DE3840375A1 - 2,4,5-Trifluoroacetophenone, and process for its preparation - Google Patents
2,4,5-Trifluoroacetophenone, and process for its preparationInfo
- Publication number
- DE3840375A1 DE3840375A1 DE19883840375 DE3840375A DE3840375A1 DE 3840375 A1 DE3840375 A1 DE 3840375A1 DE 19883840375 DE19883840375 DE 19883840375 DE 3840375 A DE3840375 A DE 3840375A DE 3840375 A1 DE3840375 A1 DE 3840375A1
- Authority
- DE
- Germany
- Prior art keywords
- trifluoroacetophenone
- acylation
- trifluorobenzene
- acetyl chloride
- reaction
- 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.)
- Withdrawn
Links
- GVTLJUZWNNFHMZ-UHFFFAOYSA-N 1-(2,4,5-trifluorophenyl)ethanone Chemical compound CC(=O)C1=CC(F)=C(F)C=C1F GVTLJUZWNNFHMZ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 8
- PEBWOGPSYUIOBP-UHFFFAOYSA-N 1,2,4-trifluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1 PEBWOGPSYUIOBP-UHFFFAOYSA-N 0.000 claims abstract description 8
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012346 acetyl chloride Substances 0.000 claims abstract description 7
- 230000010933 acylation Effects 0.000 claims description 10
- 238000005917 acylation reaction Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 abstract description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 1
- AKAMNXFLKYKFOJ-UHFFFAOYSA-N 2,4,5-trifluorobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(F)C=C1F AKAMNXFLKYKFOJ-UHFFFAOYSA-N 0.000 description 1
- XOQQVKDBGLYPGH-UHFFFAOYSA-N 2-oxo-1h-quinoline-3-carboxylic acid Chemical class C1=CC=C2NC(=O)C(C(=O)O)=CC2=C1 XOQQVKDBGLYPGH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- -1 aromatic methyl ketones Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
- C07C49/807—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen all halogen atoms bound to the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die Erfindung betrifft 2,4,5-Trifluoracetophenon, sowie ein Verfahren zu dessen Herstellung.The invention relates to 2,4,5-trifluoroacetophenone and a method for the same Manufacturing.
2,4,5-Trifluoracetophenon ist in der Literatur bisher nicht beschrieben, es stellt ein wertvolles Zwischenprodukt zur Herstellung von 2,4,5-Trifluorbenzoesäure, aus der hochwirksame Chinoloncarbonsäurederivate hergestellt werden können, dar.2,4,5-trifluoroacetophenone has not yet been described in the literature, it does a valuable intermediate for the production of 2,4,5-trifluorobenzoic acid, from which highly effective quinolonecarboxylic acid derivatives can be produced, represents.
Gegenstand der Erfindung ist demnach 2,4,5-Trifluoracetophenon.The invention accordingly relates to 2,4,5-trifluoroacetophenone.
Es ist bekannt, aromatische Methylketone durch Friedel-Crafts-Acylierung von aromatischen Kohlenwasserstoffen herzustellen. (Houben-Weyl, 1973, Band 7/2a, S. 48) Bei substituierten aromatischen Kohlenwasserstoffen erfolgt die Acylie rung entsprechend dem Dirigismus der Substituenten.It is known to aromatic methyl ketones by Friedel-Crafts acylation of to produce aromatic hydrocarbons. (Houben-Weyl, 1973, volume 7 / 2a, P. 48) Acylie occurs with substituted aromatic hydrocarbons tion according to the dirigism of the substituents.
Es konnte nun ein Verfahren zur Herstellung von 2,4,5-Trifluoracetophenon gefunden werden, bei dem ausgehend von 1,2,4-Trifluorbenzol durch Friedel- Crafts-Acylierung 2,4,5-Trifluoracetophenon selektiv erhalten wird. Die Acylie rung erfolgt trotz der starken Desaktivierung des Benzolkerns durch 3 Fluor substituenten in guter Ausbeute. Sie erfolgt überdies überraschenderweise selek tiv, obwohl auf Grund der dirigistischen Wirkung der Fluorsubstituenten neben der Acylierung in 5-Stellung - Dirigismus durch einen o- und einen p-Fluorsubsti tuenten - auch eine Acylierung in 3-Stellung - Dirigismus durch zwei o- Fluorsubstituenten - zu erwarten gewesen wäre.It was now possible to produce 2,4,5-trifluoroacetophenone are found in which starting from 1,2,4-trifluorobenzene by Friedel Crafts acylation 2,4,5-trifluoroacetophenone is obtained selectively. The Acylie tion occurs despite the strong deactivation of the benzene nucleus by 3 fluorine substituents in good yield. It is also surprisingly selective tiv, although due to the dirigistic effect of the fluorine substituents the acylation in the 5-position - dirigism through an o- and a p-fluorine substituent tuenten - also acylation in the 3-position - dirigism through two o- Fluorine substituents - would have been expected.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur selektiven Herstel lung von 2,4,5-Trifluoracetophenon, das dadurch gekennzeichnet, ist, daß man 1,2,4-Trifluorbenzol mit Acetylchlorid in Gegenwart eines Acylierungskatalysa tors und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.Another object of the invention is a method for selective manufacture lung of 2,4,5-trifluoroacetophenone, which is characterized in that 1,2,4-trifluorobenzene with acetyl chloride in the presence of an acylation catalyst tors and optionally in the presence of a diluent.
