JPS62201836A - 3-(3-halogeno-4-alkoxyphenyl)-3-methylbutanal compound and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is lower alkyl; X is F, Cl or Br). EXAMPLE:3-(3-Chloro-4-ethoxyphenyl)-3-methylbutanal. USE:A starting raw material for the production of agricultural chemicals and pharmaceuticals, especially 1-(3-phenoxyphenyl)-4-(3-halogeno-4-alkoxyphenyl)-4- methylp-entane derivative having rapid and long-acting activity and low toxicity to fish. PREPARATION:The compound of formula I can be produced by reacting 2-(3- halogeno-4-alkoxyphenyl)-2-methylpropyl halide of formula II (Y is Cl or Br) with metallic Mg, reacting the resultant compound of formula V with a trialkyl orthoformate of formula III (R<1> is lower alkyl) to obtain a novel acetal derivative of formula III and hydrolyzing the derivative under acidic condition.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a compound of the general formula (I) CH3 (wherein R represents a lower alkyl group and X represents a fluorine atom, chlorine atom or bromine atom). Show h le 3-(3
-Halogeno-4-alcoquinphenyl)-3-methylbutanals and a method for producing the same.

The compounds of the present invention are useful in various industrial fields, particularly as intermediates for agricultural medicines and insecticides.

That is, 3-(3-halogeno-4-alkoxyphenyl)-3-methylbutanals have high insecticidal and acaricidal activity, and are excellent in fast-acting, residual-acting, and low fish toxicity. (3-phenoquinophenyl) ~4-(
3-halogeny-4-furukoki/phenyl)-4-, l'
It is an important intermediate of 14 fl'pentanes and 1-(3-phenoxyphenyl)-4-(4-alkoxyphenyl)-4-methylpentane derivatives (JP-A-58-201737).

[Conventional technology]

3-(3-halogen-4-alkoxyphenyl)-3-methylbutanals represented by the general formula (I) are new compounds that have not been described in any literature, and therefore, the method for producing them is also unknown.

[Problems to be Solved by the Present Invention] The present invention provides a novel 3-(3-...)l/-4- which is a raw material for an insecticidal pentane derivative having the above-mentioned preferable characteristics.
An object of the present invention is to provide alkoxyphenyl)-3-methylbutanals and a method for producing the same.

[Means and Effects for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors found that the general formula (I) CH.

(In the formula, R and X have the above meanings.) A novel 3-(3-halogeno-4-alkoxyphenyl)
-3-Methylbutanal is useful as an insecticide 1-
(3-phenoxyphenyl)-4-(3-haokeno4
-Flucoquinophenyl)-4-methylpentane derivatives and 1-(3-phenoxyphenyl)-4-(4-flukoxyphenyl)-4-methylpenta/derivatives, and is useful as a starting material in the production of Formula (II)
2-(3-halogen-4-
The present invention was completed by discovering that it can be easily produced industrially from methylpropyl halides (flucoxyphenyl)-27.

The butanals represented by the general formula (I) have not been described in the literature and are new compounds discovered for the first time by the present inventors, and the dialkyl acetals represented by the general formula (2) have also not been described in the literature.

This is a new compound discovered for the first time by the present inventors.

In the general formula (I), the substituent R represents a lower alkyl group, and represents a straight chain or branched alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, etc., and the substituent X represents a fluorine atom.

Indicates a chlorine or bromine atom. 3-(3-halogeno-4-alkoxyphenyl/l/
) -3-Methylbutanals, specifically c,
3-(3-chloro-4-methquinphenyl)-3-methylbutanal 53-(3-chloro-4-ethoxyphenyl)-3-methylbutanal.

3-(3-chloro-4-propoxyphenyl)-3-methylbutanal, 3-(3-chloro-4-isopropoxyphenyl)-3-methylbutanal, 3-(3-chloro-4-butoquino phenyl)-3-methylbutanal,
3-(3-chloro-4-pentyloxyphenyl)-3
-Methylbutana-/l/, 3- (3-chloro-4-
hexyloxyphenyl)-3-methylbutanal, 3
-(3-bromo-4-methoxyphenyl)-3-methylbutanal, 3-(3-bromo-4-ethoxy7phenyl)-3-methylbutanal, 3-(3-bromo-4-propoxyphenyl) -3-methylbutanal.

3-(3-7”como-4-impropoxyphenyl)-
3-Methylbutanal, 3-(3-fluoro-4-methoxyphenyl)-3-methylbutanal.

Examples include 3-(3-fluoro-4-ethoxydiphenyl)-3-methylbutanal, 3-(3-fluoro-4-propoxyphenyl)-3-methylbutanal, and the like.

