U.S. patent number RE35,811 [Application Number 08/538,756] was granted by the patent office on 1998-05-26 for insecticidally active nitro guanidine compounds.
This patent grant is currently assigned to Nihon Bayer Agrochem K.K.. Invention is credited to Yumi Hattori, Ikuro Honda, Koichi Moriya, Katsuhiko Shibuya, Kozo Shiokawa, Shinichi Tsuboi.
United States Patent |
RE35,811 |
Shiokawa , et al. |
May 26, 1998 |
Insecticidally active nitro guanidine compounds
Abstract
Insecticidal novel nitro compounds of the formula ##STR1## in
which R.sup.1 and R.sup.2 are hydrogen or C.sub.1-4 alkyl, R.sup.3
is --S--R.sup.4 or ##STR2## in which R.sup.4 is C.sub.1-4 alkyl,
R.sup.5 and R.sup.6 are hydrogen or C.sub.1-4 alkyl, Y is CH or N,
and Z is a five- or six-membered heterocyclic group having at least
one nitrogen atom which may be substituted by halogen or C.sub.1-4
alkyl, provided that where Y is CH, then R.sup.1 is C.sub.1-4
alkyl.
Inventors: |
Shiokawa; Kozo (Kanagawa-ken,
JP), Tsuboi; Shinichi (Tokyo, JP), Moriya;
Koichi (Tochigi, JP), Hattori; Yumi (Ibaraki,
JP), Honda; Ikuro (Tokyo, JP), Shibuya;
Katsuhiko (Tochigi, JP) |
Assignee: |
Nihon Bayer Agrochem K.K.
(Tokyo, JP)
|
Family
ID: |
26369599 |
Appl.
No.: |
08/538,756 |
Filed: |
October 3, 1995 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
438543 |
Nov 16, 1989 |
05051434 |
Sep 24, 1991 |
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Foreign Application Priority Data
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Nov 29, 1988 [JP] |
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63-299419 |
Feb 13, 1989 [JP] |
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1-031145 |
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Current U.S.
Class: |
514/357; 544/334;
544/335; 546/331; 546/332; 548/100; 548/205; 548/125; 548/127;
548/247; 514/256; 514/361; 514/365; 514/378 |
Current CPC
Class: |
A01N
47/42 (20130101); A01N 47/44 (20130101); A01N
43/40 (20130101); C07D 213/38 (20130101); C07D
213/61 (20130101); C07D 277/32 (20130101); H01L
2924/01039 (20130101); H01L 2924/01006 (20130101) |
Current International
Class: |
A01N
43/40 (20060101); A01N 43/34 (20060101); A01N
47/42 (20060101); A01N 47/44 (20060101); A01N
47/40 (20060101); C07D 277/00 (20060101); C07D
277/32 (20060101); C07D 213/61 (20060101); C07D
213/38 (20060101); C07D 213/00 (20060101); C07D
213/38 (); A01N 043/40 () |
Field of
Search: |
;546/331,332
;544/334,335 ;548/100,205,247,125,127 ;514/256,357,361,365,378 |
References Cited
[Referenced By]
U.S. Patent Documents
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3457188 |
July 1969 |
Niemers et al. |
4499097 |
February 1985 |
Tomcufcik et al. |
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Foreign Patent Documents
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0302389 |
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Feb 1989 |
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EP |
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302833 |
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Feb 1989 |
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EP |
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303570 |
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Feb 1989 |
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EP |
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234064 |
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Oct 1987 |
|
JP |
|
233903 |
|
Sep 1988 |
|
JP |
|
2201596 |
|
Feb 1988 |
|
GB |
|
Other References
Nihon Kagaku Zasshi, vol. 83, No. 2, pp. 218-222, 1962. .
Bulletin of National Institute of Hygienic Sciences, No. 88, 1970,
"Screening Test on Anticancer and . . . ", Kamiya and Koshinuma, et
al. .
Bulletin of National Institute of Hygienic Sciences, No. 102, 1984,
"Sunthesis of 3-Nitro-1-nitroso . . . ", Kamiya and Koshinuma, et
al..
|
Primary Examiner: Davis; Zinna Northington
Attorney, Agent or Firm: Sprung Kramer Schaefer &
Briscoe
Claims
We claim:
1. A .[.novel.]. nitro compound of the formula ##STR38## wherein
R.sup.1 and R.sup.2 are hydrogen or C.sub.1-4 alkyl,
R.sup.3 is --S--R.sup.4 or ##STR39## R.sup.4 is C.sub.1-4 alkyl,
R.sup.5 and R.sup.6 are hydrogen or C.sub.1-4 alkyl, and
Z is .[.pyridyl,.]. thiazolyl, thiadiazolyl, pyrimidinyl, or
isoxazolyl which may be substituted by halogen or C.sub.1-4
-alkyl.
2. A compound according to claim 1,
wherein
R.sup.1 and R.sup.2 are hydrogen or methyl,
R.sup.3 is --S--R.sup.4 or ##STR40## R.sup.4 is methyl, R.sup.5 and
R.sup.6 are hydrogen or methyl, and
Z is .[.pyridyl,.]. thiazolyl, thiadiazolyl, pyrimidinyl, or
isoxazolyl which may be substituted by chlorine or methyl.
3. A compound according to claim 1,
wherein
R.sup.1 and R.sup.2 are hydrogen or methyl,
R.sup.3 is ##STR41## in which R.sup.5 and R.sup.6 are hydrogen or
methyl, and Z is .[.2-chloro-5-pyridyl or.].
2-chloro-5-thiazolyl.
4. A compound according to claim 1, wherein
R.sup.1 and R.sup.2 are hydrogen or methyl,
R.sup.3 is ##STR42## in which R.sup.5 and R.sup.6 are hydrogen or
methyl, and Z is .[.2-chloro-5-pyridyl or.].
2-chloro-5-thiazolyl.
5. A compound according to claim .[.1.]. .Iadd.15.Iaddend.,
wherein
R.sup.1 and R.sup.2 are hydrogen or methyl,
R.sup.3 is ##STR43## in which R.sup.5 and R.sup.6 are hydrogen or
methyl, .[.Y is N,.]. and
Z is 2-chloro-5-pyridyl.
