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US4369145A
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Preparation of fluorobenzenesulfonyl fluorides by exchange fluorination
Assignee: Rhone Poulenc Industries SA
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Filing: 1980-12-16
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Granted: 1983-01-18
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Expires: 2000-12-16
Abstract
Abstract Fluorobenzenesulfonyl fluorides are prepared by chlorine/fluorine exchange fluorinating a chlorobenzenesulfonyl fluoride with an alkali metal fluoride, in a aprotic polar solvent and at a temperature ranging from about 100° C. to about 240° C.
Inventors
- 👤 Gerard Soula
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 09:38
CPC Classifications
C; C07; C07C; C07C309/00
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
173 words
A process for the preparation of a fluorobenzenesulfonyl fluoride having the structural formula: ##STR5## wherein n ranges from 1 to 5, m ranges from 1 to 3 and the fluorine atoms m are ortho- and/or para- to the --SO 2 F moiety, comprising exchange fluorinating a chlorobenzenesulfonyl fluoride having the structural formula: ##STR6## wherein n is as defined above, with an alkali metal fluoride, in an aprotic polar solvent and at a temperature ranging from about 100° C. to about 240° C., said exchange fluorination being conducted in the presence of at least one tertiary amine sequestering agent having the formula: N--CHR.sub.1 --CHR.sub.2 --O--CHR.sub.3 --CHR.sub.4 --O.sub.n --R.sub.5 ].sub.3 (III) where 0≦n≦10, R 1 , R 2 , R 3 and R 4 , which may be the same or different, are each hydrogen or lower alkyl, R 5 is alkyl or cycloalkyl having from 1 to 12 carbon atoms, phenyl, --C m H 2m --φ or C m H 2m+1 --φ--, with m ranging from about 1 to 12 and φ being phenyl.
Claim 2
Dependent Claim
173 words
A process for the preparation of a fluorobenzenesulfonyl fluoride having the structural formula: ##STR5## wherein n ranges from 1 to 5, m ranges from 1 to 3 and the fluorine atoms m are ortho- and/or para- to the --SO 2 F moiety, comprising exchange fluorinating a chlorobenzenesulfonyl fluoride having the structural formula: ##STR6## wherein n is as defined above, with an alkali metal fluoride, in an aprotic polar solvent and at a temperature ranging from about 100° C. to about 240° C., said exchange fluorination being conducted in the presence of at least one tertiary amine sequestering agent having the formula: N--CHR.sub.1 --CHR.sub.2 --O--CHR.sub.3 --CHR.sub.4 --O.sub.n --R.sub.5 ].sub.3 (III) where 0≦n≦10, R 1 , R 2 , R 3 and R 4 , which may be the same or different, are each hydrogen or lower alkyl, R 5 is alkyl or cycloalkyl having from 1 to 12 carbon atoms, phenyl, --C m H 2m --φ or C m H 2m+1 --φ--, with m ranging from about 1 to 12 and φ being phenyl.
Claim 3
Dependent Claim
29 words
The process as defined by claim 1, wherein the aprotic polar solvent is selected from the group consisting of dimethylformamide, n-methylpyrrolidone, sulfolane, dimethylsulfoxide, hexamethyl phosphoramide, acetonitrile, propionitrile and butyronitrile.
Claim 4
Dependent Claim
14 words
The process as defined by claim 2, wherein the aprotic polar solvent is sulfolane.
Claim 5
Dependent Claim
24 words
The process as defined by claim 1, said exchange fluorination being conducted at a temperature ranging from about 130° C. to about 220° C.
Claim 6
Dependent Claim
31 words
The process as defined by claim 1, the chlorobenzenesulfonyl fluoride (I) being present in an amount of from about 0.1 to about 6 moles per liter of the aprotic polar solvent.
Claim 7
Dependent Claim
31 words
The process as defined by claim 5, the chlorobenzenesulfonyl fluoride (I) being present in an amount of from about 0.2 to about 3 moles per liter of the aprotic polar solvent.