The compound of the present invention represented by the general formula (I) can be produced by the following method.

CH3CH3 (wherein R,, X, Y, and R1 have the above meanings) 2-(3-halogen-4-alkoxyphenyl) represented by general formula (n), which is the starting material for this production method -2
- Methylpropyl halides are prepared by the known method C from 2-logenoalkoxybenzenes and methallylnolides.
It was synthesized and used according to JP-A-60-149539). Next, a manufacturing method of the present invention will be explained. That is, a Grignard reagent is obtained by reacting a tt-2-(3-halogeno-4-alkoxyphenyl)-2-methylpropyl halide represented by the general formula (n) with magnesium metal in an ethyl ether or tetrahydrofuran solvent in a conventional manner. (Grignard reagent) and then reacted with a trialkyl orthoformate represented by the general formula (4). General formula (2)
As the trialkyl orthoformates represented by, specifically, trimethyl orthoformate or triethyl orthoformate is preferable.

In this reaction, a solvent such as ether or tetrahydrofuran used in preparing the Grignard reagent may be used, but it is preferable to remove the ether or tetrahydrofuran. Namely.

Said 2 (3-halogeno-4-alkoxyphenyl)
- Is the reaction between the Grignard reagent of 2-methylbutanalnolides and the trialkyl orthoformate represented by the general formula (III) carried out without a solvent? benzene.

It is better to carry out in an inert aliphatic or aromatic hydrocarbon solvent such as toluene, hexane, heptane.

The reaction temperature and reaction time can vary widely depending on the starting materials, but generally the reaction temperature is 20'
C to 150° C1, preferably 30 to 120° C1. The reaction time is 0.5 to 24 hours, preferably 0.5 to 15 hours.

Next, the acetals represented by the general formula (5) obtained by this reaction can be easily converted into the desired 3-(3-halogen y-
4-alkoxyphenyl)-3=methylbutanals. In this case water f8'M or methanol, ethanol.

A mixed solvent of water and a water-soluble organic solvent such as acetone, tetrahydrofuran, and dioxane, or toluene, benzene, hexano, heptane, and ether.

Although it can be carried out in a mixed solvent of water and an organic solvent such as ethyl acetate, dichloromethane, or chloroform, it is preferably carried out in an aqueous solvent, or methanol, ethanol, acetate, etc.
, tetrahydrofuran, dioxane, etc., and water.

The acids used are mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, or acetic acid,
Organic acids such as propionic acid, methanesulfonic acid, penzenosulfonic acid, and p-)luenesulfonic acid are preferred, and organic acids such as acetic acid, methanesulfonic acid, benzenesulfonic acid, and p-)luenesulfoheptaic acid are more preferred. Acid is preferred.

The reaction temperature and reaction time can vary widely depending on the starting materials, but generally the reaction temperature is 0°C.
-150°C1 preferably 30°C -100°C1 The reaction time is 0.1-24 hours, preferably 0.5-20 hours.

〔Example〕

Next, the present invention will be explained in more detail with reference to one synthesis example and a reference example, but the present invention is not limited thereto.

Synthesis Example 1゜(1) After adding 2.98 g of magnesium metal (shavings) to 80 g of dry ether, 0.2 g of dibromoethane was added dropwise while stirring under a nitrogen stream. Next.

2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl chloride 30. Og was added dropwise.

After the dropwise addition was completed, the mixture was heated under reflux for 2.0 hours, and 20.0!7 of trimethyl orthoformate was added. Add benzene 60° gradually while removing ether at normal pressure until the internal temperature reaches 80-82°.
When the temperature reached C, stirring was continued for an additional 3 hours. After cooling to room temperature, water was added and the generated precipitate was removed by filtration, and the resulting benzene solution was washed with water and dried. Benzene was distilled off under reduced pressure to obtain an oily residue of 31.3%. The obtained oily residue was columnarized with 0” f togelaf (-(Wako
Gel C-200.

650f7, developing solvent: toluene) to obtain 22.8 g of the target dimethyl acetal.

nDl, 5092 1260.1125,1065° (3H, t, J=7.2Hz).

1.82 (2H, d, J=4.7Hz).

3, 09 (6H, s), 3.9-4.2 (3H,
m), 6.6-7.3 (3H, m) Elemental analysis value: C4
5H23CIO3 CHC1 Calculated value (%) 62,82 8.08 12.36 Measured value (related) 62,91 8.13 12.35 (2
) 22.0 ml of the dimethyl acetal obtained in (1) was dissolved in a mixed solution of 100 ml of acetone and 20 rnl of water.

