CN102731293A - Method for synthesizing oleoyl chloride by triphosgene - Google Patents

Abstract

The invention aims to provide a novel method for synthesizing oleoyl chloride, wherein oleic acid and triphosgene are taken as raw materials, N, N-dimethyl formamide is taken as a catalyst, and the oleic acid and triphosgene and the N,N-dimethyl formamide are reacted for 0.5-8h at 40-80 DEG C. The addition of the catalyst is 10-30% of molar weight of oleic acid, and the molar ratio of oleic acid and triphosgene is 3:1-1:1. The method is not only safe and convenient, but also mild in reaction condition, high in purity of product oleoyl chloride and high in yield.

Description

A method for synthesizing oleoyl chloride by triphosgene

1. Technical field

The invention relates to a novel synthesis method of oleoyl chloride, specifically a method for synthesizing oleoyl chloride by using oleic acid and triphosgene as raw materials.

2. Background technology

The synthesis of acid chloride is to react with carboxylic acid and acylating reagent as raw material. The main methods are as follows: the phosphorus trichloride method is convenient for preparing low boiling point acid chloride; the phosphorus pentachloride method is used for preparing carboxylic acid chloride with higher boiling point. The scope is limited and the post-treatment of the generated phosphorus-containing compounds is relatively difficult; the reaction conditions for the preparation of acid chlorides by the thionyl chloride method are mild, but the amount of thionyl chloride is large, the production cost is high, and the equipment is severely corroded; phosgene The industrial application of the method was earlier, but phosgene is a highly toxic gas, which has great dangers in the process of use, transportation and storage. Compared with the above four toxic controlled drugs, solid phosgene (triphosgene) is treated as a general toxic substance in the industry. Solid phosgene requires mild conditions for reaction, and has strong selectivity, high yield, and is safe and convenient to use. is being widely used.

Oleoyl chloride is a widely used organic synthesis intermediate, which can react with alcohols, phenols, amines and other compounds to synthesize various surfactant products, and can also be directly used in wool spinning, silk, synthetic fibers, printing and dyeing, and machinery industries and other industries.

At present, the synthesis of oleoyl chloride in industry is still mainly based on the phosphorus trichloride method, and the thionyl chloride method is partially used in the laboratory. However, these production methods have relatively large defects. It not only requires high equipment conditions, but also generates a large number of by-products (such as: phosphorous acid, etc.), and phosphorus trichloride and thionyl chloride are still toxic and harmful. Chemicals, their residues will cause great pollution to the environment, and the product purity and yield are also low. Therefore, it is an inevitable trend in the world to develop an oleoyl chloride synthesis method that is more convenient and safe to use, requires less equipment, less pollution, strong economy, and high yield. The triphosgene method basically meets the above requirements, so the triphosgene Synthesis of oleoyl chloride is a breakthrough worth looking forward to.

3. Contents of the invention

The invention aims to provide a new synthesis method of oleoyl chloride, and the technical problem to be solved is to improve the purity and yield of the product and to simplify and make the preparation process safer.

The present invention uses triphosgene instead of acylating reagents such as phosphorus trichloride, and reacts with oleic acid under proper conditions to synthesize oleoyl chloride.

The method for synthesizing oleoyl chloride by triphosgene in the present invention is characterized in that: oleic acid and triphosgene are used as raw materials, N,N-dimethylformamide is used as a catalyst, and the reaction is stirred and reacted at 40-80°C for 0.5-8h;

The amount of catalyst added is 10-30% of the molar weight of oleic acid;

The molar ratio of oleic acid and triphosgene is 3:1~1:1.

Concrete preparation steps of the present invention are as follows:

1. Take industrial product oleic acid and put it into a round bottom flask, heat and stir to raise the temperature to 110~130°C and keep it for 0.5~1h, until the oleic acid liquid surface has no steam to evaporate, and the purified oleic acid is obtained for later use;

2. Add 14.1g of purified oleic acid and 4.9g~14.8g of triphosgene to a 250ml three-necked flask under constant temperature conditions in a water bath of 40~80°C, and slowly add 0.36~1.10g of N,N-dimethylformamide dropwise, After the dropwise addition, keep the constant temperature reaction for 0.5~8h;

3. After the reaction is over, let the reaction solution stand for 0.5~1h and then separate the upper layer to obtain the product oleoyl chloride;

4. Take a small amount of oleoyl chloride and add distilled water for hydrolysis. After the hydrolysis is completed, use the Mohr method to measure the content of Cl ions in the system, and thus calculate the purity and yield of the target product. The purity and yield of the product oleoyl chloride were determined by the Mohr method, and the purity can reach up to 95%, and the yield can reach up to 95%.

Compared with the prior art, the beneficial effects of the present invention are reflected in:

1. The preparation method of the present invention is simple, requires little equipment, has little environmental pollution, and is highly feasible.

2. The yield and yield of the present invention are relatively high, and the purity and yield of the product oleoyl chloride are measured by the Mohr method, and the purity can reach up to 95%, and the yield can reach up to 95%.

3. The present invention overcomes the use of controlled drugs such as phosphorus trichloride as the acid chloride reagent in the traditional method, and is safe and convenient to operate.

4. Description of drawings

Fig. 1 is the infrared spectrum of raw material oleic acid.

Fig. 2 is the infrared spectrum of product oleoyl chloride.

Fig. 3 is the standard infrared spectrum of oleoyl chloride.

