CN105622307A

CN105622307A - Method for synthesizing 1,3-diacetylene benzene

Info

Publication number: CN105622307A
Application number: CN201510958885.0A
Authority: CN
Inventors: 叶传辉; 张芳江; 甘建刚; 刘庆曾
Original assignee: LIKE MEDICINE CHEMISTRY CO Ltd SHANGHAI; SHANGHAI RECORD CHEMISTRY TECHNOLOGY Co Ltd
Current assignee: LIKE MEDICINE CHEMISTRY CO Ltd SHANGHAI; SHANGHAI RECORD CHEMISTRY TECHNOLOGY Co Ltd
Priority date: 2015-12-21
Filing date: 2015-12-21
Publication date: 2016-06-01

Abstract

The invention discloses a method for synthesizing 1,3-diacetylene benzene. The method comprises the following steps: a) taking m-phthalaldehyde and malonic acid as raw materials, catalyzing pyridine and carrying out a reaction in a first solvent to obtain 1,3-benzene diacrylate, wherein the volume proportion of the m-phthalaldehyde to the malonic acid to the pyridine to the first solvent is 1:2.4:0.05:5; b) dispersing the 1,3-benzene diacrylate in a second solvent, then dropwise adding bromine and reacting to obtain 2,3,2',3'-tetrabromo-m-phenylene methyl malonate, wherein the volume proportion of the 1,3-[henylenediacrylic acid to the bromine to the second solvent is 1:2:5; c) reacting the 2,3,2',3'-tetrabromo-m-phenylene methyl malonate, potassium carbonate and a third solvent according to the volume proportion of 1:4:3 to obtain the 1,3-diacetylene benzene. According to the method disclosed by the invention, the synthetic efficiency of the 1,3-diacetylene benzene can be greatly improved, and the cost can be reduced.

Description

1,3-diacetylene-benzene synthetic method

Technical field

The present invention relates to a kind of diacetylene-benzene synthetic method, particularly relate to a kind of 1,3-diacetylene-benzene synthetic method.

Background technology

The aspects such as 1,3-diacetylene-benzene synthesizes at medicine, liquid crystal material, aviation and wide have highly important purposes; Highly purified 1,3-diacetylene-benzene industrialized production is very difficult, having method m-dibromobenzene is raw material, with 2-methyl-2-hydroxyl butine about palladium catalyst under carry out hack reaction, then hydrolysis obtains 1,3-diacetylene-benzene, the method uses palladium catalyst, severe reaction conditions, catalyst can not reclaim, and industrialization cost is high.

Having bibliographical information mixing divinylbenzene is raw material, eliminates and obtains mixing diacetylene-benzene, then separate after bromo; The method is difficult to obtain highly purified 1,3-diacetylene-benzene, it is difficult to meet purity requirement.

Summary of the invention

The technical problem to be solved is to provide a kind of 1,3-diacetylene-benzene synthetic method, it is possible to be greatly improved the combined coefficient of 1,3-diacetylene-benzene, reduces cost.

The present invention solves that above-mentioned technical problem employed technical scheme comprise that offer a kind of 1,3-diacetylene-benzene synthetic method, comprise the steps: a) to be raw material with m-terephthal aldehyde and malonic acid, pyridine catalysis, first solvent is obtained by reacting 1,3-benzene diacrylate, two benzaldehydes between described, malonic acid, pyridine, the first solvent volume proportion be 1:2.4:0.05:5; B) 1,3-benzene diacrylate is dispersed in the second solvent, then drips bromine, be obtained by reacting 2,3,2 ', 3 '-four bromo-isophthalic dipropionic acid methyl ester, described 1,3-benzene diacrylate, bromine, the second solvent volume proportion be 1:2:5; C) by 2,3,2 ', 3 '-four bromo-isophthalic dipropionic acid methyl ester and potassium carbonate are obtained by reacting 1,3-diacetylene-benzene in the 3rd solvent, and the volume proportion of described 2,3,2 ', 3 '-four bromo-isophthalic dipropionic acid methyl ester, potassium carbonate and the 3rd solvent is 1:4:3.

1,3-above-mentioned diacetylene-benzene synthetic method, wherein, the first solvent in described step a) is toluene, and reaction temperature is 80 DEG C, and the response time is 3 hours.

