CN102531888B - Chemical synthesis method of 3,4,5-trimethoxy benzoyl chloride - Google Patents
Chemical synthesis method of 3,4,5-trimethoxy benzoyl chloride Download PDFInfo
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- CN102531888B CN102531888B CN201110411753.8A CN201110411753A CN102531888B CN 102531888 B CN102531888 B CN 102531888B CN 201110411753 A CN201110411753 A CN 201110411753A CN 102531888 B CN102531888 B CN 102531888B
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- benzoyl chloride
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- organic amine
- trimethoxybenzoic acid
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Abstract
The invention discloses a chemical synthesis method of 3,4,5-trimethoxy benzoyl chloride. In the synthesis method, the 3,4,5-trimethoxy benzoyl chloride is prepared by taking 3,4,5- trimethoxybenzoic acid and bis(trichloromethyl)carbonate as raw materials and fully reacting in an organic solvent under the action of an organic amine catalyst at the temperature of 20-70 DEG C. The synthesis method has the advantages of reasonable process, low production cost, high reaction yield and good product quality, and is suitable for industrial production.
Description
(1) technical field
The present invention relates to a kind of gastrointestinal antispasmodic medicine Trimebutine Maleate key intermediate 3,4, the synthetic method of 5-trimethoxy-benzoyl chloride.
(2) background technology
3,4,5-trimethoxy-benzoyl chloride is the key intermediate of synthetic Trimebutine Maleate, Trimebutine Maleate is a kind of amino ester compound that French Jouveinal company develops, belong to gastrointestinal tract dynamia medicine, within 1970, go on the market in France first, within 2000, go on the market in China; Within 2004, enter national medical insurance catalogue.
Before the present invention provides, in prior art 3,4, mostly the synthetic method of 5-trimethoxy-benzoyl chloride is to prepare with the chlorination of 3,4,5-trimethoxybenzoic acid and sulfur oxychloride.As " Heilungkiang medical science " 1998,21 (3): propose following technique in 48-49: 3,4,5-trimethoxybenzoic acid 30g (0.14mol) adds in the dimethylbenzene of 140g, normal pressure dehydration.Steam after 50mL, then add aluminum trichloride (anhydrous) 0.15g (0.001mol), be incubated 80 ℃, in 3h, slowly drip sulfur oxychloride 16.6g (0.14mol).Drip and finish, be warming up to 85 ℃, after reaction 2h, make 3,4,5-trimethoxy-benzoyl chloride.
In sulfur oxychloride process tail gas, containing a large amount of asphyxiant sulfurous gas, sulphur dioxide emission are one of national environmental protection six indexs to a control of atmosphere, three wastes difficult treatment, and expense is high.The transportation of sulfur oxychloride and use are strictly controlled in addition, high to the sealing requirements of conversion unit, the investment shortcomings such as also large and production security is poor.
Prepare in the reaction of acyl chlorides at all poly carboxylic acids at present, gradually use two (trichloromethyl) carbonic ethers to substitute sulfur oxychloride as chlorination reagent.Common that method for making is, under the catalysis of organic amine, carboxylic acid chlorination is generated to acyl chlorides.But we find in experiment, using two (trichloromethyl) carbonic ethers as 3 of chlorination reagent, 4,5-trimethoxybenzoic acid synthetic 3,4, in the reaction of 5-trimethoxy-benzoyl chloride, adopt conventional as the organic amine such as triethylamine, DMF during as catalyzer reaction yield lower, be unsuitable for suitability for industrialized production.
Therefore for above industrial unfavorable factor, be necessary existing technique to improve.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of technique is reasonable, production cost is low, reaction yield is high, 3,4 of good product quality, the chemical synthesis process of 5-trimethoxy-benzoyl chloride.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of 3,4, the chemical synthesis process of 5-trimethoxy-benzoyl chloride, described synthetic method is for raw material with 3,4,5-trimethoxybenzoic acid and two (trichloromethyl) carbonic ethers, in organic solvent, under organic amine catalyst action, fully react in 20～70 ℃, described in making 3,4,5-trimethoxy-benzoyl chloride; Reaction equation is as follows:
It is one of following that described organic amine catalyzer is selected from: three (2-cyano methyl) amine, three (2-cyano ethyl) amine, three (2-cyanopropyl) amine, N, N, N ', N '-tetra-(3-cyano methyl) quadrol, N, N, N ', N '-tetra-(3-cyano ethyl) quadrol, N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, N, N-bis-(3-cyano methyl) benzylamine, N, N-bis-(3-cyano ethyl) benzylamine, N, N-bis-(3-cyanopropyl) benzylamine, N-(3-cyanopropyl) benzylamine;
It is one of following that described reaction solvent is selected from: toluene, dimethylbenzene, methylene dichloride, tetracol phenixin, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dioxane, ethyl acetate, normal hexane, tetrahydrofuran (THF), 2-methyltetrahydrofuran, acetonitrile.