The raw material oleic acid (Fig. 1) and the product oleoyl chloride (Fig. 2) were characterized by infrared spectroscopy. The results showed that the infrared absorption spectra of oleic acid and oleoyl chloride were very similar, and the 3009cm ^-1 was attributed to the carbon-carbon double bond (C=C) absorption peak; the strong absorption peaks at around 2926 and 2856 cm ^-1 are respectively assigned to the stretching vibration absorption peak of saturated hydrocarbon (CH); about 1464 cm ^-1 is attributed to the methylene (-CH ₂ ) Stretching vibration absorption peak; 1378cm ^-1 is attributed to deformation vibration absorption peak of methyl group (—CH ₃ ); 955cm ^-1 is also attributed to carbon-carbon double bond (C=C) absorption peak; 723cm ^-1 is attributed to It is the deformation stretching vibration absorption peak of multiple methylene groups (-CH ₂ ); the absorption peak at 1711cm ^-1 in Figure 1 is attributed to the absorption peak of carbonyl (C=O) in carboxylic acid; the carbonyl peak around 1711cm ^-1 in Figure 2 Basically disappear, the carbonyl (C=O) stretching vibration absorption peak appears at 1801cm ^-1 due to the strong electronegativity of Cl atoms and shifts to the high frequency direction, and the carbon-chloride (C-Cl) stretching vibration absorption peak appears at 681cm ^-1 The vibrational absorption peaks all prove that the acyl chloride reaction has occurred, converting -COOH into -COCl. Comparing the infrared spectrum of the product oleoyl chloride (Figure 1) with the standard infrared spectrum of oleoyl chloride (source: Wujing Chemical Database http://www.basechem.org/chemical/2317) Figure 3, they are basically consistent, and further Prove that the product is oleoyl chloride with high purity.

5. Specific implementation

In order to better understand the present invention, the present invention will be further described below in conjunction with specific cases, and the non-limiting examples are as follows.

Example 1:

Weigh 0.05mol of purified oleic acid and add it to a 250ml three-necked flask. The temperature of the water bath is raised to 60°C and kept constant. Add 0.025mol of triphosgene, and then slowly add 0.77ml of N,N-dimethylformamide dropwise. 2h, after the reaction is over, let it stand for 0.5h~1h to separate the upper layer of the mixture. And calculate the purity and yield of the target product.

Purity/% 92.15 Yield/% 87.14 Appearance Orange-red clear oily liquid

Example 2:

Weigh 0.05mol of purified oleic acid and add it to a 250ml three-necked flask. The temperature of the water bath is raised to 60°C and kept constant. Add 0.025mol of triphosgene, and then slowly add 0.77ml of N,N-dimethylformamide dropwise. 0.5h, after the reaction is over, let it stand for 0.5h~1h to separate the upper layer of the mixture. And calculate the purity and yield of the target product.

Purity/% 95.11 Yield/% 95.01 Appearance Orange yellow clear oily liquid

Example 3:

Weigh 0.05mol of purified oleic acid and add it to a 250ml three-necked flask. The temperature of the water bath is raised to 80°C and kept constant. Add 0.025mol of triphosgene, and then slowly add 0.77ml of N,N-dimethylformamide dropwise. h, after the reaction, let it stand for 0.5h~1h to separate the upper layer of the mixture. And calculate the purity and yield of the target product.

Purity/% 90.50 Yield/% 91.39 Appearance Orange-red clear oily liquid

Example 4:

Weigh 14.1g of purified oleic acid and add it to a 250ml three-necked flask. The temperature of the water bath is raised to 60°C and kept constant. Add 0.025mol of triphosgene, then slowly add 0.015mol of N,N-dimethylformamide dropwise. h, after the reaction, let it stand for 0.5h~1h to separate the upper layer of the mixture. And calculate the purity and yield of the target product.

Purity/% 90.73

Yield/% 90.02 Appearance Orange yellow clear oily liquid

Example 5:

Weigh 14.1 g of purified oleic acid and add it to a 250 ml three-necked flask. The temperature of the water bath is raised to 60°C and kept constant. Add 0.05 mol of triphosgene, and then slowly add 0.015 mol of N,N-dimethylformamide dropwise. h, after the reaction, let it stand for 0.5h~1h to separate the upper layer of the mixture. And calculate the purity and yield of the target product.

Purity/% 88.24 Yield/% 90.96 Appearance Orange-red clear oily liquid

Embodiment 6:

Weigh 28.2g of purified oleic acid and add it to a 250ml three-necked flask, raise the temperature of the water bath to 60°C and keep it constant, add 14.8g of triphosgene, then slowly add 1.46g of N,N-dimethylformamide dropwise, and the constant temperature reaction time is 1h , After the reaction is over, let it stand for 0.5h~1h to separate the upper layer of the mixed solution. And calculate the purity and yield of the target product.

Purity/% 91.75 Yield/% 87.77 Appearance Orange yellow clear oily liquid

Claims (1)

1. A method for synthesizing oleoyl chloride by triphosgene, characterized in that: oleic acid and triphosgene are used as raw materials, N,N-dimethylformamide is used as a catalyst, and the stirring reaction is carried out at 40~80°C for 0.5~8h; The amount of catalyst added is 10-30% of the molar weight of oleic acid; The molar ratio of oleic acid and triphosgene is 3:1~1:1.

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