GB2061919A - Cyclopropane carboxylates - Google Patents
Cyclopropane carboxylates Download PDFInfo
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- GB2061919A GB2061919A GB8028014A GB8028014A GB2061919A GB 2061919 A GB2061919 A GB 2061919A GB 8028014 A GB8028014 A GB 8028014A GB 8028014 A GB8028014 A GB 8028014A GB 2061919 A GB2061919 A GB 2061919A
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- phenoxy
- dimethyl
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- cyclopropane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/647—One oxygen atom attached in position 2 or 6 and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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Abstract
Compounds of general formula I, <IMAGE> wherein X1 and X2, which may be the same or different, each represents a fluorine, chlorine or bromine atom, the acid moiety being either of 1R, cis or of 1R, trans structure and the alcohol moiety being of (R), (S) or (RS) configuration useful as pesticides.
Description
SPECIFICATION
Cyclopropane carboxylates
This invention relates to esters of cyclopropane carboxylic acids, to their preparation, to pesticidal compositions containing them and to their use as pesticides.
In German Patent Specification No. 2,810,881 are disclosed (RS)a-cyano-6-phenoxy-2-pyridylmethyl dl cis trans 2,2-di methyl-3-(2,2-dihalovinyl)-cyclopropane-1 -carboxylates endowed with insecticidal properties.
According to the present invention there are provided compounds of general formula I,
wherein X1 and X2, which may be the same or different, each represents a fluorine, chlorine or bromine atom, the acid moiety being either of 1 R, cis or of 1 R, trans structure, and the alcoholic moiety being of (R), (S) or (RS) configuration.
Particularly preferred are those compounds of formula I in which X1 and X2 are the same.
The compounds of general formula I are endowed with pesticidal properties, particularly insecticidal and acaricidal properties as may be shown, for example, by tests on the domestic fly, on the cockroach, on larva of Spodoptera, on larva of Epilachna, on Aphis fabae or on tetranychus urticae. Such tests are described further on in the experimental part. The compounds of the invention are useful against parasitic acarids in warm-blooded animals, in particular ixodides and sarcoptides.
The activity of the compounds of the invention presents unexpected characteristics. Thus, the results of the tests given in the experimental part show that for a given acid moiety the (R) and (S) alcohol esters exhibit a substantially equal activity, which is contrary to the results obtained for the majority of known analogous molecules, and, in particular, for the corresponding esters of a-cyano-3-phenoxybenzyl alcohol.
Furthermore, for an alcohol moiety of a given configuration, in certain tests, the esters of the invention derived from 1 R, cis acids and those derived from 1R, trans acids, present nearly equal activity whereas, in other tests, the esters of the 1 R, trans series present activities superior to those of the 1 R, cis series. These results, confirmed by the experimental tests described hereinafter, are contrary to the results obtained for the majority of the known analogous molecules.
The compounds of general formula I may, for example be obtained by reacting 6-phenoxy-2-picoline aldehyde in an aqueous medium, with a compound generating CN ions and either with a 1 R, cis or with a 1 R, trans 2,2-dimethyl-3-(2,2-dihalovinyl)-cycloprnpane-1 -carboxylic acid of formula ll,
(wherein X1 and X2 are as hereinbefore defined) or with a functional derivative of the said acid, to give an (RS)a-cyano-6-phenoxy-2-pyridyl methyl 2,2-di methyl-3-(2,2-dihalovinyl )cyclopropane-1 -carboxylate of for rhula I in which the acid moiety has the same structure as the starting acid, followed, if desired by separation of the two diastereoisomers of the alcohol esters of (RS) configuration by a physical method to give an (R)a-cyano-6-phenoxy-2-pyridylmethyl 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropane-1 -carboxylate and a (S)a-cyano-6-phenoxy-2-pyridylmethyl 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropane-1 -carboxylate of which the acid moiety possesses the same structure as that of the starting acid.
In a preferred method the reaction of the aldehyde, of the compound generating CN ions and of the acid or its functional derivative is carried out by phase transfer catalysis, in an aqueous medium, in the presence of a basic agent, preferably tetradecyltrimethylammonium bromide and of a solvent immiscible with water, e.g.
toluene.
In the process according to the invention, functional derivatives of the acid which may be used include, for example, the chloride and anhydride. The compound generating CN ions is preferably an alkaline cyanide, such as e.g. sodium or potassium cyanide but, for example, tetraethyl-ammonium cyanide, 1-methyl-1-ethylethanonitrile or cuprous cyanide may alternatively be used if desired.