Claim 8
Dependent Claim
36 words
The process as defined by claim 1, wherein the sequestering agent (III), R 1 , R 2 , R 3 and R 4 , which may be the same or different, are each hydrogen or methyl.
Claim 9
Dependent Claim
13 words
The process as defined by claim 1, wherein the sequestering agent (III), 0≦n≦5.
Claim 10
Dependent Claim
23 words
The process as defined by claim 1, wherein the sequestering agent (III), R 5 is alkyl having from 1 to 4 carbon atoms.
Claim 11
Dependent Claim
49 words
The process as defined by claim 1, wherein the sequestering agent (III), R 1 , R 2 , R 3 and R 4 , which may be the same or different, are each hydrogen or methyl, 0≦n≦3, and R 5 is alkyl having from 1 to 4 carbon atoms.
Claim 12
Dependent Claim
24 words
The process as defined by claim 10, wherein the sequestering agent (III) is tris(3,6,9-trioxadecyl)amine having the formula: N--CH.sub.2 --CH.sub.2 --O--CH.sub.2 --CH.sub.2 --O--CH.sub.2 --CH.sub.2 --O--CH.sub.3).sub.3.
Claim 13
Dependent Claim
30 words
The process as defined by claim 1, the sequestering agent (III) being selected from the group consisting of tris(3-oxaheptyl)amine, tris(3,6-dioxaheptyl)amine, tris(3,6,9-trioxadecyl)amine, tris(3,6-dioxaoctyl)amine, tris(3,6,9-trioxaundecyl)amine, tris(3,6-dioxanonyl)amine, tris(3,6,9-trioxadodecyl)amine, tris(3,6-dioxadecyl)amine, tris(3,6,9-trioxatridecyl)amine, tris(3,6-dioxa-4-methylheptyl)amine, and tris(3,6-dioxa-2,4-dimethylheptyl)amine.
Claim 14
Dependent Claim
28 words
The process as defined by claim 1, wherein the alkali metal fluoride is selected from the group consisting of sodium fluoride, potassium fluoride, cesium fluoride and rubidium fluoride.
Claim 15
Dependent Claim
15 words
The process as defined by claim 13, wherein the alkali metal fluoride is potassium fluoride.
Claim 16
Dependent Claim
29 words
The process as defined by claim 1, the sequestering agent (III) being present in a molar ratio to the alkali metal fluoride ranging from about 0.001 to about 0.02.
Claim 17
Dependent Claim
29 words
The process as defined by claim 15, the sequestering agent (III) being present in a molar ratio to the alkali metal fluoride ranging from about 0.01 to about 0.1.
Claim 18
Dependent Claim
45 words
The process as defined by claim 1, the chlorobenzenesulfonyl fluoride (I) being selected from the group consisting of 4-chlorobenzenesulfonyl fluoride, 2-chlorobenzenesulfonyl fluoride, 2,5-dichlorobenzenesulfonyl fluoride, 2,4-dichlorobenzenesulfonyl fluoride, 3,4-dichlorobenzenesulfonyl fluoride, 2,6-dichlorobenzenesulfonyl fluoride, 2,3-dichlorobenzenesulfonyl fluoride, 2,4,5-trichlorobenzenesulfonyl fluoride, 2,3,4-trichlorobenzenesulfonyl fluoride, 2,4,6-trichlorobenzenesulfonyl fluoride, 2,3,5,6-tetrachlorobenzenesulfonyl fluoride, 2,3,4,5-tetrachlorobenzenesulfonyl fluoride and pentachlorobenzenesulfonyl fluoride.
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) | 1986-01-17 | 1986-07-19 | 1987-01-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-01-17 | 1990-07-19 | 1991-01-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-01-17 | 1994-07-19 | 1995-01-18 | $7700.00 | Window Closed / Lapsed |