CN104817425B

CN104817425B - A kind of synthetic method of 1,1,2,3-tetrachloropropylene

Info

Publication number: CN104817425B
Application number: CN201510155324.7A
Authority: CN
Inventors: 司志红; 司林旭
Original assignee: Sanaifu Zhonghao Chemical New Material Co Ltd Changshu
Current assignee: Sanaifu Zhonghao Chemical New Material Co Ltd Changshu
Priority date: 2015-04-03
Filing date: 2015-04-03
Publication date: 2016-07-13
Anticipated expiration: 2035-04-03
Also published as: CN104817425A

Abstract

The invention discloses the synthetic method of a kind of 1,1,2,3 tetrachloropropylene, the method comprises the following steps: in pressure reaction still, and nitrogen protection is lower adds catalysts and solvents acetonitrile, and its mass ratio is 1:15 1:25, continuously stirred 12 hours；In container, add tetrachloroethylene and dichloromethane again, be heated to 120 DEG C～130 DEG C, the most continuously stirred 14 16 hours, obtain 1 through decompression distillation, 1,1,2,2,3 chlordene propane；1,1,1,2 that above-mentioned reaction is obtained, 2,3 chlordene propane, the zinc powder of hydrochloric acid activation, dioxanes join in hermetic container, stir 48 50 hours in nitrogen atmosphere at a temperature of 45 DEG C, through decompression distillation, collect 102～104 DEG C/13.33kPa fraction and i.e. can obtain 1,1,2,3 tetrachloropropylene；The inventive method reaction process and post processing are simple and direct, and synthetic yield is higher, and cost of material is relatively low.

Description

A kind of synthetic method of 1,1,2,3-tetrachloropropylene

Technical field

The present invention relates to the synthetic method of a kind of chlorine-containing compound, specifically a kind of 1,1,2,3-tetrachloropropylene Synthetic method, belongs to technical field of organic synthesis.

Background technology

1,1,2,3-tetrachloropropylene (HCC-1230xa) is synthesis new generation of environment protection cold-producing medium HFO-1234yf With prepare chemical herbicide wheat taste cream one of main intermediate.

At present, the method for synthesis 1,1,2,3-tetrachloropropylene mainly has: with carbon tetrachloride, ethylene, chlorine be Raw material material synthesizes 1,1,2,3-tetrachloropropylene, synthesizes 1,1,2,3-tetra-with 1,2,3-trichloropropane for raw material material Chloropropene, the method chlorine of tetrachloropropylene isomerization and with pentachloropropane for Material synthesis 1,1,2,3-tetrachloro third Alkene etc., from the point of view of these current preparation methoies, generally have that synthetic route is longer, production efficiency is relatively low, By-product and the three wastes are many, relatively costly, high to the requirement of equipment, energy consumption high, process route and post processing multiple The problem such as miscellaneous.

European patent WO 2009085862 discloses a kind of with carbon tetrachloride, ethylene, chlorine as Material synthesis The method of 1,1,2,3-tetrachloropropylene, including step: (1) carbon tetrachloride and Addition on ethylene generate 1,1,1,3- Four chloropropanes, (2) 1,1,1,3-tetra-chloropropane dehydrochlorination generation 1,1,3-tri chloropropene, (3) 1,1,3- Tri chloropropene carries out chlorination reaction and generates 1,1,2,3-tetra-chloropropane, (4) 1,1,2,3-tetra-chloropropane dechlorination Hydrogen generates 1,1,2,3-tetrachloropropylene and 2,3,3,3-tetrachloropropylene, (5) 2,3,3,3-tetrachloropropylene isomeries Change reaction and generate 1,1,2,3-tetrachloropropylene.The method use cheaper starting materials, be easy to get, beneficially industrialization Produce, and atom utilization is higher.But the method synthesis route is longer, energy consumption is high, production cost relatively High.

China Patent Publication No. CN102630221A, discloses a kind of with 1, prepared by 1,1,2,3-pentachloropropane The method of 1,1,2,3-tetrachloropropylene, the method includes in the absence of a catalyst to gas phase 1,1,1,2,3-pentachloropropane heating produces 1 carrying out dehydrochlorination reaction, 1,2,3-tetrachloropropylene, reaction Temperature is 250～450 DEG C.This reaction raw materials 1,1,1,2,3-pentachloropropane is not easy to obtain, severe reaction conditions, Post processing is complicated, and reaction efficiency is low.

