Organic compounds -- part of the class 532-570 series – Organic compounds – Halogen containing
Reexamination Certificate
2003-02-26
2004-02-10
Richter, Johann (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Halogen containing
C570S124000, C570S134000, C570S155000
Reexamination Certificate
active
06689923
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a perfluoroolefin-hydrocarbon hybrid compound produced by reacting a hexafluoropropene trimer or highly branched perfluoroolefin with an organometallic compound, a method of producing the perfluoroolefin-hydrocarbon hybrid compound, and a method of producing a perfluoroalkyl radical by using the perfluoroolefin-hydrocarbon hybrid compound as a starting material.
BACKGROUND OF THE INVENTION
Highly branched perfluoroalkyl radicals are a kind of carbon radical. While carbon radicals are generally unstable and difficult to isolate due to their carbon atom having one unpaired electron, highly branched perfluoroalkyl radicals have excellent chemical stability or inertness to active chemical species such as acid, alkali and water, and can be isolated through dispersion gas chromatography or the like. Such characteristics make them usable in various industrial applications such as a synthetic intermediate for medicines or agricultural chemicals, a surface-active agent.
The highly branched perfluoroalkyl radicals can also be used as a polymerization initiator in polymer synthesis, a finishing agent, or a reagent for checking the leakage of containers having complicated shapes by taking advantage of their characteristic of releasing a low molecular weight perfluoroalkyl radical such as trifluoromethyl at a temperature of about 90° C. or more. The inventors developed a method of facilitating the release of a low molecular weight radical from a highly branched perfluoroalkyl radical, which is the subject of Japanese Patent Application No. 2001-352475.
As an example of a highly stable perfluoroalkyl radical, perfluoro-(2,4-dimethyl-3-isopropyl-3-pentyl) is disclosed in Japanese Patent Laid-open Publication No. 1-29175. The inventors also developed a method for producing a highly stable radical by fluorinating a highly branched perfluoroolefin, which is the subject of Japanese Patent Application No. 2001-352475. While this method is directed to producing a highly stable perfluoroalkyl radical by fluorinating a corresponding perfluoroolefin, the production process requires the use of a costly material, trialkylperfluoroalkylsilane, and a radical having a complicated structure cannot be synthesized through this method.
SUMMARY OF THE INVENTION
In view of the above problems, it is therefore an object of the present invention to provide an improved method of synthesizing a highly branched perfluoroolefin-hydrocarbon hybrid compound as a precursor of a new highly stable perfluoroalkyl radical from a hexafluoropropene trimer and an organometallic compound of alkali metal or alkali earth metal, and a new method of producing the highly stable perfluoroalkyl radical.
The present invention uses a hexafluoropropene trimer and an organometallic compound of alkali metal or alkali earth metal as starting materials, which are commercially available at a low cost. The kind of alkyl and aryl groups in the above organometallic compound can be selectively changed to produce various kinds of highly branched perfluoroolefin-hydrocarbon hybrid compounds, and the obtained compounds can be fluorinated to produce various kinds of highly stable perfluoroalkyl radicals.
More specifically, the present invention provides a perfluoroolefin-hydrocarbon hybrid compound represented by the following general formula (1):
[(CF
3
)
2
CX][(CF
3
)
2
CY]C═C(CF
3
)Z (1)
wherein X, Y and Z may be the same or different, and independently represent F or R, except that all of X, Y and Z are F, wherein R represents straight chain or branched alkyl having from 1 to 15 carbon atoms and aryl groups having from 1 to 15 carbon atoms.
The present invention further provides a perfluoroolefin-hydrocarbon hybrid compound represented by the following general formula (2):
[(CF
3
)
2
CX][(CF
3
)YZ]C═C(CF
3
)
2
(2)
wherein X, Y and Z may be the same or different, and independently represent F or R, except that all of X, Y and Z are F, wherein R represents straight chain or branched alkyl having from 1 to 15 carbon atoms and aryl groups having from 1 to 15 carbon atoms.