6. A compound according to claim .[.1.]. .Iadd.15.Iaddend., wherein
such compound is
3-(2-chloro-5-pyridylmethyl)-1-methyl-2-nitroguanidine of the
formula ##STR44##
7. A compound according to claim .[.1.]. .Iadd.15.Iaddend., wherein
such compound is
3-(2-chloro-5-pyridylmethyl)-1,1-dimethyl-2-nitroguanidine of the
formula ##STR45##
8. A compound according to claim .[.1.]. .Iadd.15.Iaddend., wherein
such compound is
3-(2-chloro-5-pyridylmethyl)-1,3-dimethyl-2-nitroguanidine of the
formula ##STR46##
9. A compound according to claim .[.1.]. .Iadd.15.Iaddend., wherein
such compound is
3-(2-chloro-5-pyridymethyl)-1,1,3-trimethyl-2-nitroguanidine of the
formula ##STR47##
10. A compound according to claim .[.1.]. .Iadd.15.Iaddend.,
wherein such compound is
3-(2-chloro-5-pyridylmethyl)-3-methyl-2-nitroguanidine of the
formula ##STR48## .[.
11. A compound according to claim 1, wherein such compound is
3-(2-chloro-5-thiazolylmethyl)-1-methyl-2-nitroguanidine of the
formula ##STR49##
12. An insecticidal composition comprising an insecticidally
effective amount of a compound according to claim 1 and a
diluent.
13. A method of combating insects which comprises applying to such
insects or to a locus from which it is desired to exclude such
insects an insecticidally effective amount of a compound according
to claim 1 and a diluent.
14. The method according to claim 13, wherein such compound is
.[.3-(2-chloro-5-pyridylmethyl)-1-methyl-2-nitroguanidine;
3-(2-chloro-5-pyridylmethyl)-1,1-dimethyl-2-nitroguanidine;
3-(2-chloro-5-pyridylmethyl)-1,3-dimethyl-2-nitroguanidine;
3-(2-chloro-5-pyridylmethyl)-1,1,3-trimethyl-2-nitroguanidine;
3-(2-chloro-5-pyridylmethyl)-3-methyl-2-nitroguanidine; or.].
3-(2-chloro-5-thiazolylmethyl)-1-methyl-2-nitroguanidine.
.Iadd.
15. A nitro compound of the formula ##STR50## .Iaddend.wherein
R.sup.1 and R.sup.2 are hydrogen or C.sub.1-4 -alkyl,
R.sup.3 is --S--R.sup.4 or ##STR51## R.sup.4 represents C.sub.1-4
-alkyl,
R.sup.5 and R.sup.6 represent hydrogen or C.sub.1-4 -alkyl, and
Z is pyridyl substituted by chlorine or methyl..Iadd.
16. A compound according to claim 15, wherein
R.sup.1 and R.sup.2 are hydrogen or methyl,
R.sup.3 is ##STR52## .Iaddend.R.sup.4 is methyl,
R.sup.5 and R.sup.6 are hydrogen or methyl, and
Z is pyridyl substituted by chlorine or methyl..Iadd.
17. A compound according to claim 15, wherein
R.sup.1 and R.sup.2 are hydrogen or methyl,
R.sup.3 is ##STR53## .Iaddend. in which R.sup.5 and R.sup.6 are
hydrogen or methyl, and
Z is 2-chloro-5-pyridyl..Iadd.
18. An insecticidal composition comprising an insecticidally
effective amount of a compound according to claim 15 and a
diluent..Iaddend..Iadd.19. A method of combating insects which
comprises applying to such insects or to a locus from which it is
desired to exclude such insects an insecticidally effective amount
of a compound of the formula ##STR54## .Iaddend.wherein
R.sup.1 and R.sup.2 are hydrogen or C.sub.1-4 -alkyl,
R.sup.3 is --S--R.sup.4 or ##STR55## R.sup.4 represents C.sub.1-4
-alkyl,
R.sup.5 and R.sup.6 represent hydrogen or C.sub.1-4 -alkyl, and
Z is pyridyl substituted by chlorine or methyl,
in admixture with a diluent..Iadd.20. The method according to claim
19, wherein such compound is
3-(2-chloro-5-pyridylmethyl)-1-methyl-2-nitroguanidine;
3-(2-chloro-5-pyridylmethyl)-1,1-dimethyl-2-nitroguanidine;
3-(2-chloro-5-pyridylmethyl)-1,3-dimethyl-2-nitroguanidine;
3-(2-chloro-5-pyridylmethyl)-1,1,3-trimethyl-2-nitroguanidine;
or
3-(2-chloro-5-pyridylmethyl)-3-methyl-2-nitroguanidine..Iaddend.
Description
This application is a Reissue of 07/438,543 filed Nov. 16, 1989,
U.S. Pat. No. 5,051,434..Iaddend.
The present invention relates to novel nitro compounds, to process
for their preparation and to their use as insecticides.
It has already been disclosed that a certain group of
2-nitro-1,1-ethenediamines is useful as medicaments which influence
the circulation, in particular as hypotensive agents (see U.S. Pat.
No. 4,567,188), a certain group of N-cyanoisothioureas is useful as
medicaments for treating ulcers (see Japanese Patent Laid-open No.
234,064/1987), the N-cyanoisothioureas disclosed in such Japanese
patent application have also controlling insects and
plant-destructive nematodes (see Japanese Patent Laid-open No.
233,903 and EP-A 303,570), and a certain group of
.alpha.-unsaturated amines having insecticidal/miticidal activity
(see EP-A 0302389).
There have now been found novel nitro compounds of the formula (I)
##STR3## wherein R.sup.1 and R.sup.2 are hydrogen or C.sub.1-4
alkyl,
R.sup.3 is --S--R.sup.4 or ##STR4## in which R.sup.4 is C.sub.1-4
alkyl, R.sup.5 and R.sup.6 are hydrogen or C.sub.1-4 alkyl,
Y is CH or N, and
Z is a five- or six-membered heterocyclic group having at least one
nitrogen atom which may be substituted by halogen or C.sub.1-4
alkyl, provided that where Y is CH,
then R.sup.1 is C.sub.1-4 alkyl.
