U.S. patent number RE41,357 [Application Number 12/234,140] was granted by the patent office on 2010-05-25 for process for producing a fluorine atom-containing sulfonyl fluoride compound.
This patent grant is currently assigned to Asahi Glass Company, Limited. Invention is credited to Masahiro Ito, Isamu Kaneko, Takashi Okazoe, Daisuke Shirakawa, Kunio Watanabe.
United States Patent |
RE41,357 |
Ito , et al. |
May 25, 2010 |
Process for producing a fluorine atom-containing sulfonyl fluoride
compound
Abstract
The present invention provides a process whereby fluorine
atom-containing sulfonyl fluoride compound(s) useful as e.g.
materials for ion-exchange membranes, can be produced efficiently
and at low cost without structural limitations while solving the
difficulties in production. Namely, the present invention provides
a process which comprises reacting XSO.sub.2R.sup.A-E.sup.1 (1)
with R.sup.B-E.sup.2 (2) to form XSO.sub.2R.sup.A-E-R.sup.B (3),
then reacting (3) with fluorine in a liquid phase to form
FSO.sub.2R.sup.AF-E.sup.F-R.sup.BF (4), and further, decomposing
the compound to obtain FSO.sub.2R.sup.AF-E.sup.F1 (5), wherein
R.sup.A is a bivalent organic group, E.sup.1 is a monovalent
reactive group, R.sup.B is a monovalent organic group, E.sup.2 is a
monovalent reactive group which is reactive with E.sup.1, E is a
bivalent connecting group formed by the reaction of E.sup.1 with
E.sup.2, R.sup.AF is a bivalent organic group formed by the
fluorination of R.sup.A, etc., R.sup.BF is the same group as
R.sup.B, etc., E.sup.F is a bivalent connecting group formed by the
fluorination of E, etc., E.sup.F1 is a monovalent group formed by
the decomposition of E.sup.F, and X is a halogen atom.
Inventors: |
Ito; Masahiro (Kanagawa,
JP), Watanabe; Kunio (Kanagawa, JP),
Okazoe; Takashi (Kanagawa, JP), Kaneko; Isamu
(Kanagawa, JP), Shirakawa; Daisuke (Kanagawa,
JP) |
Assignee: |
Asahi Glass Company, Limited
(Tokyo, JP)
|
Family
ID: |
18832884 |
Appl.
No.: |
12/234,140 |
Filed: |
September 19, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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11812533 |
Jun 19, 2007 |
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10442227 |
May 21, 2003 |
6790982 |
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PCT/JP01/10407 |
Nov 28, 2001 |
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Reissue of: |
10808274 |
Mar 25, 2004 |
07105697 |
Sep 12, 2006 |
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Foreign Application Priority Data
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Nov 28, 2000 [JP] |
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2000-361450 |
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Current U.S.
Class: |
560/184; 562/825;
562/824 |
Current CPC
Class: |
C07C
303/22 (20130101); C07C 51/60 (20130101); C07C
309/82 (20130101); C07C 51/60 (20130101); C07C
59/135 (20130101); C07C 303/22 (20130101); C07C
309/82 (20130101) |
Current International
Class: |
C07C
69/66 (20060101); C07C 309/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
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|
|
0 062 430 |
|
Oct 1982 |
|
EP |
|
0 265 052 |
|
Apr 1988 |
|
EP |
|
52-10221 |
|
Jan 1977 |
|
JP |
|
10-116627 |
|
May 1998 |
|
JP |
|
2006-335699 |
|
Dec 2006 |
|
JP |
|
90/06296 |
|
Jun 1990 |
|
WO |
|
00/56694 |
|
Sep 2000 |
|
WO |
|
01/46107 |
|
Jun 2001 |
|
WO |
|
02/10107 |
|
Feb 2002 |
|
WO |
|
Other References
Murata, K., et al., J. Am. Chem. Soc., vol. 120, No. 28, pp.
7117-7118, "The Thermal Decomposition of Perfluoroesters," 1998.
cited by other .
Tari, I, et al., J. Org. Chem., vol. 45, No. 7, pp. 1214-1217,
"Synthesis of Halogenated Esters of Fluorinated Carboxylic Acids by
the Regio-and Streospecific Addition of Acyl Hypochlorites to
Olefins," 1980. cited by other .
English Abstracts of WO 01/16085, Mar. 8, 2001. cited by other
.
English Abstracts of WO 01/46093, Jun. 28, 2001. cited by other
.
English Abstracts of WO 01/94285, Dec. 13, 2001. cited by other
.
English Abstracts of WO 02/04397, Jan. 17, 2002. cited by other
.
English Abstracts of WO 02/10106, Feb. 7, 2002. cited by other
.
English Abstracts of WO 02/10108, Feb. 7, 2002. cited by other
.
English Abstracts of WO 02/18314, Mar. 7, 2002. cited by other
.
English Abstracts of WO 02/20445, Mar. 14, 2002. cited by other
.
English Abstracts of WO 02/26679, Apr. 4, 2002. cited by other
.
English Abstracts of WO 02/26682, Apr. 4, 2002. cited by other
.
English Abstracts of WO 02/26686, Apr. 4, 2002. cited by other
.
English Abstracts of WO 02/26687, Apr. 4, 2002. cited by other
.
English Abstracts of WO 02/26688, Apr. 4, 2002. cited by other
.
English Abstracts of WO 02/26689, Apr. 4, 2002. cited by other
.
English Abstracts of WO 02/26693, Apr. 4, 2002. cited by other
.
James J. Krutak, et al., "Chemistry of Ethenesulfonyl Fluoride.
Flurosulfonylethlation of Organic Compounds," J. Org. Chem., vol.
44, No. 22, 1979, pp. 3847-3858. cited by other .
Methods of Organic Chemistry, 4, vol. 10b, Part 1, pp. 703. cited
by examiner .
U.S. Appl. No. 10/808,274, filed Mar. 25, 2004, Ito et al. cited by
examiner .
U.S. Appl. No. 10/830,140, filed Apr. 23, 2004, Okazoe et al. cited
by examiner .
U.S. Appl. No. 10/421,924, filed Apr. 24, 2003, Okazoe et al. cited
by examiner .
U.S. Appl. No. 11/318,978, filed Dec. 28, 2005, Murata et al. cited
by examiner .
U.S. Appl. No. 11/322,396, filed Jan. 3, 2006, Murata et al. cited
by examiner.
|
Primary Examiner: Zucker; Paul A
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier
& Neustadt, L.L.P.
Parent Case Text
CROSS-RELATED APPLICATIONS
.Iadd.More than one reissue application has been filed for the
reissue of U.S. Pat. No. 7,105,697. The reissue applications are
U.S. application Ser. Nos. 11/812,533 (the parent reissue
application), U.S. 12/234,109, and U.S. 12/234,140(the present
application). U.S. Ser. No. 12/234,109 and U.S. 12/234,140 are
divisional reissues of U.S. Pat. No. 7,105,697 and were filed based
on U.S. Ser. No. 11/812,533, the parent broadening reissue
application of U.S. Pat. No. 7,105,697. .Iaddend.
This application is a Divisional Application of 10/442,227, filed
May 21, 2003, now U.S. Pat. No. 6,790,982 which is a continuation
of PCT/JP01/10407, filed on Nov. 28, 2001.
Claims
What is claimed is:
.[.1. A process for producing a fluorine atom-containing sulfonyl
fluoride compound, which comprises reacting a compound of the
following formula (1) with a compound of the following formula (2)
to form a compound of the formula (3), then, reacting the compound
of the formula (3) with fluorine in a liquid phase to form a
compound of the following formula (4), and further, decomposing the
compound of the formula (4) to obtain a compound of the following
formula (5): XSO.sub.2R.sup.A-E.sup.1 (1) R.sup.B-E.sup.2 (2)
XSO.sub.2R.sup.A-E-R.sup.B (3) FSO.sub.2R.sup.AF-E.sup.F-R.sup.BF
(4) FSO.sub.2R.sup.AF-E.sup.F1 (5) wherein R.sup.A is a bivalent
organic group, E.sup.1 is a monovalent reactive group, R.sup.B is a
monovalent organic group, E.sup.2 is a monovalent reactive group
which is reactive with E.sup.1, E is a bivalent connecting group
formed by the reaction of E.sup.1, with E.sup.2, R.sup.AF is the
same group as R.sup.A, or a bivalent organic group formed by the
fluorination of R.sup.A, R.sup.BF is the same group as R.sup.B, or
a monovalent organic group formed by the fluorination of R.sup.B,
E.sup.F is the same group as E, or a bivalent connecting group
formed by the fluorination of E, E.sup.F1 is a monovalent group
formed by the decomposition of E.sup.F, and X is a halogen atom,
provided that at least one of R.sup.A, R.sup.B and E is a group
which can be fluorinated, and at least one of R.sup.AF, R.sup.BF
and E.sup.F is a group formed by the fluorination of R.sup.A,
R.sup.B and E, respectively..].
.[.2. The process for producing a fluorine atom-containing sulfonyl
fluoride compound according to claim 1, wherein X is a fluorine
atom..].
.[.3. The process for-producing a fluorine atom-containing sulfonyl
fluoride compound according to claim 1, wherein the fluorine
content in the compound of the formula (3) is at least 30 mass
%..].
