CN102690180B - Method for synthesizing trifluoromethyl acetophenone - Google Patents
Method for synthesizing trifluoromethyl acetophenone Download PDFInfo
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- CN102690180B CN102690180B CN201210175617.8A CN201210175617A CN102690180B CN 102690180 B CN102690180 B CN 102690180B CN 201210175617 A CN201210175617 A CN 201210175617A CN 102690180 B CN102690180 B CN 102690180B
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- Prior art keywords
- trifluoromethylbenzene
- acetophenone
- trifluoromethyl
- synthetic
- inorganic salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- LBWMQVOHFPLVBY-UHFFFAOYSA-N 3,3,3-trifluoro-1-phenylpropan-1-one Chemical compound FC(F)(F)CC(=O)C1=CC=CC=C1 LBWMQVOHFPLVBY-UHFFFAOYSA-N 0.000 title abstract 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- GVPVKKWXJXESIC-UHFFFAOYSA-N 1-[4-amino-3-chloro-5-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC(Cl)=C(N)C(C(F)(F)F)=C1 GVPVKKWXJXESIC-UHFFFAOYSA-N 0.000 claims description 10
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical group CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012346 acetyl chloride Substances 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- 229940045803 cuprous chloride Drugs 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000012454 non-polar solvent Substances 0.000 claims description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 3
- 230000021736 acetylation Effects 0.000 abstract 2
- 238000006640 acetylation reaction Methods 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 238000007040 multi-step synthesis reaction Methods 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- -1 (TrifluoroMethyl)acetophenone (3'-(Trifluoromethyl) acetophenone) Chemical compound 0.000 description 2
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 description 1
- QHMVQKOXILNZQR-UHFFFAOYSA-N 1-methoxyprop-1-ene Chemical group COC=CC QHMVQKOXILNZQR-UHFFFAOYSA-N 0.000 description 1
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 1
- NMTUHPSKJJYGML-UHFFFAOYSA-N 3-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=CC(C=O)=C1 NMTUHPSKJJYGML-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- BTCFFMPDIBWZLF-UHFFFAOYSA-N n-(5-aminopyridin-2-yl)-4-(trifluoromethyl)benzamide Chemical compound N1=CC(N)=CC=C1NC(=O)C1=CC=C(C(F)(F)F)C=C1 BTCFFMPDIBWZLF-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing trifluoromethyl acetophenone, which is characterized in that as shown in the formula (1), under the action of n-butyllithium, trifluoromethylbenze and an acetylation agent reacts in an organic solvent for 1-48 hours at the temperature of -70-0 DEG C, so as to synthesize trifluoromethyl acetophenone, wherein an inorganic salt serves as a catalyst. According to the invention provided by the invention, multi-step synthesis in the prior art is replaced by one step reaction of the trifluoromethyl acetophenone and the acetylation agent, so that the whole reaction process is simple and efficient, the reaction material is easily obtained, and the pollution is low. Moreover, sensitive groups with high selectivity are slightly affected, the yield is high, and the catalyst is can be recycled.
Description
Technical field
The present invention relates to a kind of method of synthetic (TrifluoroMethyl)acetophenone, relate to specifically under the effect of n-Butyl Lithium, in organic solvent, inorganic salt are made catalyzer, and trifluoromethylbenzene reacts the method for one-step synthesis (TrifluoroMethyl)acetophenone with acetylizing agent.
Background technology
(TrifluoroMethyl)acetophenone (3'-(Trifluoromethyl) acetophenone) is called for short TFAP, colourless or weak yellow liquid, it is important organic synthesis intermediate, be mainly used in the fields such as agricultural chemicals, medicine, liquid crystal material, be not only the key intermediate of synthesizing methoxy propylene compounds, be also the important source material of synthetic medicine, dyestuff simultaneously.The synthetic method of domestic literature report has: 3-Aminotrifluorotoluene makes its diazonium salt under the effect of Sodium Nitrite, after diazonium salt and acetaldoxime reaction, is hydrolyzed; Take trifluoromethylbenzene as raw material, after bromination, grignard reaction with anhydride reaction; Between after chloro-trifluoromethyl benzene grignard reaction with anhydride reaction; The m-Trifluoromethylbenzaldehyde of some foreign languages reports and diazomethane reaction etc. in addition, these several synthetic methods all need polystep reaction, and product yield is low, and diazomethane is explosive and hypertoxic, is difficult to carry out large-scale industrial production.