The compounds of the formula (I) can be obtained by a process in
which
a) (in the case where R.sup.3 is --S--R.sup.4 and Y is CH, then
R.sup.1 is replaced by R.sup.7, in which R.sup.7 is C.sub.1-4
alkyl) compounds of the formula (II) ##STR5## wherein R.sup.4 has
the same meaning as mentioned above, are reacted with compounds of
the formula (III) ##STR6## wherein R.sup.7, R.sup.2 and Z have the
same meanings as mentioned above, in the presence of inert
solvents,
b) (in the case where R.sup.3 is ##STR7## and Y is CH, then R.sup.1
is replaced by R.sup.7) compounds of the formula (Ia) ##STR8##
wherein R.sup.7, R.sup.2, R.sup.4 and Z have the same meanings as
mentioned above, are reacted with compounds of the formula (IV)
##STR9## wherein R.sup.5 and R.sup.6 have the same meanings as
mentioned above, in the presence of inert solvents, or
c) (in the case where R.sup.3 is --S--R.sup.4 and Y is N) compounds
of the formula (V) ##STR10## wherein R.sup.2 and R.sup.4 have the
same meanings as mentioned above, are reacted with compounds of the
formula (VI) ##STR11## wherein R.sup.1 and Z have the same meanings
as mentioned above, and Hal represents halogen atom, in the
presence of inert solvents, and if appropriate in the presence of
acid binders, or
d) (in the case where R.sup.3 is ##STR12## and Y is N) compounds of
the formula (Ic) ##STR13## wherein R.sup.1, R.sup.2, R.sup.4 and Z
have the same meanings as mentioned above, are reacted with the
above compounds of the formula (IV), in the presence of inert
solvents.
The novel nitro compounds exhibit powerful insecticidal
properties.
Surprisingly, the nitro compounds according to the invention
exhibit a substantially greater insecticidal action than those
known from the above-cited prior art.
In the formulae, the C.sub.1-4 alkyl groups R.sup.1, R.sup.2,
R.sup.4, R.sup.5 and R.sup.6 are straight-chain or branched, such
as methyl, ethyl, n- and i-propyl and n-, i-, s- and t-butyl.
Methyl is preferred.
In the formulae, the five- or six-membered heterocyclic group Z
contains at least one nitrogen atom as a ring member. Preferred are
3-pyridyl, 4-pyridyl and 5-thiazolyl, particularly preferred are
3-pyridyl and 5-thiazolyl.
The substituent halogen atoms on the five- or six-membered
heterocyclic group Z are fluorine, chlorine, bromine and iodine.
Preferred is chlorine.
The substituent C.sub.1-4 alkyl groups on the five- or six-membered
heterocyclic group Z are straight-chain or branched, such as
methyl, ethyl, n- and i-propyl and n-, i-, s- and t-butyl.
Preferred is methyl.
The substituent may be in all possible positions of the five- or
six-membered heterocyclic group Z.
Preferably it is in the 6 position of the 3-pyridyl ring and in the
2 position of the 5-thiazolyl ring.
Among the nitro compounds according to the invention of the formula
(I), preferred compounds are those in which
R.sup.1 and R.sup.2 are hydrogen or methyl,
R.sup.3 is --S--R.sup.4 or ##STR14## in which R.sup.4 is methyl,
R.sup.5 and R.sup.6 are hydrogen or methyl,
Y is CH or N, and
Z is 3-pyridyl, 4-pyridyl or 5-thiazolyl which may be substituted
by chlorine or methyl, provided that where Y is CH, then R.sup.1 is
methyl.
More preferred nitro compounds of the formula (I) are those
in which
R.sup.1 and R.sup.2 are hydrogen or methyl,
R.sup.3 is ##STR15## in which R.sup.5 and R.sup.6 are hydrogen or
methyl, Y is CH or N, and
Z is 2-chloro-5-pyridyl or 2-chloro-5-thiazolyl, provided that
where Y is CH, then R.sup.1 is methyl.
Much more preferred nitro compounds of the formula (I) are
those
in which
R.sup.1 and R.sup.2 are hydrogen or methyl,
R.sup.3 is ##STR16## in which R.sup.5 and R.sup.6 are hydrogen or
methyl, Y is CH or N, and
Z is 2-chloro-5-pyridyl or 2-chloro-5-thiazolyl, provided that
where Y is
CH then R.sup.1 is methyl, or where R.sup.2 is hydrogen and R.sup.3
is --NHCH.sub.3 then Y is N.
Very particularly preferred nitro compounds of the formula (I) are
those
in which
R.sup.1 and R.sup.2 are hydrogen or methyl,
R.sup.3 is ##STR17## in which R.sup.5 and R.sup.6 are hydrogen or
methyl, Y is N, and
Z is 2-chloro-5-pyridyl.
Specifically, the following compounds may be mentioned:
3-(2-chloro-5-pyridylmethyl)-1-methyl-2-nitroguanidine,
3-(2-chloro-5-pyridylmethyl)-1,1-dimethyl-2-nitroguanidine,
3-(2-chloro-5-pyridylmethyl)-1,3-dimethyl-2-nitroguanidine,
3-(2-chloro-5-pyridylmethyl)-1,1,3-trimethyl-2-nitroguanidine,
3-(2-chloro-5-pyridylmethyl)-3-methyl-2-nitroguanidine,
3-(2-chloro-5-thiazolylmethyl)-1-methyl-2-nitroguanidine,
1-[1-(2-chloro-5-pyridyl)ethylamino]-1-dimethylamino-2-nitroethylene,
1-amino-1-[1-(2-chloro-5-pyridyl)ethylamino]-2-nitroethylene.
1-[1-(2-chloro-5-pyridyl)ethylamino]-1-methylamino-2-nitroethylene,
and
1-{N-[1-(2-chloro-5-pyridyl)ethyl]-N-methylamino}-1-dimethylamino-2-nitroet
hylene.