.[.4. The process for producing a fluorine atom-containing sulfonyl
fluoride compound according to claim 1, wherein the molecular
weight of the compound of the formula (3) is from 200 to
1,000..].
.[.5. The process for producing a fluorine atom-containing sulfonyl
fluoride compound according to claim 1, wherein R.sup.AF is a
bivalent organic group selected from the group consisting of a
perfluoro bivalent saturated hydrocarbon group, a
perfluoro(partially halogeno bivalent saturated hydrocarbon) group,
a perfluoro(hetero atom-containing bivalent saturated hydrocarbon)
group, and a perfluoro(partially halogeno(hetero atom-containing
bivalent saturated hydrocarbon)) group, and R.sup.BF is a
monovalent organic group selected from the group consisting of a
perfluoro monovalent saturated hydrocarbon group, a
perfluoro(partially halogeno monovalent saturated hydrocarbon)
group, a perfluoro(hetero atom-containing monovalent saturated
hydrocarbon) group, and a perfluoro(partially halogeno(hetero
atom-containing monovalent saturated hydrocarbon)) group..].
.[.6. The process for producing a fluorine atom-containing sulfonyl
fluoride compound according to claim 1, wherein the compound of the
formula (4) is decomposed to obtain not only the compound of the
formula (5), but also a compound of the following formula (6):
R.sup.BF-E.sup.F2 (6) wherein E.sup.F2 is a monovalent group formed
by the decomposition of E.sup.F, which may be the same as or
different from E.sup.F1, and R.sup.BF is as defined above..].
.[.7. The process for producing a fluorine atom-containing sulfonyl
fluoride compound according to claim 1, wherein the compound of the
formula (1) is a compound of the following formula (1a), the
compound of the formula (2) is a compound of the following formula
(2a), the compound of the formula (3) is a compound of the
following formula (3a), the compound of the formula (4) is a
compound of the following formula (4a), and the compound of the
formula (5) is a compound of the following formula (5a):
XSO.sub.2R.sup.A--CH.sub.2OH (1a) R.sup.B--COY (2a)
XSO.sub.2R.sup.A--CH.sub.2OCO--R.sup.B (3a)
FSO.sub.2R.sup.AF--CF.sub.2OCO--R.sup.BF (4a)
FSO.sub.2R.sup.AF--COF (5a) wherein Y is a halogen atom which is
the same as or different from X, and R.sup.A, R.sup.B, R.sup.AF and
R.sup.BF are as defined above..].
.[.8. The process for producing a fluorine atom-containing sulfonyl
fluoride compound according to claim 7, wherein the compound of the
formula (4a) is decomposed to obtain not only the compound of the
formula (5a), but also a compound of the following formula (6a):
R.sup.BF--COF (6a) wherein R.sup.BF is as defined above..].
.[.9. The process for producing a fluorine atom-containing sulfonyl
fluoride compound according to claim 8, wherein the compound of the
formula (2a) has the same structure as the compound of the formula
(6a), and at least a part of the compound of the formula (6a)
obtained from the reaction product obtained by the decomposition of
the compound of the formula (4a), is used as at least a part of the
compound of the formula (2a) to react with the compound of the
formula (1a), to continuously obtain the compound of the formula
(5a)..].
.Iadd.10. A compound of the following formula (3a):
XSO.sub.2R.sup.A--CH.sub.2OC(O)--R.sup.BF (3a) wherein R.sup.A is a
saturated hydrocarbon group, a partially halogeno bivalent
saturated hydrocarbon group, a hetero atom-containing bivalent
saturated hydrocarbon group, and a partially halogeno(hetero
atom-containing bivalent saturated hydrocarbon)) group; R.sup.BF is
a monovalent organic group selected from the group consisting of a
perfluoro monovalent saturated hydrocarbon group, a
perfluoro(partially halogeno monovalent saturated hydrocarbon)
group, a perfluoro(hetero atom-containing monovalent saturated
hydrocarbon) group, and a perfluoro(partially halogeno(hetero
atom-containing monovalent saturated hydrocarbon)) group; and X is
Cl or F, and wherein said hetero atom-containing group, monovalent
or divalent, is group containing a hetero atom selected from the
group consisting of oxygen atom, nitrogen atom, and sulfur atom, or
said hetero atom-containing group, monovalent or divalent, is
--C--C(.dbd.C)--C-- or --C--SO.sub.2--C--. .Iaddend.
.Iadd.11. The compound according to claim 10, wherein R.sup.A is
C.sub.1-10 alkylene group or C.sub.1-20 etheric oxygen
atom-containing alkylene group. .Iaddend.
.Iadd.12. The compound according to claim 10, wherein R.sup.BF is a
perfluoro monovalent saturated hydrocarbon group or a
perfluoro(hetero atom-containing monovalent saturated hydrocarbon)
group. .Iaddend.
.Iadd.13. The compound according to claim 10, wherein X is a
fluorine atom. .Iaddend.
Description
TECHNICAL FIELD
The present invention relates to a process for producing fluorine
atom-containing sulfonyl fluoride compounds useful as e.g.
materials for ion-exchange resins, and novel chemical substances
useful as intermediates in the process.
BACKGROUND ART
Fluorine atom-containing sulfonyl fluoride compounds having a
fluoroformyl group (such as the following compound (i)) are useful
as materials for ion-exchange resins. Heretofore, compounds having
a fluoroformyl group have been synthesized by a process which
comprises reacting perfluoroalkylene oxides to a cyclic compound
obtainable by the reaction of tetrafluoroethylene with sulfur
trioxide (SO.sub.3). For example, the following compound (i) can be
obtained by reacting hexafluoropropylene oxide (HFPO) to the
above-mentioned cyclic compound, as shown by the following formula.
##STR00001##
However, the conventional synthetic process was a disadvantageous
process for practical industrial application, since a due care is
required for handling SO.sub.3. Further, reduction of the price can
hardly be accomplished because the difficulty in synthesis is high.
In addition, the obtainable compound (i) is limited to a compound
having a side chain (--CF.sub.3), whereby there has been a problem
from the viewpoint of the membrane characteristics of the
ion-exchange membrane prepared from a derivative of the compound
(i).
The present invention has been made for the purpose of solving the
problems of the prior art and provides a process which solves the
difficulty in production and whereby fluorosulfonyl fluoride
compounds having various molecular structures can be produced
efficiently and at low costs.
DISCLOSURE OF THE INVENTION
The present inventors have invented a process which comprises
reacting a sulfonyl halide compound having a certain specific
structure with fluorine in a liquid phase, followed by
decomposition of the product, and have found it possible to thereby
carry out a process for producing the desired fluorine
atom-containing sulfonyl fluoride compounds.
Namely, the present invention provides a process for producing
fluorine atom-containing sulfonyl fluoride compounds, which
comprises reacting a compound of the following formula (1) with a
compound of the following formula (2) to form a compound of the
formula (3), then, reacting the compound of the formula (3) with
fluorine in a liquid phase to form a compound of the following
formula (4), and further, decomposing the compound of the formula
(4) to obtain a compound of the following formula (5):
XSO.sub.2R.sup.A-E.sup.1 (1) R.sup.B-E.sup.2 (2)
XSO.sub.2R.sup.A-E-R.sup.B (3) FSO.sub.2R.sup.AF-E.sup.F-R.sup.BF
(4) FSO.sub.2R.sup.AF-E.sup.F1 (5) wherein R.sup.A is a bivalent
organic group, E.sup.1 is a monovalent reactive group, R.sup.B is a
monovalent organic group, E.sup.2 is a monovalent reactive group
which is reactive with E.sup.1, E is a bivalent connecting group
formed by the reaction of E.sup.1 with E.sup.2, R.sup.AF is the
same group as R.sup.A, or a bivalent organic group formed by the
fluorination of R.sup.A, R.sup.BF is the same group as R.sup.B, or
a monovalent organic group formed by the fluorination of R.sup.B,
E.sup.F is the same group as E, or a bivalent connecting group
formed by the fluorination of E, E.sup.F1 is a monovalent group
formed by the decomposition of E.sup.F and X is a halogen atom,
provided that at least one of R.sup.A, R.sup.B and E is a group
which can be fluorinated, and at least one of R.sup.AF, R.sup.BF
and E.sup.F is a group formed by the fluorination of R.sup.A,
R.sup.B and E, respectively.
Further, the present invention provides the above process, wherein
the compound of the formula (4) is decomposed to obtain not only
the compound of the formula (5), but also a compound of the
following formula (6): R.sup.BF-E.sup.F2 (6) wherein E.sup.F2 is a
monovalent group formed by the decomposition of E.sup.F, which may
be the same as or different from E.sup.F1, and R.sup.BF is as
defined above.
