb-1859 139 B.17.5 Cb-1430 140 B.13.10 Cb-1645 140 B.17.2
Cb-1860 140 B.17.5 Cb-1431 141 B.13.10 Cb-1646 141 B.17.2 Cb-1861
141 B.17.5 Cb-1432 142 B.13.10 Cb-1647 142 B.17.2 Cb-1862 142
B.17.5 Cb-1433 143 B.13.10 Cb-1648 143 B.17.2 Cb-1863 143 B.17.5
Cb-1434 144 B.13.10 Cb-1649 144 B.17.2 Cb-1864 144 B.17.5 Cb-1435
145 B.13.10 Cb-1650 145 B.17.2 Cb-1865 145 B.17.5 Cb-1436 146
B.13.10 Cb-1651 146 B.17.2 Cb-1866 146 B.17.5 Cb-1437 147 B.13.10
Cb-1652 147 B.17.2 Cb-1867 147 B.17.5 Cb-1438 148 B.13.10 Cb-1653
148 B.17.2 Cb-1868 148 B.17.5 Cb-1439 149 B.13.10 Cb-1654 149
B.17.2 Cb-1869 149 B.17.5 Cb-1440 150 B.13.10 Cb-1655 150 B.17.2
Cb-1870 150 B.17.5 Cb-1441 151 B.13.10 Cb-1656 151 B.17.2 Cb-1871
151 B.17.5 Cb-1442 152 B.13.10 Cb-1657 152 B.17.2 Cb-1872 152
B.17.5 Cb-1443 153 B.13.10 Cb-1658 153 B.17.2 Cb-1873 153 B.17.5
Cb-1444 154 B.13.10 Cb-1659 154 B.17.2 Cb-1874 154 B.17.5 Cb-1445
155 B.13.10 Cb-1660 155 B.17.2 Cb-1875 155 B.17.5 Cb-1446 156
B.13.10 Cb-1661 156 B.17.2 Cb-1876 156 B.17.5 Cb-1447 157 B.13.10
Cb-1662 157 B.17.2 Cb-1877 157 B.17.5 Cb-1448 158 B.13.10 Cb-1663
158 B.17.2 Cb-1878 158 B.17.5 Cb-1449 159 B.13.10 Cb-1664 159
B.17.2 Cb-1879 159 B.17.5 Cb-1450 160 B.13.10 Cb-1665 160 B.17.2
Cb-1880 160 B.17.5 Cb-1451 161 B.13.10 Cb-1666 161 B.17.2 Cb-1881
161 B.17.5 Cb-1452 162 B.13.10 Cb-1667 162 B.17.2 Cb-1882 162
B.17.5 Cb-1453 163 B.13.10 Cb-1668 163 B.17.2 Cb-1883 163 B.17.5
Cb-1454 164 B.13.10 Cb-1669 164 B.17.2 Cb-1884 164 B.17.5 Cb-1455
165 B.13.10 Cb-1670 165 B.17.2 Cb-1885 165 B.17.5 Cb-1456 166
B.13.10 Cb-1671 166 B.17.2 Cb-1886 166 B.17.5 Cb-1457 167 B.13.10
Cb-1672 167 B.17.2 Cb-1887 167 B.17.5 Cb-1458 168 B.13.10 Cb-1673
168 B.17.2 Cb-1888 168 B.17.5 Cb-1459 169 B.13.10 Cb-1674 169
B.17.2 Cb-1889 169 B.17.5 Cb-1460 170 B.13.10 Cb-1675 170 B.17.2
Cb-1890 170 B.17.5 Cb-1461 171 B.13.10 Cb-1676 171 B.17.2 Cb-1891
171 B.17.5 Cb-1462 172 B.13.10 Cb-1677 172 B.17.2 Cb-1892 172
B.17.5 Cb-1463 173 B.13.10 Cb-1678 173 B.17.2 Cb-1893 173 B.17.5
Cb-1464 174 B.13.10 Cb-1679 174 B.17.2 Cb-1894 174 B.17.5 Cb-1465
175 B.13.10 Cb-1680 175 B.17.2 Cb-1895 175 B.17.5 Cb-1466 176
B.13.10 Cb-1681 176 B.17.2 Cb-1896 176 B.17.5 Cb-1467 177 B.13.10
Cb-1682 177 B.17.2 Cb-1897 177 B.17.5 Cb-1468 178 B.13.10 Cb-1683
178 B.17.2 Cb-1898 178 B.17.5 Cb-1469 179 B.13.10 Cb-1684 179
B.17.2 Cb-1899 179 B.17.5 Cb-1470 180 B.13.10 Cb-1685 180 B.17.2
Cb-1900 180 B.17.5 Cb-1471 181 B.13.10 Cb-1686 181 B.17.2 Cb-1901
181 B.17.5 Cb-1472 182 B.13.10 Cb-1687 182 B.17.2 Cb-1902 182
B.17.5 Cb-1473 183 B.13.10 Cb-1688 183 B.17.2 Cb-1903 183 B.17.5
Cb-1474 184 B.13.10 Cb-1689 184 B.17.2 Cb-1904 184 B.17.5 Cb-1475
185 B.13.10 Cb-1690 185 B.17.2 Cb-1905 185 B.17.5 Cb-1476 186
B.13.10 Cb-1691 186 B.17.2 Cb-1906 186 B.17.5 Cb-1477 187 B.13.10
Cb-1692 187 B.17.2 Cb-1907 187 B.17.5 Cb-1478 188 B.13.10 Cb-1693
188 B.17.2 Cb-1908 188 B.17.5 Cb-1479 189 B.13.10 Cb-1694 189
B.17.2 Cb-1909 189 B.17.5 Cb-1480 190 B.13.10 Cb-1695 190 B.17.2
Cb-1910 190 B.17.5 Cb-1481 191 B.13.10 Cb-1696 191 B.17.2 Cb-1911
191 B.17.5 Cb-1482 192 B.13.10 Cb-1697 192 B.17.2 Cb-1912 192
B.17.5 Cb-1483 193 B.13.10 Cb-1698 193 B.17.2 Cb-1913 193 B.17.5
Cb-1484 194 B.13.10 Cb-1699 194 B.17.2 Cb-1914 194 B.17.5 Cb-1485
195 B.13.10 Cb-1700 195 B.17.2 Cb-1915 195 B.17.5 Cb-1486 196
B.13.10 Cb-1701 196 B.17.2 Cb-1916 196 B.17.5 Cb-1487 197 B.13.10
Cb-1702 197 B.17.2 Cb-1917 197 B.17.5 Cb-1488 198 B.13.10 Cb-1703
198 B.17.2 Cb-1918 198 B.17.5 Cb-1489 199 B.13.10 Cb-1704 199
B.17.2 Cb-1919 199 B.17.5 Cb-1490 200 B.13.10 Cb-1705 200 B.17.2
Cb-1920 200 B.17.5 Cb-1491 201 B.13.10 Cb-1706 201 B.17.2 Cb-1921
201 B.17.5 Cb-1492 202 B.13.10 Cb-1707 202 B.17.2 Cb-1922 202
B.17.5 Cb-1493 203 B.13.10 Cb-1708 203 B.17.2 Cb-1923 203 B.17.5
Cb-1494 204 B.13.10 Cb-1709 204 B.17.2 Cb-1924 204 B.17.5 Cb-1495
205 B.13.10 Cb-1710 205 B.17.2 Cb-1925 205 B.17.5 Cb-1496 206
B.13.10 Cb-1711 206 B.17.2 Cb-1926 206 B.17.5 Cb-1497 207 B.13.10
Cb-1712 207 B.17.2 Cb-1927 207 B.17.5 Cb-1498 208 B.13.10 Cb-1713
208 B.17.2 Cb-1928 208 B.17.5 Cb-1499 209 B.13.10 Cb-1714 209
B.17.2 Cb-1929 209 B.17.5 Cb-1500 210 B.13.10 Cb-1715 210 B.17.2
Cb-1930 210 B.17.5 Cb-1501 211 B.13.10 Cb-1716 211 B.17.2 Cb-1931
211 B.17.5 Cb-1502 212 B.13.10 Cb-1717 212 B.17.2 Cb-1932 212
B.17.5 Cb-1503 213 B.13.10 Cb-1718 213 B.17.2 Cb-1933 213 B.17.5
Cb-1504 214 B.13.10 Cb-1719 214 B.17.2 Cb-1934 214 B.17.5 Cb-1505
215 B.13.10 Cb-1720 215 B.17.2 Cb-1935 215 B.17.5 Cb-1936 1 B.17.10
Cb-2008 73 B.17.10 Cb-2080 145 B.17.10 Cb-1937 2 B.17.10 Cb-2009 74
B.17.10 Cb-2081 146 B.17.10 Cb-1938 3 B.17.10 Cb-2010 75 B.17.10
Cb-2082 147 B.17.10 Cb-1939 4 B.17.10 Cb-2011 76 B.17.10 Cb-2083
148 B.17.10 Cb-1940 5 B.17.10 Cb-2012 77 B.17.10 Cb-2084 149
B.17.10 Cb-1941 6 B.17.10 Cb-2013 78 B.17.10 Cb-2085 150 B.17.10
Cb-1942 7 B.17.10 Cb-2014 79 B.17.10 Cb-2086 151 B.17.10 Cb-1943 8
B.17.10 Cb-2015 80 B.17.10 Cb-2087 152 B.17.10 Cb-1944 9 B.17.10
Cb-2016 81 B.17.10 Cb-2088 153 B.17.10 Cb-1945 10 B.17.10 Cb-2017
82 B.17.10 Cb-2089 154 B.17.10 Cb-1946 11 B.17.10 Cb-2018 83
B.17.10 Cb-2090 155 B.17.10 Cb-1947 12 B.17.10 Cb-2019 84 B.17.10
Cb-2091 156 B.17.10 Cb-1948 13 B.17.10 Cb-2020 85 B.17.10 Cb-2092
157 B.17.10 Cb-1949 14 B.17.10 Cb-2021 86 B.17.10 Cb-2093 158
B.17.10 Cb-1950 15 B.17.10 Cb-2022 87 B.17.10 Cb-2094 159 B.17.10
Cb-1951 16 B.17.10 Cb-2023 88 B.17.10 Cb-2095 160 B.17.10 Cb-1952
17 B.17.10 Cb-2024 89 B.17.10 Cb-2096 161 B.17.10 Cb-1953 18
B.17.10 Cb-2025 90 B.17.10 Cb-2097 162 B.17.10 Cb-1954 19 B.17.10
Cb-2026 91 B.17.10 Cb-2098 163 B.17.10 Cb-1955 20 B.17.10 Cb-2027
92 B.17.10 Cb-2099 164 B.17.10 Cb-1956 21 B.17.10 Cb-2028 93
B.17.10 Cb-2100 165 B.17.10 Cb-1957 22 B.17.10 Cb-2029 94 B.17.10
Cb-2101 166 B.17.10 Cb-1958 23 B.17.10 Cb-2030 95 B.17.10 Cb-2102
167 B.17.10 Cb-1959 24 B.17.10 Cb-2031 96 B.17.10 Cb-2103 168
B.17.10 Cb-1960 25 B.17.10 Cb-2032 97 B.17.10 Cb-2104 169 B.17.10
Cb-1961 26 B.17.10 Cb-2033 98 B.17.10 Cb-2105 170 B.17.10 Cb-1962
27 B.17.10 Cb-2034 99 B.17.10 Cb-2106 171 B.17.10 Cb-1963 28
B.17.10 Cb-2035 100 B.17.10 Cb-2107 172 B.17.10 Cb-1964 29 B.17.10
Cb-2036 101 B.17.10 Cb-2108 173 B.17.10 Cb-1965 30 B.17.10 Cb-2037
102 B.17.10 Cb-2109 174 B.17.10 Cb-1966 31 B.17.10 Cb-2038 103
B.17.10 Cb-2110 175 B.17.10 Cb-1967 32 B.17.10 Cb-2039 104 B.17.10
Cb-2111 176 B.17.10 Cb-1968 33 B.17.10 Cb-2040 105 B.17.10 Cb-2112
177 B.17.10 Cb-1969 34 B.17.10 Cb-2041 106 B.17.10 Cb-2113 178
B.17.10 Cb-1970 35 B.17.10 Cb-2042 107 B.17.10 Cb-2114 179 B.17.10
Cb-1971 36 B.17.10 Cb-2043 108 B.17.10 Cb-2115 180 B.17.10 Cb-1972
37 B.17.10 Cb-2044 109 B.17.10 Cb-2116 181 B.17.10 Cb-1973 38
B.17.10 Cb-2045 110 B.17.10 Cb-2117 182 B.17.10 Cb-1974 39 B.17.10
Cb-2046 111 B.17.10 Cb-2118 183 B.17.10 Cb-1975 40 B.17.10 Cb-2047
112 B.17.10 Cb-2119 184 B.17.10 Cb-1976 41 B.17.10 Cb-2048 113
B.17.10 Cb-2120 185 B.17.10 Cb-1977 42 B.17.10 Cb-2049 114 B.17.10
Cb-2121 186 B.17.10 Cb-1978 43 B.17.10 Cb-2050 115 B.17.10 Cb-2122
187 B.17.10 Cb-1979 44 B.17.10 Cb-2051 116 B.17.10 Cb-2123 188
B.17.10 Cb-1980 45 B.17.10 Cb-2052 117 B.17.10 Cb-2124 189 B.17.10
Cb-1981 46 B.17.10 Cb-2053 118 B.17.10 Cb-2125 190 B.17.10 Cb-1982
47 B.17.10 Cb-2054 119 B.17.10 Cb-2126 191 B.17.10 Cb-1983 48
B.17.10 Cb-2055 120 B.17.10 Cb-2127 192 B.17.10 Cb-1984 49 B.17.10
Cb-2056 121 B.17.10 Cb-2128 193 B.17.10 Cb-1985 50 B.17.10 Cb-2057
122 B.17.10 Cb-2129 194 B.17.10 Cb-1986 51 B.17.10 Cb-2058 123
B.17.10 Cb-2130 195 B.17.10 Cb-1987 52 B.17.10 Cb-2059 124 B.17.10
Cb-2131 196 B.17.10 Cb-1988 53 B.17.10 Cb-2060 125 B.17.10 Cb-2132
197 B.17.10 Cb-1989 54 B.17.10 Cb-2061 126 B.17.10 Cb-2133 198
B.17.10 Cb-1990 55 B.17.10 Cb-2062 127 B.17.10 Cb-2134 199 B.17.10
Cb-1991 56 B.17.10 Cb-2063 128 B.17.10 Cb-2135 200 B.17.10 Cb-1992
57 B.17.10 Cb-2064 129 B.17.10 Cb-2136 201 B.17.10 Cb-1993 58
B.17.10 Cb-2065 130 B.17.10 Cb-2137 202 B.17.10 Cb-1994 59 B.17.10
Cb-2066 131 B.17.10 Cb-2138 203 B.17.10 Cb-1995 60 B.17.10 Cb-2067
132 B.17.10 Cb-2139 204 B.17.10 Cb-1996 61 B.17.10 Cb-2068 133
B.17.10 Cb-2140 205 B.17.10 Cb-1997 62 B.17.10 Cb-2069 134 B.17.10
Cb-2141 206 B.17.10 Cb-1998 63 B.17.10 Cb-2070 135 B.17.10 Cb-2142
207 B.17.10 Cb-1999 64 B.17.10 Cb-2071 136 B.17.10 Cb-2143 208
B.17.10 Cb-2000 65 B.17.10 Cb-2072 137 B.17.10 Cb-2144 209 B.17.10
Cb-2001 66 B.17.10 Cb-2073 138 B.17.10 Cb-2145 210 B.17.10 Cb-2002
67 B.17.10 Cb-2074 139 B.17.10 Cb-2146 211 B.17.10 Cb-2003 68
B.17.10 Cb-2075 140 B.17.10 Cb-2147 212 B.17.10 Cb-2004 69 B.17.10
Cb-2076 141 B.17.10 Cb-2148 213 B.17.10 Cb-2005 70 B.17.10 Cb-2077
142 B.17.10 Cb-2149 214 B.17.10 Cb-2006 71 B.17.10 Cb-2078 143
B.17.10 Cb-2150 215 B.17.10 Cb-2007 72 B.17.10 Cb-2079 144
B.17.10
[0313] Accordingly, the present invention furthermore relates to
compositions comprising as compound I (component 1, referred to as
"Co. 1") a (thio)phosphoric acid triamide (T) as defined herein
above and as compound II (component 2, referred to as "Co. 2") a
herbicide as defined herein, i.e. a combination of component 1 and
2. In preferred embodiments, such compositions may be selected from
the component 1 of Table 3 in the column titled "Co. 1" and from
component 2 of Table 3 in the column titled "Co. 2".
N-n-butylthiophosphoric acid triamide (NBPT) is referred to as
"(W)". N-(n-propyl) thiophosphoric acid triamide (NPPT) or any
mixtures comprising NBPT and NPPT, wherein NBPT is present in
amounts of from 1 to 99.99 wt. %, more preferably from 10 to 99.9
wt. %, most preferably from 20 to 99 wt. %, particularly preferably
from 30 to 98 wt. %, more particularly preferably from 40 to 95 wt.