Summary of the invention
The object of the present invention is to provide a kind of method of synthetic (TrifluoroMethyl)acetophenone.The method reaction raw materials is easy to get, and pollutes littlely, and the high sensitive group of selectivity institute is influenced little, and catalyzer can recycling.
The method of a kind of synthetic (TrifluoroMethyl)acetophenone provided by the present invention; it is characterized in that: suc as formula the trifluoromethylbenzene shown in (I) and acetylizing agent under the effect of n-Butyl Lithium; make catalyzer with inorganic salt; in organic solvent, at-70 ℃～0 ℃, react 1～48 hour; synthetic (TrifluoroMethyl)acetophenone, wherein:
The mol ratio of n-Butyl Lithium and trifluoromethylbenzene is 1:1～1.5:1;
The mol ratio of acetylizing agent and trifluoromethylbenzene is 1:1～1:1.5;
The mol ratio of inorganic salt and trifluoromethylbenzene is 0.01:1～0.1:1;
The weight ratio of trifluoromethylbenzene and solvent is 1:2～1:1000.
Described organic solvent is one or more polarity or non-polar solvent, and wherein polar solvent is: one or more in tetrahydrofuran (THF), ethylene glycol diethyl ether, Isosorbide-5-Nitrae-dioxane; Non-polar solvent is one or more in the replacements such as alkane, toluene, dimethylbenzene and non-substituted aromatic hydrocarbons.
Described inorganic salt are one or more in the halide salts such as aluminum chloride, iron protochloride, cuprous chloride.
Described acetylizing agent is Acetyl Chloride 98Min. or diacetyl oxide.
Formula (I):
The method of synthetic (TrifluoroMethyl)acetophenone provided by the present invention; by synthetic traditional multistep trifluoromethylbenzene and the acetylizing agent single step reaction of being reduced to; whole reaction process is simple, efficient; reaction raw materials is easy to get; pollute little; the high sensitive group of selectivity institute is influenced little, and yield is high, and catalyzer can also recycling.
Embodiment
Below by embodiment, describe the present invention in detail, but the present invention is also limited to following embodiment not to the utmost.
Embodiment 1
Under nitrogen protection, octane dry ice mixed solution is heat-eliminating medium, to emptying condenser is housed, thermometer, in 500 mL four-hole boiling flasks of stirring rod, add 29.2g (0.2mo1) trifluoromethylbenzene and 150ml anhydrous tetrahydro furan, add 2g(0.02mol) cuprous chloride, be cooled to-45 ℃, drip 113.6ml(0.2mol) n-butyllithium solution of normal hexane, insulation 1 hour after dripping, be warmed up to subsequently-35 ℃, drip 16.1g(0.2mol) Acetyl Chloride 98Min., after dripping, at this temperature, be incubated 8 hours, drip concentrated hydrochloric acid, regulation system PH is 4-5, underpressure distillation after filtering, the cut of collecting 119-121 ℃/6.67kPa obtains 35.3g, content 97%, yield 93%.
Embodiment 2
Under nitrogen protection, octane dry ice mixed solution is heat-eliminating medium, to emptying condenser is housed, thermometer, in 750 mL four-hole boiling flasks of stirring rod, add 43.8 g (0.3mo1) trifluoromethylbenzene and 225ml ethylene glycol diethyl ether, add 3g(0.03mol) cuprous chloride, be cooled to-70 ℃, drip 170.4ml(0.3mol) n-butyllithium solution of normal hexane, insulation 8 hours after dripping, be warmed up to subsequently-40 ℃, drip 24.1g(0.3mol) Acetyl Chloride 98Min., after dripping, at this temperature, be incubated 40 hours, drip concentrated hydrochloric acid, regulation system PH is 4-5, underpressure distillation after filtering, the cut of collecting 119-121 ℃/6.67kPa obtains 52.8g, content 96%, yield 92%.
Embodiment 3
Under nitrogen protection, octane dry ice mixed solution is heat-eliminating medium, to emptying condenser is housed, thermometer, in 2000 mL four-hole boiling flasks of stirring rod, add 29.2 g (0.2mo1) trifluoromethylbenzene and 1500ml anhydrous tetrahydro furan, add 0.2g(0.002mol) cuprous chloride, be cooled to-45 ℃, drip 170.4ml(0.3mol) n-butyllithium solution of normal hexane, insulation 1 hour after dripping, be warmed up to subsequently-35 ℃, drip 12.1g(0.15mol) Acetyl Chloride 98Min., after dripping, at this temperature, be incubated 8 hours, drip concentrated hydrochloric acid, regulation system PH is 4-5, underpressure distillation after filtering, the cut of collecting 119-121 ℃/6.67kPa obtains 28.9g, content 95%, yield 91%.