Further, the present invention provides the above process, wherein
the compound of the formula (1) is a compound of the following
formula (1a), the compound of the formula (2) is a compound of the
following formula (2a), the compound of the formula (3) is a
compound of the following formula (3a), the compound of the formula
(4) is a compound of the following formula (4a), and the compound
of the formula (5a) is a compound of the following formula (5a):
XSO.sub.2R.sup.A--CH.sub.2OH (1a) R.sup.B--COY (2a)
XSO.sub.2R.sup.A--CH.sub.2OCO--R.sup.B (3a)
FSO.sub.2R.sup.AF--CF.sub.2OCO--R.sup.BF (4a)
FSO.sub.2R.sup.AF--COF (5a) wherein Y is a halogen atom which is
the same as or different from X, and R.sup.A, R.sup.B, R.sup.AF and
R.sup.BF are as defined above.
Further, the present invention provides the above process, wherein
the compound of the formula (4a) is decomposed to obtain not only
the compound of the formula (5a), but also a compound of the
following formula (6a): R.sup.BF--COF (6a) wherein R.sup.BF is as
defined above.
Further, the present invention provides the above process, wherein
the compound of the formula (2a) has the same structure as the
compound of the formula (6a), and at least a part of the compound
of the formula (6a) obtained from the reaction product obtained by
the decomposition of the compound of the formula (4a), is used as
at least a part of the compound of the formula (2a) to react with
the compound of the formula (1a), to continuously obtain the
compound of the formula (5a).
Further, the present invention provides a compound of the following
formula (I) or a compound of the following formula (II):
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF(CF.sub.3)
OCF.sub.2CF.sub.2CF.sub.3 (I)
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3 (II)
BEST MODE FOR CARRYING OUT THE INVENTION
In this specification, the compound of the formula (I) will be
referred to as "the compound 1". The, compounds of other formulae
will be referred to in the same manner.
In the present invention, R.sup.A is a bivalent organic group,
R.sup.B is a monovalent organic group, R.sup.AF is the same group
as R.sup.A or a bivalent organic group formed by the fluorination
of R.sup.A, and R.sup.BF is the same group as R.sup.B or a
monovalent organic group formed by the fluorination of R.sup.B.
In this specification, "an organic group" means a group containing
at least one carbon atom. A "halogeno" group means a group having
at least one hydrogen atom bonded to a carbon atom substituted by a
halogen atom. A "perhalogeno" group means a group having
substantially all of hydrogen atoms bonded to carbon atoms
substituted by halogen atoms. A "partially halogeno" group means a
group having some of hydrogen atoms bonded to carbon atoms
substituted by halogen atoms. In a case where halogen atoms are
specified to be fluorine atoms, they may be referred to as
"perfluoro", "partially fluoro", etc. The same applies with respect
to other halogen atoms. A "perhalogeno" group and a "partially
halogeno" group may be ones containing one type of halogen atoms or
two or more types of halogen atoms.
A "perhalogeno" group is preferably a group having all of hydrogen
atoms bonded to carbon atoms substituted by halogen atoms. However,
even when unsubstituted hydrogen atoms remain, so long as-the
nature as a group is substantially equal to a "perhalogeno" group,
such a group will be included in the concept of the "perhalogeno"
group in the present invention.
In the present invention, the "fluorination" means to introduce
fluorine atoms into a compound. Specifically, it means that an
organic group is converted to a perfluoro group or a partially
fluoro group. The fluorination is carried out usually by
substituting fluorine atoms for hydrogen atoms bonded to carbon
atoms. In a case where an unsaturated bond is contained in an
organic group, fluorine atoms will be added to the unsaturated bond
by the fluorination.
In the present invention, a "saturated" group means a group wherein
carbon-carbon bonds are solely single bonds, and so long as
carbon-carbon bonds are single bonds, an unsaturated bond such as
C.dbd.O or SO.sub.2 may, for example, be present in the group.
In the present invention, a "hetero atom-containing" group means a
group containing hetero atom(s) such as oxygen atom(s), nitrogen
atom(s) or sulfur atom(s), or hetero atom group(s) such as
--C--C(.dbd.O)--C-- or --C--SO.sub.2--C--. The hetero
atom-containing group is preferred, if it is a group which is not
easily decomposed by heating. From this viewpoint, the hetero
atom-containing group is preferably a group containing etheric
oxygen atoms(s) (--O--) or .dbd.O, particularly preferably a group
containing etheric oxygen atom(s).
R.sup.A (the bivalent organic group) is preferably a bivalent
hydrocarbon group, a halogeno bivalent hydrocarbon group, a hetero
atom-containing bivalent hydrocarbon group, a halogeno(hetero
atom-containing bivalent hydrocarbon) group. The bivalent
hydrocarbon group may be a bivalent aliphatic hydrocarbon group, a
bivalent aromatic hydrocarbon group or a bivalent alicyclic
hydrocarbon group, and preferred is a bivalent aliphatic
hydrocarbon group. In the bivalent aliphatic hydrocarbon group,
single bond(s), double bond(s) or triple bond(s) may be present (or
coexistent), as carbon-carbon bond(s). Further, the bivalent
aliphatic hydrocarbon group may be of any structure such as a
linear structure, a branched structure, a cyclic structure or a
structure partially having a cyclic structure.
R.sup.A is preferably a bivalent organic group having hydrogen
atoms bonded to carbon atoms. It is more preferably a bivalent
saturated hydrocarbon group, a partially halogeno bivalent
saturated hydrocarbon group, a hetero atom-containing bivalent
saturated hydrocarbon group or a partially halogeno(hetero
atom-containing bivalent saturated hydrocarbon) group, particularly
preferably a bivalent saturated hydrocarbon group, or a hetero
atom-containing bivalent saturated hydrocarbon group.
When R.sup.A is a bivalent saturated hydrocarbon group, an alkylene
group, a cycloalkylene group or a cycloalkylalkylene group may be
mentioned. As the alkylene group, a C.sub.1-10 alkylene group is
preferred. As the cycloalkylene group, a 3- to 6-membered
cycloalkylene group or a group having at least one hydrogen atom of
such a cycloalkylene group substituted by an alkyl group, is
preferred. As the cycloalkylalkylene group, one hydrogen atom of a
C.sub.1-3 alkyl group substituted by the above-mentioned cycloalkyl
group, is preferred.
When R.sup.A is a partially halogeno bivalent saturated hydrocarbon
group, it may be a group having the above-mentioned bivalent
saturated hydrocarbon group partially halogenated. The partially
halogeno bivalent saturated hydrocarbon group may be of a linear
structure or a branched structure, or may partially have a cyclic
structure, and a partially fluoroalkylene group or a partially
fluoro(partially chloroalkylene) group is preferred. The carbon
number of the partially halogeno bivalent saturated hydrocarbon
group is preferably from 1 to 20.
When R.sup.A is a hetero atom-containing bivalent saturated
hydrocarbon group, it may be a group having a bivalent hetero atom
or a bivalent hetero atom group inserted between the carbon-carbon
atoms in the above bivalent saturated hydrocarbon group, or a group
having hetero atoms bonded to carbon atoms of the above-mentioned
bivalent saturated hydrocarbon group, or a group having bivalent
hetero atoms or bivalent hetero atom groups bonded to carbon atoms
at the bond terminals of the above bivalent saturated hydrocarbon
group. The hetero atom-containing bivalent saturated hydrocarbon
group is preferably a C.sub.1-20 group. From the usefulness of the
compounds, an etheric oxygen atom-containing bivalent saturated
hydrocarbon group is preferred, and an etheric oxygen
atom-containing alkylene group is particularly preferred.
When R.sup.A is a partially halogeno(hetero atom-containing
bivalent saturated hydrocarbon) group, it may be a group having the
above-mentioned hetero atom-containing bivalent saturated
hydrocarbon group partially halogenated. The partially
halogeno(hetero atom-containing bivalent saturated hydrocarbon)
group may be of a linear structure or a branched structure, or may
have a partially cyclic structure. A partially fluoro(hetero
atom-containing bivalent hydrocarbon) group or a partially
fluoro(partially chloro(hetero atom-containing bivalent
hydrocarbon)) group is preferred. The carbon number of the
partially halogeno(hetero atom-containing bivalent saturated
hydrocarbon) group is preferably from 1 to 20.
R.sup.B (the monovalent organic group) is preferably a monovalent
hydrocarbon group, a halogeno monovalent hydrocarbon group, a
hetero atom-containing monovalent hydrocarbon group, or a
halogeno(hetero atom-containing monovalent hydrocarbon) group. The
monovalent hydrocarbon group may be a monovalent aliphatic
hydrocarbon group, a monovalent aromatic hydrocarbon group, or a
monovalent alicyclic hydrocarbon group, and a monovalent aliphatic
hydrocarbon group is preferred. In the monovalent aliphatic
hydrocarbon group, a single bond, a double bond, or a triple bond
may be present (or coexistent) as a carbon-carbon bond. Further,
the monovalent aliphatic hydrocarbon group may be of a linear
structure, a branched structure, a cyclic structure, or a structure
partially having a cyclic structure.
R.sup.B is preferably a saturated group. When R.sup.B is a
monovalent saturated hydrocarbon group, it may be an alkyl group, a
cycloalkyl group, or a cycloalkylalkyl group. The alkyl group is
preferably a C.sub.1-10 alkyl group. The cycloalkyl group is
preferably a 3- to 6-membered cycloalkyl group or a group having at
least one hydrogen atom of such a cycloalkyl group substituted by
an alkyl group. The cycloalkylalkyl group is preferably a group
having one of hydrogen atoms of a C.sub.1-3 alkyl group substituted
by the above cycloalkyl group.
