US4216172A
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Preparation of cyclobutanones
Assignee: Bayer AG
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Filing: 1978-03-13
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Granted: 1980-08-05
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Expires: 1998-03-13
Abstract
Abstract A process for the preparation of a cyclobutanone of the formula ##STR1## in which R 1 to R 6 each independently is a hydrogen, halogen, cyano, alkoxy, alkoxycarbonyl, carboxamido, dialkylphosphono, alkyl, cycloalkyl, aryl, aralkyl or alkenyl radical, or two of them together with the carbon atom to which each is linked form a ring, comprising reacting an N,N-disubstituted carboxylic acid amide of the formula ##STR2## in which R 7 and R 8 each independently is an alkyl, cycloalkyl, alkenyl, aryl or aralkyl radical or together form a ring, with an inorganic acid halide, and then reacting the product with a tertiary amine, an olefin of the formula ##STR3## and a Lewis acid, and subsequently hydrolyzing the mass. Preferably isobutyric acid dimethylamide is employed as the carboxylic acid amide, phosgene is employed as the inorganic acid halide, triethylamine is employed as the tertiary amine and zinc chloride or titanium tetrachloride is employed as the Lewis acid. The products are known intermediates for insecticides.
Inventors
- 👤 Hans-Georg Heine
- 👤 Willy Hartmann
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 12:20
CPC Classifications
C; C07; C07C; C07C45/00; C07C45/51; C07C45/516
Claims Analysis
Total Claims: 20
Claim 1
Independent Claim
149 words
A process for the preparation of a cyclobutanone of the formula ##STR7## in which R 1 , R 2 and R 3 each independently is a hydrogen, halogen, cyano, alkoxy, alkoxycarbonyl, N,N-dialkylaminocarbonyl, alkyl, aryl, aralkyl or alkenyl radical, and R 4 , R 5 and R 6 each independently is hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, halogen, cyano, aralkyl or aryl, or any two of R 1 to R 6 together with the carbon atom to which each is linked for a ring, comprising reacting an N,N-disubstituted carboxylic acid amide of the formula ##STR8## in which R 7 and R 8 each independently is an alkyl, cycloalkyl, alkenyl, aryl or aralkyl radical or together form a ring, with an inorganic acid halide, then reacting the reaction mixture with a Lewis acid, then with a tertiary amine, and then with an olefin of the formula ##STR9## and subsequently hydrolyzing the mass.
Claim 2
Dependent Claim
149 words
A process for the preparation of a cyclobutanone of the formula ##STR7## in which R 1 , R 2 and R 3 each independently is a hydrogen, halogen, cyano, alkoxy, alkoxycarbonyl, N,N-dialkylaminocarbonyl, alkyl, aryl, aralkyl or alkenyl radical, and R 4 , R 5 and R 6 each independently is hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, halogen, cyano, aralkyl or aryl, or any two of R 1 to R 6 together with the carbon atom to which each is linked for a ring, comprising reacting an N,N-disubstituted carboxylic acid amide of the formula ##STR8## in which R 7 and R 8 each independently is an alkyl, cycloalkyl, alkenyl, aryl or aralkyl radical or together form a ring, with an inorganic acid halide, then reacting the reaction mixture with a Lewis acid, then with a tertiary amine, and then with an olefin of the formula ##STR9## and subsequently hydrolyzing the mass.
Claim 3
Dependent Claim
149 words
A process for the preparation of a cyclobutanone of the formula ##STR10## in which R 1 , R 2 and R 3 each independently is a hydrogen, halogen, cyano, alkoxy, alkoxycarbonyl, N,N-dialkylaminocarbonyl, alkyl, aryl, aralkyl or alkenyl radical, and R 4 , R 5 and R 6 each independently is hydrogen, alkyl haloalkyl, alkenyl, haloalkenyl, halogen, cyano, aralkyl or aryl, or any two of R 1 to R 6 together with the carbon atom to which each is linked form a ring. comprising reacting an N,N-disubstituted carboxylic acid amide of the formula ##STR11## in which R 7 and R 8 each independently is an alkyl, cycloalkyl, alkenyl, aryl or aralkyl radical or together form a ring, with an inorganic acid halide, then reacting the reaction mixture with an amine, then in the presence of a Lewis acid with an olefin of the formula ##STR12## and subsequently hydrolyzing the mass.
Claim 4
Dependent Claim
149 words
A process for the preparation of a cyclobutanone of the formula ##STR10## in which R 1 , R 2 and R 3 each independently is a hydrogen, halogen, cyano, alkoxy, alkoxycarbonyl, N,N-dialkylaminocarbonyl, alkyl, aryl, aralkyl or alkenyl radical, and R 4 , R 5 and R 6 each independently is hydrogen, alkyl haloalkyl, alkenyl, haloalkenyl, halogen, cyano, aralkyl or aryl, or any two of R 1 to R 6 together with the carbon atom to which each is linked form a ring. comprising reacting an N,N-disubstituted carboxylic acid amide of the formula ##STR11## in which R 7 and R 8 each independently is an alkyl, cycloalkyl, alkenyl, aryl or aralkyl radical or together form a ring, with an inorganic acid halide, then reacting the reaction mixture with an amine, then in the presence of a Lewis acid with an olefin of the formula ##STR12## and subsequently hydrolyzing the mass.
