U.S. patent application number 09/984456 was filed with the patent office on 2003-05-01 for 1-(2-chloro-5-methyl-3-pyridylmethyl)-2-nitroiminiomidazolidine and processfor the preparation thereof.
Invention is credited to Bhimapaka, Chinaraju, Rao, Vaidya Jayathirtha.
Application Number | 20030083350 09/984456 |
Document ID | / |
Family ID | 27624075 |
Filed Date | 2003-05-01 |
United States Patent
Application |
20030083350 |
Kind Code |
A1 |
Bhimapaka, Chinaraju ; et
al. |
May 1, 2003 |
1-(2-CHLORO-5-METHYL-3-PYRIDYLMETHYL)-2-NITROIMINIOMIDAZOLIDINE AND
PROCESSFOR THE PREPARATION THEREOF
Abstract
The present invention relates to
1-(2-chloro-5-methyl-3-pyridylmethyl)-2-n- itroiminoimadozolidine
of the formula 1, a novel compound of class nitroimino pyridyl
derivatives and to a process for the preparation thereof 1
Inventors: |
Bhimapaka, Chinaraju;
(Andhra Pradesh, IN) ; Rao, Vaidya Jayathirtha;
(Andhra pradesh, IN) |
Correspondence
Address: |
Norman H. Stepno, Esquire
BURNS, DOANE, SWECKER & MATHIS, L.L.P.
P.O. Box 1404
Alexandria
VA
22313-1404
US
|
Family ID: |
27624075 |
Appl. No.: |
09/984456 |
Filed: |
October 30, 2001 |
Current U.S.
Class: |
514/341 ;
546/272.7 |
Current CPC
Class: |
A01N 51/00 20130101;
C07D 401/06 20130101 |
Class at
Publication: |
514/341 ;
546/272.7 |
International
Class: |
A01N 043/40; C07D
43/02 |
Claims
We claim:
1. 1-(2-chloro-5-methyl-3-pyridylmethyl)-2-nitroiminoimadozolidine
of the general formula 1 5
2. A process for the preparation of
1-(2-chloro-5-methyl-3-pyridylmethyl)-- 2-nitroiminoimadozolidine
of the formula 1 6comprising reacting
2-chloro-3-chloromethyl-5-methyl pyridine and
2-nitroimino-1,3-diazacyclo- pentane in the presence of a base and
an organic solvent.
3. A process as claimed in claim 2 wherein said base used comprises
potassium carbonate.
4. A process as claimed in claim 2 wherein the organic solvent used
comprises acetonitrile.
5. A process as claimed in claim 2 wherein the reaction is carried
out for a time period in the range of 5 to 10 hours.
6. A process as claimed in claim 2 wherein the molar ratio of
2-chloro-3-chloromethyl-5-methyl pyridine to
2-nitroimino-1,3-diazacyclop- entane is in the range of
1:1-1.5.
7. A process as claimed in claim 6 wherein the molar ratio of
2-chloro-3-chloromethyl-5-methyl pyridine to
2-nitroimino-1,3-diazacyclop- entane is 1:1.2.
8. A process as claimed in claim 2 wherein
2-chloro-3-chloromethyl-5-methy- l pyridine used is obtained by
sodium borohydride reduction of
2-chloro-5-methylpyridine-3-carbaldehyde.
9. A process as claimed in claim 2 wherein the
2-chloro-3-chloromethyl-5-m- ethyl pyridine used is obtained by the
reaction of 2-chloro-3-hydroxymethy- l-5-methyl pyridine with
thionyl chloride.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to
1-(2-chloro-5-methyl-3-pyridylmeth- yl)-2-nitroiminoimadozolidine
of the formula 1 given below and to a process for the preparation
thereof. 2
[0002]
1-(2-chloro-5-methyl-3-pyridylmethyl)-2-nitroiminoimadozolidine of
the formula 1 is a novel compound of class nitroimino pyridyl
derivatives. The present invention also relates to a process for
the preparation of
1-(2-chloro-5-methyl-3-pyridylmethyl)-2-nitroiminoimadozol- idine
using 2-chloro-3-chloromethyl-5-methylpyridine and
2-nitroimino-1,3-diazacyclopentane in various solvents using a base
under appropriate conditions of mole ratio, time, temperature and
work up procedure with high yields and selectivity.
BACKGROUND OF THE INVENTION
[0003] 1-(6-chloronicotinyl)-2-nitroiminoimidazolidine and related
compounds are reported as effectively controlling hemiptera, other
sucking insects and against green rice leaf hopper [Biosci.