1,3-above-mentioned diacetylene-benzene synthetic method, wherein, the second solvent in described step b) is acetic acid, and reaction temperature is 40 DEG C, and after bromine dropwise adding completes, is incubated 40 DEG C and reacts 1 hour.

1,3-above-mentioned diacetylene-benzene synthetic method, wherein, the 3rd solvent in described step c) is dimethyl sulfoxide, and reaction temperature is 120 DEG C, and the response time is 4 hours.

1,3-above-mentioned diacetylene-benzene synthetic method, wherein, described synthetic method is additionally included in step c) reaction and terminates cooling, filter, first extract by ethyl acetate, then wash with saturated aqueous common salt, then dry, concentration, distillation obtains light yellow 1,3-diacetylene-benzene liquid.

The present invention contrasts prior art following beneficial effect: 1,3-diacetylene-benzene synthetic method provided by the invention, first substitutes pyridine with toluene and makees solvent, add the pyridine of catalytic amount, reduce pyridine consumption, save cost, simultaneous reactions mild condition, subsequent treatment is simple; Recycling acetic acid is solvent, improves selectivity; Last dimethyl sulfoxide is solvent, and potassium carbonate does alkali, and a step debrominate decarboxylation obtains product, and reaction scheme is short, cost is low, is substantially reduced cost.

Detailed description of the invention

Below in conjunction with embodiment, the invention will be further described.

1,3-diacetylene-benzene synthetic method provided by the invention, when preparing 1,3-benzene diacrylate, is dispersed in toluene by m-terephthal aldehyde, malonic acid under room temperature (25 DEG C), drips catalytic amount pyridine. Reaction is not added with heat and is substantially free of reaction, intensification 40-50 DEG C reaction, can react but react very slow, and temperature to 80 DEG C is reacted quickly, and reaction in 3 hours terminates; Temperature reaction can faster, but system backflow is acutely, has slug dangerous, therefore selects 80 DEG C of reactions; Reaction system is first molten has solids manufacture clearly in course of reaction, reaction terminates a large amount of solid of rear system, and HPLC follows the tracks of m-terephthal aldehyde less than 0.5%, cools to room temperature, is filtrated to get white solid, product purity usual more than 95%, yield more than 95%.

Present invention toluene substitutes pyridine and makees solvent, adds the pyridine of catalytic amount, reduces pyridine consumption, saves cost, simultaneous reactions mild condition, the advantages such as post processing is simple.

Preparation 2,3,2 ', 3 '-four bromo-isophthalic dipropionic acid methyl ester are by 1,3-benzene diacrylate is dispersed in acetic acid, dropping bromine reaction, and time temperature is low, selectivity is low, having the by-product of benzene bromine in ring, temperature is higher than 40 DEG C, and the bromine of dropping can be excessive, therefore selects 40 DEG C of reactions; The complete rear insulation reaction of bromine dropwise adding is until raw material disappears (HPLC tracking). Reaction cools to room temperature after terminating, and filters, and washing is dried, obtained white solid, the usual purity more than 90% of product, yield more than 90%.

The present invention utilizes acetic acid for solvent, improves selectivity, and reaction terminates directly to be filtrated to get product, improves acetic acid recovery reuse ratio, it is to avoid acetic acid is poured into water by tradition, polluted-water;

Preparation 1,3-diacetylene-benzene is by 2, and 3,2 ', 3 '-four bromo-isophthalic dipropionic acid methyl ester are dissolved in dimethyl sulfoxide, adds Anhydrous potassium carbonate powdered reaction, and temperature low reaction is slow, and temperature selects 120 DEG C of the bests, and temperature is high again has by-product to generate; Heating and thermal insulation reaction, until intermediate disappears (HPLC tracking), has been reacted for general 4 hours, and reaction cools to room temperature after terminating, and filters, and filtrate is extracted with ethyl acetate, saturated common salt water washing, dry, filters, concentration, and distillation obtains product; Product purity is usually above 98%, and yield is usually above 80%;

Having the similar reaction of bibliographical information, first drip triethylamine in DMF, obtain ��-bromstyrol scaffold intermediate, then debrominate obtains product in the basic conditions, and this operating procedure is long, and yield is low, and cost is high. Present invention dimethyl sulfoxide is solvent, and potassium carbonate does alkali, and a step debrominate decarboxylation obtains product, therefore has that route is short, low cost and other advantages.