The present invention further provides a method for producing the above perfluoroolefin-hydrocarbon hybrid compound, wherein a hexafluoropropene trimer is reacted with an organometallic compound of alkali metal or alkali earth metal. The organometallic compound is represented by the following general formula (3):
RG (3)
wherein R represents a straight chain or branched alkyl and aryl group having from 1 to 15 carbon atoms; and G represents at least one of Li, Na, K, MgX, ZnX and CdX, wherein X represents Cl, Br and I.
The present invention further provides a method for producing a perfluoroalkyl radical, wherein the above perfluoroolefin-hydrocarbon hybrid compounds are fluorinated to form a highly stable perfluoroalkyl radical represented by the following general formula (1R):
[(CF
3
)
2
CRf
1
][(CF
3
)
2
CRf
2
]Ra—CF(CF
3
)Rf
3
(1R)
wherein Ra represents a carbon atom having one unpaired electron; and Rf
1
, Rf
2
and Rf
3
may be the same or different, and independently represent F or Rf, except that all of Rf
1
, Rf
2
and Rf
3
are F, wherein Rf represents a perfluoroalkyl group having from 1 to 15 carbon atoms or perfluorocycloalkyl group having from 1 to 15 carbon atoms.
The present invention further provides a method for producing a perfluoroalkyl radical, wherein the above perfluoroolefin-hydrocarbon hybrid compound is fluorinated to form a highly stable perfluoroalkyl radical represented by the following general formula (2R):
[(CF
3
)
2
CRf
1
][(CF
3
)CRf
2
Rf
3
]Ra—CF(CF
3
)
2
(2R)
wherein Ra represents a carbon atom having one unpaired electron; and Rf
1
, Rf
2
and Rf
3
may be the same or different, and independently represent F or Rf, except that all of Rf
1
, Rf
2
and Rf
3
are F, wherein Rf represents a perfluoroalkyl group having from 1 to 15 carbon atoms or perfluorocycloalkyl group having from 1 to 15 carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
The suitable hexafluoropropene trimers include perfluoro-(4-methyl-3-isopropyl-2-pentene) [hereinafter referred to as “trimer A”], perfluoro-(2,4-dimethyl-3-ethyl-2-pentene) [hereinafter referred to as “trimer B”], and perfluoro-(2,4-dimethyl-3-heptene) [hereinafter referred to as “trimer C”]. Among them, the trimer A and the trimer B are preferred because of their high yield. Other hexafluoropropene trimers will be apparent to one of ordinary skill in the art.
Further, in the present invention, one or more kinds of hexafluoropropene trimers may be used. For example, the trimer may be only the trimer A, only the trimer B, or a mixture of the trimer A and trimer B. The trimer may also be a mixture of the trimer C and trimer A and/B. In this case, the amount of the trimer C is preferably minimized to maintain adequate yields of desired hybrid compounds in the reaction solution.
R in the above general formula (3) may be any alkyl or aryl group having from 1 to 15 carbon atoms. When R is an alkyl group, it may be a straight chain type or a branched type. When R is an aryl group, its aromatic ring may have one or more substituents such as a lower alkyl group having from 1 to 3 carbon atoms, and may be a condensed ring. R is preferably an alkyl group having from 1 to 4 carbon atoms, more preferably, a methyl group, to assure reliable stability of the radical to be produced.
While G in the above general formula (3) may include Li, Na, K, MgX, ZnX, and CdX (wherein X represents Cl, Br and I), and any other metal that its metal complex has ability of releasing carbanions, Li or MgBr is prefered in view of the stability and/or handleability of an associated reagent. Further, in view of the selectivity of the reagent, MgBr is preferred to obtain a monosubstituted compound represented by the general formula (1) or (2) in which one of X, Y and Z is substituted with R, or Li is more prefe
Nishida Masakazu
Ono Taizo
National Institute of Advanced Industrial Science and Technology
Price Elvis O.
Richter Johann
Sughrue & Mion, PLLC
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