U.S. patent number RE39,129 [Application Number 10/067,192] was granted by the patent office on 2006-06-13 for heterocyclic compounds.
This patent grant is currently assigned to Bayer Cropscience K.K.. Invention is credited to Yumi Hatori, Shinzo Kagabu, Koichi Moriya, Shoko Sasaki, Kozo Shiokawa, Shinichi Tsuboi.
United States Patent |
RE39,129 |
Shiokawa , et al. |
June 13, 2006 |
Heterocyclic compounds
Abstract
Novel heterocyclic compounds of the formula ##STR00001##
wherein, R.sup.1 represents a hydrogen atom or an alkyl group, A
represents an ethylene group which may be substituted by alkyl or a
trimethylene group which may be substituted by alkyl, X represents
an oxygen or sulfur atom or the group ##STR00002## in which R.sup.2
represents a hydrogen atom of an optionally substituted alkyl, an
alkenyl, an alkynyl or an acyl group, and R.sup.3 represents a
hydrogen atom or an alkyl group, and Z represents an optionally
substituted 5- or 6-membered heterocyclic group which contains at
least two hetero atoms selected from oxygen, sulfur and nitrogen
atoms, or an optionally substituted 3- or 4-pyridyl group. The
above defined novel heterocyclic compounds of formula (I) exhibit
powerful insecticidal properties.
Inventors: |
Shiokawa; Kozo (Kanagawa-ken,
JP), Tsuboi; Shinichi (Tokyo, JP), Kagabu;
Shinzo (Gifu-ken, JP), Sasaki; Shoko (Tokyo,
JP), Moriya; Koichi (Tokyo, JP), Hatori;
Yumi (Tokyo, JP) |
Assignee: |
Bayer Cropscience K.K. (Tokyo,
JP)
|
Family
ID: |
12808675 |
Appl.
No.: |
10/067,192 |
Filed: |
February 4, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
07017641 |
Feb 24, 1987 |
04849432 |
Jul 18, 1989 |
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Foreign Application Priority Data
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Mar 7, 1986 [JP] |
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61-48629 |
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Current U.S.
Class: |
514/340; 544/333;
544/336; 544/55; 548/143; 548/146; 548/193; 548/214; 546/256;
546/270.7; 546/271.4; 546/274.7; 546/279.1; 548/127; 548/131;
548/134; 548/136; 544/96; 544/409; 544/334; 544/242; 514/341;
544/238; 514/342; 514/333 |
Current CPC
Class: |
C07D
417/06 (20130101); C07D 277/28 (20130101); C07D
401/06 (20130101); C07D 413/06 (20130101); A01N
47/40 (20130101); C07D 403/06 (20130101) |
Current International
Class: |
A61K
31/44 (20060101); A61K 31/4439 (20060101); C07D
417/06 (20060101); C07D 401/06 (20060101) |
Field of
Search: |
;546/275,211.4
;514/340 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2205745 |
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Aug 1973 |
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DE |
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3409801 |
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Sep 1984 |
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DE |
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2 542 740 |
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Sep 1984 |
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FR |
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2126220 |
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Mar 1984 |
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GB |
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2126222 |
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Mar 1984 |
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GB |
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59-196877 |
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Nov 1987 |
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JP |
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Other References
Patent Abstracts of Japan, vol. 9, No. 241 (C-306), (1964) Sep. 27,
1985. cited by examiner .
Patent Abstracts of Japan, vol. 8, No. 122 (C-227), (1959) Jun. 8,
1984. cited by examiner .
Tsuboi, Chem. Abstr., vol. 109, entry 144610r (1988). cited by
examiner .
Tsuboi, Chem. Abstr., vol. 109, entry 144611s (1988). cited by
examiner.
|
Primary Examiner: Raymond; Richard L.
Attorney, Agent or Firm: Norris McLaughlin & Marcus
PA
Parent Case Text
.Iadd.Notice: More than one reissue application has been filed for
the reissue of U.S. Pat. No. 4,849,432. The reissue applications
are application Nos. 08/254,202 (the present application), filed on
Jun. 6, 1994; 10/067,189, filed on Feb. 4, 2002; 10/067,190, filed
on Feb. 4, 2002; 10/067,191, filed on Feb. 4, 2002; and 10/167,192,
filed on Feb. 4, 2002, all of which are divisional reissues of U.S.
Pat. No. 4,849,432.
This application is a reissue of U.S. Pat. No. 4,849,432, issued on
Jul. 18, 1989. Another pending reissue application related to the
same patent is U.S. Ser. No. 08/254,202, filed Jun. 6,
1994..Iaddend.
Claims
We claim:
1. A heterocyclic compound of the formula ##STR00176## wherein
R.sup.1 represents a hydrogen atom or a methyl group, A represents
an ethylene group which may be substituted by methyl, X represents
an oxygen .[.or sulfur atom or the group ##STR00177## in which
R.sup.2 represents a hydrogen atom, a C.sub.1-C.sub.4 alkyl group
which may be substituted by a substituent selected from halogens,
C.sub.1-C.sub.4 alkoxy groups, C.sub.1-C.sub.4 alkylthio groups and
cyano, a C.sub.2-C.sub.4 alkenyl group, a C.sub.2-C.sub.4 alkynyl
group, a pyridylmethyl group, which may be substituted by halogen
and/or methyl, a benzyl group which may be substituted by halogen
and/or methyl, a formyl group, an alkylcarbonyl group having 1 to 2
carbon atoms in the alkyl moiety which may be substituted by
halogen, a phenylcarbonyl group which may be substituted by halogen
and/or methyl, an alkoxy or alkylthiocarbonyl group having 1 to 4
carbon atoms in the alkyl moiety, a phenoxycarbonyl group, a
C.sub.1-C.sub.4 alkylsulfonyl group which may be substituted by
halogen or a phenylsulfonyl group which may be substituted by
methyl, R.sup.3 represents a hydrogen atom or a C.sub.1-C.sub.7
alkyl group,.]. and Z represents a 3-pyridyl group or 4-pyridyl
group optionally substituted by at least one substituent selected
from halogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy
groups having 1 to 4 carbon atoms, alkylthio groups having 1 to 4
carbon atoms, haloalkyl groups having 1 to 4 carbon atoms,
haloalkoxy groups having 1 to 4 carbon atoms, alkylsulfonyl groups
having 1 to 4 carbon atoms, a cyano group and a nitro group.
