JPS61147890A - Production of unsaturated higher fatty acid - Google Patents

Abstract

PURPOSE:To produce easily a specific unsatd. higher fatty acid at a high yield and high purity by obtaining an unsatd. higher fatty acid ester by electrolytic condensation of monoester of dicarboxylic acid and unsatd. carboxylic acid then hydrolyzing the same. CONSTITUTION:The unsatd. higher fatty acid ester expressed by the general formula CH2=CH(CH2)y(CH2)xCOOR (where; x+y=z; 11-30 integer) is obtd. by the crossed Kolbe type electrolytic condensation of the monoester of dicarboxylic acid such as monomethyl malonate expressed by the general formula HOOC(CH2)xCOOR (where R; alkyl group, x; 1-24 integer) and the unsatd. carboxylic acid such as acrylic acid expressed by the general formula CH2=CH (CH2)yCOOH (where y; 0-12 integer) in a soln. consisting essentially of alcohol such as methanol. The unsatd. ester is hydrolyzed, by which the unsatd. higher fatty acid expressed by the general formula CH2=CH(CH2)zCOOH and useful as a material for forming a Langmuir film is obtd.

Description

[Detailed description of the invention]

(a) Technical field of the invention The present invention relates to unsaturated higher fatty acids (CH2=CH(CH2)
It relates to the manufacturability of Z COOH1 (in the formula, 2 represents an integer of 11-24). (b) Prior art and problems Unsaturated higher fatty acids are useful as raw materials for various synthetic industries and as intermediate raw materials for pharmaceuticals, agricultural chemicals, etc., but especially in the general formula %.

[In the formula, Z represents an integer of 11 to 24. ] The unsaturated higher fatty acids represented by the following are attracting attention as a material for forming Fungmiea film. Langmuir film (hereinafter referred to as LB film) is an ultra-thin film formed by arranging organic molecules on the water surface to form a monolayer and stacking this on a solid surface. The LB film is formed by polymerizing a thin film by applying an electron beam to it.
As a highly ordered ultra-thin film, it has excellent chemical, mechanical, and electrical properties, and new applications in electronics-related fields are being developed. Conventionally, as a method for producing the above-mentioned unsaturated higher fatty acid, for example, ω-tricosenic acid, the method described in Journal of and Interface Science, Vol. 62, No. 3, 19
1977, December issue, page 509 (Journal of
Co11oid and interface 5c
iencet Vol 62. NO3, December
1977 p509) is known. In this method, as shown in the reaction formula below, undecenoyl chloride is first reacted with N-(1-cyclohexene)-morpholine to obtain undedinoylcyclohexanone, which is then hydrolyzed under alkaline conditions. 7-ke)-16
, 17-hebutadecenoic acid is obtained, which is further reduced with potassium hydroxide and hydrazine to obtain 16.17-hebutadecenoic acid. Next, 16.17-hebutadenoic acid chloride is derived from this 16.17-hebutadenoic acid using a conventionally known method,
By repeating the same reaction as above using this as a raw material, ω-tricosenic acid is obtained. (Left space below) 7-Kedo 16.17-Hebutadecenoic acid reaction step B - Step 16.17-Hebutadecenoic acid chloride CH2=CH-(CH2), 4-C,0-(CH2-,
-COOH7-kedo22.23-) licosenic acid However, in this method, the reaction steps are extremely long, the reaction operations are complicated, and the reaction reagents are expensive and underground stable reagents are used, so C11 products are also produced. This method has problems such as being easy to process, and is disadvantageous from an industrial perspective. (e) Purpose of the present invention In view of the current situation, the present invention aims to solve the general formula % formula %.

[In the formula, Z represents an integer of 11 to 24. The object of the present invention is to provide an industrially advantageous method for producing the unsaturated higher fatty acid represented by the following formula, and to eliminate the above-mentioned problems. (d) Structure of the invention, that is, the present invention is based on the general formula % formula % (1)

[In the formula, R represents an alkyl group, and X represents an integer of 1 to 24. ] Nocarboxylic acid monoester represented by the general formula % formula %
(2)

[In the formula, y represents an integer of O to 12] is subjected to cross-Kolbe electrolytic condensation with an unsaturated carboxylic acid represented by the formula % in a solution mainly containing alcohol to obtain the general formula % formula % (3)

[In the formula, R, x and y are the same as above. However, the sum of 2 of X and y represents an integer of 11 to 24. ] Obtain the unsaturated higher fatty acid ester represented by the formula, and then hydrolyze it to obtain the general formula % formula % (4)