%, most particularly preferably from 50 to 90 wt. %, especially
from 60 to 85 wt. %, especially preferably from 72 to 80 wt. %, for
example from 74 to 77 wt. %, in each case based on the total weight
of the (thio)phosphoric acid triamides (T) contained in the
composition (Q), is referred to as "(Y)". N-n-butylthiophosphoric
acid triamide (NBPT) but not comprising any nitrification inhibitor
of the compound of formula I is referred to as "(Z)", thus, all
compositions or mixtures i517 to i774 do not comprise any
nitrification inhibitor of the compound of formula I. NBPT and/or
NPPT and additionally comprising a urea-containing fertilizer is
referred to as "(U)", wherein such urea-containing fertilizer is
preferably urea, formaldehyde urea, UAN, urea sulfur, stabilized
urea, urea based NPK-fertilizers, or urea ammonium sulfate and is
most preferably UAN. The application of the compositions or
mixtures i1 to i1032 can be carried out in a way that its
individual components (for example Co. 1 and Co. 2, in case of i775
to i1032 NBPT/NPPT and the urea-containing fertilizer and Co. 2)
are applied either simultaneously or with a time lag as further
specified below. Preferred embodiments thus include the specified
combinations or compositions comprising component 1 and 2 as
defined in the compositions or mixtures i1 to i1032 of the
following Table 3:
TABLE-US-00003 Mixt. Co. 1 Co. 2 i1 (W) B.1.0 i2 (W) B.1.1 i3 (W)
B.1.2 i4 (W) B.1.3 i5 (W) B.1.4 i6 (W) B.1.5 i7 (W) B.1.6 i8 (W)
B.1.7 i9 (W) B.1.8 i10 (W) B.1.9 i11 (W) B.1.10 i12 (W) B.1.11 i13
(W) B.1.12 i14 (W) B.1.13 i15 (W) B.1.14 i16 (W) B.1.15 i17 (W)
B.2.0 i18 (W) B.2.1 i19 (W) B.2.2 i20 (W) B.2.3 i21 (W) B.2.4 i22
(W) B.3.0 i23 (W) B.3.1 i24 (W) B.3.2 i25 (W) B.3.3 i26 (W) B.3.4
i27 (W) B.3.5 i28 (W) B.3.6 i29 (W) B.3.7 i30 (W) B.3.8 i31 (W)
B.3.9 i32 (W) B.4.0 i33 (W) B.4.1 i34 (W) B.4.2 i35 (W) B.5.0 i36
(W) B.5.1 i37 (W) B.5.2 i38 (W) B.5.3 i39 (W) B.5.4 i40 (W) B.5.5
i41 (W) B.5.6 i42 (W) B.5.7 i43 (W) B.5.8 i44 (W) B.5.9 i45 (W)
B.5.10 i46 (W) B.5.11 i47 (W) B.5.12 i48 (W) B.5.13 i49 (W) B.5.14
i50 (W) B.6.0 i51 (W) B.6.1 i52 (W) B.6.2 i53 (W) B.6.3 i54 (W)
B.6.4 i55 (W) B.6.5 i56 (W) B.6.6 i57 (W) B.6.7 i58 (W) B.7.0 i59
(W) B.7.1 i60 (W) B.7.2 i61 (W) B.7.3 i62 (W) B.7.4 i63 (W) B.7.5
i64 (W) B.7.6 i65 (W) B.8.0 i66 (W) B.8.1 i67 (W) B.8.2 i68 (W)
B.8.3 i69 (W) B.8.4 i70 (W) B.8.5 i71 (W) B.8.6 i72 (W) B.8.7 i73
(W) B.8.8 i74 (W) B.9.0 i75 (W) B.9.1 i76 (W) B.9.2 i77 (W) B.9.3
i78 (W) B.10.0 i79 (W) B.10.1 i80 (W) B.10.2 i81 (W) B.10.3 i82 (W)
B.10.4 i83 (W) B.10.5 i84 (W) B.10.6 i85 (W) B.11.0 i86 (W) B.11.1
i87 (W) B.11.2 i88 (W) B.11.3 i89 (W) B.11.4 i90 (W) B.11.5 i91 (W)
B.11.6 i92 (W) B.11.7 i93 (W) B.11.8 i94 (W) B.11.9 i95 (W) B.11.10
i96 (W) B.11.11 i97 (W) B.11.12 i98 (W) B.11.13 i99 (W) B.11.14
i100 (W) B.12.0 i101 (W) B.12.1 i102 (W) B.12.2 i103 (W) B.12.3
i104 (W) B.12.4 i105 (W) B.12.5 i106 (W) B.12.6 i107 (W) B.12.7
i108 (W) B.12.8 i109 (W) B.12.9 i110 (W) B.13.0 i111 (W) B.13.1
i112 (W) B.13.2 i113 (W) B.13.3 i114 (W) B.13.4 i115 (W) B.13.5
i116 (W) B.13.6 i117 (W) B.13.7 i118 (W) B.13.8 i119 (W) B.13.9
i120 (W) B.13.10 i121 (W) B.13.11 i122 (W) B.13.12 i123 (W) B.13.13
i124 (W) B.13.14 i125 (W) B.13.15 i126 (W) B.13.16 i127 (W) B.13.17
i128 (W) B.13.18 i129 (W) B.13.19 i130 (W) B.13.20 i131 (W) B.13.21
i132 (W) B.13.22 i133 (W) B.13.23 i134 (W) B.13.24 i135 (W) B.13.25
i136 (W) B.13.26 i137 (W) B.13.27 i138 (W) B.13.28 i139 (W) B.13.29
i140 (W) B.13.30 i141 (W) B.13.31 i142 (W) B.13.32 i143 (W) B.13.33
i144 (W) B.14.0 i145 (W) B.14.1 i146 (W) B.14.2 i147 (W) B.14.3
i148 (W) B.14.4 i149 (W) B.14.5 i150 (W) B.14.6 i151 (W) B.14.7
i152 (W) B.14.8 i153 (W) B.14.9 i154 (W) B.14.10 i155 (W) B.14.11
i156 (W) B.14.12 i157 (W) B.14.13 i158 (W) B.15.0 i159 (W) B.15.1
i160 (W) B.15.2 i161 (W) B.15.3 i162 (W) B.15.4 i163 (W) B.15.5
i164 (W) B.15.6 i165 (W) B.15.7 i166 (W) B.15.8 i167 (W) B.16.0
i168 (W) B.16.1 i169 (W) B.16.2 i170 (W) B.16.3 i171 (W) B.16.4
i172 (W) B.16.5 i173 (W) B.16.6 i174 (W) B.16.7 i175 (W) B.16.8
i176 (W) B.16.9 i177 (W) B.16.10 i178 (W) B.16.11 i179 (W) B.16.12
i180 (W) B.16.13 i181 (W) B.16.14 i182 (W) B.16.15 i183 (W) B.16.16
i184 (W) B.16.17 i185 (W) B.16.18 i186 (W) B.17.1 i187 (W) B.17.2
i188 (W) B.17.3 i189 (W) B.17.4 i190 (W) B.17.5 i191 (W) B.17.6
i192 (W) B.17.7 i193 (W) B.17.8 i194 (W) B.17.9 i195 (W) B.17.10
i196 (W) B.17.11 i197 (W) B.17.12 i198 (W) B.17.13 i199 (W) B.17.14
i200 (W) B.17.15 i201 (W) B.17.16 i202 (W) B.17.17 i203 (W) B.17.18
i204 (W) B.17.19 i205 (W) B.17.20 i206 (W) B.17.21 i207 (W) B.17.22
i208 (W) B.17.23 i209 (W) B.17.24 i210 (W) B.17.25 i211 (W) B.17.26
i212 (W) B.17.27 i213 (W) B.17.28 i214 (W) B.17.29 i215 (W) B.17.30
i216 (W) B.17.31 i217 (W) B.17.32 i218 (W) B.17.33 i219 (W) B.17.34
i220 (W) B.17.35 i221 (W) B.17.36 i222 (W) B.17.37 i223 (W) B.17.38
i224 (W) B.17.39 i225 (W) B.17.40 i226 (W) B.17.41 i227 (W) B.17.42
i228 (W) B.17.43 i229 (W) B.17.44 i230 (W) B.17.45 i231 (W) B.17.46
i232 (W) B.17.47 i233 (W) B.17.48 i234 (W) B.17.49 i235 (W) B.17.50
i236 (W) B.17.51 i237 (W) B.17.52 i238 (W) B.17.53 i239 (W) B.17.54
i240 (W) B.17.55 i241 (W) B.17.56 i242 (W) B.17.57 i243 (W) B.17.58
i244 (W) B.17.59 i245 (W) B.17.60 i246 (W) B.17.61 i247 (W)
B.17.62
i248 (W) B.17.63 i249 (W) B.17.64 i250 (W) B.17.65 i251 (W) B.17.66
i252 (W) B.17.67 i253 (W) B.17.68 i254 (W) B.17.69 i255 (W) B.17.70
i256 (W) B.17.71 i257 (W) B.17.72 i258 (W) B.17.73 i259 (Y) B.1.0
i260 (Y) B.1.1 i261 (Y) B.1.2 i262 (Y) B.1.3 i263 (Y) B.1.4 i264
(Y) B.1.5 i265 (Y) B.1.6 i266 (Y) B.1.7 i267 (Y) B.1.8 i268 (Y)
B.1.9 i269 (Y) B.1.10 i270 (Y) B.1.11 i271 (Y) B.1.12 i272 (Y)
B.1.13 i273 (Y) B.1.14 i274 (Y) B.1.15 i275 (Y) B.2.0 i276 (Y)
B.2.1 i277 (Y) B.2.2 i278 (Y) B.2.3 i279 (Y) B.2.4 i280 (Y) B.3.0
i281 (Y) B.3.1 i282 (Y) B.3.2 i283 (Y) B.3.3 i284 (Y) B.3.4 i285
(Y) B.3.5 i286 (Y) B.3.6 i287 (Y) B.3.7 i288 (Y) B.3.8 i289 (Y)
B.3.9 i290 (Y) B.4.0 i291 (Y) B.4.1 i292 (Y) B.4.2 i293 (Y) B.5.0
i294 (Y) B.5.1 i295 (Y) B.5.2 i296 (Y) B.5.3 i297 (Y) B.5.4 i298
(Y) B.5.5 i299 (Y) B.5.6 i300 (Y) B.5.7 i301 (Y) B.5.8 i302 (Y)
B.5.9 i303 (Y) B.5.10 i304 (Y) B.5.11 i305 (Y) B.5.12 i306 (Y)
B.5.13 i307 (Y) B.5.14 i308 (Y) B.6.0 i309 (Y) B.6.1 i310 (Y) B.6.2
i311 (Y) B.6.3 i312 (Y) B.6.4 i313 (Y) B.6.5 i314 (Y) B.6.6 i315
(Y) B.6.7 i316 (Y) B.7.0 i317 (Y) B.7.1 i318 (Y) B.7.2 i319 (Y)
B.7.3 i320 (Y) B.7.4 i321 (Y) B.7.5 i322 (Y) B.7.6 i323 (Y) B.8.0
i324 (Y) B.8.1 i325 (Y) B.8.2 i326 (Y) B.8.3 i327 (Y) B.8.4 i328
(Y) B.8.5 i329 (Y) B.8.6 i330 (Y) B.8.7 i331 (Y) B.8.8 i332 (Y)
B.9.0 i333 (Y) B.9.1 i334 (Y) B.9.2 i335 (Y) B.9.3 i336 (Y) B.10.0
i337 (Y) B.10.1 i338 (Y) B.10.2 i339 (Y) B.10.3 i340 (Y) B.10.4
i341 (Y) B.10.5 i342 (Y) B.10.6 i343 (Y) B.11.0 i344 (Y) B.11.1
i345 (Y) B.11.2 i346 (Y) B.11.3 i347 (Y) B.11.4 i348 (Y) B.11.5
i349 (Y) B.11.6 i350 (Y) B.11.7 i351 (Y) B.11.8 i352 (Y) B.11.9
i353 (Y) B.11.10 i354 (Y) B.11.11 i355 (Y) B.11.12 i356 (Y) B.11.13
i357 (Y) B.11.14 i358 (Y) B.12.0 i359 (Y) B.12.1 i360 (Y) B.12.2
i361 (Y) B.12.3 i362 (Y) B.12.4 i363 (Y) B.12.5 i364 (Y) B.12.6
i365 (Y) B.12.7 i366 (Y) B.12.8 i367 (Y) B.12.9 i368 (Y) B.13.0
i369 (Y) B.13.1 i370 (Y) B.13.2 i371 (Y) B.13.3 i372 (Y) B.13.4
i373 (Y) B.13.5 i374 (Y) B.13.6 i375 (Y) B.13.7 i376 (Y) B.13.8
i377 (Y) B.13.9 i378 (Y) B.13.10 i379 (Y) B.13.11 i380 (Y) B.13.12
i381 (Y) B.13.13 i382 (Y) B.13.14 i383 (Y) B.13.15 i384 (Y) B.13.16
i385 (Y) B.13.17 i386 (Y) B.13.18 i387 (Y) B.13.19 i388 (Y) B.13.20
i389 (Y) B.13.21 i390 (Y) B.13.22 i391 (Y) B.13.23 i392 (Y) B.13.24
i393 (Y) B.13.25 i394 (Y) B.13.26 i395 (Y) B.13.27 i396 (Y) B.13.28
i397 (Y) B.13.29 i398 (Y) B.13.30 i399 (Y) B.13.31 i400 (Y) B.13.32
i401 (Y) B.13.33 i402 (Y) B.14.0 i403 (Y) B.14.1 i404 (Y) B.14.2
i405 (Y) B.14.3 i406 (Y) B.14.4 i407 (Y) B.14.5 i408 (Y) B.14.6
i409 (Y) B.14.7 i410 (Y) B.14.8 i411 (Y) B.14.9 i412 (Y) B.14.10
i413 (Y) B.14.11 i414 (Y) B.14.12 i415 (Y) B.14.13 i416 (Y) B.15.0
i417 (Y) B.15.1 i418 (Y) B.15.2 i419 (Y) B.15.3 i420 (Y) B.15.4
i421 (Y) B.15.5 i422 (Y) B.15.6 i423 (Y) B.15.7 i424 (Y) B.15.8
i425 (Y) B.16.0 i426 (Y) B.16.1 i427 (Y) B.16.2 i428 (Y) B.16.3
i429 (Y) B.16.4 i430 (Y) B.16.5 i431 (Y) B.16.6 i432 (Y) B.16.7
i433 (Y) B.16.8 i434 (Y) B.16.9 i435 (Y) B.16.10 i436 (Y) B.16.11
i437 (Y) B.16.12 i438 (Y) B.16.13 i439 (Y) B.16.14 i440 (Y) B.16.15
i441 (Y) B.16.16 i442 (Y) B.16.17 i443 (Y) B.16.18 i444 (Y) B.17.1
i445 (Y) B.17.2 i446 (Y) B.17.3 i447 (Y) B.17.4 i448 (Y) B.17.5
i449 (Y) B.17.6 i450 (Y) B.17.7 i451 (Y) B.17.8 i452 (Y) B.17.9
i453 (Y) B.17.10 i454 (Y) B.17.11 i455 (Y) B.17.12 i456 (Y) B.17.13
i457 (Y) B.17.14 i458 (Y) B.17.15 i459 (Y) B.17.16 i460 (Y) B.17.17
i461 (Y) B.17.18 i462 (Y) B.17.19 i463 (Y) B.17.20 i464 (Y) B.17.21
i465 (Y) B.17.22 i466 (Y) B.17.23 i467 (Y) B.17.24 i468 (Y) B.17.25
i469 (Y) B.17.26 i470 (Y) B.17.27 i471 (Y) B.17.28 i472 (Y) B.17.29
i473 (Y) B.17.30 i474 (Y) B.17.31 i475 (Y) B.17.32 i476 (Y) B.17.33
i477 (Y) B.17.34 i478 (Y) B.17.35 i479 (Y) B.17.36 i480 (Y) B.17.37
i481 (Y) B.17.38 i482 (Y) B.17.39 i483 (Y) B.17.40 i484 (Y) B.17.41
i485 (Y) B.17.42 i486 (Y) B.17.43 i487 (Y) B.17.44 i488 (Y) B.17.45
i489 (Y) B.17.46 i490 (Y) B.17.47 i491 (Y) B.17.48 i492 (Y) B.17.49
i493 (Y) B.17.50 i494 (Y) B.17.51 i495 (Y) B.17.52 i496 (Y) B.17.53
i497 (Y) B.17.54 i498 (Y) B.17.55
i499 (Y) B.17.56 i500 (Y) B.17.57 i501 (Y) B.17.58 i502 (Y) B.17.59
i503 (Y) B.17.60 i504 (Y) B.17.61 i505 (Y) B.17.62 i506 (Y) B.17.63
i507 (Y) B.17.64 i508 (Y) B.17.65 i509 (Y) B.17.66 i510 (Y) B.17.67
i511 (Y) B.17.68 i512 (Y) B.17.69 i513 (Y) B.17.70 i514 (Y) B.17.71
i515 (Y) B.17.72 i516 (Y) B.17.73 i517 (Z) B.1.0 i518 (Z) B.1.1
i519 (Z) B.1.2 i520 (Z) B.1.3 i521 (Z) B.1.4 i522 (Z) B.1.5 i523
(Z) B.1.6 i524 (Z) B.1.7 i525 (Z) B.1.8 i526 (Z) B.1.9 i527 (Z)
B.1.10 i528 (Z) B.1.11 i529 (Z) B.1.12 i530 (Z) B.1.13 i531 (Z)
B.1.14 i532 (Z) B.1.15 i533 (Z) B.2.0 i534 (Z) B.2.1 i535 (Z) B.2.2
i536 (Z) B.2.3 i537 (Z) B.2.4 i538 (Z) B.3.0 i539 (Z) B.3.1 i540
(Z) B.3.2 i541 (Z) B.3.3 i542 (Z) B.3.4 i543 (Z) B.3.5 i544 (Z)
B.3.6 i545 (Z) B.3.7 i546 (Z) B.3.8 i547 (Z) B.3.9 i548 (Z) B.4.0
i549 (Z) B.4.1 i550 (Z) B.4.2 i551 (Z) B.5.0 i552 (Z) B.5.1 i553
(Z) B.5.2 i554 (Z) B.5.3 i555 (Z) B.5.4 i556 (Z) B.5.5 i557 (Z)
B.5.6 i558 (Z) B.5.7 i559 (Z) B.5.8 i560 (Z) B.5.9 i561 (Z) B.5.10
i562 (Z) B.5.11 i563 (Z) B.5.12 i564 (Z) B.5.13 i565 (Z) B.5.14
i566 (Z) B.6.0 i567 (Z) B.6.1 i568 (Z) B.6.2 i569 (Z) B.6.3 i570
(Z) B.6.4 i571 (Z) B.6.5 i572 (Z) B.6.6 i573 (Z) B.6.7 i574 (Z)
B.7.0 i575 (Z) B.7.1 i576 (Z) B.7.2 i577 (Z) B.7.3 i578 (Z) B.7.4
i579 (Z) B.7.5 i580 (Z) B.7.6 i581 (Z) B.8.0 i582 (Z) B.8.1 i583
(Z) B.8.2 i584 (Z) B.8.3 i585 (Z) B.8.4 i586 (Z) B.8.5 i587 (Z)
B.8.6 i588 (Z) B.8.7 i589 (Z) B.8.8 i590 (Z) B.9.0 i591 (Z) B.9.1
i592 (Z) B.9.2 i593 (Z) B.9.3 i594 (Z) B.10.0 i595 (Z) B.10.1 i596
(Z) B.10.2 i597 (Z) B.10.3 i598 (Z) B.10.4 i599 (Z) B.10.5 i600 (Z)
B.10.6 i601 (Z) B.11.0 i602 (Z) B.11.1 i603 (Z) B.11.2 i604 (Z)
B.11.3 i605 (Z) B.11.4 i606 (Z) B.11.5 i607 (Z) B.11.6 i608 (Z)
B.11.7 i609 (Z) B.11.8 i610 (Z) B.11.9 i611 (Z) B.11.10 i612 (Z)
B.11.11 i613 (Z) B.11.12 i614 (Z) B.11.13 i615 (Z) B.11.14 i616 (Z)
B.12.0 i617 (Z) B.12.1 i618 (Z) B.12.2 i619 (Z) B.12.3 i620 (Z)