When R.sup.B is a partially halogeno monovalent saturated
hydrocarbon group, it may be a group having the above monovalent
saturated hydrocarbon group partially halogenated. The partially
halogeno monovalent saturated hydrocarbon group may be of a linear
structure or a branched structure, or may have a partially cyclic
structure, and a partially fluoroalkyl group or a partially
fluoro(partially chloro alkyl) group is preferred. The carbon
number of the partially halogeno monovalent hydrocarbon group is
preferably from 1 to 20.
When R.sup.B is a hetero atom-containing monovalent saturated
hydrocarbon group, it is preferably a group having a bivalent
hetero atom or a bivalent hetero atom group inserted between the
carbon-carbon atoms in the above monovalent saturated hydrocarbon
group, or a group having a hetero atom bonded to a carbon atom in
the above monovalent saturated hydrocarbon group, or a group having
a bivalent hetero atom or a bivalent hetero atom group bonded to a
carbon atom at the bond terminal of the above monovalent saturated
hydrocarbon group. The hetero atom-containing monovalent saturated
hydrocarbon group is preferably a group having a carbon number of
from 1 to 20. In view of the availability, the production
efficiency and the usefulness of the formed product, an etheric
oxygen atom-containing alkyl group is preferred, and an alkoxyalkyl
group or an alkoxyl group is particularly preferred.
When R.sup.B is a partially halgeno(hetero atom-containing
monovalent hydrocarbon) group, it may be a group having the above
hetero atom-containing monovalent saturated hydrocarbon group
partially halogenated. The partially halogeno(hetero
atom-containing monovalent saturated hydrocarbon) group may be of a
linear structure or a branched structure, or may partially have a
cyclic structure, and a partially fluoro(hetero atom-containing
monovalent hydrocarbon) group or a partially fluoro(partially
chloro(hetero atom-containing monovalent hydrocarbon)) group is
preferred. The carbon number of the partially halgeno(hetero
atom-containing monovalent saturated hydrocarbon) group is
preferably from 1 to 20.
R.sup.AF is the same group as R.sup.A, or a bivalent organic group
formed by the fluorination of R.sup.A. R.sup.AF is the same group
as R.sup.A in a case where R.sup.A is a group which can not be
fluorinated, or in a case where R.sup.A is not fluorinated, even if
it is a group which can be fluorinated. For example, in a case
where R.sup.A is a perhalogeno bivalent hydrocarbon group or a
perhalogeno(hetero atom-containing bivalent hydrocarbon) group, the
halogen atoms in such a group will not be changed even if reacted
with fluorine in a liquid phase, and therefore, R.sup.AF will be
the same group as R.sup.A. R.sup.BF is the same group as R.sup.B,
or a group formed by the fluorination of R.sup.B. R.sup.BF is the
same group as R.sup.B in a case where R.sup.B is a group which can
not be fluorinated, or in a case where R.sup.B is not fluorinated
even if it is a group which can be fluorinated. For example, in a
case where R.sup.B is a perhalogeno monovalent hydrocarbon group or
a perhalogeno(hetero atom-containing monovalent hydrocarbon) group,
the halogeno atoms in such a group will not be changed even if
reacted with fluorine in a liquid phase, and therefore R.sup.BF
will be the same group as R.sup.B.
R.sup.AF is preferably a perfluoro bivalent saturated hydrocarbon
group, a perfluoro(partially halogeno bivalent saturated
hydrocarbon) group, a perfluoro(hetero atom-containing bivalent
saturated hydrocarbon) group, or a perfluoro(partially
halogeno(hetero atom-containing bivalent saturated hydrocarbon))
group. R.sup.A in such a case is preferably a bivalent saturated
hydrocarbon group, a partially halogeno bivalent saturated
hydrocarbon group, a hetero atom-containing bivalent saturated
hydrocarbon) group, or a partially halogeno(hetero atom-containing
bivalent saturated hydrocarbon) group, which has the same number of
carbon atoms as R.sup.AF and has a carbon skeleton structure
corresponding to R.sup.AF. Such a group may be a saturated group,
or a group containing at least one carbon-carbon double bond and/or
triple bond (hereinafter referred to simply as "an unsaturated
group").
Further, R.sup.BF is preferably a perfluoro monovalent saturated
hydrocarbon group, a perfluoro(partially halogeno monovalent
saturated hydrocarbon) group, a perfluoro(hetero atom-containing
monovalent saturated hydrocarbon) group, or a perfluoro(partially
halogeno(hetero atom-containing monovalent saturated hydrocarbon))
group. R.sup.B is not particularly limited so long as it can be
converted to R.sup.BF by a fluorination reaction, and it is
particularly preferably the same group as R.sup.BF, since the
after-described fluorination reaction can thereby be carried out
easily, and a continuous process can be carried out. Namely,
R.sup.B is preferably a perfluoro monovalent saturated hydrocarbon
group, a perfluoro(partially halogeno monovalent saturated
hydrocarbon) group, a perfluoro(hetero atom-containing monovalent
saturated hydrocarbon) group, or a perfluoro(partially
halogeno(hetero atom-containing monovalent saturated hydrocarbon))
group.
E.sup.1 is a monovalent reactive group, E.sup.2 is a monovalent
reactive group which is reactive with E.sup.1, E is a bivalent
connecting group formed by the reaction of E.sup.1 with E.sup.2,
E.sup.F is the same group as E, or a bivalent connecting group
formed by the fluorination of E, and E.sup.F1 is a monovalent group
formed by the decomposition of E.sup.F. As a case where E.sup.F is
the same group as E, a case may, for example, be mentioned where E
is a perhalogeno bivalent connecting group. E.sup.2 is preferably a
group which is readily reactive with E.sup.1 rather than with
XSO.sub.2-- in the compound 1. Particularly preferably, E.sup.2 is
a group capable of reacting with E.sup.1 without reacting with
XSO.sub.2--.
E.sup.1 and E.sup.2 are not particularly limited. For example, E to
be formed is --CH.sub.2OCO-- (or --COOCH.sub.2--) in a case where
either one of E.sup.1 and E.sup.2 is --COZ (Z is a halogen atom),
and the other is --CH.sub.2OH. This E is reacted with fluorine in a
liquid phase to form --CF.sub.2OCO-- (or --COOCF.sub.2--) as
E.sup.F. Further, by decomposition of this E.sup.F, --COF will be
formed as E.sup.F1. In the present invention, it is preferred that
the compound 4 is decomposed to obtain not only the compound 5 but
also the compound 6 represented by R.sup.BF-E.sup.F2. When E.sup.1
and E.sup.2 are the above groups, E.sup.F2 will also be --COF (i.e.
the same group as E.sup.F1).
The compounds 1 to 5 are preferably compounds 1a to 5a,
respectively. The compounds 1a to 5a are cases where E.sup.1 is
--CH.sub.2OH, E.sup.2 is --COY (Y is a halogen atom), E is
--CH.sub.2OCO--, E.sup.F is --CF.sub.2OCO--, and E.sup.F1 is --COF.
Accordingly, the compound obtainable together with the compound 5a
by the decomposition of the compound 4a, will be the compound 6a
represented by R.sup.BF--COF.
In the present invention, the fluorine content of the compound 3 is
preferably at least 30 mass %. If the fluorine content of the
compound 3 is less than 30 mass %, the solubility in the liquid
phase at the time of the fluorination reaction, tends to be
inadequate. The fluorine content of the compound 3 may be suitably
adjusted to be at least 30% depending upon the type of the liquid
phase for the fluorination reaction. However, the fluorine content
is more preferably from 30 to 86 mass %, still further preferably
from 30 to 76 mass %. It is economically disadvantageous to employ
the compound 3 having a fluorine content exceeding 86 mass %, and
the available compound tends to be limited in such a case.
Further, the molecular weight of the compound 3 is preferably from
200 to 1,000. If the molecular weight of the compound 3 is less
than 200, the boiling point of the compound 3 tends to be low, and
the compound 3 is likely to evaporate during the process of
fluorination, whereby the yield of the fluorinated product tends to
be low. Further, a decomposition reaction may also take place. On
the other hand, if the molecular weight exceeds 1,000, the
solubility in the liquid phase tends to be low, and the
purification tends to be difficult.
In the present invention, X is preferably a fluorine atom. When X
is a fluorine atom, there is a merit that the yield of the
fluorination reaction will be remarkably improved as compared with
a case where X is other halogen atom. Further, in the present
invention, also Y is preferably a fluorine atom.
Further, at least one of the above R.sup.A, R.sup.B and E is a
group which can be fluorinated, and at least one R.sup.AF, R.sup.BF
and E.sup.F is a group formed by the fluorination of R.sup.A,
R.sup.B and E, respectively.
A preferred embodiment of the present invention is a process
wherein the compound 1a is reacted with the compound 2a to form the
compound 3a (hereinafter referred to as "the esterification step"),
then, the compound 3a is reacted with fluorine in a liquid phase to
form the compound 4a (hereinafter referred to as "the fluorination
step"), and further, the compound 4a is decomposed to obtain the
following compound 5a (hereinafter referred to as "decomposition
step"). The respective reaction steps of this process will be
described in detail. XSO.sub.2R.sup.A--CH.sub.2OH (1a) R.sup.B--COY
(2a) XSO.sub.2R.sup.A--CH.sub.2OCO--R.sup.B (3a)
FSO.sub.2R.sup.AF--CF.sub.2OCO--R.sup.BF (4a)
FSO.sub.2R.sup.AF--COF (5a)
Firstly, the esterification step will be described.
