Fluorine-containing complex compound, and production method for fluorine-containing organic compound employing same

Patent metadata

Field	Value
Publication number	US-RE49222-E
Application number	US-201416668703-A
Country	US
Kind code	E1
Filing date	Oct 2, 2014
Priority date	Oct 2, 2013
Publication date	Sep 27, 2022
Grant date	Sep 27, 2022

Abstract

An object of the present invention is to enable the synthesis of various fluorine-containing compounds having an organic group at both terminals of their tetrafluoroethylene structure (—CF2—CF2—). The present invention provides a fluorine-containing complex compound includinga fluorine-containing organic metal compound represented by formula (1a):R1—CF2—CF2-M1  (1a)wherein M1 is a metal selected from the group consisting of copper, zinc, nickel, iron, cobalt, and tin; and R1 represents an organic group, andat least one ligand selected from the group consisting of pyridine ring-containing compounds and phosphines.

First claim

The invention claimed is:

1. A fluorine-containing compound represented by formula (4-1):
(R a1S —) ma1 R a1L —CF 2 —CF 2 —R a2L (—R a2S ) ma2   (4-1)

wherein
the moiety represented by formula:(R a1S —) ma1 R a1L indicates R a1L substituted with ma1 R a1S ;
the moiety represented by formula: R a2L (—R a2S ) ma2 indicates R a2L substituted with ma2 R a2S ;
R a1S and R a2S are the same or different, and each represents independently a moiety selected from the group consisting of
(1) aldehyde,
(2) alkenyl optionally substituted with at least one halogen atom,
(3) (2) alkynyl optionally substituted with at least one substituent selected from the group consisting of halogen and trimethylsilyl, and
(4) epoxy,
(5) (meta)acryloyl optionally substituted with at least one halogen atom, and
(6) (3) alkyl and alkoxy each substituted with at least one substituent selected from the group consisting of:
(a) cyano group,
(b) aldehyde,
(c) alkynyl optionally substituted with at least one halogen atom,
(d) vinyl alkenyl optionally substituted with at least one halogen atom,
(e) epoxy, and
(f) (meta)acryloyl (meth)acryloyl optionally substituted with at least one halogen atom,
ma1 and ma2 are independently 0 or 1, and the sum of ma1 and ma2 is 1 or 2 ;
R a1L and R a2L are the same or different, and each represents a phenyl group optionally having, in addition to ma1 R a1S or ma2 R a2S , at least one substituent selected from the group consisting of fluoro group, perfluoro organic group, and pentafluorosulfanyl.

2. A fluorine-containing compound represented by formula (4-3):
(R a1S —) ma1 R a1L —CF 2 —CF 2 R a2L (—R a2S ) ma2   (4-3),

wherein
the moiety represented by (R a1S —) ma1 R a1L indicates R a1L substituted with ma1 R a1S ; p1
the moiety represented by R a2L (—R a2S ) ma2 indicates R a2L substituted with ma2 R a2S ;
R a1S represents 1,3-dioxo-1,3-dihydroisobenzofuran 5-yl 1,3-dioxo-1,3-dihydroisobenzofuran-5-yl;
R a2S represents
(1) 1,3-dioxo-1,3-dihydroisobenzofuran 5-yl 1,3-dioxo-1,3-dihydroisobenzofuran-5-yl,
(2) amino,
(3) carboxy at para-position, or
(4) halogenocarbonyl;
ma1 is 1;
ma2 is 0 or 1; and
R a1L and R a2L are the same or different, and each represents (a) a phenyl group or a biphenyl group, or (b) a bond, with the proviso that when R a2S is (2) amino, (3) carboxy at para-position, or (4) halogenocarbonyl, R a2L is (a) a phenyl group or a biphenyl group.

3. The fluorine-containing compound according to claim 1 , wherein R a1S and R a2S are the same or different, and each represents independently a moiety selected from the group consisting of (1) cyano, (2) aldehyde, (3) alkenyl, (4) (2) alkynyl optionally substituted with trimethylsilyl, (5) epoxy, (6) (meta)acryloyl optionally substituted with at least one halogen atom, and (7) (3) alkoxy substituted with epoxy.

4. The fluorine-containing compound according to claim 1 , which is selected from the following compounds:

wherein TMS represents a trimethylsilyl group.

5. The fluorine-containing compound according to claim 2 , which is selected from the following compounds:

6. A method for producing the fluorine-containing compound according to claim 1 , the method comprising reacting a fluorine-containing complex compound comprising:
a fluorine-containing organic metal compound represented by formula (1a):
R 1 —CF 2 —CF 2 —M 1   (1a)

wherein M 1 is a metal selected from the group consisting of copper, zinc, nickel, iron, cobalt, and tin; and R 1 represents (R a1S —) ma1 R a1L as defined above, and
at least one ligand selected from the group consisting of pyridine ring-containing compounds and phosphines-fluorine-containing complex compound,
with a halogen compound represented by formula (5):
X—R 2   (5)

wherein R 2 represents R a2L (—R a2S ) ma2 as defined above; and X represents a halogen atom.

7. A method for producing the fluorine-containing compound according to claim 2 , the method comprising reacting a fluorine-containing complex compound comprising:
a fluorine-containing organic metal compound represented by formula (1a):
R 1 —CF 2 —CF 2 —M 1 (1a)

wherein M 1 is a metal selected from the group consisting of copper, zinc, nickel, iron, cobalt, and tin; and R 1 represents (R a1S —) ma1 R a1L as defined above, and
at least one ligand selected from the group consisting of pyridine ring-containing compounds and phosphines-fluorine-containing complex compound,
with a halogen compound represented by formula (5):
X—R 2   (5)

wherein R 2 represents R a2L (—R a2S ) ma2 as defined above; and X represents a halogen atom.

Assignees

• Daikin Ind Ltd
• Univ Osaka

Inventors

• Adachi Kenji
• Shibanuma Takashi
• Nagai Takabumi
• Ogoshi Sensuke
• Ohashi Masato

Classifications

• C07C47/55

  containing halogen · CPC title

• C07C41/30

  by increasing the number of carbon atoms, e.g. by oligomerisation · CPC title

• C07D307/87

  Benzo [c] furans; Hydrogenated benzo [c] furans · CPC title

• C07F7/18

  Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages · CPC title

• Y02E60/50

  Fuel cells · CPC title