.[.2. A compound according to claim 1, wherein R.sup.1 represents a
hydrogen atom, A represents an ethylene group, X represents a
sulfur atom or the group ##STR00178## and Z represents a 3-pyridyl
group or 4-pyridyl group-optionally substituted by at least one
substituent selected from a fluorine atom, a chlorine atom, a
bromine atom, a methyl group, a methoxy group, a methylthio group,
a trifluoromethyl group, a trifluoromethoxy group, a methylsulfonyl
group, a cyano group and a nitro group..].
.[.3. A compound according to claim 1, wherein such compound is
1-(2-chloro-5-pyridylmethyl)-2-cyanoiminoimidazolidine of the
formula ##STR00179## .].
.[.4. A compound according to claim 1, wherein such compound is
1-(2-fluoro-5-pyridylmethyl)-2-cyanoiminoimidazolidine of the
formula ##STR00180## .].
.[.5. A compound according to claim 1, wherein such compound is
1-(2-methyl-5-pyridylmethyl)-2-cyanoiminoimidazolidine of the
formula ##STR00181## .].
.[.6. A compound according to claim 1, wherein such compound is
1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazolidine of the
formula ##STR00182## .].
7. An insecticidal composition comprising an insecticidally
effective amount of a compound according to claim 1 and a
diluent.
8. A method of combating insects which comprises applying to such
insects or to an insect habitat an insecticidally effective amount
of a compound according to claim 1.
.[.9. The method according to claim 8, wherein such compound is
1-(2-chloro-5-pyridylmethyl)-2-cyanoiminoimidazolidine,
1-(2-fluoro-5-pyridylmethyl)- 2-cyanoiminoimidazolidine,
1-(2-chloro-5-pyridylmethyl)-2-cyanoiminotetrahydropyrimidine,
1-(2-methyl-5-pyridylmethyl)-2-cyanoiminoimidazolidine,
1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminoimidazolidine,
1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminotetrahydropyrimidine,
1-(2-methyl-5-pyrazinylmethyl)-2-cyanoiminoimidazolidine,
1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazolidine,
1-(2-chloro-5-pyridylmethyl)-2-cyanoiminotetrahydro-2H-1,3-thiazine
1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminothiazolidine,
1-(2-methyl-5-pyrazinylmethyl)-2-cyanoiminothiazolidine,
1-(2-methyl-5-thiazolylmethyl)-2-cyanoiminothiazolidine,
1-(1,2,5-thiaziazol-3-ylmethyl)-2-cyanoiminothiazolidine..].
Description
The present invention relates to novel heterocyclic compounds, to
processes for their preparation, and to their use as
insecticides.
It has already been disclosed that certain cyanoimino-substituted
heterocyclic compounds are useful as intermediates for fungicidal,
antidiabetic, viral tranquilizing or diuretic active substances
(see DE-OS No. 2,205,745) and also as antiulcer agents (see DE-OS
No. 3,409,801).
There have now been found novel heterocyclic compounds of the
formula (I) ##STR00003## wherein, R.sup.1 represents a hydrogen
atom or an alkyl group, A represents an ethylene group which may be
substituted by alkyl or a trimethylene group which may be
substituted by alkyl, X represents an oxygen or sulfur atom or the
group ##STR00004## in which R.sup.2 represents a hydrogen atom or
an optionally substituted alkyl, alkenyl, alkynyl or acyl group,
and R.sup.3 represents a hydrogen atom or an alkyl group, and Z
represents an optionally substituted 5- or 6-membered heterocyclic
group which contains at least two hetero atoms selected from
oxygen, sulfur and nitrogen atoms, or an optionally substituted 3-
or 4-pyridyl group.
The compounds of the formula (I) are obtained by a process in
which
(a) compounds of the formula (II) ##STR00005## wherein A and X are
as defined, are reacted with compounds of the formula (III)
##STR00006## wherein R.sup.1 and Z are as defined above, and
M.sup.1 represents a halogen atom or the group --OSO.sub.2--M.sup.2
in which M.sup.2 represents a lower alkyl group or an aryl group,
in the presence of inert solvent, if appropriate in the presence of
a base, or
(b) in the case where X in the formula (I) represents an oxygen or
sulfur atom or the group ##STR00007## in which R.sup.4 represents a
hydrogen atom, an alkyl group which may be substituted, an alkenyl
group or an alkynyl group, and for which case in the following
formula (IV) X is replaced by the symbol X.sup.1: Compounds of the
formula (IV) ##STR00008## wherein R.sup.1, A, Z and X.sup.1 are as
defined, are reacted with compounds of the formula (V)
(R'--S).sub.2C.dbd.N--CN (V) wherein R' represents a lower alkyl
group or a benzyl group, or two R' groups may together represent a
lower alkylene group having at least 2 carbon atoms and may form a
ring together with the adjacent sulfur atoms, in the presence of
inert solvents, or
(c) in the case where X in the formula (I) represents the group
##STR00009## in which R.sup.2 represents an acyl group which may be
substituted, and for which case in the following formula (VI)
R.sup.2 is replaced by the symbol R.sup.5: Compounds of the formula
(Ib) ##STR00010## wherein R.sup.1, A and Z are as defined above,
are reacted with compounds of the formula (VI) R.sup.5--Hal (VI)
wherein R.sup.5 is as defined above, and Hal represents a halogen
atom, in the presence of inert solvents and a base.