B.12.4 i621 (Z) B.12.5 i622 (Z) B.12.6 i623 (Z) B.12.7 i624 (Z)
B.12.8 i625 (Z) B.12.9 i626 (Z) B.13.0 i627 (Z) B.13.1 i628 (Z)
B.13.2 i629 (Z) B.13.3 i630 (Z) B.13.4 i631 (Z) B.13.5 i632 (Z)
B.13.6 i633 (Z) B.13.7 i634 (Z) B.13.8 i635 (Z) B.13.9 i636 (Z)
B.13.10 i637 (Z) B.13.11 i638 (Z) B.13.12 i639 (Z) B.13.13 i640 (Z)
B.13.14 i641 (Z) B.13.15 i642 (Z) B.13.16 i643 (Z) B.13.17 i644 (Z)
B.13.18 i645 (Z) B.13.19 i646 (Z) B.13.20 i647 (Z) B.13.21 i648 (Z)
B.13.22 i649 (Z) B.13.23 i650 (Z) B.13.24 i651 (Z) B.13.25 i652 (Z)
B.13.26 i653 (Z) B.13.27 i654 (Z) B.13.28 i655 (Z) B.13.29 i656 (Z)
B.13.30 i657 (Z) B.13.31 i658 (Z) B.13.32 i659 (Z) B.13.33 i660 (Z)
B.14.0 i661 (Z) B.14.1 i662 (Z) B.14.2 i663 (Z) B.14.3 i664 (Z)
B.14.4 i665 (Z) B.14.5 i666 (Z) B.14.6 i667 (Z) B.14.7 i668 (Z)
B.14.8 i669 (Z) B.14.9 i670 (Z) B.14.10 i671 (Z) B.14.11 i672 (Z)
B.14.12 i673 (Z) B.14.13 i674 (Z) B.15.0 i675 (Z) B.15.1 i676 (Z)
B.15.2 i677 (Z) B.15.3 i678 (Z) B.15.4 i679 (Z) B.15.5 i680 (Z)
B.15.6 i681 (Z) B.15.7 i682 (Z) B.15.8 i683 (Z) B.16.0 i684 (Z)
B.16.1 i685 (Z) B.16.2 i686 (Z) B.16.3 i687 (Z) B.16.4 i688 (Z)
B.16.5 i689 (Z) B.16.6 i690 (Z) B.16.7 i691 (Z) B.16.8 i692 (Z)
B.16.9 i693 (Z) B.16.10 i694 (Z) B.16.11 i695 (Z) B.16.12 i696 (Z)
B.16.13 i697 (Z) B.16.14 i698 (Z) B.16.15 i699 (Z) B.16.16 i700 (Z)
B.16.17 i701 (Z) B.16.18 i702 (Z) B.17.1 i703 (Z) B.17.2 i704 (Z)
B.17.3 i705 (Z) B.17.4 i706 (Z) B.17.5 i707 (Z) B.17.6 i708 (Z)
B.17.7 i709 (Z) B.17.8 i710 (Z) B.17.9 i711 (Z) B.17.10 i712 (Z)
B.17.11 i713 (Z) B.17.12 i714 (Z) B.17.13 i715 (Z) B.17.14 i716 (Z)
B.17.15 i717 (Z) B.17.16 i718 (Z) B.17.17 i719 (Z) B.17.18 i720 (Z)
B.17.19 i721 (Z) B.17.20 i722 (Z) B.17.21 i723 (Z) B.17.22 i724 (Z)
B.17.23 i725 (Z) B.17.24 i726 (Z) B.17.25 i727 (Z) B.17.26 i728 (Z)
B.17.27 i729 (Z) B.17.28 i730 (Z) B.17.29 i731 (Z) B.17.30 i732 (Z)
B.17.31 i733 (Z) B.17.32 i734 (Z) B.17.33 i735 (Z) B.17.34 i736 (Z)
B.17.35 i737 (Z) B.17.36 i738 (Z) B.17.37 i739 (Z) B.17.38 i740 (Z)
B.17.39 i741 (Z) B.17.40 i742 (Z) B.17.41 i743 (Z) B.17.42 i744 (Z)
B.17.43 i745 (Z) B.17.44 i746 (Z) B.17.45 i747 (Z) B.17.46 i748 (Z)
B.17.47 i749 (Z) B.17.48
i750 (Z) B.17.49 i751 (Z) B.17.50 i752 (Z) B.17.51 i753 (Z) B.17.52
i754 (Z) B.17.53 i755 (Z) B.17.54 i756 (Z) B.17.55 i757 (Z) B.17.56
i758 (Z) B.17.57 i759 (Z) B.17.58 i760 (Z) B.17.59 i761 (Z) B.17.60
i762 (Z) B.17.61 i763 (Z) B.17.62 i764 (Z) B.17.63 i765 (Z) B.17.64
i766 (Z) B.17.65 i767 (Z) B.17.66 i768 (Z) B.17.67 i769 (Z) B.17.68
i770 (Z) B.17.69 i771 (Z) B.17.70 i772 (Z) B.17.71 i773 (Z) B.17.72
i774 (Z) B.17.73 i775 (U) B.1.0 i776 (U) B.1.1 i777 (U) B.1.2 i778
(U) B.1.3 i779 (U) B.1.4 i780 (U) B.1.5 i781 (U) B.1.6 i782 (U)
B.1.7 i783 (U) B.1.8 i784 (U) B.1.9 i785 (U) B.1.10 i786 (U) B.1.11
i787 (U) B.1.12 i788 (U) B.1.13 i789 (U) B.1.14 i790 (U) B.1.15
i791 (U) B.2.0 i792 (U) B.2.1 i793 (U) B.2.2 i794 (U) B.2.3 i795
(U) B.2.4 i796 (U) B.3.0 i797 (U) B.3.1 i798 (U) B.3.2 i799 (U)
B.3.3 i800 (U) B.3.4 i801 (U) B.3.5 i802 (U) B.3.6 i803 (U) B.3.7
i804 (U) B.3.8 i805 (U) B.3.9 i806 (U) B.4.0 i807 (U) B.4.1 i808
(U) B.4.2 i809 (U) B.5.0 i810 (U) B.5.1 i811 (U) B.5.2 i812 (U)
B.5.3 i813 (U) B.5.4 i814 (U) B.5.5 i815 (U) B.5.6 i816 (U) B.5.7
i817 (U) B.5.8 i818 (U) B.5.9 i819 (U) B.5.10 i820 (U) B.5.11 i821
(U) B.5.12 i822 (U) B.5.13 i823 (U) B.5.14 i824 (U) B.6.0 i825 (U)
B.6.1 i826 (U) B.6.2 i827 (U) B.6.3 i828 (U) B.6.4 i829 (U) B.6.5
i830 (U) B.6.6 i831 (U) B.6.7 i832 (U) B.7.0 i833 (U) B.7.1 i834
(U) B.7.2 i835 (U) B.7.3 i836 (U) B.7.4 i837 (U) B.7.5 i838 (U)
B.7.6 i839 (U) B.8.0 i840 (U) B.8.1 i841 (U) B.8.2 i842 (U) B.8.3
i843 (U) B.8.4 i844 (U) B.8.5 i845 (U) B.8.6 i846 (U) B.8.7 i847
(U) B.8.8 i848 (U) B.9.0 i849 (U) B.9.1 i850 (U) B.9.2 i851 (U)
B.9.3 i852 (U) B.10.0 i853 (U) B.10.1 i854 (U) B.10.2 i855 (U)
B.10.3 i856 (U) B.10.4 i857 (U) B.10.5 i858 (U) B.10.6 i859 (U)
B.11.0 i860 (U) B.11.1 i861 (U) B.11.2 i862 (U) B.11.3 i863 (U)
B.11.4 i864 (U) B.11.5 i865 (U) B.11.6 i866 (U) B.11.7 i867 (U)
B.11.8 i868 (U) B.11.9 i869 (U) B.11.10 i870 (U) B.11.11 i871 (U)
B.11.12 i872 (U) B.11.13 i873 (U) B.11.14 i874 (U) B.12.0 i875 (U)
B.12.1 i876 (U) B.12.2 i877 (U) B.12.3 i878 (U) B.12.4 i879 (U)
B.12.5 i880 (U) B.12.6 i881 (U) B.12.7 i882 (U) B.12.8 i883 (U)
B.12.9 i884 (U) B.13.0 i885 (U) B.13.1 i886 (U) B.13.2 i887 (U)
B.13.3 i888 (U) B.13.4 i889 (U) B.13.5 i890 (U) B.13.6 i891 (U)
B.13.7 i892 (U) B.13.8 i893 (U) B.13.9 i894 (U) B.13.10 i895 (U)
B.13.11 i896 (U) B.13.12 i897 (U) B.13.13 i898 (U) B.13.14 i899 (U)
B.13.15 i900 (U) B.13.16 i901 (U) B.13.17 i902 (U) B.13.18 i903 (U)
B.13.19 i904 (U) B.13.20 i905 (U) B.13.21 i906 (U) B.13.22 i907 (U)
B.13.23 i908 (U) B.13.24 i909 (U) B.13.25 i910 (U) B.13.26 i911 (U)
B.13.27 i912 (U) B.13.28 i913 (U) B.13.29 i914 (U) B.13.30 i915 (U)
B.13.31 i916 (U) B.13.32 i917 (U) B.13.33 i918 (U) B.14.0 i919 (U)
B.14.1 i920 (U) B.14.2 i921 (U) B.14.3 i922 (U) B.14.4 i923 (U)
B.14.5 i924 (U) B.14.6 i925 (U) B.14.7 i926 (U) B.14.8 i927 (U)
B.14.9 i928 (U) B.14.10 i929 (U) B.14.11 i930 (U) B.14.12 i931 (U)
B.14.13 i932 (U) B.15.0 i933 (U) B.15.1 i934 (U) B.15.2 i935 (U)
B.15.3 i936 (U) B.15.4 i937 (U) B.15.5 i938 (U) B.15.6 i939 (U)
B.15.7 i940 (U) B.15.8 i941 (U) B.16.0 i942 (U) B.16.1 i943 (U)
B.16.2 i944 (U) B.16.3 i945 (U) B.16.4 i946 (U) B.16.5 i947 (U)
B.16.6 i948 (U) B.16.7 i949 (U) B.16.8 i950 (U) B.16.9 i951 (U)
B.16.10 i952 (U) B.16.11 i953 (U) B.16.12 i954 (U) B.16.13 i955 (U)
B.16.14 i956 (U) B.16.15 i957 (U) B.16.16 i958 (U) B.16.17 i959 (U)
B.16.18 i960 (U) B.17.1 i961 (U) B.17.2 i962 (U) B.17.3 i963 (U)
B.17.4 i964 (U) B.17.5 i965 (U) B.17.6 i966 (U) B.17.7 i967 (U)
B.17.8 i968 (U) B.17.9 i969 (U) B.17.10 i970 (U) B.17.11 i971 (U)
B.17.12 i972 (U) B.17.13 i973 (U) B.17.14 i974 (U) B.17.15 i975 (U)
B.17.16 i976 (U) B.17.17 i977 (U) B.17.18 i978 (U) B.17.19 i979 (U)
B.17.20 i980 (U) B.17.21 i981 (U) B.17.22 i982 (U) B.17.23 i983 (U)
B.17.24 i984 (U) B.17.25 i985 (U) B.17.26 i986 (U) B.17.27 i987 (U)
B.17.28 i988 (U) B.17.29 i989 (U) B.17.30 i990 (U) B.17.31 i991 (U)
B.17.32 i992 (U) B.17.33 i993 (U) B.17.34 i994 (U) B.17.35 i995 (U)
B.17.36 i996 (U) B.17.37 i997 (U) B.17.38 i998 (U) B.17.39 i999 (U)
B.17.40 i1000 (U) B.17.41
i1001 (U) B.17.42 i1002 (U) B.17.43 i1003 (U) B.17.44 i1004 (U)
B.17.45 i1005 (U) B.17.46 i1006 (U) B.17.47 i1007 (U) B.17.48 i1008
(U) B.17.49 i1009 (U) B.17.50 i1010 (U) B.17.51 i1011 (U) B.17.52
i1012 (U) B.17.53 i1013 (U) B.17.54 i1014 (U) B.17.55 i1015 (U)
B.17.56 i1016 (U) B.17.57 i1017 (U) B.17.58 i1018 (U) B.17.59 i1019
(U) B.17.60 i1020 (U) B.17.61 i1021 (U) B.17.62 i1022 (U) B.17.63
i1023 (U) B.17.64 i1024 (U) B.17.65 i1025 (U) B.17.66 i1026 (U)
B.17.67 i1027 (U) B.17.68 i1028 (U) B.17.69 i1029 (U) B.17.70 i1030
(U) B.17.71 i1031 (U) B.17.72 i1032 (U) B.17.73
[0314] In further specific embodiments, the present invention
relates to compositions comprising as compound I (component A) at
least one nitrification inhibitor as defined in Table 1, i.e. at
least one of compound A #1 to #215 and as compound II (component B)
at least one herbicide selected from B.1.1, B.1.2, B.1.3, B.1.4,
B.1.5, B.1.6, B.2.2, B.2.3, B.3.1, B.3.2, B.3.3, B.3.4, B.4.1,
B.5.1, B.6.1, B.6.3, B.6.4, B.6.5, B.7.1, B.7.2, B.7.3, B.8.1,
B.10.2, B.10.3, B.10.4, B.10.5, B.11.1, B.11.2, B.12.1, B.12.2,
B.12.3, B.12.4, B.13.1, B.13.2, B.13.3, B.13.4, B.13.5, B.13.6,
B.13.8, B.13.9, B.14.1, B.14.2, B.15.1, B.16.1, B.16.2, B.17.1,
B.17.3, B.17.4, B.17.6, B.17.7, B.17.8, B.17.9, B.17.11, and
B.17.12, as defined herein above.
[0315] In further specific embodiments, the present invention
relates to compositions comprising [0316] as compound I
N-n-butylthiophosphoric acid triamide (NBPT), or N-(n-propyl)
thiophosphoric acid triamide (NPPT), or any mixtures comprising
NBPT and NPPT and [0317] as compound II at least one herbicide
selected from B.1.1, B.1.2, B.1.3, B.1.4, B.1.5, B.1.6, B.2.2,
B.2.3, B.3.1, B.3.2, B.3.3, B.3.4, B.4.1, B.5.1, B.6.1, B.6.3,
B.6.4, B.6.5, B.7.1, B.7.2, B.7.3, B.8.1, B.10.2, B.10.3, B.10.4,
B.10.5, B.11.1, B.11.2, B.12.1, B.12.2, B.12.3, B.12.4, B.13.1,
B.13.2, B.13.3, B.13.4, B.13.5, B.13.6, B.13.8, B.13.9, B.14.1,
B.14.2, B.15.1, B.16.1, B.16.2, B.17.1, B.17.3, B.17.4, B.17.6,
B.17.7, B.17.8, B.17.9, B.17.11, and B.17.12, as defined herein
above, more preferably as compound II at least one herbicide
selected from dicamba (B.17.5), glyphosate (B.2.1), propaquizafop
(B.3.5), cycloxydim (B.6.2), bomoxynil (B.9.1), imazamox (B.10.1),
nicosulfuron (B.13.7), tribenuron (B.13.10), saflufenacil
(B.17.10), topramezone (B.17.2), dimethenamid (B.1.2), and
2,4-dichlorophenoxyacetic acid (2,4-D) (B.11.1), most preferably as
compound II at least one herbicide selected from dicamba (B.17.5),
glyphosate (B.2.1), saflufenacil (B.17.10), dimethenamid (B.1.2),
and 2,4-dichlorophenoxyacetic acid (2,4-D) (B.11.1).
[0318] In further specific embodiments, the present invention
relates to the use of compositions for increasing the health of a
plant, which comprise the combination of a herbicide and (T) or a
nitrification inhibitor as defined herein and additionally a
fertilizer. Such compositions may be used and provided as
agrochemical mixtures.
[0319] The use of a combination as defined herein above, in
particular of a combination of (T) or a nitrification inhibitor as
defined herein above and a herbicide as defined herein above, or of
a composition as defined herein for increasing the health of a
plant may be a single use, or it may be a repeated use. As single
use, the combination or corresponding compositions may be provided
to their target sites, e.g. soil or loci, or objects, e.g. plants,
only once in a physiologically relevant time interval, e.g. once a
year, or once every 2 to 5 years, or once during the lifetime of a
plant.
[0320] In other embodiments, the use may be repeated at least once
per time period, e.g. the combination as defined herein above, or a
composition as defined herein may be used for increasing the health
of a plant two times within a time interval of days, weeks or
months. The term "at least once" as used in the context of a use of
the combination means that the combination may be used two times,
or several times, i.e. that a repetition or multiple repetitions of
an application or treatment with the combination may be envisaged.
Such a repetition may a 2 times, 3 times, 4 times, 5 times, 6
times, 7 times, 8 times, 9 times, 10 times or more frequent
repetition of the use.
[0321] The combination according to the present invention or its
components may be used in any suitable form. For example, it may be
used as coated or uncoated granule, in liquid or semi-liquid form,
as sprayable entity, or in irrigation approaches etc. In further
embodiments, the components may be used in different forms. In
specific embodiments, the components may be applied or used as
such, i.e. without formulations, fertilizer, additional water,
coatings, or any further ingredient.
[0322] The term "irrigation" as used herein refers to the watering
of plants or loci or soils or soil substituents where a plant grows
or is intended to grow, wherein said watering includes the
provision of the combination or a corresponding composition
according to the present invention together with water.
