CN1994990A - Process for preparing trifloro methyl phenol - Google Patents
Process for preparing trifloro methyl phenol Download PDFInfo
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- CN1994990A CN1994990A CN 200610130681 CN200610130681A CN1994990A CN 1994990 A CN1994990 A CN 1994990A CN 200610130681 CN200610130681 CN 200610130681 CN 200610130681 A CN200610130681 A CN 200610130681A CN 1994990 A CN1994990 A CN 1994990A
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Abstract
The invention discloses a making method of trifluoro methyl phenol, which comprises the following steps: adding trifluoromethyl chlorobenzene and sodium alkylol with molar rate at 11-4 in the relative alkylol, dimethyl sulfoxide, cyclobutasulfoxide, N, N-dimethyl formamide or N, N-dimethyl acetamide solvent; stirring under 120-180 deg. c; filtering to remove organics; evaporating solvent; decompressing; rectifying to obtain relative trifluoro methyl phenyl alkyl ether; adding trifluoro methyl phenyl alkyl ether and thiolsodium alkyl with molar rate at 11-10 in the tetrahydrofuran N, N-dimethyl formamide or N, N-dimethyl acetamide solvent; stirring under 25-110 deg. c; evaporating thioether and solvent; rectifying to obtain the product.
Description
Technical field
The present invention relates to a kind of preparation method of trifloro methyl phenol, belong to the technology of preparing of trifluoromethylbenzene phenolic compound.
Background technology
The trifluoromethylbenzene phenolic compound is attached most importance to, and what want is important medicine and pesticide intermediate, fluoxetine can be widely used in the synthetic of multiple new antitumor drug, AIDS resisting medicine, Rezulin, antiphlogistic drug, thymoleptic, so lot of documents has been reported the synthetic method of relevant such intermediate.
The known preparation method's of trifluoromethylbenzene phenolic compound example comprises: it is starting raw material that a kind of method of synthetic this compounds is to use corresponding 5-trifluoromethylaniline, generates corresponding phenol by the diazotization hydrolysis.The employed cost of material of this method is higher, and productive rate is lower, and the industrialization cost is higher; It is starting raw material that the another kind of method (US4168388) of synthetic this compounds is to use corresponding trifluoromethyl chlorobenzene, at first generates corresponding benzylic ether, and hydrogenation is sloughed benzyl then, obtains the corresponding phenolic compound.Though this method has reduced the prices of raw and semifnished materials, it is relatively complicated to generate technology, the aftertreatment difficulty; It is starting raw material that the another kind of method of synthetic this compounds is to use corresponding methylphenol, at first protects phenolic hydroxyl group, and methyl tri-chlorination, fluorine replacement, deprotection generate the corresponding phenolic compound then.Though this method has reduced material cost, generates complex process, the poisonous and harmful chemical of using is more.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of trifluoromethylbenzene phenolic compound, this method operating process is simple, is easy to industrialization.
The present invention is realized that by following technical proposals a kind of preparation method of trifluoromethylbenzene phenolic compound is characterized in that comprising following process;
1, synthetic trifluoromethyl alkyl oxide: with p-chloro benzo trifluoride-99, meta-chlorobenzotrifluoride or chlorobenzotrifluoride and sodium methylate, sodium ethylate, n-propyl alcohol sodium, carbon chain lengths is 1 at the aliphatic hydrocarbon sodium alkoxide or the carbon chain lengths of the straight chain of 1-6 at the aliphatic hydrocarbon sodium alkoxide of the side chain of 1-6 in molar ratio: 1-10 adds benzene, toluene, dimethylbenzene, chlorobenzene, pentane, hexane, hexanaphthene, heptane, corresponding alkyl alcohol, dimethyl sulfoxide (DMSO), tetramethylene sulfone, N, dinethylformamide or N, in the N-dimethylacetamide solvent, stir down and reacted 1-10 hour, after reaction is finished, remove by filter the inorganic salt of generation at 0-200 ℃, steam solvent, rectification under vacuum obtains corresponding trifluoromethyl alkyl oxide.