In the present invention, described 3,4, the ratio of the amount of substance that feeds intake of 5-trimethoxybenzoic acid, two (trichloromethyl) carbonic ether, organic amine is 1: 0.33～3.0: 0.03～3.0, preferably 1: 0.33～1.0: 0.05～0.3, more preferably 1: 0.33～0.5: 0.1～0.2.
In the present invention, the quality consumption of described reaction solvent is 1～20 times of 3,4,5-trimethoxybenzoic acid, preferably 5～20 times, and more preferably 10～20 times.
Further, the described preferred N of organic amine catalyzer, N, N ', N '-tetra-(3-cyanopropyl) quadrols or three (2-cyano ethyl) amine, more preferably N, N, N ', N '-tetra-(3-cyanopropyl) quadrol.
Further, described reaction solvent is preferably methylene dichloride, tetrahydrofuran (THF) or 2-methyltetrahydrofuran, more preferably 2-methyltetrahydrofuran.
Reaction of the present invention, the reaction times is preferably 4～10 hours; Temperature of reaction is preferably 50～70 ℃.
The present invention is concrete recommends described chemical synthesis process to carry out in accordance with the following steps: by 3,4,5-trimethoxybenzoic acid and organic amine are dissolved in organic solvent, at 20～70 ℃, stir and drip two (trichloromethyl) carbonate solutions with organic solvent dissolution, dropwise rear insulation reaction 4～10h, reaction finishes rear recovery organic solvent, and residual solids obtains described 3 through recrystallization, 4,5-trimethoxy-benzoyl chloride.Described 3,4, the ratio of the amount of substance that feeds intake of 5-trimethoxybenzoic acid, two (trichloromethyl) carbonic ether, organic amine is 1: 0.33～1.0: 0.03～0.1; Described organic solvent is 2-methyltetrahydrofuran; Described organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol; The quality consumption of described 2-methyltetrahydrofuran is 5～20 times of 3,4,5-trimethoxybenzoic acid quality; The sherwood oil that described recrystallization solvent was dried with calcium chloride or hexanaphthene.
Compared with prior art, the present invention is take two (trichloromethyl) carbonic ether as chlorination reagent, by selecting suitable organic amine catalyzer and coordinating suitable reaction solvent, reaction generates 3,4,5-trimethoxy-benzoyl chloride, have that equipment corrosion is little, production cost is low, reaction conditions is gentle, the few and easy processing of safety simple to operate, the three wastes, the advantage such as product yield is high, quality is good, avoided to water and air sensitivity the use of aluminum chloride, be a kind of novel method of applicable suitability for industrialized production.
Therefore synthetic method of the present invention, has larger implementary value and economic results in society.
(4) embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, but protection scope of the present invention is not limited to this.
Embodiment 1
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.33: 0.1,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 9.8g (0.033mol); Organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, the quality that feeds intake 3.28g (0.01mol); Organic solvent is tetrahydrofuran (THF) 212g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
3,4,5-trimethoxybenzoic acid and organic amine are dissolved in to organic solvent (consumption of organic solvent is 7 times of 3,4,5-trimethoxybenzoic acid quality).Will two (trichloromethyl) carbonic ethers be dissolved in organic solvent (consumption of organic solvent is 3,4,5-trimethoxybenzoic acid quality 3 times), slowly drop in the solution of 3,4,5-trimethoxybenzoic acid and organic amine, temperature of reaction is 70 ℃, 5 as a child reaction end afterwards.
