Process for producing a fluorine-containing compound by...

Details Process for producing a fluorine-containing compound by... Process for producing a fluorine-containing compound by...

2001-09-24

2003-07-01

Rotman, Alan L. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic halides

C562S861000, C562S856000, C562S852000, C562S851000, C562S849000, C560S125000

Reexamination Certificate

active

06586626

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a process for producing a fluorine-containing compound such as an industrially useful acid fluoride compound. Further, the present invention provides a novel compound which is useful as a precursor for a fluorine resin material.
BACKGROUND ART
Heretofore, as a method for fluorinating all of C—H portions in a C—H containing compound to C—F, a method of employing cobalt trifluoride, a method of direct fluorination with fluorine gas, or a method of carrying out a fluorination reaction in an electrolytic cell using electrolyzed hydrogen fluoride as a fluorine source (hereinafter referred to as electrochemical fluorination) has been known. The method of employing cobalt trifluoride is one wherein the reaction is carried out at a high temperature by a gas-solid reaction, whereby isomerization or bond breakage takes place, and there is a problem that various types of by-products will form. In the case where a direct fluorination method is carried out with fluorine gas, a gas phase method or a liquid phase method has been known. However, the gas phase reaction has a problem that during the fluorination reaction, dissociation of C—C single bonds takes place, and various types of by-products will form. In recent years, a liquid phase method has been reported.
On the other hand, a method for fluorination in a liquid phase by reacting fluorine gas to a non-fluorine containing compound, has also been reported (U.S. Pat. No. 5,093,432). Further, a method for obtaining an acid fluoride compound by thermal decomposition of a perfluorinated ester compound having a carbon number of at least 16, has also been known, and it is disclosed that the compound can be obtained by direct fluorination of a hydrocarbon ester compound having a corresponding structure in a liquid phase with fluorine gas (J. Am. Chem. Soc., 120,7117(1998)).
The method of employing cobalt trifluoride or electrochemical fluorination has had a problem such that an isomerization reaction takes place or a problem such that breakage of the main chain, a re-union reaction, etc., may occur, and has had a drawback that the desired compound can not be obtained in good purity. In a case where a fluorination reaction is carried out in a liquid phase with fluorine gas, it is common to employ a solvent capable of dissolving fluorine gas, as the solvent for the reaction. However, a hydrocarbon compound as a starting material in a conventional method, usually has a low solubility in a solvent to be used for the fluorination reaction, and accordingly, the reaction is carried out in a very low concentration, whereby there has been a problem that the production efficiency is poor or a problem that the reaction will have to be carried out in a suspension which is disadvantageous to the reaction. Further, if it is attempted to fluorinate a hydrocarbon compound of a low molecular weight in a liquid phase, a problem has been observed such that the reaction yield tends to be remarkably low.
On the other hand, a fluorine-containing monomer such as a perfluoro(alkylvinyl ether) is useful as a starting material monomer for a fluorinated resin having heat resistance and chemical resistance. Heretofore, the perfluoro(alkylvinyl ether) has been industrially produced by a dimerization reaction of a perfluorinated epoxide or by reacting a perfluoroalkanoyl fluoride with a perfluorinated epoxide in the presence of an alkali Or metal fluoride to form a perfluoro(2-alkoxyalkanoyl)fluoride, followed by thermal decomposition. However, such a method has had a problem that control of the reaction of the dimerization reaction is difficult, and the price of the starting material is high and economically disadvantageous.
DISCLOSURE OF THE INVENTION
