KR800000903B1 - Process for the preparation of propargyl(or alkenyl)phenyl ether derivatives - Google Patents

Abstract

Title compds. (I; X=Me, CL; Y=C1-6 lower alkyl, allyl; R=propargyl, C3-18 alkenyl; n=0, 1, 2), useful as acaricides, were prepd. by condensation of alkali metal salt of compd. II and compd. III (z=halogen),. Thus, 6g /4-chloro-e-ethyl thiophenol and 2.1g KON(purity 85.5%) were dissolved in 30ml N, N-dimethylacetamide and cooled to 18↿-20≰C. Then 3.5g 3-chloropropene-2-yl chloride was added to the cooled products, refluxed for 3hrs. at 70≰-80≰C, washed with 5% HCl soln., 5% NaOH soln. and Na2SO4, and distilled to give 67g 3-chloro-propene-2-yl-4`-chloro-3`-ethylthiophenylether.

Description

Process for preparing propargyl (or alkenyl) phenyl ether derivatives

The present invention relates to a process for the preparation of propargyl or alkenyl) phenylether derivatives of formula (I) used as acaricide.

X is a methyl group or a chlorine atom

Y is a C ₁ -C ₆ lower alkyl group or an allyl group, R is a propargyl group or a C ₃ -C ₁₈ alkenyl group which may be substituted with a chlorine atom,

n is 0, 1 or 2.

Tetranychus urticae causes a wide range of damage to fruit crops such as apples, pears and peaches, vegetables such as eggplants, cucumbers, various legumes, hops, mulberry trees, and kansaishon. citri) is known to cause great damage to fruit trees, such as tangerines, pears, apples, peaches, and mulberry trees, and many acaricides have been used for these treatments. However, resistance to most of these acaricides reduces the acaricide effect.

It is therefore an object of the present invention to prepare a new derivative of propargyl (or alkenyl) phenylether with excellent acaricide.

This production method of the present invention condenses the alkali metal salt of the compound of formula (II) with an equivalent amount of the compound of formula (III) to produce a new derivative of structure (I).

In the above structural formula,

X, Y, n and R are as described above,

Z is a halogen atom.

The method for removing mites in the present invention is to add an effective amount of the compound of formula (I) to the mites and their eggs.

The acaricide composition of the present invention consists of 0.5 to 70% by weight of the compound of formula (I) and 95.5 to 30% by weight of a suitable adjuvant.

Adjuvants used herein mean additives that do not have acaricide activity and may include other carriers or auxiliaries which are commonly used in pesticides.

The carrier may be a solid, liquid or gas, and the solid carrier may be, for example, lime talc, bentonite, white coal, kaolin, diatomaceous earth or silica, and the liquid carrier may be water, benzene, alcohol, acetone, xylene, methylnaphthalene, cyclohexane, Animal and vegetable oils, fatty acids or fatty acid esters, and gas carriers include air, nitrogen, carbonate gas and pleon. Auxiliaries are commonly used in agrochemical prescriptions, for example electrodeposition agents, emulsifiers, fixing agents, wetting agents or surfactants, i.e. polyoxyethylene alkylallyl ether, polyvinyl alcohol, polyoxy-ethylene sorbitan monooleate, alkyldimethylbenzyl Esters with ammonium chloride, alkylbenzenesulfonates, tigninsulfonates, higher alcohols and sulfuric acid.

Formula (I) compounds prepared by the method of the present invention are shown in Table 1.

TABLE 1

Preferred compounds for acaricide include X is methyl group or chlorine atom, Y is ethyl group, n-propyl group or allyl group, R is propargyl group, allyl group, buten-2-yl group, 3-methylbuten-2-yl Groups, 1-methylallyl group or 3-chloro allyl group, and n is 0 or 1. Most preferred compounds for acaricides include X is a methyl group or a chlorine atom, Y is an n-propyl group, R is a propargyl group, allyl group, 3-chloroallyl group, or buten-2-yl group and n is 0 or 1 Structural formula (II) compounds. Most preferred compounds are for example 1,2,3,4,5,6,8,14,24,25,26,27 and 28 in Table 1.

The compound of formula (I) may be prepared by condensing an alkali metal salt of the compound of formula (II) with a compound of formula (III). In the case of condensation, the alkali metal salt of the compound of formula (II) may be prepared first and reacted with the compound of formula (III), or reacted by coexisting three compounds of the compound of formula (II), alkaline compound and compound of formula (III). good.