The novel heterocyclic compounds of formula (I) exhibit powerful
insecticidal properties.
Surprisingly, the novel heterocyclic compounds according to the
invention exhibit a substantially greater insecticidal action than
those known from the aforesaid prior art, and in particular the the
compounds have extremely superior activities as insecticides
against stinging and sucking insects typified by hemipterous
insects such as aphids, planthoppers and leafhoppers, which have
attained resistance to organophosphate and carbamate insecticides
as a result of their long-term use.
Among the compounds according to the invention, of the formula (I),
preferred compounds are those in which
R.sup.1 represents a hydrogen atom or a methyl group,
A represents an ethylene group which may be substituted by methyl
or a trimethylene group which may be substituted by methyl, X
represents an oxygen or sulfur atom or the group ##STR00011## in
which R.sup.2 represents a hydrogen atom, a C.sub.1-C.sub.4 alkyl
group which may be substituted by a substituent selected from
halogens, C.sub.1-C.sub.4 alkoxy groups, C.sub.1-C.sub.4 alkylthio
groups and cyano, a C.sub.2-C.sub.4 alkenyl group, a
C.sub.2-C.sub.4 alkynyl group, a pyridylmethyl group which may be
substituted by halogen and/or methyl, a benzyl group which may be
substituted by halogen and/or methyl, a formyl group, an
alkylcarbonyl group having 1 to 2 carbon atoms in the alkyl moiety
which may be substituted by halogen, a phenylcarbonyl group which
may be substituted by halogen and/or methyl, an alkoxy- or
alkylthiocarbonyl group having 1 to 4 carbon atoms in the alkyl
moiety, a phenoxycarbonyl group, a C.sub.1-C.sub.4 alkylsulfonyl
group which may be substituted by halogen or a phenylsulfonyl group
which may be substituted by methyl, and R.sup.3 represents a
hydrogen atom, and
Z represents a 5- or 6-membered heterocyclic group containing 2 to
3 hetero atoms selected from oxygen, sulfur and nitrogen atoms at
least one of which is a nitrogen atom, or a 3-pyridyl group, the
heterocyclic group and the 3-pyridyl group being optionally
substituted by at least one substituent selected from halogen
atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy groups
having 1 to 4 carbon atoms, alkylthio groups having 1 to 4 carbon
atoms, haloalkyl groups having 1 to 4 carbon atoms, haloalkoxy
groups having 1 to 4 carbon atoms, alkylsulfonyl groups having 1 to
4 carbon atoms, a cyano group and a nitro group.
Very particularly preferred compounds of the formula (I) are those
in which
R.sup.1 represents a hydrogen atom,
A represents an ethylene or trimethylene group,
X represents a sulfur atom or the group --NH, and
Z represents a 5- or 6-membered heterocyclic group containing two
hetero atoms selected from oxygen, sulfur and nitrogen atoms at
least one of which is a nitrogen atom, or a 3-pyridyl group, the
heterocyclic group and the 3-pyridyl group being optionally
substituted by at least one substituent selected from a fluorine
atom, a chlorine atom, a bromine atom, a methyl group, a methoxy
group, a methylthio group, a trifluoromethyl group, a
trifluoromethoxy group, a methylsulfonyl group, a cyano group and a
nitro group.
The 3-pyridyl group in the definition of Z is structurally
synonymous with 5-pyridyl.
Specific examples of the compounds of formula (I) in accordance
with this invention especially include
1-(2-chloro-5-pyridylmethyl)-2-cyanoiminoimidazolidine,
1-(2-fluoro-5-pyridylmethyl)-2-cyanoiminoimidazolidine,
1-(2-chloro-5-pyridylmethyl)-2-cyanoiminotetrahydropyrimidine,
1-(2-methyl-5-pyridylmethyl)-2-cyanoiminoimidazolidine,
1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminoimidazolidine,
1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminotetrahydropyrimidine,
1-(2-methyl-5-pyrazinylmethyl)-2-cyanoiminoimidazolidine,
1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazolidine,
1-(2-chloro-5-pyridylmethyl)-2-cyanoiminotetrahydro-2H-1,2-thiazine
1-(2-chloro-5-thiazolylmethyl)-2-cyanoiminothiazolidine,
1-(2-methyl-5-pyrazinylmethyl)-2-cyanoiminothiazolidine,
1-(2-methyl-5-thiazolylmethyl)-2-cyanoiminothiazolidine, and
1-(1,2,5-thiaziazol-3-yl)-2-cyanoiminothiazolidine.
When in process (a) for the production of the compound of formula
(I), 2-cyanoiminothiazolidine and 2-chloro-5-pyridylmethyl chloride
are used as the starting materials, the reaction is represented by
the following reaction scheme: ##STR00012##
When N-(2-chloro-5-pyridylmethyl)ethylenediamine and
dimethylcyanodithioimide carbonate are used as the starting
materials in process (b) for the production of the compound of
formula (I), the reaction is represented by the following reaction
scheme: ##STR00013##
When 1-(2-chloro-5-pyridylmethyl)-2-cyanoiminoimidazolidine and
acetyl chloride are used as the starting materials in process (c)
for the production of the compound of formula (I), the reaction is
represented by the following reaction scheme: ##STR00014##
In process (a), the starting compound of the formula (II) means one
based on the definitions of A and X. Preferably, A and X are
synonymous with the preferred definitions given hereinabove.