[0323] In a further aspect the invention relates to a composition
for increasing the health of a plant comprising (T) or at least one
nitrification inhibitor wherein said nitrification inhibitor is a
compound of formula I or a derivative as defined herein above; and
at least one herbicide as defined herein above. In a preferred
embodiment, the composition comprises the combination of
nitrification inhibitor and herbicide as defined in Table 2, supra.
In another preferred embodiment, the composition comprises the
combination of a (thio)phosphoric acid triamide (T) and herbicide
as defined in Table 3, supra. In another preferred embodiment, the
composition for increasing the health of a plant comprises the
combination of a (thio)phosphoric acid triamide (T) and herbicide
as defined in Table 3, supra. In another preferred embodiment, the
composition for increasing the herbicidal activity of a herbicide
comprises the combination of a (thio)phosphoric acid triamide (T)
and herbicide as defined in Table 3, supra.
[0324] In further specific embodiments, the agricultural
composition further comprises an carrier.
[0325] The term "composition for increasing the health of a plant"
as used herein refers to a composition which is suitable, e.g.
comprises effective concentrations and amounts of ingredients such
as (T) or nitrification inhibitors, in particular compounds of
formula I or derivatives as defined herein, and herbicides for.
This includes the reduction of nitrification in any context or
environment in which nitrification may occur and the reduction of
biotic stress factors due to a herbicidal effect to competing
plants such as weeds. In one embodiment, the nitrification and
biotic stress may be reduced in or on or at the locus of a plant.
Typically, the nitrification may be reduced in the root zone of a
plant. In specific embodiments, the composition may be an
agricultural composition, i.e. a composition adapted to the use in
the agricultural field. "Effective amounts" or "effective
concentrations" of (T) or nitrification inhibitors and herbicides
as defined herein may be determined according to suitable in vitro
and in vivo testings known to the skilled person. These amounts and
concentrations may be adjusted to the locus, plant, soil, climate
conditions or any other suitable parameter which may have an
influence on nitrification processes, and/or on competitive plant
growth.
[0326] An "carrier" as used herein is a substance or composition
which facilitates the delivery and/or release of the ingredients to
the place or locus of destination. The term includes, for instance,
agrochemical carriers which facilitate the delivery and/or release
of agrochemicals in their field of use, in particular on or into
plants.
[0327] Examples of suitable carriers include solid carriers such as
phytogels, or hydrogels, or mineral earths e.g. silicates, silica
gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays,
dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,
magnesium oxide, ground synthetic materials, fertilizers, such as,
e.g., urea, urea based NPK, UAN, ammonium sulfate, ammonium
phosphate, ammonium nitrate, ureas, and products of vegetable
origin, such as cereal meal, tree bark meal, wood meal and nutshell
meal, cellulose powders and other solid carriers. Further suitable
examples of carriers include fumed silica or precipitated silica,
which may, for instance, be used in solid formulations as flow aid,
anti-caking aid, milling aid and as carrier for liquid active
ingredients. Additional examples of suitable carriers are
microparticles, for instance microparticles which stick to plant
leaves and release their content over a certain period of time. In
specific embodiments, agrochemical carriers such as composite gel
microparticles that can be used to deliver plant-protection active
principles, e.g. as described in U.S. Pat. No. 6,180,141; or
compositions comprising at least one phytoactive compound and an
encapsulating adjuvant, wherein the adjuvant comprises a fungal
cell or a fragment thereof, e.g. as described in WO 2005/102045; or
carrier granules, coated with a lipophilic tackifier on the
surface, wherein the carrier granule adheres to the surface of
plants, grasses and weeds, e.g. as disclosed in US 2007/0280981 may
be used. In further specific embodiments, such carriers may include
specific, strongly binding molecule which assure that the carrier
sticks to the plant till its content is completely delivered. For
instance, the carrier may be or comprise cellulose binding domains
(CBDs) have been described as useful agents for attachment of
molecular species to cellulose (see U.S. Pat. No. 6,124,117); or
direct fusions between a CBD and an enzyme; or a multifunctional
fusion protein which may be used for delivery of encapsulated
agents, wherein the multifunctional fusion proteins may consist of
a first binding domain which is a carbohydrate binding domain and a
second binding domain, wherein either the first binding domain or
the second binding domain can bind to a microparticle (see also WO
03/031477). Further suitable examples of carriers include
bifunctional fusion proteins consisting of a CBD and an anti-RR6
antibody fragment binding to a microparticle, which complex may be
deposited onto treads or cut grass (see also WO 03/031477). In
another specific embodiment the carrier may be active ingredient
carrier granules that adhere to the surface of plants, grasses and
weeds etc. using a moisture-active coating, for instance including
gum arabic, guar gum, gum karaya, gum tragacanth and locust bean
gum. Upon application of the inventive granule onto a plant
surface, water from precipitation, irrigation, dew, co-application
with the granules from special application equipment, or guttation
water from the plant itself may provide sufficient moisture for
adherence of the granule to the plant surface (see also US
2007/0280981).
[0328] In another specific embodiment the carrier, e.g. an
agrochemical carrier may be or comprise polyaminoacids.
Polyaminoacids may be obtained according to any suitable process,
e.g. by polymerization of single or multiple amino acids such as
glycine, alanine, valine, leucine, isoleucine, phenylalanine,
proline, tryptophan, serine, tyrosine, cysteine, methionine,
asparagine, glutamine, threonine, aspartic acid, glutamic acid,
lysine, arginine, histidine and/or ornithine. Polyaminoacids may be
combined with a combination of a nitrification inhibitor or (T) and
a herbicide according to the present invention and, in certain
embodiments, also with further carriers as mentioned herein above,
or other (thio)phosphoric acid triamide(s) (T) or nitrification
inhibitors as mentioned herein in any suitable ratio. For example,
polyaminoacids may be combined with a nitrification inhibitor
according to the present invention in a ratio of 1 to 10
(polyaminoacids) vs. 0.5 to 2 (combination according to the present
invention, or (T) or nitrification inhibitor according to the
present invention).
[0329] For compositions according to the invention comprising
nitrification inhibitor as defined herein above and a herbicide,
the weight ratio of the nitrification inhibitor as defined herein
above and the herbicide generally depends from the properties of
the active substances used, usually it is in the range of from
1:1000 to 1000:1, regularly in the range of from 1:500 to 500:1,
preferably in the range of from 1:250 to 250:1, more preferably in
the range of from 1:100 to 100:1, most preferably in the range of
from 1:70 to 70:1, particularly preferably in the range of from
1:50 to 50:1, particularly more preferably in the range of from
1:30 to 30:1, particularly most preferably in the range from 1:20
to 20:1, particularly in the range of from 1:15 to 15:1, especially
preferably in the range of from 1:10 to 10:1, especially more
preferably in the range of from 1:8 to 8:1, especially most
preferably in the range of from 1:6.5 to 6.5:1, especially in the
range of from 1:5 to 5:1, in particular preferably in the range of
1:4 to 4:1, in particular more preferably in the range of from 1:3
to 3:1, in particular most preferably in the range of from 2.5:1 to
1:2.5, in particular in the range of from 1:2 to 2:1, for example
in the range of from 1:1.5 to 1.5:1. For compositions according to
the invention, the weight ratio of the nitrification inhibitor as
defined herein above and the herbicide generally depends from the
properties of the active substances used, usually it is not more
than 1000:1, regularly not more than 250:1, preferably not more
than 100:1, more preferably not more than 50:1, most preferably not
more than 30:1, particularly preferably not more than 15:1,
particularly more preferably not more than 8:1, particularly most
preferably not more than 4:1, particularly not more than 2:1,
especially preferably not more than 1:1, especially more preferably
not more than 1:2, especially most preferably not more than 1:4,
especially not more than 1:8, in particular preferably not more
than 1:15, in particular more preferably not more than 1:30, in
particular most preferably not more than 1:50, in particular not
more than 1:100, for example preferably not more than 1:250, for
example not more than 1:1000. For compositions according to the
invention, the weight ratio of the nitrification inhibitor as
defined herein above and the herbicide generally depends from the
properties of the active substances used, usually it is at least
1000:1, regularly at least 250:1, preferably at least 100:1, more
preferably at least 50:1, most preferably at least 30:1,
particularly preferably at least 15:1, particularly more preferably
at least 8:1, particularly most preferably at least 4:1,
particularly at least 2:1, especially preferably at least 1:1,
especially more preferably at least 1:2, especially most preferably
at least 1:4, especially at least 1:8, in particular preferably at
least 1:15, in particular more preferably at least 1:30, in
particular most preferably at least 1:50, in particular at least
1:100, for example preferably at least 1:250, for example at least
1:1000.
[0330] For compositions according to the invention comprising (T)
and a herbicide, the weight ratio of (T) and the herbicide
generally depends from the properties of the active substances
used, usually it is in the range of from 1:1000 to 1000:1,
regularly in the range of from 1:500 to 500:1, preferably in the
range of from 1:250 to 250:1, more preferably in the range of from
1:100 to 100:1, most preferably in the range of from 1:70 to 70:1,
particularly preferably in the range of from 1:50 to 50:1,
particularly more preferably in the range of from 1:30 to 30:1,
particularly most preferably in the range from 1:20 to 20:1,
particularly in the range of from 1:15 to 15:1, especially
preferably in the range of from 1:10 to 10:1, especially more
preferably in the range of from 1:8 to 8:1, especially most
preferably in the range of from 1:6.5 to 6.5:1, especially in the
range of from 1:5 to 5:1, in particular preferably in the range of
1:4 to 4:1, in particular more preferably in the range of from 1:3
to 3:1, in particular most preferably in the range of from 2.5:1 to
1:2.5, in particular in the range of from 1:2 to 2:1, for example
in the range of from 1:1.5 to 1.5:1. For compositions according to
the invention, the weight ratio of (T) and the herbicide generally
depends from the properties of the active substances used, usually
it is not more than 1000:1, regularly not more than 250:1,
preferably not more than 100:1, more preferably not more than 50:1,
most preferably not more than 30:1, particularly preferably not
more than 15:1, particularly more preferably not more than 8:1,
particularly most preferably not more than 4:1, particularly not
more than 2:1, especially preferably not more than 1:1, especially
more preferably not more than 1:2, especially most preferably not
more than 1:4, especially not more than 1:8, in particular
preferably not more than 1:15, in particular more preferably not
more than 1:30, in particular most preferably not more than 1:50,
in particular not more than 1:100, for example preferably not more
than 1:250, for example not more than 1:1000. For compositions
according to the invention, the weight ratio of (T) and the
herbicide generally depends from the properties of the active
substances used, usually it is at least 1000:1, regularly at least
250:1, preferably at least 100:1, more preferably at least 50:1,
most preferably at least 30:1, particularly preferably at least
15:1, particularly more preferably at least 8:1, particularly most
preferably at least 4:1, particularly at least 2:1, especially
preferably at least 1:1, especially more preferably at least 1:2,
especially most preferably at least 1:4, especially at least 1:8,
in particular preferably at least 1:15, in particular more
preferably at least 1:30, in particular most preferably at least
1:50, in particular at least 1:100, for example preferably at least
1:250, for example at least 1:1000.
[0331] The composition for increasing the health of a plant
comprising (T) or at least one nitrification inhibitor as defined
herein and at least one herbicide may further comprise additional
ingredients, for example at least one additional pesticidal
compound. For example, the composition may additionally comprise at
least one fungicidal compound and/or at least one insecticidal
compound and/or at least one nematicide compound and/or at least
one biopesticide compound and/or at least one biostimulant.
[0332] In further embodiments, the composition may, in addition to
the above indicated ingredients, in particular in addition to (T)
or the nitrification inhibitor of the compound of formula I,
further comprise one or more alternative or additional
nitrification inhibitors. Examples of envisaged alternative or
additional nitrification inhibitors are linoleic acid,
alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl
3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton,
p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine
(nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl
pyrazole phosphate (DMPP, ENTEC), 4-amino-1,2,4-triazole
hydrochloride (ATC), 1-amido-2-thiourea (ASU),
2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole
(MBT), 5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole,
etridiazole), 2-sulfanilamidothiazole (ST), ammoniumthiosulfate
(ATU), 3-methylpyrazol (3-MP), 3,5-dimethylpyrazole (DMP),
1,2,4-triazole, thiourea (TU), N-(1H-pyrazolyl-methyl)acetamides
such as N-((3(5)-methyl-1H-pyrazole-1-yl)methyl)acetamide, and
N-(1H-pyrazolyl-methyl)formamides such as
N-((3(5)-methyl-1H-pyrazole-1-yl)methyl formamide,
N-(4-chloro-3(5)-methyl-pyrazole-1-ylmethyl)-formamide,
N-(3(5),4-dimethyl-pyrazole-1-ylmethyl)-formamide, mixtures of
3,4-dimethylpyrazole phospate succinic acid and
4,5-dimethylpyrazole phosphate succinic acid, neem, products based
on ingredients of neem, cyan amide, melamine, zeolite powder,
catechol, benzoquinone, sodium tetra borate, and zinc sulfate.
[0333] In a preferred embodiment, the composition according to the
present invention may comprise a combination of a herbicide as
defined herein above, of (T) or the nitrification inhibitor of the
compound of formula I and 2-chloro-6-(trichloromethyl)-pyridine
(nitrapyrin or N-serve).
[0334] In a further preferred embodiment, the composition according
to the present invention may comprise a combination of a herbicide
as defined herein above, of (T) or the nitrification inhibitor of
the compound of formula I and
5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole,
etridiazole).
[0335] In a further preferred embodiment, the composition according
to the present invention may comprise a combination of a herbicide
as defined herein above, of (T) or the nitrification inhibitor of
the compound of formula I and dicyandiamide (DCD, DIDIN).
[0336] In a further preferred embodiment, the composition according
to the present invention may comprise a combination of a herbicide
as defined herein above, of (T) or the nitrification inhibitor of
the compound of formula I and 3,4-dimethyl pyrazole phosphate
(DMPP, ENTEC).
[0337] In a further preferred embodiment, the composition according
to the present invention may comprise a combination of a herbicide
as defined herein above, of (T) or the nitrification inhibitor of
the compound of formula I and 2-amino-4-chloro-6-methylpyrimidine
(AM).
[0338] In a further preferred embodiment, the composition according
to the present invention may comprise a combination of a herbicide
as defined herein above, of (T) or the nitrification inhibitor of
the compound of formula I and 2-mercapto-benzothiazole (MBT).
[0339] In a further preferred embodiment, the composition according
to the present invention may comprise a combination of a herbicide
as defined herein above, of (T) or the nitrification inhibitor of
the compound of formula I and 2-sulfanilamidothiazole (ST).
[0340] In a further preferred embodiment, the composition according
to the present invention may comprise a combination of a herbicide
as defined herein above, of (T) or the nitrification inhibitor of
the compound of formula I and 3-methylpyrazol (3-MP).
[0341] In a further preferred embodiment, the composition according
to the present invention may comprise a combination of a herbicide
as defined herein above, of (T) or the nitrification inhibitor of
the compound of formula I and 3,5-dimethylpyrazole (DMP).
[0342] In a further preferred embodiment, the composition according
to the present invention may comprise a combination of a herbicide
as defined herein above, of (T) or the nitrification inhibitor of
the compound of formula I and 1,2,4-triazol.
[0343] In a further preferred embodiment, the composition according
to the present invention may comprise a combination of a herbicide
as defined herein above, of (T) or the nitrification inhibitor of
the compound of formula I and thiourea (TU).
[0344] In yet another preferred embodiment, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and linoleic acid.
[0345] In yet another preferred embodiment, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and alpha-linolenic
acid.
[0346] In yet another preferred embodiment, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and methyl p-coumarate.
[0347] In yet another preferred embodiment, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and methyl
3-(4-hydroxyphenyl) propionate (MHPP).
[0348] In yet another preferred embodiment, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and methyl ferulate.
[0349] In yet another preferred embodiment, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and Karanjin.
[0350] In yet another preferred embodiment, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and brachialacton.
[0351] In yet another preferred embodiment, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and p-benzoquinone
sorgoleone.
[0352] In yet another preferred embodiment, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and 4-amino-1,2,4-triazole
hydrochloride (ATC).
[0353] In yet another preferred embodiment, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and 1-amido-2-thiourea
(ASU).
[0354] In further embodiments, the composition according to the
present invention may comprise a combination of a herbicide as
defined herein above, of (T) or the nitrification inhibitor of the
compound of formula I and two entities selected from the group
comprising: linoleic acid, alpha-linolenic acid, methyl
p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate
(MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone,
2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve),
dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP,
ENTEC), 4-amino-1,2,4-triazole hydrochloride (ATC),
1-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM),
2-mercapto-benzothiazole (MBT),
5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole,
etridiazole), 2-sulfanilamidothiazole (ST), ammoniumthiosulfate
(ATU), 3-methylpyrazol (3-MP), 3,5-dimethylpyrazole (DMP),
1,2,4-triazol and thiourea (TU).
[0355] In yet another group of embodiments, the composition
according to the present invention may comprise a combination of a
herbicide as defined herein above, of (T) or the nitrification
inhibitor of the compound of formula I and three, four or more
entities selected from the group comprising: linoleic acid,
alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl
3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton,
p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine
(nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl
pyrazole phosphate (DMPP, ENTEC), 4-amino-1,2,4-triazole
hydrochloride (ATC), 1-amido-2-thiourea (ASU),
2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole
(MBT), 5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole,
etridiazole), 2-sulfanilamidothiazole (ST), ammoniumthiosulfate
(ATU), 3-methylpyrazol (3-MP), 3,5-dimethylpyrazole (DMP),
1,2,4-triazol and thiourea (TU).
[0356] In further specific embodiments, the composition may
comprise the combination of nitrification inhibitor and herbicide
as defined in Table 2 and at least one element selected from the
group comprising: linoleic acid, alpha-linolenic acid, methyl
p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate
(MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone,
2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve),
dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP,
ENTEC), 4-amino-1,2,4-triazole hydrochloride (ATC),
1-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM),
2-mercapto-benzothiazole (MBT),
5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole,
etridiazole), 2-sulfanilamidothiazole (ST), thiourea (TU),
N-(1H-pyrazolyl-methyl)acetamides such as
N-((3(5)-methyl-1H-pyrazole-1-yl)methyl)acetamide, and
N-(1H-pyrazolyl-methyl)formamides such as
N-((3(5)-methyl-1H-pyrazole-1-yl)methyl formamide,
N-(4-chloro-3(5)-methyl-pyrazole-1-ylmethyl)-formamide,
N-(3(5),4-dimethyl-pyrazole-1-ylmethyl)-formamide, mixtures of
3,4-dimethylpyrazole phospate succinic acid and
4,5-dimethylpyrazole phosphate succinic acid, neem, products based
on ingredients of neem, cyan amide, melamine, zeolite powder,
catechol, benzoquinone, sodium tetra borate, and zinc sulfate.