If, for example, in the above process a),
1,1-bis-methylthio-2-nitroethylene and
1-(2-chloro-5-pyridyl)ethylamine are used as starting materials,
the course of the reaction can be represented by the following
equation: ##STR18##
If, for example, in the above process b),
1-[1-(2-chloro-5-pyridyl)ethylamino]-1-methylthio-2-nitroethylene
and methylamine are used as starting materials, the course of the
reaction can be represented by the following equation:
##STR19##
If, for example, in the above process c),
2-methyl-3-nitroisothiourea and 2-chloro-5-chloromethylpyridine are
used as starting materials, the course of the reaction can be
represented by the following equation: ##STR20##
If, for example, in the above process d),
1-(2-chloro-5-pyridylmethyl)-3-nitro-2-methylisothiourea and
dimethylamine are used as starting materials, the course of the
reaction can be represented by the following equation:
##STR21##
In the process a), the compounds of the formula (II) as starting
materials mean those based on the aforementioned definition of
R.sup.4.
In the formula (II), R.sup.4 preferably has the meaning already
given above.
The compounds of the formula (II) include known compounds (see e.g.
Chem. Ber., vol. 100, pages 591-604, 1967) and, as an example,
1,1-bis-methylthio-2-nitroethylene can be exemplified.
The compounds of the formula (III) as starting materials mean those
based on the aforementioned definitions of R.sup.1, R.sup.2 and
Z.
In the formula (III), R.sup.1, R.sup.2 and Z preferably have the
meanings already given above.
The compounds of the formula (III) include in part known compounds
[see Nihon Kagaku Zasshi (Periodical of Japanese Chemistry), vol.
83, pages 218-222, 1962, J. Chem. Soc. Perkin I, 1979, pages
2364-2368].
The compounds of the formula (III), for instance, may be prepared
in accordance with the method described in the above reference, J.
Chem. Soc. Perkin I, 1979, pages 2364-2368.
The compounds of the formula (III), where R.sup.2 is hydrogen, can
be obtained when compounds of the formula (VII) ##STR22## wherein
R.sup.7 and Z have the same meanings as mentioned above, are
hydrolyzed.
The compounds of the formula (VII) can be obtained when
Schiff-bases of the formula (VIII) ##STR23## wherein Z has the same
meaning as mentioned above, are alkylated by reacting with
compounds of the formula (IX)
wherein R.sup.7 has the same meaning as mentioned above, and Hal is
halogen, in the presence of a catalytic amount of butyl-lithium and
in the presence of an inert solvent such as tetrahydrofuran.
The compounds of the formula (VIII) can be obtained when compounds
of the formula (X)
wherein Z has the same meaning as mentioned above, are reacted with
mesitaldehyde in the presence of inert solvents.
The compounds of the formula (X) include those described in the
U.S. Pat. No. 4,499,097, and the aforesaid Nihon Kagaku Zasshi.
In the process b), the compounds of the formula (Ia) as a starting
material correspond in part to the compounds of formula (I) which
can be prepared by the above process a).
The compounds of the formula (IV) as a starting material mean those
based on the aforementioned definitions of R.sup.5 and R.sup.6.
In the formula (IV), R.sup.5 and R.sup.6 preferably have the
meanings already given above.
The compounds of the formula (IV) are well known in the field of
organic chemistry and, as examples, there may be mentioned:
methylamine, diethylamine, and the like.
In the process c), the compounds of the formula (V) as a starting
material mean those based on the aforementioned definitions of
R.sup.2 and R.sup.4.
In the formula (V), R.sup.2 and R.sup.4 preferably have the
meanings already given above.
The compounds of the formula (V) are known (see e.g. J. Am. Chem.
Soc., vol. 76, pages 1877-1879, 1954) and, as examples, there may
be mentioned: 3-nitro-2-methylisothiourea,
1,2-dimethyl-3-nitroisothiourea,
1,1,2-trimethyl-3-nitroisothiourea, and the like.
The compounds of the formula (VI) as a starting material mean those
based on the aforementioned definitions of R.sup.1, Z and Hal.
In the formula (VI), R.sup.1 and Z preferably have the meanings
already given above, and Hal preferably represents chlorine or
bromine.
The compounds of the formula (VI) are known (see Japanese Patent
Laid-open Nos. 178981/1986, 178982/1986 or 183271/1986) and, as
examples, there may be mentioned: 2-chloro-5-chloromethylpyridine,
2-chloro-5-chloromethylthiazole and so on.
In the process d), the compounds of the formula (Ic) as a starting
material correspond in part to the compounds of the formula (I)
which can be prepared by the above process c).
The compounds of the formula (IV) are the same as those used in the
above process b).
Suitable diluents are all inert solvents. These preferentially
include water; aliphatic, cycloaliphatic and aromatic, optionally
chlorinated, hydrocarbons, such as hexane, cyclohexane, petroleum
ether, ligroin, benzene, toluene, xylene, methylene chloride,
chloroform, carbon tetrachloride, ethylene chloride,
trichloroethylene, chorobenzene and the like; ethers such as
diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl
ether, propylene oxide, dioxane, tetrahydrofuran and the like;
ketones such as acetone, methylethyl ketone, methyl-iso-propyl
ketone, methyl-iso-butyl ketone; nitriles such as acetonitrile,
propionitrile, acrylonitrile and the like; alcohols such as
methanol, ethanol, iso-propanol, butanol, ethylene glycol and the
like; esters such as ethyl acetate, amyl acetate; acid amides such
as dimethyl formamide, dimethyl acetamide and the like; and
sulfones and sulfoxides such as dimethyl sulfoxide, sulfolane and
the like; and bases, for example, such as pyridine.
In the above-mentioned process a), the reaction temperature can be
varied within a wide range. In general, the reaction is carried out
at a temperature of from about 0.degree. C. to 150.degree. C.,
preferably from about 20.degree. C. to about 90.degree. C.
In general, the reaction is preferably carried out under normal
pressure, and also elevated or reduced pressure.
In carrying out the process a), for instance, about 0.9 to slightly
above equimolar amounts of the compounds of the formula (III) may
be employed per mole of the compounds of the formula (II), and the
mixture is reacted in the presence of inert solvents under
heat-reflux until the generation of mercaptan ceases, so that the
desired compounds of the formula (I) can be obtained.