2, the preparation of trifloro methyl phenol: will be through step 1 synthetic trifluoromethyl alkyl oxide and sodium methyl mercaptide, sulfur alcohol sodium, carbon chain lengths are at the alkyl sulfide sodium alkoxide of 1-10 or beneze methane thiol sodium in molar ratio 1: 0.5-15 adds methyl alcohol, ethanol, propyl alcohol, tetrahydrofuran (THF), N, dinethylformamide or N, in the N-dimethylacetamide solvent, stir down 0-150 ℃ of reaction 1-10 hour, after reaction is finished, steam the thioether and the solvent of generation, rectifying obtains trifloro methyl phenol.
The solvent that above-mentioned trifluoromethyl chlorobenzene and sodium alkyl alcohol reaction are adopted is a dimethyl sulfoxide (DMSO), tetramethylene sulfone, and N, dinethylformamide or N,N-dimethylacetamide, temperature of reaction are 120-180 ℃, the reaction times is 3-5 hour; Trifluoromethyl alkyl oxide and alkyl sulfide sodium alkoxide are 1 in molar ratio: 1-4, and the solvent that reaction is adopted is a methyl alcohol, ethanol, N, dinethylformamide, N,N-dimethylacetamide or toluene, temperature of reaction is 25-110 ℃, the reaction times is 3-5 hour.
The invention has the advantages that its preparation process is simple, easy handling, the reaction times is short, yield is high, be easy to suitability for industrialized production.
Embodiment
Provide embodiment below illustrating in greater detail the present invention, but scope of the present invention is not limited to these embodiment.
Embodiment 1
Add p-chloro benzo trifluoride-99 (70.2g in the reaction flask, 0.4mol), phenylcarbinol sodium (65g, 0.5mol) and N, dinethylformamide (200ml), be warming up to 120 ℃ of reactions 5 hours, remove by filter the sodium-chlor of generation, remove N under reduced pressure, dinethylformamide, rectifying gets 4-trifluoromethyl benzylic ether (92.7g, 92%).
Embodiment 2
Add in the autoclave chlorobenzotrifluoride (70.2g, 0.4mol), sodium methylate (27g, 0.5mol) and methyl alcohol (200ml), sealing autoclave, in 140 ℃ of reactions 4 hours, cooling discharging removed by filter sodium-chlor, steam methyl alcohol, rectifying gets 2-trifluoromethyl methyl ether (62.7g, 89%).
Embodiment 3
Add in the autoclave chlorobenzotrifluoride (70.2g, 0.4mol), sodium methylate (27g, 0.5mol) and methyl alcohol (200ml), sealing autoclave, in 160 ℃ of reactions 2 hours, cooling discharging removed by filter sodium-chlor, steam methyl alcohol, rectifying gets 2-trifluoromethyl methyl ether (67.0g, 95%).
Embodiment 4
Add 4-trifluoromethyl methyl ether (35.2g in the reaction flask, 0.2mol) and sulfur alcohol sodium (25.2g, 0.3mol) and methyl alcohol (150ml), 70 ℃ were reacted 2 hours, and decompression steams methyl alcohol wherein, residuum is poured in the water, with ethyl acetate extraction twice, merge organic phase, concentrating under reduced pressure is removed ethyl acetate, residuum rectifying gets 4-trifloro methyl phenol (21.1g, 65%).
Embodiment 5
Add 2-trifluoromethyl methyl ether (35.2g in the reaction flask, 0.2mol) and sulfur alcohol sodium (25.2g, 0.3mol) and methyl alcohol (150ml), 70 ℃ were reacted 2 hours, and decompression steams methyl alcohol wherein, residuum is poured in the water, with ethyl acetate extraction twice, merge organic phase, concentrating under reduced pressure is removed ethyl acetate, residuum rectifying gets 4-trifloro methyl phenol (23.3g, 72%).
Embodiment 6
Add 3-trifluoromethyl benzylic ether (50.4g in the reaction flask, 0.2mol) and the ethylene dithiol sodium alkoxide (27.6g, 0.2mol), methyl alcohol (150ml), 70 ℃ were reacted 3 hours, decompression steams methyl alcohol wherein, and residuum is poured in the water, uses twice of ethyl acetate extraction, merge organic phase, concentrating under reduced pressure is removed ethyl acetate, and residuum rectifying gets 3-trifloro methyl phenol (24.3g, 75%).
