JPH02282344A - 1-(2-haloethoxy)-4-(2-alkoxyethyl)dialkylbenzenes, its synthetic intermediate and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R<1> to R<3> are lower alkyl; X<1> is halogen). EXAMPLE:1-(2-Chloroethoxy)-4-(2-ethoxyethyl)-2,3-dimethylbenzene. USE:A synthetic intermediate for pharmacenticals or agricultural chemicals, especially a compound exhibiting high activity as an insecticide. PREPARATION:The compound of formula I can be produced e.g. by reacting a compound of formula II with formaldehyde or its polymer and a hydrogen halide and reacting the resultant novel compound of formula III (X<2>=X<1>) with a compound of formula IV (X<3>=X<1>) in N2 gas stream usually at <=80 deg.C optionally in the presence of a solvent (e.g. tetrahydrofuran) and a catalyst (e.g. I2).

Description

Detailed Description of the Invention [Object of the Invention] (Industrial Application Field) The present invention provides novel 1-(2-haloethoxy)-4-(2
-alkoxyethyl]dialkylbenzenes (hereinafter referred to as “
This invention relates to compounds (referred to as "■)"), synthetic intermediates thereof, and methods for producing them.

Compound (I) is generally known to be a useful intermediate for pharmaceuticals and agricultural chemicals, and in particular to belong to a group of compound intermediates that exhibit high activity as insecticides, but it has not been described in any literature so far. It is a new compound.

(Prior art and problems to be solved by the invention) When producing compound (I) using conventionally known technology, industrially inexpensive dialkylphenols are used as a starting material, and a chloroethyl group is first introduced into this. However, the method of producing compound (I) by producing 1-(2-chloroethoxy)dialkylbenzenes and then introducing an alkoxyethyl group is advantageous because it requires fewer steps.

First, regarding the introduction of tetraloethyl groups, the haloethyl etherification method of phenols is well known (for example, Organic 5ynthesis Ca1l
↓.

435), in this case, 1-(2-chloroethoxy)dialkylbenzenes can be easily produced by reacting dialkylphenol with inexpensive 1,2-dichloroethane in a similar manner.

However, it is difficult to introduce an alkoxyethyl group in the next step with a good yield using conventionally known methods. For example, (2
-alkoxyethyl)benzenes, conventional methods include reduction of 1-alkoxy-2-phenylacetylene +
T, LJacobs, W,R,5cott
Jr,, J, Am, Chem, 5oc7
5, 5497 (1953)), phenyllithium and 1
-Reaction with chloro-2-alkoxyethane [L, Su
mmersM, L, Larson J, Am.
Chem, Soc, 74.4498 (1952
)), 〇-ethylation of phenethyl alcohol (S,
Mamedov, D.N., Khydyrov,
Zh, 0bsh.

Khim, 32.1431 (1962);
Mers, Angew, ChemInternat
, Edit, , 12.816 (197311) and other methods are known.

However, these methods are unsatisfactory as industrial production methods because they have disadvantages such as expensive raw materials, poor economic efficiency, and a large number of steps.

In view of these circumstances, the present inventors conducted intensive studies with the aim of developing an industrial manufacturing method that can produce compound (I) from inexpensive raw materials with a small number of steps, and as a result, the following results were obtained: 1-
The present invention was completed by successfully producing compound (I) by utilizing various synthetic intermediates that can be produced from (2-haloethoxy)dialkylbenzenes at low cost and in a small number of steps.

[Structure of the Invention] (Means and Effects for Solving the Problems) The present invention provides the following formula (1): (wherein, R1, R2 and R3 each independently represent a lower alkyl group; x' represents a halogen atom.

), their synthetic intermediates, and their production methods.

Compound (I) of the present invention can be synthesized according to various routes shown below.

In the above formula, R', R2, R3 and R5 each independently represent a lower alkyl group; XX2 and X4 each independently represent a halogen atom.

The lower alkyl group refers to a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group,
Examples of the halogen atom include propyl group, isopropyl group, butyl group, isobutyl group, 5ec-butyl group, tert-butyl group, pentyl group, and hexyl group.
Examples include chlorine atom, bromine atom, and iodine atom.

Specific examples of the compound (I) of the present invention include the following compounds.

1-(2-chloroethoxy)-4-(2-ethoxyethyl)-2,3-dimethylbenzene, 1-(2-chloroethoxy)-4-(2-methoxyethyl)-2,3-dimethylbenzene, 1-(2-chloroethoxy)-4-(
2-ethoxyethyl)-2,5-dimethylbenzene, 1
-(2-chloroethoxy)-4-(2-methoxyethyl)-2,5-dimethylbenzene, 1-(2-chloroethoxy)-4-(2-en[·xyethyl)-2,6-dimethylbenzene , 1-(2-chloroethoxy)-4-(2
-methoxyethyl)-2,6-dimethylbenzene, 1-
(2-chloroethoxy)-4-(2-ethoxyethyl)
-3,5-dimethylbenzene, 1-(2-chloroethoxy)-4-(2-methoxyethyl)-3,5-dimethylbenzene, 1-(2-chloroethoxy)-4-(2-ethoxyethyl) -3,5-di-tert-butylbenzene, 1-(2-chloroethoxy)-4-(2-methoxyethyl)-3,5-di-tert-butylbenzene, 1-(2-chloroethoxy)-4- (2-ethoxyethyl)-3,5-di5ec-butylbenzene, ■-(2-chloroethoxy)-4-(2-methoxyethyl)-3,5-di5eC-butylbenzene, 1-(2- chloroethoxy)-4-(2-ethoxyethyl)-2,5-di-tert-butylbenzene, 1-(2-chloroethoxy)-4-(2-methoxyethyl)-2,5-di-tert-butylbenzene , 1-(2-chloroethoxy)-4-(2-ethoxyethyl)-2,6-tert-butylbenzene, 1-(2-chloroethoxy)-4-(2-methoxyethyl)-2,6 -tert-butylbenzene.

Step "If) The compound represented by the formula (II) can be produced by reacting the compound represented by the formula (III), formaldehyde or a polymer thereof, and hydrogen halide. .

This reaction is usually carried out by placing compound (III) in a suitable organic solvent and hydrohalic acid, and then introducing heformaldehyde or a polymer thereof and hydrogen halide gas therein. Moreover, this reaction can also be carried out using only an organic solvent or only a hydrohalic acid.

Formaldehyde used in this reaction is used as it is or in the form of an aqueous solution (formalin). When formalin is used, its concentration is preferably 50 to 10% by weight. If the concentration is too high, precipitation is likely to occur, and if the concentration is too low, the reaction rate will be slow and the yield will be reduced. As the formaldehyde polymer, rose formaldehyde and trioxane are used. Formaldehyde is usually used in an amount of 1 to 20 times (molar ratio), preferably 2 to 10 times (molar ratio) relative to compound (III) (in the case of formalin or a polymer, it is used in terms of formaldehyde). If there is too little formaldehyde, the reaction solution will not mix well and the yield will decrease, while if it is too much, by-products will increase.