In carrying out the process b), suitable diluents include the same
solvents as exemplified for the process a).
In the above-mentioned process b), the reaction temperature can be
varied within a wide range. For example, the reaction is carried
out at a temperature in the range of from about 0.degree. C. to
about 150.degree. C., preferably from about 20.degree. C. to about
90.degree. C.
In general, the reaction is preferably carried out under normal
pressure, and also elevated or reduced pressure.
In carrying out process b), for instance, equimolar to a slight
molar excess of the compounds of formula (IV) may be employed per
mole of the compounds of the formula (Ia), and the mixture is
reacted in the presence of inert solvents, so that the desired
compounds of the formula (I) can be obtained.
In carrying out the process c), suitable diluents include the same
solvents as exemplified for the process a).
The above-mentioned process c) may be carried out in the presence
of acid binders such as, for example, conventionally used
hydroxide, hydride, carbonate, bicarbonate and alcolate of alkali
metal, tertiary amines such as, for example, triethyl amine,
diethyl aniline, pyridine, etc.
In the above-mentioned process c), the reaction temperature can be
varied within a wide range. In general, the reaction is carried out
at a temperature of from about 0.degree. C. to the boiling point of
the reactant mixture, preferably from about 0.degree. C. to about
80.degree. C.
In general, the reaction is preferably carried out under normal
pressure, or also elevated or reduced pressure.
In carrying out the process c), for instance, about 1 to 1.2 moles,
preferably 1 mole of compound (VI) may be employed per mole of the
compounds of the formula (V), and the mixture is reacted in the
presence of inert solvents, such as e.g. dimethylsulfoxide, and in
the presence of acid binder, such as e.g. sodium hydride, so that
the desired compounds of the formula (I) can be obtained.
In carrying out the process d), suitable diluents include the same
solvents as exemplified for the process a).
In the above-mentioned process d), the reaction temperature can be
varied within a wide range. In general, the reaction is carried out
at a temperature in the range of from about 0.degree. C. to about
150.degree. C., preferably from about 20.degree. C. to about
90.degree. C.
In general, the reaction is preferably carried out under normal
pressure, or also elevated or reduced pressure.
In carrying out the process d), for instance, equimolar to a slight
molar excess of the compounds of formula (IV) may be employed per
mole of the compounds of the formula (Ic), and the mixture is
reacted in the presence of inert solvents, so that the desired
compounds of the formula (I) can be obtained.
The active compounds are well tolerated by plants, have a favorable
level of toxicity to warm-blooded animals, and can be used for
combating arthropod pests, especially insects which are encountered
in agriculture, in forestry, in the protection of stored products
and of materials, and in the hygiene field. They are active against
normally sensitive and resistant species and against all or some
stages of development. The above-mentioned pests include:
from the class of the Isopoda, for example Oniscus Asellus,
Armadillidium vulgare and Porcellio scaber;
from the class of the Diplopoda, for example, Blaniulus
guttulatus;
from the class of the Chilopoda, for example, Geophilus carpophagus
and Scutigera spec.;
from the class of the Symphyla, for example, Scutigerella
immaculata;
from the order of the Thysanura, for example, Lepisma
saccharina;
from the order of the Collembola, for example, Onychiurus
armatus;
from the order of the Orthoptera; for example, Blatta orientalis,
Periplaneta americana, Leucophaea maderae, Blattella germanica,
Acheta domesticus, Gryllotalpa spp., Locusta migrato ria
migratorioides, Melanoplus differentialis and Schistocerca
gregaria;
from the order of the Dermaptera, for example, Forficula
auricularia;
from the order of the Isoptera, for example, Reticulitermes
spp.;
from the order of the Anoplura, for example, Phylloxera vastatrix,
Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and
Linognathus spp.;
from the order of the Mallophaga, for example, Trichodectes spp.
and Damalinea spp.;
from the order of the Thysanoptera, for example, Hercinothrips
femoralis and Thrips tabaci,
from the order of the Heteroptera, for example, Eurygaster spp.,
Dysdercus intermedius, Piesma guadrata, Cimex lectularius, Rhodnius
prolixus and Triatoma spp.;
from the order of the Homoptera, for example, Aleurodes brassicae,
Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii,
Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis
pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum
avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca
spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni,
Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,
Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and
Psylla spp.;
from the order of the Lepidoptera, for example, Pectinophora
gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis
blancardella, Hyponomeuta padella, Plutella maculipennis,
Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.,
Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp.,
Euxoa spp., Feltia spp., Earias insulana, Heliothis spp.,
Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia
litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella,
Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella,
Galleria mellonella, Cacoecia podana, Capua reticulana,
Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and
Tortrix viridana;
from the order of the Coleoptera, for example, Anobium punctatum,
Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides
obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa
decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes
chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus
surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus
sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera
postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus
spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus
hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor,
Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon
solstitialis and Costelytra zealandica;
from the order of the Hymenoptera for example, Diprion spp.,
Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa
spp.;
from the order of the Diptera, for example, Aedes spp., Anopheles
spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp.,
Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra
spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus
spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus,
Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis
capitata, Dacus oleae and Tipula paludosa;
from the order of the Siphonaptera, for example, Xenopsylla cheopis
and Ceratophyllus spp.;
from the class of the Arachnida, for example, Scorpio maurus and
Latrodectus mactans;
from the order of the Aranina, for example Acarus siro, Argas spp.,
Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis,
Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp.,
Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,
Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia
praetiosa, Panonychus spp. and Tetranychus spp.
The plant-parasitic nematodes include Pratylenchus spp., Radopholus
similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera
spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp.,
Xiphinema spp., and Trichodorus spp..
Furthermore, in the field of veterinary medicine, the novel
compound of the present invention can effectively be employed for
combating a variety of noxious animal-parasitic pests (internal-
and external-parasitic pests), e.g., parasitic insects and
nematodes. Such animal-parasitic pests may be exemplified as
follows:
From the class of insects, e.g., Gastrophilus spp., Stomoxys spp.,
Tricodectes spp., Rhodius spp., Ctenocephalides canis and the
like.