The reaction of the compound 1a with the compound 2a in the
esterification step, can be carried out under the conditions for
known esterification reactions. Such a reaction can be carried out
in the presence of a solvent (hereinafter referred to as "the
solvent 1"), but it is preferred to carry out the reaction in the
absence of the solvent 1 from the viewpoint of the volume
efficiency. When the solvent 1 is employed, it is preferably
dichloromethane, chloroform, triethylamine or a solvent mixture of
triethylamine and tetrahydrofuran. The amount of the solvent 1 to
be used, is preferably from 50 to 500 mass %, based on the total
amount of the compound 1a and the compound 2a.
By the reaction of the compound 1a with the compound 2a, an acid
represented by HY will be formed. In a case where as the compound
2a, a compound wherein Y is a fluorine atom, is employed, HF will
be formed. Therefore, as a scavenger for HF, an alkali metal
fluoride (preferably NaF or KF) or a trialkylamine may be present
in the reaction system. In a case where the compound 1a or the
compound 2a is a compound unstable against an acid, it is preferred
to use a scavenger for HF. Otherwise, in a case where no scavenger
for HF is employed, it is preferred to discharge HF out of the
reaction system, as carried by a nitrogen stream. When the alkali
metal fluoride is employed, its amount is preferably from 1 to 10
times by mol, relative to the compound 2a.
The temperature for the reaction of a compound 1a with the compound
2a is preferably at least -50.degree. C. and at most +100.degree.
C. or at most the boiling temperature of the solvent. Further, the
reaction time for the reaction may suitably be changed depending
upon the supply rate of the materials and the amounts of the
compounds to be used for the reaction. The presence for the
reaction (the gauge pressure, the same applied hereinafter) is
preferably from normal pressure to 2 MPa.
Further, as mentioned above, the molecular weight of the compound
3A is preferably from 200 to 1,000. Further, the fluorine compound
(the proportion of fluorine atoms in the molecule) of the compound
3a is preferably at least 30 mass %, more preferably from 30 to 86
mass %, still more preferably from 30 to 76 mass %.
A crude product containing the compound 3a formed by the reaction
of the compound 1a with the compound 2a, may be purified depending
upon the purpose, or may be used as it is for e.g. the next
reaction. It is advisable to carry out the purification, so that
the fluorination reaction in the next step can be proceeded
smoothly.
The purification of the crude product may, for example, be a method
of distilling the crude product as it is, a method of treating the
crude product with a dilute alkali aqueous solution, followed by
liquid separation, a method of extracting the crude product with a
suitable organic solvent, followed by distillation, or silica gel
column chromatography.
The following compounds may be mentioned as specific examples of
the compound 1a. FSO.sub.2CH.sub.2CH.sub.2OH,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH(CH.sub.3)CH.sub.2OH.
The compound 1a is a compound which is readily available or which
can easily be prepared by a known method. For example,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH can be obtained by
synthesizing 2-chloroethanesulfonyl fluoride and then reacting
2-chloroethanesulfonyl fluoride with ethylene glycol, by the method
disclosed, for example, in J. Org. Chem., 44, 3847 (1979).
Further, the following compounds may be mentioned as specific
examples of the compound 2a to be used in the esterification step.
CF.sub.3CF.sub.2COF, CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)COF,
CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCF(CF.sub.3)COF,
FSO.sub.2CF.sub.2COF, FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2COF,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF(CF.sub.3)COF.
The following compounds may be mentioned as specific examples of
the compound 3a obtainable in the esterification step.
FSO.sub.2CH.sub.2CH.sub.2OCOCF.sub.2CF.sub.3,
FSO.sub.2CH.sub.2CH.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.2CF.sub.3,
FSO.sub.2CH.sub.2CH.sub.2OCOCF(CF.sub.3)OCF.sub.2CF(C F.sub.3),
OCF.sub.2CF.sub.2CF.sub.3,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF.sub.2CF.sub.3,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3 (I),
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF(CF.sub.3)OCF.sub.2CF(CF.s-
ub.3) OCF.sub.2CF.sub.2CF.sub.3,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH(CH.sub.3)CH.sub.2OCOCF.sub.-
2CF.sub.3,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH(CH.sub.3)CH.sub.2-
OCOCF(CF.sub.3), OCF.sub.2CF.sub.2CF.sub.3,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH(CH.sub.3)CH.sub.2OCOCF(CF.s-
ub.3) OCF.sub.2CF(CF.sub.3)OCF.sub.2CF.sub.2CF.sub.3,
FSO.sub.2CH.sub.2CH.sub.2OCOCF.sub.2SO.sub.2F,
FSO.sub.2CH.sub.2CH.sub.2OCOCF.sub.2OCF.sub.2CF.sub.2SO.sub.2F,
FSO.sub.2CH.sub.2CH.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.2OCF.sub.2CF.sub.-
2SO.sub.2F,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF.sub.2SO.sub.2F,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF.sub.2OCF.sub.2CF.sub.2SO.-
sub.2F, FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF(CF.sub.3),
OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2SO.sub.2F,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH(CH.sub.3)CH.sub.2OCOCF.sub.-
2SO.sub.2F FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH(CH.sub.3)
CH.sub.2OCOCF.sub.2OCF.sub.2CF.sub.2SO.sub.2F,
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH(CH.sub.3)CH.sub.2OCOCF(CF.s-
ub.3) OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2SO.sub.2F.
The compound 3a may be led to a material for ion-exchange resins,
by the reaction which will be described hereinafter. Further, the
above compound 1 is a novel compound which is useful particularly
in the case of producing a high performance fluororesin.
Now, the fluorination step will be described.
The fluorination reaction in the fluorination step is carried out
in a liquid phase from the viewpoint of the yield and the operation
efficiency of the reaction. Such a fluorination reaction may be
carried out theoretically by an ECF method, a cobalt fluorination
method, or a method of reaction with fluorine with a gas phase.
However, from the viewpoint of the reaction yield and the
efficiency in the reaction operation, fluorination in a liquid
phase is a remarkably advantageous method.
The fluorination reaction is preferably carried out by a method
wherein the compound 3a is reacted with fluorine (F.sub.2) in the
presence of a solvent (hereinafter referred to as "the solvent 2")
to form the compound 4a. As the fluorine, fluorine gas may be
employed as it is, or fluorine gas diluted with an inert gas may be
employed. As such an inert gas, nitrogen gas or helium gas is
preferred, and from the economical reason, nitrogen gas is
particularly preferred. The amount of fluorine in nitrogen gas is
not particularly limited, it is preferably at least 10 vol % from
the viewpoint of efficiency, particularly preferably at least 20
vol %.
The solvent 2 is preferably a solvent which does not contain C--II
bond(s) and which contain C--F bond(s) essentially. More preferred
is a perfluoroalkane or an organic solvent obtained by
perfluorinating a known organic solvent having in its structure at
least one atom selected from the group consisting of a chlorine
atom, a nitrogen atom, and an oxygen atom. Further, as the solvent
2, it is preferred to employ a solvent in which the solubility of
the compound 3a is high, and it is particularly preferred to employ
a solvent which is capable of dissolving at least 1 mass % of the
compound 3a, essentially preferred to employ a solvent capable of
dissolving at least 5 mass % of the compound 3a.
Examples of the solvent 2 include the compound 4a in the case where
it is a perfluorinated compound, a perfluoralkane (tradename:
FC-72, etc.), a perfluoroether (FC-75, FC-77, etc.), a
perfluoropolyether (tradename: KRYTOX, FOMBLIN, GALDEN, DEMNUM,
etc.) , a chlorofluorocarbon (tradename: FLON LUBE), a
chlrofluoropolyether, a perfluoroalkylamine (such as
perfluorotrialkylamine), and an inert fluid (tradename:
FLUORINERT). Among them, a perfluorotrialkylamine or the compound
4a in the case where it is a perfluorinated compound, is preferred.
Especially when the compound 4a is employed, there is a merit that
work up after the reaction will be easy. The amount of the solvent
2 is preferably at least five time by mass, particularly preferably
from 10 to 100 times by mass, relative to the compound 3a.
The reaction system for the fluorination reaction may be a batch
system or a continuous system. The continuous system may be the
following continuous system 1 or 2, but from the viewpoint of the
reaction yield and the selectivity, the continuous system 2 is
preferred. Further, the fluorine gas may be one diluted with an
inert gas such as a nitrogen gas in either case where the reaction
is carried out in a batch system or in a continuous system.
Continuous System 1
A method wherein the compound 3a and the solvent 2 are charged into
a reactor, and stirring is initiated to control the reaction
temperature and the reaction pressure to prescribed levels, and
then fluorine gas, or fluorine gas and the solvent 2, are
continuously supplied for the reaction.