Examples of the organic solvent used in this reaction include carbon tetrachloride, chloroform, methylene chloride, dichloroecune, tetrachloroethane, dioxane, acetic acid, benzene, toluene, chlorobenzene, and saturated hydrocarbons having 4 to 10 carbon atoms. . Among these, carbon tetrachloride is most preferably used. The concentration of compound (III) is usually 0.1 to 15 mol/flood, preferably 0.5 to 15 mol/f of the organic solvent.
It is 10 mol/°C. If the concentration is too high, stirring becomes difficult, and if the concentration is too low, the reaction rate slows and the yield decreases.

Hydrohalic acid (10-60% aqueous solution of hydrogen halide) is usually 0-50% per mole of compound (III).
mol, preferably 0.2 to 10 mol is used. If the amount of hydrohalic acid is too large, the reaction rate will be slow, and a large amount of hydrogen halide gas will be required to be introduced. If it is too small, the introduced hydrogen halide will not be absorbed sufficiently. The amount of hydrogen halogen gas introduced may be increased by replacing this hydrohalic acid with the corresponding water.

The hydrogen halide gas is usually used in an amount of 1 to 200 mol, preferably 5 to 50 mol, per 1 mol of compound (Ill). If the amount of hydrogen halide gas is too small, the reaction rate will be very slow and the yield will decrease; if it is too large, excess hydrogen halide gas will not be absorbed and will be wasted, and by-products will increase.

The reaction temperature is usually -30 to 20°C, preferably -20°C.
~10°C. If the reaction temperature is too high, side reactions will proceed and the yield will decrease; if the reaction temperature is too low, the reaction rate will decrease and the yield will decrease.

The introduction of the hydrogen halide gas is usually carried out for 5 to 50 hours, preferably for 1 to 20 hours. If it is too short, hydrogen halide gas will not be absorbed sufficiently and temperature control will also become difficult.

If the process is not carried out for a long time, by-products will increase and the yield will decrease. Formaldehyde or its polymer is added during the introduction of the hydrogen halide gas.

If unreacted raw materials remain after the introduction of the hydrogen halide gas, the reaction is continued for an additional 0.5 to 5 hours. If it is too long, side reactions will proceed.

Further, the compound represented by the formula (II) is the compound represented by the formula (I)
II) and the compound represented by the following formula (C): R'0CH2X2 (C) (wherein R4 represents the above-mentioned lower alkyl group, and X2 has the same meaning as above), acetic acid It can also be produced by reacting in the presence of an aqueous hydrogen halide solution corresponding to x2.

This reaction does not require expensive metal catalysts, does not use hydrogen halide gas or difficult-to-handle acids such as sulfuric acid or fuming sulfuric acid, and can be carried out under mild conditions with simple equipment and equipment. Since it can produce (II), it is an excellent production method that is industrially suitable.

Specific examples of the compound represented by the formula (C) include tetraromethyl methyl ether, bromomethyl methyl ether, iodomethyl methyl ether, chloromethyl ethyl ether, bromomethyl ethyl ether, iodomethyl ethyl ether, and chloromethyl butyl ether. , chloromethyl-tertbutyl ether, chloromethylpropyl ether, and the like.

Compound (C) is usually Ol
~20.0 times the mole, preferably 10 to 50 times the mole.

The amount of acetic acid used is usually 0.5 ml per compound (Ill).
It is preferable that the amount is twice the molar amount or more.

Although it may be less than this, the reaction rate will decrease.

The halogen hydrogen concentration of the hydrogen halide aqueous solution is 5% or more,
Preferably 15% or more, particularly preferably 20 to 50%
It is. The amount of hydrogen halide is usually 0.2 mol or more, preferably 0.5 mol or more, based on compound (Ill).

A solvent may or may not be used, but when used, the solvent may be carbon tetrachloride, chloroform, methylene chloride, dichloroethane, dioxane, benzene, tetralobenzene, or a saturated hydrocarbon having 5 to 10 carbon atoms. is used.

Among them, carbon tetrachloride is preferred. The reaction temperature is usually 80
℃ or less, preferably 0 to 40°C. It may be less than this, but the reaction rate will decrease.

The compound represented by the formula (II) and the following formula (A): X"CH20R' (A) (
In the formula, R1 has the same meaning as above; x3 represents the above-mentioned halogen atom. ) The compound represented by formula (I) can be produced by reacting the compound represented by formula (I) in the presence of metal magnesium.

There are no particular limitations on the shape or other aspects of metallic magnesium as long as it is normally used in Grignard reactions.

Compound (A) is usually 0.1 to compound (II).
It is used in an amount of 200 to 200 times the mole, preferably 10 to 5.0 times the mole. Magnesium metal usually has an amount of 1 to 20.0 times the gram atom of compound (II), preferably 1.0 to 5
．． Use 0x gram atoms.

The solvent may or may not be used as long as compound (II) is dissolved, but when used, solvents generally used in Grignard reactions, such as diethyl ether, tetrahydrofuran, dioxane, Examples include single or mixed solvents of ethers such as dimethyl cellosolve, diglyme, dimethoxymethane and jetoxymethane, and hydrocarbons such as hexane, cyclohexane, benzene and toluene.

The reaction temperature is usually 80°C or lower, preferably 30°C or lower, particularly preferably 0°C to -20°C.

A catalyst may be present in the reaction. When used together, examples of the catalyst include catalysts commonly used in Rigniard reactions, such as iodine, mercuric chloride, methyl bromide, and ethyl bromide.

Although this reaction may be carried out in the presence of air, it is usually more suitable to carry out it in an inert gas atmosphere such as argon, helium, or nitrogen gas.

Next, a method for carrying out the reaction will be explained.

In the presence or absence of a solvent or a catalyst, compound (1) is made to act on magnesium to produce a Kliniyar anti-core agent, and compound (A) is made to act on this to produce compound (1). can do.

However, the order in which compound (1 block) and (A) are made to act on magnesium is not limited to this, and even if compound (II) is made to act on magnesium after compound (A) is made to act on it, Compound (ii) and (A>) may be allowed to act on magnesium simultaneously.

The compound represented by the formula (A) used in this reaction preferably contains an alkali and has the following formula (B): R'
It can be produced by reacting the alcohol represented by OF((B) (wherein R1 has the same meaning as above) with paraformaldehyde and then treating with hydrogen halide.

The paraformaldehyde used in this reaction is preferably commercially available and has a purity of 80% or more.

Alcohol (B) is for paraformaldehyde,
Usually 0.5 to 2 times the mole, preferably 0.7 to 1.5 times the mole, more preferably 0.9 to 1.1 times the mole. If the alcohol (B) is too small, unreacted Formaldehyde remains, and if there is too much formaldehyde, the by-product of formaldehyde dialkyl acetal increases.