[0357] In further specific embodiments, the composition may
comprise the combination of (thio)phosporic acid triamide (T) and
herbicide as defined in Table 3 and at least one element selected
from the group comprising: linoleic acid, alpha-linolenic acid,
methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl)
propionate (MHPP), Karanjin, brachialacton, p-benzoquinone
sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or
N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole
phosphate (DMPP, ENTEC), 4-amino-1,2,4-triazole hydrochloride
(ATC), 1-amido-2-thiourea (ASU),
2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole
(MBT), 5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole,
etridiazole), 2-sulfanilamidothiazole (ST), thiourea (TU),
N-(1H-pyrazolyl-methyl)acetamides such as
N-((3(5)-methyl-1H-pyrazole-1-yl)methyl)acetamide, and
N-(1H-pyrazolyl-methyl)formamides such as
N-((3(5)-methyl-1H-pyrazole-1-yl)methyl formamide,
N-(4-chloro-3(5)-methyl-pyrazole-1-ylmethyl)-formamide,
N-(3(5),4-dimethyl-pyrazole-1-ylmethyl)-formamide, mixtures of
3,4-dimethylpyrazole phospate succinic acid and
4,5-dimethylpyrazole phosphate succinic acid, neem, products based
on ingredients of neem, cyan amide, melamine, zeolite powder,
catechol, benzoquinone, sodium tetra borate, and zinc sulfate.
[0358] In further embodiments, the composition may, in addition to
the above indicated ingredients, in particular in addition to a
herbicide as defined herein above, and to the nitrification
inhibitor of the compound of formula I, further comprise one or
more urease inhibitors. Examples of envisaged urease inhibitors
include N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain),
N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl
phosphoric triamide (2-NPT), further NXPTs known to the skilled
person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium
thiosulfate, and LIMUS, i.e. a mixture of NBPT and NPPT with about
NBTP at 63% and NPPT at 22%, secondary compounds at 10%, further
secondary compounds such as amines below 4% and dimerease
derivatives below 1%.
[0359] In a preferred embodiment, the composition according to the
present invention may comprise a herbicide as defined herein above
and a combination of the nitrification inhibitor of the compound of
formula I and N-(n-butyl) thiophosphoric acid triamide (NBPT,
Agrotain).
[0360] In a further preferred embodiment, the composition according
to the present invention may comprise a herbicide as defined herein
above and a combination of (T) or the nitrification inhibitor of
the compound of formula I and phenylphosphorodiamidate
(PPD/PPDA).
[0361] In a further preferred embodiment, the composition according
to the present invention may comprise a herbicide as defined herein
above and a combination of the nitrification inhibitor of the
compound of formula I and N-(n-propyl) thiophosphoric acid triamide
(NPPT).
[0362] In a further preferred embodiment, the composition according
to the present invention may comprise a herbicide as defined herein
above and a combination of the nitrification inhibitor of the
compound of formula I and 2-nitrophenyl phosphoric triamide
(2-NPT).
[0363] In a further preferred embodiment, the composition according
to the present invention may comprise a herbicide as defined herein
above and a combination of (T) or the nitrification inhibitor of
the compound of formula I and hydroquinone.
[0364] In a further preferred embodiment, the composition according
to the present invention may comprise a herbicide as defined herein
above and a combination of (T) or the nitrification inhibitor of
the compound of formula I and ammonium thiosulfate.
[0365] In a further preferred embodiment, the composition according
to the present invention may comprise a herbicide as defined herein
above and a combination of the nitrification inhibitor of the
compound of formula I and LIMUS.
[0366] In further embodiments, the composition according to the
present invention may comprise a herbicide as defined herein above
and a combination of the nitrification inhibitor of the compound of
formula I and two or more entities selected from the group
comprising: N-(n-butyl) thiophosphoric acid triamide (NBPT,
Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT),
2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to
the skilled person, phenylphosphorodiamidate (PPD/PPDA),
hydroquinone, ammonium thiosulfate, and LIMUS.
[0367] In further specific embodiments, the agricultural
composition as defined herein above may additionally comprises an
fertilizer. In case the combination of herbicides and (T) or
nitrification inhibitors is used together with a fertilizer, or
when a composition is provided in combination with a fertilizer,
such mixtures may be provided or used as agrochemical mixtures.
[0368] In further embodiments, the composition may, in addition to
one, more or all of the above indicated ingredients, in particular
in addition to (T) or the nitrification inhibitor of the compound
of formula I and a herbicide, further comprise one or more plant
growth regulators. Examples of envisaged plant growth regulators
are antiauxins, auxins, cytokinins, defoliants, ethylene
modulators, ethylene releasers, gibberellins, growth inhibitors,
morphactins, growth retardants, growth stimulators, and further
unclassified plant growth regulators.
[0369] In a preferred embodiment, the composition according to the
present invention may comprise a combination of the nitrification
inhibitor of the compound of formula I and a herbicide and at least
one compound selected from the group comprising: abscisic acid,
amidochlor, ancymidol, 6-benzylaminopurine (.dbd.N-6
benzyladenine), brassinolide, butralin, chlormequat (chlormequat
chloride), choline chloride, cyclanilide, daminozide,
diflufenzopyr, dikegulac, dimethipin, 2,6-dimethylpyridine,
ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron,
gibberellic acid, inabenfide, indole-3-acetic acid, maleic
hydrazide, mefluidide, mepiquat (mepiquat chloride),
1-methylcyclopropene (1-MCP), naphthaleneacetic acid, N-6
benzyladenine, paclobutrazol, prohexadione (prohexadione calcium),
prohydrojasmon, thidiazuron, triapenthenol, tributyl
phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl,
and uniconazole.
[0370] In a preferred embodiment, the composition according to the
present invention may comprise a combination of the
(thio)phosphoric acid triamide (T) and a herbicide and at least one
compound selected from the group comprising: abscisic acid,
amidochlor, ancymidol, 6-benzylaminopurine (.dbd.N-6
benzyladenine), brassinolide, butralin, chlormequat (chlormequat
chloride), choline chloride, cyclanilide, daminozide,
diflufenzopyr, dikegulac, dimethipin, 2,6-dimethylpyridine,
ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron,
gibberellic acid, inabenfide, indole-3-acetic acid, maleic
hydrazide, mefluidide, mepiquat (mepiquat chloride),
1-methylcyclopropene (1-MCP), naphthaleneacetic acid, N-6
benzyladenine, paclobutrazol, prohexadione (prohexadione calcium),
prohydrojasmon, thidiazuron, triapenthenol, tributyl
phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl,
and uniconazole.
[0371] In a preferred embodiment, the composition according to the
present invention may comprise a combination of (T) and a herbicide
as defined herein above and at least one compound selected from the
group comprising: abscisic acid, amidochlor, ancymidol,
6-benzylaminopurine (.dbd.N-6 benzyladenine), brassinolide,
butralin, chlormequat (chlormequat chloride), choline chloride,
cyclanilide, daminozide, diflufenzopyr, dikegulac, dimethipin,
2,6-dimethylpyridine, ethephon, flumetralin, flurprimidol,
fluthiacet, forchlorfenuron, gibberellic acid, inabenfide,
indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat
(mepiquat chloride), 1-methylcyclopropene (1-MCP),
naphthaleneacetic acid, N-6 benzyladenine, paclobutrazol,
prohexadione (prohexadione calcium), prohydrojasmon, thidiazuron,
triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic
acid, trinexapac-ethyl, and uniconazole.
[0372] In the terms of the present invention "agrochemical mixture"
means a combination of at three or more compounds. The term is,
however, not restricted to a physical mixture comprising three or
more compounds, but refers to any preparation form of said
compounds, the use of which many be time- and/or locus-related.
[0373] The agrochemical mixtures may, for example, be formulated
separately but applied in a temporal relationship, i.e.
simultaneously or subsequently, the subsequent application having a
time interval which allows a combined action of the compounds.
[0374] Furthermore, the individual compounds of the agrochemical
mixtures according to the invention such as parts of a kit or parts
of the mixture may be mixed by the user himself in a suitable
mixing device. In specific embodiments further auxiliaries may be
added, if appropriate.
[0375] The term "fertilizers" is to be understood as chemical
compounds applied to promote plant and fruit growth. Fertilizers
are typically applied either through the soil (for uptake by plant
roots), through soil substituents (also for uptake by plant roots),
or by foliar feeding (for uptake through leaves). The term also
includes mixtures of one or more different types of fertilizers as
mentioned below.
[0376] The term "fertilizers" can be subdivided into several
categories including: a) organic fertilizers (composed of decayed
plant/animal matter), b) inorganic fertilizers (composed of
chemicals and minerals) and c) urea-containing fertilizers.
[0377] Organic fertilizers include manure, e.g. liquid manure,
semi-liquid manure, biogas manure, stable manure or straw manure,
slurry, liquid dungwater, sewage sludge, worm castings, peat,
seaweed, compost, sewage, and guano. Green manure crops are also
regularly grown to add nutrients (especially nitrogen) to the soil.
Manufactured organic fertilizers include compost, blood meal, bone
meal and seaweed extracts. Further examples are enzyme digested
proteins, fish meal, and feather meal. The decomposing crop residue
from prior years is another source of fertility.
[0378] Inorganic fertilizers are usually manufactured through
chemical processes (such as the Haber-Bosch process), also using
naturally occurring deposits, while chemically altering them (e.g.
concentrated triple superphosphate). Naturally occurring inorganic
fertilizers include Chilean sodium nitrate, mine rock phosphate,
limestone, sulfate of potash, muriate of potash, and raw potash
fertilizers.
[0379] Typical solid fertilizers are in a crystalline, prilled or
granulated form. Typical nitrogen containing inorganic fertilizers
are ammonium nitrate, calcium ammonium nitrate, ammonium sulfate,
ammonium sulfate nitrate, calcium nitrate, diammonium phosphate,
monoammonium phosphate, ammonium thio sulfate and calcium
cyanamide.
[0380] The inorganic fertilizer may be an NPK fertilizer. "NPK
fertilizers" are inorganic fertilizers formulated in appropriate
concentrations and combinations comprising the three main nutrients
nitrogen (N), phosphorus (P) and potassium (K) as well as typically
S,
[0381] Mg, Ca, and trace elements. "NK fertilizers" comprise the
two main nutrients nitrogen (N) and potassium (K) as well as
typically S, Mg, Ca, and trace elements. "NP fertilizers" comprise
the two main nutrients nitrogen (N) and phosphorus (P) as well as
typically S, Mg, Ca, and trace elements.
[0382] The inorganic fertilizer may, in a specific embodiment, be a
NPK fertilizer. "NPK fertilizers" are inorganic fertilizers
formulated in appropriate concentrations and combinations
comprising the three main nutrients nitrogen (N), phosphorus (P)
and potassium (K).
[0383] The inorganic fertilizer may, in a specific embodiment, be a
NPK fertilizer. "NPK fertilizers" are inorganic fertilizers
formulated in appropriate concentrations and combinations
comprising the three main nutrients nitrogen (N), phosphorus (P)
and potassium (K).
[0384] Urea-containing fertilizer may, in specific embodiments, be
formaldehyde urea, UAN, urea sulfur, stabilized urea, urea based
NPK-fertilizers, or urea ammonium sulfate. Also envisaged is the
use of urea as fertilizer. In case urea-containing fertilizers or
urea are used or provided, it is particularly preferred that urease
inhibitors as defined herein above may be added or additionally be
present, or be used at the same time or in connection with the
urea-containing fertilizers.
[0385] Fertilizers may be provided in any suitable form, e.g. as
coated or uncoated granules, in liquid or semi-liquid form, as
sprayable fertilizer, or via fertigation etc.
[0386] Coated fertilizers may be provided with a wide range of
materials. Coatings may, for example, be applied to granular or
prilled nitrogen (N) fertilizer or to multi-nutrient fertilizers.
Typically, urea is used as base material for most coated
fertilizers. The present invention, however, also relates to the
use of other base materials for coated fertilizers, any one of the
fertilizer materials defined herein. In certain embodiments,
elemental sulfur may be used as fertilizer coating. The coating may
be performed by spraying molten S over urea granules, followed by
an application of sealant wax to close fissures in the coating. In
a further embodiment, the S layer may be covered with a layer of
organic polymers, preferably a thin layer of organic polymers. In
another embodiment, the coated fertilizers are preferably physical
mixtures of coated and non-coated fertilizers.
[0387] Further envisaged coated fertilizers may be provided by
reacting resin-based polymers on the surface of the fertilizer
granule. A further example of providing coated fertilizers includes
the use of low permeability polyethylene polymers in combination
with high permeability coatings.
[0388] In specific embodiments the composition and/or thickness of
the fertilizer coating may be adjusted to control, for example, the
nutrient release rate for specific applications.
[0389] The duration of nutrient release from specific fertilizers
may vary, e.g. from several weeks to many months. The presence of
(T) or nitrification inhibitors and herbicides in a mixture with
coated fertilizers may accordingly be adapted. It is, in
particular, envisaged that the nutrient release involves or is
accompanied by the release of (T) or an nitrification inhibitor and
herbicide according to the present invention.
[0390] Coated fertilizers may be provided as controlled release
fertilizers (CRFs). In specific embodiments these controlled
release fertilizers are fully coated N--P--K fertilizers, which are
homogeneous and which typically show a pre-defined longevity of
release. In further embodiments, the CRFs may be provided as
blended controlled release fertilizer products which may contain
coated, uncoated and/or slow release components. In certain
embodiments, these coated fertilizers may additionally comprise
micronutrients. In specific embodiments these fertilizers may show
a pre-defined longevity, e.g. in case of N--P--K fertilizers.
[0391] Additionally envisaged examples of CRFs include patterned
release fertilizers. These fertilizers typically show a pre-defined
release patterns (e.g. hi/standard/lo) and a pre-defined longevity.
In exemplary embodiments fully coated N--P--K, Mg and
micronutrients may be delivered in a patterned release manner.
[0392] Also envisaged are double coating approaches or coated
fertilizers based on a programmed release.
[0393] In further embodiments the fertilizer mixture may be
provided as, or may comprise or contain a slow release fertilizer.
The fertilizer may, for example, be released over any suitable
period of time, e.g. over a period of 1 to 5 months, preferably up
to 3 months. Typical examples of ingredients of slow release
fertilizers are IBDU (isobutylidenediurea), e.g. containing about
31-32% nitrogen, of which 90% is water insoluble; or UF, i.e. an
urea-formaldehyde product which contains about 38% nitrogen of
which about 70% may be provided as water insoluble nitrogen; or CDU
(crotonylidene diurea) containing about 32% nitrogen; or MU
(methylene urea) containing about 38 to 40% nitrogen, of which
25-60% is typically cold water insoluble nitrogen; or MDU
(methylene diurea) containing about 40% nitrogen, of which less
than 25% is cold water insoluble nitrogen; or MO (methylol urea)
containing about 30% nitrogen, which may typically be used in
solutions; or DMTU (diimethylene triurea) containing about 40%
nitrogen, of which less than 25% is cold water insoluble nitrogen;
or TMTU (tri methylene tetraurea), which may be provided as
component of UF products; or TMPU (tri methylene pentaurea), which
may also be provided as component of UF products; or UT (urea
triazone solution) which typically contains about 28% nitrogen.
[0394] Any of the above mentioned fertilizers or fertilizer forms
may suitably be combined. For instance, slow release fertilizers
may be provided as coated fertilizers. They may also be combined
with other fertilizers or fertilizer types. The same applies to the
presence of (T) or a nitrification inhibitor or herbicide according
to the present invention, which may be adapted to the form and
chemical nature of the fertilizer and accordingly be provided such
that its release accompanies the release of the fertilizer, e.g. is
released at the same time or with the same frequency. The present
invention further relates to fertilizer or fertilizer forms as
defined herein above in combination with nitrification inhibitors
as defined herein above and herbicides and further in combination
with urease inhibitors as defined herein above. Such combinations
may be provided as coated or uncaoted forms and/or as slow or fast
release forms. Preferred are combinations with slow release
fertilizers including a coating. In further embodiments, also
different release schemes are envisaged, e.g. a slower or a faster
release.
[0395] The term "fertigation" as used herein refers to the
application of fertilizers, optionally soil amendments, and
optionally other water-soluble products together with water through
an irrigation system to a plant or to the locus where a plant is
growing or is intended to grow, or to a soil substituent as defined
herein below. For example, liquid fertilizers or dissolved
fertilizers may be provided via fertigation directly to a plant or
a locus where a plant is growing or is intended to grow. Likewise,
(T) or nitrification inhibitors according to the present invention,
or in combination with additional nitrification inhibitors, may be
provided via fertigation to plants or to a locus where a plant is
growing or is intended to grow. Fertilizers and (T) or
nitrification inhibitors according to the present invention, or in
combination with additional nitrification inhibitors, may be
provided together, e.g. dissolved in the same charge or load of
material (typically water) to be irrigated. In further embodiments,
fertilizers and (T) or nitrification inhibitors may be provided at
different points in time. For example, the fertilizer may be
fertigated first, followed by (T) or the nitrification inhibitor,
or preferably, (T) or the nitrification inhibitor may be fertigated
first, followed by the fertilizer. The time intervals for these
activities follow the herein above outlined time intervals for the
application of fertilizers and (T) or nitrification inhibitors.
Also envisaged is a repeated fertigation of fertilizers and (T) or
nitrification inhibitors according to the present invention, either
together or intermittently, e.g. every 2 hours, 6 hours, 12 hours,
24 hours, 2 days, 3 days, 4 days, 5 days, 6 days or more.
[0396] In particularly preferred embodiments, the fertilizer is an
ammonium-containing fertilizer.
[0397] The agrochemical mixture according to the present invention
may comprise one fertilizer as defined herein above and (T) or one
nitrification inhibitor of formula I as defined herein above and
one herbicide as defined herein above. In further embodiments, the
agrochemical mixture according to the present invention may
comprise at least one or more than one fertilizer as defined herein
above, e.g. 2, 3, 4, 5, 6, 6, 7, 8, 9, 10 or more different
fertilizers (including inorganic, organic and urea-containing
fertilizers) and (T) or at least one nitrification inhibitor of
formula I and at least one herbicide as defined herein above,
preferably a combination as defined in Table 2 or Table 3.