Where it is desired to separate the two diastereoisomers of the (Rs)a-cyano-6-phenoxy-2-pyridylmethyl 2,2-dimethyl-3-(2,2-dihalovinyl)-cyclopropane-1 -carboxylate separation may, for example, be carried out by chromatography. Separation of one of the two diasteroisomers may, however equally, if desired, be carried
out by crystallization.Thus, for example where the racemic alcohol ester obtained is either (RS)a-cyano-6
phenoxy-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-1 -carboxylate; (RS)a
cyano-6-phenoxy-2-pyridyl methyl 1 R, trans 2,2-dimethyl-3-(2,2-dibromovinyl )cyclopropane-1 -carboxylate;
or (RS)a-cyano-6-phenoxy-2-pyridyl methyl 1 R, trans 2,2-dimethyl-3-(2,2-difluorovinyl )-cyclopropane-1 - carboxylate there may be isolated by crystallization respectively the (R)a-cyano-6-phenoxy-2-pyridylmethyl
1 R, trans 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-1-carboxylate. (R)a-cyano-6-phenoxy-2
pyridylmethyl ZR, trans 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropane-1 -carboxylate;; or (R)a-cyano-6- phenoxy-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-difluorovinyl)cyclopropane-1-carboxylate di
astereoisomer.
According to a further feature of the invention there are provided pesticidal compositions, and in particular
insecticidal and acaricidal compositions, comprising, as active ingredient at least one compound of formula I
according to the invention in association with a carrier or excipient. Thus, for example, the invention
includes such compositions in the form of acaricidal compositions adapted for veterinary use.
The compositions according to the invention can, for example, be presented in the form of powders,
granules, suspensions, emulsions, solutions, solutions for aerosols, combustible strips, baits or other
preparations classically employed for the utilization of this class of compounds.
In addition to the active principle, these compositions contain, in general, a vehicle and/or surface-active
agent, non-ionic, to ensure a uniform dispersion of the substances which constitute the mixture. The vehicle
may be a liquid such as e.g. water, an alcohol, a hydrocarbon or some other organic solvent, a mineral,
animal or vegetable oil, or a powder such as e.g. talc, clay, a silicate or kieselguhr.
The insecticidal or acaricidal compositions according to the invention preferably contain from 0.2 to 90%
of active material.
To enhance the insecticidal activity of the compound of the invention a synergist may be used e.g. one of the classical synergists utilized in similar cases such as e.g. 1 -(2,5,8-trioxadodecyl-2-propyl-4,5
methylenedioxy-benzene (piperonyl butoxide) or N-(ethyl heptyl)bicyclo[2,2,1]-5-heptene-2,3-dicarboximide.
The following non-limiting examples serve to illustrate the present invention.
Example 1- {RS)a-cyano-6-phenoxy-2-pyridylmethyl 1R, trans2,2-dimethyl-3-F2,2-dichlorovinyl)cyclopropane-1- carboxylate
19.9 g of sodium cyanide and 0.360 g oftetradecyltrimethylammonium bromide are introduced into 216
cm3 of water, followed slowly and at 23"C, by a solution of 72 g of 6-phenoxy-2-picoline aldehyde, 0.360 g of
tetradecyltrimethylammonium bromide and 84.7 g of 1 R, trans 2,2-dimethyl-3-(2,2
dichlorovinyl)cyclopropane-1 -carboxylic acid chloride in 290 cm3 oftoluene (the acid chloride being
introduced last into the solution.) After agitating for 21 hours at 23"C under an inert atmosphere, the organic
phase is separated by decanting, washed with water, dried and concentrated to dryness by distillation under
reduced pressure. Isopropanol is added to the residue and the mixture obtained is again concentrated to
dryness. 158 g of (RS)a-cyano-6-phenoxy-2-pyridyl methyl 1 R, trans 2,2-dimethyl-3-(2,2 dichlorovinyl)cyclopropane-l -carboxylate are obtained.
Example 2 (R)a-cyano-6-phenoxy-2-pyridylmethyl 1R, trans 2,2-dim eth yl-3-(2,2-dichloro vin yl)cyclopropane- 1
carboxylate
The 158 g of (RS)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2
dichlorovinyl)cyclopropane-1-carboxylate obtained in Example 1 is crystallized from isopropanol.75.2 g of (R)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-dichlorovinyl )cyclopropane-1 carboxylate are obtained.
M.Pt = 102"C, [alD = -8 (c = 3% toluene).
Analysis: C11H1803N2C12 (417.29)
Calculated; C% 60.44 H% 4.34 N% 6.71 01% 16.99
Found: 60.6 4.3 6.7 17.3
NMR Spectrum (deuterochloroform)
Peaks at 1.23 - 1.32 p.p.m. attributed to the hydrogens of the twinned methyls.
Peaks at 1.65 - 1.73 p.p.m. attributed to the hydrogen in position 1 of the cyclopropyl.
Peaks at 2.17 - 2.25 - 2.30 - 2.38 p.p.m. attributed to the hydrogen in position 3 of the cyclopropyl.
Peaks at 5.53; 5.67 p.p.m. attributed to the ethylene hydrogen.
Peak at 6.32 p.p.m. attributed to the hydrogen carried by the same carbon as the -CN.