Biotech. Biochem, 56(8), 1364 & 56(2), 364, 1992]. Structural
modification in the 6-chloropyridyl and introduction of five
membered hetero cyclic compounds are reported as insecticidal
compounds [Biosci. Biotech. Biochem., 57(1), 127, 1993].
1-(2-chloro-5-pyridylmethyl) 2-nitoiminoimidazolidine
(Imidacloropid/Confidor) is a potent insecticide (EP 0192061, 1990
and Angew.Chem.Int.Ed. 39, 1724, 2000) and acts at the nicotinic
acetylcholine receptor (J.Labelled.Compd.Radiopharm, 31(8), 609,
1992; CA 117:171316w).
[0004] Substituted pyridinyl, pyurazinyl or pyrimidyl
nitromethylene and nitroimininoimidazolidines and their synergistic
mixtures are reported for moth proofing (EP 387663, 1989; CA
114:p201780 a). 2-nitroimino or cyano iminoimidazolidines and
hexahydropyrimidine derivatives are reported as insecticides (JP
63156786, 1988; CA 110:p8210d). 1-diazinyl methyl-2-nitro methylene
and 2-nitroiminoimidazolidines reported as new potential
insecticides against green leaf hoppers on rice seedling in spray
applications (Nippon Noyaku Gakkaishi 18(1), 119, 1993; CA
119:111238d). N-nitroiminoimidazolidines derivatives of
2-chloropyridine-5-yl, 2-chlorothiazol-5-yl are reported as active
ingredients of insecticides (JP 06122680, 1994; CA 121:p157642a
& JP 06100557, 1994; CA 121:255796y).
N-nitroiminodithiocarbonate compounds serve as intermediates for
insecticides and pharmaceuticals (U.S. Pat. No. 5,453,529, 1995; CA
124:p55973d). N-substituted alkyl, haloalkenyl, alkynyl, aralkyl,
aromatic heterocyclymethyl compounds serve as insecticides (JP
02207083, 1990; CA 114:62097t). N-vinyl imidazolidine derivatives
and 2-phenyl dicyano imidazoles are reported as insecticides and
anthelminitics (EP 547557, 1993; CA119:225953p and Ger.Offen DE
19548914, 1994; CA 125:142731n).
[0005] The discovery of new compounds for use as pesticides is
still desired for effective crop protection.
OBJECTS OF THE INVENTION
[0006] The main object of the invention is to provide new compounds
for use as pesticides for effective crop protection.
[0007] It is another object of the invention to provide new
compounds for use as pesticides with good yield and
selectivity.
[0008] It is a further object of the invention to provide a new
compound
1-(2-chloro-5-methyl-3-pyridylmethyl)-2-nitroiminoimadozolidine of
the class of nitroimino pyridyl derivatives for use as
pesticide.
[0009] It is another object of the invention to provide a process
for the preparation of a novel compound
1-(2-chloro-5-methyl-3-pyridylmethyl)-2-n- itroiminoimadozolidine
where the reaction time is short and the temperature conditions are
mild.
SUMMARY OF THE INVENTION
[0010] Accordingly, the present invention relates to a novel
compound
1-(2-chloro-5-methyl-3-pyridylmethyl)-2-nitroiminoimadozolidine of
the formula 1 given below 3
[0011] The present invention also relates to a process for the
preparation of
1-(2-chloro-5-methyl-3-pyridylmethyl)-2-nitroiminoimadozolidine of
the formula 1 4
[0012] using 2-chloro-3-chloromethyl-5-methyl pyridine and
2-nitroimino-1,3-diazacyclopentane in the presence of a base and an
organic solvent.
[0013] In one embodiment of the invention, the organic solvent used
comprises acetonitrile.
[0014] In another embodiment of the invention, the base used
comprises potassium carbonate.
[0015] In a further embodiment of the invention, the reaction is
carried out for a time period in the range of 5 to 10 hours.
[0016] In yet another embodiment of the invention, the molar ratio
of 2-chloro-3-chloromethyl-5-methyl pyridine to
2-nitroimino-1,3-diazacyclop- entane is in the range of 1:1-1.5,
preferably 1:1.2.
[0017] In another embodiment of the invention,
2-chloro-3-chloromethyl-5-m- ethyl pyridine is obtained by the
reaction of 2-chloro-3-hydroxymethyl-5-m- ethyl pyridine with
thionyl chloride with 90% yield.
[0018] In another embodiment of the reaction,
2-chloro-3-chloromethyl-5-me- thyl pyridine is obtained by the
sodium borohydride reduction of
2-chloro-5-methylpyridine-3-carbaldehyde with 88% yield.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The invention will be described in detail with reference to
the following examples, which are illustrative and should not be
construed as limiting the scope of the invention in any manner.
