US4310704A
Expired / Lapsed
US
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Process for manufacturing methyl ketones by oxidation of terminal olefins
Assignee: IFP Energies nouvelles
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Filing: 1979-12-18
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Granted: 1982-01-12
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Expires: 1999-12-18
Abstract
Abstract Methyl ketones are prepared in liquid phase by oxidizing terminal olefins of the formula R-CH=CH2, where R is a hydrocarbon radical. The oxidizing agent is hydrogen peroxide or an organic hydroperoxide, and the catalyst is a palladium catalyst of the formula Pd AA', (Lm) where A is fluoborate, acetate or trefrafluoroacetate A' is the same as A or is pi -allyl, m is 0 or 2, and L is a ligand selected from the amines, the phosphines, the arsines, the stibines and the amides.
Inventors
- 👤 Hubert Mimoun
- 👤 Robert Charpentier
- 👤 Michel Roussel
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 15:33
CPC Classifications
C; C07; C07C; C07C45/00; C07C45/27; C07C45/28
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
129 words
A process for producing a methyl ketone of the formula ##STR2## from an olefin of the formula CH 2 ═CHR wherein R is C 1-20 hydrocarbyl, said process comprising the step consisting essentially of contacting said olefin in the liquid phase, optionally in the presence of a solvent, with a palladium catalyst and a peroxide oxidizing agent; wherein said palladium catalyst has the formula PdAA'(L) m , wherein A is fluoborate, acetate or trifluoroacetate; A' is the same as A or a π-allyl radical; L is an amine, phosphine, arsine, stibine or amide ligand; and m is 0 or 2; and wherein said oxidizing agent is hydrogen peroxide or an organic hydroperoxide of the formula R 2 OOH, wherein R 2 is C 4-20 tertiary alkyl, aralkyl or alkylaryl.
Claim 2
Dependent Claim
129 words
A process for producing a methyl ketone of the formula ##STR2## from an olefin of the formula CH 2 ═CHR wherein R is C 1-20 hydrocarbyl, said process comprising the step consisting essentially of contacting said olefin in the liquid phase, optionally in the presence of a solvent, with a palladium catalyst and a peroxide oxidizing agent; wherein said palladium catalyst has the formula PdAA'(L) m , wherein A is fluoborate, acetate or trifluoroacetate; A' is the same as A or a π-allyl radical; L is an amine, phosphine, arsine, stibine or amide ligand; and m is 0 or 2; and wherein said oxidizing agent is hydrogen peroxide or an organic hydroperoxide of the formula R 2 OOH, wherein R 2 is C 4-20 tertiary alkyl, aralkyl or alkylaryl.
Claim 3
Dependent Claim
101 words
A process according to claim 1, wherein the catalyst is one of palladium acetate, palladium trifluoracetate, palladium fluoborate or a complex of the formula: Pd(CH 3 CO 2 ) 2 [P(C 6 H 5 ) 3 ] 2 (CF 3 CO 2 ) 2 Pd[P(C 6 H 5 ) 3 ] 2 CF 3 CO 2 Pd--O--O--C(CH 3 ) 3 CH 3 CO 2 Pd--O--O--C(CH 3 ) 3 Pd(CH 3 CO 2 ) 2 (HMPT) 2 Pd(CF 3 CO 2 ) 2 (HMPT) 2 (CH 3 CO 2 )Pd-π-C 6 H 11 (CF 3 CO 2 )Pd-π-C 6 H 11 .
Claim 4
Dependent Claim
37 words
A process according to claim 2, wherein said oxidizing agent is hydrogen peroxide, the molar ratio H 2 O 2 /olefin being from 0.1 to 10, and the ratio by weight olefin/catalyst being from 10 to 10,000.
Claim 5
Dependent Claim
30 words
A process according to claim 3, wherein the molar ratio H 2 O 2 /olefin is from 1.5 to 5, the ratio by weight olefin/catalyst being from 100 to 1,000.
Claim 6
Dependent Claim
14 words
A process according to claim 4, wherein hydrogen peroxide is used in aqueous solution.
Claim 7
Dependent Claim
33 words
A process according to claim 5, wherein the olefin is further diluted in an organic solvent, said solvent being a chlorinated hydrocarbon, an ester, an aromatic solvent, an alcohol, or a monocarboxylic acid.
Claim 8
Dependent Claim
18 words
A process according to claim 6, wherein the solvent is chloroform, ethyl acetate, tert-butyl alcohol, or acetic acid.
Claim 9
Dependent Claim
30 words
A process according to claim 4, wherein the hydrogen peroxide and the olefin are dissolved in an organic solvent, said solvent being an alcohol, a cyclic ether, or an amide.
Claim 10
Dependent Claim
34 words
A process according to claim 2, wherein said oxidizing agent is tert-butyl or cumyl hydroperoxide, the molar ratio olefin/hydroperoxide being from 0.1 to 10 and the molar ratio olefin/catalyst being from 10 to 10,000.
Claim 11
Dependent Claim
25 words
A process according to claim 9, wherein the molar ratio olefin/hydroperoxide is from 0.1 to 0.5, the molar ratio olefin/catalyst being from 100 to 1,000.
Claim 12
Dependent Claim
26 words
A process according to claim 1, wherein in said catalyst, the π-allyl radical is a 1-methyl-3-ethyl-π-allyl radical; and L is one of triphenylphosphine, dimethylformamide and hexamethylphosphoramide.
Claim 13
Dependent Claim
17 words
A process according to claim 1, wherein said step is effected in the absence of chloride ions.
Claim 14
Dependent Claim
85 words
A process according to claim 1, wherein the catalyst is one of palladium acetate, palladium trifluoroacetate palladium fluoborate or a complex of the formula: Pd(CH 3 CO 2 ) 2 [P(C 6 H 5 ) 3 ] 2 (CF 3 CO 2 ) 2 Pd[P(C 6 H 5 ) 3 ] 2 Pd(CH 3 CO 2 ) 2 (HMPT) 2 Pd(CF 3 CO 2 ) 2 (HMPT) 2 (CH 3 CO 2 )Pd-π-C 6 H 11 (CF 3 CO 2 )Pd-π-C 6 H 11 .
Claim 15
Dependent Claim
20 words
A process according to claim 3, wherein said step is effected at a temperature of from 0° to 130° C.
Claim 16
Dependent Claim
20 words
A process according to claim 4, wherein said step is effected at a temperature of from 40° to 70° C.
Claim 17
Dependent Claim
20 words
A process according to claim 8, wherein said organic solvent is methanol, ethanol, isopropanol, tert.-butanol, tetrahydrofuran dioxane, dimethylformamide, or hexamethylphosphoramide.
Claim 18
Dependent Claim
20 words
A process according to claim 9, wherein said step is effected at a temperature of from 0° to 120° C.
Claim 19
Dependent Claim
20 words
A process according to claim 10, wherein said step is effected at a temperature of from 20° to 80° C.
Claim 20
Dependent Claim
30 words
A process according to claim 10, wherein said step is effected in the presence of a solvent, said solvent being a chlorinated hydrocarbon, an aromatic solvent, or a nitrogen-containing solvent.
Claim 21
Dependent Claim
18 words
A process according to claim 19, wherein said solvent is dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, xylene, or nitrobenzene.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-01-11 | 1985-07-13 | 1986-01-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-01-11 | 1989-07-13 | 1990-01-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-01-11 | 1993-07-13 | 1994-01-12 | $7700.00 | Window Closed / Lapsed |