JPS5959639A - Preparation of 1-phenyl-2-alkoxypropylenes - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an intermediate for various kinds of agricultural chemicals, perfume, drugs, etc. by an extremely simple operation, by bringing a 1-phenyl-2,2-dialkoxy-propane to be easily synchesized into contact with a solid acid catalyst in a liquid phase. CONSTITUTION:For example, a 3-phenylpropylene shown by the formula I (X, Y, and Z are H, OH, halogen, nitro, amino, alkyl, or alkoxy; any two of X, Y, and Z together with part of benzene ring form 5-7-membered heterocyclic ring; R is alkyl, or benzyl) is reacted with an alkyl ester nitrite in the presence of an alcohol and palladium catalyst to give a 1-phenyl-2,2,-dialkoxypropane shown by the formula II, which is brought into contact with a solid acid catalyst such as strongly acidic cation exchange resin, etc. in a liquid phase to give a 1-phenyl- 2-alkoxypropylene shown by the formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a novel method for producing 1-phenyl-2-alcoquine propylene.

1-phenyl-2-alkoxypropylenes c.

As an intermediate piece for various agricultural chemicals, fragrances, pharmaceuticals, etc.

It has many industrial uses.

The present invention consists of liquid phase contacting of 1-phenyl-2,2-dialkoxy7propanes with a solid acid catalyst. Due to extremely simple operation. A method for producing 1-phenyl-2-alkoxypropylenes is provided.

Next, two inventions will be explained in detail.

In the 1-phenyl-2,2-dialkoxypropanes that are the raw materials of the present invention, a substituent may be attached to the benzene ring. Examples of substituents are:

Hydroxyl group, halogen atom, nitro group, amine group, carbon number 6
Examples include a lower alkyl group having up to 6 carbon atoms, and a lower alkoxy group having up to 6 carbon atoms. These substituents can be attached to the benzene ring in a total number of substituents or less. That is, the 1-phenyl-2,2-dialkoxy7propanes used in the present invention can be represented by the following formula (1).

R (However, in formula 2, X, Y, and Z are each hydrogen atoms.

Represents a substituent selected from the group consisting of a hydroxyl group, a halogen atom, a nitro group, an amine group, a lower alkyl group, and a lower alkoxy group, even if X, Y, and Z are the same.

Each of them may be different, and any two of x, y, and z together with a part of the benzene ring form a 5- to 7-membered heterocycle containing 1 to 2 oxygen atoms. It's okay. In the formula, R represents an alkyl group having 1 to 10 carbon atoms or a benzyl group.

The 1-phenyl-2,2-dialkoxypropanes represented by the general formula (+) are 1-phenylpropylenes, which can be represented by the following formula (1), for example, in the presence of an alcohol and a palladium salt catalyst. It can be easily synthesized by reacting with an alkyl nitrite ester as described below.

CH2-CH=CH2 (X, Y and Z in the 2 formulas 117i, uil i
It has the same meaning as i+shi. ).

This reaction 1d, 3-phenylpropylene force "11
About 2 to about 5 moles of 1 to 10 carbon atoms per mole
・Nitrite alkyl ester having 1 and about 1 to about 1o
using an L-alcohol in the presence of a palladium salt such as palladium chloride, optionally in a solvent such as acetic acid ester, at a temperature of from about 5 to about 150°C.

When carried out at a pressure of normal pressure to about 200 Kg/crlI (gauge), 7 can be obtained.

According to the present invention, for example, by bringing 1-phenyl-2,2-dialkoxypropanes, which can be synthesized in this way, into liquid phase contact with a solid acid catalyst, a phenylalkoxypropylene corresponding to the propanes can be produced. is manufactured.

Examples of solid acid catalysts that can be used include silica, alumina, magnesia, boria, solicar alumina, /liquor magnesia, and /licarboria.

Alumina-boria, magnesium sulfate, manganese sulfate,
Inorganic compounds such as zinc sulfate and aluminum sulfate, cation exchange resins with sulfonic groups, and various types of sodium silicate called zeolites.

Further examples include acid clay, activated clay, kaolin, natural clay minerals such as montmorillonite, and the like.

These solid acid catalysts are suitable for their uses: 1. If j is too small, the reaction will not progress sufficiently, and even if a large amount is used, the reaction will not be adversely affected.

