JPS5885844A - Carboxylic ester - Google Patents

Abstract

NEW MATERIAL:A compound of formulaI[R<1> is 2,2-dimethyl-3-(2,2-dimethylvinyl)cyclopropyl, etc.; R<2> is H or cyano; R<3> and R<4> are H, alkyl, allyl, aryl which may have a substituent group, etc.]. EXAMPLE:alpha-Cyano-3-(N,N-diallylaminomethyl)benzyl 2,2-dimethyl-3-(2,2-dimethylvinyl)cyclopropanecarboxylate. USE:An insecticide, effective for sanitary injurious insects, e.g. mosquitoes or flies, having higher light stability than the well-known compound of the pyrethroid type compound, and further effective as agricultural and horticultural insecticides for injurious insects, e.g. oriental tobacco budworm, tobacco cutworm or tetranychids. PROCESS:A carbyxlic acid halide of formula II (Z is a halogen, e.g. Cl) is reacted with an alcohol of formula III in an inert solvent, e.g. benzene, in the presence of a deacidifying agent, e.g. pyridine, to give the compound of formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel carboxylic acid esters. In detail, the present invention relates to carboxylic acid ester 1IIK, which is effective as an insecticide for agriculture, horticulture, or epidemic prevention.

Conventionally, DDT has been used as an agricultural and horticultural pest control insecticide.
A large number of organic chlorine compounds such as %BHO, organophosphorus insecticides such as barathion and malathion, and carbamate insecticides such as carbaryl and menmyl have been used in agriculture.
*It has been used in large quantities to eliminate pests and sanitary pests, and has greatly contributed to the prevention of agricultural crops.

However, in recent years, these insecticides have become problematic, such as environmental pollution, and their residual and accumulation problems. In addition, 0% of these 0% OK products have developed resistant pests due to long-term use.

The present inventors have proposed the above 0. AK has been working hard to develop pyrethroid compounds, which generally have low durability, are biodegradable in the environment, have little persistence, and are known to have no seismic bioproducts. As a result of intensive research, it was discovered that a specific carboxylic acid ester represented by the following general formula (I) has an excellent insecticidal effect, and the present invention has been brought to fruition.

That is, the key point W of the present invention is the general formula (wherein ljs is co, -1 dimethyl-,7-(J,!-
dimethylvinyl) Schiftabil group, ko, J-d/thyl-5-(ko, kojiha 4gutvinyl) cyclo"hi"
ft, t tJ: '(dahalochenophenyl)inobutyl group; R represents a hydrogen atom or a cyano group; R Hatake, r are hydrogen atoms, alkyl groups, allyl groups which may be the same or different from each other , represents an aryl group which may have a substituent, and R'' and R' are bonded to each other to form a J-bitetralin-7-yl group%/-, a 'loricinyl group, 'eco, tei- triacyaludayl group,
or may form a 6-membered or more-membered heterocyclic group containing 11 atoms.

To explain the present invention below, the carboxylic acid esters of the present invention (hereinafter referred to as "compounds of the present invention") have the general formula CI
).

When considering IR hazy activity, in the general formula (1), R1 is co, Kodimethyl-J-(Co, J-dimethylvinyl)cyclopropyl group, Co, Kodimethyl-, 7=
(Co, J-dikuta rubinyl) cyclopropyl group, co, kodimethyl-J- (J, J-sifurombinyl) cyclotubiru group, co, J, J, J-? silamethylshitagastricpropyl group, or d/-(II-Yutaruphenyl)isobutyl group: formed by combining R1 and R4, ToJ
-Virolin-I-yl group and morpholino group are preferably I-indolyl group.

The food according to the invention can be easily produced, for example, by reactions such as those shown in (1) and (2) below.

(1) (1) (1) (mV)
(V) (1) (Above reaction formula ■
, 111 in ■. y, R' and have the same meanings as above, and represent a halogen atom of the ZFi chlorine group) In other words, in the method (2), a carboxylic acid halide represented by the general formula (1) and a carboxylic acid halide represented by the general formula (1) If reacted with alfur in an inert solvent such as penuzene, toluene or petroleum benzene in the presence of a deoxidizing agent such as pyridine or F-ethylamine, the reaction will be effective.

In the method (2), the carboxylic acid represented by the general formula (IV) is used as an alkali metal salt, which can be used even if a base and an acid are added simultaneously to form them during the reaction. When reacting with the halide represented by the general formula (V), the presence of a solvent such as dimethylformamide or benzene is required! tL<
, if the reaction is carried out at or below the boiling point of the solvent, it will turn out to be a jujube.

In addition, in the above general formula (1), when ft1 is a cyano group, 411 can be manufactured by the following method (2).