[In the formula, Z is the same as above. ]

It is characterized by producing an unsaturated higher fatty acid represented by Examples of the furkyl group represented by R in the above general formula (1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, etc. Examples include alkyl groups having 1 to 6 carbon atoms, preferably a methyl group or an ethyl group. Specific examples of dicarboxylic acid monoesters include monomethyl malonate, monoethyl malonate, mo/methyl succinate, monoethyl succinate, monomethyl 7nobate, monoethyl 7cipate, monomethyl perate, monoethyl perate, monomethyl azelate, and azelain. Monoethyl acid, monomethyl sebacate, monomethyl sebacate, moamethyl decane-1゜10-dicarboxylate, monomethyl decane-I + 12-dicarboxylate, dodecane-I,
Monomethyl 1z-dicarboxylate, tetradecane-1,1
Monomethyl 4-dicarboxylate, tetradecane-1゜14
-Monoethyl dicarboxylate, hexadecane-1,16-
More methyl dicarboxylate, more methyl hexadecane-1,16-dicarboxylate, more methyl octadecane-1,18-dicarboxylate, monoethyl octadecane-1,18-nocarboxylate, mono-n-propyl octadecane-1,18-dicarboxylate, octadecane-1,18-dicarboxylate 1,18-dicarboxylic acid mo/isopropyl, octadecane-1,18
-mono n-butyl dicarboxylate, octadecane-1,
Monopentyl 18-dicarboxylate, mono-hexyl octadecane-1,18-dicarboxylate, monomethyl eifsanoate-1,20-dicarboxylate, monoethyl eicosane fil-1,20-dicarboxylate, tocosan-1,22- Moremethyl dicarboxylate, tocosan-1
, 2Z-monoethyl cicafrefonic acid, tetracosane-1
, 24-dicarboxylic acid monomethyl, tetracosane-1,
It refers to moamethyl 24-dicarboxylate, but is not limited thereto, as long as it is included in the above general formula (1). Further, specific examples of unsaturated carboxylic acids include acrylic acid, acrylic acetic acid, 6-heptenoic acid, 8-nonenoic acid, 10-undecenoic acid, 12-tridecenic acid, 1
It refers to 4-pentadecenoic acid and the like, but is not limited thereto, as long as it is included in the above general formula (2). Further, the ratio of dicarboxylic acid monoester and unsaturated carboxylic acid to be used is not particularly limited and can be appropriately selected within a wide range, but usually the latter is at least 0.5 times the former by mole, preferably It is preferable to use about equimolar to twice the molar amount. In the electrolytic condensation of the present invention, it may be carried out batchwise until a certain amount of raw material nocarboxylic acid monoester and unsaturated carboxylic acid is used up, or it may be carried out continuously so that the raw material concentration is maintained at a constant concentration. It's okay. Examples of the alcohol used as a solvent in the electrolytic condensation of the present invention include methanol, ethanol, impropatol, and mixtures thereof. The solubility of the dicarboxylic acid monoester and unsaturated carboxylic acid may be improved by adding an organic solvent with the above dicarboxylic acid monoester and unsaturated carboxylic acid. These alcohols may contain some amount of water. The concentration of water contained is usually 20% or less, preferably about 0.5 to 15%. The concentration of dicarboxylic acid monoester and unsaturated carboxylic acid, which are the starting materials of the present invention, to be present in the reaction system is usually 2 to 30% by weight in total, preferably 2 to 20% by weight. . In the present invention, it is desirable to prepare an electrolytic solution by allowing an electrolyte to be present in the reaction system in order to improve conductivity during electrolytic condensation. Examples of electrolytes include lithium, potassium,
Hydroxides of sodium, calcium, magnesium, etc.
Examples include carbonate, bicarbonate, methylate, ethylate, or amine salt. Among these, especially sodium,
Particular preference is given to using potassium hydroxides, carbonates and methylates. The amount of such electrolyte added is not particularly limited, but it usually depends on the degree of neutralization of the mixture of nocarboxylic acid monoester and unsaturated carboxylic acid (hereinafter referred to as "mixed acid") (the mixed acid is neutralized with the electrolyte). molar ratio) is 2 to 60 mol%,