Als Katalysatoren werden Acylierungskatalysatoren, wie Eisen-III-chlorid, Zink chlorid oder Aluminiumchlorid eingesetzt. Bevorzugt wird Aluminiumchlorid eingesetzt. Pro mol 1,2,4-Trifluorbenzol werden etwa 1 bis 3 Mol Acylierungs katalysator eingesetzt. Acetylchlorid wird in äquimolaren Mengen eingesetzt, wobei auch ein bis zu 3molarer Überschuß möglich ist.Acylation catalysts such as ferric chloride and zinc are used as catalysts chloride or aluminum chloride used. Aluminum chloride is preferred used. About 1 to 3 moles of acylation are used per mole of 1,2,4-trifluorobenzene catalyst used. Acetyl chloride is used in equimolar amounts, an up to 3 molar excess is also possible.
Die Acylierung wird bevorzugt ohne Verdünnungsmittel durchgeführt. Es können jedoch auch unter Reaktionsbedingungen inerte Verdünnungsmittel wie z. B. Dichlorethan verwendet werden.The acylation is preferably carried out without a diluent. It can but also under the reaction conditions inert diluents such. B. Dichloroethane can be used.
Die Reaktionstemperatur kann in einem weiten Bereich schwanken, vorzugsweise wird die Acylierung bei Temperaturen von etwa 60-170°C durchgeführt. Die Reaktionsdauer beträgt abhängig von den übrigen Reaktionsbedingungen etwa 2 bis 5 Stunden. Das bei der Acylierung entstandene Trifluoracetophenon kann durch übliche Methoden wie Extraktion und Destillation isoliert werden.The reaction temperature can vary within a wide range, preferably the acylation is carried out at temperatures of about 60-170 ° C. The Depending on the other reaction conditions, the reaction time is about 2 up to 5 hours. The trifluoroacetophenone formed during the acylation can can be isolated by conventional methods such as extraction and distillation.
Zur Isolierung wird das Reaktionsgemisch auf Eis gegossen, mit einem organi schen Lösungsmittel, beispielsweise Dichlormethan oder Chloroform, extrahiert, getrocknet und das Lösungsmittel verdampft und der Rückstand anschließend destilliert.For isolation, the reaction mixture is poured onto ice with an organic extracted solvents, for example dichloromethane or chloroform, dried and the solvent evaporated and then the residue distilled.
Zu einer Mischung aus 1016 g (7,6 mol) AlCl3 und 400 g (3,03 mol) 1,2,4- Trifluorbenzol wurden in einem Doppelmantelkolben 435 g (5,5 mol) Acetyl chlorid so zugetropft, daß die Temperatur der Reaktionslösung 40°C nicht überstieg. Anschließend wurde die Manteltemperatur auf 140°C erhöht und nach Erreichen einer Innentemperatur von 135°C etwa 1 Stunde gerührt. Das noch heiße Reaktionsgemisch wurde auf etwa 10 kg Eis gegossen, 45 Minuten gerührt, anschließend die Phasen getrennt und die wäßrige Phase mit CH2Cl2 mehrmals extrahiert. Die vereinigten organischen Phasen wurden mit Natriumhydrogencar bonat und Natriumsulfat versetzen, filtriert und das Lösungsmittel durch Destil lation über eine 50 cm Raschigringkolonne entfernt. Der Rückstand wurde in Vakuum über eine 70 cm-Vigreuxkolonne destilliert. Es wurde 301 g (57,1% d. Th.) an 2,4,5-Trifluoracetophenon mit einem Fp. von 76-82°C 0,02 bar erhalten.435 g (5.5 mol) of acetyl chloride were added dropwise to a mixture of 1016 g (7.6 mol) of AlCl 3 and 400 g (3.03 mol) of 1,2,4-trifluorobenzene in a jacketed flask so that the temperature the reaction solution did not exceed 40 ° C. The jacket temperature was then raised to 140 ° C. and, after reaching an internal temperature of 135 ° C., stirred for about 1 hour. The still hot reaction mixture was poured onto about 10 kg of ice, stirred for 45 minutes, then the phases were separated and the aqueous phase was extracted several times with CH 2 Cl 2 . The combined organic phases were mixed with sodium hydrogen carbonate and sodium sulfate, filtered and the solvent was removed by distillation through a 50 cm Raschig ring column. The residue was distilled in vacuo over a 70 cm Vigreux column. 301 g (57.1% of theory) of 2,4,5-trifluoroacetophenone with an mp of 76-82 ° C. 0.02 bar were obtained.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19883840375 DE3840375A1 (en) | 1988-11-30 | 1988-11-30 | 2,4,5-Trifluoroacetophenone, and process for its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19883840375 DE3840375A1 (en) | 1988-11-30 | 1988-11-30 | 2,4,5-Trifluoroacetophenone, and process for its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3840375A1 true DE3840375A1 (en) | 1990-05-31 |
Family
ID=6368182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19883840375 Withdrawn DE3840375A1 (en) | 1988-11-30 | 1988-11-30 | 2,4,5-Trifluoroacetophenone, and process for its preparation |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE3840375A1 (en) |
-
1988
- 1988-11-30 DE DE19883840375 patent/DE3840375A1/en not_active Withdrawn
Non-Patent Citations (2)
| Title |
|---|
| - DD-Buch: BEYER, H.: Lehrbuch der organischen Chemie, Hirzel Verlag, Leipzig, 1963, S.422 * |
| Beilstein E III 7, S.973, 1968 * |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OM8 | Search report available as to paragraph 43 lit. 1 sentence 1 patent law | ||
| 8139 | Disposal/non-payment of the annual fee |