JPS626700B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing 9-octadecenedioic acid diester, and more particularly, to a novel industrial production method for obtaining 9-octadecenedioic acid diester from natural animal and vegetable oils. 9-octadecenioic acid diester is an extremely useful compound that can be ring-closed to produce civetone, which is important as a musk fragrance. Conventionally, as a method for producing this compound, a method is known in which oleic acid methyl ester is subjected to an olefin metathesis reaction [PBVan Dam
et al.: J.Am.Oil Chem.Soc., 51 , 389―392
(1974) and Japanese Patent Application Laid-Open No. 118447/1983]. However, this method is not satisfactory as an industrial production method because the raw material, oleic acid methyl ester, is more expensive than natural oils and fats, and its reactivity is not very high. On the other hand, a report on olefin metathesis reaction for olive oil [○IJCSChem.Comm.
, 1121-1222 (1972), and ○Ro J. Am. Oil Chem.
Soc., 51 , 389-392 (1974)], but the literature in ○B only confirms 9-octadecene in the reaction product, and the literature in ○B does not discuss the product. has been carried out, but it has not been isolated or quantified. As a result of extensive research into the olefin metathesis reaction of olive oil, the present inventors discovered that 9-octadecenedioic acid diester can be obtained by treating this reaction product with an alcoholic alkali metal alcoholate. Furthermore, the present inventor has found that 9-octadecendioic acid diester can be obtained not only from triglycerides such as olive oil whose main constituent fatty acid is oleic acid, but also from triglycerides whose constituent fatty acids are linoleic acid and linolenic acid. I discovered that. The present invention was completed based on this new knowledge, and involves subjecting triglyceride whose main fatty acids are oleic acid, linoleic acid, and linolenic acid to an olefin metathesis reaction, and then treating the resulting product with an alcoholic alkali. This is a method for producing 9-octadecenedioic acid diester by treatment with a metal alcoholate. In the present invention, when the unsaturated fatty acid residue in the oil or fat is only oleic acid, the olefin metathesis reaction proceeds according to the following reaction formula, when the reaction formula is expressed by one constituent fatty acid of triglyceride. 2.C ₈ H ₁₇ CH=CH (CH ₂ ) ₇ COOR′ 〓C ₈ H ₁₇ CH=CHC ₈ H ₁₇ +R′OOC (CH ₂ ) ₇ CH=CH (CH ₂ ) ₇ COOR′ Olefin metathesis reaction is reversible Since it is a reaction, many olefin compounds can be produced when the fatty acid residue contains linoleic acid or linolenic acid. For example, linoleic acid residue, C ₅ H ₁₁ (CH=
CHCH ₂ ) ₂ (CH ₂ ) ₆ COOR′, in the reaction between them, C ₅ H ₁₁ CH=CH
(CH ₂ ) ₇ COOR′, C ₅ H ₁₁ - (CH=CHCH ₂ ) ₃
(CH ₂ ) ₆ COOR′, C ₅ H ₁₁ CH＝CHC ₅ H ₁₁ , C ₅ H ₁₁ ―
(CH=CHCH ₂ ) ₃ C ₄ H ₉ , R′OOC(CH ₂ ) ₇ CH=CH
(CH ₂ ) ₇ COOR′, R′OOC(CH ₂ ) ₇ (CH=
CHCH ₂ ) ₃ (CH ₂ ) ₆ COOR′,

[Formula] is formed, but the unreacted linoleic acid residues and these primary products can further react with each other to give many secondary reaction products. However, due to the unique stability of the six-membered ring, the 1,4-cyclohexadiene produced in the polyene reaction no longer undergoes the metathesis reaction and exits the equilibrium system of the metathesis reaction, resulting in the following reaction. will be held. Even when the fatty acid residue is linolenic acid, the same reaction as in the case of linoleic acid takes place. R-(CH=CHCH ₂ ) _o (CH ₂ ) ₆ COOR'→R-CH=CH-R+R'OOC(CH ₂ ) ₇ CH=CH(CH ₂ ) ₇ COOR'+n-1/2

[Formula] In the case of linoleic acid: R=C ₅ H ₁₁ , n=2 In the case of linolenic acid: R=C ₂ H ₅ , n=3 For convenience, these reactions can be considered by breaking them down into the following two reactions. I can do it. R-(CH=CHCH ₂ ) _o (CH ₂ ) ₆ COOR'→ n-1/2

[Formula] +R-CH=CH (CH ₂ ) ₇ COOR' ...Reaction (A) 2.R-CH=CH (CH ₂ ) ₇ COOR'〓R-CH=CH-R+R'OOC (CH ₂ ) ₇ CH =CH _{( CH2} ) _7COOR '... _Reaction (B) When R= _C8H17 , n=1 _{, oleic acid R=C5H11, when n=2, linoleic acid R=C2H5 , n} = 3, linolenic acid The reaction product is a complex mixture composition that is difficult to analyze, but from the results of the post-processing described later, reaction (B) is an equilibrium reaction, and the reaction rate is theoretically 50 %. The reaction product obtained in reaction (B) and unreacted triglyceride are further treated with an alcoholic alkali metal alcoholate to obtain 9-octadecenioic acid alkyl ester and saturated and unsaturated fatty acid alkyl ester. The recovered unsaturated fatty acid alkyl ester was recovered using a known method [P.
