JPH09309853A - 2-(2-alkenyl)1,3-dialkoxypropane and production of 2,2-dialkyl-1,3-dialkoxypropane using alkenyl-1,3-dialkoxypropane as a raw material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel 2-(2-alkenyl)-1,3-dialkoxypropane useful as a starting substance for 2,2-disubstituted-1,3-dialkoxypropane which is useful as a lubricant, a metallic ion complex-forming agent and an organic solvent. SOLUTION: This novel compound is 2-(2-alkenyl)1,3-dialkoxypropane represented by formula I (R1 is a 1-18C alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl; R2 -R6 are each H, a 1-18C alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl or 2 or more of R1 -R6 may bond to form a cyclic structure; R7 and R8 are each a lower alkyl), typically 2-allyl-2-methyl-1,3-dimethoxypropane. The compound of formula I is prepared by allowing 2-(2-alkenyl)-1,3-propanediol of formula II to react with a lower alkyl sulfate or a lower alkyl halide in the presence of a base. The hydrogenation of the compound of formula I affords 1,3-dialkoxypropanes of formula III.

Description

Detailed Description of the Invention

[0001]

The present invention relates to 2- (2-alkenyl) -1,3-
Dialkoxypropanes and 2,2-using these as raw materials
The present invention relates to a method for producing disubstituted-1,3-dialkoxypropanes.

[0002]

2. Description of the Related Art 2,2-Disubstituted-1,3-dialkoxypropanes are compounds useful as lubricants, metal ion complexing agents, organic solvents and the like. The 1,3-dialkoxypropane is conventionally produced by reduction of a malonic acid diester with a metal hydride or dialkylation of a 1,3-diol obtained by a Cannizzaro reaction with a saturated aldehyde and an alkaline formaldehyde.

[0003]

However, these methods are expensive and dangerous for reducing malonic acid diesters in the production of 1,3-propanediol, which is a raw material for 1,3-dialkoxypropane. Use high metal hydrides. In addition, in the Cannizzaro reaction of saturated aldehydes, except for some cases, the raw material saturated aldehydes are produced by selective reduction of carbon-carbon double bonds of 2-alkenals and 4-alkenals. However, at this time, there is a problem that unreacted unsaturated aldehydes, which are difficult to separate, are mixed in because the selectivity of reduction is not sufficiently high, and an over-reduced unsaturated alcohol is by-produced.

On the other hand, the present inventors have found that they are simple, highly selective,
A method for producing 2-alkenyl-1,3-propanediol in high yield is provided in Japanese Patent Application No. 7-183928. The object of the present invention is to dialkyl 2- (2-alkenyl) -1,3-propanediol obtained by the method of the present inventors to solve the above-mentioned problems of the conventional method, and to carry out 2,2-disubstituted To provide a novel 2- (2-alkenyl) -1,3-dialkoxypropane which can be a precursor pair of -1,3-alkoxypropane, and the unsaturated 2- (2-alkenyl) -1,3 -To provide a method capable of obtaining 2,2-disubstituted-1,3-dialkoxypropane from dialkoxypropane.

[0005]

The present invention provides a compound represented by the general formula (1):

Embedded image [In the formula, R1 is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and R2, R3,
R4, R5 and R6 are a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and R1, R2, R3, R4 and R5. And R6 are the same or different, and two or more can combine to form a cyclic structure, and R7 and R8 are lower alkyl groups and are the same or different] 2- (2-alkenyl)-
1,3-dialkoxypropanes. And the general formula (1)
Hydrogenation of 2- (2-alkenyl) -1,3-dialkoxypropanes represented by the general formula (2):

Embedded image [In the formula, R1, R2, R3, R4, R5, R6, R7 and R8 are as defined in the above general formula (1)].
A method for producing 1,3-dialkoxypropanes represented by: I will provide a.

The 2- (2-alkenyl) -1,3-dialkoxypropanes represented by the general formula (1) include 2-allyl.
-2-Methyl-1,3-dimethoxypropane, 2- (1-methylethyl) -2- (2-methyl-2-propenyl) -1,3-dimethoxypropane, 2- (1-methylethyl) -2 -(3-Methyl-2-butenyl) -1,3
-Dimethoxypropane, 2- (1-methylethyl) -2- (2-methyl-2-propenyl) -1-ethoxy-3-methoxypropane, 2-
(1-Methyl-2-butenyl) -2- (1-methylethyl) -1,3-dimethoxypropane, 2- (1-methyl-2-propenyl) -2- (1-methylpropyl) -1,3 -Dimethoxypropane, 2- (2-cyclohexenyl) -2- (1-methylethyl) -1,3-dimethoxypropane, 2- (1-methylbutyl) -2- (1-methyl-2-propenyl)
-1-Butoxy-3-methoxypropane, 2- (2-methyl-2-propenyl) -2- (2-methylpropyl) -1,3-dimethoxypropane, 2- (2-cyclohexenyl) -2-cyclohexyl Examples include -1,3-dimethoxypropane and 2-phenyl-2-prenyl-1,3-dimethoxypropane.

The novel 2- (2-alkenyl) -1,3-dialkoxypropanes have the general formula (3):

[0008]

Embedded image

[In the formula, R1, R2, R3, R4, R5 and R6 are as defined in the above general formula (1)]
It can be produced by reacting 2- (2-alkenyl) -1,3-propanediol represented by with a lower alkyl sulfate ester or a lower alkyl halide in the presence of a base.