Example 3 (S)a-cyano-6-phenoxy-2-pyridylmethyl 7R, trans 2,2-dimethyl-3-(2,2-dichlorovinyljcyclopropane- 1carboxylate
The mother liquors obtained from the crystallization of the 158 g of (RS)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-1 -carboxylate in Example 2 are concentrated to dryness under reduced pressure. The residue is chromatographed under pressure eluting with petroleum ether (B.Pt.35-70"C) and diisopropyl ether. 38.68 g of (S)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-1 -carboxylate are obtained.
[a]D = +20 .5 (c = 4% toluene).
NMR Spectrum (deuterochloroform)
Peaks at 1.20 - 1.24 p.p.m. attributed to the hydrogens of the twinned methyls.
Peaks at 1.65 - 1.74 p.p.m. attributed to the hydrogen in position 1 of the cyclopropyl.
Peaks at 2.2 - 2.28 - 2.40 - 2.42 p.p.m. attributed to the hydrogen at position 3 of the cyclopropyl.
Peaks at 5.55 - 5.68 p.p.m. attributed to the ethylene hydrogen.
Peak at 6.32 p.p.m. attributed to the hydrogen carried by the same carbon at the CN.
Peaks at 6.83 - 7.9 p.p.m. attributed to the aromatic nuclei.
Example 4 (RS)a-cyano-6-phenoxy-2-pyridylmethyl 1R, cis Z2-dimethyl-3-(2,2-d/chlorn vinyl)cyclopropane- 1- carboxylate
1.352 g of sodium cyanide and 0.025 g of tetra-decyltrimethylammonium bromide are introduced into 15 cm3 of water, followed slowly at 25"C, by a solution of 4.99 of 6-phenoxy-2-picoline aldehyde, 0.025 g of tetradecyltrimethylammonium bromide and 6.15 g of 1 R, cis 2,2-dimethyl-3-(2,2-dichlorovinyl)cycloprnpane 1-carboxylic acid chloride in 20 cm3 of toluene. After agitating under an inert atmosphere for 15 hours at 23"C, the resultant mixture is allowed to stand. The organic phase is separated by decanting and washed with water.The aqueous phases are combined and washed with toluenethen concentrated to dryness by distillation under reduced pressure. 10.8 g of crude (RS)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, cis 2,2-di methyl-3-(2,2-dich lorovinyl)cyclopropane-1 -carboxylate are obtained.
NMR Spectrum (deuterochloroform)
Peaks at 1.80 - 1.90 - 1.93 p.p.m. attributed to the hydrogens of the twinned methyls and to the hydrogens of the methyl.
Peaks at 2.83 - 3.5 p.p.m. attributed to the hydrogens of the cyclopropyl.
Peaks at 9.17 - 9.36 p.p.m. attributed to the ethylene hydrogen of the vinyl chain.
Peak at 9.48 p.p.m. attributed to the hydrogen carried by the carbon a two the CN.
Peaks at 10.3 - 10.46 - 11.5 - 11.7 - 11.8 p.p.m. attributed to the pyridine nucleus.
Peaks at 10.7 - 11.3 p.p.m. attributed to the other aromatic hydrogens.
Example 5 (R)a-cyano-6-phenoxy-2-pyridylmethyl 1R, cis 22-dimethyl-3-/2,2-dichloro vin y/lcyclopropane- 1-carboxylate
Under pressure 10.4 g of (RS)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, cis 2,2-dimethyl-3-(2,2dichlorovinyl)-cyclopropane-1-carboxylate are chromatographed on silica gel, eluting with a mixture of petroleum ether (B.Pt. 35-70"C) and diisopropyl ether (80-20). 4.812 g of (R)a-cyano-6-phenoxy-2pyridylmethyl 1 R, cis 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-1 -carboxylate are obtained.
[a]D = -17 (c = 4% toluene).
NMR Spectrum (deuterochloform)
Peak at 1.29 p.p.m. attributed to the hydrogens of the twinned methyls.
Peak at 6.32 p.p.m. attributed to the hydrogen carried by the same carbon as the CN.
4.75 g of the product obtained is chromatographed again on silica, eluting with methylene chloride.
3.992 g of purified (R)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, cis 2,2-dimethyl-3-(2,2 dich lorovinyl )cyclopropa ne-1 -carboxylate are obtained.
Analysis: C11H1803N2C12 (417.89)
Calculated: C% 60.44 H%4.34 N%6.71 Cl%16.99 Found 60.3 4.3 6.5 17.2
Example 6 (S) a-c yano-6-ph en ox y-2-p yrid ylmeth yl 1R, c/s 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane- 1-carboxylate The chromatography of the 10.4 g of (RS)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, cis 2,2-dimethyl-3-(2,2dichlorovinyl)cyclopropane-1-carboxylate described in Example 5 is continued. 2.97 g of (S)a-cyano-6phenoxy-2-pyridylmethyl 1 R, cis 2,2-dimethyl-3(2,2-dichlorovinyl)cyclopropane-1 -carboxylate are obtained.