The active compounds can be converted into the customary
formulations, such as solutions, emulsions, wettable powders,
suspensions, powders, foams, pastes, granules, aerosols, natural
and synthetic materials impregnated with active compound, very fine
capsules in polymeric substances, coating compositions for use on
seed, and formulations used with burning equipment, such as
fumigating cartridges, fumigating cans and fumigating coils, as
well as ULV cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by
mixing the active compounds with extenders, that is to say liquid
or liquefied gaseous or solid diluents or carriers, optionally with
the use of surface-active agents, that is to say emulsifying agents
and/or dispersing agents and/or foam-forming agents. In the case of
the use of water as an extender, organic solvents can, for example,
also be used as auxiliary solvents.
As liquid solvents diluents or carriers, there are suitable in the
main, aromatic hydrocarbons, such as xylene, toluene or alkyl
napthalenes, chlorinated aromatic or chlorinated aliphatic
hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene
chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins,
for example mineral oil fractions, alcohols, such as butanol or
glycol as well as their ethers and esters, ketones, such as
acetone, methyl ethyl ketone, methyl isobutyl ketone or
cyclohexanone, or strongly polar solvents, such as
dimethylformamide and dimethyl-sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which
would be gaseous at normal temperature and under normal pressure,
for example aerosol propellants, such as halogenated hydrocarbons
as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such
as kaolins, clays, talc, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, and ground synthetic
minerals, such as highly-dispersed silicic acid, alumina and
silicates. As solid carriers for granules there may be used crushed
and fractionated natural rocks such as calcite, marble, pumice,
sepiolite and dolomite, as well as synthetic granules of inorganic
and organic meals, and granules of organic material such as
sawdust, coconut shells, corn cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there may be used
non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty
acid esters, polyoxyethylene-fatty alcohol ethers, for example
alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates,
aryl sulphonates as well as albumin hydrolysis products. Dispersing
agents include, for example, lignin sulphite waste liquors and
methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic
polymers in the form of powders, granules or latices, such as gum
arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the
formulation.
It is possible to use colorants such as inorganic pigments, for
example iron oxide, titanium oxide and Prussian Blue, and organic
dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal
phthalocyanine dyestuffs, and trace nutrients, such as salts of
iron, manganese boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by
weight of active compound, preferably from 0.5 to 90 per cent by
weight.
The active compounds according to the invention can be present in
their commercially available formulations and in the use forms,
prepared from these formulations, as a mixture with other active
compounds, such as insecticides, baits, sterilising agents,
acaricides, nematicides, fungicides, growth-regulating substances
or herbicides. The insecticides include, for example, phosphates,
carbamates, carboxylates, chlorinated hydrocarbons, phenylureas,
substances produced by microorganisms.
The active compounds according to the invention can furthermore be
present in their commercially available formulations and in the use
forms, prepared from these formulations, as a mixture with
synergistic agents. Synergistic agent are compounds which increase
the action of the active compounds, without it being necessary for
the synergistic agent added to be active itself.
The active compound content of the use forms prepared from the
commercially available formulations can vary within wide limits.
The active compound concentration of the use forms can be from
0.0000001 to 100% by weight of active compound, preferably between
0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate for
the use forms.
When used against hygiene pests and pests of stored products, the
active compounds are distinguished by an excellent residual action
on wood and clay as well as a good stability to alkali on limed
substrates.
The preparation and use of the active compounds according to the
invention can be seen from the following examples.
Preparative Examples
EXAMPLE 1 ##STR24##
A mixture of 1-(2-chloro-5-pyridyl)ethylamine (4.7 g),
1,1-bis-methylthio-2-nitroethylene (5.0 g) and ethanol (50 ml) was
refluxed under heating until the generation of mercaptan ceased.
Then, the ethanol was distilled off from the mixture under reduced
pressure and the resulting residue was purified on a
chromatographic column (the eluent mixture=ethanol+chloroform) to
obtain the desired
1-{1-(2-chloro-5-pyridyl)ethylamino}-1-methylthio-2-nitroethylene
(3.3 g) having a melting point in the range of from 136.degree. to
140.degree. C.
EXAMPLE 2 ##STR25##
To a solution comprising
1-{1-(2-chloro-5-pyridyl)ethylamino}-1-methylthio-2-nitroethylene
(2.7 g) in ethanol (50 ml) was added dropwise an aqueous solution
of methylamine (40%, 3 g) at 50.degree. C., followed by a two
hours' stirring at the same temperature.
Upon the solution having been cooled to room temperature, the aimed
product was separated in the form of crystals, which were filtered
and washed with ethanol to obtain the desired
1-{1-(2-chloro-5-pyridyl)ethylamino}-1-methylamino-2-nitroethylene
(1.5 g) having a melting point in the range of from 183.degree. to
186.degree. C.
EXAMPLE 3 ##STR26##
To a solution of 2-methyl-3-nitroisothiourea (15.0 g) in
dimethylsulfoxide (100 ml) was gradually added sodium hydride (oil
free 2.9 g) at 5.degree. C., while being stirred for one hour.
Thereafter, 2-chloro-5-chloromethyl pyridine (18.0 g) was added to
the solution at a temperature in the range of from 5.degree. to
10.degree. C., followed by overnight stirring thereof at room
temperature. After the dimethylsulfoxide in the solution was
distilled off under reduced pressure, the resulting residue was
purified on a chromatographic column (the eluent was a mixture of
ethanol and chloroform), so as to obtain the desired
1-(2-chloro-5-pyridylmethyl)-2-methyl-3-nitroisothiourea (2.0 g)
having a melting point in the range of from 141.degree. to
143.degree. C.
EXAMPLE 4 ##STR27##
1-(2-chloro-5-pyridylmethyl)-2-methyl-3-nitroisothiourea (1.3 g)
was dissolved in ethanol (20 ml) and to the solution was added an
aqueous solution (50%) of dimethylamine (0.5 g) at room
temperature, followed by one-day stirring at 30.degree. C. The
ethanol in the solution was distilled off under reduced pressure
and it was purified on a chromatographic column (the eluent was a
mixture of methanol and chloroform) so as to obtain the desired
3-(2-chloro-5-pyridylmethyl)-1,1-dimethyl-2-nitroguanidine (1.2 g)
having a melting point in the range of from 158.degree. to
160.degree. C.