[0398] In another group of embodiments the agrochemical mixture
according to the present invention may comprise at least one or
more than one (thio)phosphoric acid triamide (T) or at least one or
more than one nitrification inhibitor of formula I as defined
herein above, preferably more than one nitrification inhibitor of
formula I selected from Table 1, e.g. 2, 3, 4, 5, 6, 6, 7, 8, 9, 10
or more different nitrification inhibitors as defined herein above
or as provided in Table 1 and at least one fertilizer as defined
herein above and at least one herbicide as defined herein
above.
[0399] The term "at least one" is to be understood as 1, 2, 3 or
more of the respective compound selected from the group consisting
of fertilizers as defined herein above (also designated as compound
C), and (thio)phosphoric acid triamide(s) (T) or nitrification
inhibitors of formula I as defined herein above (also designated as
compound A), and herbicides (also designated as compound B).
[0400] In addition to at least one fertilizer and (T) or at least
one nitrification inhibitor as defined herein above and at least
one herbicide, an agrochemical mixture may comprise further
ingredients, compounds, active compounds or compositions or the
like. For example, the agrochemical mixture may additionally
comprise or composed with or on the basis of a carrier, e.g. an
agrochemical carrier, preferably as defined herein. In further
embodiments, the agrochemical mixture may further comprise at least
one additional pesticidal compound. For example, the agrochemical
mixture may additionally comprise at least one fungicidal compound
and/or at least one insecticidal compound.
[0401] In further embodiments, the agrochemical mixture may, in
addition to the above indicated ingredients further comprise
alternative or additional nitrification inhibitors such as linoleic
acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate,
MHPP, Karanjin, brachialacton, p-benzoquinone sorgoleone,
nitrapyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate
(DMPP), 4-amino-1,2,4-triazole hydrochloride (ATC),
1-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM),
5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole),
ammoniumthiosulfate (ATU), 3-methylpyrazol (3-MP),
3,5-dimethylpyrazole (DMP), 1,2,4-triazol and thiourea (TU) and/or
sulfathiazole (ST).
[0402] Furthermore, the invention relates to a method for
increasing the health of a plant, comprising treating a plant
growing on soil and/or the locus where the plant is growing or is
intended to grow with a combination of (T) or at least one
nitrification inhibitor and at least one herbicide as defined
herein above, preferably with a combination as defined in Table 2
or Table 3, or a composition comprising said combination.
[0403] Furthermore, the invention relates to a method for
increasing the herbicidal activity of a herbicide, comprising
treating a plant growing on soil and/or the locus where the plant
is growing or is intended to grow with a combination of (T) or at
least one nitrification inhibitor and at least one herbicide as
defined herein above, preferably with a combination as defined in
Table 2 or Table 3, or a composition comprising said
combination.
[0404] The term "plant" is to be understood as a plant of economic
importance and/or men-grown plant. In certain embodiments, the term
may also be understood as plants which have no or no significant
economic importance. The plant is preferably selected from
agricultural, silvicultural and horticultural (including
ornamental) plants. The term also relates to genetically modified
plants.
[0405] The term "plant" as used herein further includes all parts
of a plant such as germinating seeds, emerging seedlings, plant
propagules, herbaceous vegetation as well as established woody
plants including all belowground portions (such as the roots) and
aboveground portions.
[0406] Within the context of the method for increasing the health
of plant it is assumed that the plant is growing on soil. In
specific embodiments, the plant may also grow differently, e.g. in
synthetic laboratory environments or on soil substituents, or be
supplemented with nutrients, water etc. by artificial or technical
means. In such scenarios, the invention relates to a treatment of
the zone or area where the nutrients, water etc. are provided to
the plant. Also envisaged is that the plant grows in green houses
or similar indoor facilities.
[0407] The term "locus" is to be understood as any type of
environment, soil, soil substituents area or material where the
plant is growing or intended to grow. Preferably, the term relates
to soil or soil substituent on which a plant is growing.
[0408] In one embodiment, the plant to be treated according to the
method of the invention is an agricultural plant. "Agricultural
plants" are plants of which a part (e.g. seeds) or all is harvested
or cultivated on a commercial scale or which serve as an important
source of feed, food, fibres (e.g. cotton, linen), combustibles
(e.g. wood, bioethanol, biodiesel, biomass) or other chemical
compounds. Preferred agricultural plants are for example cereals,
e.g. wheat, rye, barley, triticale, oats, sorghum or rice, beet,
e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits
or soft fruits, e.g. apples, pears, plums, peaches, almonds,
cherries, strawberries, raspberries, blackberries or gooseberries;
leguminous plants, such as lentils, peas, alfalfa or soybeans; oil
plants, such as rape, oil-seed rape, canola, linseed, mustard,
olives, sunflowers, coconut, cocoa beans, castor oil plants, oil
palms, ground nuts or soybeans; cucurbits, such as squashes,
cucumber or melons; fiber plants, such as cotton, flax, hemp or
jute; citrus fruit, such as oranges, lemons, grapefruits or
mandarins; vegetables, such as spinach, lettuce, asparagus,
cabbages, carrots, onions, tomatoes, potatoes, cucurbits or
paprika; lauraceous plants, such as avocados, cinnamon or camphor;
energy and raw material plants, such as corn, soybean, rape,
canola, sugar cane or oil palm; tobacco; nuts; coffee; tea;
bananas; vines (table grapes and grape juice grape vines); hop;
turf; natural rubber plants.
[0409] In a further embodiment, the plant to be treated according
to the method of the invention is a horticultural plant. The term
"horticultural plants" are to be understood as plants which are
commonly used in horticulture, e.g. the cultivation of ornamentals,
vegetables and/or fruits. Examples for ornamentals are turf,
geranium, pelargonia, petunia, begonia and fuchsia. Examples for
vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers,
melons, watermelons, garlic, onions, carrots, cabbage, beans, peas
and lettuce and more preferably from tomatoes, onions, peas and
lettuce. Examples for fruits are apples, pears, cherries,
strawberry, citrus, peaches, apricots and blueberries.
[0410] In a further embodiment, the plant to be treated according
to the method of the invention is an ornamental plants. "Ornamental
plants" are plants which are commonly used in gardening, e.g. in
parks, gardens and on balconies. Examples are turf, geranium,
pelargonia, petunia, begonia and fuchsia.
[0411] In another embodiment of the present invention, the plant to
be treated according to the method of the invention is a
silvicultural plants. The term "silvicultural plant" is to be
understood as trees, more specifically trees used in reforestation
or industrial plantations. Industrial plantations generally serve
for the commercial production of forest products, such as wood,
pulp, paper, rubber tree, Christmas trees, or young trees for
gardening purposes. Examples for silvicultural plants are conifers,
like pines, in particular Pinus spec., fir and spruce, eucalyptus,
tropical trees like teak, rubber tree, oil palm, willow (Salix), in
particular Salix spec., poplar (cottonwood), in particular Populus
spec., beech, in particular Fagus spec., birch, oil palm, and
oak.
[0412] The term "plant propagation material" is to be understood to
denote all the generative parts of the plant such as seeds and
vegetative plant material such as cuttings and tubers (e.g.
potatoes), which can be used for the multiplication of the plant.
This includes seeds, grains, roots, fruits, tubers, bulbs,
rhizomes, cuttings, spores, offshoots, shoots, sprouts and other
parts of plants, including seedlings and young plants, which are to
be transplanted after germination or after emergence from soil,
meristem tissues, single and multiple plant cells and any other
plant tissue from which a complete plant can be obtained.
[0413] The term "genetically modified plants" is to be understood
as plants, which genetic material has been modified by the use of
recombinant DNA techniques in a way that under natural
circumstances it cannot readily be obtained by cross breeding,
mutations or natural recombination. Typically, one or more genes
have been integrated into the genetic material of a genetically
modified plant in order to improve certain properties of the plant.
Such genetic modifications also include but are not limited to
targeted post-translational modification of protein(s), oligo- or
polypeptides e. g. by glycosylation or polymer additions such as
prenylated, acetylated or farnesylated moieties or PEG
moieties.
[0414] Plants that have been modified by breeding, mutagenesis or
genetic engineering, e. g. have been rendered tolerant to
applications of specific classes of herbicides, such as auxin
herbicides such as dicamba or 2,4-D; bleacher herbicides such as
hydroxylphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene
desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors
such as sulfonyl ureas or imidazolinones;
enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such
as glyphosate; glutamine synthetase (GS) inhibitors such as
glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid
biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase)
inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a
result of conventional methods of breeding or genetic engineering.
Furthermore, plants have been made resistant to multiple classes of
herbicides through multiple genetic modifications, such as
resistance to both glyphosate and glufosinate or to both glyphosate
and a herbicide from another class such as ALS inhibitors, HPPD
inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide
resistance technologies are e. g. described in Pest Managem. Sci.
61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61,
2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108;
Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1185;
and references quoted therein. Several cultivated plants have been
rendered tolerant to herbicides by conventional methods of breeding
(mutagenesis), e. g. Clearfield.RTM. summer rape (Canola, BASF SE,
Germany) being tolerant to imidazolinones, e. g. imazamox, or
ExpressSun.RTM. sunflowers (DuPont, USA) being tolerant to sulfonyl
ureas, e. g. tribenuron. Genetic engineering methods have been used
to render cultivated plants such as soybean, cotton, corn, beets
and rape, tolerant to herbicides such as glyphosate and
glufosinate, some of which are commercially available under the
trade names RoundupReady.RTM. (glyphosate-tolerant, Monsanto,
U.S.A.), Cultivance.RTM. (imidazolinone tolerant, BASF SE, Germany)
and LibertyLink.RTM. (glufosinate-tolerant, Bayer CropScience,
Germany).
[0415] Furthermore, plants are also covered that are by the use of
recombinant DNA techniques capable to synthesize one or more
insecticidal proteins, especially those known from the bacterial
genus Bacillus, particularly from Bacillus thuringiensis, such as
.delta.-endotoxins, e. g. CryIA(b), CryIA(c), CryIF, CryIF(a2),
CryIIA(b), CryIIlA, CryIIIB(b1) or Cry9c; vegetative insecticidal
proteins (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A; insecticidal
proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
or Xenorhabdus spp.; toxins produced by animals, such as scorpion
toxins, arachnid toxins, wasp toxins, or other insect-specific
neurotoxins; toxins produced by fungi, such Streptomycetes toxins,
plant lectins, such as pea or barley lectins; agglutinins;
proteinase inhibitors, such as trypsin inhibitors, serine protease
inhibitors, patatin, cystatin or papain inhibitors;
ribosome-inactivating proteins (RIP), such as ricin, maize-RIP,
abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such
as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase,
cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion
channel blockers, such as blockers of sodium or calcium channels;
juvenile hormone esterase; diuretic hormone receptors (helicokinin
receptors); stilbene synthase, bibenzyl synthase, chitinases or
glucanases. In the context of the present invention these
insecticidal proteins or toxins are to be understood expressly also
as pre-toxins, hybrid proteins, truncated or otherwise modified
proteins. Hybrid proteins are characterized by a new combination of
protein domains, (see, e. g. WO 02/015701). Further examples of
such toxins or genetically modified plants capable of synthesizing
such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO
95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO
03/52073.
[0416] The methods for producing such genetically modified plants
are generally known to the person skilled in the art and are
described, e. g. in the publications mentioned above. These
insecticidal proteins contained in the genetically modified plants
impart to the plants producing these proteins tolerance to harmful
pests from all taxonomic groups of arthropods, especially to
beetles (Coeloptera), two-winged insects (Diptera), and moths
(Lepidoptera) and to nematodes (Nematoda). Genetically modified
plants capable to synthesize one or more insecticidal proteins are,
e. g., described in the publications mentioned above, and some of
which are commercially available such as YieldGard.RTM. (corn
cultivars producing the Cry1Ab toxin), YieldGard.RTM. Plus (corn
cultivars producing Cry1Ab and Cry3Bb1 toxins), Starlink.RTM. (corn
cultivars producing the Cry9c toxin), Herculex.RTM. RW (corn
cultivars producing Cry34Ab1, Cry35Ab1 and the enzyme
phosphinothricin-N-acetyltransferase [PAT]); NuCOTN.RTM. 33B
(cotton cultivars producing the Cry1Ac toxin), Bollgard.RTM. I
(cotton cultivars producing the Cry1Ac toxin), Bollgard.RTM. II
(cotton cultivars producing Cry1Ac and Cry2Ab2 toxins); VIPCOT.RTM.
(cotton cultivars producing a VIP-toxin); NewLeaf.RTM. (potato
cultivars producing the Cry3A toxin); Bt-Xtra.RTM.,
NatureGard.RTM., KnockOut.RTM., BiteGard.RTM., Protecta.RTM., Bt11
(e. g. Agrisure.RTM. CB) and Bt176 from Syngenta Seeds SAS, France,
(corn cultivars producing the Cry1Ab toxin and PAT enyzme), MIR604
from Syngenta Seeds SAS, France (corn cultivars producing a
modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863
from Monsanto Europe S.A., Belgium (corn cultivars producing the
Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton
cultivars producing a modified version of the Cry1Ac toxin) and
1507 from Pioneer Overseas Corporation, Belgium (corn cultivars
producing the Cry1F toxin and PAT enzyme).
[0417] Furthermore, plants are also covered that are by the use of
recombinant DNA techniques capable to synthesize one or more
proteins to increase the resistance or tolerance of those plants to
bacterial, viral or fungal pathogens. Examples of such proteins are
the so-called "pathogenesis-related proteins" (PR proteins, see, e.
g. EP-A 392 225), plant disease resistance genes (e. g. potato
cultivars, which express resistance genes acting against
Phytophthora infestans derived from the Mexican wild potato Solanum
bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of
synthesizing these proteins with increased resistance against
bacteria such as Erwinia amylvora). The methods for producing such
genetically modified plants are generally known to the person
skilled in the art and are described, e. g. in the publications
mentioned above.
[0418] Furthermore, plants are also covered that are by the use of
recombinant DNA techniques capable to synthesize one or more
proteins to increase the productivity (e. g. bio mass production,
grain yield, starch content, oil content or protein content),
tolerance to drought, salinity or other growth-limiting
environmental factors or tolerance to pests and fungal, bacterial
or viral pathogens of those plants.
[0419] Furthermore, plants are also covered that contain by the use
of recombinant DNA techniques a modified amount of substances of
content or new substances of content, specifically to improve human
or animal nutrition, e. g. oil crops that produce health-promoting
long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids
(e. g. Nexera.RTM. rape, DOW Agro Sciences, Canada).
[0420] Furthermore, plants are also covered that contain by the use
of recombinant DNA techniques a modified amount of substances of
content or new substances of content, specifically to improve raw
material production, e. g. potatoes that produce increased amounts
of amylopectin (e. g. Amflora.RTM. potato, BASF SE, Germany).
[0421] The term "soil substituent" as used herein refers to a
substrate which is able to allow the growth of a plant and does not
comprise usual soil ingredients. This substrate is typically an
anorganic substrate which may have the function of an inert medium.
It may, in certain embodiments, also comprise organic elements or
portions. Soil substituents may, for example, be used in
hydroculture or hydroponic approaches, i.e. wherein plants are
grown in soilless medium and/or aquatic based environments.
Examples of suitable soil substituents, which may be used in the
context of the present invention, are perlite, gravel, biochar,
mineral wool, coconut husk, phyllosilicates, i.e. sheet silicate
minerals, typically formed by parallel sheets of silicate
tetrahedra with Si.sub.2O.sub.5 or a 2:5 ratio, or clay aggregates,
in particular expanded clay aggregates with a diameter of about 10
to 40 mm. Particularly preferred is the employment of vermiculite,
i.e. a phyllosilicate with 2 tetrahedral sheets for every one
octahedral sheet present.
[0422] The use of soil substituents may, in specific embodiments,
be combined with fertigation or irrigation as defined herein.
[0423] In specific embodiments, the treatment may be carried out
during all suitable growth stages of a plant as defined herein. For
example, the treatment may be carried out during the BBCH principle
growth stages.
[0424] The term "BBCH principal growth stage" refers to the
extended BBCH-scale which is a system for a uniform coding of
phenologically similar growth stages of all mono- and
dicotyledonous plant species in which the entire developmental
cycle of the plants is subdivided into clearly recognizable and
distinguishable longer-lasting developmental phases. The BBCH-scale
uses a decimal code system, which is divided into principal and
secondary growth stages. The abbreviation BBCH derives from the
Federal Biological Research Centre for Agriculture and Forestry
(Germany), the Bundessortenamt (Germany) and the chemical
industry.
[0425] In one embodiment the invention relates to a method for
increasing the health of a plant comprising treating a plant
growing on soil or soil substituents and/or the locus where the
plant is growing with a combination as defined herein above, or a
corresponding composition or agricultural composition as defined
herein above at a growth stage (GS) between GS 00 and GS 65 BBCH of
the plant.
[0426] In one embodiment the invention relates to a method for
increasing the health of a plant comprising treating a plant
growing on soil or soil substituents and/or the locus where the
plant is growing with a combination as defined herein above, or a
corresponding composition or agricultural composition as defined
herein above at a growth stage (GS) between GS 00 to GS 33 BBCH of
the plant.
[0427] In a preferred embodiment the invention relates to a method
for increasing the health of a plant comprising treating a plant
growing on soil or soil substituents and/or the locus where the
plant is growing with a combination as defined herein above, or a
corresponding composition or agricultural composition as defined
herein above at an early growth stage (GS), in particular a GS 00
to GS 05, or GS 00 to GS 10, or GS 00 to GS 15, or GS 00 to GS 20,
or GS 00 to GS 25 or GS 00 to GS 33 BBCH of the plant. In
particularly preferred embodiments, the method comprises treating a
plant growing on soil or soil substituents and/or the locus where
the plant is growing with a combination as defined herein above, or
a corresponding composition or agricultural composition as defined
herein above during growth stages including GS 00.
[0428] In a further, specific embodiment of the invention a
combination as defined herein above, or a corresponding composition
or agricultural composition as defined herein above is applied to a
plant growing on soil or soil substituents and/or the locus where
the plant is growing or is intended to grow at a growth stage
between GS 00 and GS 55 BBCH, or of the plant.
[0429] In a further embodiment of the invention a combination as
defined herein above, or a corresponding composition or
agricultural composition as defined herein above is applied to a
plant growing on soil or soil substituents and/or the locus where
the plant is growing or is intended to grow at the growth stage
between GS 00 and GS 47 BBCH of the plant.