It is preferably added in an amount of 5 to 40 mol%. As the electrode material used in the electrolytic condensation of the present invention, platinum, gold, silver, ronium, ruthenium, iridium, etc. may be used alone or in an alloy for the anode (or titanium, tantalum, etc. may be used in place of these). It may be used by plating, but a material with a high oxygen overvoltage is particularly preferred.Also, a material with a low hydrogen overvoltage is preferred for the cathode, but there is no particular limitation, and platinum, iron, stainless steel, titanium, etc. The electrolytic condensation of the present invention is usually carried out at 1 to 40 A/dm2, preferably 5 to 30 A/dm2, and the temperature of the electrolytic solution is usually 20 to 65°C, preferably 50 to 60°C. As the electrolytic cell used for the electrolytic condensation of the present invention, a wide variety of those used for ordinary organic electrode reactions can be used, and for example, a beaker-shaped or box-shaped electrolytic cell may be used. The reaction of hydrolyzing the unsaturated higher fatty acid ester represented by the general formula (3) to obtain the unsaturated higher fatty acid involves various hydrolysis reactions normally used to convert a carboxylic acid ester into the corresponding primary fatty acid. A wide range of conditions can be applied. In the present invention, it is particularly preferable to perform hydrolysis with a small amount of alkali addition to directly produce unsaturated higher fatty acids. For example, the pressure method and T witsche
ll) method, both of which are batch-type manufacturing methods. Specifically, in the pressurization method, 40 to 70 parts by weight of the unsaturated fatty acid ester, 30 to 60 parts by weight of water, and 0.5 to 1.
A mixture consisting of 5 parts by weight is heated at a temperature of 150-175°C and a pressure of 2-10 atm, preferably 3-6 atm.
Hydrolysis is carried out by heating for ~20 hours. At this time, the decomposing agent produces oil-soluble metal soap, which acts as an emulsifier, so that hydrolysis is carried out smoothly. In addition, in the Toifthiel method, the above unsaturated fatty acid ester 5
0 to 75 parts by weight, 25 to 50 parts by weight of water, 0.75 to 1.5 parts by weight of decomposing agent (alkylbenzenesulfonic acid, alkylnaphthalene sulfonic acid, etc.), 0.1 to 1.0 parts by weight of concentrated sulfuric acid.
A mixture consisting of 0.3 to 0.6 parts by weight, preferably 0.3 to 0.6 parts by weight, is placed in a corrosion-resistant container and heated for 24 to 50 hours by directly blowing live steam into the tank at normal pressure. Although this method requires a long reaction time, the unsaturated fatty acid ester
~95% is hydrolyzed, and unsaturated fatty acids are liberated, so they can be easily separated, and together with fresh water, 8 to 1
By repeating boiling and separation for 5 hours, the purity of the unsaturated higher fatty acids can be improved. Furthermore, the unsaturated fatty acid ester may be charged at an appropriate rate to the bottom of a stainless steel hydrolysis tower, and live steam may be directly blown into the bottom to continuously hydrolyze the unsaturated fatty acid ester. 1. After the completion of the above reaction, the unsaturated fatty acid produced in the present invention is
It can be easily isolated and purified from the reaction mixture by conventionally known conventional means such as recrystallization, distillation (including vacuum distillation), dissolution and removal of impurities with hot water, etc. (e) Effects of the invention According to the method of the invention, the reaction steps are short, the reaction operation is simple, and the target unsaturated higher fatty acid can be produced by 50% or more, in some cases 55% or more, under mild reaction conditions. It can be produced with high yield and high purity of 99% or more. Moreover, in the present invention, there is no need to use special reaction reagents, and all starting materials used are known compounds that are relatively easily available. Furthermore, in the present invention, the reaction has good selectivity and produces few by-products. Therefore, the present invention is an industrially extremely advantageous method. (f) Examples of the present invention Example 1 (a) In a beaker type non-diaphragm electrolytic cell with a capacity of 100 mf, a titanium plate with a thickness of 1-1 (3, oct.
