CN101717324B - Green synthesizing method of triphenylchloromethane - Google Patents
Green synthesizing method of triphenylchloromethane Download PDFInfo
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- CN101717324B CN101717324B CN 200910154775 CN200910154775A CN101717324B CN 101717324 B CN101717324 B CN 101717324B CN 200910154775 CN200910154775 CN 200910154775 CN 200910154775 A CN200910154775 A CN 200910154775A CN 101717324 B CN101717324 B CN 101717324B
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Abstract
The invention discloses a green synthesizing method of triphenylchloromethane. The synthesizing method comprises the following steps of: using triphenylmethanol as raw material; reacting the triphenylmethanol with triphosgene in an organic solvent for 0.1-20 hours at a temperature of -20-150 DEG C; after reacting, separating to obtain a crude product; and recrystallizing the crude product to obtain the triphenylchloromethane, wherein the mass ratio of the triphenylchloromethane to the triphosgene is 1:(0.33-2). The synthesizing method has the advantages of reasonable process, high reaction yield, low production cost, less three waste and simple aftertreatment.
Description
(1) technical field
The present invention relates to a kind of synthetic method of medicine intermediate triphenylmethyl chloride.
(2) background technology
Triphenylmethyl chloride is a kind of important medicine intermediate and industrial chemicals, because its unique structure, different in kind is widely used in protecting hydroxyl in general organic chloride in organic and medicine synthesize.
Before the present invention provided, the chemical synthesis process of triphenylmethyl chloride mainly was with triphenylcarbinol and sulfur oxychloride in the existing technology, and Acetyl Chloride 98Min. or hydrogen chloride gas chloro prepare.Use sulfur oxychloride work and substrate reactions to obtain target product such as document [J.Am.Chem.Soc., (1989), 111 (11), 3966-72.].Document [Organic Syntheses, 23,1943.] uses Acetyl Chloride 98Min. to prepare triphenylmethyl chloride as the chloro thing.Sulfur oxychloride technique has in organic synthesis widely and uses as traditional processing technology.But well-known, this technique also exists larger drawback, and major cause is to contain a large amount of sulfurous gas in the tail gas that produces of sulfur oxychloride, and sulfurous gas is national environmental protection to one of six indexs of the strict control of atmosphere, and difficult treatment is poisoned large.In addition, the transportation of sulfur oxychloride and use also are problems.Along with the raising of China to environmental requirement, in future, the sulfur oxychloride use that will inevitably be under an embargo.Use Acetyl Chloride 98Min., because its character is very active, uses and transport and all easily bring difficulty.Use hydrogen chloride gas that production unit is had higher requirement, and be difficult for controlling, be unfavorable for large-scale industrialization production, so it is imperative to seek the effective chlorinating agent of a kind of green.
(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, reaction yield is high, production cost is low, the three wastes are few and the green synthesis method of the simple triphenylmethyl chloride of aftertreatment.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
The synthetic method of the triphenylmethyl chloride shown in a kind of formula (I), as raw material take the triphenylcarbinol shown in the formula (II), in organic solvent, reacted 0.1～20 hour in-20～150 ℃ with two (trichloromethyl) carbonic ethers, react complete rear separation and obtain crude product, crude product obtains triphenylmethyl chloride through recrystallization; Described triphenylcarbinol is 1: 0.33～2 with the ratio of the amount of substance of two (trichloromethyl) carbonic ethers;
Further, also can add organic alkali catalyst in the reaction system to promote the carrying out of reaction, described organic alkali catalyst is selected from following a kind of or any several mixture: triethylamine, pyridine, N, N-Dimethylamino pyridine, N-methylmorpholine, triethylene diamine (DABCO), DMF, N, the N-N,N-DIMETHYLACETAMIDE, N, N-dimethyl benzamide, one of preferred following: triethylamine, pyridine, DMF.The molar ratio that feeds intake of described organic alkali catalyst and triphenylcarbinol is 0.001～1: 1, is preferably 0.001～0.1: 1, most preferably be 0.01～0.05: 1.