The alkali used in this reaction is thorium hydroxide,
Examples include potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithium hydroxide, sodium alcoholade, potassium alcoholade, magnesium alcoholade, and lithium alcoholade (alcolade is preferably derived from the alcohol used in the reaction), and is preferred. Sodium hydroxide, potassium hydroxide, sodium alcoholade, and potassium alcoholade are used.

These alkalis are added to the alcohol as such or as an aqueous or alcoholic solution. The amount of alkali used is usually 0.00001 to 1 mole of O per paraformaldehyde, preferably 0.000
It is 1 to 0.01 times the mole. If the amount of alkali is too small, the dissolution rate of paraformaldehyde will be slow, and if it is too large, heat generation will increase in the initial stage of introduction of the hydrogen halide gas, making temperature control difficult.

The temperature at which the alkali-containing alcohol is allowed to act on rose formaldehyde is usually 10 to 200°C, preferably 30°C.
~100°C. If the temperature is too low, it will take time to dissolve formaldehyde, and if the temperature is too high, it will take time to cool down before introducing hydrogen halide.

The amount of hydrogen chloride gas is usually 1 % of paraformaldehyde.
．． It is 2 to 3 times the mole. If the amount of hydrogen halide gas is too small, formaldehyde dialkyl acecule will increase, and if it is too large, the amount of halomethyl alkyl ether dissolved in the aqueous layer will increase.

The temperature when hydrogen halide gas is introduced is usually 15 to -25
℃, preferably 10 to -20℃. If the reaction temperature is too high, formaldehyde dialkyl acecure will increase, and if the reaction temperature is too low, the reaction rate will be slow. The time for introducing hydrogen halide varies greatly depending on the cooling capacity. Usually 1-10
The introduction takes about an hour, but if it is too short, it will be difficult to control the temperature. However, even if the time for introducing the hydrogen halide gas far exceeds 10 hours, there is no problem in the reaction.

The compound represented by the above formula (VIII) is converted into the following formula (D):
(R'CC00)n (D) (wherein, R6 has the same meaning as above, and 1M represents a monovalent or divalent metal;
n represents 1 or 2. ) By reacting with a compound represented by the formula (■)
A compound represented by can be produced.

In the formula (D), the metal atom represented by M is 1
It is a valent or divalent alkali metal or alkaline earth metal, preferably sodium or potassium.

The solvent used may be any solvent as long as it dissolves the raw material (■), all or part of the carboxylic acid metal salt (D), and does not inhibit the reaction, such as methanol, ethanol, acetone, dimethylformamide. , dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, etc., with dimethylformamide being particularly preferred.

The reaction temperature is usually 0 to 100°C, preferably 30 to 60°C.
It is °C. The amount of carboxylic acid metal salt (D) used is usually 1 to 10 times, preferably 1.5 to 10 times, relative to the raw material (■).
It is 3 times equivalent.

The progress of the reaction can be monitored by taking a portion of the reaction solution and analyzing it by gas chromatography. material(
When (ii) is consumed, the reaction solvent is distilled off under normal pressure or reduced pressure, the residue is poured into water, and after extraction with an organic solvent,
Compound (V) is obtained by washing with water, drying, and distilling off the extraction solvent. If necessary, it can be purified using methods such as column chromatography, recrystallization, distillation, etc.
Usually, sufficient purity can be obtained without purification.

The compound represented by the formula (VIII) used in this reaction can be produced, for example, as follows.

A phenol represented by the above formula (IX) and the following formula (E)
: Z'CH2CH,X' (E) (in the formula, Z
' represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group; xl has the same meaning as above. ) is reacted in the presence of a base to obtain a compound represented by the formula (III).

Next, this compound (IfF) is converted into the following formula (F) in the presence of a Lewis acid: X5COCH2X' (F)
(In the formula, ×6 is a halogen atom, a hydroxyl group, or a formula
It represents a group represented by H and X', and +X' has the same meaning as above. ) By reacting with the compound shown in (■)
can be manufactured.

Examples of the compound represented by the formula (F) include acid halides such as chloroacetic acid chloride and bromoacetic acid bromide; acid anhydrides such as chloroacetic anhydride and bromoacetic anhydride; and carboxylic acids such as chloroacetic acid and bromoacetic acid. Among them, chloroacetic acid chloride is preferred. The amount used is usually 1 to 3 times equivalent, preferably 1 to 1.5 times equivalent, relative to compound (III).

Any solvent may be used as long as it does not participate in the reaction, such as nitrobenzene, tetralobenzene, dichlorobenzene, nitromethane, methylene chloride, carbon tetrachloride, and carbon disulfide.

The reaction temperature is usually -20 to 100°C, preferably 0 to 3
It is 0°C.

Examples of the Lewis acid used include aluminum chloride, aluminum bromide, boron trichloride, titanium tetrachloride, boron trifluoride, stannic chloride, and zinc chloride. The amount used is usually 1 to 5 times equivalent to compound (III),
Preferably it is 1 to 3 times equivalent.

The progress of the reaction can be monitored by adding water to a portion of the reaction solution to stop the reaction and analyzing the organic layer by gas chromatography. When compound (III) is consumed, water is added to decompose the Lewis acid, extracted with an organic solvent, washed with water, and dried. By distilling off the solvent, the compound (■
) can be obtained. If necessary, it can be purified by column chromatography, recrystallization, distillation, etc.

Kamihira ■ → IV The compound represented by the above formula (IV) can be produced by treating the compound represented by the above formula (V) with a reducing agent consisting of sodium borohydride and boron trifluoride ether complex salt. can.

Conventionally, several methods are known for reducing aromatic ketones to methylene chains, such as Clemensen reduction using zinc amalgam, Orfu-Kishner reduction using hydrazine and alkali hydroxide, and hydrogenation using a metal catalyst. Laws etc. are common. However, when reducing compound (V) using these methods, there are the following problems.

l) In the Wolff-Kishner reduction, the acyloxyacyl group of the raw material is decomposed and polymerized because a strong base is used.

2) Talemensen reduction uses mercury, so it is not suitable for the synthesis of pharmaceutical and agricultural intermediates, and there is also a risk of ignition of the amalgam and problems with post-reaction treatment.

3) In hydrogenation using metal catalysts, for example, RL,
C1ark et al. J, Am, Chem, S
oc, 77, 661 (1955), the acyloxyacyl group is reduced to an acyl group on Pd-carbon, and the desired hydroxyethyl group is not provided in this reaction.

Also, H. Adkins et al., J. Am. Chem.
, 5oc53, 1091 (1931) and 70.31
21 (1948) using a CuC'r○ catalyst to reduce ethyl acetoacetate to 3-hydroxybutyric acid and 1.3
-butanediol is selectively synthesized,
Conventionally, there has been no literature describing a method for selectively and simultaneously reducing the ketone moiety of a ketoester to methylene and the ester moiety to alcohol.

