JPS594409B2 - Production method of cyclopropane alkylene ester - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing new compounds.

The compounds produced by the method of the present invention are effective in controlling mites, particularly red mites. Red mites are plant pests that cause serious damage to fruit trees, crops, greenhouse plants and other plants. They are widely distributed and feed on the leaves or fruits of a very wide range of crops and trees. Tetranych
iNO. es) red mites such as Tetranychus urticae, Tetranychus canadensis
nadensis), Tetranychus cinnabarinus
, Tetranychu
spacificus), Bryovia praeciosa (
BryObiapraetiOsa), orif::'Gas platensis (01ig0nychusprate
nsis), Oligonicus irissis (01ig0ny
chusi1icis), Hanonicus citri (Pan
Onychuscitri), Panonicus urumi (P
Onychusulmi), and similar related species are of particular biological interest and economic importance.

Also Tarsonemidae
For example, Steneotarsonemas pallidus (Ste.
There is a mite called neOtarsOnemuspallidus). The following general formulas A and B (wherein, when X is -0- and n is 0, R is an alkyl group, an alkenyl group, or an alkynyl group, and X- is -0
- and when n is an integer of 1 to 4, R is an alkyl group, and
is -S- and n is o, R is an alkyl group, and p is o
When X is -0- and n is o, A is an alkynylene group, arylene group, alkylene group or cycloalkylene group, and when p is -0- and n is 2, A is arylene. group or alkynylene group, where p is 1 and w
is an alkylene group, X is -0- and n is 0, A is an arylene group or a cycloalkylene group, p is 1, π is an alkylene group, X is -o- and n is 2. The compound of the present invention represented by A is an arylene group is an effective repellent against mites.

Below, unless otherwise specified, X, R, . R', N, p and A are each as described above. General formulas A and C
The compound represented by is effective in suppressing the development of eggs, suppressing their normal development, leading to death, preventing them from progressing from one stage of growth to the next, or rendering them sterile. Applied to mites at the nymph stage.

Some of these compounds also exhibit persistent ovicidal effects. The compound of general formula A or B is 0.001% to 1% (
% by weight), usually from 0.01 to 0.1% by weight. Suitable carrier materials include liquid or solid inert carriers such as water, acetone, xylene, mineral oil, vegetable oil, talc, vermiculite and silica. The mite treatment according to the present invention is accomplished by spraying, dusting, or other direct or indirect contact with mites and/or their eggs or larvae. Generally, formulations with concentrations of up to 25% active compound are used, depending on the type of application device. Such formulations may contain emulsifying and wetting agents to facilitate application and to ensure efficacy of the active ingredient. Esters of general formulas A and B are suitable monohydric or dihydric alcohols, i.e. R-
0H or D −(k)p − A−(W)p −
It is produced by reacting 0H with at least 1 mole or 2 mole equivalents of an acid represented by the general formula or its acid halide.

This reaction is carried out in the absence of solvent. However, preference is given to using solvents which are inert to the reaction, such as ethers or hydrocarbon solvents. The reaction usually proceeds satisfactorily at room temperature, but higher or lower temperatures can also be used. If the alcohol is sensitive to mineral acids, it is preferred to carry out the reaction in the presence of pyridine at a low temperature, for example -10°C to 0°C. Similarly, thiol esters of general formulas A and B are acid halides of general formula (where r is chlorine or bromine) and acid halides of formula RSH. R
SNa or HS-(W)p-A-(R/)p-SH
Alternatively, a mercaptan represented by HaS-(k)p-A-(R')p-SNa is mixed in an organic solvent inert to the reaction.
It is usually produced by reaction in the presence of pyridine.

Acids lard are conveniently prepared by treating the corresponding acid with a rogogenating agent such as thionyl chloride, phosphorus pentachloride, oxalyl chloride or phosphorus tribromide.

As used herein, the term "alkyl" refers to 10 carbon atoms.
-22 straight or branched chain saturated aliphatic hydrocarbon groups such as dodecyl, tetradecyl, octadecyl, hexadecyl and decyl.

The term "alkenyl" refers to a straight or branched chain unsaturated aliphatic hydrocarbon group having 10 to 22 carbon atoms and having 1 to 3 olefinic unsaturations, such as octadec-9-en-1-yl, oleyl. , meaning linoleyl and eleostearyl. The word "alkynyl" has 10 carbon atoms
~22 linear or branched aliphatic hydrocarbon groups having 1 to 2 acetylenic unsaturations, such as dec-2-
Means yn-1-yl, dec-3-yn-1-yl, erythrogenyl and tarilyl. The term "aryl" refers to monovalent aromatic hydrocarbon groups from 6 to 14 carbon atoms, such as phenyl, tolyl, xylyl, myristyl, naphthyl, ethyl phenyl, t-butylphenyl and isopropylphenyl.

The term "cycloalkyl" refers to monovalent cycloalkyl groups having from 4 to 6 carbon atoms in the ring, such as cyclobutyl, cyclopentyl, cyclohexyl and 2-methylcyclohexyl. Unless otherwise specified, the term "alkylene" refers to divalent radicals derived from straight or branched chain alkanes of 1 to 20 carbon atoms. The term "alkenylene" refers to a divalent radical derived from a straight or branched chain hydrocarbon having 2 to 20 carbon atoms and having 1 to 3 olefinic unsaturations. The term "alkynylene" refers to a divalent group derived from a straight or branched chain hydrocarbon having 2 to 20 carbon atoms and having 1 to 2 acetylenic unsaturations. The term "cycloalkylene" refers to a divalent radical derived from a cycloalkyl group having 4 to 6 carbon atoms in the ring, such as 1,3-cyclobutylene, 1,4
- means cyclohexylene and 2-ethyl-1,4-cyclohexylene. The term "arylene" refers to divalent radicals derived from aromatic radicals of 6 to 20 carbon atoms, which may consist of two phenylene radicals linked by dissimilar oxygen or sulfur atoms. The term "alkoxy" refers to the groups methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and t-butoxy. The following examples illustrate the synthesis of compounds of the invention and the practice of the invention.