The organic solvent that the present invention is suitable for can be selected from the mixture of following a kind of or any several arbitrary proportions: methylene dichloride, trichloromethane, tetracol phenixin, 1, the 1-ethylene dichloride, 1, the 2-ethylene dichloride, 1,1, the 1-trichloroethane, 1,1, the 2-trichloroethane, 1,1,2,2-tetrachloroethane, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, acetone, butanone, ether, propyl ether, isopropyl ether, butyl ether, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, dithiocarbonic anhydride, Nitromethane 99Min., toluene, benzene, oil of mirbane, chlorobenzene, acetonitrile.
Preferred organic solvent is selected from the mixture of following a kind of or any several arbitrary proportions: methylene dichloride, trichloromethane, ethyl acetate, acetone, ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, toluene, chlorobenzene, Nitromethane 99Min., acetonitrile.
The temperature of reaction of chlorination of the present invention is-20～150 ℃, preferred 20～100 ℃, and more preferably 50～100 ℃, most preferably 70～90 ℃.
The reaction times of chlorination of the present invention is preferably 0.1～5 hour generally at 0.1～20 hour, and more preferably 1～3 hour, most preferably 2～3 hours.
The ratio of triphenylcarbinol of the present invention and the amount of substance of two (trichloromethyl) carbonic ethers is generally 1: 0.33～2, be preferably 1: 0.33～and 1, more preferably 1: 0.33～0.8, most preferably 1: 0.33～0.5.The volumetric usage of organic solvent is recommended as 1～10ml/g in the quality of triphenylcarbinol.
The present invention is after reaction finishes, the conventional separation method such as desolventize by steaming and can obtain crude product, crude product obtains final product through recrystallization, and applicable recrystallization solvent can be selected from following a kind of or any several mixture: sherwood oil, hexanaphthene, normal hexane, ethyl acetate, toluene, acetone.It is one of following that preferred recrystallization solvent is selected from: hexanaphthene, sherwood oil, toluene.
Compared with prior art, beneficial effect of the present invention is embodied in: 1) reaction yield high (can reach more than 95%), production cost are low; 2) has operational path advanced person, reaction conditions gentleness, safety simple to operate; 3) environmentally friendly, the three wastes are few.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
In thermometer and churned mechanically 1000ml four-hole bottle are housed, add triphenylcarbinol 130g (0.5mol), two (trichloromethyl) carbonic ether 50g, toluene dissolving and stirring with 200ml add triethylamine 1.5g again, are heated to 80 ℃.Keep temperature of reaction and stirred 2 hours.React complete after, toluene is reclaimed in underpressure distillation, crude product sherwood oil recrystallization obtains white sterling 136.5g, yield 98%, fusing point 109-111 ℃.
Embodiment 2:
In thermometer and churned mechanically 1000ml four-hole bottle are housed, add triphenylcarbinol 130g (0.5mol), two (trichloromethyl) carbonic ether 80g, methylene dichloride dissolving and stirring with 200ml add pyridine 1.5g again, are heated to 40 ℃.Keep temperature of reaction and stirred 5 hours.React complete after, methylene dichloride is reclaimed in underpressure distillation, crude product sherwood oil recrystallization obtains white sterling 124g, yield 89%, fusing point 109-112 ℃.
Embodiment 3:
In thermometer and churned mechanically 1000ml four-hole bottle are housed, add triphenylcarbinol 130g (0.5mol), two (trichloromethyl) carbonic ether 80g, (V/V=1: 1) mixed solvent dissolving and stirring are heated to 80 ℃ to toluene/chlorobenzene of usefulness 200ml.Keep temperature of reaction and stirred 2 hours.React complete after, vacuum distillation recovered solvent, crude product sherwood oil recrystallization obtains sterling 129g, yield 93%, fusing point 109-112 ℃.