The condensation reaction is usually carried out in inert solvents N, N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), methanol, ethanol, benzene, acetone and water, preferably DMAC, DMSO And in DMF but may be performed without solvent.

The reaction temperature is from 0 ° to 160 ° C., preferably from 10 ° to 120 ° C. and the alkaline compound is an alkali metal carbonate such as, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, potassium carbonate and sodium carbonate. The alkali metal salts of the compound of formula (II) are, for example, sodium and potassium salts. When the compound of formula (I) is a sulfide, it is oxidized with an oxidizing agent such as hydrogen peroxide, potassium permanganate, potassium persulfate, perbenzoic acid, nitric acid, Obtain sulfone.

An effective amount of the compound of formula (I) is adapted to the mite and used as acaricide.

The active substances prepared according to the preparation method of the present invention may be made, for example, of a composition such as an emulsion, a wetting agent, a powder or a granule. 50% by weight and 95 to 30% by weight of additives, preferably 90 to 50% by weight.

Emulsions or emulsifiers can be diluted with water so that the compound of formula (I) is in a concentration of 0.1 to 0.01% by weight, and an emulsion or a preparation capable of spraying an amount of 100 to 1,000 liters per 10 liters can be obtained.

Powders or granules contain 0.5 to 10% by weight of the compound of formula (I), 95.5 to 90% by weight of suitable additives, and can be sprinkled with an amount of 1 to 5 kg per 10 ars.

The acaricide composition may also be used in combination with other pesticides such as insecticides, herbicides, fungicides or acaricides. The following examples list some of the preparation methods for compounds of formula (I) and all parts are by weight.

Example 1

[Manufacturing method of 3-chloro-propen-2-yl-4'-chloro-3'-ethylthiophenyl ether (compound 24)]

6 g of 4-chloro-3-ethylthiophenol and 2.1 g of potassium hydroxide (purity: 85.5%) were dissolved in 30 ml of DMAC having a temperature of 90 ° C. or higher, cooled to 18 to 28 ° C., and 3.5 g of 3-chloropropen-2-yl chloride. Add and stir for 3 hours at 70 to 80 ℃. The reaction mixture is poured into 100 ml of water, extracted with benzene and the extract is washed with 5% hydrochloric acid solution and 5% sodium hydroxide solution. After washing with sodium sulfate and distillation to remove benzene, 67 g of 3-chloro-propen-2-yl4'-chloro-3'-ethylthiophenylether (80.1% of theory) were obtained.

Elemental Analysis C ₁₁ H ₁₂ Cl ₂ OS

Found: C 50.08; H 4.60%

Theoretic value: C 50.16; H 4.56%

In this example, instead of 6 g of 4-chloro-3-ethylthiophenol and 2.1 g of potassium hydroxide (purity 85.5%), 7.3 g of potassium salt of 4-chloro-3-ethylthiophenol was used and the same procedure was repeated. 3-chloro-propen-2-yl-4'-chloro-3'-ethylthiophenyl ether can be obtained.

Example 2

The compounds of Table 2 may be prepared according to the same method as in Example 1.

TABLE 2

Example 3

[Preparation of 3-chloro-buten-2-yl 4'-methyl-3'-iso-propylsulfinylphenyl ether (Compound 18)]

2 g of 4-methyl-3-isopropylsulfinylphenol, 1.4 g of potassium carbonate, 30 ml of DMAC, and 1.3 g of 3-chloro-buten-2-yl chloride were mixed and reacted at 90 to 100 ° C. for 5 hours and then poured into 100 ml of water. Put in and extract with benzene. The extract was washed with 5% sodium hydroxide solution and water, dehydrated with sodium sulfate, benzene was distilled off and 3-chlorobuten-2-yl 4'-methyl-3'-isopropylsulfinyl-phenylether 2g 71.2 (71.2% of theory) ).

Elemental Analysis C ₁₄ H ₁₉ ClO ₂ S

Found: C 58.49; H 6.78%

Theoretical: C 8.64; H 6.63%

In the same way compounds 2,4,6,8,10,12,15,16,20,23,26,28,30,32 and 34 can be prepared.

Example 4

Preparation of Allyl 4-methyl-3-n-propylsulfinylphenyl ether (Compound 2) 3.0 g of allyl 4-methyl-3-n-propylthiophenyl ether (Compound 1) was dissolved in 30 ml of acetic acid and cooled to 5 ° C or lower. Then 2.5 g of 30% hydrogen peroxide solution is added. After stirring for 1 hour at room temperature, poured into 100 ml of water, extracted with benzene, the extract was washed with 5% sodium carbonate solution and water and dehydrated with sodium sulfate.