The amount of sodium borohydride used is usually 1 to 10 times the equivalent, preferably 2 to 5 times the equivalent of the raw material (V).

The amount of boron trifluoride ether anchor salt used is 5 to 50 equivalents, preferably 10 to 30 sonic equivalents, based on the raw material (V).

Although this reaction can be carried out without a solvent, a solvent is usually used. Any solvent may be used as long as it does not inhibit the reaction, but ether solvents such as tetrahydrofuran, diglyme, dioxane, diethyl ether, and isopropyl ether are preferred.

The reaction temperature is usually 0 to 80°C.

The progress of the reaction can be monitored by taking a portion of the reaction solution, decomposing the reaction reagent with water or dilute acid, extracting with a suitable organic solvent, and analyzing the organic layer by gas chromatography or thin layer chromatography. I can do something. When the raw materials are consumed, add water or dilute mineral acid to decompose the reaction reagent, extract with a suitable organic solvent, wash with water, dry and distill off the extraction solvent to obtain compound (IV)6. Depending on the situation, it can be purified using methods such as column chromatography or distillation, but usually products of sufficient purity can be obtained without purification.

Process 1 (IV → (■) The compound represented by the formula (IV) is reacted with dialkyl sulfuric acid in the presence of an alkali to form the compound represented by the formula (I).
) can be produced.

1. (V → Vl) The compound represented by the formula (V) is treated under hydrogen pressure in the presence of Raney nickel to form the compound represented by the formula (VI).
A compound represented by can be produced.

Conventionally, no method has been known for selectively reducing an acyloxyacyl group to a 2-acyloxyethyl group.

The solvent used may be any solvent commonly used in catalytic hydrogenation (for example, methanol, ethanol, diethyl ether, ethyl acetate, dioxane, etc.).
Examples include cyclohexane, water, tetrahydrofuran, dimethylformamide, and the like.

The reaction temperature is usually 50-200°C, preferably 80-200°C.
The temperature is 150°C.

The amount of Raney nickel used is usually 1 to 100% by weight, preferably 5 to 50% by weight, based on the raw material (V).

The hydrogen pressure is usually 10 to 100 kg/cm2G, preferably 20 to 70 kg/cm2G. The progress of the reaction can be monitored by reducing the pressure during the reaction or by taking a portion of the reaction solution and analyzing it by gas chromatography. After the reaction, crude compound (VI) can be obtained by allowing the reaction mixture to cool to release hydrogen, separating out the Raney nickel, and distilling off the reaction solvent. If necessary, it can be purified using methods such as column chromatography distillation and recrystallization.

(■ → ■) The compound represented by the formula (vn) can be produced by treating the compound represented by the formula (V) at normal pressure in the presence of Raney nickel.

Hitherto, no method has been known for selectively reducing an acyloxyacyl group to a 1-hydroxy-2-acyloxyethyl group.

The solvent to be used may be any solvent used in normal catalytic hydrogenation, such as methanol, ethanol, ethyl acetate, dioxane, water, tetrahydrofuran, dimethylformamide, etc., but preferably ethanol and methanol. .

The reaction temperature is usually 0 to 100°C, preferably 20 to 8°C.
It is 0°C.

The amount of Raney nickel used is usually 1 to 150% by weight, preferably 5 to 50% by weight, based on the original $1(V).

The progress of the reaction can be tracked by taking a portion of the reaction solution and analyzing it by thin layer chromatography. After the reaction, the compound (vn) can be obtained by separating the Raney nickel and distilling off the reaction solvent. Usually, a product of sufficient purity can be obtained without purification, but if necessary, it can be purified by column chromatography, recrystallization, etc.

1 Presentation vn → Vl By reducing the compound represented by the above formula (vn) with atmospheric hydrogen in the presence of Raney nickel, the above formula (VI
) can be produced.

By reacting the compound represented by the above formula (VI) with dialkyl sulfuric acid in the presence of an alkali, the above formula (I)
A compound represented by can be produced.

As detailed above, the compound (I) of the present invention has the root [1] (Ix) -(Irr) -(H) -(I ), the root [2] (IX) -(Ill) -(■ )-(V)-(IV)
-(I), Root [3] (IX) -(1 piece) -(■) -(V) -(Vr
) −(IV) → (I), root [4]: (IX) −(III) −(VII[) −(V)
-(Vn) -(VI) -(JV)→(I), and root [5] (IX) -(IIT) -(■)-(V)-(V old→
It can be produced by five synthetic routes: (vr)→(I), but route [1] with fewer steps is particularly preferred.

(Examples of the Invention) Hereinafter, the present invention will be explained in more detail with reference to Examples, but these Examples are not intended to limit the scope of the present invention in any way.

Example 1 Synthesis of l-(2-chloroethoxy)-4(chloromethyl)-2,3-dimethylbenzene (1■) 184.69 g of 1-(2-chloroethoxy)-2,3-dimethylbenzene (1, 00 mol) to carbon tetrachloride 40
The mixture was dissolved in 300°C of 36% concentrated hydrochloric acid and cooled to -5°C. While stirring, hydrogen chloride gas was introduced and 430.90 g (5.00 mol) of 35% formalin was added dropwise. Formalin was added dropwise over 3 hours. The introduction of 665.0 g (18.20 mol) of hydrogen chloride gas was completed in 4 hours. During this time, the temperature was maintained at -10-0°C. After completing the introduction of hydrogen chloride gas, the mixture was stirred at -5°C for 45 minutes.

The organic phase was separated and dried over anhydrous calcium chloride. 293. was obtained by introducing nitrogen to remove hydrogen chloride gas and concentrating it.
The OOg residue was purified by vacuum distillation.

Yield 195.84g (84%) bp 145-152℃ (2.5mmHg)m
p 58-61°C Elemental analysis CHCff Theoretical value 5667% 6.05% 30.41% Actual value 56.43% 6.01% 3069% MS (
m/e): 233H-NMR ((1:DC)δ: 2.20 (3H,
sl, 2.33 (3H, s) 3,82 (2H,
t, J・6Hz), 4.21 (2Ht, J-6
Hzl, 4.61 (2H, s), 6.65 (IH,
d, J=8Hzl, 7.11DH,d.

J=8Hz) IRfKBr)cm-':2915. 1585. 1
475. 12951255, 1100.1030.7
95.650 Example 2l-(2-chloroethoxy)-4
Synthesis of -(chloromethyl)-2,3-dimethylbenzene (II) 1-60.00 g (0,348 mol) of -(2-chloroethoxy)-2,3-dimethylbenzene was added to 17 mol of carbon tetrachloride.
0- was dissolved in 0-, water 68- was added, and hydrogen chloride gas was introduced at room temperature for 20 minutes. Cool to -5°C and add 149.39 g (1,67 imol) of 35% formalin to 1.5
It dripped in time. Hydrogen chloride gas was continuously introduced while formalin was being added, and 224.0 g (6,145 mol) was
Added in time. During this time, the temperature was kept at -8 to -2°C and vigorously stirred. The mixture was further stirred at that temperature for 0.5 hour. Post-treatment and purification were performed in the same manner as in Example 1.