The compounds of the formula (II) include known compounds.
2-Cyanoiminoimidazolidine and 2-cyanoiminotetrahydropyridine are
described in J. Org. Chem., vol. 38, pages 155-156, and can be
easily obtained by the reaction of dimethyl
cyanodithioimidocarbonate with ethylenediamine or
trimethylenediamine. Likewise, reaction with ethylenediamine or
trimethylenediamine N-substituted by substituents other than acyl
gives the corresponding 3-substituted-2-cyanoiminoimidazolidine or
3-substituted-2-cyanoiminotetrahydropyrimidine.
Use of aminoalkanols in place of the alkylenediamines can give the
corresponding oxazolidines or 1,3-oxazine derivatives (Japanese
Laid-Open Patent Publication No. 91064/1973).
2-Cyanoiminothiazolidine is described in Arch. Pharm., vol. 305,
pages 731-737. Likewise, the reaction of 2-aminopropanethiol with
dimethyl cyanodithioimidocarbonate gives
2-cyanoiminotetrahydro-1,3-thiazine.
2-Cyanoiminopyrrolidine is described in Khim. Farm. Zh., vol. 19,
pages 154-158, and can be easily obtained by reacting
2-methoxypyrroline-2 and cyanamide. Similarly,
2-cyanoiminopiperidine is obtained from
2-methoxy-3,4,5,6-tetrahydropyridine with cyanamide.
Likewise, the starting compounds of the formula (III) are those
based on the definitions of R.sup.1, Z and M.sup.1. Preferably,
R.sup.1, Z are synonymous with the preferred definitions given
hereinabove. M.sup.1 is preferably a chlorine or bromine atom.
The compounds of the formula (III) are described in Japanese Patent
Applications Nos. 18627/1985, 18628/1985, and 106853/1985 filed by
the same applicants as the present one. Specific examples include
2-fluoro-5-pyridylmethyl chloride, 2-chloro-5-pyridylmethyl
chloride, 2-bromo-5-pyridylmethyl chloride,
2-methyl-5-pyridylmethyl chloride, 2-chloro-5-thiazolylmethyl
chloride, 2-methyl-5-pyrazinylmethyl chloride,
2-methyl-5-oxazolylmethyl chloride, 1,2,5-thiaziazol-3-ylmethyl
chloride, 3-methyl-5-isoxazolylmethyl chloride, and
2-chloro-5-pyrimidinylmethyl chloride.
In process (b), the starting compounds of the formula (IV) are
those based on the definitions of R.sup.1, A and Z, and R.sup.1, A
and Z are synonymous with the preferred definitions given
hereinabove.
The compounds of the formula (IV) are described in Japanese Patent
Applications Nos. 18627/1985, 18628/1985, 23683/1985, 106853/1985,
and 219082/1985. Specific examples include
N-(2-chloro-5-pyridylmethyl)-ethylenediamine trimethylenediamine,
N-(2-fluoro-5-pyridylmethyl)-ethylenediamine trimethylenediamine,
N-(2-methyl-5-pyridylmethyl)-ethylenediamine trimethylenediamine,
N-(2-methyl-5-thiazolylmethyl)-ethylenediamine trimethylenediamine,
and N-(2-methyl-5-pyrazinylmethyl)-ethylenediamine
trimethylenediamine. Other examples include
2-(2-chloro-5-pyridylmethyl)aminoethanethiol,
3-(2-chloro-5-pyridylmethyl)aminopropanethiol,
2-(2-chloro-5-thiazolylmethyl)aminoethanethiol, and
2-(2-methyl-5-pyrazinylmethyl)aminoethanethiol.
The starting compounds of the formula (V) are described in J. Org.
Chem., vol. 32, pages 1566-1572.
In process (c), the starting compounds of the formula (Ib) are
included within the compounds of formula (I) in accordance with
this invention which can be produced by process (a) or (b).
The starting compounds of the formula (VI) are well known in the
field of organic chemistry, and their specific examples include
propionyl chloride, acetyl chloride, chloroacetyl chloride,
methylsulfonyl chloride, tosyl chloride and methoxycarbonyl
chloride.
In the practice of process (a), suitable diluents are used which
include all inert organic solvents.
Examples of the diluent include aliphatic, alicyclic and aromatic
hydrocarbons (optionally chlorinated) such as hexane, cyclohexane,
petroleum ether, ligroin, benzene, toluene, xylene, methylene
chloride, chloroform, carbon tetrachloride, ethylene chloride,
trichloroethylene and chlorobenzene; ethers such as diethyl ether,
methyl ethyl ether, di-isopropyl ether, dibutyl ether, propylene
oxide, dioxane and tetrahydrofuran; ketones such as acetone, methyl
ethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone;
nitriles such as acetonitrile, propionitrile and acrylonitrile;
esters such as ethyl acetate and amyl acetate; acid amides such as
dimethylformamide and dimethylacetamide; and sulfones and
sulfoxides such as dimethyl sulfoxide and sulfolane.
The reaction of process (a) may be carried out in the presence of a
base. Examples of the base are alkali metal hydrides such as sodium
hydride and potassium hydride, and hydroxides and carbonates of
alkali metals.
Process (a) can be carried out over a broad temperature range, for
example between about 0.degree. and about 100.degree. C.,
preferably between about 10.degree. and about 80.degree. C.
Desirably, the reaction is carried out under atmospheric pressure,
but it is also possible to operate under reduced pressure.