Embodiment

Adding 670 milliliters of toluene in the bottle of 1 liter, then be separately added into m-terephthal aldehyde 134 grams, malonic acid 229 grams and pyridine 4 grams, stir, be warming up to 80 degree, react 3 hours, liquid phase is followed the tracks of until the peak area of raw material m-terephthal aldehyde is less than 0.5%. After being cooled to 25 degree, filter, dry and obtain white powdery solids 210 grams, purity 98.2%, yield 96%;

2 liters of reaction bulbs add 210 gram of 1,3-benzene diacrylate, adds 1050 milliliters of acetic acid, it is heated to 40 degree, is slowly added dropwise 308 grams of bromines, within 2 hours, be added dropwise to complete, after being added dropwise to complete, being incubated 40 degree and react 1 hour, liquid phase is followed the tracks of until raw material 1, the peak area of 3-benzene diacrylate is less than 0.5%, after cooling to 25 DEG C, filters, washing is to neutral, dry and obtain white powdery solids 470g, purity 92%, yield 90.3%;

3 liters of reaction bulbs add dimethyl sulfoxide 1410 milliliters, adds 470 gram 2,3,2 ', 3 '-four bromo-isophthalic dipropionic acid methyl ester, are dividedly in some parts 482 grams of potassium carbonate, have gas to produce, after being wholly absent in bubble, being warmed up to 120 degree of insulation reaction 4 hours, liquid phase is followed the tracks of until intermediate peak area is less than 1%, after reaction terminates, cool to 25 degree, filtering, filtrate adds 1 liter of ethyl acetate, washes twice with 1 liter of saturated aqueous common salt, dry organic facies, filtering, concentrate, obtain crude product, crude product obtains light yellow liquid 90g through distillation, purity 98.5%, yield 81.8%.

Although the present invention discloses as above with preferred embodiment; so it is not limited to the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; when doing a little amendment and perfect, therefore protection scope of the present invention is when with being as the criterion that claims define.

Claims

1. a diacetylene-benzene synthetic method, it is characterised in that comprise the steps:

A) be raw material with m-terephthal aldehyde and malonic acid, pyridine catalysis, the first solvent is obtained by reacting 1,3-benzene diacrylate, two benzaldehydes between described, malonic acid, pyridine, the first solvent volume proportion be 1:2.4:0.05:5;

B) 1,3-benzene diacrylate is dispersed in the second solvent, then drips bromine, be obtained by reacting 2,3,2 ', 3 '-four bromo-isophthalic dipropionic acid methyl ester, described 1,3-benzene diacrylate, bromine, the second solvent volume proportion be 1:2:5;

C) by 2,3,2 ', 3 '-four bromo-isophthalic dipropionic acid methyl ester and potassium carbonate are obtained by reacting 1,3-diacetylene-benzene in the 3rd solvent, and the volume proportion of described 2,3,2 ', 3 '-four bromo-isophthalic dipropionic acid methyl ester, potassium carbonate and the 3rd solvent is 1:4:3.

2. 1,3-diacetylene-benzene synthetic method as claimed in claim 1, it is characterised in that the first solvent in described step a) is toluene, and reaction temperature is 80 DEG C, and the response time is 3 hours.

3. 1,3-diacetylene-benzene synthetic method as claimed in claim 1, it is characterised in that the second solvent in described step b) is acetic acid, and reaction temperature is 40 DEG C, and after bromine dropwise adding completes, be incubated 40 DEG C and react 1 hour.

4. 1,3-diacetylene-benzene synthetic method as claimed in claim 1, it is characterised in that the 3rd solvent in described step c) is dimethyl sulfoxide, and reaction temperature is 120 DEG C, and the response time is 4 hours.

5. 1 as described in any one of Claims 1 to 4,3-diacetylene-benzene synthetic method, it is characterized in that, described synthetic method is additionally included in step c) reaction and terminates cooling, filters, first extract by ethyl acetate, wash with saturated aqueous common salt again, then dry, concentration, distillation obtains light yellow 1,3-diacetylene-benzene liquid.