In the present invention, 2- (2-alkenyl) -1,3-
The catalyst used for the hydrogenation of dialkoxypropanes is an ordinary catalyst used for the hydrogenation of carbon-carbon double bonds, for example, palladium, platinum or the like activated carbon, barium sulfate, calcium carbonate, diatomaceous earth, alumina or Those supported on silica, platinum oxide, palladium oxide, palladium black, Raney nickel, ruthenium and the like and rhodium complex, ruthenium complex, iridium complex, platinum complex, homogeneous metal complex catalysts such as cobalt complex and the like, preferably platinum. A catalyst and a nickel catalyst.
The amount of the catalyst used varies depending on the type of the catalyst and the raw material, but is 0.05 to 50% by weight, preferably,
It is 0.1 to 30% by weight.

In the present invention, 2- (2-alkenyl) -1,3-
In the hydrogenation of dialkoxypropanes, a solvent inert to the reaction can be used as a reaction solvent. Specific examples of such a reaction solvent include aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, o-, m- or p-xylene and mesitylene. Examples include hydrogen-based solvents, ether-based solvents such as ethyl ether, butyl ether, and tetrahydrofuran, ester-based solvents such as methyl acetate and ethyl acetate, alcohol-based solvents such as ethanol, propanol, isopropanol, butanol, and t-butanol, and water solvents. it can. These solvents can be used alone or in combination.

The hydrogenation reaction of the present invention may be carried out continuously or batchwise. The reaction temperature and time vary depending on the raw materials used, but the reaction temperature is usually about 0 to 150 ° C., and the reaction time is usually 0.
It is about 1 to 30 hours. Hydrogen pressure is normal pressure to 100kg / c
m2.

Since the reaction mixture obtained by the hydrogenation reaction of the present invention usually contains by-products, unreacted starting materials, etc., the 2,2-disubstituted-1,3-substance which is the object of the present invention. The dialkoxypropanes can be obtained by separating and purifying from the reaction mixture. The separation method used is not particularly limited, and for example, known separation methods such as distillation, adsorption, extraction, recrystallization and the like may be used.

2,2-disubstituted obtained by the method of the present invention
-1,3-dialkoxypropanes are compounds useful as lubricants, metal ion complexing agents, and organic solvents.

[0015]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 11 2- (2-alkenyl) -1,3-dialkoxypropane In a 100 ml round-bottomed flask, 0.05 mol of 2- (2-alkenyl) -1,3-propanediol, dimethylsulfate and diethylsulfate were added. Alternatively, 0.05 mol of butyl tosylate, 30 ml of toluene, and 0.5 mmol of tetrabutylammonium hydrogensulfate were added, and 33.3 g of 48% sodium hydroxide aqueous solution was added dropwise at room temperature over 1 hour. After further stirring at room temperature for 5 hours, 30 ml of water was added and the aqueous layer was removed. The organic layer was washed 3 times with 30 ml of water and then dehydrated by azeotropic distillation. Next, in a 100 ml eggplant-shaped flask, potassium tert-
0.1 mol of butoxide and 40 ml of toluene were added, and the above dehydrated organic layer was added dropwise at room temperature for 1 hour. After stirring for 2 hours, 0.1 mol of dimethylsulfate was added dropwise at room temperature for 1 hour, and the mixture was further stirred for 1 hour. After completion of the reaction, 20 ml of water was added and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, concentrated, and purified by distillation. Raw materials, products,
The yield and NMR data of the product are shown in Tables 1 and 2.

[0017]

[Table 1]

[0018]

[Table 2]

Examples 12 to 20 Preparation of 2,2-disubstituted-1,3-dialkoxypropane 2- (2-alkenyl) was added to a 50 ml stainless steel autoclave.
-1,3-dialkoxypropane 0.01mol, 2% platinum-activated carbon 0.
After charging 2 g and 10 ml of ethanol and replacing the inside of the reaction system with hydrogen, the reaction was carried out at room temperature under a hydrogen pressure of 50.49 MPa, and the reaction was stopped when hydrogen absorption was stopped. The reaction mixture was analyzed by gas chromatography. The results are shown in Table 3.

[0020]

[Table 3]

[0021]

According to the present invention, a novel 2- (2-alkenyl) -1,3-dialkoxypropane which can be a precursor of 2,2-disubstituted-1,3-dialkoxypropane is provided. Further, by hydrogenating the alkenylpropanediol, 2,2-disubstituted-1,3-dialkoxypropane useful as a lubricant, a metal ion complexing agent, an organic solvent and the like can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 43/162 7419-4H C07C 43/162 43/166 7419-4H 43/166 43/168 7419- 4H 43/168 (54) [Title of Invention] 2- (2-alkenyl) -1,3-dialkoxypropanes and alkenyl-1,3-dialkoxypropanes as raw materials 2, Method for producing 2-dialkyl-1,3-dialkoxypropanes

Claims (3)

[Claims] 1. General formula (1): [In the formula, R1 is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and R2, R3,
R4, R5 and R6 are a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and R1, R2, R3, R4 and R5. And R6 are the same or different, and two or more can combine to form a cyclic structure, and R7 and R8 are lower alkyl groups and are the same or different] 2- (2-alkenyl)-
1,3-dialkoxypropanes. 2. The 2- (2-alkenyl) -1,3-dialkoxypropanes represented by the general formula (1) are hydrogenated to give the general formula (2): [In the formula, R1, R2, R3, R4, R5, R6, R7 and R8 are as defined in the above general formula (1)].
A method for producing 1,3-dialkoxypropanes represented by: 3. The method according to claim 1, wherein R1 is an alkyl group having 1 to 6 carbon atoms, and R2, R3, R4, R5 and R6 are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.
The method for producing 2,2-disubstituted-1,3-dialkoxypropanes according to claim 2, wherein (2-alkenyl) -1,3-dialkoxypropanes are used as a raw material.