In the practice of process (a), for example, 1 mole of the
compounds of the formula (II) is reacted with 1 to about 1.2 moles,
preferably 1 to about 1.1 moles, of the compounds of the formula
(III) in an inert solvent such as dimethylformamide in the presence
of a base to give the desired compound of general formula (I).
In the practice of process (b), suitable diluents include water and
alcohols in addition to the inert organic solvents illustrated for
process (a).
Process (b) can be carried out over a broad temperature range, for
example between 0.degree. C., and the boiling point of the reaction
mixture, preferably between about 0.degree. C. and about
100.degree. C. Preferably, the reaction is carried out under
atmospheric pressure, but can also be carried out under elevated or
reduced pressure.
In the practice of process (b), for example, 1 mole of the compound
of formula (IV) is reacted with 1 to about 1.2 moles, preferably 1
to about 1.1 moles, of the compound of formula (v) in an inert
solvent such as an alcohol (e.g., methanol or ethanol) until the
generation of mercaptan ceases, to obtain the desired novel
compound of general formula (I).
In the practice of process (c), suitable diluents may be the same
as those illustrated above for process (a). Process (c) may be
carried out in the presence of a base. The same alkali metal
hydrides illustrated above for process (a) may be cited as examples
of such a base.
Process (c) may be practiced over a broad temperature range,
preferably between 0.degree. C. and the boiling point of the
mixture, especially between 0.degree. C. and 100.degree. C.
Desirably, the reaction is carried out under atmospheric pressure,
but may be carried out under elevated or reduced pressure
conditions.
The compounds of the formula (I) in accordance with this invention
may be present in the form of salts such as inorganic acid salts,
sulfonates, organic acid salts and metal salts. Accordingly, the
novel heterocyclic compounds of the formula (I) in this invention
are meant to denote their salts as well.
The active compounds are well tolerated by plants, have a
favourable level of toxicity to warm-blooded animals, and can be
used for combating arthropod pests, especially insects which are
encountered in agriculture, 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.]. .Iadd.Diplopoda.Iaddend., for
example Oniscus Asellus, Armadillidium vulgare and Porcellio
scaber;
from the class of the Diplogoda, 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 migratoria
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 bilobazus, Nephotettix cincticeps, Lecanium corni,
Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,
Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and
Psylla spp.;
from the order of Lepidoptera, for example Pectinophora
gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis
blancardella, Hyponomeuta padella, Plutella maculinpennis,
Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.,
Buccalatrix 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., Pyrousta nubilatis, 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 bafulus, 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., Stomoxya spp., Oestrus
spp., Hypoderma spp., Tabanus spp., Tannis spp., Bibio hortulanus,
Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis
capitata, Dacus oleae and Tipula paludosa;
In the field of veterinary medicine, the novel compounds of this
invention are effective against various noxious animal parasites
(endo- and ecto-parasites) such as insects and worms.
Examples of such animal parasites are insects such as Gastrophilus
spp., Stomoxys spp., Trichodectes spp., Rhodnius spp., and
Ctenocephalides canis.
The active compounds can be converted into the customary
formulations, such as solutions, emulsions, 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 salt 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 of active compound.
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, sterilizing 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 following examples illustrate the present invention
more specifically. It should be understood however that the
invention is in no way limited to these examples alone.
PRODUCTION EXAMPLE
EXAMPLE 1
##STR00015##
N-(2-chloro-5-pyridylmethyl)ethylenediamine (3.7 g) and dimethyl
cyanodithioimidocarbonate (1.3 g) were added to 50 ml of ethanol,
and the mixture was gradually heated with stirring and subsequently
refluxed for 3 hours. After the reaction, ethanol was distilled off
under reduced pressure, whereupon the residue solidified. The
solidified residue was pulverized and washed with a mixture of
ether and a small amount of ethanol. The amount of the product
yielded after drying was 3.5 g. mp. 167.degree.-170.degree. C.
EXAMPLE 2
##STR00016##
N-(2-chloro-5-pyridylmethyl)cysteamine (2.0 g) and dimethyl
cyanodithioimidocarbonate (1.3 g) were added to 50 ml of ethanol.
In a stream of nitrogen gas, the mixture was refluxed for 8 hours
with stirring. After the reaction, about 2/3 of ethanol was
distilled off under reduced pressure. When the residue was left to
stand at room temperature, the final product precipitated as
crystals. The crystals were collected by filtration, washed with
ether and dried. The amount of yielded was 2.4 g. mp.
128.degree.-129.degree. C.
EXAMPLE 3
##STR00017##
A mixture of 2-cyanoiminothiazolidine (2.5 g), anhydrous potassium
carbonate (3.0 g), 2-chloro-5-chloromethylthiazole (3.3 g) and dry
acetonitrile was refluxed for 3 hours with good stirring. After the
reaction, acetonitrile was distilled off under reduced pressure,
and dichloromethane was added to the residue. The mixture was
washed with water and a 1% aqueous solution of sodium hydroxide.
The dichloromethane layer was dried and concentrated. The
precipitate was collected by filtration, and dried. The amount
yielded was 3.3 g. mp. 145.degree.-146.degree. C.
EXAMPLE 4
##STR00018##
2-Cyanoiminoimidazolidine (2.2 g) was dissolved in 25 ml of dry
dimethylformamide, and sodium hydride (1 g) was added little by
little at less than 10.degree. C. and the mixture was stirred at
10.degree. C. until the generation of hydrogen ceased. Then, a
solution of 2-chloromethyl-5-methylpyrazine (2.8 g) in
dimethylformamide (10 ml) was added dropwise at 10.degree. C. After
the addition, the mixture was stirred at room temperature for 1
hour. Ice water was added to the mixture, and the pH of the aqueous
solution was adjusted to 7. The aqueous layer was extracted with
dichloromethane, and the dichloromethane layer was washed with
water and dried. After concentrating dichloromethane, the remaining
solid was recrystallized from dilute ethanol to give 1.8 g of the
final product, mp. 144.degree.-147.degree. C.