Accordingly, it would be desirable to seek more effectively, simple and direct, economic method, synthetic yield higher 1,1,2,3- Tetrachloropropylene.

Summary of the invention

It is an object of the invention to for the deficiencies in the prior art, it is provided that a kind of production efficiency is higher, by-product and The three wastes are less, cost is relatively low, atom utilization is higher, process route and the simpler and more direct synthesis of post processing The new method of 1,1,2,3-tetrachloropropylene.

In order to realize above-mentioned technical purpose, the technical scheme is that

The synthetic method of a kind of 1,1,2,3-tetrachloropropylene, it is characterised in that comprise the following steps:

(1) in pressure reaction still, nitrogen protection is lower adds catalysts and solvents acetonitrile, described catalyst Active component and Supplementary active ingredients mass ratio are 1:6, and the active component of described catalyst is acetopyruvic acid One or more in copper, Cu-lyt., iron chloride；The Supplementary active ingredients of described catalyst be n-butylamine, One or more in triethyl group phosphoric acid, ethylenediamine, ethanolamine.

The mass ratio of catalysts and solvents acetonitrile is 1:15-1:25, continuously stirred 1-2 hour；Again in container The mol ratio adding tetrachloroethylene and dichloromethane, tetrachloroethylene and dichloromethane is 1:2.2, tetrachloroethylene Quality is 50-55 times of catalyst active component quality, is heated to 120 DEG C～130 DEG C, holds under nitrogen atmosphere Continuous stirring 14-16 hour, obtains 1 through decompression distillation, 1,1,2,2,3-chlordene propane；

(2) the 1,1,1,2,2,3-chlordene propane that above-mentioned reaction obtained, the zinc powder of hydrochloric acid activation, dioxanes Join in hermetic container, 1,1,1,2,2,3-chlordene propane, the zinc powder of hydrochloric acid activation and the quality of dioxanes Ratio is 40:1:10, stirs 48-50 hour in nitrogen atmosphere at a temperature of 45 DEG C, through decompression distillation, receives Collection 102～104 DEG C/13.33kPa fraction i.e. can obtain 1,1,2,3-tetrachloropropylene.

The inventive method reaction process and post processing are simpler and more direct, product 1,1, the product of 2,3-tetrachloropropylene Rate is high.The synthetic method of the present invention compared with prior art has the advantage that

(1) products collection efficiency is higher；

(2) reaction process and post processing are simple and direct；

(3) requirement to equipment is the highest, it is easy to accomplish.

(4) energy consumption is low, cost-effective.

Detailed description of the invention

Embodiment 1

(1) in the pressure reaction still of 500ml, nitrogen protection is lower adds Cu-lyt. 1g, n-butylamine 6g With solvent acetonitrile 120ml, continuously stirred 2 hours；Tetrachloroethylene 50g and dichloromethane is added again in container 56.3g, is heated to 120 DEG C, the most continuously stirred 14 hours, obtains through decompression distillation 1,1,1,2,2,3-chlordene propane, conversion ratio is 92%；

(2) the 1,1,1,2,2,3-chlordene propane 40g that above-mentioned reaction obtained, the zinc powder 1g of hydrochloric acid activation, Dioxanes 10g joins in hermetic container, stirs 48 hours, warp in nitrogen atmosphere at a temperature of 45 DEG C Decompression distillation, collects 102～104 DEG C/13.33kPa fraction and i.e. can obtain 1,1,2,3-tetrachloropropylene.

Test indicate that, the productivity of 1,1,2, the 3-tetrachloropropylene that the present embodiment obtains is 85%.

Embodiment 2

(1) in the pressure reaction still of 500ml, nitrogen protection is lower adds iron chloride 1g, triethyl phosphate 6g and solvent acetonitrile 120ml, continuously stirred 2 hours；Tetrachloroethylene 52g and dichloro is added again in container Methane 58.6g, is heated to 120 DEG C, the most continuously stirred 15 hours, obtains through decompression distillation 1,1,1,2,2,3-chlordene propane, conversion ratio is 90%；

(2) the 1,1,1,2,2,3-chlordene propane 40g that above-mentioned reaction obtained, the zinc powder 1g of hydrochloric acid activation, Dioxanes 10g joins in hermetic container, stirs 49 hours, warp in nitrogen atmosphere at a temperature of 45 DEG C Decompression distillation, collects 102～104 DEG C/13.33kPa fraction and i.e. can obtain 1,1,2,3-tetrachloropropylene.