Claims (2)
1. the preparation method of a trifloro methyl phenol is characterized in that comprising following process;
1) synthetic trifluoromethyl alkyl oxide: with p-chloro benzo trifluoride-99, meta-chlorobenzotrifluoride or chlorobenzotrifluoride and sodium methylate, sodium ethylate, n-propyl alcohol sodium, carbon chain lengths is 1 at the aliphatic hydrocarbon sodium alkoxide or the carbon chain lengths of the straight chain of 1-6 at the aliphatic hydrocarbon sodium alkoxide of the side chain of 1-6 in molar ratio: 1-10 adds benzene, toluene, dimethylbenzene, chlorobenzene, pentane, hexane, hexanaphthene, heptane, corresponding alkyl alcohol, dimethyl sulfoxide (DMSO), tetramethylene sulfone, N, dinethylformamide or N, in the N-dimethylacetamide solvent, stir down and reacted 1-10 hour, after reaction is finished, remove by filter the inorganic salt of generation at 0-200 ℃, steam solvent, rectification under vacuum obtains corresponding trifluoromethyl alkyl oxide;
2) preparation of trifloro methyl phenol: will be through step 1) synthetic trifluoromethyl alkyl oxide and sodium methyl mercaptide, sulfur alcohol sodium, carbon chain lengths are at the alkyl sulfide sodium alkoxide of 1-10 or beneze methane thiol sodium in molar ratio 1: 0.5-15 adds methyl alcohol, ethanol, propyl alcohol, tetrahydrofuran (THF), N, dinethylformamide or N, in the N-dimethylacetamide solvent, stir down 0-150 ℃ of reaction 1-10 hour, after reaction is finished, steam the thioether and the solvent of generation, rectifying obtains trifloro methyl phenol.
2. press the preparation method of the described trifloro methyl phenol of claim 1, it is characterized in that, the solvent that trifluoromethyl chlorobenzene and sodium alkyl alcohol reaction are adopted is a dimethyl sulfoxide (DMSO), tetramethylene sulfone, N, dinethylformamide or N,N-dimethylacetamide, temperature of reaction is 120-180 ℃, and the reaction times is 3-5 hour; Trifluoromethyl alkyl oxide and alkyl sulfide sodium alkoxide are 1 in molar ratio: 1-4, and the solvent that reaction is adopted is a methyl alcohol, ethanol, N, dinethylformamide, N,N-dimethylacetamide or toluene, temperature of reaction is 25-110 ℃, the reaction times is 3-5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610130681 CN1994990A (en) | 2006-12-29 | 2006-12-29 | Process for preparing trifloro methyl phenol |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200610130681 CN1994990A (en) | 2006-12-29 | 2006-12-29 | Process for preparing trifloro methyl phenol |
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| CN1994990A true CN1994990A (en) | 2007-07-11 |
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| CN 200610130681 Pending CN1994990A (en) | 2006-12-29 | 2006-12-29 | Process for preparing trifloro methyl phenol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781174A (en) * | 2010-03-17 | 2010-07-21 | 天津大学 | Improved method for synthesizing m-trifluoromethyl phenol |
| CN113582817A (en) * | 2021-08-16 | 2021-11-02 | 常州大学 | Method for synthesizing m-trifluoromethyl phenol |
-
2006
- 2006-12-29 CN CN 200610130681 patent/CN1994990A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781174A (en) * | 2010-03-17 | 2010-07-21 | 天津大学 | Improved method for synthesizing m-trifluoromethyl phenol |
| CN101781174B (en) * | 2010-03-17 | 2013-05-15 | 天津大学 | Improved method for synthesizing m-trifluoromethyl phenol |
| CN113582817A (en) * | 2021-08-16 | 2021-11-02 | 常州大学 | Method for synthesizing m-trifluoromethyl phenol |
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Open date: 20070711 |