B. Van Dam et al.: J. Am. Oil Chem. Soc., 51 , 389
392 (1974) and JP-A No. 52-118447], an olefin metathesis reaction can be carried out to obtain an alkyl 9-ocdadecenioic acid ester. As the triglyceride that is the raw material of the present invention, most of the commercially available natural animal and vegetable oils and fats can be used, except for erucic acid type oils and fats such as rapeseed oil and mustard oil, and oxyacid type oils and fats such as castor oil. Oleic acid as a constituent fatty acid,
Fats and oils containing a large amount of linoleic acid or linolenic acid can be appropriately selected using, for example, the table in "Oil and Fat Chemistry Handbook", edited by Japan Oil Chemists' Association, published by Maruzen Co., Ltd. (published in 1955), pages 26-31. Preferred triglycerides include, for example, olive oil, sasanqua oil,
Camellia oil, tea oil, kpotsk oil, sesame oil, rice bran oil,
Examples include soybean oil, corn oil, palm oil, sunflower oil, safflower oil, cottonseed oil, peanut oil, beef tallow, and the like. When these fats and oils are used as raw materials for the present invention, it is necessary that active hydrogen compounds such as free fatty acids, antioxidants, and water that inhibit the olefin metathesis reaction are not present therein. Since free fatty acids are sufficiently removed from refined oils and fats currently supplied in the oil and fat industry, it is preferable to use oils and fats that do not contain antioxidants. In addition, in the case of fats and oils that have deteriorated in quality due to aging and have high acid values and peroxide values, for example, "Oil and Fat Chemical Product Handbook" edited by the Oil and Fat Chemical Product Handbook Editorial Committee, Nikkan Kogyo Shimbun Publishing Co., Ltd. (1966) It is used after being purified by a method such as washing with a caustic soda solution as described on pages 264-265 (Publishing). The olefin metathesis reaction was described by the aforementioned J.Am.
It is carried out under the conditions described in Oil Chem. Soc., 51 , 389-392 (1974) and "Oil Chem. Soc." 25 , No. 11, 779-783 (1976). At this time, it is preferable to use tungsten hexachloride-tetraalkyltin as the catalyst. Sn in tetraalkyltin (n-C ₄ H ₉ ) ₄
is particularly suitable because it is cheaper than Sn(CH ₃ ) ₄ and Sn(C ₂ H ₅ ) ₄ , has a high boiling point and is easy to handle, has low toxicity, and has high activity. The amount of tungsten hexachloride-Sn(n- _C4H9 ) ₄ to be used is such that the ratio of the number of moles of the fatty acid ester group of the triglyceride to the _number of moles of tungsten hexachloride is 15 to 15.
The ratio of Sn(n-C ₄ H ₉ ) ₄ to tungsten hexachloride is preferably 4:1 to 6:1. Solvents for this reaction include benzene, chlorobenzene, bromobenzene, o-dichlorobenzene,
m-dichlorobenzene, 1,2,4-trichlorobenzene, tetrachloroethylene, 1,1,2,
2-tetrachloroethane can be used. The larger the amount of solvent, the higher the solubility of the catalyst.
Since the viscosity decreases, the yield improves, but in reality, using the same amount (volume) as the raw material oil gives good results. This reaction needs to be carried out in the substantial absence of water, and for this purpose, the mixture of fat and oil and solvent is heated in advance and distillation is carried out until there is no cloudy distillate. This reaction can be carried out on a small scale in a laboratory using a polymerization ampoule or a pressure-resistant glass tube with a pot.