Yield 59.79g (73.7%) Example 3l-(
2-chloroethoxy)-4-(chloromethyl)-2,3
- Synthesis of dimethylbenzene (II) 1-89.20 g (0,483 mol) of -(2-chloroethoxy)-2,3-dimethylbenzene was added to 20 g of carbon tetrachloride.
36% concentrated hydrochloric acid was added thereto, and the mixture was cooled to -4°C. Introducing hydrogen chloride gas while stirring and 3.
85.78 g (1,000 mol) of 5% formalin was added dropwise. Formalin was added dropwise over 2 hours. The introduction of 820 g (22.50 mol) of hydrogen chloride gas was completed in 4 hours. During this time, the temperature was maintained at -5 to 0°C. After completing the introduction of hydrogen chloride gas, the mixture was further stirred at that temperature for 2 hours. Post-treatment and purification were performed in the same manner as in Example 1.

Yield 80.40g (71%) Example 4 Synthesis of l-(2-chloroethoxy)-4=(chloromethyl)-2,3-dimethylbenzene (II) 1-(2-chloroethoxy)-2,3- Take 2.98 g (15.6 mmol) of dimethylbenzene, 5-1 acetic acid, 5-1 concentrated hydrochloric acid (35%), 5-1 carbon tetrachloride, and add to this 3, Log (32,4 mm
ol) was added dropwise.

After stirring at room temperature for 2 hours, the mixture was separated. After drying the organic phase with calcium chloride, analysis by gas chromatography revealed that 1-(2-chloroethoxy)-4-(chloromethyl)
-2,3-dimethylbenzene was produced with a yield of 92%.

Example 5 Synthesis of l-(2-chloroethoxy)-4(chloromethyl)-2,3-dimethylbenzene (II) 9.35 g (48.9 mmol) of 1-(2-chloroethoxy)-2,3-dimethylbenzene ), 45 d of acetic acid, 15 i of concentrated hydrochloric acid (35%), and 15 ml of carbon tetrachloride, and to this were added 9.56 g of chloromethyl ethyl ether (
l O0, 1 mmol) was added dropwise. After stirring at room temperature for 3 hours, the mixture was separated. After drying the organic phase with calcium chloride, analysis by gas chromatography revealed that 1-(2
-chloroethoxy)-4-(chloromethyl)-2,3-
Dimethylbenzene was produced with a yield of 86%.

Example 6 Synthesis of l-(2-chloroethoxy)-4-(chloromethyl)-2,3-dimethylbenzene (IT) 1-(2-chloroethoxy)-2,3-dimethylbenzene 46.0 g (240, 5 mmol), acetic acid 50 d,
Concentrated hydrochloric acid (35%) 50-1 carbon tetrachloride 5O-In! ! and chloromethyl ethyl ether 4.7. 5
6 g (497.8 mmol) were added dropwise. After stirring at room temperature for 3 hours, the mixture was separated. After drying the organic phase with calcium chloride, the solvent was distilled off to obtain 53.77 g of residue.

Distill this under reduced pressure to 120-125°C10.5mm
45.60 g of 1-(2-chloroethoxy)-4-[chloromethyl)-2,3-dimethylbenzene was obtained as a Hg fraction. (Yield 80%) Comparative Example 1 l-(2-chloroethoxy)-2,3-dimethylbenzene3. Ol g (15.7 mmol), acetic acid 5-
1 Carbon tetrachloride 5- was taken, and 3.08 g (32.2 mmol) of chloromethyl ethyl ether was added dropwise.

After stirring at room temperature for 13 hours, the layers were separated and the organic phase was analyzed by gas chromatography. As a result, 79% of 1-(2-chloroethoxy)-2,3-dimethylbenzene remained unreacted, and bis[4- (2-chloroethoxy)-2,3-dimethylphenyl]methane was produced in a yield of 19%.

Comparative Example 2 l-(2-chloroethoxy)-2,3-dimethylbenzene 9.32g (48.7mmol), acetic acid 15ml,
Carbon tetrachloride 15- was taken, and while cooling with water and blowing hydrogen chloride gas into it, 9.63 g of chloromethyl ethyl ether (
100.8 mmol) was added dropwise. After 5 hours of reaction, the blowing of hydrogen chloride gas was stopped and the mixture was separated. Analysis of the organic phase by gas chromatography revealed that bis[4-(
2-chloroethoxy)-2,3-dimethylphenyl 1 mecne was produced in a yield of 92%.

Comparative example 3 l-(2-chloroethoxy)-2,3-dimethylbenzene 3.00 g (15.7 mmol), carbon tetrachloride 5
mA', concentrated hydrochloric acid (35%) 5- was taken, and 3.10 g (32.4 mmol) of chloromethyl ethyl ether was added dropwise thereto. After stirring for 1 hour at room temperature, the layers were separated and the organic phase was analyzed by gas chromatography.
57% chloroethoxy)-2,3-dimethylbenzene
It remained unreacted, and bis[4-(2-chloroethoxy)-2,3-dimethylphenyl 1 mecne was produced in a yield of 38%.

Comparative Example 4 3.03 g (15.8 mmol) of l-(2-chloroethoxy)-2,3-dimethylbenzene, 5 parts of acetic acid, 5 parts of concentrated hydrochloric acid (35%) of 5 parts of carbon tetrachloride were taken, and formalin was added to this. (37%) 2.55 g (31.4 mmol) were added dropwise. After stirring at room temperature for 20 hours, the mixture was separated. When the organic phase was analyzed by gas chromatography, it was found that 1-(
2-chloroethoxy)-2,3-dimethylbenzene is 3
5% remained unreacted, and bis[4-(2-chloroethoxy)-2,3-dimethylphenylcomethane was produced at a yield of 44%.

Example 7 Synthesis of chloromethyl ethyl ether (A) 1.20 g (0,0279 mol) of thorium hydroxide was added to 1018.6 g (22,00 mol) of ethanol and dissolved by stirring at 65°C.

Then rose formaldehyde (commercially available 80%) 825.
8g (22.00 moles in terms of formaldehyde)
was added, and the mixture was heated and stirred at 65° C. for 1 hour to dissolve the formaldehyde.

After dissolving the formaldehyde, 1127 g (30.92 mol) of hydrogen chloride gas was introduced and stirred over 65 hours while cooling and maintaining the temperature at 0 to 10°C.

After the reaction is completed, the organic phase is separated and anhydrous calcium chloride5.
After adding OOg and drying, separate the oven and heat at 80°C for 1.
Hydrogen chloride gas was removed by heating for 5 hours, followed by distillation.