Test indicate that, the productivity of 1,1,2, the 3-tetrachloropropylene that the present embodiment obtains is 83%.

Embodiment 3

(1) in the pressure reaction still of 500ml, nitrogen protection is lower adds cupric acetylacetonate 1g, n-butylamine 6g and solvent acetonitrile 150ml, continuously stirred 2 hours；Tetrachloroethylene 50g and dichloro is added again in container Methane 56.3g, is heated to 130 DEG C, the most continuously stirred 14 hours, obtains through decompression distillation 1,1,1,2,2,3-chlordene propane, conversion ratio is 94%；

Test indicate that, the productivity of 1,1,2, the 3-tetrachloropropylene that the present embodiment obtains is 90%.

Embodiment 4

(1) in the pressure reaction still of 500ml, nitrogen protection is lower adds Cu-lyt. 1g, ethylenediamine 6g With solvent acetonitrile 140ml, continuously stirred 1 hour；Tetrachloroethylene 50g and dichloromethane is added again in container 56.3g, is heated to 120 DEG C, the most continuously stirred 16 hours, obtains through decompression distillation 1,1,1,2,2,3-chlordene propane, conversion ratio is 92%；

Test indicate that, the productivity of 1,1,2, the 3-tetrachloropropylene that the present embodiment obtains is 87%.

Embodiment 5

(1) in the pressure reaction still of 500ml, nitrogen protection is lower adds cupric acetylacetonate 1g, ethanolamine 6g and solvent acetonitrile 140ml, continuously stirred 1 hour；Tetrachloroethylene 50g and dichloro is added again in container Methane 56.3g, is heated to 130 DEG C, the most continuously stirred 14 hours, obtains through decompression distillation 1,1,1,2,2,3-chlordene propane, conversion ratio is 92%；

(2) the 1,1,1,2,2,3-chlordene propane 40g that above-mentioned reaction obtained, the zinc powder 1g of hydrochloric acid activation, Dioxanes 10g joins in hermetic container, stirs 50 hours, warp in nitrogen atmosphere at a temperature of 45 DEG C Decompression distillation, collects 102～104 DEG C/13.33kPa fraction and i.e. can obtain 1,1,2,3-tetrachloropropylene. Test indicate that, the productivity of 1,1,2, the 3-tetrachloropropylene that the present embodiment obtains is 90%.

Above-described embodiment limits the present invention, every employing equivalent or the side of equivalent transformation never in any form The technical scheme that formula obtains all falls within protection scope of the present invention.

Claims

1. one kind 1, the synthetic method of 1,2,3-tetrachloropropylene, it is characterised in that comprise the following steps:

(1) in pressure reaction still, nitrogen protection is lower adds catalysts and solvents acetonitrile, and the active component of described catalyst and Supplementary active ingredients mass ratio are 1:6, and the mass ratio of catalysts and solvents acetonitrile is 1:15-1:25, continuously stirred 1-2 hour；Tetrachloroethylene and dichloromethane is added again in container, the mol ratio of tetrachloroethylene and dichloromethane is 1:2.2, the quality of tetrachloroethylene is 50-55 times of catalyst active component quality, is heated to 120 DEG C ~ 130 DEG C, the most continuously stirred 14-16 hour, 1 is obtained through decompression distillation, 1,1,2,2,3-chlordene propane；

(2) 1,1,1 that above-mentioned reaction is obtained, 2,2,3-chlordene propane, the zinc powder of hydrochloric acid activation, dioxanes join in hermetic container, 1,1,1, the mass ratio of 2,2,3-chlordene propane, the zinc powder of hydrochloric acid activation and dioxanes is 40:1:10, nitrogen atmosphere stirs 48-50 hour at a temperature of 45 DEG C, through decompression distillation, collects 102～104 DEG C/13.33 kPa fractions and i.e. can obtain 1,1,2,3-tetrachloropropylene；

The active component of described catalyst is one or more in cupric acetylacetonate, Cu-lyt., iron chloride；The Supplementary active ingredients of described catalyst is one or more in n-butylamine, triethyl phosphate, ethylenediamine, ethanolamine.