It is preferable to carry out the process so that the space is at least 5 times the volume of the liquid, but industrially it can be carried out using a stirrer and a cooling pipe, and under reduced pressure or dry inert gas, such as nitrogen or carbon dioxide. It is carried out using a reaction vessel. To carry out this reaction, tungsten hexachloride, a solvent solution of oil and fat, and then Sn(n-C ₄ H ₉ ) ₄ are sequentially placed in a container purged with dry nitrogen gas, and the reaction is preferably carried out under reduced pressure. Reaction temperature is 80-120
℃, and the reaction time is suitable for 2 to 3 hours. When the reaction is carried out under normal pressure, it is preferable to divide the catalyst into two parts, add one part first to carry out the reaction, and then add the remaining part to carry out further reaction. In this case, the yield should be close to the theoretical value. can be carried out. Dilute ammonia water is added to the reaction solution to decompose the catalyst, the aqueous layer is removed, and the organic layer is fractionally distilled. In the early stage of fractional distillation, 1,4-cyclohexadiene (72.3-72.5℃), 3-hexene (68℃), 6-
Dodecene (220℃), Sn (n-C ₄ H ₉ ) ₄ (270℃),
9-octadecene (280℃) etc. are recovered in this order. Sn(n-C ₄ H ₉ ) ₄ thus recovered can be reused in the next reaction. An alcoholic alkali metal alcoholate is added to the distillation residue obtained in this manner, and the mixture is heated and reacted.
The alkali metal alcoholate has a theoretical amount of 1.3 to 1.5 calculated from the ester value of the raw material triglyceride.
A twice molar amount is used, which is preferably used as a 0.2N alcohol solution. The reaction is completed by heating to reflux for 40-60 minutes. The reaction solution is made acidic with hydrochloric acid, etc., extracted with n-hexane, etc., thoroughly washed with water, and then dried. After the solvent is distilled off, the residue is distilled under reduced pressure to recover unreacted triglycerides as saturated and unsaturated fatty acid esters as a pre-distillate, and then to obtain the desired 9-octadecenioic acid diester. The recovered unsaturated fatty acid ester can be converted into 9-octadecenedioic acid diester by subjecting it to an olefin metathesis reaction, so it can be reused. Comparing the method of the present invention with the known method of subjecting oleic acid methyl ester to an olefin metathesis reaction, it is found that while the known method uses oleic acid methyl ester produced and purified from fats and oils as a raw material, the present method uses fats and oils as a raw material. Since the raw materials can be used as is, the raw materials are easy to obtain and inexpensive, and in the olefin metathesis reaction, ester groups act as catalyst poisons and reduce the activity of the catalyst, but the ester groups of triglycerides have greater steric hindrance than that of methyl oleate. The method of the present invention has advantages such as a better yield because it has a weaker ability to poison the catalyst. As described above, according to the present invention, 9-octadecendioic acid diester can be obtained from triglyceride (oil), which is cheaper and more easily available than oleic acid methyl ester. And this is AT Blomquist et al.: J.Am.
The diketene method described in Chem.Soc., 70 , 34-36 (1948), the Deitzkmann method described in JP-A-52-118447,
The musk fragrance civetone can be derived by the Ziegler method, the Ruchika method, the acyloin condensation method, etc. Next, examples of the present invention and a diketene method with the highest yield for producing civetone from 9-octadecenedioic acid diester will be shown as a reference example. In this example, the theoretical yield refers to the reaction rate.
This value is based on the yield at 50% as 100%, so the highest theoretical yield is 200%. Example 1 1.3 g of tungsten hexachloride, olive oil (oleic acid
82% (containing linoleic acid, 4%) and 3.0 g of tetra-n-butyltin were taken, and then sealed in a vacuum tube under cooling with a dry ice-methanol solution.
This polymerization ampoule was heated at 80° C. for 3 hours while shaking, and after cooling, it was opened. 50 ml of benzene and 15 ml of 5% aqueous ammonia were added to the resulting reaction mixture to decompose the catalyst, then the aqueous layer was removed, and the benzene layer was
After washing twice with water, benzene was distilled off. Furthermore, after removing tetra-n-butyltin and 9-octadecene by vacuum distillation (135℃/2mmHg), 0.2N was added to the residual liquid.
120 ml of sodium methylate-methanol was added and heated under reflux for 40 minutes. Add 120ml of water to this reaction solution.
and 60ml of 2N-hydrochloric acid, and then diluted with n-hexane.
After extraction, the n-hexane layers were combined, washed with water until neutral, and dried over anhydrous sodium sulfate. After distilling off n-hexane, vacuum distillation (168-170
℃/0.3 mmHg), 2.8 g (theoretical yield: 61.0%) of 9-octadecenioic acid dimethyl ester was obtained. Example 2 3.0 9-octadecenioic acid dimethyl ester was prepared in the same manner as in Example 1 except that an 80 ml polymerization ampoule was used and 0.66 g of tungsten hexachloride, 18.5 g of olive oil, 1.5 g of tetra-n-butyltin and 30 ml of chlorobenzene were used. g (theoretical yield 65.3%)
I got it. Example 3 Under dry nitrogen atmosphere, 0.7 g of tungsten hexachloride, 15 g of safflower oil (containing 15% oleic acid and 65% linoleic acid) and 2.3 g of tetra-n-butyltin were placed in a 50 ml polymerization ampoule and sealed. The mixture was shaken while heating at 80°C for 3 hours, and opened after cooling. Add 50 ml of benzene and 15 ml of 5% ammonia water to the resulting reaction mixture.