Reaction finishes rear underpressure distillation and reclaims organic solvent, and remain in solid in the reaction flask sherwood oil recrystallization through being dried with calcium chloride and obtain white solid, 3,4,5-trimethoxy-benzoyl chloride 20.2g, yield 88%, purity 98.7%.
Nuclear magnetic resonance spectrum (Bruke):
1h NMR (CDCl
3, 500MHz): δ (ppm)=3.91 (6H, s), 3.92 (3H, s), 7.36 (2H, s);
13c NMR (CDCl
3, 125MHz): δ (ppm)=56.2,60.9,107.4,124.1,142.9,152.9,171.8.
Embodiment 2
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.33: 0.1,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 9.8g (0.033mol); Organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, the quality that feeds intake 3.28g (0.01mol); Organic solvent is tetrahydrofuran (THF) 212g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 70 ℃, and in 8 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 18.9g, yield 82%, purity 99.0%.
Embodiment 3
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.5: 0.1,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 14.85g (0.05mol); Organic amine catalyzer is three (2-cyano ethyl) amine, the quality that feeds intake 1.76g (0.01mol); Organic solvent is 2-methyltetrahydrofuran 212g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 70 ℃, and in 8 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 17.9g, yield 78%, purity 99.2%.
Embodiment 4
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.5: 0.1,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 14.85g (0.05mol); Organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, the quality that feeds intake 3.28g (0.01mol); Organic solvent is methylene dichloride 212g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 40 ℃, and in 10 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 16.3g, yield 71%, purity 98.6%.
Embodiment 5
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.33: 0.05,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 9.8g (0.033mol); Organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, the quality that feeds intake 1.64g (0.005mol); Organic solvent is 2-methyltetrahydrofuran 212g, and its total consumption is 8 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 50 ℃, and in 7 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 15.9g, yield 69%, purity 98.8%.
Embodiment 6
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.33: 0.2,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 9.8g (0.033mol); Organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, the quality that feeds intake 6.56g (0.02mol); Organic solvent is 2-methyltetrahydrofuran 212g, and its total consumption is 15 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 70 ℃, and in 9 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 19.8g, yield 86%, purity 99.0%.
Embodiment 7
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.5: 0.1,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 14.85g (0.05mol); Organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, the quality that feeds intake 3.28g (0.01mol); Organic solvent is 2-methyltetrahydrofuran 212g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 50 ℃, and in 4 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 18.6g, yield 81%, purity 98.9%.
Embodiment 8
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.5: 0.1,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 14.85g (0.05mol); Organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, the quality that feeds intake 3.28g (0.01mol); Organic solvent is 2-methyltetrahydrofuran 212g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 40 ℃, and in 8 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 14.4g, yield 68%, purity 97.9%.
Embodiment 9
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.5: 0.1,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 14.85g (0.05mol); Organic amine catalyzer is N, N-bis-(3-cyanopropyl) benzylamine, the quality that feeds intake 2.41g (0.01mol); Organic solvent is 2-methyltetrahydrofuran 212g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 70 ℃, and in 6 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 16.2g, yield 70%, purity 98.6%.
Embodiment 10
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.5: 0.1,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 14.85g (0.05mol); Organic amine catalyzer is N, N-bis-(3-cyanopropyl) benzylamine, the quality that feeds intake 2.27g (0.01mol); Organic solvent is 2-methyltetrahydrofuran 212g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 70 ℃, and in 10 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 14.6g, yield 63%, purity 99.2%.
Comparative example 1
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.5: 0.05,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 14.85g (0.05mol); Organic amine catalyzer is 1,3-dimethyl-2-imidazolidone, the quality that feeds intake 0.57g (0.05mol); Organic solvent is methylene dichloride 318g, and its total consumption is 15 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 30 ℃, and in 15 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 13.1g, yield 57%, purity 98.6%.
Comparative example 2
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.33: 0.1,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 9.8g (0.033mol); Organic amine catalyzer is triethylamine, the quality that feeds intake 1.01g (0.01mol); Organic solvent is tetrahydrofuran (THF) 212g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 70 ℃, and in 5 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 11.7g, yield 51%, purity 98.4%.
