US4423249A
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Preparation of halofluoroalkyl ethers
Assignee: Dow Chemical Co
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Filing: 1981-08-26
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Granted: 1983-12-27
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Expires: 2001-08-26
Abstract
Abstract Alkyl or aryl 1,1-difluoroalkyl ethers, e.g., 1,1,2-trifluoro-2-chloro-2-iodoethyl phenyl ether, are prepared by reacting an alkoxide or phenoxide with a 1,1-difluoro-1,2-dihaloethane (with the proviso that halo is not fluoro and at least one of the halo substituents is bromo or iodo) in an organic solvent at temperatures ranging from about -30° C. to about 100° C. These compounds may be dehalogenated with zinc to form the corresponding vinyl ethers. The reaction of halogen derivatives of fluorocarbons with nucleophiles is dramatically facilitated by a bromo or iodo substituent in the beta position.
Inventors
- 👤 William P. Carl
- 👤 Bobby R. Ezzell
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 18:58
CPC Classifications
C; C07; C07C; C07C41/00; C07C41/01; C07C41/16; C07C41/18; C07C41/24
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
162 words
A process comprising contacting in an aprotic solvent a metal hydrocarboxide with a halofluoroalkyl compound represented by formula I ##STR5## wherein X is selected from the group consisting of Cl, Br and I; X' is selected from the group consisting of Br and I; and Y and Z are independently selected from the group consisting of F, Cl, Br, I and R', wherein R' is selected from the group consisting aryl, alkyl including cycloalkyl, or substituted alkyl with the proviso that R' does not interfere with the reaction between the metal hydrocarboxide and the compound of formula I; under conditions sufficient to form an ether represented by formula II ##STR6## wherein Y and Z are as previously described; X" is selected form the group consisting of Br, I and H; and R is aryl or alkyl with the proviso that the carbon of said alkyl which is bonded to the oxygen atom shown in formula II must not have any fluorine substituent.
Claim 2
Dependent Claim
162 words
A process comprising contacting in an aprotic solvent a metal hydrocarboxide with a halofluoroalkyl compound represented by formula I ##STR5## wherein X is selected from the group consisting of Cl, Br and I; X' is selected from the group consisting of Br and I; and Y and Z are independently selected from the group consisting of F, Cl, Br, I and R', wherein R' is selected from the group consisting aryl, alkyl including cycloalkyl, or substituted alkyl with the proviso that R' does not interfere with the reaction between the metal hydrocarboxide and the compound of formula I; under conditions sufficient to form an ether represented by formula II ##STR6## wherein Y and Z are as previously described; X" is selected form the group consisting of Br, I and H; and R is aryl or alkyl with the proviso that the carbon of said alkyl which is bonded to the oxygen atom shown in formula II must not have any fluorine substituent.
Claim 3
Dependent Claim
33 words
The process of claim 1 wherein the metal hydrocarboxide is a metal salt of an alcohol or phenol, said metal salt being represented by formula III R--O--M III wherein M is a metal.
Claim 4
Dependent Claim
202 words
A process comprising contacting in an aprotic solvent and in a reaction system from which water or protic materials are substantially excluded a metal hydrocarboxide, which is a metal salt or an alcohol or phenol, said metal salt being represented by the formula R--O--M wherein M is a metal and R is aryl or alkyl with the proviso that the carbon of said alkyl which is bonded to the oxygen atom shown in formula II must not have any fluorine substituent, with a halofluoroalkyl compound represented by formula I ##STR7## wherein X is selected from the group consisting of Cl, Br and I; X' is selected from the group consisting of Br and I; and Y and Z are independently selected from the group consisting of F, Cl, Br, I and R', wherein R' is selected from the group consisting of aryl, alkyl including cycloalkyl, or substituted alkyl with the proviso that R' does not interfere with the reaction between the metal hydrocarboxide and the compound of formula I; under conditions sufficient to form an ether represented by formula II ##STR8## wherein R, Y and Z are as previously described, and X" is selected from the group consisting of Br, and I.