Temperatures are shown in degrees Celsius. Example 1 Dissolve 2.25% of cyclopropanecarboxylic acid chloride in dry benzene and add 87% of cyclopropanecarboxylic acid chloride to the stirring solution under a nitrogen stream.
- Added dodecanol.

The mixture was stirred overnight and then diluted with pentane. The reaction mixture was washed with water and then with brine to remove the solvent and convert to dodecylcyclopropane carboxylate ({Formula A, n-0
, X-10-, R=-(CH2)11) (active substance black 1
), a boiling point of 99-100 (melting temperature) was obtained at 0.03 m dew.
Example 2 0.27 cyclopropaneacetic acid, 30 d anhydrous ether, and 1.3 ml thionyl chloride (DlO=1.66
0.3 d of dimethylformamide was added to the mixture.

The mixture was stirred for 5.5 hours and the upper layer of the resulting biphasic mixture was decanted into a separate flask and all solvents and volatiles were removed by rotary evaporation. Add 40 g of dry ether and 2.19 t of 1-pentadecanol dissolved in 20 g of anhydrous ether to the residue, then add 1 ml of 00 g
of anhydrous pyridine (DO=0.982) was added.
The reaction mixture was allowed to warm to room temperature and stirred overnight. Water, ether and pentane were added to the reaction mixture, the organic layer was separated, washed with 3N sulfuric acid, 15% potassium carbonate aqueous solution, water and brine, dried over potassium sulfate, and the solvent was removed to give the product. Pentadecyl cyclopropyl acetate (general formula A(7) n=1, X=10-, R=1(CH2)14
CH3) (Active substance ▲2) Boiling point at 0.04 mm 11
8-123°C (melting temperature) was separated. The following compound of general formula A was obtained in the same manner as described in Examples 1 and 2.

Example 3 To a mixture of 3.0 f 1,4-butynediol, 150 ml dry diethyl ether, and 16.9 W 11 dry pyridine was added 10.9 y of cyclopropane carboxylic acid chloride under a stream of argon at 0000 over 10 minutes. added.

The mixture was stirred for 2 hours and then water and pentane were added. The mixture was sequentially mixed with a 3N aqueous sulfuric acid solution, an aqueous potassium carbonate solution, water, a saturated aqueous copper sulfate solution, and water? The biscyclopropane carboxylate of 1,4-butynediol (general formula B'(
'n-0. ．． X=-0-, p=0, A=-CH2-C-CH2-) (active substance black 26) boiling point at 0.05 mm 108-111 (bath temperature) was obtained. The following compound of general formula B was obtained in the same manner as described in Example 3.

The mite control agents of the present invention can be used alone in an inert pesticide carrier material for mite control or, for a broader range of application, can be used with insecticides and/or immature insecticides well known to those skilled in the art. Used in mixtures with hormones.

The compounds of the invention are also effective against mites as well as mites that infest animals and birds.

These compounds are applied in the conventional manner in the form of solutions or powders. The efficacy of the compounds of the present invention is illustrated below.

Adults (Tetranicus urticae) are allowed to oviposit for 24 hours on bean leaf discs (1 cm in diameter) placed on moist cotton wool.

After 24 hours, the adults are removed and the leaf discs with eggs attached are placed in a 0.1% acetone solution of the test compound.

After applying it for 1 second, allow the solvent on the leaf disc to dry, and then stick the leaf disc on the back side to a Plasnac Petri dish to prevent wrinkles.

After 6 days (all eggs on the untreated disks have hatched), the number of unhatched eggs is calculated as a percentage of the total number initially present, and this value is calculated using the Abbott formula.
Journal of Economics Endomorphology 2657 (1925) was once corrected for non-natural changes observed in control discs treated with solvent only.

The test results are shown in the table below. Wettable powders suitable for dilute field use include 20 to 30% of the ester or thioester of the invention and a solid carrier such as Atakure 60 to 30%.
70%, anionic surfactant such as Igepon T-J model
V, 1-3% and a dispersant such as Malasperse N22,
3 to 5% and air milling the mixture.

Wettable powders are applied using an ultra-low volume spreader after dilution with water.

Dilutions containing this ester at concentrations of about 0.005% to 1% are commonly used. These compounds can also be formulated as a 25% active ingredient powder with the following composition:

Active substance 25% synthetic calcium silicate 5%

Claims (1)

[Claims] 1 An acid or its acid halide represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and the general formula RX
General formulas characterized by reacting alcohols or thiols selected from R and HX(R')_p-A-(R')_p-XH, or their alkali metal salts▲There are mathematical formulas, chemical formulas, tables, etc.▼ (A) and ▲Mathematical formulas, chemical formulas, tables, etc.▼(B) (where X is -
When O- and n is 0, R is an alkyl group, alkenyl group or alkynyl group; when X is -O- and n is an integer from 1 to 4, R is an alkyl group; when X is -S- and n is 0, R is an alkyl group, p is 0, X is -O- and n is 0
, A is an alkynylene group, arylene group, alkylene group, or cycloalkylene group, and when p is 0, X is -O-, and n is 2, A is an arylene group or an alkynylene group, and p is 1 R' is an alkylene group and X is -
When O- and n is 0, A is an arylene group or a cycloalkylene group; when p is 1 and R' is an alkylene group; when X is -O- and n is 2, A is an arylene group) The manufacturing method of the compound.