JPS6015610B2 - Process for producing acetic ester of unsaturated chlorine-containing alcohol - Google Patents

Description

Detailed Description of the Invention The present invention is a method for producing acetate ester of unsaturated chlorine-containing alcohol, and its characteristics are represented by the general formula (in the formula, R and R2 are hydrogen atoms or alkyl groups). By reacting unsaturated chlorine-containing alcohol and acetic anhydride at 80 to 95 qo in the presence of 80 to 85% phosphoric acid, the general formula (R and R2 in the formula have the same meanings as above) can be obtained in good yield. The present invention relates to a method for producing an acetate ester of an unsaturated chlorine-containing alcohol.

The present inventor has researched the acetylation of unsaturated chlorine-containing alcohol, and has prevented the dehydration or resinization reaction by using an auxiliary agent added during acetylation of unsaturated chlorine-containing alcohol as a raw material. As a result of intensive research on a method for synthesizing acetate ester of saturated chlorinated alcohol, we found that phosphoric acid was added to a mixture of unsaturated chlorinated alcohol and acetic anhydride at low temperature, and then the reaction was carried out by heating. We have discovered a method for producing an acetylated product with high purity and good yield.

When acetylating the hydroxyl group of alcohols,
As the acetylation reagent, acetic acid, acetyl anhydride, acetyl chloride, and the like are used together with various auxiliaries.

When unsaturated chlorine-containing alcohol is acetylated, it is surprising that the desired acetylated product can be obtained in high purity and in good yield, with the production of a diene compound by dehydration of the raw material. The acetylation method according to the present inventor's method uses acetic anhydride as an acetylation mystery agent as an auxiliary agent in order to prevent the formation of a compound and resin formation due to dehydration of the unsaturated chlorine alcohol as a raw material. This method improves these drawbacks by using an acid. The ratio of acetic anhydride as the acetylated mystery agent to the chlorine-containing alcohol is up to 10 moles per mole.

However, the appropriate amount of acetic anhydride to be used is 5 to 6 moles. As the auxiliary phosphoric acid to be added, phosphorus, metaphosphoric acid, polyphosphoric acid, etc. can be used alone or in combination. For compounds that have a structure that is easily dehydrated, highly pure phosphoric acid is not possible, and 80-85% phosphoric acid is generally suitable. Note when using phosphoric acid as a catalyst for esterification,
What must be done is to generate a diene compound by eliminating the raw material alcohol. Furthermore, since it is difficult to separate the produced thiogen compound from the ester, conditions for obtaining a highly pure ester are required. Although mild phosphoric acid is suitable for this purpose, since it has a chlorine atom with strong heminegative properties, an appropriate range of phosphoric acid and reaction temperature is used. If the phosphoric acid concentration is low or the reaction temperature is low, raw materials may remain unreacted, which is not preferable. In the attached table, add 0.6 liters of acetic anhydride to 0.1 mol of chlorinated alcohol, and add 0.046 mols of 85% phosphoric acid to 0.1 mols of chlorinated alcohol.
We compared the results of heating reactions at different temperatures on a moat after addition at 5°C and the yields when using other catalysts. A high purity ester was obtained in good yield. The amount of phosphoric acid added is 1 to 100% by weight based on the unsaturated chlorine-containing alcohol.

If the amount of phosphoric acid added is large, a diene compound will be produced, so it should be kept as low as possible depending on the conditions. Further, phosphoric acid should be added at a low temperature of 0 to 1,000 ℃, and if the temperature is 1 to 0 or higher, it will cause the formation of diene compounds and resin formation. A heating time of 1 to 1Q hours after addition of the auxiliary agent is sufficient, and the reaction is usually completed within 3 hours. If the heating time is prolonged, it may cause generation of gen compounds and the like.

The ester of the present invention is useful as a raw material for organic synthesis intermediates, agricultural chemicals, food attractants, chick burning treatment agents, and the like.

The present invention will be specifically explained by the following examples.

Example 1 CC12=CCIC ratio A mixture of OH16.17 (0.10 mol) and acetic anhydride 61.25 (0.60 mol) was cooled to 0-5°C, and 85% phosphoric acid 4 0.5 mol (0.039 mol) was added dropwise over 30 minutes.

During this time, the reaction temperature is kept properly below 5°C. After dropping, the mixture is heated and reacted for 3 hours at a temperature of about 90 to 95 oo. The reaction mixture was decomposed in ice water and extracted several times with carbon tetrachloride. The carbon tetrachloride solution is washed with an acidic sodium hydrogen solution and a saturated aqueous solution of common salt, and then dried over calcium chloride. Carbon tetrachloride was recovered to obtain 19.87 ml of hammer oil. The crude oil was fractionated to bp74.5-76.0oo/8 Hg (d reed ol
．． 4130, n force 1.4873 chlorine content 52.25%
) unsaturated ester CH3C0・OCH2CCI=CC
12 was obtained in 15.97 days (78.4%). Example 2 A mixed solution of 17.54 mmol (0.10 mol) and acetic anhydride 61.25 mmol (0.06 mol) was
Cool to 5°C and add 4.5% 85% phosphoric acid to this mixture.
(0.039 mol) was added dropwise over 30 minutes.

After the dropwise addition, the mixture was further heated and reacted on a hot water bath for 3 hours. After the reaction, the mixture was decomposed in ice water and extracted with carbon tetrachloride. The extract is washed with a saturated solution of sodium hydrogen acid and common salt and then dried. The solvent was removed to obtain a residual oil of 20.39 g. This oil is fractionated and has a bp of 71.0 to 72.0oo/
18.47 unsaturated esters (yield: .9%) of 8-side Hg (reed ol. 3 spots 7, nickel ol. 4784, chlorine content 48.73%) were obtained.

Example 3 A mixed solution of 18.94 mmol (0.10 mol) and acetic anhydride 61.25 mmol (0.60 mol) was
Cool to ~5°C and add 4.85% phosphoric acid to this mixture.
5 (0.039 mol) was added dropwise over 30 minutes.

After the dropwise addition, the mixture was further heated and reacted on a hot water bath for 3 hours. After the reaction, the same treatment as in Example 1 is carried out to obtain a carbon tetrachloride extract. Carbon tetrachloride was recovered to obtain 20.56 ml of residual oil. This was fractionated and bp79.0~83.000/8 side Hg (d reed ol
．． 295fu n color ol. 478 Chlorine content rate 45.87
%) of unsaturated ester (yield 75.6%) was obtained.

Example 4 A mixture of 6.07 mm (0.03 mol) and acetic anhydride (0.30 mol) was cooled to 0 to 5°C, and 2.0 mm of 85% phosphoric acid was added to this mixture. 22 (0.019 mol) was added dropwise in 3 portions.

After the dropwise addition, the mixture was further heated and reacted on a hot water bath for 3 hours. After the reaction, the same treatment as in Example 1 is carried out to obtain a carbon tetrachloride extract. After removing the carbon tetrachloride, 7.52 g of residual oil was obtained. The residual oil was fractionated and bp88.0-89.0℃/8 legs Hg (d reed.1.
250 n color ol. 476F chlorine content 43.13%
6.71 fractions (yield 91.6%) of ) were obtained.

Claims (1)

[Claims] 1. Unsaturated chlorine-containing alcohol and acetic anhydride represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (R_1 and R_2 in the formula are hydrogen atoms or alkyl groups) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_1 and R_2 in the formula have the same meanings as above)
A method for producing acetic ester of unsaturated chlorine-containing alcohol represented by