Continuous System 2
A method wherein the solvent 2 is charged into the reactor, and
stirring is initiated to control the reaction temperature and the
reaction pressure to prescribed levels, and then the compound 3a
and fluorine gas are continuously and simultaneously supplied in a
prescribed molar ratio.
In the continuous system 2, when the compound 3a is supplied, it is
preferred to supply the compound 3a diluted with the solvent 2,
whereby the selectivity can be improved, and the amount of
by-products can be suppressed. Further, in the continuous system 2,
when the compound 3a is diluted with the solvent, the amount of the
solvent 2 to the compound 3a is preferably at least 5 times by
mass, particularly preferably at least 10 times by means.
With respect to the amount of fluorine to be used for the
fluorination reaction, in either case where the reaction is carried
out by a batch system or a continuous system, it is preferred that
fluorine gas is present so that the amount of fluorine is always in
excess equivalent to hydrogen atoms to be fluorinated, and it is
particularly preferred to use fluorine gas so that it would be at
least 1.5 times by equivalent (i.e. at least 1.5 times by mol) from
the viewpoint of the selectivity. Further, the amount of fluorine
gas is preferably maintained in an excess amount always from the
initiation to the termination of the reaction.
The reaction temperature for the fluorination reaction is usually
preferably at least -60.degree. C. and at most the boiling point of
the compound 3a, and from the viewpoint of the reaction yield, the
selectivity and the efficiency for industrial operation, it is
particularly preferably from -50.degree. C. to +100.degree. C.,
especially preferably from -20.degree. C. to +50.degree. C. The
reaction pressure for the fluorination reaction is not particularly
limited, and from the viewpoint of the reaction yield, the
selectivity and the efficiency for industrial operation, it is
particularly preferably from normal pressure to 2 MPa.
Further, in order to let the fluorination reaction proceed
efficiently, it is preferred to add a C--H bond-containing compound
to the reaction system at a later stage of the reaction or to carry
out ultraviolet irradiation. For example, in a batch system
reaction, it is preferred to add a C--H bond-containing compound to
the reaction system at a later stage of the fluorination reaction,
or to carry out ultraviolet irradiation, and in a continuous system
reaction, it is preferred to supply a C--H bond-containing compound
to the vicinity of the portion where the fluorination reaction
product is withdrawn from the reaction apparatus, or, to irradiate
ultraviolet rays. Thus, the compound 3a present in the reaction
system can efficiently be fluorinated, whereby the conversion can
remarkably be improved.
The C--H bond-containing compound may be an organic compound other
than the compound 3a, and particularly preferred is an aromatic
hydrocarbon. Benzene or toluene is, for example, particularly
preferred. The amount of the C--H bond-containing compound is
preferably from 0.1 to 10 mol %, particularly preferably from 0.1
to 5 mol %, based on hydrogen atoms in the compound 3a.
It is preferred to add the C--II bond-containing compound in a
stage where fluorine gas is present in the reaction system.
Further, in a case where the C--H bond-containing compound is
added, it is preferred that the reaction system is pressurized. The
pressure at the time of pressurizing is preferably from 0.01 to 5
MPa.
In a case where a reaction to substitute fluorine atoms for
hydrogen atoms takes place in the reaction for fluorination of the
compound 3a in a liquid phase, HF will be formed as a by-product.
To remove the by-product HF, it is preferred to let a scavenger for
HF be present in the reaction system or to contact the discharge
gas with a HF scavenger at the gas outlet of the reactor. As the HF
scavenger, the same one as described above may be employed, and NaF
is preferred.
When the HF scavenger is permitted to be present in the reaction
system, its amount is preferably from 1 to 20 times by mol,
particularly preferably from 1 to 5 times by mol, based on the
total amount of hydrogen atoms present in the compound 3a. In a
case where the HF scavenger is placed at the gas outlet of the
reactor, it is preferred that (1) a cooler, (which is preferably
maintained at a level of from 10.degree. C. to room temperature,
particularly preferably at about 20.degree. C.) (2) a packed layer
of NaF pellets, and (3) a cooler (which is preferably maintained at
a level from -78.degree. C. to +10.degree. C., more preferably from
-30.degree. C. to 0.degree. C.) are installed in series in the
order of (1)-(2)-(3). Further, a liquid-returning line to return a
condensed liquid from the cooler of (3) to the reactor, may be
installed.
The crude product containing the compound 4a obtained in the
fluorination step, may be employed as it is for the next step, or
may be purified to one having high purity. As the purification
method, a method of distilling the crude product as it is under
normal pressure or reduced pressure may, for example, be
mentioned.
The following compounds may be mentioned as specific examples of
the compound 4a obtainable in the fluorination step.
FSO.sub.2CF.sub.2CF.sub.2OCOCF.sub.2CF.sub.3,
FSO.sub.2CF.sub.2CF.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.2,
CF.sub.3,
FSO.sub.2CF.sub.2CF.sub.2OCOCF(CF.sub.3)OCF.sub.2CF(CF.sub.3)OCF.sub.2CF.-
sub.2CF.sub.3,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCOCF.sub.2CF.sub.3,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3 (II)
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCOCF(CF.sub.3)OCF.sub.2CF(CF.s-
ub.3) OCF.sub.2CF.sub.2CF.sub.3,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCOCF.sub.-
2CF.sub.3,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2-
OCOCF(CF.sub.3) OCF.sub.2CF.sub.2CF.sub.3,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2
OCF(CF.sub.3)CF.sub.2OCOCF(CF.sub.3)
OCF.sub.2CF(CF.sub.3)OCF.sub.2CF.sub.2CF.sub.3,
FSO.sub.2CF.sub.2CF.sub.2OCOCF.sub.2SO.sub.3F,
FSO.sub.2CF.sub.2CF.sub.2OCOCF.sub.2OCF.sub.2CF.sub.2SO.sub.2F,
FSO.sub.2CF.sub.2CF.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.2OCF.sub.2CF.sub.-
2SO.sub.2F,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCOCF.sub.2SO.sub.2F,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.3CF.sub.2OCOCF.sub.2OCF.sub.2CF.sub.2SO.-
sub.2F, FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCOCF(CF.sub.3)
OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2SO.sub.2F,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCOCF.sub.-
2SO.sub.2F, FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF(CF.sub.3)
CF.sub.2OCOCF.sub.2OCF.sub.2CF.sub.2SO.sub.2F,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCOCF(CF.s-
ub.3) OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2SO.sub.2F.
Like the compound 3a, the compound 4a is also useful as an
intermediate for a material for fluororesins and may be led to a
material for ion-exchange resins by a reaction which will be
described hereinafter. Further, the above compound II is a novel
compound particularly useful in a case where a high performance
fluororesin is to be produced.
Now, the decomposition step of decomposing the ester bond will be
described.
The reaction in this decomposition step is carried out preferably
by a pyrolytic reaction or a decomposition reaction which is
carried out in the presence of a nucleophilic agent or an
electrophilic agent.
The pyrolytic reaction can be carried out by heating the compound
4a. The reaction system for the pyrolytic reaction is preferably
selected depending upon the boiling point and stability of the
compound 4a. For example, in a case where a readily vaporizable
compound 4a is to be pyrolized, it is possible to employ a gas
phase pyrolytic method wherein the pyrolysis is continuously
carried out in a gas phase, and a discharge gas containing the
obtained compound 5a is condensed and recovered.
The reaction temperature in the gas phase pyrolytic method is
preferably from 50 to 350.degree. C., particularly preferably from
50 to 300.degree. C., especially preferably from 150 to 250.degree.
C. Further, an inert gas which is not directly involved in the
reaction, may also be present in the reaction system. As such an
inert gas, nitrogen or carbon dioxide may, for example, be
mentioned. Such an inert gas is preferably added in an amount of
from 0.01 to 50 vol %, based on the compound 4a. If the amount of
the added inert gas is large, the yield of the product may
sometimes be reduced.
On the other hand, in a case where the compound 4a is a hardly
vaporizable compound, it is preferred to employ a liquid phase
pyrolytic method wherein it is heated in the state of a liquid in
the reactor. The pressure for the reaction in this case is not
particularly limited. In a usual case, the product containing the
compound 5a has a lower boiling point, and therefore, it is
preferred to obtain it: by a method of a reaction distillation
system wherein the product is vaporized and continuously withdrawn.
Otherwise, a method may be employed wherein after completion of the
heating, the product is withdrawn all at once from the reactor. The
reaction temperature in such a liquid phase pyrolytic method is
preferably from 50 to 300.degree. C., particularly preferably from
100 to 250.degree. C.
In a case where pyrolysis is carried out by the liquid phase
pyrolytic method, it may be carried out in the absence of any
solvent or in the presence of a solvent (hereinafter referred to as
"the solvent 3"). The solvent 3 is not particularly limited, so
long as it is one which is not reactive with the compound 4a and is
soluble in each other with the compound 4a and which is not
reactive with the compound 5a to be formed. Further, as the solvent
3, it is preferred to select one which can readily be separated at
the time of purification of the compound 5a. Specific examples of
the solvent 3 include inert solvents such as
perfluorotrialkylamine(s) and perfluoronaphthalene(s), and
chlorotrifluoroethylene oligomer(s) (for example, tradename: FLON
LUBE) having a high boiling point among the chlorofluoro-carbon(s),
are preferred. Further, the amount of the solvent 3 is preferably
from 10 to 1,000 mass %, based on the compound 4a.