Yield 1613.4g (78%) bp 80-84℃ Example 8 Synthesis of chloromethyl butyl ether (A) Add 0.05g (0,001 mol) of sodium hydroxide to 74.12 g (1,00 mol) of butanol and add 65
Stir to dissolve at ℃. 37.54 g (1.000 mol in terms of formaldehyde) of rose formaldehyde (commercially available 80%) was added thereto, and the mixture was heated and stirred at 65°C for 1 hour.

After dissolving the formaldehyde, 51.23 g (1,406 mol) of hydrogen chloride gas was introduced and stirred over 3 hours while cooling and maintaining the temperature at 0 to 10°C.

After the reaction is completed, the organic phase is separated and anhydrous calcium chloride is added.
30g was added, and after drying, it was separated in the oven, and the oven liquid was heated to 130℃.
．． Hydrogen chloride gas was removed by heating for 5 hours, followed by distillation.

Yield 105.43g (86%) bp 130-134°C Comparative Example 5 35% formalin 128.70g (1,500 mol)
and 69.45 g (1,500 mol) of ethanol were mixed, and 199.0 g (5,614 mol) of hydrogen chloride gas was introduced over 5.5 hours and stirred. The temperature was maintained at 3 to 8°C during the introduction of hydrogen chloride gas.

After hydrogen chloride gas introduction, anhydrous calcium chloride 30.0
(If this salting out is not performed, the target substance will be dissolved in the aqueous layer.)

The organic matter was separated and dried over anhydrous calcium chloride.

Desiccant? Hydrogen chloride was removed by passing nitrogen through each door for 30 minutes, and the mixture was distilled.

Yield 95.95g bp 77-83°C As a result of measuring the NMR spectrum of the oil obtained here, it was found that the molar ratio of chloromethyl ethyl ether: tetraromethyl methyl ether was 87:13.

Therefore, the yield of chloromethyl ethyl ether was as low as 61%. Furthermore, when attempting to isolate chloromethyl ethyl ether by distillation alone, the yield decreased to about 20-30%.

Example 9 Synthesis of l-(2-chloroethoxy)-4-(2-ethoxyethyl)-2,3-dimethylbenzene (1) 27.43 g (1,13 gatml) of magnesium metal
, 200 ml of tetrahydrofuran was taken and heated under nitrogen stream.
Cooled to 0.degree. C. with stirring. To this, a solution of 188.8 g (809.8 mmol) of 1-(2-chloroethoxy)-4-(chloromethyl)-2,3-dimethylbenzene in tetrahydrofuran (1140 mf') was added at a temperature of 0.
The mixture was added dropwise over 3.5 hours so as not to exceed .degree.

Next, 1082 g of chloromethyl ethyl ether (11
32,5 mmol) of tetrahydrofuran (200 mf
f) The solution was added dropwise over 2 hours. -5~10℃
The reaction took place for 30 minutes. After adding 300 ml of water and stirring for 30 minutes, 500 ml of toluene was added.

After separation, the organic phase was washed with 200 i of saturated brine. This was concentrated to obtain 213.84 g of residue. This was distilled under reduced pressure to obtain 166.3 g of 1-(2-chloroethoxy)-4-(2-ethoxyethyl)2.3-dimethylbenzene as a fraction of 137-b Hg. Yield 80% Elemental analysis CHCβ Theoretical value 65.49 B, 24 13.87 Actual value 65,26 8.01 13.91 MS (m/
e): 256(M″″1.197(M″-CH20C
Jsl.

135 (197-CH2=CHC, &1'H-NM
R(fl; Cmu) δ: 1.15-1.23 (3H,
t), 2, 15 (3H, s) 2, 20 (3H, s).

2.82-2.90 2H,t 3.45-3.60 4H, m 3.75-3.80 2H, t.

4.10~4.20 2H,t 6.60-6.65 1H, d.

6.95-7.00 LH, d IRjNaCJ board) cm-': 2850-2960.1
590.14801370.1300.1260.11
00 Example 10 1-(2-chloroethoxy)-4-(
Synthesis of 2-ethoxyethyl)-2,3 dimethylbenzene (I) Metallic magnesium 9.75g (401,2mgatm
), 50% of tetrahydrofuran was taken and cooled to 0°C while stirring under a nitrogen stream. To this, a solution of 4692 g (201.3 mmol) of (2-chloroethoxy)-4-(chloromethyl)-2,3-dimethylbenzene in tetrahydrofuran (150 d) was added. After confirming that the Grignard reaction had started, the above solution was further diluted with tetrahydrofuran (150i), which was added dropwise so that the temperature of the reaction solution did not exceed O'C. After dropping, -
The reaction was carried out at 8-0°C for 2 hours. After separating the insoluble magnesium, 21.26 g of chloromethyl ethyl ether (
222,5 mmol) of tetrahydrofuran (50 m&
) solution was added dropwise. After the dropwise addition, the mixture was further reacted at the same temperature for 2 hours. After adding 500 parts of toluene and 50 parts of water,
The mixture was made acidic by adding 20% of IN hydrochloric acid. After separation, the aqueous phase was extracted with 250 g of toluene, and the organic phases were combined and washed twice with 200 g of water. After drying with Glauber's salt, the solvent was distilled off to obtain 54.44 g of a pale yellow liquid. This was distilled under reduced pressure to give 136~
32.82 as a fraction at 139°C/2 mmHg
g of 1-(2-chloroethoxy)-4-(2-ethoxyethyl)-2,3-dimethylbenzene was obtained. Yield 6
7% Example 11 1-(2-chloroethoxy)-4-(2-
Synthesis of magnesium metal (ethoxyethyl)-2,3 dimethylbenzene (I) 1.81g (74,47mgatm
), a trace amount of iodine was collected, and it was heated at room temperature under a stream of nitrogen (1-(
2-chloroethoxy)-4-(chloromethyl)-2,3
- A solution of 996 g (42.72 mmol) of dimethylbenzene in 40 ml of tetrahydrofuran was added several times. After confirming that the Grignard reaction had occurred, the above solution was further diluted with 30% of tetrahydrofuran, cooled, and added dropwise so that the temperature of the reaction solution did not exceed O'C. After dropping, -5
After reacting at ~0°C for 3 hours, a solution of chloromethyl ethyl ether 7, OOg (73.27 mmol) in 50% tetrahydrofuran was added dropwise at the same temperature. After the dropwise addition, the mixture was reacted at the same temperature for 2 hours, and then 300 g of a 10% aqueous ammonium chloride solution was added, and after stirring for 1 hour, 500 g of toluene was added for extraction. After drying with Glauber's salt, the solvent was distilled off, and 50 g of hexane was added to the resulting residue to separate out insoluble materials. The seven door liquid was concentrated to obtain 10.47 g of pale yellow liquid. This was subjected to a silica gel ram (toluene developer) to separate 9.02 g of 1-(2-chloroethoxy)-4-(2-ethoxyethyl)-23-dimethylbenzene. Yield 82% Example 12 1-(2-chloroethoxy)-4-(2-
Synthesis of magnesium metal (ethoxyethyl)-2,3-dimethylbenzene (I) 12.51g (514.6mgat
m), trace amounts of iodine and 100 g of tetrahydrofuran were taken under a nitrogen stream, and 1-(2-chloroethoxy)- was added under cooling.
4-(rishikou methyl)-2゜3-dimethylbenzene 10
A solution of 0.3 g (430.2 mmol) and 49.20 g (515.0 mmol) of chloromethyl ethyl ether in 600 mf' of tetrahydrofuran was added at a reaction temperature of 0°.
It was added dropwise over 2.5 hours so as not to exceed C.