Embodiment 4:
In thermometer and churned mechanically 1000ml four-hole bottle are housed, add triphenylcarbinol 130g (0.5mol), two (trichloromethyl) carbonic ether 150g, ether solvent dissolving and stirring with 200ml are cooled to-20 ℃.Keep temperature of reaction and stirred 5 hours.React complete after, vacuum distillation recovered solvent, crude product sherwood oil recrystallization obtains sterling 108.6g, yield 78%, fusing point 108-110 ℃.
Embodiment 5:
Reaction solvent is changed to ethylene dichloride/trichloromethane, and (V/V=1: 1), temperature of reaction is 40 ℃, and other operate with example 1, yield 75.0%, fusing point 109.5-112 ℃.
Embodiment 6:
Reaction solvent is changed to tetrahydrofuran (THF), and temperature of reaction is 60 ℃, and other operate with example 1, yield 90.0%, fusing point 109.5-111 ℃.
Embodiment 7:
Catalysts is changed to DMF, and other operate with example 1, yield 93.7%, fusing point 108-111 ℃.
Embodiment 8:
Catalysts is changed to N, the N-Dimethylamino pyridine, and other operate with example 2, yield 85.2%, fusing point 109.3-113 ℃.
Embodiment 9:
Two (trichloromethyl) carbonic ether consumption becomes 100g, and other operate with example 1, yield 97.5%, fusing point 109-112 ℃.
Embodiment 10:
Two (trichloromethyl) carbonic ether consumption becomes 130g, and other operate with example 1, yield 98.5%, fusing point 109-112 ℃.
Embodiment 11:
Reaction times becomes 0.1 hour, and other operate with example 2, yield 55%, fusing point 107-112 ℃.
Embodiment 12:
Reaction times becomes 20 hours, and other operate with example 2, yield 85.3%, fusing point 107-110 ℃.
Embodiment 13:
Recrystallization solvent is changed to normal hexane, and other operate with example 2, yield 90%, fusing point 109-112 ℃.
Embodiment 14:
Recrystallization solvent is changed to toluene, and other operate with example 2, yield 84%, fusing point 108-112 ℃.
Embodiment 15:
In thermometer and churned mechanically 1000ml four-hole bottle are housed, add triphenylcarbinol 130g (0.5mol), two (trichloromethyl) carbonic ether 50g, toluene dissolving and stirring with 200ml are heated to 80 ℃.Keep temperature of reaction and stirred 3 hours.React complete after, toluene is reclaimed in underpressure distillation, crude product sherwood oil recrystallization obtains white sterling 124g, yield 89%, fusing point 108-110 ℃.
Embodiment 16:
Reaction solvent is changed to chlorobenzene, and temperature of reaction is 130 ℃, and other operate with example 15, yield 82%, fusing point 109.5-112 ℃.
Embodiment 17:
Reaction solvent is changed to ether, and temperature of reaction is 20 ℃, and other operate with example 15, yield 75.0%, fusing point 109-111 ℃.
Embodiment 18:
Two (trichloromethyl) carbonic ether consumption becomes 100g, and other operate with example 15, yield 90%, fusing point 109-112 ℃.
Embodiment 19:
Reaction times becomes 1 hour, and other operate with example 15, yield 65%, fusing point 106-110 ℃.
Embodiment 20:
Reaction times becomes 20 hours, and other operate with example 15, yield 75%, fusing point 108-110 ℃.
Embodiment 21:
Reaction solvent is changed to oil of mirbane, and temperature of reaction is 50 ℃, and other operate with example 15, yield 95.0%, fusing point 109-111 ℃.
Embodiment 22:
Reaction solvent is changed to oil of mirbane, and temperature of reaction is 150 ℃, and other operate with example 15, yield 91.0%, fusing point 109-111 ℃.