Claim 5
Dependent Claim
45 words
A process according to claim 1 or 2, in which the reaction product of the carboxylic acid amide and inorganic acid halide is first dehydrohalogenated with the tertiary amine, the Lewis acid is then added, the product is reacted with the olefin, and then hydrolyzed.
Claim 6
Dependent Claim
50 words
A process according to claim 1 or 2, in which the Lewis acid is first added to the reaction product of the carboxylic acid amide with the inorganic acid halide, the tertiary amine and thereafter the olefin are added and the mixture is allowed to react, and is then hydrolyzed.
Claim 7
Dependent Claim
15 words
A process according to claim 1 or 2, in which the amide is a dimethylamide.
Claim 8
Dependent Claim
59 words
A process according to claim 1 or 2, in which the amide is an amide of isobutyric acid, isovaleric acid, butyric acid, caproic acid, isovaleric acid, chloroacetic acid, phenylacetic acid, α-methylbutyric acid, adipic acid, adipic acid monoethyl ester, β,β-dimethylbutyric acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclobutylacetic acid, cyclopentanecarboxylic acid, cyclobutanecarboxylic acid or ω-chlorocaproic acid, 2-phenylbutyric acid, 2-phenylpropionic acid, 2-ethylbutyric acid.
Claim 9
Dependent Claim
17 words
A process according to claim 1 or 2, in which the inorganic acid halide is a chloride.
Claim 10
Dependent Claim
24 words
A process according to claim 1 or 2, in which the acid halide is thionyl chloride, phosgene, phosphorus pentachloride, thionyl bromide or phosphorus trichloride.
Claim 11
Dependent Claim
32 words
A process according to claim 1 or 2, in which the Lewis acid is zinc chloride, titanium tetrachloride, aluminum chloride, zinc bromide, iron (III) chloride, tin (II) chloride or tin (IV) chloride.
Claim 12
Dependent Claim
23 words
A process according to claim 1 or 2, in which the tertiary amine is trimethylamine, triethylamine, dimethylaniline, pyridine, quinoline, tributylamine, dicyclohexylmethylamine or dimethylbenzylamine.
Claim 13
Dependent Claim
15 words
A process according to claim 1 or 2, in which the olefin is a butadiene.
Claim 14
Dependent Claim
47 words
A process according to claim 1 or 2, in which isobutyric acid dimethylamide is employed as the carboxylic acid amide, phosgene is employed as the inorganic acid halide, triethylamine is employed as the tertiary amine and zinc chloride or titanium tetrachloride is employed as the Lewis acid.
Claim 15
Dependent Claim
46 words
A process according to claim 1 or 2, in which the reaction between the amide and the inorganic acid halide is effected at about -10° to +100° C. and about 1 to 1.3 moles of the inorganic acid halide are employed per mol of the amide.
Claim 16
Dependent Claim
37 words
A process according to claim 1 or 2, in which the dehydrohalogenation with the tertiary amine is effected at about -30° C. to +100° C. and the tertiary amine is employed in at least the stoichiometric amount.
Claim 17
Dependent Claim
24 words
A process according to claim 1 or 2, in which the reaction with the olefin is effected at about -10° C. to +80° C.
Claim 18
Dependent Claim
45 words
A process according to claim 1 or 2, in which the hydrolysis is effected by addition of water, aqueous acid or aqueous base and the cyclobutanonimonium salt immediately formed is converted to the corresponding cyclobutanone by heating the solution to about 20° to 100° C.
Claim 19
Dependent Claim
171 words
A process according to claim 6, in which the acid halide is thionyl chloride, phosgene, phosphorus pentachloride, thionyl bromide or phosphorus trichloride, the Lewis acid is zinc chloride, titanium tetrachloride, aluminum chloride, zinc bromide, iron (III) chloride, tin (II) chloride or tin (IV) chloride, the tertiary amine is trimethylamine, triethylamine, dimethylaniline, pyridine, quinoline, tributylamine, dicyclohexylmethylamine or dimethylbenzylamine and the olefin is a butadiene, the reaction between the amide and the inorganic acid halide is effected in an inert organic solvent at about 31 10° to +40° C. with about 1 to 1.3 times as many moles of inorganic acid halide as amide, the dehydrohalogenation is effected with at least the stoichiometric amount of the tertiary amine at about -20° to +40° C., the reaction with the olefin is effected at about 20° to 40° C., and the hydrolysis is effected by addition of water, aqueous acid or aqueous base and the cyclobutanonimonium salt immediately formed is converted to the corresponding cyclobutanone by heating the solution to about 40° to 60° C.
Claim 20
Dependent Claim
45 words
A process according to claim 17, in which isobutyric acid dimethylamide is employed as the carboxylic acid amide, phosgene is employed as the inorganic acid halide, triethylamine is employed as the tertiary amine and zinc chloride or titanium tetrachloride is employed as the Lewis acid.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-08-05 | 1984-02-04 | 1984-08-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-08-05 | 1988-02-04 | 1988-08-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-08-05 | 1992-02-04 | 1992-08-05 | $7700.00 | Window Closed / Lapsed |