Furthermore, after reacting at -5 to -10°C for 2 hours, water 150
Added a bow. After stirring for 30 minutes, 250 g of toluene was added to separate the layers. The organic phase was concentrated to obtain 115.72 g of pot residue.

This was distilled under reduced pressure and the fraction at 142-149°C/3mmHg was 69.59 1-(2-chloroethoxy)-4-(2-ethoxyethyl)-2,3-dimethylbenzene.
I got g. Yield 63% Example 13 Synthesis of 1-(2-chloroethoxy)-4-(2-methoxyethyl)-2,3-dimethylbenzene (I) Metallic magnesium 1.94g (79,82mgatm
), a trace amount of iodine was collected, and it was heated at room temperature under a stream of nitrogen (1-(
2-Chloroethoxy)-4-(di-4-methyl)-2,3
-dimethylbenzene 12.41g (53.23mmal
) in tetrahydrofuran were added several times. After confirming that the Grignard reaction had occurred, the above solution was further diluted with 30% of tetrahydrofuran, cooled, and added dropwise so that the temperature of the reaction solution did not exceed 0°C. After dropping, -
After reacting for 3 hours at 5-0°C, a solution of 6.40 g (79.49 mmol) of chloromethyl ethyl ether in tetrahydrofuran 50 was added dropwise at the same temperature. After being reacted at the same temperature for 2 hours after the dropwise addition, 300% of a 10% ammonium chloride aqueous solution was added, and after stirring for 1 hour, 500% of toluene was added.
d was added and extracted. After drying with Glauber's salt, the solvent was distilled off, and 50% of hexane was added to the obtained residue to remove insoluble matter. The furnace liquid was concentrated to obtain 9.69 g of pale yellow liquid. This was applied to a silica gel column (toluene developer) to separate 8.40 g of 1-(2-chloroethoxy)-4-(2-methoxyethyl)-2,3-dimethylbenzene. Yield 65% Elemental analysis CHC flood theoretical value 63.93% 861% 14.34% Actual value 63.75% 8.53% 14.52% MSf
m/el: 244 (M”), 197.135 Example 14 Synthesis of 1-(2-chloroethoxy)-4-(chloroacetyl)-2,3-dimethylbenzene (■) 360 units of nitrobenzene and 87 units of aluminum chloride .25
g (0.65 mol) was dissolved and cooled on ice. To this, 65.05 g (0.66 mol) of Rirowa acetic chloride was added to 3
0 minutes, then 1-(2-chloroethoxy)-
2,3-dimethylbenzene 92.35g (0.5ma
1 liter was added dropwise. After stirring for 1 hour under water cooling,
．． Stirred for 5 hours. The mixture was cooled with water again, and 400 d of ice water was added to decompose the aluminum chloride. After the aluminum chloride was completely decomposed, the solution was allowed to stand and the nitrobenzene layer was separated. The aqueous layer was extracted with 200 mm of methylene chloride, and this was combined with the previous nitrobenzene layer, washed twice with 300 mm of 3% hydrochloric acid, then twice with 300 mm of saturated aqueous sodium bicarbonate solution, and finally washed with water and dried.

After distilling off the solvent, the mixture was dissolved in 100% methylene chloride, 400% hexane was added thereto, and the precipitated white solid was collected. The furnace collection was dried under reduced pressure to obtain 97.22 g of 1-(2-
chloroethoxy)4-(chloroacetyl)-2,3-dimethylbenzene was obtained. Yield 75% MS (m/e): M”2B0.211.149.1
211R(c+t+-'): 1770.1260.1
22 (1,1095,795'H-NMR (C; DC) δ 2.20 (3H, s), 2.40 (3H, s)
3.87F2H,tl, 4.27(2+(,tl4.
56 (3H, s), 6.70 (], H, d) 7, 44
(11(,d) Example 15 Synthesis of 4-acetoxyacetyl-1-(2-chloroethoxy)-2,3 dimethylbenzene (V) 1-(2-chloroethoxy)-4-(chloroacetyl)
-2,3-dimethylbenzene 13.06g (0,05
mol), sodium acetate 8.20g (0, 1mail
was added to 120 ml' of dimethylformamide (DMF) and stirred at 50°C for 1.5 hours.

Thereafter, DMF was distilled off under reduced pressure (5-8 mmHg). After cooling, 100 g of 5% hydrochloric acid and 100 g of toluene were added to separate the layers. The aqueous layer was extracted with 70ml of toluene, combined with the previous toluene layer, washed once with 100ml of 5% hydrochloric acid, twice with 100ml of water, and dried. After that, toluene was distilled off, and 4-
Acetoxyacetyl-1-(2-chloroethoxy)-2
13.61 g of 3-dimethylbenzene was obtained. Yield 96% MS (m/el: M”284.211.149.1
211R (cm-'): 1745.1590.123
0.1110.101060H-N [COOm)δ:
2.15 (6H, s), 2.38 (31 (, s13
．． 82 (2H, tl, 4.22 (2H, t,)5.
1Of2)1. s), 6.68 [IH, d).

7.42 (IH, d) Example 16 Synthesis of 1-(2-chloroethoxy)-23-dimethyl-4-(2-hydroxyethyl)benzene (IV) Under a nitrogen stream, 1.33 g of sodium borohydride was added. The suspension was suspended in 15mj+ of tetrahydrofuran (THF) and cooled on ice. To this, at the same temperature, boron trifluoride ether complex salt 24.5
g (173 mmol) was added dropwise over 10 minutes, and 4
-acetoxyacetyl-1-(2-chloroethoxy)-
2,3-dimethylbenzene4. 72 g (16,6
A solution of 5 mmol) dissolved in THF was added dropwise over 5 minutes. After stirring for 1 hour under water cooling, the mixture was refluxed for 2 hours. After the reaction, the mixture was cooled on ice again, 5% hydrochloric acid was added dropwise to completely decompose the reaction reagent, and 100-isopropyl ether was added for extraction. The organic phase was washed with a saturated aqueous sodium bicarbonate solution and then with water, and then dried over anhydrous sodium sulfate. After separating off the sodium sulfate, the isopropyl ether was distilled off and 1-(2-chloroethoxy)-2,3-dimethyl-4-
3.63 g of (2-hydroxyethyl)benzene was obtained.