Next, 1 part of methanosulfonic acid was added and the mixture was stirred at 50°C for 2 hours. After distilling off the acetonate, extraction was performed with toluene, and the obtained toluene solution was washed with water and dried.

Toluene was distilled off under reduced pressure to obtain an oily residue of 18.59%. Column chromatography (Wako Ge1C-
200,350 ml, developing solvent: toluene), purified with target 3-(3-chloro-4-ethoxyphenyl)-3
-17.6 ml of methylbutanal were obtained.

n 1,5298 t, J=6.9Hz), 2.56 (2H.

d, J = 2.4Hz>, 4.03 (2H, q.

J = = 6.9Hz) 6.7-7.4 (3H.

m), 9.39 (LH, t, J=2.4Hz) Elemental analysis value: C13H17C1O□ CHC1 Calculated value (ch) 64.86 7,12 14.73 Measured value (correspondence) 64,95 7.08 14 .70 Synthesis Example 2゜(1) After adding 23.89 kg of magnesium metal (shavings) to 6001 rLt of dry ether, 2rnt of dibromoethane was added dropwise while stirring under a nitrogen stream. Next.

240.09 g of 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl chloride was added dropwise.

After completion of the dropwise addition, the mixture was heated under reflux for 2.0 hours, and 160% of trimethyl orthoformate was added. Added Og. While removing ether at normal pressure, gradually add 500% of benzene to bring the internal temperature to 80-82°.
When the temperature reached C, stirring was continued for an additional 3 hours. After cooling to room temperature, water was added and the resulting precipitate was removed by filtration. The resulting benzene solution was washed with water and then dried. Benzene was distilled off under reduced pressure to obtain 252.8 g of an oily residue. The obtained oily residue was distilled under reduced pressure (126,0~126.5℃ 10
, 221Hg) to obtain the target dimethyl acetal 185.39. Results of analysis by gas chromatography.

The purity was 98.6%.

(2) Dimethyl acetal obtained in (1) 250.09
was dissolved in a mixed solvent of 1,000 fd of acetone and 300 fd of water. Then, methanesulfonic acid 10- was added and stirred at room temperature for 4 hours. After distilling off the acetone, extraction was performed with toluene, and the resulting toluene solution was washed with water and dried. Toluene was distilled off under reduced pressure to obtain an oily residue of 210.5 (j).

As a result of analysis by gas chromatography, it was found that 3-(3-chloro-4-ethoxyphenyl)-3-methylbutanal of 98.1 was contained.

Synthesis Example 3 (1) The procedure of Synthesis Example 1 (1) was repeated except that dry tetrahydrofuran (3 gml) was used instead of dry ether 80-, and toluene 50 ml was used instead of benzene 60 ml, and the desired dimethyl acetal 21 I got .27.

(2) Add 20.0 liters of dimethyl acetal obtained in (1) to a mixed solvent of 50-1 acetic acid and 50 d water and heat at 40°C for 6 hours.
Stir for hours. It was poured into ice water and extracted with toluene. After washing the toluene extract with water and drying, toluene was distilled off under reduced pressure to obtain 15.4 g of an oily residue.

Analysis by gas chromatography revealed that 97.3 chino-3-(3-40 rho-4-ethoxyphenyl)-3-methylbutanal was contained.

Synthesis Example 4 (1) After adding 2.55 g of magnesium metal (shavings) to 70 g of dry ether, 0.2 g of dibromoethane was added dropwise while stirring under a nitrogen stream. Next.

2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl chloride 24.7! ;2 was added dropwise.

After the dropwise addition was completed, the mixture was heated under reflux for 2.0 hours, and 80-trimethyl orthoformate was gradually added at normal pressure while removing ether, and the internal temperature was maintained at 85° C. for 5 hours.

After cooling to room temperature, water was added and the resulting precipitate was removed by filtration, and the P solution was extracted with toluene. The obtained toluene solution was washed with water and dried. Toluene and triethyl orthoformate were distilled off under reduced pressure to obtain oily residues 27 and 29.

The obtained oily residue was subjected to column chromatography (
Wako Gel, C-200,650), developing solvent: toluene) to purify the desired dimethyl acetal 13.
．． 1! ;' was obtained.

(2) 12.0 ml of dimethyl acetal obtained in (1) was hydrolyzed according to Synthesis Example 1 (2) to obtain an oily residue of 9.7 ml.
I got it. Gas chromatography analysis results 9
8.5% 3-(3-chloro-4-ethoxyphenyl)
-3-methylbutanal was contained.