Embodiment 4
Under nitrogen protection, octane dry ice mixed solution is heat-eliminating medium, to emptying condenser is housed, thermometer, in 750 mL four-hole boiling flasks of stirring rod, add 43.8 g (0.3mo1) trifluoromethylbenzene and 225ml ethylene glycol diethyl ether, add 3g(0.03mol) cuprous chloride, be cooled to-25 ℃, drip 170.4ml(0.3mol) n-butyllithium solution of normal hexane, insulation 8 hours after dripping, be warmed up to subsequently 0 ℃, drip 24.1g(0.3mol) Acetyl Chloride 98Min., after dripping, at this temperature, be incubated 40 hours, drip concentrated hydrochloric acid, regulation system PH is 4-5, underpressure distillation after filtering, the cut of collecting 119-121 ℃/6.67kPa obtains 53.8g, content 97%, yield 94%.
Claims (2)
1. the method for a synthetic (TrifluoroMethyl)acetophenone; it is characterized in that: trifluoromethylbenzene and acetylizing agent, under the effect of n-Butyl Lithium, are made catalyzer with inorganic salt, in organic solvent, at-70 ℃～0 ℃, react 1～48 hour; synthetic (TrifluoroMethyl)acetophenone, wherein:
The mol ratio of n-Butyl Lithium and trifluoromethylbenzene is 1:1～1.5:1;
The mol ratio of acetylizing agent and trifluoromethylbenzene is 1:1～1:1.5;
The mol ratio of inorganic salt and trifluoromethylbenzene is 0.01:1～0.1:1;
The weight ratio of trifluoromethylbenzene and solvent is 1:2～1:1000;
Described inorganic salt are one or more in aluminum chloride, iron protochloride, cuprous chloride;
Described acetylizing agent is Acetyl Chloride 98Min. or diacetyl oxide.
2. the method for a kind of synthetic (TrifluoroMethyl)acetophenone according to claim 1, it is characterized in that: described organic solvent is polarity or non-polar solvent, wherein polar solvent is: one or more in tetrahydrofuran (THF), ethylene glycol diethyl ether, Isosorbide-5-Nitrae-dioxane; Non-polar solvent is one or more in alkane, toluene, dimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210175617.8A CN102690180B (en) | 2012-05-31 | 2012-05-31 | Method for synthesizing trifluoromethyl acetophenone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210175617.8A CN102690180B (en) | 2012-05-31 | 2012-05-31 | Method for synthesizing trifluoromethyl acetophenone |
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| Publication Number | Publication Date |
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| CN102690180A CN102690180A (en) | 2012-09-26 |
| CN102690180B true CN102690180B (en) | 2014-05-07 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170058883A (en) * | 2014-09-19 | 2017-05-29 | 도오레 화인케미칼 가부시키가이샤 | Method for producing 2'-trifluoromethyl group-substituted aromatic ketone |
| EP4110750A4 (en) | 2020-02-25 | 2024-03-27 | Laxmi Organic Industries Limited | A process for synthesis of high purity 1-[3-(trifluoromethyl)phenyl]ethanone oxime |
| CN111302916A (en) * | 2020-03-18 | 2020-06-19 | 湖南复瑞生物医药技术有限责任公司 | Preparation method of 3, 5-bis (trifluoromethyl) acetophenone |
| CN113956143A (en) * | 2021-11-15 | 2022-01-21 | 山东华阳农药化工集团有限公司 | Preparation method of m-trifluoromethyl acetophenone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161621A (en) * | 2007-11-15 | 2008-04-16 | 浙江工业大学 | A method for preparing trifluoromethyl acetophenone compound |
| CN101844972A (en) * | 2010-05-28 | 2010-09-29 | 常州工程职业技术学院 | Improved method for preparing aromatic ketone |
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| CN101492351A (en) * | 2008-01-25 | 2009-07-29 | 亚邦化工集团有限公司 | Process for producing asarin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161621A (en) * | 2007-11-15 | 2008-04-16 | 浙江工业大学 | A method for preparing trifluoromethyl acetophenone compound |
| CN101844972A (en) * | 2010-05-28 | 2010-09-29 | 常州工程职业技术学院 | Improved method for preparing aromatic ketone |
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| CN102690180A (en) | 2012-09-26 |
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