EXAMPLE 5
##STR00019##
1-(2-Chloro-5-pyridylmethyl)-2-cyanoiminoimidazolidine (2.4 g) was
dissolved in 30 ml of dry dimethylformamide, and sodium hydride
(0.26 g) was added at 10.degree. C. The mixture was stirred at room
temperature until the generation of hydrogen ceased. Then, benzoyl
chloride (1.4 g) was added, and the mixture was stirred at
40.degree. C. for 30 minutes, and poured into ice water. The
aqueous layer was extracted with dichloromethane. The
dichloromethane layer was washed with water, and dichloromethane
was concentrated. The residue was purified by silica gel column
chromatography to give the final product. The amount yielded was
1.3 g, mp. 158.degree.-161.degree. C.
The compounds shown in Table 1 can be prepared in the same way as
exemplified in Examples 1 to 5. Table 1 also discloses the
compounds obtained in Examples 1 to 5.
TABLE-US-00001 TABLE 1 ##STR00020## Compound No. ##STR00021## A X 1
##STR00022## --CH.sub.2CH.sub.2-- NH 2 ##STR00023##
--CH.sub.2CH.sub.2-- NH mp. 191.about.193.degree. C. 3 ##STR00024##
--(CH.sub.2).sub.3-- NH mp. 214.about.216.degree. C. 4 ##STR00025##
--CH.sub.2CH.sub.2-- NH mp. 154.about.157.degree. C. 5 ##STR00026##
--CH.sub.2CH.sub.2-- NH mp. 167.about.170.degree. C. 6 ##STR00027##
--CH.sub.2CH.sub.2-- NH 7 ##STR00028## ##STR00029## NH mp.
155.about.160.degree. C. 8 ##STR00030## --(CH.sub.2).sub.3-- NH mp.
166.about.167.5.degree. C. 9 ##STR00031## --CH.sub.2CH.sub.2-- NH
10 ##STR00032## --CH.sub.2CH.sub.2-- NH 11 ##STR00033##
--(CH.sub.2).sub.3-- NH mp. 184.about.188.degree. C. 12
##STR00034## ##STR00035## NH 13 ##STR00036## --CH.sub.2CH.sub.2--
NH 14 ##STR00037## --CH.sub.2CH.sub.2-- NH 15 ##STR00038##
--CH.sub.2CH.sub.2-- NH 16 ##STR00039## --CH.sub.2CH.sub.2-- NH 17
##STR00040## --CH.sub.2CH.sub.2-- NH 18 ##STR00041##
--CH.sub.2CH.sub.2-- NH 19 ##STR00042## --(CH.sub.2).sub.3-- NH 20
##STR00043## --CH.sub.2CH.sub.2-- NH 21 ##STR00044##
--CH.sub.2CH.sub.2-- NH 22 ##STR00045## --CH.sub.2CH.sub.2-- NH 23
##STR00046## --(CH.sub.2).sub.3-- NH 24 ##STR00047##
--(CH.sub.2).sub.3-- NH 25 ##STR00048## --CH.sub.2CH.sub.2-- NH mp.
161.about.162.degree. C. 26 ##STR00049## --CH.sub.2CH.sub.2-- NH 27
##STR00050## --(CH.sub.2).sub.3-- NH mp. 182.about.185.degree. C.
28 ##STR00051## --(CH.sub.2).sub.3-- NH 29 ##STR00052##
##STR00053## NH mp. 224.about.227.degree. C. 30 ##STR00054##
--CH.sub.2CH.sub.2-- NH 31 ##STR00055## --CH.sub.2CH.sub.2-- NH 32
##STR00056## --CH.sub.2CH.sub.2-- NH 33 ##STR00057##
--(CH.sub.2).sub.3-- NH mp. 145.about.148.degree. C. 34
##STR00058## --CH.sub.2CH.sub.2-- NH mp. 129.about.131.degree. C.
35 ##STR00059## --(CH.sub.2).sub.3-- NH 36 ##STR00060##
--CH.sub.2CH.sub.2-- NH 37 ##STR00061## --(CH.sub.2).sub.3-- NH 38
##STR00062## --CH.sub.2CH.sub.2-- NH 39 ##STR00063##
--(CH.sub.2).sub.3-- NH mp. 137.about.140.degree. C. 40
##STR00064## --(CH.sub.2).sub.3-- NH 41 ##STR00065##
--(CH.sub.2).sub.3-- NH 42 ##STR00066## --CH.sub.2CH.sub.2-- NH 43
##STR00067## --(CH.sub.2).sub.3-- NH 44 ##STR00068##
--CH.sub.2CH.sub.2-- NH 45 ##STR00069## --CH.sub.2CH.sub.2-- NH 46
##STR00070## --CH.sub.2CH.sub.2-- NH 47 ##STR00071##
--CH.sub.2CH.sub.2-- NH 48 ##STR00072## --(CH.sub.2).sub.3-- NH 49
##STR00073## --CH.sub.2CH.sub.2-- NH 50 ##STR00074##
--CH.sub.2CH.sub.2-- NH 51 ##STR00075## --(CH.sub.2).sub.3-- NH mp.
185.about.188.degree. C. 52 ##STR00076## --CH.sub.2CH.sub.2-- NH 53
##STR00077## --CH.sub.2CH.sub.2-- NH 54 ##STR00078##
--CH.sub.2CH.sub.2-- NH mp. 144.about.147.degree. C. 55
##STR00079## --CH.sub.2CH.sub.2-- N--CHO 56 ##STR00080##
--CH.sub.2CH.sub.2-- N--COCH.sub.3 n.sub.D.sup.20 1.5895 57
##STR00081## --CH.sub.2CH.sub.2-- ##STR00082## mp.