Comparative example 3
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.33: 0.1,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 9.8g (0.033mol); Organic amine catalyzer is DMF, the quality that feeds intake 0.73g (0.01mol); Organic solvent is tetrahydrofuran (THF) 212g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 70 ℃, and in 8 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 10.8g, yield 47%, purity 98.3%.
Comparative example 4
Feed intake amount of substance than 3,4,5-trimethoxybenzoic acid: two (trichloromethyl) carbonic ether: organic amine catalyzer is to feed intake at 1: 0.5: 0.05,3,4,5-trimethoxybenzoic acid 21.2g (0.1mol); Two (trichloromethyl) carbonic ether 14.85g (0.05mol); Organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, the quality that feeds intake 3.28g (0.01mol); Organic solvent is methylene dichloride 318g, and its total consumption is 10 times of 3,4,5-trimethoxybenzoic acid quality.
Temperature of reaction is 90 ℃, and in 2 hours reaction times, other operates with example 1,3,4,5-trimethoxy-benzoyl chloride 10.6g, yield 46%, purity 98.6%.
Claims (8)
1. one kind 3,4, the chemical synthesis process of 5-trimethoxy-benzoyl chloride, it is characterized in that: described synthetic method is for raw material with 3,4,5-trimethoxybenzoic acid and two (trichloromethyl) carbonic ethers, in reaction solvent, under organic amine catalyst action, fully react in 20-70 ℃, described in making 3,4,5-trimethoxy-benzoyl chloride;
It is one of following that described organic amine catalyzer is selected from: three (2-cyano ethyl) amine, N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, N, N-bis-(3-cyanopropyl) benzylamine;
It is one of following that described reaction solvent is selected from: methylene dichloride, tetrahydrofuran (THF), 2-methyltetrahydrofuran;
Described 3,4, the ratio of the amount of substance that feeds intake of 5-trimethoxybenzoic acid, two (trichloromethyl) carbonic ether, organic amine is 1:0.33-1.0:0.05-0.3; The quality consumption of described reaction solvent is 5-20 times of 3,4,5-trimethoxybenzoic acid.
2. as claimed in claim 13, the chemical synthesis process of 4,5-trimethoxy-benzoyl chloride, is characterized in that: described 3, the ratio of the amount of substance that feeds intake of 4,5-trimethoxybenzoic acid, two (trichloromethyl) carbonic ether, organic amine is 1:0.33-0.5:0.1-0.2; The quality consumption of described reaction solvent is 10-20 times of 3,4,5-trimethoxybenzoic acid.
As described in one of claim 1-2 3,4, the chemical synthesis process of 5-trimethoxy-benzoyl chloride, it is characterized in that: described organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrols or three (2-cyano ethyl) amine.
As described in one of claim 1-2 3,4, the chemical synthesis process of 5-trimethoxy-benzoyl chloride, it is characterized in that: described organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol, described reaction solvent is 2-methyltetrahydrofuran.
5. as claimed in claim 13,4, the chemical synthesis process of 5-trimethoxy-benzoyl chloride, is characterized in that: the reaction times is 4-10 hour.
6. as claimed in claim 53,4, the chemical synthesis process of 5-trimethoxy-benzoyl chloride, is characterized in that: temperature of reaction is 50-70 ℃.
7. as claimed in claim 63,4, the chemical synthesis process of 5-trimethoxy-benzoyl chloride, is characterized in that: described organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrols or three (2-cyano ethyl) amine.
8. as claimed in claim 63, the chemical synthesis process of 4,5-trimethoxy-benzoyl chloride, is characterized in that: described 3, the ratio of the amount of substance that feeds intake of 4,5-trimethoxybenzoic acid, two (trichloromethyl) carbonic ether, organic amine is 1:0.33-0.5:0.1-0.2; Described organic amine catalyzer is N, N, N ', N '-tetra-(3-cyanopropyl) quadrol; Described reaction solvent is 2-methyltetrahydrofuran.
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| CN107176908A (en) * | 2017-05-12 | 2017-09-19 | 江苏科菲特生化技术股份有限公司 | A kind of synthetic method of the methoxy benzoyl chloride of 2 methyl 3 |
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| CN101607942A (en) * | 2008-06-17 | 2009-12-23 | 中国人民解放军第二军医大学 | Novel imidazolone anti-tumor compound and preparation method thereof |
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