Further, in the case where the compound 4a is reacted with a
nucleophilic agent or an electrophilic agent in a liquid phase for
decomposition, such a reaction may be carried out in the absence of
any solvent or in the presence of a solvent (hereinafter referred
to as "the solvent 4"). The solvent 4 is preferably the same as the
solvent 3. The nucleophilic agent is preferably F.sup.-,
particularly preferably F.sup.- derived from an alkali metal
fluoride. The alkali metal fluoride is preferably NaF, NaHF.sub.2,
KF or CsF. Among them, NaF or KF is particularly preferred from the
viewpoint of the economical efficiency and the reactivity.
In a case where a nucleophilic agent (such as F.sup.-) is employed,
the nucleophilic agent to be used at the initial stage of the
reaction may be in a catalytic amount or in an excess amount. The
amount of the nucleophilic agent such as F.sup.- is preferably from
1 to 500 mol %, particularly preferably from 1 to 100 mol %,
especially preferably from 5 to 50 mol %, based on the compound 4.
The reaction temperature is preferably at a level of from
-30.degree. C. to the boiling point of the solvent or the compound
4a, particularly preferably from -20.degree. C. to 250.degree. C.
This method is also preferably carried out in a reactor equipped
with a distillation column.
The following compounds may be mentioned as specific examples of
the compound 5a to be obtained in the decomposition step.
FSO.sub.2CF.sub.2COF, FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2COF,
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF(CF.sub.3)COF,
In the present invention, it is possible to obtain not only the
compound 5a but also the following compound 6a by the decomposition
of the compound 4a. R.sup.BF--COF (6a) wherein R.sup.BF is as
defined above.
In the present invention, it is preferred that the compound 2a has
the same structure as the compound 6a. Namely, it is preferred that
in the compound 2a, R.sup.B is R.sup.BF, Y is F, and in the
compound 3a, R.sup.B is R.sup.BF. In such a case, it is possible to
continuously obtain the compound 5a (continuous process) by
employing at least a part of the compound 6a obtained from the
reaction product obtained by the decomposition of the compound 4a,
as at least a part of the compound 2a to react with the compound
1a. Further, when the compound 5a and the compound 6a have the same
structure, the decomposition reaction product of the compound 4a
can be used for the reaction with the compound 1a, without the
necessity to separate the decomposition reaction product. The
reaction scheme of the compound 1a, the compound 2a (=the compound
6a), and the compounds 3a to 6a, in such a case, may be represented
by the following chemical formulae. ##STR00002##
As one embodiment of the above continuous process, the following
reactions employing compounds I to V may be mentioned. Namely, it
is a continuous process wherein the following compound V is reacted
with the following compound IV to form the following compound I,
then, the compound I is reacted with fluorine in a liquid phase to
form the following compound II, and further, the compound II is
decomposed to obtain not only the following compound III but also
the compound IV, and at least a part of the compound IV is reacted
with the compound V. Here, the compounds I and II are the
above-mentioned novel compounds. ##STR00003##
The compound V having a FSO.sub.2-- group in its terminal
structure, can be synthesized by fluorinating a compound having a
ClSO.sub.2-- group in its terminal structure by means of potassium
fluoride. Otherwise, the compound V may be synthesized also by
reacting the following compound Va with SO.sub.2Cl to form the
following compound Vb, then fluorinating the compound Vb with
potassium fluoride to form the following compound Vc, and further,
reacting the compound Vc with the following compound Vd.
NaOSO.sub.2(CH.sub.2).sub.2OH (Va) ClSO.sub.2(CH.sub.2).sub.2Cl
(Vb) FSO.sub.2(CH.sub.2).sub.2Cl (Vc) NaO(CH.sub.2).sub.2OH
(Vd)
As a second embodiment of the above continuous process, the
following reactions employing compounds 1b to 6b may be mentioned.
Namely, it is a continuous process wherein the following compound
1b is reacted with the following compound 6b to form the following
compound 3b, then, the compound 3b is reacted with fluorine in a
liquid phase to form the following compound 4b, further, the
compound 4b is decomposed to obtain not only the following compound
5b but also the compound 6b, and at least a part of the compound 6b
is reacted with the compound 1b. ##STR00004##
The compound 5b can also be prepared by a method of reacting the
compound III-obtained in the first embodiment, with HFPO. Like the
compound 5b, a compound essentially having a partial structure of
"C.sup.1F--C.sup.2--COF" at its molecular terminal (hereinafter
referred to as "the specific terminal fluorine atom-containing
sulfonyl fluoride compound"), can be converted so that the
molecular terminal is changed to "C.sup.1.dbd.C.sup.2", by a
pyrolytic reaction (for example, the method disclosed in Methods of
Organic Chemistry, 4, Vol 10b, Part 1, pp. 703). From the compound
5b obtained by such a method, the following compound A which is
useful as a monomer for the synthesis of ion-exchange membranes,
can be produced. ##STR00005##
The pyrolytic reaction to obtain the unsaturated compound
(hereinafter referred to as "the fluorine atom-containing sulfonyl
fluoride vinyl ether") represented by the compound A from the
specific terminal, fluorine atom-containing sulfonyl fluoride
compound represented by the compound 5b, may, for example, be a gas
phase pyrolytic reaction of the specific terminal fluorine
atom-containing sulfonyl fluoride compound, or a pyrolytic reaction
of an alkali salt of a carboxylic acid obtained by the reaction of
the specific terminal fluorine atom-containing sulfonyl fluoride
compound with an alkali metal hydroxide.
The reaction temperature in the gas phase pyrolytic reaction of the
specific terminal fluorine atom-containing sulfonyl fluoride
compound is preferably from 250 to 400.degree. C., more preferably
from 250 to 350.degree. F. Further, the reaction temperature in the
pyrolytic reaction of the above alkali salt of a carboxylic acid is
preferably from 150 to 350.degree. C., more preferably from 200 to
280.degree. C. If the reaction temperature in the gas phase
pyrolytic reaction is less than 250.degree. C., or if the reaction
temperature in the pyrolytic reaction of the alkali salt of a
carboxylic acid is less than 150.degree. C., the conversion to the
fluorine atom-containing sulfonyl fluoride vinyl ether tends to be
low, and if the reaction temperature in the gas phase pyrolytic
reaction exceeds 400.degree. C., or if the reaction temperature in
the pyrolytic reaction of the alkali salt of a carboxylic acid
exceeds 350.degree. C., the specific terminal fluorine
atom-containing sulfonyl fluoride compound tends to be hardly
pyrolized to the fluorine atom-containing sulfonyl fluoride vinyl
ether, and pyrolysates other than the fluorine atom-containing
sulfonyl fluoride vinyl ether tend to increase.
The gas phase pyrolytic reaction of the specific terminal fluorine
atom-containing sulfonyl fluoride compound is preferably carried
out by continuous reaction. The continuous reaction is preferably
carried out by a method wherein a vaporized specific terminal
fluorine atom-containing sulfonyl fluoride compound is passed
through a heated reaction tube, the formed fluorosulfonyl fluoride
vinyl ether is obtained as a discharge gas, which is condensed and
continuously recovered. In a case where the pyrolytic reaction is
carried out in a gas phase, it is preferred to employ a tubular
reactor. When the tubular reactor is employed, the space time is
preferably from 0.1 second to 10 minutes on the basis of
superficial velocity. The pressure of the reaction in not
particularly limited. Further, when the specific terminal fluorine
atom-containing sulfonyl fluoride compound is a high boiling
compound, it is preferred to carry out the reaction under reduced
pressure. Especially when the specific terminal fluorine
atom-containing sulfonyl fluoride compound is a low boiling point
compound, as decomposition of the product will be suppressed and
the conversion will be high, it is preferred to carry out the
reaction under pressure.
In a case where the gas phase pyrolytic reaction is carried out by
means of a tubular reactor, it is preferred to pack glass, an
alkali metal salt, or an alkaline earth metal salt into the reactor
for the purpose of accelerating the reaction. As the alkali metal
salt or the alkali earth metal salt, a carbonate or a fluoride is
preferred. As the glass, common soda glass may be mentioned, and
glass bead formed into a bead shape and having improved
flowability, are particularly preferred. The alkali metal salt may,
for example, be sodium carbonate, sodium fluoride, potassium
carbonate, or lithium carbonate. The alkaline earth metal salt may,
for example, be calcium carbonate, calcium fluoride, or magnesium
carbonate. Further, in a case where the glass, the alkali metal
salt, or the alkaline earth metal salt, is to be packed into the
reaction tube, it is particularly preferred to employ glass beads
or light ash of sodium carbonate having a particle size of from
about 100 to 250 .mu.m, whereby a reaction system of a fluidized
layer type may be employed.