Background Example 1 ##STR28##
A mixture of 5-aminomethyl-2-chloropyridine (14.25 g),
mesitaldehyde (14.8 g) and toluene (100 ml) was heated under reflux
for 3 hours. The water which was formed during the reaction was
trapped by Dean and Stark constant water separator.
The toluene was distilled off from the mixture under reduced
pressure, so as to obtain
N-(2,4,6-trimethylbenzylidene)-2-chloro-5-pyridylmethylamine (27
g). m.p. 47.degree.-48.degree. C.
Background Example 2 ##STR29##
To a stirred solution of
N-(2,4,6-trimethylbenzylidene)-2-chloro-5-pyridylmethylamine (10.9
g) in dried tetrahydrofuran (150 ml) cooled to -70.degree. C. under
N.sub.2 atmosphere was added butyl-lithium (10 w/v % in hexane, 26
ml), causing an immediate intense color to occur. After 30 minutes
stirring at the temperature, methyl iodide (5.7 g) was added
dropwise, and then the mixture was stirred for three hours without
cooling. The solvent was removed under reduced pressure.
To the residue, ethanol (50 ml) and 2N-hydrochloric acid (50 ml)
were added and heated under reflux for one hour.
The cooled solution was poured into water (100 ml) and extracted
with methylene chloride (50 ml .times.2).
The aqueous fraction was neutralized with 2N-sodium hydroxide and
extracted with methylene chloride (50 ml .times.2). The extract was
dried over sodium sulfate and evaporated to obtain
1-(2-chloro-5-pyridyl)ethylamine (4 g). n.sub.D.sup.20 1.5440
Compounds of the formula (I) according to the invention which can
be prepared in the same way as in Examples 1 to 4: are set forth in
the following Tables 1 and 2.
Where Y is CH in the formula (I), the compounds of the formula (I)
are shown in Table 1, and where Y is N in the formula (I), the
compounds are shown in Table 2.
TABLE 1 ______________________________________ ##STR30## Compd. No.
Z R.sup.1 R.sup.2 R.sup.3 ______________________________________ 1
2-chloro-5-pyridyl CH.sub.3 H SCH.sub.3 m.p. 136- 140.degree. C. 2
2-methyl-5-pyridyl C.sub.2 H.sub.5 H SCH.sub.3 3 2-bromo-5-pyridyl
C.sub.2 H.sub.5 H SCH.sub.3 4 2-chloro-5-thiazolyl CH.sub.3 H
SCH.sub.3 5 2-chloro-5-pyridyl CH.sub.3 CH.sub.3 NH.sub.2 6
2-fluoro-5-pyridyl C.sub.3 H.sub.7 -n H NH.sub.2 7
2-methyl-5-pyridyl CH.sub.3 H NHCH.sub.3 8 2-chloro-5-pyridyl
CH.sub.3 H NHCH.sub.3 m.p. 183- 186.degree. C. 9 2-chloro-5-pyridyl
CH.sub.3 H N(CH.sub.3).sub.2 m.p. 150- 155.degree. C. 10
2-chloro-5-pyridyl CH.sub.3 H NH.sub.2 11 2-chloro-5-pyridyl
CH.sub.3 CH.sub.3 NHCH.sub.3 11a 1.2.3.thiadiazol-5-yl CH.sub.3
C.sub.2 H.sub.5 SC.sub.3 H.sub.7 -n
______________________________________
TABLE 2
__________________________________________________________________________
##STR31## Compd. No. Z R.sup.1 R.sup.2 R.sup.3
__________________________________________________________________________
12 2-pyridyl H H SCH.sub.3 13 3-pyridyl H H SCH.sub.3 14 4-pyridyl
H H SCH.sub.3 15 2-chloro-5-pyridyl H H SCH.sub.3 m.p.
141-143.degree. C. 16 2-fluoro-5-pyridyl CH.sub.3 H SCH.sub.3 17
2-chloro-5-pyridyl H CH.sub.3 SCH.sub.3 18 2-methyl-5-pyridyl H H
SC.sub.2 H.sub.5 19 2-chloro-5-pyridyl CH.sub.3 CH.sub.3 SC.sub.2
H.sub.5 20 2-bromo-5-pyridyl H H SC.sub.3 H.sub.7 -n 21
2-chloro-5-pyridyl H H NH.sub.2 m.p. 197-199.degree. C. 22
2-chloro-5-pyridyl H CH.sub.3 NH.sub.2 m.p. 166-168.degree. C. 23
2-chloro-5-pyridyl H C.sub.2 H.sub.5 NH.sub.2 24 2-chloro-5-pyridyl
H C.sub.3 H.sub.7 -n NH.sub.2 25 2-chloro-5-pyridyl CH.sub.3 H
NH.sub.2 n.sub.D .sup.20 1.5739 26 2-bromo-5-pyridyl H H NH.sub.2
27 2-chloro-5-thiazolyl H H NH.sub.2 28 2-chloro-5-pyridyl H H
NHCH.sub.3 m.p. 151-155.degree. C. 29 2-chloro-5-pyridyl H CH.sub.3
NHCH.sub.3 m.p. 135-139.degree. C. 30 2-chloro-5-pyridyl H C.sub.2
H.sub.5 NHCH.sub.3 31 2-chloro-5-pyridyl H C.sub.3 H.sub.7 -n
NHCH.sub.3 32 2-chloro-5-pyridyl CH.sub.3 H NHCH.sub.3 33
2-chloro-5-thiazolyl H H NHCH.sub.3 34 2-chloro-5-thiazolyl H
CH.sub.3 NHCH.sub.3 35 2-chloro-5-pyridyl H H NHC.sub.2 H.sub.5
m.p. 123-127.degree. C. 36 2-chloro-5-pyridyl H CH.sub.3 NHC.sub.2
H.sub.5 37 2-chloro-5-pyridyl C.sub.4 H.sub.9 -n C.sub.2 H.sub.5
NHC.sub.2 H.sub.5 38 2-fluoro-5-pyridyl H H NHC.sub.2 H.sub.5 39
2-chloro-5-pyridyl H H NHC.sub.3 H.sub.7 -n 40 2-chloro-5-pyridyl H
CH.sub.3 NHC.sub.3 H.sub.7 -n 41 2-chloro-5-thiazolyl H H NHC.sub.3
H.sub.7 -n 42 2-chloro-5-pyridyl H C.sub.2 H.sub.5 NHC.sub.3
H.sub.7 -n 43 2-chloro-5-pyridyl H H NHC.sub.3 H.sub.7 -iso m.p.