[a]D = +24o (c = 4% toluene).
NMR Spectrum (deuterochloroform) Peaks at 1.20 - 1.27 p.p.m. attributed to the hydrogens of the twinned methyls.
Peak at 5.3 p.p.m. attributed to the hydrogen carried by the same carbon as the CN.
Peaks at 6.14 - 6.23 p.p.m. attributed to the ethylene hydrogen.
Peaks at 1.87 - 1.97 p.p.m. attributed to the hydrogen in position 1 of the cyclopropyl.
Peaks at 6.89 - 7.88 p.p.m. attributed to the hydrogens of the aromatic nuclei.
2.92 g of the product are chromatographed again on silica eluting with methylene chloride. 2.307 g of purified (S)α-cyano-6-phenoxy-2-pyridylmethyl IR, cis 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-1- carboxylate are obtained.
Analysis: C21H18O3N2Cl2(417.89)
Calculated: 0% 60.44 H%4.34 N% 6.71 Cl% 16.99
Found: 60.2 4.4 6.6 17.1
Example 7 (RS)α-cyano-6-phenoxy-2-pyridylmethyl lR, cis2,2-dimethyl-3-{2,2-dibromovinyl)cyclopropane- 1carboxylate
Operating as indicated in Example 1, starting with 5.55 g of sodium cyanide, 0.22 g of tetradecyltrimethylammonium bromide, 20 g of 6-phenoxy-2-picoline aldehyde and 33.1 g of XR, cis 2,2-dimethyl-3 (2,2-dibromovinyl)cyclopropane-1 -carboxylic acid chloride, 51 g of the desired product are obtained
Analysis: C21H18O3N2Br2 (506.20)
Calculated: C% 49.82 H% 3.58 N%5.53 Br% 31.57
Found: 49.7 3.6 5.4 31.6.
Example 8 (R)α-cyano-6-phenoxy-2-pyridylmethyl 1R, cis 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropane- 1-carboxylate
Under pressure, 10 g of the product obtained in Example 7 are chromatographed on silica gel, eluting with a mixture of petroleum ether (B.Pt. 35-70'C) and diisopropyl ether (80-20).42 g of the desired (R) isomer are obtained. (Rf = 0.68).
[α]D = -17 5 1 5 (c = 1%toluene). M.Pt. = 78 C
Analysis: C21H1803N2Br2 (506.20)
Calculated: C% 49.82 H% 3.58 N% 5.53 Br% 31.57
Found. 49.9 3.5 5.6 31.5
Example 9 (S)α-cyano-6-phenoxy-2-pyridylmethyl iF?, cis 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropane-1-carboxylate
The chromatography described in Example 8 is continued to give 3.85 g of the desired (S) isomer.
(Rf = 0.59).
[a3D+20o5 1 5 (c = 1%toluene).
Analysis: C21H1803N2Br3 (506.20)
Calculated: C% 49.82 H% 3.58 N% 5.53 Br% 31.57
Found: 50.0 3.7 5.5 31.5
Example 10 (RS)α-cyano-6-phenoxy-2-pyridylmethyl 1R, trans 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropane- 1carboxylate
Operating as indicated in Example 7, starting with 33.1 g of 1 R, trans 2,2-dimethyl-3-(2,2 dibr6movinyl)cyclopropane-l -carboxylic acid chloride, 54.5 g of the desired product are obtained.
Example ii (R)α-cyano-6-phenoxy-2-pyridylmethyl 1R, trans2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropane-1- carboxylate
The product obtained in Example 10 is crystallized from 200 cm3 of isopropanol by cooling after dissolution under reflux. The crystals formed are separated and washed with isopropanol. 21.75 g of the desired product are obtained. M.Pt. = 11000.
= = +7 5 (e 10(c=1%toluene).
Analysis: C21H18O3N2Br2 (506.20)
Calculated: C%49.82 H%3.58 N% 5.53 Br%31.57
Found: 49.9 3.5 5.6 31.4 Example 92 (S)α-cyano-6-phenoxy-2-pyridylmethyl 1R, trans2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropane-1- carboxylate
The mother liquors of crystallization obtained in Example 11 are recovered, concentrated to dryness and the residue is chromatographed under pressure on silica, eluting with a mixture of petroleum ether (B.Pt.35-70 C) and diisopropyl ether (80-20). 5.9 g of the desired product are obtained. (Rf = 0.55).
[a]D = +27 5 (c = 1% toluene).