Yield 96% IR (cm-'l: 3400.1260.11
05. 800'H-NMR (COOm) δ: 1.
69 (IH, s), 2.19 (3H, s) 2.22 (
3H,s), 2.86(2H,tl3.762H,
t, 3.80 (2H, t) 4.18 (2H, tl
, 6.64 (ILdl.

6.96 1H,d MS (m/e): M”228.197.13
5. 105 Example 17 1-(2-chloroethoxy)
Synthesis of -23-dimethyl-4-(2-hydroxyethyl)benzene (IV) Under a nitrogen stream, 0.27 g of sodium borohydride (7
, 02 mmol) was suspended in TF (F6-) and cooled with water.To this, 100 g of 4-acetoxyacetyl-1-(2-chloroethoxy)-2,3-dimethylbenzene was dissolved in 557 g of boron trifluoride ether complex salt. was added dropwise over 1 hour.

After the addition, the mixture was further refluxed for 1 hour. After the reaction, the mixture was cooled on ice and the reaction reagent was completely decomposed with 5% hydrochloric acid, followed by extraction with 50 parts of isopropyl ether. After washing with a saturated aqueous sodium bicarbonate solution and then with water, drying with anhydrous sodium sulfate and distilling off isopropyl ether, 1-(2-
0.73 g of chloroethoxy)-2,3-dimethyl-4-(2-hydroxyethyl)benzene was obtained. Yield 9
1% Example 18 Synthesis of 1-(2-chloroethoxy)-2゜3-dimethyl-4-(2-acetoxyethyl)benzene (vr) 4-acetoxyacedel-1-(2-chloroethoxy)
-2,3-dimethylbenzene 0.89 g (3,1 mmo
l), dioxane 10ml, Raney nickel (W21
Put 0.5g into an autoclave and add 30kg of hydrogen.
/'cm2G and reacted at 120°C for 6 hours. After cooling, hydrogen was released, nickel was separated, and the solvent was distilled off. The residue was separated by column chromatography (silica gel/methylene chloride) to obtain 80 g of 1-(2-chloroethoxy)-2,3-dimethyl-4-(2-acetoxyethyl)benzene. Yield 72% MS (m/e): M”270.210.197.1
48.135IR (cm-'l: 1730.126
0.1235HNMR (CDCI:+)δ: 2. D4
f3H,s), 2.19(3H,s)2,24 (3
H,s), 2.91 (2H,t).

3.8Of2)T, tl, 4.1-4.25(4H,
m16.64 (IH, d), 6.96 (l) T, d+
Example 19 Synthesis of 1-(2-chloroethoxy)-2゜3-dimethyl-4-(l-hydroxy-2-acetoxyethyl)benzene (vn) 4-acetoxyacetyl-1-(2-chloroethoxy)
-2,3-dimethylbenzene 1.29 g (4,5 mmo
1) was dissolved in ethanol, 10.6 g of Raney nickel (W2) was added thereto, and the inside of the reaction vessel was filled with hydrogen.The inside of the reaction vessel was always kept at normal pressure with hydrogen at 50°C. The mixture was stirred for 8 hours. After the reaction, the Raney nickel was separated from each other, the solvent was distilled off, and 1-(2-chloroethoxy)
1.22 g of -23-dimethyl-4-(1-hydroxy-2-acetoxyethyl)benzene was obtained. Yield 94% IR (cm-'): 3400. 1740. 12
60. 1230MS (m/el: M”286.2
69.226.197.179.149'H-NMR (
COOm) δ: 2.11 (3H, s), 2.19 (
3H, s) 2.25 (3H, s), 2.50 (LH,
s) 3.82 (2H, t), 4.0-4.3 (4H,
m) 5.17 (lH, dd), 6.72T11 (, d
d) 7, 31 (LH, dl [Effects of the Invention] According to the present invention, compounds useful as medicines, agricultural chemicals, and especially insecticides can be provided.

Claims (15)

[Claims] (1) The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1, R^2 and R^3 each independently represent a lower alkyl group; X^1 represents a halogen atom.) A compound represented by: (2) The following formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^2 and R^3 each independently represent a lower alkyl group; X^1 and X^2 each independently represents a halogen atom). (3) The compound according to claim 2, and the following formula (A): X^3CH_2OR^1(A) (in the formula, R
^1 represents a lower alkyl group; X^3 represents a halogen atom. 2. The method for producing a compound according to claim 1, wherein the compound represented by the following formula is reacted in the presence of metallic magnesium. (4) After reacting an alkali-containing alcohol represented by the following formula (B): R^1OH (B) (in the formula, R^1 represents a lower alkyl group) with paraformaldehyde, halogenation Claim 3 characterized in that the treatment is performed with hydrogen.
A method for producing a compound represented by formula (A). (5) The following formula (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (In the formula, R^2 and R^3 each independently represent a lower alkyl group; X^1 is 3. The method for producing a compound according to claim 2, which comprises reacting a compound represented by (representing a halogen atom), formaldehyde or a polymer thereof, and hydrogen halide. (6) A compound represented by formula (III) in claim 5, and the following formula (C): R^4OCH_2X^2(C) (in the formula, R
^4 represents a lower alkyl group; X^2 represents a halogen atom. 3. The method for producing a compound according to claim 2, characterized in that the compound represented by the following formula is reacted in the presence of acetic acid and an aqueous hydrogen halide solution corresponding to X^2. (7) The following formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) (In the formula, R^2 and R^3 each independently represent a lower alkyl group; X^1 is ) represents a halogen atom. (8) The following formula (V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (V) (In the formula, R^2, R^3 and R^5 each independently represent a lower alkyl group; X^1 represents a halogen atom.) A compound represented by: (9) A method for producing the compound according to claim 7, which comprises treating the compound according to claim 8 with a reducing agent consisting of sodium borohydride and boron trifluoride ether complex salt. (10) The following formula (VI): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VI) (In the formula, R^2, R^3 and R^5 each independently represent a lower alkyl group; X^1 represents a halogen atom.) A compound represented by: (11) Claim 1, characterized in that the compound according to Claim 8 is treated under hydrogen pressure in the presence of Raney nickel.
Method for producing the compound described in 0. (12) The following formula (VII): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VII) (In the formula, R^2, R^3 and R^5 each independently represent a lower alkyl group; X^1 represents a halogen atom.) A compound represented by: (13) A method for producing the compound according to claim 12, which comprises treating the compound according to claim 8 at normal pressure in the presence of Raney nickel. (14) The following formula (VIII): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VIII) (In the formula, R^2 and R^3 each independently represent a lower alkyl group; X^4 each independently represents a halogen atom.) A compound represented by the following formula (D): (R^5COO)_nM (D) where R^
5 represents a lower alkyl group; M represents a monovalent or divalent metal; n represents 1 or 2; 9. The method for producing the compound according to claim 8, which comprises reacting with a compound represented by: (15) A compound represented by formula (VIII) in claim 14.