A plate plated with 4 micron platinum (Oe theory) and a 1-thick stainless steel plate (3°0c-X8
．． 0cm) at intervals of approximately 5C, and also a thermometer and a reflux condenser. 2.2 g (0.03 mol) of acrylic acid, 8.3 g (0.03 mol) of monomethyl dodecane-1゜12-dicarboxylate, 1.0 g of water and 0.224 g (0.03 mol) of potassium hydroxide.
,004 mol) dissolved in 60 g of methanol was introduced into the above electrolytic cell, and heated under constant current conditions (0,004 mol) while vigorously stirring with a magnetic cooler at 50 to 60°C.
Electrolysis is carried out at 45A), the current carrying area of both the anode and cathode is 7,
5 am", and the current density is 6 A/dta".
5 for monomethyl dodecane-1,12-dicarboxylate
．． After energizing 1 mole of 277 rad, the reaction mixture was cooled to room temperature, and the precipitated solid was filtered under reduced pressure. After distilling and removing methanol from the filtrate under reduced pressure, the residue was oxidized and extracted with ether, and 0.58 g of acrylic acid and 1.3 g of monomethyl dodecane-1°12-dicarboxylate were recovered from the ether solution. Analysis of the filtered solid by gas chromatography revealed that it contained the raw material monomethyl dodecane-1,12-dicarboxylate, the main product methyl 14-pentadecenoate, and a trace amount of butidiene. After dissolving in hot n-hexane, it was isolated and purified by fractional crystallization to obtain 2.1 g of monomethyl dodecane-1,12-dicarboxylate, 1
4.25 g of methyl 4-pentadecenoate was obtained. The structure of the obtained methyl 14-pentadecenoate was confirmed by comparing its behavior in various spectroscopic spectra and melting point. Further, as a result of analysis by gas chromatography, it has a purity of about 99.2%. The yields of methyl 14-pentadecenoate and butadiene based on the consumed monomethyl dodecane-1,12-dicarboxylate were 68% and (/3°5%), respectively. (b) By the method of (a) above. Obtained methyl 14-pentadecenoate 30g 1 water 16g 1 alkylbenzenesulfonic acid 0
．． 5g and concentrated sulfuric acid 0.15. into a 100ml three-neck flask. Next, in the three-bottle flask,
If a glass live steam introduction tube, a thermometer, and a reflux condenser are installed, and live steam is directly blown for 30 hours, the above 14-
92% of methyl pentadecenoate is hydrolyzed to liberate 14-pentadecenoic acid. The obtained 14-pentadecenoic acid was boiled for 10 hours and separated 5 times with water.
Furthermore, a mixed solvent of petroleum ether and ether (volume ratio 1:
1) to obtain 20.8 g of 14-pentadecenoic acid with a purity of 99.8%. Example 2 In Example 1, 0.03 mol of monomethyl tetradecane-1,14-nocarboxylate was used instead of monomethyl dodecane-1,12-dicarboxylate, and Example 1 (a
) and (b), purity 99.0-99.5%
16-hebutadecenoic acid was obtained in a yield of 62% from monomethyl tetradecane-1,14-dicarboxylate. Example 3 In Example 1, 0.03 mol of monomethyl hexadecane-1,16-dicarboxylate was used instead of monomethyl dodecane-1,12-dicarboxylate, and Example 1 (a
) and (b), 18-nonenoic acid with a purity of 99.5% was obtained in a yield of 57% from monomethyl hexadecane-1,16-dicarboxylate. Example 4 In Example 1, 0.03 mol of monomethyl eicosane-1゜20-dicarboxylate was used instead of monomethyl dodecane-1,12-dicarboxylate, and Example 1(a)
In the same manner as (b), ω-tricosenoic acid with a purity of 99.8% was obtained in a yield of 54% from monomethyl eicosane-1,20-dicarboxylate. Example 5 In Example 1, 0.03 mol of monomethyl tocosan-1,22-dicarboxylate was used instead of monomethyl dodecane-1,12-dicarboxylate, and the same procedure as in Example 1 (a) and (b) was carried out. 2 with a purity of 99°5 to 99.8%
4-bentacosenoic acid was obtained in a yield of 55% from monomethyl tocosan-1,22-dicarboxylate. Example 6 In Example 1, 0.03 mol of monomethyl tetracosane-1,24-dicarboxylate was used instead of monomethyl dodecane-1f12-dicarboxylate, and Example 1 (a
) and (b), purity 99.2-99.9%
26-heptacosenic acid was obtained in a yield of 57% from monomethyl tetracosane-1,24-dicarboxylate. Example 7 In Example 1, 0.03 mol of acrylic acetic acid was used instead of acrylic acid, and 0.03 mol of monomethyl octadecane-1,18-dicarboxylate was used instead of monomethyl dodecane-1,12-dicarboxylate. Example 1(a)