Analysis: C21H1803N2Br2 (506.20)
Calculated: C% 49.82 H% 3.58 N% 5.53 Br% 31.57
Found: 49.9 3.5 5.6 31.4
Example 13 (R,S)α-cyano-6-phenoxy-2-pyridylmethyl 1R, cis 2,2-dimethyl-3-(2,2-difluorovinyl)cyclopropane- 1carboxylate
Operating as indicated in Example 1, starting with 2.1 g of sodium cyanide, 0.08 g of tetradecyltrimethylammonium bromide, 7.6 g of 6-phenoxy-2-picoline aldehyde and 8.2 g of 1 R, cis 2,2-dimethyl-3-(2,2difluorovinyl)-cyclopropane-1 -carboxylic acid chloride, 15.1 g of the desired product are obtained.
Example 14 (R)a-cyano-6-phenoxy-2-p yr/dylmethyl 1R, cis 2,2-dimethyl-3-(2,2-difluorovinyl)cyclopropane- 1-carboxylate
The 15.1 g of product obtained in Example 13 is chromatographed under pressure on silica gel, eluting with a mixture of petroleum ether (B.Pt. 35-70 C) and diisopropyl ether (80-20). 6.5 g of the desired (R) isomer are obtained. (Rf = 0.39).
[a]D= 16"5 (e = 1.5% toluene).
Analysis: CP1H1803N2F2 (384.38)
Calculated: C% 65.62 H% 4.72 N% 7.29
Found: 65.5 4.7 7.2
Example 15 fSlcr-cyano-6-phenoxy-2-pyridylmethyl 1R, cis 2,2-dimethyl-S-(2,2-difluorovinyl)cyclopropane- 1-carboxylate
The chromatography described in Example 14 is continued to give 3.8 g of the desired (S) isomer.
(Rf = 0.33).
{a1= = +19 (c= 1.5%toluene).
Analysis: C21H1803N2F2 (384.38)
Calculated: C% 65.62 H% 4.72 N% 7.29
Found: 65.5 4.7 7.1
Example 16 (R,S)α-cyano-6-phenoxy-2-pyridylmethyl 1R, trans 2,2-difluorovinyl)cyclopropane- 1-carboxylate
Operating as indicated in Example 1, starting with 2.3 g of sodium cyanide, 0.08 g of tetradecyltrimethylammonium bromide, 8.85 g of 6-phenoxy-2-picoline aldehyde and 8.85 g of 1 R, trans 2,2-dimethyl-3-(2,2 difluorovinyl)cyclop.ropane-1-carboxylic acid chloride, 16.7 g of the desired product are obtained.
Example 17 (RJa-cyano-6-phenoxy-2-pyridylmethyl 1R, trans2,2-dimethyl-3-r2,2-difluorovinylJcyclopropane-l- carboxylate
The 16.7 g of product obtained in Example 16 is chromatographed under pressure on silica gel, eluting with a mixture of petroleum ether (B.Pt. 35-70 C) and diisopropyl ether (80-20). 8 g of the desired (R) isomer are obtained. (Rf = 0.75).
[a]D = -20" + 1"5 (e = 1%toluene).
Analysis: C21H1803N2F2 (384.38)
Calculated: C% 65.62 H%4.72 N%7.29 F%9.88
Found: 65.5 4.9 7.3 9.8
Example 18 (S)α-cyano-6-phenoxy-2-pyridylmethyl 1R, trans 2,2-dimethyl-3-62,2-difluorovinyl cyclopropane- 1carboxylate
The chromatography described in Example 14 is continued to give 5.8 g of the desired (S) isomer.
(Rf = 0.70).
[a]D = 0 (c = 1%toluene) Analysis: C21H1803N2F2 (384.38)
Calculated: C%65.62 H%4.72 N%7.29 F%9.88
Found: 65.5 4.8 7.3 9.6
Example 19: Composftion according to the invention
(R)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane- 1-carboxylate ........................................ 0.02 g
Tween 80* ............................................ 5.0 g Topanol A** .......................................... 0.1 g Xylene ........................................ 94.88 g * Merck Index 9th edition page 7360
**or 2,4-dimethyl-6-terbutyl-phenol Example 20:Composition according to the invention (S)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, cis
2,2-dimethyl-3-(2,2-dich lorovinyl )cyclopropane
f-carboxylate ........................................ 0.03g Atlox 4851 * ........................................ 6.0g Atlox4855** v 3.0 g
Xylene ........................................ 90.97 g
*Mixture of alkyl aryl sulphonate and of polyoxyethylene
triglyceride, viscosity at 25 C, 300-700 cps.
** Mixture of alkyl aryl sulphonate and of polyoxy ethylene
triglyceride, viscosity at 25 C, 1500-1900 cps.
Example 21: Acaricidal composition for veterinary use
according to the invention
Solutions corresponding to the following formulation were prepared: (R)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, cis
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-
1-carboxylate 5 9 5g Piperonyl butoxide ........................................ 25 g Polysorbate80 10 9 10g Triton X 100 ........................................ 25 g
Tocopherol acetate ........................................ 1 g
Ethyl alcohol q.s.for ........................................ 100 ml
In this way a solution is obtained which is diluted in 5 litres of water for use.