The benzene is then removed to give 3.1 g (96.3% of theory) of allyl 4-methyl-3-n-propylsulfinylphenyl ether.

Elemental Analysis C ₁₃ H ₁₈ O ₂ S

Found: C 70.11; H 8.13%

Theoretic value: C 70.16; H 8.10%

In the same way the corresponding sulfide is oxidized to afford compounds 4,6,8,10,12,15,16,20,23,26,28,30,32 and 34.

Example 5

[Preparation of 2-methyl-propen-2-yl 4'-methyl-3'-n-propylsulfonylphenyl ether (Compound 13)]

5 g of 2-methyl-propen-2-yl 4'-methyl-3'-n-propyl-thiophenyl ether (Compound 11) was dissolved in 30 ml of acetic acid, cooled to 5 ° C or lower, and 6.2 g of 30% hydrogen peroxide was added dropwise. Stir at 80 ° C. for 3 hours, pour the reaction mixture into 100 ml of water, extract with ether, wash with 5% sodium bicarbonate solution and water, dehydrate on sodium sulfate and distill ether to distill 2-methyl-propen-2-yl 4 ′ 4.46 g (78.4% of theory) of -methyl-3'-n-propyl sulfonylphenyl ether are obtained.

Elemental Analysis C ₁₄ H ₂₀ O ₃ S

Found: C 62.51; H 7.53%

Theoretic value: C 62.60; H 7.45%

Example 6

Emulsion

20 parts of compound 3

Xylene Part 65

15 parts mixture of condensation products of calcium alkylbenzenesulfonates and alkylphenols with ethylene oxide

Mix the ingredients well, mix them with an emulsion, and dilute with water to spread.

Example 7

Hydrating agent

Compound 8 30 parts

Kaolin 40

15 parts of lime

Diatomaceous Earth 7.5

7.5 parts of a mixture of sodium laurate and dinaphthylmethane sulfonic acid

Mix the ingredients well to make a hydration and dilute with water.

Example 8

Powder

Compound 26 3 parts

Talc 48

Lime 49

Mix and pulverize the above ingredients to get fine powder for use.

Example 9

) 15개를 접종시킨다. 이 잎들을 본 발명의 화합물 0.043%(중량)을 함유하는 용액에 10초간 담근후 비닐하우스에서 48시간 방치한다. 살아남은 성충의 수와 죽은수를 계산하여 살충율을 계산한다음 살아남은 성충을 제거하고 비닐하우스에서 7일간 방치한 후 부화하지 않은 알의 수를 측정한다.Two gangnam bean leaves cultivated in a 6 cm diameter pot are squeezed into pieces of about 3 cm 2, and then for each leaf,

15) are inoculated. The leaves are soaked for 10 seconds in a solution containing 0.043% (by weight) of the compound of the present invention and left for 48 hours in a plastic house. Calculate the insecticide rate by counting the number of surviving adults and the number of surviving adults, then removing the surviving adults and leaving them in the plastic house for 7 days before measuring the number of unhatched eggs.

The results are shown in Table 3.

TABLE 3

Example 10

) 10개를 접종시킨후 비닐하우스에서 2일간 산란시킨다.Cut off only 2 leaves of summer persimmon (summer tangerine) cultivated in a 12cm diameter pot and apply the adhesive to the stems of both leaves to prevent the escape of adult insects.

10) inoculate and spawn for 2 days in a plastic house.

Next, a solution containing 0.04% (by weight) of the compound of the present invention is sprayed on each leaf for 10 seconds with a spray layer, and the leaves are left for 2 days in a plastic house. After calculating the insecticidal effect by measuring the surviving and dead water of the adult under a microscope, the adult is removed from each leaf and left in the plastic house for 7 days to count the number of eggs. The scattering rate is calculated by measuring the number of eggs that are not hatched under a microscope.

The results are shown in Table 4.

TABLE 4

Claims (1)

A method for producing a propargyl (or alkenyl) phenylether derivative of formula (I) by condensing an alkali metal salt of the formula (II) compound with an equivalent amount of the formula (III) compound.

X is a methyl group or a chlorine atom, Y is a C ₁ -C ₆ lower alkyl group or an allyl group, R is a propargyl group or a C ₃ -C ₁₈ alkenyl group which may be substituted with a chlorine atom and n is 0,1, or 2 and Z is a halogen atom.