Claims (9)
1. the synthetic method of the triphenylmethyl chloride shown in the formula (I), it is characterized in that described synthetic method is as raw material take the triphenylcarbinol shown in the formula (II), in organic solvent, reacted 0.1～20 hour in-20～150 ℃ with two (trichloromethyl) carbonic ethers, react complete rear separation and obtain crude product, crude product obtains triphenylmethyl chloride through recrystallization; Described triphenylcarbinol is 1:0.33～2 with the ratio of the amount of substance of two (trichloromethyl) carbonic ethers; Described organic solvent is selected from the mixture of following a kind of or any several arbitrary proportions: methylene dichloride, trichloromethane, tetracol phenixin, 1, the 1-ethylene dichloride, 1, the 2-ethylene dichloride, 1,1, the 1-trichloroethane, 1,1, the 2-trichloroethane, 1,1,2,2-tetrachloroethane, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, acetone, butanone, ether, propyl ether, isopropyl ether, butyl ether, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, dithiocarbonic anhydride, Nitromethane 99Min., toluene, benzene, oil of mirbane, chlorobenzene, acetonitrile;
2. the synthetic method of triphenylmethyl chloride as claimed in claim 1, it is characterized in that also adding in the reaction system organic alkali catalyst, described organic alkali catalyst is selected from following a kind of or any several mixture: triethylamine, pyridine, N, N-Dimethylamino pyridine, N-methylmorpholine, triethylene diamine, DMF, N, the N-N,N-DIMETHYLACETAMIDE, N, N-dimethyl benzamide.
3. the synthetic method of triphenylmethyl chloride as claimed in claim 2 is characterized in that the molar ratio that feeds intake of described organic alkali catalyst and triphenylcarbinol is 0.001～1:1.
4. the synthetic method of triphenylmethyl chloride as claimed in claim 1 is characterized in that described organic solvent is selected from the mixture of following a kind of or any several arbitrary proportions: methylene dichloride, trichloromethane, ethyl acetate, acetone, ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, toluene, chlorobenzene, Nitromethane 99Min., acetonitrile.
5. such as the synthetic method of the described triphenylmethyl chloride of one of claim 1 ~ 3, the temperature of reaction that it is characterized in that described reaction is 20～100 ℃, and the reaction times is 0.1～5 hour.
6. the synthetic method of triphenylmethyl chloride as claimed in claim 5, the temperature of reaction that it is characterized in that described reaction is 50～100 ℃, the reaction times is 1～3 hour.
7. such as the synthetic method of the described triphenylmethyl chloride of one of claim 1 ~ 3, it is characterized in that described triphenylcarbinol and the ratio of the amount of substance of two (trichloromethyl) carbonic ethers are 1:0.33～1.
8. such as the synthetic method of the described triphenylmethyl chloride of one of claim 1 ~ 3, it is characterized in that recrystallization solvent is selected from following a kind of or any several mixture: sherwood oil, hexanaphthene, normal hexane, ethyl acetate, toluene, acetone.
9. the synthetic method of triphenylmethyl chloride as claimed in claim 8 is characterized in that recrystallization solvent is selected from one of following: hexanaphthene, sherwood oil, toluene.
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| CN 200910154775 CN101717324B (en) | 2009-12-07 | 2009-12-07 | Green synthesizing method of triphenylchloromethane |
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| CN 200910154775 CN101717324B (en) | 2009-12-07 | 2009-12-07 | Green synthesizing method of triphenylchloromethane |
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| CN101717324B true CN101717324B (en) | 2013-01-23 |
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| CN102633594A (en) * | 2012-03-27 | 2012-08-15 | 巨化集团公司 | Method for synthesizing triphenylchloromethane by using triphenylmethyl alkyl ether |
| CN102718624B (en) * | 2012-06-21 | 2014-08-13 | 台州市华南医化有限公司 | Method for synthesizing triphenylchloromethane |
| CN104788429B (en) * | 2015-03-06 | 2018-07-06 | 浙江美诺华药物化学有限公司 | A kind of method for preparing sartans by removing trityl-protecting group |
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