[0430] In one embodiment of the invention a combination as defined
herein above, or a corresponding composition or agricultural
composition as defined herein above is applied to a plant growing
on soil or soil substituents and/or the locus where the plant is
growing or is intended to grow before and at sowing, before
emergence, and until harvest (GS 00 to GS 89 BBCH), or at a growth
stage (GS) between GS 00 and GS 65 BBCH of the plant.
[0431] In a preferred embodiment the invention relates to a method
increasing the health of a plant comprising treating a plant
growing on soil or soil substituents and/or the locus where the
plant is growing with a combination as defined herein above, or a
corresponding composition or agricultural composition as defined
herein above wherein the plant and/or the locus where plant is
growing or is intended to grow is additionally provided with at
least one fertilizer. The fertilizer may be any suitable
fertilizer, preferably a fertilizer as defined herein above. Also
envisaged is the application of more than one fertilizer, e.g. 2,
3, 4, 5, 6, 7, 8, 9, 10 fertilizers, or of different fertilizer
classes or categories.
[0432] In specific embodiments of the invention, a combination as
defined herein above, or a corresponding composition or
agricultural composition as defined herein above and at least one
fertilizer is applied to a plant growing on soil or soil
substituents and/or the locus where the plant is growing or is
intended to grow at a growth stage between GS 00 and GS 33 BBCH of
the plant.
[0433] In specific embodiments of the invention a combination as
defined herein above, or a corresponding composition or
agricultural composition as defined herein above r is applied to a
plant growing on soil or soil substituents and/or the locus where
the plant is growing or is intended to grow at a growth stage
between GS 00 and GS 55 BBCH of the plant.
[0434] In further specific embodiments of the invention a
combination as defined herein above, or a corresponding composition
or agricultural composition as defined herein above and at least
one fertilizer is applied to a plant growing on soil or soil
substituents and/or the locus where the plant is growing or is
intended to grow at sowing, before emergence, or at a growth stage
(GS) between GS 00 and GS 65 BBCH of the plant.
[0435] According to a preferred embodiment of the present invention
the application of (T) or said nitrification inhibitor as defined
herein (component A) and of said herbicide (component B) is carried
out simultaneously or with a time lag. The term "time lag" as used
herein means that either (T) or the nitrification inhibitor is
applied before the herbicide to the plant growing on soil or soil
substituents and/or the locus where the plant is growing or is
intended to grow; or the herbicide is applied before (T) or the
nitrification inhibitor to the plant growing on soil or soil
substituents and/or the locus where the plant is growing or is
intended to grow. Such time lag may be any suitable period of time
which still allows to provide a nitrification inhibiting effect in
the context of herbicide usage, or which provides for a reduction
in growth of competing weeds in the context of the usage of (T) or
a nitrification inhibitor. For example, the time lag may be a time
period of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8
days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks
4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks, 11
weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months,
9 months, 10 months or more or any time period in between the
mentioned time periods. Preferably, the time lag is an interval of
1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. The time lag
preferably refers to situations in which (T) or the nitrification
inhibitor as defined above is provided 1 day, 2 days, 3 days, 4
days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12
days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks,
8 weeks, 9 weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 months,
6 months, 7 months, 8 months, 9 months, 10 months or more or any
time period in between the mentioned time periods before the
application of a herbicide as defined herein above.
[0436] According to a preferred embodiment of the present invention
the application of said combination of a nitrification inhibitor or
(T) and a herbicide as defined herein above, or a corresponding
composition or agricultural composition as defined herein above and
of said fertilizer (component C) as defined herein above is carried
out simultaneously or with a time lag. The term "time lag" as used
herein means that either (T) or the nitrification inhibitor and/or
herbicide is applied before the fertilizer to the plant growing on
soil or soil substituents and/or the locus where the plant is
growing or is intended to grow; or the fertilizer is applied before
(T) or the nitrification inhibitor and/or herbicide to the plant
growing on soil and/or the locus where the plant is growing or is
intended to grow. Such time lag may be any suitable period of time
which still allows to provide a nitrification inhibiting effect in
the context of fertilizer usage, or which provides for a reduction
in growth of competing weeds in the context of the usage of (T) or
nitrification inhibitor. For example, the time lag may be a time
period of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8
days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks
4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks, 11
weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months,
9 months, 10 months or more or any time period in between the
mentioned time periods. Preferably, the time lag is an interval of
1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. The time lag
preferably refers to situations in which (T) or the nitrification
inhibitor as defined above is provided 1 day, 2 days, 3 days, 4
days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12
days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks,
8 weeks, 9 weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 months,
6 months, 7 months, 8 months, 9 months, 10 months or more or any
time period in between the mentioned time periods before the
application of a fertilizer as defined herein above.
[0437] In another specific embodiment of the invention one
component of a combination as defined herein above, or of a
corresponding composition or agricultural composition as defined
herein above is applied between GS 00 to GS 33 BBCH of the plant,
or between GS 00 and GS 65 BBCH of the plant, provided that the
application of the other component of said combination as defined
herein above, or a of corresponding composition or agricultural
composition as defined herein above is carried out with a time lag
of at least 1 day, e.g. a time lag of 1 day, 2 days, 3 days, 4
days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12
days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks,
8 weeks, 9 weeks, 10 weeks, or more or any time period in between
the mentioned time periods. It is preferred that one component of
the combination as defined herein above, or of a corresponding
composition or agricultural composition as defined herein above,
which is applied between GS 00 to GS 33 BBCH of the plant, is
provided 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8
days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks
4 weeks, weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks, 11
weeks, or 12 weeks before the application of the other
component.
[0438] In another specific embodiment of the invention, at least
one fertilizer as defined herein above is applied between GS 00 to
GS 33 BBCH of the plant or between GS 00 and GS 65 BBCH of the
plant, provided that the application of a combination as defined
herein above, or of at least one component of said combination, or
a corresponding composition or agricultural composition as defined
herein above, is carried out with a time lag of at least 1 day,
e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7
days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days,
3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10
weeks or more or any time period in between the mentioned time
periods.
[0439] According to a specific embodiment of the present invention
a plant growing on soil or soil substituents and/or the locus where
the plant is growing or is intended to grow is treated at least
once with at least one component of a combination as defined herein
above or of a corresponding composition or agricultural composition
as defined herein above, or with said combination. In a further
specific embodiment of the present invention a plant growing on
soil and/or the locus where the plant is growing or is intended to
grow is treated at least once with a combination as defined herein
above, or one of its components, or a corresponding composition or
agricultural composition as defined herein above, and at least once
with a fertilizer as defined herein above.
[0440] The term "at least once" means that the application may be
performed one time, or several times, i.e. that a repetition of the
treatment with (T) or a nitrification inhibitor and/or a fertilizer
may be envisaged. Such a repetition may a 2 times, 3 times, 4
times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or
more frequent repetition of the treatment with a combination as
defined herein above, or one of its components, or a corresponding
composition or agricultural composition as defined herein above
and/or a fertilizer. The repetition of treatment with a combination
as defined herein above, or one of its components, or a
corresponding composition or agricultural composition as defined
herein above and a fertilizer may further be different. For
example, while the fertilizer may be applied only once, the a
combination as defined herein above, or one of its components, or a
corresponding composition or agricultural composition as defined
herein above may be applied 2 times, 3 times, 4 times etc.
Alternatively, while (T) or the nitrification inhibitor may be
applied only once, the fertilizer may be applied 2 times, 3 times,
4 times etc. Further envisaged are all combinations of numerical
different numbers of repetitions for the application of a
combination as defined herein above, or one of its components, or a
corresponding composition or agricultural composition as defined
herein above and optionally a fertilizer as defined herein
above.
[0441] Such a repeated treatment may further be combined with a
time lag between the treatment of the combination as defined herein
above, or one of its components, or a corresponding composition or
agricultural composition as defined herein above and optionally a
fertilizer as described above.
[0442] The time interval between a first application and second or
subsequent application of a combination as defined herein above, or
one of its components or a corresponding composition or
agricultural composition as defined herein above and/or a
fertilizer may be any suitable interval. This interval may range
from a few seconds up to 3 months, e.g. from a few seconds up to 1
month, or from a few seconds up to 2 weeks. In further embodiments,
the time interval may range from a few seconds up to 3 days or from
1 second up to 24 hours.
[0443] In further specific embodiments, a method for increasing the
health of a plant as described above is carried out by treating a
plant growing on soil or soil substituents and/or the locus where
the plant is growing or is intended to grow with at least one
agrochemical mixture as defined herein above.
[0444] In another embodiment of the invention, an agrochemical
mixture comprising an ammonium or urea-containing fertilizer and
(T) or at least one nitrification inhibitor as defined herein above
is applied before and at sowing, before emergence, and until
shooting/shoot development (GS 00 to GS 33 BBCH) of the plant. In
case the agrochemical mixture is provided as kit of parts or as
non-physical mixture, it may be applied with a time lag between the
application of (T) or the nitrification inhibitor and the
fertilizer or between the application of (T) or the nitrification
inhibitor a secondary or further ingredient, e.g. a pesticidal
compound as mentioned herein above.
[0445] In a further embodiment plant propagules are preferably
treated simultaneously (together or separately) or
subsequently.
[0446] The term "propagules" or "plant propagules" is to be
understood to denote any structure with the capacity to give rise
to a new plant, e.g. a seed, a spore, or a part of the vegetative
body capable of independent growth if detached from the parent. In
a preferred embodiment, the term "propagules" or "plant propagules"
denotes for seed.
[0447] For a method as described above, or for a use according to
the invention, the application rates of (T) or nitrification
inhibitors, i.e. of the compound of formula I are between 0.01 g
and 5 kg of active ingredient per hectare, preferably between 1 g
and 1 kg of active ingredient per hectare, especially preferred
between 50 g and 300 g of active ingredient per hectare depending
on different parameters such as the specific active ingredient
applied and the plant species treated. In the treatment of seed,
amounts of from 0.001 g to 20 g per kg of seed, preferably from
0.01 g to 10 g per kg of seed, more preferably from 0.05 to 2 g per
kg of seed of (T) or nitrification inhibitors may be generally
required.
[0448] As a matter of course, if (T) or nitrification inhibitors
and fertilizers (or other ingredients), or if mixtures thereof are
employed, the compounds may be used in an effective and
non-phytotoxic amount. This means that they are used in a quantity
which allows to obtain the desired effect but which does not give
rise to any phytotoxic symptoms on the treated plant or on the
plant raised from the treated propagule or treated soil. For the
use according to the invention, the application rates of
fertilizers may be between 10 kg and 300 kg per hectare, preferably
between 50 kg and 250 kg per hectare.
[0449] (T) or the nitrification inhibitor compounds according to
the invention, e.g. compound I as defined herein above, or
derivative thereof as defined herein above can be present in
different structural or chemical modifications whose biological
activity may differ. They are likewise subject matter of the
present invention.
[0450] (T) or the nitrification inhibitor compounds according to
the invention, their N-oxides and/or salts etc. may be converted
into customary types of compositions, e.g. agrochemical or
agricultural compositions such as solutions, emulsions,
suspensions, dusts, powders, pastes and granules.
[0451] The composition type depends on the particular intended
purpose; in each case, it should ensure a fine and uniform
distribution of the compound according to the invention. Examples
for composition types are suspensions (SC, 00, FS), emulsifiable
concentrates (EC), emulsions (EW, EO, ES), microemulsions (ME),
pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, OP,
OS) or granules (GR, FG, GG, MG), which can be watersoluble or
wettable, as well as gel formulations for the treatment of plant
propagation materials such as seeds (GF). Usually the composition
types (e.g. SC, 00, FS, EC, WG, SG, WP, SP, SS, WS, GF) are
employed diluted. Composition types such as OP, OS, GR, FG, GG and
MG are usually used undiluted.
[0452] The compositions are prepared in a known manner (see, for
example, U.S. Pat. No. 3,060,084, EP 707 445 (for liquid
concentrates), Browning: "Agglomeration", Chemical Engineering,
Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th
Ed., McGraw-Hili, New York, 1963, S. 8-57 und ff. WO 91/13546, U.S.
Pat. No. 4,172,714, U.S. Pat. No. 4,144,050, U.S. Pat. No.
3,920,442, U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701, U.S.
Pat. No. 5,208,030, GB 2,095,558, U.S. Pat. No. 3,299,566,
Klingman: Weed Control as a Science (J. Wiley & Sons, New York,
1961), Hance et al.: Weed Control Handbook (8th Ed., Blackwell
Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.:
Formulation technology (Wiley VCH Verlag, Weinheim, 2001).
Agrochemical compositions or mixtures may also comprise auxiliaries
which are customary in agrochemical compositions. The auxiliaries
used depend on the particular application form and active
substance, respectively.
[0453] Examples for suitable auxiliaries are solvents, solid
carriers, dispersants or emulsifiers (such as further solubilizers,
protective colloids, surfactants and adhesion agents), organic and
anorganic thickeners, bactericides, anti-freezing agents,
anti-foaming agents, if appropriate colorants and tackifiers or
binders (e.g. for seed treatment formulations). Suitable solvents
are water, organic solvents such as mineral oil fractions of medium
to high boiling point, such as kerosene or diesel oil, furthermore
coal tar oils and oils of vegetable or animal origin, aliphatic,
cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin,
tetrahydronaphthalene, alkylated naphthalenes or their derivatives,
alcohols such as methanol, ethanol, propanol, butanol and
cyclohexanol, glycols, ketones such as cyclohexanone and
gamma-butyrolactone, fatty acid dimethylamides, fatty acids and
fatty acid esters and strongly polar solvents, e.g. amines such as
N-methylpyrrolidone.
[0454] Suitable surfactants (adjuvants, wetters, tackifiers,
dispersants or emulsifiers) are alkali metal, alkaline earth metal
and ammonium salts of aromatic sulfonic acids, such as
ligninsoulfonic acid (Borresperse.RTM. types, Borregard, Norway)
phenolsulfonic acid, naphthalenesulfonic acid (Morwet.RTM. types,
Akzo Nobel, U.S.A.), dibutylnaphthalenesulfonic acid (Nekal.RTM.
types, BASF, GermanY), and fatty acids, alkylsulfonates,
alkylarylsulfonates, alkyl sulfates, laurylether sulfates, fatty
alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates,
sulfated fatty alcohol glycol ethers, furthermore condensates of
naphthalene or of naphthalenesulfonic acid with phenol and
formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated
isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol
ethers, tributylphenyl polyglycol ether, tristearylphenyl
polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty
alcohol/ethylene oxide condensates, ethoxylated castor oil,
polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl
alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite
waste liquors and proteins, denatured proteins, polysaccharides (e.
g. methylcellulose), hydrophobically modified starches, polyvinyl
alcohols (Mowiol.RTM. types, Clariant, Switzerland),
polycarboxylates (Sokolan.RTM. types, BASF, Germany),
polyalkoxylates, polyvinylamines (Lupasol.RTM. types, BASF,
Germany), polyvinylpyrrolidone and the copolymers thereof. Examples
of suitable thickeners (i.e. compounds that impart a modified
flowability to compositions, i.e. high viscosity under static
conditions and low viscosity during agitation) are polysaccharides
and organic and anorganic clays such as Xanthan gum (Kelzan.RTM.,
CP Kelco, U.S.A.), Rhodopol.RTM. 23 (Rhodia, France), Veegum.RTM.
(R.T. Vanderbilt, U.S.A.) or Attaclay.RTM. (Engelhard Corp., NJ,
USA).
[0455] In specific embodiments, bactericides may be added for
preservation and stabilization of the composition. Examples for
suitable bactericides are those based on dichlorophene and benzyl
alcohol hemi formal (Proxel.RTM. from ICI or Acticide.RTM. RS from
Thor Chemie and Kathon.RTM. MK from Rohm & Haas) and
isothiazolinone derivatives such as alkylisothiazolinones and
benzisothiazolinones (Acticide.RTM. MBS from Thor Chemie).
[0456] Examples for suitable anti-freezing agents are ethylene
glycol, propylene glycol, urea and glycerin. Examples for
anti-foaming agents are silicone emulsions (such as e.g.
Silikon.RTM. SRE, Wacker, Germany or Rhodorsil.RTM., Rhodia,
France), long chain alcohols, fatty acids, salts of fatty acids,
fluoroorganic compounds and mixtures thereof.
[0457] Suitable colorants are pigments of low water solubility and
water-soluble dyes, e.g. rhodamin B, C. I. pigment red 112, C. I.
solvent red 1, pigment blue 15:4, pigment blue 15:3, pigment blue
15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment
yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1,
pigment red 57:1, pigment red 53:1, pigment orange 43, pigment
orange 34, pigment orange 5, pigment green 36, pigment green 7,
pigment white 6, pigment brown 25, basic violet 10, basic violet
49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow
23, basic red 10, basic red 108.
[0458] Examples for tackifiers or binders are polyvinylpyrrolidons,
polyvinylacetates, polyvinyl alcohols and cellulose ethers
(Tylose.RTM., Shin-Etsu, Japan).
[0459] Powders, materials for spreading and dusts can be prepared
by mixing or concomitantly grinding compound of formula I and, if
appropriate, further active substances, with at least one solid
carrier. Granules, e.g. coated granules, impregnated granules and
homogeneous granules, can be prepared by binding the active
substances to solid carriers. Examples of such suitable solid
carriers are mineral earths such as silica gels, silicates, talc,
kaolin, attaclay, limestone, lime, chalk, bole, loess, clay,
dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,
magnesium oxide, ground synthetic materials, fertilizers, such as,
e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas,
and products of vegetable origin, such as cereal meal, tree bark
meal, wood meal and nutshell meal, cellulose powders and other
solid carriers.
[0460] Examples for composition types are:
[0461] i) Water-soluble concentrates (SL, LS) 10 parts by weight of
(T) or a nitrification inhibitor such as a compound of formula I
according to the invention are dissolved in 90 parts by weight of
water or in a water-soluble solvent. As an alternative, wetting
agents or other auxiliaries are added. The active substance
dissolves upon dilution with water. In this way, a composition
having a content of 10% by weight of active substance is
obtained.
[0462] ii) Dispersible concentrates (DC) 20 parts by weight of (T)
or a nitrification inhibitor such as a compound of formula I
according to the invention are dissolved in 70 parts by weight of
cyclohexanone with addition of 10 parts by weight of a dispersant,
e.g. polyvinylpyrrolidone. Dilution with water gives a dispersion.