/ (1) (VI) (■) (In the above reaction formula, lj1%Ra and R4 have the same meanings as above, z represents a hydrogen atom such as salt fish bromine, and M Company sodium, potassium, etc. To further explain, the carbon halide represented by the general formula (1) and the aldehyde represented by the general formula (vl) are combined with water, sodium cyanide, a water-soluble cyanide,
Water-immiscible monotetratonic solvents such as n-hexano, toluene, dichloromethane and triethylbenzyl 7-4 emulsion compound, nat-2-! By reacting in the presence of a phase transfer catalyst such as 1-butyl ammonium pro-odide, an ester represented by the general formula (■) can be obtained. Next, the compound (I) of the present invention is obtained by reacting the ester represented by the general formula (■) with the amine or nitrogen-containing heterocyclic compound represented by the general formula (■) in a solvent in the presence of a deoxidizing agent. can be easily obtained.

As the solvent, benzene, toluene, ether, dichloromethane, dimethylformand, etc. are preferred, and as the deoxidizing agent, potassium carbonate, sodium hydride, etc. are preferred.

Further, it is usually sufficient to carry out the reaction at -10 to /DO°C for 7 to 10 hours.

The compound of the present invention thus obtained is effective as a killing agent for sanitary pests such as mosquitoes and insects. In addition, the compound of the present invention is more stable against light than conventional pyrethroid compounds; Therefore, agricultural pests such as cotton crop pests such as tapako moth, fruit tree pests such as spider mites, red aphids, and rice crop pests such as black-spotted staghorn aphid, etc.
M is also effective as an insecticide.

The Honjitsu 110 compound can be used as an insecticide even in the seven cases, but it can also be advantageously used as a fumigation agent such as emulsions, oils, powders, wettable powders, granules, and aerosols prepared by known methods. . At that time, other known insecticides may be used as necessary.
It is also possible to use a miticide or the like.

In addition, one compound of the present invention is tetrahydro-/-(J, methylenediokitaphenoxy)-kotoichi (3, dermethylenediosituenyl)-' HsJl! -711(
7,4l-0)7ten(5f*gamlin),!
-(J,It-methylenediokitaphenoxy)-J,4
．． ? -) Riokinau y decane (8esam・X), l-
Methyl-co (j, 11-methylenedioxyphenyl)
ethyl octylsul7oxy)' (8ux-foxi
l*), (J, tei-methylenedioxy-6-p4pylbenzyl)(butyl)diethylene glycol ether (
Piperonyl butoxle), G-n-
Propyl-J-methyl-Shimacoumethylenedioxy-1,
methylene diophenyl compounds such as λ, J, Tetrahydronaphthalene/, J-dicarboxylene (propyllsome), biveronal bis[-1(coptoxyethoxy)ethyl]acetal (Trotal); M (- 1 to ethyl.
- O-imide compounds such as dicarboxylic compound (M() ni 41); propylcope vinyl phenyl 7 osphoone) %O-4 softyl 〇'-7' lovargylzenyl phospho $-), o-10 pill -0'-Probargyl phenyl phosphonate, B, B, II-) Organophosphorus compounds such as butyl phosphatide and trithiony F, etc.
; i9ha, 7'a If propynyl compounds such as hinyl enitel, furohinyl oxime, propylene carbamate, etc. are used in combination, an even better insecticidal effect will be achieved due to their synergistic action and radiation enhancement effect. preferable.

Next, the present invention FRt[K will be specifically explained with reference to synthesis examples of the compounds of the present invention and insecticidal test examples using the compounds of the present invention.

Synthesis Example 1 α-Cyano-j-(IJ-diallylamitumethyl)benzyl co,J-dimethyl-Sc'= (co,dimethylvinyl)Schift carbonate plupokitalate (compound A
I> 1.1-Dimethyl-J-(J,J-dimethylvinyl)citarpancarboxylic acid El lid9. JJg<o,
ozahl), J-brimmethyl paezaldehyde9.
9! ICO, tl! A mixture of sodium cyanide a, Dedal l/(0,044 l), triethylbenzyl ammonium chloride o, Jtlp, hesene 10 (1- and water!-) was stirred at room temperature for 1 hour. .

Water was added to separate the organic layer, and the aqueous layer was further extracted with a small amount of benzene. The organic layers were combined and washed with saturated brine. After drying the organic layer with Glauber's salt, the solvent was distilled off under reduced pressure and the resulting oil was purified. α-cyano-3-bromomethylpenzylco, cordimethyl-j −
(J, J-dimethylvinyl) cyclopropane glutoxylate tz, 71 (yield 90%) was obtained, and its refractive index (nIs, e ) was ! It was Dako O.

The above α-cyano-3-bromomethylpenzylco, -1dimethyl-J-(co, -1dimethylvinyl)cyclopropanecarboxylate) 2,111 (0,00&mineru),
Violet, M-diallylamine o, b San 11 (o, oo mol), anhydrous potassium carbonate θ, t J I C0,0 (I
A mixture of water and 30 d of dry benzene was stirred at room temperature for 10 hours. Then, it was poured into water and extracted with benzene. The extract was washed with saturated brine and dried over sodium sulfate.