Study of the insecticidal activity of compounds accordng to the invention
The tests described hereinafter have been carried out on: (S)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, cis 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-1- carboxylate (compound A),
(R)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, cis 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropane-1- carboxylate (compound B), (S)α-cyano-6-phenoxyl-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-dichlorovinyl )cyclopropane-1
carboxylate (compound C),
(R)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-dichiorovinyl )cyclopropane 1
carboxylate (compound D).
A) Study of the lethal effect on the domestic fly
The test insects are 4 day old female domestic files. 1 1ll of a solution of the test compound in acetone is administered topically to the dorsal thorax of the insects with an Arnold micro-manipulator. 50 individuals are used per treatment. The mortality check is made 24 hours after treatment.
The experimental results, summarized in the following Table, are expressed in LD50, i.e. the dose necessary to kill 50% of the insects.
LD 50
Compound A 8 mg/l
Compound B 8 mg/l
Compound C 18 mg/l
Compound D 17 mg/l
Conclusion: The compounds A, B, C and D possess a useful insecticidal activity against the domestic fly.
B) Study ofthe knock-down activity on the domestic fly
The tested insects are 4 day old female domestic flies. The test compound is directly atomized into a
Kearns and March chamber, using as solvent a mixture of equal volumes of acetone and kerosene (quantity of solution used, 2 x 0.2 cm3). About 50 insects are used per treatment Checks are made every minutes up to 10 minutes, then at 15 minutes and the KT 50 is determined by the usual methods.
The experimental results obtained are summarized in the following Table:
KT50
Compound A 3 mn
Compound B 2.45 mn
Compound C 2 mn
Compound D 3.30 mn
Conclusion: The compounds A, B, C and Dare endowed with a knock-down effect against the domestic fly.
C) Study ofthe insecticidal activity on Blatella Germanica
Jars of about 1 litre are used, closed with a tergal gauze.
The compound to be tested is dissolved in acetone at various concentrations. This solution is introduced into the jar, then evaporated into the atmosphere of the laboratory.
The cockroaches are introduced into the jars.
The percentage mortality is determined at the end of 5 days, as compared to an untreated control test.
The experimental results obtained, expressed in LC 50 (lethal concentration 50), in mg/m2 are summarized in the following Table:
LC 50
Compound A 0.125 mg/m2
Compound B 0.200 mg/m2
Compound C 0.250 mg/m2
Compound D 0.700 mg/m2
Conclusion: The compounds A, B, C and D are endowed with useful insecticidal activity against Blatella
Germanica.
D) Study ofthe lethal effect on larvae ofSpodoptera littorals
The tests are carried out by topical application of an acetone solution, using an Arnold micro manipulator, to the dorsal thorax of the larvae. 10 to 15 larvae are used per dose of product to be tested. The larvae used are larvae of the fourth larval stage, that is to say about 10 days old when raised at 24OC at 65% relative humidity. After treatment the individuals are placed on an artificial nutrient medium (Poitoit medium).
The mortality check is carried out 48 hours after treatment.
The experimental results, expressed in LD 50, are summarised in the following Table:
LD 50
Compound A 3.6 mg/l
Compound B 4.0 mg/l
Compound C 0.9 mg/i Compound D 1.5 mg/l
Conclusion: the compounds A, B, C and D are endowed with strong insecticidal activity with respect to larvae of Spodoptera littoralis.
E) Study of the insecticidal activity on larvae ofEpilachna varivestris
The tests are carried out by topical application in a manner similar to that used for the larvae of
Spodoptera. Larvae in the penultimate larval stage are used and aftertreatmentthe larvae are fed with haricot bean slips. The mortality check is carried out 72 hours after treatment.
The experimental results, expressed in LD 50, are summarized in the the following Table:
LD 50
Compound A 2 mg/l
Compound B 1.5 mg/l
Compound C 0.3 mg/l
Compound D 0.3 mg/l
Conclusion: the compounds A, B, C and D are endowed with strong insecticidal activity with respect to
Epilachna Varivestris.
F) Test on Aphis fabae
This is a plots test carried out in the open air on bean plantations. Each plot of beans, measuring 360 x 120
cm, contains 4 rows of beans. When the natural contamination by Aphis fabae is estimated to be sufficient,
an aqueous solution containing the insecticide is sprayed on to each of the plots. 2 plots (= 2 repeats) are
taken per dose of product. The treatment is carried out on the basis of 2 litres of insecticidal spray per basic
plot. Population checks are carried out 1 hours before treatment, then 2 weeks aferthe application.
The LD 50 are determined. The experimental results are given below:
LD 50
Compound A 0.5 mg/l
Compound B 0.65 mg/l
Compound C 0.75 mg/i Compound D 0.4 mg/l
Conclusion: the compounds A, B, C and D are endowed with strong insecticidal activity with respect to the
bean aphis.