Using more than the necessary amount is uneconomical. In view of these considerations, 0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight (?1 It is good to have part IIj.

The solvents used in the present invention include:

1-phenyl-2,2-sialcoquinzo-r'' Any material that dissolves breads well and is inert to the reaction is acceptable.
: L-1;l:, Aromatic hydrocarbons such as henzene, toluene, and quinoa, low H fatty acid esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. Alternatively, a mixed solvent thereof can be used.

The solvent for cholera is usually about 5 to about 20 parts by weight of 1-phenylene/l/-2,2-dialkoxypropanes.
0 parts by weight are used.

In addition, the catalytic reaction in the present invention is usually carried out at about 10° to about 80°.
At a temperature of C, under normal pressure or pressurization, about 0.5 to about 20
Do time.

1-Phenyl- produced in this way according to the present invention
2-Alkoxypropylenes H1, ft secondary formula (Il
l).

R (However, in formula 2, X, Y, Z and R have the same meanings as above.)

After the contact reaction is completed, the 1-phenyl-2-alkoxypropylene compound represented by the general formula (III) can be isolated and obtained by conventional methods such as distillation and extraction.

Next, two examples of the present invention will be described. In addition, all 1-phenyl-2,2-dialkoxypropanes used as raw materials in each example were manufactured according to the following synthesis example.

Synthesis example - (4-hydroxyphenyl)propylene 0.10 mol, methyl nitrite 0.25 mol, methyl alcohol 0.
5 tons and 0.006 mol of palladium chloride as a catalyst were charged into a reaction vessel, and the reaction was carried out under the following conditions: 2 reaction temperature: 20° C. 2 reaction time: 1.5 hours.

After the reaction was completed, one reaction solution was distilled to obtain 1-(4-hydroxyphenyl)-2,2-dimethoxy/propane with a yield of 85%.

Example 1 After dissolving 0.1 mol of 1-phenyl-2,2-diethoxy/propane in 0.5 t of ethyl acetate, 9 strongly acidic cation exchange resin (trade name: AmberiSl, -15+ manufactured by Rohm and Haas Co., Ltd. ) Add filter 07 and mix well 2
A contact reaction was carried out at 5°C for an hour.

After the reaction was completed, the catalyst recovered by filtration was washed with 0.1 t of ethyl acetate, and the washing liquid was added to the solution.

The liquid was then quantitatively analyzed by gas chromatography. The results are shown in the table below.

Examples 2 to 12 0.1 mol of each of the 1-phenyl-2,2-dialkoxypropanes shown in the secondary table was used as a raw material.

Further, an experiment was conducted in the same manner as in Example 1, except that each of the various solid acid catalysts shown in the following table was used.

The results are also shown in the table below.

Example 1'5 Instead of ethyl acetate, 0.5 t of methyl in butyl ketone
The experiment was conducted in the same manner as in Example 1, except that the following was used as the solvent. The results were as follows.

1-(4-hydroquinphenyl)-2,2-dime[・
Conversion rate of quinopropane: 92% Yield of 1-(4-hydroxyphenyl)-2-methoxypropylene: 85% Yield of 1-(4-hydroxyphenyl)-2-methoxy7propylene, 2% Example 14 An experiment was conducted in the same manner as in Example 9, except that toluene O, SZ was used as the molten U instead of ethyl acetate. The results were as follows.

Conversion rate of 1-(lo, 4-dimethoxyphenyl)-2,2-dimethoxy/propane: 95% Yield of 1-(lo, 4-dimethoxyphenyl)-2-notokinlopyrene: 90% , 4-dimethoxyphenyl)-2-7propylene yield, 2. Example 15 The experiment was carried out in the same manner as in Example 11, except that 0.5 t of dioxane was used as the solvent instead of ethyl acetate. went. The results were as follows.

1-43.4-methylenedioxyphenyl)-2,2-
Conversion rate of dimethoxypropane: 9 filtration ratio 1-(3,4-methylenedioquinophenyl)-2-methoxy 7 Yield of propylene: 87 ratio 3-(3,4-methylenedioxy/phenyl)-2-meth Yield of ginpropylene: 2chi patent applicant Ube Industries, Ltd.

Claims (1)

[Claims] Bringing 1-phenyl-2,2-dialkoxy-7-propanes into liquid phase contact with a solid acid catalyst is defined as 1=J. Method for producing 1-phenyl-2-alkoxypropylenes.