ml was added, the catalyst was decomposed by stirring, the aqueous layer was removed, and the benzene layer was washed three times with water. After 1,4-cyclohexadiene and benzene were distilled off, 6-dodecene, followed by tetra-n-butyltin and 9-octadecene were distilled off under reduced pressure. This residual liquid
0.2N sodium methylate-methanol solution 120
ml and heated under reflux for 40 minutes, 120 ml of water and 60 ml of 2N-hydrochloric acid were added to the resulting reaction solution, and the mixture was extracted three times with n-hexane. Combine the n-hexane layers,
After washing with water until neutral, it was dried over anhydrous sodium sulfate. After distilling off n-hexane, distillation under reduced pressure yields 2.4 g of 9-octadecenioic acid dimethyl ester.
(Theoretical yield: 65%). Example 4 Under dry nitrogen atmosphere, 0.66 g of tungsten hexachloride and 1.5 g of tetra-n-butyltin in an 80 ml polymerization ampoule.
g, 18.5 g of olive oil and 20 ml of chlorobenzene
The tube was then sealed in vacuo while cooling with a dry ice-methanol solution. After reacting at 80℃ for 3 hours with shaking, open the package and add 0.4 hexachlorotungsten.
g, and 1.0 g of tetra-n-butyltin were added. Seal the polymerization ampoule again as described above and add 80
The reaction was carried out at ℃ for 3 hours. This reaction mixture was treated in the same manner as in Example 1 to obtain 4.0 g (theoretical yield: 87%) of 9-octadecenioic acid dimethyl ester. Reference example (1) Hydrolysis of 9-octadecenioic acid dimethyl ester: 16 g of caustic potassium was mixed with 9.5 ml of water and 72 ml of ethanol.
ml, 20 g of 9-octadecenioic acid dimethyl ester was added thereto, and the mixture was heated under reflux for 1.5 hours. After most of the ethanol was then distilled off, the mixture was neutralized with 6N hydrochloric acid to liberate the dicarboxylic acid and extracted with ether. The ether extract was washed twice with water, dried over anhydrous sodium sulfate, the ether was distilled off, and thoroughly dried under reduced pressure to give 9-
Octadecenniic acid was obtained and used as a raw material for the next synthesis reaction of civetone by ring closure. (2) Synthesis of civetone: 10 ml of thionyl chloride and 25 ml of ether were added to 9 g of 9-octadeceneniic acid and heated. 30
After a few minutes, the temperature was raised to 70°C and kept at the same temperature for 1 hour. Then, the ether was distilled off and excess thionyl chloride was removed under reduced pressure to obtain 9-octadecenenioyl chloride. 4 g of the obtained 9-octadecenenioyl chloride was dissolved in 400 ml of ether, and this was added dropwise into a three-necked flask 2 containing ether 1 and triethylamine 20 ml under reflux and stirring for 16 hours. To adjust the drip rate and prevent clogging of the drip tube, Hershberg
Dripping funnel (Organic Synthesis Vol 18, 16
Page WJ Scott et al.) is preferred. After the reaction, ether 1 was distilled off, the residual liquid was washed with 3N-hydrochloric acid, and the ether was further distilled off. The above ring-closing reaction was carried out twice, and the two batches of ketene dimer were combined. To this was added 4 g of caustic potassium, 8 ml of water, and 120 ml of methanol, and the mixture was stirred at room temperature for 2 days. After heating under reflux for another 4 hours, water
ml and extracted repeatedly with n-hexane.
If the obtained n-hexane layer is dried with anhydrous magnesium sulfate and then distilled under reduced pressure, the temperature is 143-148℃/
1.68 g (yield 29%) of civetone was obtained at 3 mmHg. 34% was cis form and 66% was trans form.

Claims (1)

[Claims] 1. A triglyceride whose main constituent fatty acids are oleic acid, linoleic acid, and linolenic acid is subjected to an olefin metathesis reaction, and the resulting product is then treated with an alcoholic alkali metal alcoholate. A method for producing 9-octadecenedioic acid diester. 2. The production method according to claim 1, wherein the olefin metathesis reaction is carried out in the presence of a catalyst consisting of tungsten hexachloride and tetraalkyltin. 3. Claim 1 in which the triglyceride is olive oil, camellia oil, tea oil, kapoku oil, quince oil, safflower oil, bran oil, soybean oil, corn oil, palm oil, sunflower oil, cottonseed oil, peanut oil, or beef tallow. Manufacturing method described in section.