53.about.55.degree. C. 58 ##STR00083## --CH.sub.2CH.sub.2--
N--COC(CH.sub.3).sub.3 59 ##STR00084## --CH.sub.2CH.sub.2--
##STR00085## 60 ##STR00086## --(CH.sub.2).sub.3-- ##STR00087## 61
##STR00088## --(CH.sub.2).sub.3-- N--COOC.sub.2H.sub.5 62
##STR00089## --CH.sub.2CH.sub.2-- ##STR00090## 63 ##STR00091##
--CH.sub.2CH.sub.2-- S 64 ##STR00092## --CH.sub.2CH.sub.2-- S mp.
117.about.120.degree. C. 65 ##STR00093## --CH.sub.2CH.sub.2-- S mp.
128-129.degree. C. 66 ##STR00094## --CH.sub.2CH.sub.2-- S 67
##STR00095## --(CH.sub.2).sub.3-- S mp. 124-125.degree. C. 68
##STR00096## --CH.sub.2CH.sub.2-- S 69 ##STR00097##
--CH.sub.2CH.sub.2-- S mp. 145-146.degree. C. 70 ##STR00098##
--(CH.sub.2).sub.3-- S 71 ##STR00099## --(CH.sub.2).sub.3-- S 72
##STR00100## --(CH.sub.2).sub.3-- S 73 ##STR00101##
--CH.sub.2CH.sub.2-- S mp. 153.about.157.degree. C. 74 ##STR00102##
--(CH.sub.2).sub.3-- S 75 ##STR00103## --CH.sub.2CH.sub.2-- S 76
##STR00104## --CH.sub.2CH.sub.2-- S 77 ##STR00105##
--CH.sub.2CH.sub.2-- S 78 ##STR00106## --(CH.sub.2).sub.3-- S 79
##STR00107## --CH.sub.2CH.sub.2-- S mp. 132-135.degree. C. 80
##STR00108## --CH.sub.2CH.sub.2-- O 81 ##STR00109##
--CH.sub.2CH.sub.2-- O 82 ##STR00110## --CH.sub.2CH.sub.2-- O 83
##STR00111## --CH.sub.2CH.sub.2-- O mp. 113-114.degree. C. 84
##STR00112## --(CH.sub.2).sub.3-- O 85 ##STR00113##
--CH.sub.2CH.sub.2-- O 86 ##STR00114## --CH.sub.2CH.sub.2-- O 87
##STR00115## --(CH.sub.2).sub.3-- O 88 ##STR00116##
--CH.sub.2CH.sub.2-- N--COCCl.sub.3 89 ##STR00117##
--CH.sub.2CH.sub.2-- ##STR00118## mp. 158-161.degree. C. 90
##STR00119## --CH.sub.2CH.sub.2-- N--COOCH.sub.3 91 ##STR00120##
--CH.sub.2CH.sub.2-- ##STR00121## 92 ##STR00122##
--CH.sub.2CH.sub.2-- N--COCH.sub.3 93 ##STR00123##
--CH.sub.2CH.sub.2-- N--COOCH.sub.3 94 ##STR00124##
--(CH.sub.2).sub.3-- N--COSC.sub.2H.sub.5 95 ##STR00125##
--(CH.sub.2).sub.3-- ##STR00126## 96 ##STR00127##
--CH.sub.2CH.sub.2-- N--COC.sub.2H.sub.5 97 ##STR00128##
--CH.sub.2CH.sub.2-- S mp. 138.about.140.degree. C. 98 ##STR00129##
--(CH.sub.2).sub.3-- S 99 ##STR00130## --CH.sub.2CH.sub.2-- O 100
##STR00131## --CH.sub.2CH.sub.2-- O 101 ##STR00132##
--CH.sub.2CH.sub.2-- O 102 ##STR00133## --(CH.sub.2).sub.3-- O 103
##STR00134## --CH.sub.2CH.sub.2-- O mp. 130-134.degree. C. 104
##STR00135## --CH.sub.2CH.sub.2-- CH.sub.2 105 ##STR00136##
--CH.sub.2CH.sub.2-- CH.sub.2 106 ##STR00137## --CH.sub.2CH.sub.2--
CH--CH.sub.3 107 ##STR00138## --(CH.sub.2).sub.3-- CH.sub.2 mp.
74.about.76.degree. C. 108 ##STR00139## --CH.sub.2CH.sub.2--
CH.sub.2 109 ##STR00140## --CH.sub.2CH.sub.2-- CH.sub.2 110
##STR00141## --CH.sub.2CH.sub.2-- CH.sub.2 111 ##STR00142##
--(CH.sub.2).sub.3-- CH.sub.2 mp. 122-125.degree. C. 112
##STR00143## --(CH.sub.2).sub.3-- CH.sub.2 113 ##STR00144##
--CH.sub.2CH.sub.2-- CH.sub.2 114 ##STR00145## --CH.sub.2CH.sub.2--
O 115 ##STR00146## --CH.sub.2CH.sub.2-- O 116 ##STR00147##
--(CH.sub.2).sub.3-- NH mp. 185.about.190.degree. C. 117
##STR00148## --CH.sub.2CH.sub.2-- N--CH.sub.3 mp.