It was obtained in the same manner as in (b) and 55% yield from monomethyl octadecane-1,18-dicarboxylate. Example 8 In Example 1, 0003 mol of 6-heptenoic acid was used instead of acrylic acid, and 0.03 mol of monomethyl hexadecane-1,16-dicarboxylate was used instead of monomethyl dodecane-1,12-dicarboxylate. Example 1 (a
) and (b), purity 99°3-99.5%
ω-tricosenic acid was obtained in a yield of 59% from monomethyl hexadecane-1t16-dicarboxylate. Example 9 In Example 1, 0.03 mol of 8-nonenoic acid was used instead of acrylic acid, and 0.03 mol of monomethyl tetradecane-1,14-dicarboxylate was used instead of monomethyl dodecane-1,12-dicarboxylate. , Example 1(a)
In the same manner as in (b), ω-tricosenic acid with a purity of 99.5 to 99.8% was obtained in a yield of 57% from monomethyl tetradecane-1,14-dicarboxylate. Example 10 In Example 1, 0.03 mol of 10-undecenoic acid was used instead of acrylic acid, and Example 1(a) and 1/(b
), ω-trifcenic acid with a purity of 99.5 to 99.7% was obtained in a yield of 53% from monomethyl dodecane-1,12-dicarboxylate. Example 11 In Example 1, 0.02 mol of 12-tridecenic acid was used instead of acrylic acid, and 0.02 mol of monomethyl decane-1,10-dicarboxylate was used instead of monomethyl dodecane-1,12-dicarboxylate. , Example 1(a)
In the same manner as in (b), ω-tricosenic acid with a purity of 99.2 to 99.8% was obtained in a yield of 52% from monomethyl decane-1,10-dicarboxylate. Example 12 In Example 1, 0.02 mol of 14-pentadecenoic acid was used instead of acrylic acid, and 0.02 mol of monomethyl sebacate was used instead of monomethyl dodecane-I112-dicarboxylate, and Example 1(a) In the same manner as (b), ω-t, licosenic acid with a purity of 99.1-99.5% was obtained in a yield of 52% from monomethyl sebacate.6 Patent applicant: Okamura Oil Co., Ltd. (Voluntary) March 15, 1985 Manabu Shiga, Commissioner of the Patent Office2, Title of invention: Process for producing unsaturated higher fatty acids 3, Relationship to the case concerning the person conducting the procedure Patent applicant (t. Reiben Osaka Prefecture, Aihara, Osaka Prefecture) 4-5 Ichikawaramachi
Mr. Dajikake Name (Name) Okamura Oil Co., Ltd. 0
) Details ko;, 2nd page:;i Jth) 1] = 24J to 1
11-30”. (2) In the specification, page 2, page 15-11H11-24,1 is corrected to 111-30. (3) Correct 111 = 24J, page 6, line 9, to “11-30” in Book #llI. (4) Specification, page 7, line 6, “11-2・↓” []1
Corrected to "~30". (5) In the Notes to the Specification, page 22, line 6, "I got it." is corrected to the following sentence. [Obtained. Example 13 In Example 1, 0.03 mol of 10-undecenoic acid was used instead of acrylic acid, and 0.03 mol of monomethyl Eifsan-1,20-dicarboxylate was used instead of monomethyl dodecane-1.12-dicarboxylate. Example 1 (a
) and (i]), &i[99,4J% of 3
O-hentriacontinic acid was obtained in a yield of 55% from monomethyl eicosane-1,20-dicarboxylate. (6) Amend the claims as shown in the attached sheet. [Claims (1) General formula % formula %

[In the formula, (■) represents an alkyl group, and y represents an integer from 1 to 24.] The unsaturated carboxylic acid represented by the integer is subjected to cross-Kolbe electrolytic condensation in an alcohol-based solution' [general formula % formula %

[In the formula, R, x and y are the same as above. However, the total Z of X and y is an integer of 11 to 1. ] The unsaturated higher fatty acid ester represented by a) 1 is then hydrolyzed to give the general formula % formula %

[In the formula, Z is the same as above. ]

Claims (1)

[Claims] (1) General formula HOOC(CH_2)xCOOR [In the formula, R represents an alkyl group and x represents an integer of 1 to 24. ] A dicarboxylic acid monoester represented by the general formula CH_2=CH(CH_2)yCOOH [wherein y represents an integer of 0 to 12]. ] An unsaturated carboxylic acid represented by
[In the formula, R, x and y are the same as above. However, the sum z of x and y represents an integer of 11 to 24. ] An unsaturated higher fatty acid ester represented by the formula is obtained, which is then hydrolyzed to give the general formula CH_2=CH(CH_2)zCOOH [where z is the same as above. ] A method for producing unsaturated higher fatty acids, characterized by obtaining unsaturated higher fatty acids represented by