Reference [IH, 1-(3-phenoquino-4-fluorophenyl)-4-(3-chloro-4-ethoxyphenyl)-
Synthesis of 4-methylpentane (1) Add 55.79 ml of 3-phenoxy-4-fluorobenzyltriphenylphosphonium bromide to 120 rnl of dry tetrahydrofuran and hydrogenate while maintaining the temperature at 250-60°C) IJium (60% IRO oil) 4 ．．
09 was charged in portions over 1 hour. After charging, the mixture was heated under reflux for 5.0 hours. Next, while maintaining the temperature at 25°C, 3-(
3-Chloro-4-ethoxyphenyl)-3-methylbutanal31. i was added dropwise over 30 minutes. After stirring at 400G for 30 minutes, 10-10-100 ml of ethanol and 10-10% water were added while cooling to decompose excess sodium hydride. After distilling off tetrahydrofuran, water was added and the mixture was extracted with benzene. After washing the benzene solution with water and drying, benzene was distilled off under reduced pressure. When 500% of hexane was added to this residue, triphenylphosphine oxyto was precipitated.

Next, triphenylphosphine oxide was removed by filtration to obtain a hexane solution. hexane distillation, 53
．． 4 g of oily residue was obtained. Column chromatography (
Silica gel, 12009. Purified with toluene-hexane (1:2)) to give 40.9 g of 1-(3-phenoxy-4-fluorophenyl)-4-(3-chloro-4-ethoxyphenyl)-4-methyl- 1-I got pentene.

J=6.9Hz), 2.37(2H,d, J=7.5H
z), 3.98 (2H, q, J=6.9Hz), 5.6
~6.3 (3H, m), 6.7 ~ 7.4 (11H, m
) (2) 10.27% of the 1-(3-phenoxylene-4-fluorophenyl)-4-(3-chloro-4-ethoxyphenyl)-4-methyl-1-pentene obtained in (1) was dissolved in 50% of ethyl acetate. After dissolving in the solution, 1.0 liters of Pd-C was added and stirred at room temperature for 3 hours under a hydrogen pressure of 20 kg/cIftG. Next, Pd-C was separated and ethyl acetate was distilled off. 10.
An oily residue of Ill was obtained. Column chromatography (
Purified using silica gel, 200 g, developing solvent: toluene-hexane (1:2).

Target 1-(3-phenoxy-4-fluorophe=#)
-4-(3-40rho-4-ethoxyphenyl)-4-methylpentane was obtained at 9.52 t, J=6.9Hz)
, 2.41 (2H.

d, J=7.5Hz), 3.96 (2H.

q, J=5.9Hz), 6.6-7.4 (IIH
, m) Reference Example 2, 1-(3-phenoxy-4-fluorophenyl)-4-(3-chloro-4-ethoxyphenyl#) obtained in Reference Example 1
-20 parts of 4-methylpentane.

Tsurupol 355 (Toho Chemical @), Surfactant Sai D10
1 part and 70 parts of xylene were uniformly stirred and mixed to obtain an emulsion. This emulsion was diluted with water to an active ingredient concentration of 1,100 pp, and used on paddy rice seedlings (three-leaf stage) planted in Wagner Bonoto at -1/10,000 are.

The chemical solution was sprayed on a turntable until it dripped. After air-drying, the seedlings were covered with a wire mesh cylinder, and 10 adult female insects of the resistant leafhopper (medium protozoa) were released into the seedlings and allowed to stand at room temperature. Mortality was investigated after 24 hours. All tests were 2
It was carried out in tandem. As a result, the mortality rate was 100.

〔Effect of the invention〕

As is clear from the above explanation, 1. Novel aspects related to the present invention 3.
-(3-halogen-4-alkoxyphenyl)-3-methylbutanals are useful compounds in the field of agricultural medicine, particularly as intermediates for insecticides.

Moreover, it can be easily manufactured by the manufacturing method according to the present invention. Therefore, the present invention is useful.

Claims (1)

[Claims] 1) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R represents a lower alkyl group, and X represents a fluorine atom, chlorine atom, or bromine atom. ) represented by 3-(3
-halogeno-4-alkoxyphenyl)-3-methylbutanals. 2) General formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R represents a lower alkyl group, X represents a fluorine atom, chlorine atom, or bromine atom, and Y represents a chlorine atom or 2-(3-halogeno-4-
After reacting the alkoxyphenyl)-2-methylpropyl halides with magnesium metal, the compound has the general formula (III) CH(OR^1)_3(III) (wherein R^1 represents a lower alkyl group). The compound is reacted with trialkyl orthoformates represented by the general formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R, X and R^1 have the above meanings.) General formula (I) which is characterized by being made into an acetal derivative and then hydrolyzed under acidic conditions ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R and X indicate the above meanings. ) 3-(3-halogeno-4-alkoxyphenyl)-3
- A method for producing methylbutanals.