101.about.103.degree. C. 118 ##STR00149## --CH.sub.2CH.sub.2--
N--CH.sub.2CN n.sub.D.sup.20 1.6015 119 ##STR00150##
--CH.sub.2CH.sub.2-- N--CH.sub.2CF.sub.3 120 ##STR00151##
--(CH.sub.2).sub.3-- N--CH.sub.2CH.sub.2OCH.sub.3 121 ##STR00152##
--CH.sub.2CH.sub.2-- N--CH.sub.2CH.sub.2SC.sub.1H.sub.5 122
##STR00153## --CH.sub.2CH.sub.2-- ##STR00154## n.sub.D.sup.20
1.6145 123 ##STR00155## --CH.sub.2CH.sub.2-- ##STR00156## 124
##STR00157## --CH.sub.2CH.sub.2-- N--CH.sub.2CH.dbd.CH.sub.2 125
##STR00158## --CH.sub.2CH.sub.2-- N--CH.sub.2C.ident.CH 126
##STR00159## --CH.sub.2CH.sub.2-- N--CH.sub.2CH.sub.2CN 127
##STR00160## --(CH.sub.2).sub.3-- S mp. 141.about.145.degree. C.
128 ##STR00161## --CH.sub.2CH.sub.2-- CH.sub.2 mp.
85.about.90.degree. C. 129 ##STR00162## --CH.sub.2CH.sub.2--
##STR00163## mp. 161.about.163.degree. C. 130 ##STR00164##
--CH.sub.2CH.sub.2-- N--COOC.sub.2H.sub.5 n.sub.D.sup.20 1.5880 131
##STR00165## ##STR00166## ##STR00167## mp. 82-85.degree. C. 132
##STR00168## --(CH.sub.2).sub.3-- N--CH.sub.2C.ident.CH
n.sub.D.sup.20 1.5667 133 ##STR00169## --CH.sub.2CH.sub.2--
##STR00170## n.sub.D.sup.20 1.5446 134 ##STR00171## ##STR00172## O
mp. 119-121.degree. C.
Use Examples
Comparison compounds of the closest state of the art: ##STR00173##
(described in Japanese Laid-Open Patent Publication No. 91064)
##STR00174## (described in the above-cited patent document)
##STR00175## (described in Japanese Laid-Open Patent Publication
No. 196877/1984).
EXAMPLE 6 (biological test)
Test on organophosphate-resistant green rice leafhoppers
(Nephotettix cincticeps)
Preparation of a test chemical
Solvent: 3 parts by weight of xylene
Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl
ether
To prepare a preparation of a suitable active compound, 1 part by
weight of the active compound was mixed with the above amount of
the solvent containing the above amount of the emulsifier, and the
mixture was diluted with water to a predetermined
concentration.
Testing method
A water dilution of each of the active compounds in a predetermined
concentration prepared as above was sprayed onto rice plants, about
10 cm tall, grown in pots having a diameter of 12 cm at a rate of
10 ml per pot. The sprayed chemical was dried, and a wire net
having a diameter of 7 cm and a height of 14 cm was put over each
of the pots, and 30 female imagoes of rice leafhopper of a strain
having resistance to organophosphate chemicals were released into
the net. The pots were placed in a constant-temperature chamber.
Two days later, the number of dead insects was examined, and the
kill ratio was calculated.
Compared with comparison compounds W-1, W-2 and Q 2 for example the
following compounds according to the invention exhibited a
considerably better efficiacy: Compound Nos. 4, 5, 8, 9, 25, 27,
54, 65, 67, 69, 79.
EXAMPLE 7 (biological test)
Test on planthoppers
Testing method
A water dilution of each of the active compounds in a predetermined
concentration prepared as in the preceding example was sprayed onto
rice plants, 10 cm tall, grown in pots having a diameter of 12 cm
at a rate of 10 ml per pot. The sprayed chemical was dried, and a
wire net having a diameter of 7 cm and a height of 14 cm was put
over each of the pots, and 30 female imagoes of brown planthopper
(Nilaparvata lugens) of a strain having resistance to
organophosphate chemicals were released into the net and the pots
were placed in a constant temperature chamber. Two days later, the
number of dead insects was examined, and the kill ratio was
calculated.
In the same way as above, the kill ratio on white-backed
planthopper (Sogatella furcifera) and organophosphate-resistant
smaller brown planthopper (Laodelphax striatellus) was
calculated.
Compared with comparison compounds W-1, W-2 and Q-1 for example the
following compounds according to the invention exhibited a
considerably better efficacy against brown planthoppers, brown
smaller planthoppers and white-backed planthoppers: Compounds No.
4, 5, 8, 9, 25, 27, 65, 67.
EXAMPLE 8 (biological test)
Test on green peach aphids (Myzus persicae) having resistance to
organophosphate and carbamate chemicals
Testing method
Bred green peach aphids having resistance to organophosphates and
carbamates were inoculated on eggplant (black elongate variety)
seedlings, about 20 cm tall, grown in unglazed pots having a
diameter of 15 cm at a rate of about 200 per seedling. One day
after the inoculation, a water dilution of each of the active
compounds in a predetermined concentration prepared as in Example 6
was sprayed in sufficient amounts by means of a spray gun. After
spraying, the pots were left to stand in a greenhouse kept at
28.degree. C. Twenty-four hours after the spraying, the kill ratio
was calculated. The above test was carried out through two
replicates.
Compared with comparison compounds W-1, W-2 and Q-2 for example the
following compounds according to the invention exhibited a
considerably better efficacy against Myzus persicae: Compounds No.
4, 5, 25, 27, 65, 67, 69.
The biological tests shown in Examples 6, 7 and 8 are only typical
examples of the insecticidal use of the compounds of this
invention. The compounds of this invention shown herein are typical
examples, and the utility of the invention is not to be limited to
these examples alone.
It will be 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.
* * * * *