The oily substance obtained by distilling off the solvent under reduced pressure was subjected to silica gel column chromatography (eluent; benzene:ethyl acetate z10:/'
) l' (9 to carry out refinement.

The objective was to obtain 1α-cyano-J-(N, violet-diallylamitumethyl)benzyl-chodimethyl-J-(J,J-dimethylvinyl)cyclopropanecarboxylate whose refractive index (n;-)! Ii1,! ;/1 reference.

Synthesis example J-(/-indolylmethyl)penzylco, J.

3.3-Nato-2-methylcyclopropanecarboxylate (Kakkinobentei) Dry dimethylformide J51LIK%, ↓J.

J-tetramethylciclepropane carpo/acid 0.131
(0,003) The meeting was resolved and Nasylium Hydrogenide 0. Co01 (7 moles of 0.00 Da) was added and stirred until the generation of hydrogen gas stopped.

Next, a solution prepared by dissolving J-(/-indolylmethyj&/)pesodylprodone in dry dimethylformamide 3- was added dropwise, and the mixture was allowed to stand overnight at room temperature.

The solvent was condensed under reduced pressure, and then poured into water and extracted with ethyl ether. The organic layer was washed with saturated brine and then dried over sodium sulfate.

The resulting oil was purified by silica gel column chromatography (eluent: benzene; n-hexane=--l).

purpose. l-(/-indolylmethyl)benzyl J, J, J, J-tetramethylsif-propanecarboxylate is obtained, and its O@fold'It (n"-'
) ha/, j? It was J.J. Representative examples of nine invented metal products synthesized according to the above Synthesis Example 1 and Synthesis Example 1 are shown in the table below.

Test Example 1 Insecticidal test against adult house fly (local application method) Compound A-tei in Table 1! , 10% l1%l-tei, ib, 2
6. Dissolve predetermined amounts of 0 and J3 in acetone, and drop 1 μl of the solution per house fly onto the thoracic dorsal plate of house flies using a z/q syringe. The diameter of this drug-treated house fly is 8! α, placed on water-impregnated absorbent cotton in a styrene cup of height 4 IcIL. Next, this styrofoam cup was stored in a constant temperature room at 10°C. - After a certain period of time, the number of dead insects of house flies was investigated, and the Blis lethal dose (I, D) was determined.
,,) were calculated. The results are shown in the table. The test was conducted in series with 10 WRs in each section. Also, for reference, the results of one reaction using commercially available allethrin in place of the compound of the present invention are also listed.

Allethrin: (±)-J-allyl-co-methyl-deroxocyclobecyto-coenyl (±)-cis, trans-chrysanthemate [(±)-j-allyl-co-methyl-41-oxoayalop@nt-
1-*nyl (±)-cis, trans-ohr
ysanth@mate) Test Example Ko Insecticidal test against Spodoptera japonica (S side and insect body immersion method) Compound A in Table 7,! , 101l-1 and , J
, 7 was dissolved in acetone, and this was combined with the activator BorporI.
A chemical solution was prepared by diluting each compound with J 00 k (trade name, manufactured by Toho Chemical Co., Ltd.) so that the concentration of each compound was θOppm. At this time, the amount of acetone was set to be less than IIG of the total liquid amount.

The J instar larvae of Spodoptera f1.
It was immersed for D seconds. After the immersion treatment, excess chemical solution was removed using a piece of paper, and the sample was placed in a flat petri dish with a diameter of 9 CIK and a height of jcwL. This flat petri dish contains 6 ml of the chemical solution.
Cabbage leaves soaked for 0 seconds and then air-dried (yicll)
I put it in. Next, add the nine flat petri dishes containing the larvae! It was stored in a constant temperature room at ℃ for 1 hour. As a result, in each case, 100 times the insects were killed.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - Continued from page 11 0 shots by Hiroshi Kamiyama ・2000 Nagatsudacho, Yokohama 0 shots, written by Kazuo Ishii Tokyo Parts Ward Futaba 4-26-6 issue

Claims (1)

[Claims] (1) General formula J
[In the ceremony, R'FiJ,! -dimethyl-3-(J,J-dimethylvinyl)Schiff-propyl group, co,1-di'methyl-J-(J,!-shiba-tetragenovinyl)Schiff-bouvil group, J,J,J,J-tetra Methyl group also represents an isobutyl group; r represents a hydrogen atom type or a cyano group; Ra, R
'Fi water atoms which may be the same or slightly different;
an alkyl group, an allyl group, a substituent which is substituted with each other, a J-bisyl group, a l-bis-diyl group, a
% teco, ref-trifzol-ref-yl group, or
A 6-membered or more-membered heterocyclic group containing a nitrogen atom may be formed. ] Carboxylic acid esters.