161-165.degree. C. 44 2-chloro-5-pyridyl H CH.sub.3 NHC.sub.3
H.sub.7 -iso 45 2-chloro-5-pyridyl H H N(CH.sub.3).sub.2 m.p.
158-160.degree. C. 46 2-chloro-5-thiazolyl H H N(CH.sub.3).sub.2 47
2-chloro-5-thiazolyl H CH.sub.3 N(CH.sub.3).sub.2 48
2-chloro-5-pyridyl H CH.sub.3 N(CH.sub.3).sub.2 m.p. 96-99.degree.
C. 49 2-chloro-5-pyridyl H C.sub.2 H.sub.5 N(CH.sub.3).sub.2 50
2-chloro-5-thiazotyl CH.sub.3 H N(CH.sub.3).sub.2 51
2-chloro-5-pyridyl H H ##STR32## 52 2-chloro-5-pyridyl H CH.sub.3
##STR33## 53 2-chloro-5-thiazolyl H H ##STR34## 54
2-chloro-5-thiazolyl H CH.sub.3 ##STR35## 55 2-chloro-5-pyridyl H H
##STR36## 56 2-chloro-5-pyridyl H H N(C.sub.2 H.sub.5).sub.2 57
2-chloro-5-pyridyl H CH.sub.3 N(C.sub.2 H.sub.5).sub.2 58
2-chloro-5-pyridyl H C.sub.2 H.sub.5 N(C.sub.2 H.sub.5).sub.2 59
2-chloro-5-pyridyl H C.sub.4 H.sub.9 -n NHCH.sub.3 60
2-chloro-5-pyridyl H H NHC.sub.4 H.sub.9 -n 61 4-pyridyl H CH.sub.3
NH.sub.2 m.p. 153-155.degree. C. 62 2-pyridyl H CH.sub.3 NH.sub.2
63 3-pyridyl H CH.sub.3 NH.sub.2 m.p. 139-141.degree. C. 64
4-pyridyl H H NHCH.sub.3 65 4-pyridyl H CH.sub.3 NHCH.sub.3 66
3-pyridyl H H NHCH.sub.3 67 3-pyridyl H CH.sub.3 NHCH.sub.3 68
2-pyridyl H H NHCH.sub.3 69 2-pyridyl H CH.sub.3 NHCH.sub.3 70
4-pyridyl H H N(CH.sub.3).sub.2 71 3-pyridyl H H N(CH.sub.3).sub.2
72 2-pyridyl H H N(CH.sub.3).sub.2 73 2-methyl-5-pyrazinyl H
CH.sub.3 NH.sub.2 74 2-pyrimidynyl H H NH.sub.2 75
3-methyl-5-isoxazolyl H H NH.sub.2 76 3-methyl-5-isoxazolyl H H
NHCH.sub.3 77 3-methyl-5-isoxazolyl H H N(CH.sub.3)2
__________________________________________________________________________
Biological Tests
Comparative compound E-1 ##STR37##
EXAMPLE 5 (Biological Test)
Test on Nephotettix cincticeps having resistance to
organophosphorus agents:
Preparation of a test chemical
Solvent: 3 parts by weight of xylene
Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl
ether
To form a suitable preparation, 1 part by weight of the active
compound was mixed with the aforesaid amount of the solvent
containing the aforesaid amount of the emulsifier. The mixture was
diluted with water to a predetermined concentration.
Testing Method
Onto rice plants, about 10 cm tall, planted in pots each having a
diameter of 12 cm was sprayed 10 ml per pot of the water-dilution
of each active compound in a predetermined concentration prepared
as above. The sprayed chemical was dired, and a wire net having a
diameter of 7 cm and a height of 14 cm was put over each pot, and
30 female imagoes of Nephotettix cincticeps showing resistance to
organophosphorus agents were released into the net. The pots were
each placed in a constant temperature chamber and the number of
dead insects was examined 2 days later, and the Insect mortality
was calculated.
The results are shown in Table 3.
TABLE 3 ______________________________________ Concentration of
Insect the active component, mortality, Compound No. ppm %
______________________________________ 8 8 100 9 8 100 22 8 100 45
8 100 Control E-1 50 0 ______________________________________
EXAMPLE 6 (Biological Test)
Test on planthoppers:
Testing method
A water dilution in a predetermined concentration of the active
compound prepared as in Example 5 was sprayed onto rice plants,
about 10 cm tall, grown in pots with a diameter of 12 cm in an
amount of 10 ml per pot. The sprayed chemical was dried, and a wire
net, 7 cm in diameter and 14 cm tall, was put over each of the
pots. Thirty female imagoes of Nilaparvata lugens Stal of a strain
which showed resistance to organophosphorus chemicals were released
into the net. The pots were left to stand in a constant temperature
chamber and the number of dead insects was examined two days later.
The kill ratio was then calculated.
In the same way as above, the insect mortality was calculated on
Sogatella furcifera Horvath and organophosphorus-resistant
Laodelphax striatellus Fallen.
The results are shown in Table 4.
TABLE 4 ______________________________________ Concentration Com-
of the active Insect mortality, % pound component, Nilaparvata
Laodelphax Sogatella No. ppm lugens striatellus furcifera
______________________________________ 8 8 100 100 100 9 8 100 100
100 22 8 100 100 100 45 8 100 100 100 Control E-1 50 0 0 0
______________________________________
It is understood that the specification and examples are
illustrative but not limitative of the present invention and that
other embodiments within the spirit and scope of the invention will
suggest themselves to those skilled in the art.
* * * * *