Claim 5
Dependent Claim
202 words
A process comprising contacting in an aprotic solvent and in a reaction system from which water or protic materials are substantially excluded a metal hydrocarboxide, which is a metal salt or an alcohol or phenol, said metal salt being represented by the formula R--O--M wherein M is a metal and R is aryl or alkyl with the proviso that the carbon of said alkyl which is bonded to the oxygen atom shown in formula II must not have any fluorine substituent, with a halofluoroalkyl compound represented by formula I ##STR7## wherein X is selected from the group consisting of Cl, Br and I; X' is selected from the group consisting of Br and I; and Y and Z are independently selected from the group consisting of F, Cl, Br, I and R', wherein R' is selected from the group consisting of aryl, alkyl including cycloalkyl, or substituted alkyl with the proviso that R' does not interfere with the reaction between the metal hydrocarboxide and the compound of formula I; under conditions sufficient to form an ether represented by formula II ##STR8## wherein R, Y and Z are as previously described, and X" is selected from the group consisting of Br, and I.
Claim 6
Dependent Claim
217 words
A process comprising contacting at a temperature between about -30° C. up to about 100° C. in the presence of an aprotic solvent and in a reaction system from which water or protic materials are substantially excluded, a metal hydrocarboxide, which is a metal salt of an alcohol or phenol, said metal salt being represented by the formula R--O--M wherein M is a metal and R is aryl or alkyl with the proviso that the carbon of said alkyl which is bonded to the oxygen atom shown in formula II must not have any fluorine substituent, with a halofluoroalkyl compound represented by formula I ##STR9## wherein X is selected from the group consisting of Cl, Br and I; X' is selected from the group consisting of Br and I; and Y and Z are independently selected from the group consisting of F, Cl, Br, I and R', wherein R' is selected from the group consisting of aryl, alkyl including cycloalkyl, or substituted alkyl with the proviso that R' does not interfere with the reaction between the metal hydrocarboxide and the compound of formula I; under conditions sufficient to form an ether represented by formula II ##STR10## wherein R, Y and Z are as previously described, and X" is selected from the group consisting of Br and I.
Claim 7
Dependent Claim
217 words
A process comprising contacting at a temperature between about -30° C. up to about 100° C. in the presence of an aprotic solvent and in a reaction system from which water or protic materials are substantially excluded, a metal hydrocarboxide, which is a metal salt of an alcohol or phenol, said metal salt being represented by the formula R--O--M wherein M is a metal and R is aryl or alkyl with the proviso that the carbon of said alkyl which is bonded to the oxygen atom shown in formula II must not have any fluorine substituent, with a halofluoroalkyl compound represented by formula I ##STR9## wherein X is selected from the group consisting of Cl, Br and I; X' is selected from the group consisting of Br and I; and Y and Z are independently selected from the group consisting of F, Cl, Br, I and R', wherein R' is selected from the group consisting of aryl, alkyl including cycloalkyl, or substituted alkyl with the proviso that R' does not interfere with the reaction between the metal hydrocarboxide and the compound of formula I; under conditions sufficient to form an ether represented by formula II ##STR10## wherein R, Y and Z are as previously described, and X" is selected from the group consisting of Br and I.
Claim 8
Dependent Claim
21 words
The process of claim 4 wherein Y and Z are independently selected from the group consisting of F, Cl and R'.
Claim 9
Dependent Claim
20 words
The process of claim 5 wherein M is selected from the group consisting of alkali metals and alkaline earth metals.
Claim 10
Dependent Claim
22 words
The process of claim 6 wherein the solvent is selected from the group consisting of glyme, diglyme, triglyme, tetraglyme, dimethylformamide and acetonitrile.
Claim 11
Dependent Claim
23 words
The process of claim 7 wherein the process is conducted at a temperature between about 0° C. and 25° C. at atmospheric pressure.
Claim 12
Dependent Claim
15 words
The process of claim 8 wherein R is benzene and M is sodium or potassium.
Claim 13
Dependent Claim
26 words
The process of claim 9 wherein Y and Z are F, and X and X' are independently selected from the group consisting of Br and I.
Claim 14
Dependent Claim
22 words
The process of claim 10 wherein X, X' and X" are Br, Y and Z are F, and the solvent is tetraglyme.
References Cited (Backward Citations)
US3926989A
Cited
US4377711A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-12-26 | 1987-06-27 | 1987-12-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-12-26 | 1991-06-27 | 1991-12-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-12-26 | 1995-06-27 | 1995-12-27 | $7700.00 | Window Closed / Lapsed |