In the gas phase pyrolytic reaction, it is preferred to carry out
the reaction in the presence of an inert gas which is not directly
involved in the pyrolytic reaction, for the purpose of accelerating
the vaporization of the specific terminal fluorine atom-containing
sulfonyl fluoride compound. As such an inert gas, nitrogen, carbon
dioxide, helium or argon may, for example, be mentioned. The amount
of the inert gas is preferably from about 0.01 to 50 vol %, based
on the specific terminal fluorine atom-containing sulfonyl fluoride
compound. If the amount of the inert gas is too large, the recovery
of the product tends to be low, such being undesirable. On the
other hand, in a case where the boiling point of the specific
terminal fluorine atom-containing sulfonyl fluoride compound is
high, the pyrolysis can be carried out by a liquid phase
reaction.
As described above, according to the process of the present
invention, it is unnecessary to employ a perfluoroalkylene ether in
the preparation of a fluorine atom-containing sulfonyl fluoride
compound, whereby the safety in the preparation can be increased,
and sulfonyl fluoride compounds having various structures (compound
1, compound 1a, compound V, compound 1b, etc.) can be produced at a
relatively low cost. Further, the process of the present invention
can be a continuous process, and further, the compound 4a as a
reaction product, can be re-used as the solvent 2 to be used for
the reaction of the compound 3a with fluorine in a liquid phase,
whereby the amount of the materials at the time of the preparation
and the amount of waste can be reduced, and the fluorine
atom-containing sulfonyl fluoride compound can be prepared very
economically.
EXAMPLES
Now, the present invention will be described in detail with
reference to Examples, but the present invention is by no means
thereby restricted. In the following, gas chromatography will be
referred to as GC, and gas chromatography mass spectrometry will be
referred to as GC-MS. Further, the purity determined from the peak
area ratio of GC will be referred to as GC purity, the yield will
be referred to as GC yield, and the yield obtained from the peak
area ratio of the NMR spectrum will be referred to as NMR yield.
Further, tetramethylsilane will be referred to as TMS,
CCl.sub.2FCClF.sub.2 as R-113, and tetrahydrofuran as THF. Further,
the NMR spectrum data are shown as being within an apparent
chemical shift range. The standard value of the standard substance
CDCl.sub.3 in the .sup.13C-NMR as 76.9 ppm. In the quantitative
analysis by the .sup.19F-NMR, C.sub.6F.sub.6 was used as the
internal standard.
Example 1
Production of FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH
Into a round flask, HO(CH.sub.2).sub.2OH (140.9 g) and a methanol
solution of sodium methylate (28 wt %, 96.4 g) were charged and
stirred, and heated under reduced pressure to distill off methanol
thereby to obtain a solution of HOCH.sub.2CH.sub.2ONa. It was
confirmed by GC that no methanol remained in the reaction solution.
Into a four necked flask, FSO.sub.2CH.sub.2CH.sub.2Cl (50 g) and
THF (100 mL) were charged and stirred under cooling with ice bath,
and the previously obtained solution of HOCH.sub.2CH.sub.2ONa was
dropwise added thereto over a period of 2.5 hours, while
maintaining the internal temperature to be at most 10.degree. C.
After completion of the dropwise addition, it was stirred at room
temperature for 2 hours and then added to water (400 mL), and
dichloromethane (183 g) was added. The obtained crude liquid was
subjected to liquid separation, and the obtained aqueous layer was
extracted with dichloromethane (124 g). The separated aqueous layer
was further extracted with dichloromethane (126 g), and the organic
layers were put together. It was dried over magnesium sulfate, and
after filtration, the solvent was distilled off to obtain a crude
product (47.1 g). The obtained crude liquid was used for the next
step without carrying out purification.
.sup.1H-NMR (300.4 MHz, CDCl.sub.3, TMS) .delta. (ppm): 3.63 to
3.71 (m, 4H), 3.74 to 3.79(m, 2H, ), 3.99 to 4.05(m, 2H)
.sup.19F-NMR (282.7 MHz, CDCl.sub.3, CFCl.sub.3) .delta. (ppm):
58.4 (1F).
Example 2
Production of
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3(esterification step)
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH (47.1 g) having a
purity of 64%, obtained in Example 1, and triethylamine (19.5 g)
were put into a flask and stirred under cooling with ice bath.
FCOCF(CF.sub.3)OCF.sub.2CF.sub.2CF.sub.3(64.1 g) was dropwise added
thereto over a period of 40 minutes, while maintaining the internal
temperature to be at most 10.degree. C. After completion of the
dropwise addition, it was stirred for two hours at room temperature
and then added to ice water (100 mL).
The obtained crude liquid was subjected to liquid separation, and
the lower layer was washed twice with water (100 mL) and dried over
magnesium sulfate, followed by filtration to obtain a crude liquid.
The crude liquid was purified by silica gel column chromatography
(developing solvent: dichloropentafluoropropane (tradename:
AK-225)) to obtain
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3(21.2 g). The GC purity was 88%.
.sup.1H-NMR (300.4 MHz, CDCl.sub.3, TMS) .delta. (ppm): 3.57 to
3.63 (m, 2H), 3.81(t, J=4.5 Hz, 2H), 3.95 to 4.00(m, 2H), 4.48 to
4.60(m, 2H)
.sup.19F-NMR (282.7 MHz, CDCl.sub.3, CFCl.sub.3) .delta. (ppm):
58.2 (1F), -79.8(1F), -81.3(3F), -82.1(3F), -86.6(1F), -129.4 (2F),
-131.5(1F).
Example 3
Production of
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3(fluorination step)
Into a 500 mL autoclave made of nickel, R-113(313 g) was added,
stirred and maintained at 25.degree. C. At the gas outlet of the
autoclave, a cooler maintained at 20.degree. C., a packed layer of
NaF pellets and a cooler maintained at -10.degree. C., were
installed in series. Further, a liquid-returning line was installed
to return a condensed liquid from the cooler maintained at
-10.degree. C. to the autoclave. After supplying nitrogen gas for
1.0 hour, fluorine gas diluted to 20% by nitrogen gas (hereinafter
referred to as diluted fluorine gas) was supplied for one hour at a
flow rate of 7.78 L/hr. Then, while supplying the diluted fluorine
gas at the same flow rate, a solution obtained by dissolving
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3 (7.01 g) obtained in Example 2, in R-113(140 g), was
supplied over a period of 5.5 hours.
Then, while supplying the diluted fluorine gas at the same flow
rate and maintaining the pressure of the reactor to be 0.15 MPa, a
R-113 solution having a benzene concentration of 0.01 g/mL, was
supplied (6 mL) while raising the temperature from 25.degree. C. to
40.degree. C. And the benzene inlet of the autoclave was closed and
stirring was continued for 0.3 hour. Then, while maintaining the
pressure of the reactor to be 0.15 MPa and the internal temperature
of the reactor to be 40.degree. C., the above-mentioned benzene
solution (6 mL) was supplied, and stirring was continued for 0.3
hour. Further, the same operation was repeated three times. The
total amount of benzene supplied, was 0.31 g, and the total amount
of R-113 supplied was 30 mL. Further, nitrogen gas was supplied for
1.0 hour. The desired product was quantitatively analyzed (internal
standard: C6F6) by .sup.19F-NMR, whereby the yield of the above
identified compound was 84%.
.sup.19F-NMR (376.0 MHz, CDCl.sub.3, CFCl.sub.3) .delta. (ppm):
45.2 (1F), -79.9(1F), -82.0(3F), -82.2(3F), -82.6(2F), -87.0(1F),
-88.5(2F), -92.3(2F); -112.9(2F), -130.2(2F), -132.1(1F).
Example 4
Production of FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2COF (decomposition
step)
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3(3.1 g) obtained in Example 3 was charged into a flask
together with NaF powder (0.02 g) and heated at 140.degree. C. for
10 hours in an oil bath with vigorous stirring. At the upper
portion of the flask, a reflux condenser having the temperature
adjusted at 20.degree. C., was installed. After cooling, the liquid
sample (3.0 g) was recovered. As a result of the analysis by GC-MS
CF.sub.3CF(OCF.sub.2CF.sub.2CF.sub.3)COF and
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2COF were confirmed to be the main
products, and the NMR yield was 71.2%. Further,
FCOCF(CF.sub.3)OCF.sub.2CF.sub.2CF.sub.3 was obtained in a yield of
74.0%.
Example 5
Recycling of FCOCF(CF.sub.3)OCF.sub.2CF.sub.2CF.sub.3(continuous
process)
FCOCF(CF.sub.3)OCF.sub.2CF.sub.2CF.sub.3 obtained in Example 4 was
reacted with FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH under the
same conditions as in the above esterification to obtain
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3. The obtained
FSO.sub.2CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3 was fluorinated under the same conditions as in the above
fluorination step to obtain
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3. The obtained
FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2OCOCF(CF.sub.3)OCF.sub.2CF.sub.-
2CF.sub.3 was decomposed under the same conditions as in the above
decomposition step to obtain FSO.sub.2CF.sub.2CF.sub.2OCF.sub.2COF
and FCOCF(CF.sub.3)OCF.sub.2CF.sub.2CF.sub.3.
INDUSTRIAL APPLICABILITY
According to the present invention, a process can be presented
whereby fluorine atom-containing sulfonyl fluoride compounds having
various molecular structures can be produced efficiently and at low
costs and whereby the difficulties in the production are
solved.
The entire disclosure of Japanese Patent Application No.
2000-361450 on Nov. 28, 2000 including specification, claims and
summary is incorporated herein by reference in its entirety.
* * * * *