Study of the acaricidal activity of the compounds A, B, C and D
Tests on tetranychus urticae
Haricot bean leaves are used, infected with 25 adults of Tetranychus urticae per leaf and smeared with
bird-lime on their periphery. The haricot bean leaves thus infected with acarids are divided into two groups:
a) Afirst group is treated with the compound to be tested. Treatment is carried out by spraying an aqueous
solution of the compound to be tested onto the leaves, using various concentrations.
b) A second group of leaves used as a control group is not treated.
The dead adults are counted at the end of 48 hours after the treatment.
The experimental results obtained, expressed in LD 50, are summarized in the following Table:
LD 50
Compound A 3 gel Compound B 3.2 g/hl
Compound C 2.8 g/hl
Compound D 5 g/hl
Conclusion: The compounds A, B, C and Dare endowed with good acaricidal activity with respect to
Tetranychus urticae.
Study of the activity on acarids found on animals of the compounds A and B a) Study of the activity on larva of Boophilus Microplus
The substance to be tested is dissolved in a mixture of dimethylformamide, emulsifiers and Arcopal so as
to obtain a 10% emulsifying concentrate. This concentrate is diluted with water to obtain solutions of desired
concentration of 100, 10 and 1 p.p.m.
By means of a spraying turret the different solutions above are sprayed onto the larvae of ticks of tropical
cattle of type Boophilus Microplus, and after 24 hours the percentage mortality is determined by counting
the dead and live larvae.
The results are as follows:
Doses of product Compound A Compound B
in p.p.m. % mortality % mortality
100 100 100
10 100 100
1 68 88
Conclusion: The compounds A and B show, remarkable activity.
b) Study of the activity on the inhibition of the reproduction of Boophilus Microplus ticks
Females of Boophilus Microplus, ready to lay, are immersed for 5 minutes in the above prepared solutions, then they are taken into a heated enclosure for laying.
a) The percentage of ticks which have not laid, b, the amount of eggs laid as a function of a control, and
c) the percentage of larvae which have hatched are determined.
As a function of the numbers obtained the percentage inhibition of the production is calculated; 100% signifies that the inhibition is complete and 0% that the reproduction is identical to that obtained with the controls. There are obtained:
% inhibition % inhibition
Doses in p.p.m. (compound A) (compound B)
100 100 100
50 92 100
25 58 93
12.5 35 87
6.2 31 76
3.1 25 48
1.5 24 53
0.75 16 24
0.38 11 33
0.19 34 17
Conclusion: The compounds A and B show remarkable activity.
Claims (23)
1. Compounds of general formula I,
wherein X1 and X2, which may be the same or different, each represents a fluorine, chlorine or bromine atom, the acid moiety being either of 1 R, cis or of 1 R, trans structure and the alcohol moiety being of (R), (S) or (RS) configuration.
2. Compounds as claimed in claim 1 wherein X1 and X2 are the same.
3. Compounds as claimed in claim 1 as herein specifically disclosed in any one of Examples 1 to 18.
4. A process for preparing compounds of general formula I as defined in claim 1 which comprises reacting 6-phenoxy-2-picoline aldehyde in aqueous medium, with a compound generating CN ions and either with a 1 R, cis or with a 1 R, trans 2,2-dimethyl-3-(2,2-dihalovinyl)-cyclopropane-1 -carboxylic acid of formula II,
(wherein X1 and X2 are as defined in claim 1) or with a functional derivative of the said acid, to give an (RS) -cyano-6-phenoxy-2-pyridylmethyl (2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropane-1 -carboxylate of formula I in which the acid moiety has the same structure as the starting acid, followed, if desired, by separation of the two diastereisomers of the alcohol esters of (RS) configuration by a physical method to give an (R)a-cyano-6-phenoxy-2-pyridylmethyl 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropane-1 -carboxylate and a (S)a-cyano-6-phenoxy-2-pyridylmethyl 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropane-1 -carboxylate of which the acid moiety possesses the same structure as that of the starting acid.
5. A process as claimed in claim 4wherein the reaction of the aldehyde, of the compound generating CN ions and of the acid or of its functional derivative is carried out by phase transfer catalysis, in an aqueous medium, in the presence of a basic agent and of a solvent immiscible with water.
6. A process as claimed in claim 5 wherein the basic agent is tetradecyltrimethylammonium bromide and the solvent immiscible with water is toluene.
7. A process as claimed in any one of claims 4 to 6 wherein the two diastereoisomers of the (RS)a-cyano-6-phenoxy-2-pyridylmethyl 2,2-dimethyl-3-(2,2-dihalovinyl)-cyclopropane-1 -carboxylate are separated by chromatography.