In the present invention, as a result of various studies on the cause for problems of the conventional methods, firstly, it has been found that the cause for the low yield in the fluorination reaction in a liquid phase with fluorine gas, is attributable to the fact that if the boiling point of the starting material is low, the starting material will react in a gas phase so that a decomposition reaction takes place. Then, it has been found that the decomposition reaction can be prevented by using an inexpensively available C—H containing compound as the starting material, converting it to a compound of a specific structure which has a high molecular weight so that a gas phase reaction hardly takes place and which is soluble in a solvent for the fluorination reaction, followed by fluorination in a liquid phase. Further, it has been found that the desired fluorine-containing compound can be produced by dissociation of a bonded group after fluorination (for example, dissociation by means of a thermal decomposition reaction or a decomposition reaction carried out in the presence of a nucleophile or an electrophile). Further, an industrial continuous process by recycling the formed compound, has been found.
Namely, the present invention provides a process for producing a fluorine-containing compound, characterized by reacting the following compound (I) with the following compound (II) to form the following compound (III), fluorinating the compound (III) in a liquid phase to form the following compound (IV) and then converting the compound (IV) to the following compound (V) and/or the following compound (VI):
R
A
—E
1
(I)
 R
B
—E
2
(II)
R
A
—E—R
B
(III)
R
AF
—E
F
R
BF
(IV)
R
AF
—E
F1
(V)
R
BF
—E
F2
(VI)
wherein
R
A
, R
B
: each independently is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group, a halogeno(hetero atom-containing monovalent saturated hydrocarbon) group, or a monovalent organic group (R
H
) which can be converted to R
HF
by a liquid-phase fluorination reaction,
R
HF
: a group having at least one hydrogen atom in a group selected from a monovalent saturated hydrocarbon group, a partially halogeno monovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group, and a partially halogeno(hetero atom-containing monovalent hydrocarbon) group, substituted by a fluorine atom;
R
AF
, R
BF
: R
AF
is a group corresponding to R
A
, and R
BF
is a group corresponding to R
B
; and in a case where each of R
A
and R
B
is a monovalent saturated hydrocarbon group, a halogeno momovalent saturated hydrocarbon group, a hetero atom-containing monovalent saturated hydrocarbon group, or a halogeno(hetero atom-containing saturated hydrocarbon) group, R
AF
and R
BF
are the same groups as R
A
and R
B
, respectively, or groups having at least one fluorine atom present in the groups of R
A
and R
B
substituted by a fluorine atom, and in a case where R
A
and R
B
are monovalent organic groups (R
H
), R
AF
and R
BF
are R
HF
, respectively;
E
1
, E
2
: reactive groups which are mutually reactive to form a bivalent connecting group (E);
E: a bivalent connecting group formed by the reaction of E
1
and E
2;
E
F
: the same group as E, or a group having E fluorinated, provided that at least one of R
AF
, R
BF
and E
F
, is not the same group as the corresponding R
A
, R
B
and E, respectively;
E
F1
, E
F2
: each independently is a group formed by dissociation of E
F
.
Further, the present invention provides the following novel compounds, provided that in this specification, Cy is a cyclohexyl group, Ph is a phenyl group, and Cy
F
is a perfluoro(cyclohexyl) group;
CF
3
(CF
3
CF
2
CF
2
O)CFCOOCH
2
CH (OCH
2
CH
2
CH
3
)CH
3
,
CF
3
CF
2
COOCH
2
CH
2
CHClCH
2
Cl,
CF
2
ClCFClCF
2
COOCH
2
CH
2
CHClCH
2
Cl,
CF
2
ClCF
2
CFClCOOCH
2
CH
2
CHClCH
2
Cl,
CF
3
(CF
3
CF
2
CF
2
O)CFCOOCH
2
CH(OCH
2
CH
2
CHClCH
2
Cl) CH
3
,
CF
3
(CF
3
CF
2
CF
2
O)CFCOOCH
2
CH (OCH
2
Cy) CH
3
,
CF
3
(CF
3
CF
2
CF
2
O)CFCOOCH
2
CH(OCH
2
Ph)CH
3
,
CF
3
(CF
3
CF
2
CF
2
O)CFCOOCH
2
CH(O(CH
2
)
9
CH
3
)CH
3
,
CF
3
(CF
3
CF
2
CF
2
O)CFCOO(CH
2
)
3
OCH
2
Ph,
 CF
3
(CF
3
CF
2
CF
2
O)CFCOO(CH
2
)
3
OCH
2
CH═CH
2
,
 CF
3
(CF
3
CF
2
CF
2
O)CFCOOCF
2
CF(OCF
2
CF
2
CF

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