METHOD FOR PREPARING 2,6-DICHLOROPYRIDINE THROUGH LIQUID PHASE PHOTOCHLORINATION OF PYRIDINE

• US 20200131128A1
• Filed: 12/17/2018
• Published: 04/30/2020
• Est. Priority Date: 10/30/2018
• Status: Active Grant

• Current Assignee: Zhejiang Avilive Chemical Co., Ltd.
• Original Assignee: Zhejiang Avilive Chemical Co., Ltd.
• Inventors: LI, HUIYUE, JIN, KEQIANG, ZHU, JIAQUAN
• Granted Patent: US 10,851,060 B2
• Time in Patent Office: Days
• CPC Class Codes: B01D 3/143 by two or more of a fractionation, separation or rectification step
• CPC Class Codes: B01J 19/123 Ultraviolet light
• CPC Class Codes: B01J 2219/00033 Continuous processes
• CPC Class Codes: B01J 2219/00051 Controlling the temperature
• CPC Class Codes: B01J 2219/0869 Feeding or evacuating the reactor
• CPC Class Codes: B01J 2219/0884 Gas-liquid
• CPC Class Codes: C07B 39/00 Halogenation
• CPC Class Codes: C07D 213/61 Halogen atoms or nitro radicals

Abstract

The present invention relates to a method for preparing 2,6-dichloropyridine with product purity greater than or equal to 99.0% by using trifluoromethyl chlorobenzene as a solvent for reaction between pyridine and chlorine gas. The preparation process comprises the following steps: enabling pyridine and chlorine gas to continuously experience chlorination reaction under irradiation of ultraviolet light by using pyridine and chlorine gas as starting materials and using trifluoromethyl chlorobenzene as a solvent, and cooling a chlorination reaction product and the solvent to obtain pyridine chlorination solution. Advantages: firstly, it pioneers the precedent of direct and high-selectivity preparation of 2,6-dichloropyridine through liquid phase photochlorination, and not only can the 2,6-dichloropyridine product with purity greater than or equal to 99.0% be obtained, but also industrial production is facilitated; and secondly, not only can the reuse of the separated solvent in the preparation process of the 2,6-dichloropyridine product with purity greater than or equal to 99.0% be realized, but also the purposes of low pollution, low energy consumption and low cost in the preparation process can be realized.

Claims

1. A method for preparing 2,6-dichloropyridine through liquid phase photochlorination of pyridine, wherein pyridine and chlorine gas are enabled to continuously experience chlorination reaction at temperature of 150-210°

C. under irradiation of ultraviolet light by using pyridine and chlorine gas as starting materials and using trifluoromethyl chlorobenzene as a solvent, and a chlorination reaction product and the solvent are cooled to obtain pyridine chlorination solution.

2. The method for preparing 2,6-dichloropyridine through liquid phase photochlorination of pyridine according to claim 1, wherein pyridine and chlorine gas are enabled to continuously experience chlorination reaction at temperature of 150-210°

C. under irradiation of ultraviolet light by using pyridine and chlorine gas as starting materials and using trifluoromethyl chlorobenzene as a solvent, a chlorination reaction product and the solvent are cooled to obtain pyridine chlorination solution, the chlorination solution is subjected to crude distillation, then tar and high-boiling-point substances are separated, the obtained distillate is pyridine chloride containing the solvent, and the content of 2,6-dichloropyridine in the pyridine chloride after the solvent is removed is greater than or equal to 65%.

3. The method for preparing 2,6-dichloropyridine through liquid phase photochlorination of pyridine according to claim 1, wherein pyridine and chlorine gas are enabled to continuously experience chlorination reaction at temperature of 150-210°

C. under irradiation of ultraviolet light by using pyridine and chlorine gas as starting materials and using trifluoromethyl chlorobenzene as a solvent, a chlorination reaction product and the solvent are cooled to obtain pyridine chlorination solution, the chlorination solution is subjected to crude distillation, then tar and high-boiling-point substances are separated, the obtained distillate is pyridine chloride containing the solvent, the content of 2,6-dichloropyridine in the pyridine chloride after the solvent is removed is greater than or equal to 65%, the pyridine chloride containing the solvent is separated by adopting cooling crystallization, the solvent is removed, and then 2,6-dichloropyridine with purity greater than or equal to 99.0% is obtained, or the pyridine chloride containing the solvent is purified by adopting a rectification method to obtain a 2,6-dichloropyridine product with purity greater than or equal to 99.0%.

4. The method for preparing 2,6-dichloropyridine through liquid phase photochlorination of pyridine according to claim 1, wherein pyridine, trifluoromethyl chlorobenzene and chlorine gas are simultaneously and continuously fed into a photochlorination reactor for continuous chlorination reaction.

5. The method for preparing 2,6-dichloropyridine through liquid phase photochlorination of pyridine according to claim 4, wherein, at the start of chlorination reaction, the amount of the added solvent is 60%-80% of the volume of the reactor, heating is performed to increase temperature to above 150°

C., then chlorine gas is continuously fed, the amount of fed chlorine gas is 1.8-2.7 times the weight of pyridine, at the same time the mixture of pyridine and the solvent is continuously dripped according to proportions, and reaction solution is continuously discharged into a chlorination material collector or a crude distillation kettle.

6. The method for preparing 2,6-dichloropyridine through liquid phase photochlorination of pyridine according to claim 1, wherein the weight ratio of pyridine to the solvent is 1:

0.2-4.

7. The method for preparing 2,6-dichloropyridine through liquid phase photochlorination of pyridine according to claim 1, wherein the rectification purification method is to separate and purify 2,6-dichloropyridine from pyridine chloride containing the solvent to obtain the product with purity greater than or equal to 99.0% and the solvent with purity greater than or equal to 95.0%, wherein the solvent is reused;

and the crystallization separation purification method is to separate pyridine chloride containing the solvent through cooling crystallization, and to perform filter cake rectification to remove the solvent to obtain the 2,6-dichloropyridine product with purity greater than or equal to 99.0% and the solvent with purity greater than or equal to 95.0%, wherein the solvent is reused and filtrate is directly applied to the next-batch reaction, or the solvent and part of the product are recovered through a rectification method.

8. The method for preparing 2,6-dichloropyridine through liquid phase photochlorination of pyridine according to claim 1, wherein the ultraviolet light for irradiation comes from an ultraviolet light source or blue light source with a wavelength of 254-400 nm;

and the solvent includes, but not limited to, trifluoromethyl monochlorobenzene, trifluoromethyl dichlorobenzene and trifluoromethyl trichlorobenzene.

9. The method for preparing 2,6-dichloropyridine through liquid phase photochlorination of pyridine according to claim 1, wherein the liquid phase photochlorination method may also be implemented intermittently.