The active substance content is 20% by weight.
[0463] iii) Emulsifiable concentrates (EC) 15 parts by weight of
(T) or a nitrification inhibitor such as a compound of formula I
according to the invention are dissolved in 75 parts by weight of
xylene with addition of calcium dodecylbenzenesulfonate and castor
oil ethoxylate (in each case 5 parts by weight). Dilution with
water gives an emulsion. The composition has an active substance
content of 15% by weight.
[0464] iv) Emulsions (EW, EO, ES) 25 parts by weight of (T) or a
nitrification inhibitor such as a compound of formula I according
to the invention are dissolved in 35 parts by weight of xylene with
addition of calcium dodecylbenzenesulfonate and castor oil
ethoxylate (in each case 5 parts by weight). This mixture is
introduced into 30 parts by weight of water by means of an
emulsifying machine (Ultraturrax) and made into a homogeneous
emulsion. Dilution with water gives an emulsion. The composition
has an active substance content of 25% by weight.
[0465] v) Suspensions (SC, 00, FS) In an agitated ball mill, 20
parts by weight of (T) or a nitrification inhibitor such as a
compound of formula I according to the invention are comminuted
with addition of 10 parts by weight of dispersants and wetting
agents and 70 parts by weight of water or an organic solvent to
give a fine active substance suspension. Dilution with water gives
a stable suspension of the active substance. The active substance
content in the composition is 20% by weight.
[0466] vi) Water-dispersible granules and water-soluble granules
(WG, SG) 50 parts by weight of (T) or a nitrification inhibitor
such as a compound of formula I according to the invention are
ground finely with addition of 50 parts by weight of dispersants
and wetting agents and prepared as water-dispersible or
water-soluble granules by means of technical appliances (e.g.
extrusion, spray tower, fluidized bed). Dilution with water gives a
stable dispersion or solution of the active substance. The
composition has an active substance content of 50% by weight.
[0467] vii) Water-dispersible powders and water-soluble powders
(WP, SP, SS, WS) 75 parts by weight of (T) or a nitrification
inhibitor such as a compound of formula I according to the
invention are ground in a rotor-stator mill with addition of 25
parts by weight of dispersants, wetting agents and silica gel.
Dilution with water gives a stable dispersion or solution of the
active substance. The active substance content of the composition
is 75% by weight.
[0468] viii) Gel (GF) In an agitated ball mill, 20 parts by weight
of (T) or a nitrification inhibitor such as a compound of formula I
according to the invention are comminuted with addition of 10 parts
by weight of dispersants, 1 part by weight of a gelling agent
wetters and 70 parts by weight of water or of an organic solvent to
give a fine suspension of the active substance. Dilution with water
gives a stable suspension of the active substance, whereby a
composition with 20% (w/w) of active substance is obtained. 2.
Composition types to be applied undiluted
[0469] ix) Oustable powders (OP, OS) 5 parts by weight of (T) or a
nitrification inhibitor such as a compound of formula I according
to the invention are ground finely and mixed intimately with 95
parts by weight of finely divided kaolin. This gives a dustable
composition having an active substance content of 5% by weight.
[0470] x) Granules (GR, FG, GG, MG) 0.5 parts by weight of (T) or a
nitrification inhibitor such as a compound of formula I according
to the invention is ground finely and associated with 99.5 parts by
weight of carriers. Current methods are extrusion, spray-drying or
the fluidized bed. This gives granules to be applied undiluted
having an active substance content of 0.5% by weight.
[0471] xi) ULV solutions (UL) 10 parts by weight of (T) or a
nitrification inhibitor such as a compound of formula I according
to the invention are dissolved in 90 parts by weight of an organic
solvent, e.g. xylene. This gives a composition to be applied
undiluted having an active substance content of 10% by weight.
[0472] The agrochemical compositions generally comprise between
0.01 and 95%, preferably between 0.1 and 90%, most preferably
between 0.5 and 90%, by weight of active substance. The active
substances are employed in a purity of from 90% to 100%, preferably
from 95% to 100% (according to NMR spectrum).
[0473] Water-soluble concentrates (LS), flowable concentrates (FS),
powders for dry treatment (OS), water-dispersible powders for
slurry treatment (WS), water-soluble powders (SS), emulsions (ES)
emulsifiable concentrates (EC) and gels (GF) are usually employed
for the purposes of treatment of plant propagation materials,
particularly seeds.
[0474] These compositions can be applied to plant propagation
materials, particularly seeds, diluted or undiluted.
[0475] The compositions in question give, after two-to-tenfold
dilution, active substance concentrations of from 0.01 to 60% by
weight, preferably from 0.1 to 40% by weight, in the ready-to-use
preparations. Application can be carried out before or during
sowing.
[0476] Methods for applying or treating agrochemical or
agricultural compounds or mixtures, or compositions as defined
herein, respectively, on to plant propagation material, especially
seeds, are known in the art, and include dressing, coating,
pelleting, dusting, soaking and in-furrow application methods of
the propagation material. In a preferred embodiment, the compounds
or the compositions thereof, respectively, are applied on to the
plant propagation material by a method such that germination is not
induced, e.g. by seed dressing, pelleting, coating and dusting.
[0477] In a preferred embodiment, a suspension-type (FS)
composition may be used. Typically, a FS composition may comprise
1-800 g/l of active substance, 1 200 g/I surfactant, o to 200 g/I
antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a
pigment and up to 1 liter of a solvent, preferably water.
[0478] The active substances can be used as such or in the form of
their compositions, e.g. in the form of directly sprayable
solutions, powders, suspensions, dispersions, emulsions, oil
dispersions, pastes, dustable products, materials for spreading, or
granules, by means of spraying, atomizing, dusting, spreading,
brushing, immersing or pouring.
[0479] The application forms depend entirely on the intended
purposes; it is intended to ensure in each case the finest possible
distribution of the active substances according to the invention.
Aqueous application forms can be prepared from emulsion
concentrates, pastes or wettable powders (sprayable powders, oil
dispersions) by adding water.
[0480] To prepare emulsions, pastes or oil dispersions, the
substances, as such or dissolved in an oil or solvent, can be
homogenized in water by means of a wetter, tackifier, dispersant or
emulsifier. Alternatively, it is possible to prepare concentrates
composed of active substance, wetter, tackifier, dispersant or
emulsifier and, if appropriate, solvent or oil, and such
concentrates are suitable for dilution with water.
[0481] The active substance concentrations in the ready-to-use
preparations can be varied within relatively wide ranges. In
general, they are from 0.0001 to 10%, preferably from 0.001 to 1%
by weight of active substance. The active substances may also be
used successfully in the ultra-low-volume process (ULV), it being
possible to apply compositions comprising over 95% by weight of
active substance, or even to apply the active substance without
additives.
[0482] Various types of oils, wetters, adjuvants, bactericides,
fungicides and/or pesticides may be added to the active substances
or the compositions comprising them, if appropriate not until
immediately prior to use (tank mix). These agents can be admixed
with the compositions according to the invention in a weight ratio
of 1:100 to 100:1, preferably 1:10 to 10:1.
[0483] Adjuvants which can be used are in particular organic
modified polysiloxanes such as Break Thru S 240.RTM.; alcohol
alkoxylates such as Atplus 245.RTM., Atplus MBA 1303.RTM., Plurafac
LF 300.RTM. and Lutensol ON 30.RTM.; EO/PO block polymers, e.g.
Pluronic RPE 2035.RTM. and Genapol B.RTM.; alcohol ethoxylates such
as Lutensol XP 80.RTM.; and dioctyl sulfosuccinate sodium such as
Leophen RA.RTM..
[0484] The following example is provided for illustrative purposes.
It is thus understood that the example is not to be construed as
limiting. The skilled person in the art will clearly be able to
envisage further modifications of the principles laid out
herein.
EXAMPLE 1
[0485] Soil was sampled fresh from a field (e.g. Limburgerhof),
dried and sieved through a 500 .mu.m sieve. Approximately 200 mg of
soil were placed into each well of a 48 well plate. Compounds, or
DMSO alone, were added at a concentration of 10 ppm, dissolved in
1% DMSO. 6 .mu.mol ammonium sulfate was added per well as well as
4.8 mg NaClO.sub.3.
[0486] Subsequently, the samples were incubated at room temperature
for up to 72 hrs. After the incubation period 64 mg KCl were added
and mixed. 25 .mu.l of the supernatant were placed into a fresh
plate and 260 .mu.l of a color reaction solution (from Merck Nr
1.11799.0100) were added.
[0487] Measurements were taken with a Tecan plate Reader at 540 nm
wavelength.
[0488] The results of the measurements (with a dose of 10 ppm) were
that all compounds #1 to #215 as shown in Table 1, supra
demonstrated an inhibition of .gtoreq.10% compared to a control
(DMSO only).
EXAMPLE 2
[0489] Roundup Powermax (also referred to as "Roundup") is a SL
formulation containing approx. 540 g/L glyphosate (as potassium
salt) as active ingredient. Verdict is an EC formulation containing
approx. 6 wt. % saflufenacil and approx. 55 wt. % dimethenamid-P as
active ingredients. Weedone is an EC formulation containing approx.
640 g/L 2,4-dichlorophenoxyacetic acid, isooctyl ester as active
ingredient. UAN is a solution of urea and ammonium nitrate in
water. MSO is methylated seed oil. Limus is a mixture of NBPT and
NPPT with about NBTP at 63% and NPPT at 22%, secondary compounds at
10%, further secondary compounds such as amines below 4% and
dimerease derivatives below 1%. "DAT" stands for "days after
treatment". The Latin names for the weeds used in Example 2 are
shown below:
[0490] Giant foxtail=Setaria faberi
[0491] Velvetleaf=Abutilon theophrasti
[0492] Waterhemp=Amaranthus rudis
[0493] Lambsquarters=Chenopodium album
[0494] Pigweed=Amaranthus palmeri
[0495] Morningglory=Ipomoea L. sp.
[0496] Cutleaf Evening Primrose=Oenothera laciniata
[0497] Marestail=Conyza canadensis
[0498] Greenhouse Burndown
[0499] This experiment conducted in the BASF greenhouses in RTP,
North Carolina, USA. Herbicides and adjuvants were mixed with 28%
UAN (UAN=a solution of urea and ammonium nitrate in water) or 32%
UAN as a carrier, using a mixing order of UAN->Limus->MSO (if
applicable)->herbicide. Solutions were agitated before
spraying.
[0500] Weeds were grown in greenhouse flats to an average height of
giant foxtail=6'', velvetleaf=5.25'', waterhemp=6'', and
lambsquarters=7.5'' before solution was applied. Plants were
sprayed in a spray chamber with a 20'' boom height and 8003E
nozzles at a rate of 47 gal solution/acre.
[0501] Treatments were rated for % control over a 25 day
period.
[0502] Limus: 9.6 fl oz/acre
[0503] Roundup Powermax (high rate): 32 fl oz/acre
[0504] Roundup Powermax (low rate): 8 fl oz/acre
[0505] Weedone: 16 fl oz/acre
[0506] Verdict: 14 fl oz/acre [0507] w/MSO concentrate w/Leci-Tech:
16 fl oz/acre
[0508] The weed control rate (in %) achieved with the different
treatments are shown in Table 4.
TABLE-US-00004 TABLE 4 (all values in %) (weed control in
greenhouse burndown): UAN 28 UAN 28 Roundup UAN Roundup (low UAN 28
UAN 28 (low rate) UAN 28 Weedone Check 28 Limus rate) Limus Weedone
Limus 3 DAT giant foxtail 0.0 7.5 -- 10.0 12.5 10.0 10.0 velvetleaf
0.0 8.8 7.5 10.0 11.3 28.8 30.0 waterhemp 0.0 20.0 -- 28.8 30.0
42.5 55.0 lambsquarters 0.0 0.0 0.0 8.8 10.0 45.0 45.0 7 DAT giant
foxtail 0.0 5.0 5.0 12.5 12.5 5.0 5.0 velvetleaf 0.0 7.5 7.5 17.5
17.5 40.0 40.0 waterhemp 0.0 17.5 16.3 35.0 33.8 60.0 58.8
lambsquarters 0.0 0.0 0.0 15.0 15.0 52.5 55.0 12 DAT giant foxtail
0.0 0.0 -- 13.8 12.5 5.0 6.3 velvetleaf 0.0 1.3 -- 18.8 20.0 48.8
46.3 waterhemp 0.0 32.5 -- 42.5 38.8 70.0 72.5 lambsquarters 0.0
0.0 0.0 13.8 13.8 57.5 57.5 25 DAT giant foxtail 0.0 0.0 -- 50.0
50.0 0.0 0.0 velvetleaf 0.0 0.0 0.0 40.0 40.0 81.3 80.0 waterhemp
0.0 11.3 -- 67.5 75.0 75.0 96.3 lambsquarters 0.0 0.0 0.0 10.0 11.3
77.5 78.8 UAN 32 UAN 32 Round- Roundup UAN UAN UAN up (high UAN 32
UAN 32 UAN 32 (high rate) 32 Verdict 32 Weedone 32 Limus rate)
Limus Verdict Limus Weedone Limus 3 DAT giant foxtail 7.5 -- 21.3
25.0 40.0 36.3 13.8 17.5 velvetleaf 11.3 10.0 12.5 15.0 55.0 57.5
28.8 30.0 waterhemp 27.5 21.3 31.3 31.3 70.0 75.0 47.5 48.8
lambsquarters 0.0 -- 13.8 17.5 52.5 52.5 40.0 50.0 7 DAT giant
foxtail 5.0 5.0 28.8 28.8 35.0 36.3 5.0 5.0 velvetleaf 10.0 -- 23.8
25.0 72.5 75.0 40.0 40.0 waterhemp 18.8 17.5 28.8 27.5 87.5 87.5
52.5 57.5 lambsquarters 0.0 0.0 23.8 23.8 72.5 73.8 50.0 50.0 12
DAT giant foxtail 5.0 5.0 40.0 40.0 40.0 41.3 5.0 5.0 velvetleaf
5.0 5.0 31.3 32.5 95.0 92.5 47.5 47.5 waterhemp 42.5 42.5 38.8 38.8
100.0 97.5 53.8 62.5 lambsquarters 0.0 0.0 37.5 35.0 85.0 90.0 50.0
50.0 25 DAT giant foxtail 0.0 0.0 97.5 96.3 78.8 78.8 0.0 0.0
velvetleaf 0.0 0.0 66.3 68.8 95.0 95.0 81.3 80.0 waterhemp 55.0
25.0 70.0 75.0 98.8 97.5 90.0 92.5 lambsquarters 0.0 0.0 63.8 65.0
90.0 88.8 80.0 80.0
[0509] Field Pre-Emergence
[0510] This experiment took place at the BASF Research Farm in Pine
Level, N.C., USA. Solutions were mixed as described above and
sprayed at 47 gal/acre using a 2 row boom, 18'' high, with 11004DG
nozzles.
[0511] Weed control was rated periodically over 35 days following
initial application.
[0512] Limus: 9.6 fl oz/acre
[0513] Verdict (med rate): 7 fl oz/acre
[0514] Verdict (high rate): 14 fl oz/acre
[0515] The weed control rate (in %) achieved with the different
treatments are shown in Table 5.
TABLE-US-00005 TABLE 5 (all values in %) (weed control in fied
pre-emergence): UAN UAN 28 UAN 28 28 Verdict UAN 28 Verdict UAN
Verdict (high Verdict (medium UAN 28 (high rate) (medium rate)
Check 28 Limus rate) Limus rate) Limus 7DAT Pigweed 0.0 50.0 50.0
95.0 95.0 95.0 95.0 15DAT Pigweed 0.0 30.0 30.0 100.0 100.0 98.3
100.0 Morning 0.0 0.0 0.0 86.7 93.3 85.0 86.7 glory 22DAT Pigweed
0.0 0.0 0.0 98.3 98.3 90.0 95.0 Morning 0.0 0.0 0.0 95.0 96.7 85.0
90.0 glory 35DAT Pigweed 0.0 0.0 0.0 98.3 98.3 86.7 93.3 Morning
0.0 0.0 0.0 93.3 95.0 85.0 90.0 glory
[0516] Field Burndown
[0517] This experiment took place at the BASF Research Farm in Pine
Level, N.C., USA. Solutions were mixed as described above and
sprayed at 47 gal/acre using a 2 row boom, 18'' high, with 11004DG
nozzles.
[0518] The weeds evaluated were cutleaf evening primrose and mare's
tail. Primrose averaged 10-18'' in height and mare's tail averaged
3-6'' at 8 DAT.
[0519] Treatments were rated for % control over a 25 day
period.
[0520] Limus: 9.6 fl oz/acre
[0521] Roundup Powermax (high rate): 32 fl oz/acre
[0522] Roundup Powermax (med rate): 16 fl oz/acre
[0523] Weedone: 16 fl oz/acre
[0524] The weed control rate (in %) achieved with the different
treatments are shown in Table 6.
TABLE-US-00006 TABLE 6 (all values in %) (weed control in fied
burndown): UAN 28 UAN 28 UAN 28 Roundup UAN 28 Roundup Roundup
Power- Roundup Power- Power- max Power- max UAN max (high max
(medium UAN 28 (high rate) (medium rate) Check 28 Limus rate) Limus
rate) Limus 8 DAT Cutleaf 0.0 21.7 21.7 35.0 33.3 36.7 40.0 Evening
Primrose Marestail 0.0 10.0 10.0 35.0 35.0 38.3 40.0 18 DAT Cutleaf
0.0 5.0 5.0 61.7 63.3 65.0 68.3 Evening Primrose Marestail 0.0 5.0
5.0 68.3 68.3 65.0 65.0 25 DAT Cutleaf 0.0 5.0 5.0 66.7 68.3 70.0
71.7 Evening Primrose Marestail 0.0 5.0 5.0 71.7 81.7 71.7 71.7 UAN
28 UAN 28 Roundup Roundup Power- UAN 28 Power- max (low UAN 28
Weedone max (low rate) Weedone LV 6 rate) Limus LV 6 Limus 8 DAT
Cutleaf 31.7 33.3 53.3 53.3 Evening Primrose Marestail 33.3 35.0
51.7 51.7 18 DAT Cutleaf 55.0 55.0 66.7 68.3 Evening Primrose
Marestail 53.3 51.7 63.3 65.0 25 DAT Cutleaf 61.7 68.3 81.7 83.3
Evening Primrose Marestail 61.7 60.0 78.3 73.3
* * * * *