EXAMPLE 1
[0020] 2-chloro-3-chloromethyl-5-methylpyridine (1.3 g, 0.0076
moles) was added to a well-stirred material comprising of
2-nitroimino-1,3-diazacycl- opentane (1.18 g, 0.00912 moles),
potassium carbonate (1.16g, 0.0083 moles), cesium chloride (0.04 g,
0.00024 moles) in acetonitrile (10 ml) solvent at room temperature.
The reaction mixture was refluxed for 5 hours. Solvent was removed
under reduced pressure and the mass diluted with water (25 ml). The
mass was then extracted with methylene chloride (2.times.50 ml) and
the layers were separated. Organic layer was dried over sodium
sulphate and solvent removed under reduced pressure. The residue
obtained was subjected to chromatographic purification on silica
gel to give 1-(2-chloro-5-methyl-3-pyridylmethyl)
2-nitroiminoimidazolidi- ne in 90% yield.
[0021] NMR (CDCl.sub.3+DMSO d.sub.6): .delta.2.38 (s, 3H,
CH.sub.3), 3.58 (t, 2H, N--CH.sub.2), 3.74 (t, 2H--CH.sub.2), 4.52
(s, 2H, CH.sub.2), 7.54 (s, 1H, aromatic), 8.12 (s, 1H, aromatic),
8.86 (1H, NH). Mass: M+. 269.
EXAMPLE 2
[0022] 2-chloro-3-chloromethyl-5-methylpyridine (1.3 g, 0.0076
moles) was added to a well-stirred material comprising of
2-nitroimino-1,3-diazacycl- opentane (1.18 g, 0.00912 moles),
potassium carbonate (1.16 g, 0.0083 moles), cesium chloride (0.04
g, 0.00024 moles) in acetonitrile (20 ml) solvent at room
temperature. The reaction mixture was refluxed for 8 hours. The
solvent was removed under reduced pressure and the mass diluted
with water (25 ml). The mass was then extracted with methylene
chloride (2.times.50 ml) and the layers were separated. Organic
layer was dried over sodium sulphate and solvent removed under
reduced pressure. The residue thus obtained was subjected to
chromatographic purification on silica gel to give
1-(2-chloro-5-methyl-3-pyridylmethyl) 2-nitroiminoimidazolidine in
90% yield.
EXAMPLE 3
[0023] Sodium borohydride (0.65 g, 0.0167 moles) was added slowly
to a well-stirred solution of
2-chloro-5-methylpyridine-3-carbaldehyde (1.3 g, 0.0084 moles) in
methanol (20 ml) at 0.degree. C. temperature over a period of 15
minutes. The reaction mass was further stirred for 2 hours at the
same temperature. The solvent was removed under reduced pressure
and the mass was quenched with water (25 ml). The mass was
extracted with ethyl acetate (2.times.50 ml) and the layers
separated. The organic layer was removed under reduced pressure.
The residue so obtained was subjected to chromatographic
purification on silica gel to give
2-chloro-3-hydroxymethyl-5-methylpyridine as a solid in 88%
yield.
[0024] NMR (CDCl.sub.3): .delta.2.34 (s, 3H, CH.sub.3), 3.7 (1H,
OH), 4.68 (s, 2H, CH.sub.2), 7.68 (s, 1H, aromatic), 8.04 (s, 1H,
aromatic). Mass: M+. 157.
EXAMPLE 4
[0025] Thionyl chloride (2.73 g, 0.023 moles) was added slowly to a
well-stirred solution of 2-chloro-3-hydroxymethyl-5-methylpyridine
(1.2 g, 0.0076 moles) in methylenechloride (20 ml) at 0.degree. C.
temperature over a period of 20 minutes. The reaction mass was
further stirred for 6 hours at the same temperature. The solvent
and excess thionylchloride was removed under reduced pressure and
the mass was quenched with water (25 ml). The mass was extracted
with methylene chloride (2.times.50 ml) and the layers separated.
The organic layer was dried over sodium sulphate and the solvent
removed under reduced pressure. The residue so obtained was
subjected to chromatographic purification on silica gel to give
2-chloro-3-chloromethyl-5-methylpyridine as a solid in 92%
yield.
[0026] NMR (CDCl.sub.3): .delta.2.36 (s, 3H, CH.sub.3), 4.6 (s, 2H,
CH.sub.2), 7.62 (s, 1H, aromatic), 8.16 (s, 1H, aromatic). Mass:
M+. 175.
[0027] Advantages of the Invention
[0028] 1. The compound of the invention is a novel compound and is
useful as a pesticide.
[0029] 2. The yield of the compound is high
[0030] 3. The reaction is carried out at low temperature and short
reaction times making the process cost effective
[0031] 4. Isolation of the product is simple.
* * * * *