8. A process as claimed in any one of claims 4 to 6 wherein one of the two diastereoisomers of the
(RS)a-cyano-6-phenoxy-2-pyridylmethyl 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropane1 -carboxylate is
separated by crystallisation.
9. A process as claimed in claim 8 wherein the racemic alcohol ester is (RS)a-cyano-6-phenoxy-2- pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-dichiorovinyl )cyclopropane-l -carboxylate and the di
astereoisomer isolated by crystallisation is (R)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3 (2,2-dichlorovinyl)cyclopropane-1 -carboxylate.
10. A process as claimed in claim 8 wherein the racemic alcohol ester is (R,S)a-cyano-6-phenoxy-2
pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-dibromovinyl)cyclorpropane-1 -carboxylate or (R,S)a-cyano-6
phenoxy-2-pyridyl methyl 1 R, trans 2,2-dimethyl-3-(2,2-difluorovinyl)-cyclopropane-1 -carboxylate and the
diastereoisomer isolated by crystallisation is respectively (R)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, trans
2,2-dimethyl 3-(2,2-dibromovinyl)cyclopropane-1 -ca rboxylate or (R)a-cyano-6-phenoxy-2-pyridylmethyl 1 R, trans 2,2-dimethyl-3-(2,2-difluorovinyl)cyclopropane-1-carboxylate.
11. A process for the preparation of compounds as claimed in claim 1 substantially as herein described.
12. A process for the preparation of compounds as claimed in claim 1 substantially as herein described in
any one of Examples 1 to 18.
13. Compounds as claimed in claim 1 whenever prepared by a process as claimed in any one of claims 4
to 12.
14. Pesticidal compositions comprising, as active ingredient, at least one compound of formula las claimed in claim 1 in association with a carrier or excipient.
15. Acaricidal compositions comprising as active ingredient, at least one compound of formula I as
claimed in claim 1 in association with a carrier or excipient.
16. Insecticidal compositions comprising as active ingredient, at least one compound of formula I as
claimed in claim 1 in association with a carrier or excipient.
17. Compositions as claimed in claim 15 or claim 16 containing from 0.2 to 90% by weight of active
ingredient.
18. Pesticidal compositions as claimed in claim 14 substantially as herein described.
19. Pesticidal compositions substantially as herein described in any one of Examples 19 to 21.
20. Compounds as claimed in claim 1 for use as pesticides.
21. A method of combating pests which comprises applying to a site infested with or susceptible to
infestation by pests an effective amount of a compound as claimed in claim 1.
22. A method as claimed in claim 21 wherein the pests are insects and/or acarids.
23. Each and every novel method, process, compound and composition herein disclosed.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7921744A FR2464253A1 (en) | 1979-08-30 | 1979-08-30 | CYCLOPROPANE CARBOXYLIC ACID ESTERS, PROCESS FOR THEIR PREPARATION AND PESTICIDE COMPOSITIONS COMPRISING THE SAME |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2061919A true GB2061919A (en) | 1981-05-20 |
Family
ID=9229206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8028014A Withdrawn GB2061919A (en) | 1979-08-30 | 1980-08-29 | Cyclopropane carboxylates |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5634667A (en) |
| DE (1) | DE3032617A1 (en) |
| FR (1) | FR2464253A1 (en) |
| GB (1) | GB2061919A (en) |
| IT (1) | IT1145446B (en) |
| NL (1) | NL8004945A (en) |
| OA (1) | OA06590A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4163787A (en) * | 1977-03-14 | 1979-08-07 | The Dow Chemical Company | Substituted pyridine methyl esters of cyclopropane carboxylic acids and their use as insecticides |
| DE2829329A1 (en) * | 1977-07-05 | 1979-01-25 | Ciba Geigy Ag | Pyridyl:oxy-benzyl cyclopropane carboxylate ester(s) - useful as pesticides esp. against insects and acarids |
-
1979
- 1979-08-30 FR FR7921744A patent/FR2464253A1/en active Granted
-
1980
- 1980-07-24 OA OA57184A patent/OA06590A/en unknown
- 1980-08-29 DE DE19803032617 patent/DE3032617A1/en not_active Withdrawn
- 1980-08-29 JP JP11853380A patent/JPS5634667A/en active Pending
- 1980-08-29 IT IT49573/80A patent/IT1145446B/en active
- 1980-08-29 NL NL8004945A patent/NL8004945A/en not_active Application Discontinuation
- 1980-08-29 GB GB8028014A patent/GB2061919A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| FR2464253B1 (en) | 1984-07-27 |
| NL8004945A (en) | 1981-03-03 |
| IT1145446B (en) | 1986-11-05 |
| JPS5634667A (en) | 1981-04-06 |
| OA06590A (en) | 1981-08-31 |
| IT8049573A0 (en) | 1980-08-29 |
| DE3032617A1 (en) | 1981-04-09 |
| FR2464253A1 (en) | 1981-03-06 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |