WO1998058895A1 - Process for the preparation of trifluoromethyl acetophenone - Google Patents
Process for the preparation of trifluoromethyl acetophenone Download PDFInfo
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- WO1998058895A1 WO1998058895A1 PCT/EP1998/003639 EP9803639W WO9858895A1 WO 1998058895 A1 WO1998058895 A1 WO 1998058895A1 EP 9803639 W EP9803639 W EP 9803639W WO 9858895 A1 WO9858895 A1 WO 9858895A1
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- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/516—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of nitrogen-containing compounds to >C = O groups
Definitions
- the invention relates to a process for the preparation of trifluoromethyl acetophenone derivatives of formula I
- Y is a group that is inert for the reactions, preferably a hydrocarbyl; and m is from 0 to 4; preferably 0; in which process a) a compound of formula II
- X is chlorine, bromine or iodine, preferably bromine
- Y and m are as defined for formula I, is reacted with a vinylether of formula Ilia or an enamide of formula Illb
- CH 2 CH-OR ⁇ (Ilia)
- CH 2 CH-N(R 2 )-CO-R 3 (Illb)
- Ri and R 2 are each independently of the other C C- 8 alkyl, C 2 -C 8 alkenyl, C _-
- R 3 is C C 8 alkyI, C 2 -C 8 alkenyl, C C 8 alkoxyalkyl, C 3 -C 6 cycloalkyl or phenyl-CrC 2 alkyl, which groups are optionally substituted, in a solvent, in the presence of a base and of a catalytic amount of a palladium compound comprising a monodental or bidental phosphine ligand; b) the resulting intermediate of formula IVa and IVb resp.
- EP-A-688,757 discloses the vinylation of halogen benzene derivatives in the presence of a palladium/phosphine catalyst; the regioselectivity of the reaction with respect to the vinyl group is not discussed therein, but according to the working examples the vinyl group reacts predominantly in (b) position.
- the strongly electron withdrawing trifluoromethyl group is expected to favour substitution at (b)-position over (a)-position resulting in low yields of trifluoromethyl acetophenone.
- R _, R 2 and R 3 may be substituted by any functional group which does not negatively affect the reaction; examples are C C 8 alkyl, halo-Cj-C ⁇ alkyl, C 2 -C 8 alkenyl, halo-
- Suitable palladium compounds which can be used as catalysts are for example palladium bis-(dibenzalacetone)-palladium, palladium acetate, palladium dichloride, palladium dibromide, palladium trifluoroacetate, palladium diphosphine halogenide complexes and acetate complexes as palladium-bis(triphenylphosphine) dichloride and palladium- bis(triphenylphosphine) acetate; furtheron palladium tetrachloro complexes; preferred is bis- (dibenzalacetone)-palladium.
- Suitable phosphine ligands are aryl phosphines as triphenyl phosphine, methyl diphenylphosphine or 1 ,3-bis-(diphenylphosphino)-propane, preferably triphenyl phosphine.
- the amount of palladium catalyst is 0.01 to 10 mol%, preferably 0.1 to 1 mol% in relation to the compound of formula II.
- the molar ratio of palladium to phosphine is from 1 :1 to 1 :4, preferably ca. 1 :2.
- Suitable solvents for reaction step a) are aprotic, polar solvents, preferably propylene carbonate, anisole, N-methyl-2-pyrrolidone, N,N-dimethyl acetamide, dimethylformamide, tetram ethyl urea, gamma-butyrolacone, N,N-dimethylimidazolidinon and dimethyl sulfoxide.
- Suitable bases are amines, as triethylamine, triethylenediamine, cyclohexylamine, N- cyclohexyl-N,N-dimethyl-amine, N,N-diethylaniiine, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine and 1 ,8-diazabicyclo[5.4.0]undec-5-ene (DBU); alkali metal or alkaline earth metal hydroxides, carbonates, hydrogencarbonates and phosphates, preferably potassium salts; or salts of carboxyiic acids, preferably alkali salts of C 2 -C 4 carboxylic acids.
- Preferred are triethylamine, potassium hydroxide, -carbonate.-hydrogencarbonate and - phosphate, and sodium acetate; particularly preferred is triethylamine.
- Reaction step a) is carried out at from 50°C to 200°C, preferably from 70°C to 150°C; most preferably from 90°C to 120°C.
- Reaction step b) (hydrolysis) is carried out with diluted acid, as hydrochloric acid, sulfuric acid or acetic acid, preferably in mixture with a solvent, wherein the product is soluble.
- the temperature is not critical and may vary from 0 °C to +70°C.
- CH 2 CH-OR, (Ilia) wherein R, is C ⁇ -C 8 alkyl; preferably C 4 -C 6 alkyl.
- Example 1 3-Trifluoromethyl-1-butoxystyrene a) To 22.5 g (100 mmol) 3-bromo-benzotrifluoride and 80 ml propylene carbonate under argon 20.2 g (200 mmol) triethyl amine, 20.0 g (200 mmol) butyl vinyl ether, 518 mg (0.5 mmol) bis-(dibenzalacetone)-chloroform-pailadium and 525 mg (2 mmol) triphenyl phospine are added. The reaction mixture is heated to 110 °C for 20 hours, cooled to room tern pera- ture and filtered. The filtrate is extracted twice with 50 ml hexane.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for the preparation of a compound of formula (I), wherein Y is a group that is inert for the reactions, preferably a hydrocarbyl; and m is from 0 to 4, preferably 0; in which process a) a compound of formula (II), wherein X is chlorine, bromine or iodine, preferably bromine, and Y and m are as defined for formula (I), is reacted with a vinylether of formula (IIIa) or an enamide of formula (IIIb): CH2=CH-OR1 (IIIa), CH2=CH-N(R2)-CO-R3 (IIIb), wherein R1 and R2 are each independently of the other C1-C8alkyl, C2-C8alkenyl, C1-C8alkoxyalkyl, C3-C6cycloalkyl, phenyl-C1-C2alkyl or C1-C8acyl, which groups are optionally substituted, R3 is C1-C8alkyl, C2-C8alkenyl, C1-C8alkoxyalkyl, C3-C6cycloalkyl or phenyl-C1-C2alkyl, which groups are optionally substituted, in a solvent, in the presence of a base and of a catalytic amount of a palladium compound comprising a monodental or bidental phosphine ligand; b) the resulting intermediate of formula (IVa) and resp. (IVb), is hydrolyzed to the compound of formula (I).
Description
Process for the preparation of trifluoromethyl acetophenone
The invention relates to a process for the preparation of trifluoromethyl acetophenone derivatives of formula I
Y is a group that is inert for the reactions, preferably a hydrocarbyl; and m is from 0 to 4; preferably 0; in which process a) a compound of formula II
wherein
X is chlorine, bromine or iodine, preferably bromine, and
Y and m are as defined for formula I, is reacted with a vinylether of formula Ilia or an enamide of formula Illb
CH2=CH-ORι (Ilia) CH2=CH-N(R2)-CO-R3 (Illb)
wherein Ri and R2 are each independently of the other C C-8alkyl, C2-C8alkenyl, C _-
C8alkoxyalkyl, C3-C6cycloalkyl, phenyl-C C2alkyl or CrC-sacyl, which groups are optionally substituted,
R3 is C C8alkyI, C2-C8alkenyl, C C8alkoxyalkyl, C3-C6cycloalkyl or phenyl-CrC2alkyl, which groups are optionally substituted, in a solvent, in the presence of a base and of a catalytic amount of a palladium compound comprising a monodental or bidental phosphine ligand;
b) the resulting intermediate of formula IVa and IVb resp.
is hydroiyzed to the compound of formula I.
These compounds are important intermediates for the preparation of pharmaceuticals, pesticides, dyestuffs, perfumes and other products.
The palladium catalyzed vinylation of aromatic halogen compounds is the well known "Heck"-reaction. In this reaction, vinyl ethers can react in (a) or in (b) position, resulting in compounds A and B respectively, as shown the scheme 1. Only compound A can be hydroiyzed to the acetophenone C. Thus, for the preparation of acetophenones by the "Heck"-reaction, the initial vinylation reaction should predominantly occur in (a) position.
Scheme 1
X: I, Br, Cl
Z: unreactive group
The preparation of acetophenones by palladium catalyzed reaction of aryl halides with vinyl ethers is described in J. Org. Chem. Vol.52, 1987, 3529-3536.
The regioselectivity of this reaction is dependent, amongst others, on the catalyst and the substituent on the aryl group. Substitution at (a)-position is increased by adding phosphine ligands to the palladium catalyst (J. Org. Chem. Vol.57, 1992, 1481 -1486), whereas electron withdrawing groups on the aryl moiety favour substitution at (b)-position (J. Org.
Chem. Vol.52, 1987, 3529-3536).
Accordingly, the strongly electron withdrawing trifluoromethyl group is expected to favour substitution at (b)-position over (a)-position resulting in low yields of trifluoromethyl acetophenone.
Surprisingly it has been found that a high ratio of (a)-substitution over (b)-substitution can be obtained in the reaction according to this invention, resulting after hydrolysis in good yields of the corresponding trifluoromethyl acetophenone. The method provided herewith is distinguished by ready availability of the starting materials, good technical feasibility and is economically and ecologically favorable.
The groups R _, R2 and R3 may be substituted by any functional group which does not negatively affect the reaction; examples are C C8alkyl, halo-Cj-Cβalkyl, C2-C8alkenyl, halo-
C2-C8alkenyl, C C8alkoxyalkyl, C3-C6cycloalkyl, phenyl, phenoxy, phenyl-C C2alkyl, hetaryl, hetaryloxy or C C8acyl.
Suitable palladium compounds which can be used as catalysts are for example palladium bis-(dibenzalacetone)-palladium, palladium acetate, palladium dichloride, palladium dibromide, palladium trifluoroacetate, palladium diphosphine halogenide complexes and acetate complexes as palladium-bis(triphenylphosphine) dichloride and palladium- bis(triphenylphosphine) acetate; furtheron palladium tetrachloro complexes; preferred is bis- (dibenzalacetone)-palladium.
Suitable phosphine ligands are aryl phosphines as triphenyl phosphine, methyl diphenylphosphine or 1 ,3-bis-(diphenylphosphino)-propane, preferably triphenyl phosphine. The amount of palladium catalyst is 0.01 to 10 mol%, preferably 0.1 to 1 mol% in relation to the compound of formula II.
The molar ratio of palladium to phosphine is from 1 :1 to 1 :4, preferably ca. 1 :2.
Suitable solvents for reaction step a) are aprotic, polar solvents, preferably propylene carbonate, anisole, N-methyl-2-pyrrolidone, N,N-dimethyl acetamide, dimethylformamide, tetram ethyl urea, gamma-butyrolacone, N,N-dimethylimidazolidinon and dimethyl sulfoxide.
Suitable bases are amines, as triethylamine, triethylenediamine, cyclohexylamine, N- cyclohexyl-N,N-dimethyl-amine, N,N-diethylaniiine, pyridine, 4-(N,N-dimethylamino)pyridine, N-methylmorpholine and 1 ,8-diazabicyclo[5.4.0]undec-5-ene (DBU); alkali metal or alkaline earth metal hydroxides, carbonates, hydrogencarbonates and phosphates, preferably potassium salts; or salts of carboxyiic acids, preferably alkali salts of C 2-C4carboxylic acids. Preferred are triethylamine, potassium hydroxide, -carbonate.-hydrogencarbonate and - phosphate, and sodium acetate; particularly preferred is triethylamine.
Reaction step a) is carried out at from 50°C to 200°C, preferably from 70°C to 150°C; most preferably from 90°C to 120°C. Reaction step b) (hydrolysis) is carried out with diluted acid, as hydrochloric acid, sulfuric acid or acetic acid, preferably in mixture with a solvent, wherein the product is soluble. The temperature is not critical and may vary from 0 °C to +70°C.
Preferred is the preparation of 3-trifiuoromethylacetophenone, wherein 3-bromo- benzotrifluorid is reacted with a vinylether of formula Ilia
CH2=CH-OR, (Ilia) wherein R, is Cι-C8alkyl; preferably C4-C6alkyl.
Preparation Examples
Example 1 : 3-Trifluoromethyl-1-butoxystyrene a) To 22.5 g (100 mmol) 3-bromo-benzotrifluoride and 80 ml propylene carbonate under argon 20.2 g (200 mmol) triethyl amine, 20.0 g (200 mmol) butyl vinyl ether, 518 mg (0.5 mmol) bis-(dibenzalacetone)-chloroform-pailadium and 525 mg (2 mmol) triphenyl phospine are added. The reaction mixture is heated to 110 °C for 20 hours, cooled to room tern pera- ture and filtered. The filtrate is extracted twice with 50 ml hexane. The hexane phase is
washed twice with 50 ml water, dried with Na2S0 and the solvent is evaporated. 26 g of an oil are obtained that contains 21 g of 3-trifluoromethyl-1 -butoxystyrene (yield 80 %).
b) To 22.5 g (100 mmol) 3-bromo-benzotrifluoride, potassium carbonate (200 mmol) and 80 ml propylene carbonate under argon 20.0 g (200 mmol) butyl vinyl ether, 518 mg (0.5 mmol) bis-(dibenzalacetone)-chloroform-palladium and 788 mg (3 mmol) triphenyl phospine are added. The reaction mixture is heated to 140 °C for 20 hours, cooled to room temperature and filtered. The filtrate is extracted twice with 50 ml hexane. The hexane phase is washed twice with 50 ml water, dried with Na2SO4 and the solvent is evaporated. 26 g of an oil are obtained that contains 20 g of 3-trifluoromethyl-1 -butoxystyrene (yield 77 %).
Example 2: 3-Trifluoromethyl-acetophenone
To 26 g of raw 3-trifluoromethyl-1-butoxystyrene (80 mmol) 30 ml N,N-dimethylformamide and 30 ml 1 M hydrochloric acid are added and the mixture is stirred for 10 hours at room temperature. 100 ml water are added and the mixture is extracted twice with 100 ml methylene chloride. The organic phase is washed with 50 ml water, dried with Na 2S0 , and the solvent evaporated under reduced pressure. The residue is destilled to give 11 g trifluoromethyl-acetophenone (bp. 96°C/50mbar, 73 % yield).
Example 3: 3-Trifluoromethyl-1-ethoxystyrene
To 22.5 g (100 ml) of 3-bromo-benzotrifluoride and 80 ml propylene carbonate under argon
20.2 g (200 mmol) triethyl amine, 14.4 g (200 mmol) ethyl vinyl ether, 518 mg (0.5 mmol) bis-(dibenzalacetone)-chloroform-palladium and 525 mg (2 mmol) triphenyl phospine are added. The reaction mixture is heated in an autoclave to 120 °C for 20 hours, cooled to room temperature, filtered and the filtrate extracted twice with 50 ml hexane. The hexane phase is washed twice with 50 ml water, dried with Na S04 and the solvent is evaporated.
The residue is distilled to give 16 g 3-trifluoromethyl-1-ethoxystyrene (b.p. 113 °C / 50 mbar, yield 75 %).
Hydrolysis according to Example 2 results in trifluoromethyl-acetophenone (76 % yield).
Example 4: Different phosphine to palladium ratios
3-Trifluoromethyl-1 -butoxystyrene
26 mg (0.025 mmol) bis-(dibenzalacetone)-chloroform-palladium and different amounts of triphenyl phosphine are placed in a Schlenk-tube under argon. 4 ml propylene carbonate,
1.12 g (5 mmol) 3-bromo-benzotrifluoride 0.76 g (7.5 mmol) triethyl amine and 0.75 g (7.5 mmol) butyl vinyl ether are added. The reaction mixture is heated to 120 °C for 20 hours. It is cooled to room temperature and 200 mg hexadecane (internal standard) and 15 ml diethyl ether are added. The mixture is analysed by GC.
Example 5: Different solvents 3-Trifluoromethyl-1 -butoxystyrene
26 mg (0.025 mmol) bis-(dibenzalacetone)-chloroform-palladium and 27 mg (0.1 mmol) triphenyl phosphine are placed in a Schlenk-tube under argon. 4 ml solvent, 1.12 g (5 mmol) 3-bromo-benzotrifluoride 0.76 g (7.5 mmol) triethyl amine and 0.75 g (7.5 mmol) butyl vinyl ether are added. The reaction mixture is heated to 120 °C for 20 hours. It is cooled to room temperature and 200 mg hexadecane (internal standard) and 15 ml diethylether are added. The mixture is analysed by GC.
Example 6: Different Ligands
3-Trifluoromethyl-1 -butoxystyrene
26 mg (0.025 mmol) bis-(dibenzalacetone)-chloroform-palladium and 0.1 mmol of a ligand are placed in a Schlenk-tube under argon. 4 ml N,N-dimethyl-acetamide, 1.12 g (5 mmol) 3- bromo-benzotrifluoride 0.76 g (7.5 mmol) triethyl amine and 0.75 g (7.5 mmol) butyl vinyl ether are added. The reaction mixture is heated to 120 °C for 20 hours. It is cooled to room
temperature and 200 mg hexadecane (internal standard) and 15 ml diethylether are added. The mixture is analysed by GC.
Example 7: Preparation of 3-bromo-benzotrifluoride (educt)
3280 g of bromine are added to a mixture of 6046 g benzotrifluoride, 68 g FeCI 3 and 2 g
Si02 at about 20°C within ca. 2 hours. The reaction temperature is then slowly rised within ca. 7 hours to ca 40°C, 300 g water and 130 g Na 2S203 are added and stirred for ca. 15 minutes. The phases are separated and the organic phase is destilled resulting in 4160 g bromo-benzotrifluoride (isomeric ratio 3 : 4 = 96 : 4) and 3290 g benzotrifluoride which is recycled.
Claims
1. A process for the preparation of a compound of formula
wherein:
Y is a group that is inert for the reactions, preferably a hydrocarbyl; and m is from 0 to 4; preferably 0; in which process
a) a compound of formula II
wherein
X is chlorine, bromine or iodine, preferably bromine, and
Y and m are as defined for formula I, is reacted with a vinylether of formula Ilia or an enamide of formula Illb
CH2=CH-OR1 (Ilia) CH2=CH-N(R2)-CO-R3 (Illb) wherein R . and R2 are each independently of the other C C8alkyl, C2-C8alkenyl, C _- C8alkoxyalkyl, C3-C6cycloalkyl, phenyl-C C2alkyl or C C8acyl, which groups are optionally substituted,
R3 is C C8alkyl, C2-C8alkenyl, C C8alkoxyalkyl, C3-C6cycloalkyl or phenyl-C C2alkyl, which groups are optionally substituted,
R3 is d-Cβalkyl, C Csalkenyl, CrC8alkoxyalkyl, C3-C6cycloalkyl or phenyl-CrC2alkyl, in a solvent, in the presence of a base and of a catalytic amount of a palladium compound comprising a monodental or bidental phosphine ligand;
b) the resulting intermediate of formula IVa and resp. IVb
is hydroiyzed to the compound of formula I.
2. A process according to claim 1 , wherein the palladium compound is selected from bis-(dibenzalacetone)-palladium, palladium acetate, palladium dichloride, palladium dibromide, palladium trifluoroacetate, palladium diphosphine halogenide complexes and acetate complexes, palladium tetrachloro complexes; preferably bis- (dibenzalacetone)- palladium.
3. A process according to claim 1 , wherein the phosphine ligand is an aryl phosphine.
4. A process according to claim 3, wherein the phosphine ligand is selected from triphenyl phosphine, methyl diphenylphosphine and 1 ,3-bis-(diphenylphosphino)-propane, preferably triphenyl phosphine.
5. A process according to claim 1 , wherein the amount of palladium compound is 0.01 to 10 mol%, preferably 0.1 to 1 mol% in relation to the compound of formula II.
6. A process according to claim 1 , wherein the molar ratio of palladium to phosphine is from 1 :1 to 1 :4, preferably ca. 1 :2.
7. A process according to claim 1 , wherein the solvent for reaction step a) is an aprotic, polar solvent, preferably propylene carbonate, anisole, N-methyl-2-pyrrolidone, N,N- dimethyl acetamide, dimethylformamide, tetramethyiurea, gamma-butyrolacone, N,N- dimethylimidazolidinon and dimethyl sulfoxide.
8. A process according to claim 1 , wherein the base is selected from amines, alkali metal or alkaline earth metal hydroxides, -carbonates, -hydrogencarbonates and -phosphates; and salts of carboxylic acids.
9. A process according to claim 1 , wherein reaction step a) is carried out at 50°C to 200°C, preferably at 70°C to 150°C; and reaction step b) is carried out at 0 °C to 70°C.
10. A process according to claim 1 for the preparation of 3-trifluoromethylacetophenone, wherein 3-bromo-benzotrifluorid is reacted with a vinylether of formula Ilia
CHz SH-OR, (Ilia)
wherein R . is C C8alkyl; preferably C4-C6alkyl.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT98933622T ATE225762T1 (en) | 1997-06-19 | 1998-06-17 | METHOD FOR PRODUCING TRIFLUOROMETHYL-ACETOPHENONE |
| DE69808624T DE69808624T2 (en) | 1997-06-19 | 1998-06-17 | METHOD FOR PRODUCING TRIFLUOROMETHYL ACETOPHENONE |
| DK98933622T DK0993432T3 (en) | 1997-06-19 | 1998-06-17 | Process for Preparation of Triflourmethyl Acetophenones |
| BR9810169-2A BR9810169A (en) | 1997-06-19 | 1998-06-17 | Process for preparation of trifluoromethyl acetophenone |
| AU83377/98A AU8337798A (en) | 1997-06-19 | 1998-06-17 | Process for the preparation of trifluoromethyl acetophenone |
| EP98933622A EP0993432B1 (en) | 1997-06-19 | 1998-06-17 | Process for the preparation of trifluoromethyl acetophenone |
| US09/446,233 US6420608B1 (en) | 1997-06-19 | 1998-06-17 | Process for the preparation of trifluoromethyl acetophenone |
| JP50373599A JP2002504133A (en) | 1997-06-19 | 1998-06-17 | Method for producing trifluoromethylacetophenone |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9712999.3A GB9712999D0 (en) | 1997-06-19 | 1997-06-19 | Process for the preparation of trifluoromethyl acetophenone |
| GB9712999.3 | 1997-06-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998058895A1 true WO1998058895A1 (en) | 1998-12-30 |
Family
ID=10814610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1998/003639 Ceased WO1998058895A1 (en) | 1997-06-19 | 1998-06-17 | Process for the preparation of trifluoromethyl acetophenone |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US6420608B1 (en) |
| EP (1) | EP0993432B1 (en) |
| JP (1) | JP2002504133A (en) |
| AT (1) | ATE225762T1 (en) |
| AU (1) | AU8337798A (en) |
| BR (1) | BR9810169A (en) |
| DE (1) | DE69808624T2 (en) |
| DK (1) | DK0993432T3 (en) |
| ES (1) | ES2185183T3 (en) |
| GB (1) | GB9712999D0 (en) |
| WO (1) | WO1998058895A1 (en) |
| ZA (1) | ZA985296B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19725038B4 (en) * | 1997-06-13 | 2007-06-06 | Henkel Kgaa | Low emission aqueous dispersion adhesive and its use |
| JP4649733B2 (en) * | 2000-12-04 | 2011-03-16 | 旭硝子株式会社 | Method for producing acetophenone compound containing trifluoromethyl group |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0688757A1 (en) * | 1994-06-22 | 1995-12-27 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic olefines by catalysis of palladacycles |
-
1997
- 1997-06-19 GB GBGB9712999.3A patent/GB9712999D0/en active Pending
-
1998
- 1998-06-17 DE DE69808624T patent/DE69808624T2/en not_active Expired - Fee Related
- 1998-06-17 AT AT98933622T patent/ATE225762T1/en not_active IP Right Cessation
- 1998-06-17 EP EP98933622A patent/EP0993432B1/en not_active Expired - Lifetime
- 1998-06-17 DK DK98933622T patent/DK0993432T3/en active
- 1998-06-17 JP JP50373599A patent/JP2002504133A/en active Pending
- 1998-06-17 AU AU83377/98A patent/AU8337798A/en not_active Abandoned
- 1998-06-17 ES ES98933622T patent/ES2185183T3/en not_active Expired - Lifetime
- 1998-06-17 US US09/446,233 patent/US6420608B1/en not_active Expired - Fee Related
- 1998-06-17 BR BR9810169-2A patent/BR9810169A/en not_active IP Right Cessation
- 1998-06-17 WO PCT/EP1998/003639 patent/WO1998058895A1/en not_active Ceased
- 1998-06-18 ZA ZA985296A patent/ZA985296B/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0688757A1 (en) * | 1994-06-22 | 1995-12-27 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic olefines by catalysis of palladacycles |
Non-Patent Citations (1)
| Title |
|---|
| C-M. ANDERSSON AND A. HALLBERG: "Regiochemistry of Palladium-catalyzed Arylation Reactions of Enol Ethers.", J. ORG. CHEM., vol. 52, no. 16, 1987, pages 3529 - 3536, XP002081250 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US6420608B1 (en) | 2002-07-16 |
| JP2002504133A (en) | 2002-02-05 |
| DE69808624T2 (en) | 2003-02-06 |
| EP0993432B1 (en) | 2002-10-09 |
| ATE225762T1 (en) | 2002-10-15 |
| DE69808624D1 (en) | 2002-11-14 |
| AU8337798A (en) | 1999-01-04 |
| ES2185183T3 (en) | 2003-04-16 |
| ZA985296B (en) | 1998-12-21 |
| EP0993432A1 (en) | 2000-04-19 |
| GB9712999D0 (en) | 1997-08-27 |
| DK0993432T3 (en) | 2003-01-27 |
| BR9810169A (en) | 2000-08-08 |
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