Preparation method of 5-chlorovaleryl chloride

Abstract

The invention relates to a preparation method of 5-chlorovaleryl chloride and belongs to the field of synthesis of pesticide intermediates. The preparation method comprises the following steps: in delta-valerolactone, adding iron or aluminum with the mass being 0.05-1% of that of the delta-valerolactone and water with the weight of 1-5% of that of the delta-valerolactone as a cocatalyst, then introducing a certain amount of phosgene into a reaction system, and after the reaction mixed liquid reacts for 2-10 hours at the temperature of 60-100 DEG C, obtaining a crude 5-chlorovaleryl chloride product, and carrying out decompressed distillation on the crude 5-chlorovaleryl chloride product to obtain high-purity 5-chlorovaleryl chloride. The preparation method adopts the iron (or aluminum) andthe water as the cocatalyst, does not need introduction of hydrogen chloride gas, has the advantages of simple and easy obtaining of the materials and the catalyst, mild reaction condition and simpleoperation and the like, and has a good industrial application prospect.

Description

technical field

[0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for preparing a pesticide synthesis intermediate-5-chlorovaleryl chloride. Background technique

[0002] 5-chlorovaleryl chloride is an important synthetic intermediate of pyrazole herbicides. 5-chloropentanoyl chloride is used as the raw material of 1,1,7-trichloro-1-hepten-3-one, and then the third generation pyrazole herbicides can be synthesized. Pyrazole herbicides have the characteristics of ultra-efficient herbicidal activity, high selectivity, extremely low mammalian toxicity and good environmental characteristics, and have become a hot spot in the research and development of herbicides in the world in recent years. With the continuous expansion of the demand for high-efficiency herbicides, the demand for 5-chlorovaleryl chloride as an intermediate is also gradually increasing. At present, the method for synthesizing 5-chloropentanoyl chloride mainl...

Examples

Embodiment 1

[0029] In a two-necked round-bottomed flask (one is connected to the condenser and the other is used as passing through phosgene), add δ-valerolactone (100g, 1mol) successively, catalyst Fe powder (0.5g, 0.5wt%) and water ( 2g, 2wt%), heated the mixed solution to 100°C and started to feed phosgene (107g, 1.1mol). The time for feeding phosgene was about 4 hours, during which the temperature was maintained at about 100°C. After adding phosgene, continue to react at about 80°C for 1 hour, then cool down the reaction solution to room temperature, and replace excess phosgene with nitrogen. The reaction solution was distilled under reduced pressure and the fraction at 120°C (1.0kPa) was collected to obtain 5-chlorovaleryl chloride (142g, yield 93%).

[0030] Replacement example:

[0031] The preparation method is the same as in Example 1, the difference is that the amount of Fe catalyst, water, phosgene, and reaction temperature are adjusted, and the impact on the reaction yield is...

Embodiment 2

[0035] In a two-necked round-bottomed flask (one is connected to the condenser tube and the other is used as passing through phosgene), add δ-valerolactone (100g, 1mol) successively, and the catalyst Fe 2 o 3 (1g, 1wt%) and water (2g, 2wt%), begin to pass into phosgene (107g, 1.1mol) after the mixed solution is heated up to 100 ℃, the time of passing into phosgene is about 4 hours, and temperature maintains during At around 100°C. After adding phosgene, continue to react at about 80°C for 1 hour, then cool down the reaction solution to room temperature, and replace excess phosgene with nitrogen. The reaction solution was distilled under reduced pressure and the fraction at 120°C (1.0kPa) was collected to obtain 5-chlorovaleryl chloride (122g, yield 80%).

Embodiment 3

[0037] In a two-necked round-bottomed flask (one is connected to the condenser tube, the other is used for passing through phosgene), successively add δ-valerolactone (100g, 1mol), catalyst FeCl 3 (1.0g, 1wt%) and water (2g, 2wt%), begin to pass into phosgene (107g, 1.1mol) after the mixed solution is heated up to 100 ℃, the time of passing into phosgene is about 4 hours, during the temperature Maintained at around 100°C. After adding phosgene, continue to react at about 80°C for 1 hour, then cool down the reaction solution to room temperature, and replace excess phosgene with nitrogen. The reaction solution was distilled under reduced pressure and the fraction at 120°C (1.0kPa) was collected to obtain 5-chlorovaleryl chloride (132g, yield 86%).

technical field

[0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for preparing a pesticide synthesis intermediate-5-chlorovaleryl chloride. Background technique

[0002] 5-chlorovaleryl chloride is an important synthetic intermediate of pyrazole herbicides. 5-chloropentanoyl chloride is used as the raw material of 1,1,7-trichloro-1-hepten-3-one, and then the third generation pyrazole herbicides can be synthesized. Pyrazole herbicides have the characteristics of ultra-efficient herbicidal activity, high selectivity, extremely low mammalian toxicity and good environmental characteristics, and have become a hot spot in the research and development of herbicides in the world in recent years. With the continuous expansion of the demand for high-efficiency herbicides, the demand for 5-chlorovaleryl chloride as an intermediate is also gradually increasing. At present, the method for synthesizing 5-chloropentanoyl chloride mainl...

Examples

Embodiment 1

[0029] In a two-necked round-bottomed flask (one is connected to the condenser and the other is used as passing through phosgene), add δ-valerolactone (100g, 1mol) successively, catalyst Fe powder (0.5g, 0.5wt%) and water ( 2g, 2wt%), heated the mixed solution to 100°C and started to feed phosgene (107g, 1.1mol). The time for feeding phosgene was about 4 hours, during which the temperature was maintained at about 100°C. After adding phosgene, continue to react at about 80°C for 1 hour, then cool down the reaction solution to room temperature, and replace excess phosgene with nitrogen. The reaction solution was distilled under reduced pressure and the fraction at 120°C (1.0kPa) was collected to obtain 5-chlorovaleryl chloride (142g, yield 93%).

[0030] Replacement example:

[0031] The preparation method is the same as in Example 1, the difference is that the amount of Fe catalyst, water, phosgene, and reaction temperature are adjusted, and the impact on the reaction yield is...

Embodiment 2

[0035] In a two-necked round-bottomed flask (one is connected to the condenser tube and the other is used as passing through phosgene), add δ-valerolactone (100g, 1mol) successively, and the catalyst Fe 2 o 3 (1g, 1wt%) and water (2g, 2wt%), begin to pass into phosgene (107g, 1.1mol) after the mixed solution is heated up to 100 ℃, the time of passing into phosgene is about 4 hours, and temperature maintains during At around 100°C. After adding phosgene, continue to react at about 80°C for 1 hour, then cool down the reaction solution to room temperature, and replace excess phosgene with nitrogen. The reaction solution was distilled under reduced pressure and the fraction at 120°C (1.0kPa) was collected to obtain 5-chlorovaleryl chloride (122g, yield 80%).

Embodiment 3

[0037] In a two-necked round-bottomed flask (one is connected to the condenser tube, the other is used for passing through phosgene), successively add δ-valerolactone (100g, 1mol), catalyst FeCl 3 (1.0g, 1wt%) and water (2g, 2wt%), begin to pass into phosgene (107g, 1.1mol) after the mixed solution is heated up to 100 ℃, the time of passing into phosgene is about 4 hours, during the temperature Maintained at around 100°C. After adding phosgene, continue to react at about 80°C for 1 hour, then cool down the reaction solution to room temperature, and replace excess phosgene with nitrogen. The reaction solution was distilled under reduced pressure and the fraction at 120°C (1.0kPa) was collected to obtain 5-chlorovaleryl chloride (132g, yield 86%).

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