JPS6317835A - Production of fluorine-containing unsaturated carbon compound - Google Patents

Abstract

PURPOSE:To readily produce a fluorine-containing unsaturated carbon compound to be a raw material for fluorine-containing polymers, by reacting a readily available polyfluoroalkyl iodide with a terminal acetylene in the presence of a palladium catalyst and base. CONSTITUTION:A polyfluoroalkyl iodide expressed by formula I (R<1> and R<2> are H, halogen or polyfluorocarbon), e.g. perfluorooctyl iodide, etc., is reacted with a terminal acetylene expressed by formula II (R<3> is H, alkyl, alkenyl, aryl, aralkyl or silyl), e.g. 1-hexyne, etc., in the presence of a palladium catalyst, particularly preferably a palladium complex, e.g. dichlorobis(triphenylphosphine) palladium, etc., and a base, e.g. alkali metal hydride, triethylamine, etc., to afford the aimed fluorine-containing unsaturated compound expressed by formula III, e.g. 2-butyl-1-perfluorooctyl-1-octen-3-yne, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a fluorine-containing unsaturated carbon compound that is a raw material for a fluorine-containing polymer.

Fluorine-containing unsaturated carbon compounds such as fluorine-containing olefins, acetylenes, dienes, and enynes are important as monomers for fluorine-containing functional polymers including water- and oil-repellent polymers [for example, organic fluorine-containing Chemistry (f [) Gihodo (1)
973)].

[Conventional technology]

Among the above-mentioned fluorine-containing unsaturated carbon compounds, especially for enyne compounds, there are almost no easy and general manufacturing methods that can be carried out industrially.

Nodada-''7 A commonly known manufacturing method is to react trifluoropropyne with ethylmagnesium bromide and then react with allyl halide, but this method requires the use of dangerous organometallic reagents. Moreover, it is not possible to produce a conjugated enyne compound.

[Problem that the invention seeks to solve]

The present inventors have overcome the above-mentioned drawbacks and developed a simple method for producing fluorine-containing conjugated enyne compounds, which have been difficult to synthesize in the past, and have also developed a technology that can provide the world with new fluorine-containing monomers. was established and the present invention was completed.

[Means to solve the problem]

The present invention is based on the general formula [wherein R1 and R2 are a hydrogen atom, a halogen atom, or a polyfluorocarbon group, and R3 is a hydrogen atom, an alkyl group, an alkenyl group, an aryol group, an aralkyl group, or a silyl group] . ] is a method for producing a fluorine-containing unsaturated carbon compound represented by the general formula (1) in the presence of a palladium catalyst and a base. It can be produced by reacting a polyfluoroalkyl iodide represented by the same formula with a terminal acetylene represented by the general formula %) [wherein R3 is the same as above].

The present invention requires that the reaction be carried out in the presence of a palladium catalyst. Palladium catalysts that can be used include palladium metal such as palladium fine powder and palladium black, palladium salts such as palladium halides, acetates and nitrates, palladium supported on carriers such as palladium carbon and palladium alumina, palladium acetate,
Examples include catalysts in which tertiary phosphine is added to palladium salts such as palladium chloride, palladium complexes such as dichlorobis(triphenylphosphine)palladium and tetrakis(triphenylphosphine)palladium, and catalysts in which these palladium complexes are supported on carriers. However, from the viewpoint of yield, it is preferable to use a palladium complex.

The amount of the palladium catalyst to be used can be appropriately selected from a range of 1/10000 to 115 equivalents based on the compound represented by the general formula (II).

When carrying out the present invention, the yield may be improved by adding a copper compound, and in such cases, it may be added as a co-catalyst as appropriate.

Examples of copper compounds that can be used include metallic steel, copper salts such as copper chloride, copper bromide, copper iodide, and copper acetate. The amount of the copper compound to be used can be appropriately selected from a range of 1/l O00 to 115 equivalents relative to the compound represented by the general formula (II).

The present invention must be carried out in the presence of a base! subject. As bases, alkali metal hydrides, hydroxides,
Examples include amines such as carbonates, hydrogen carbonates, alkali metal alkoxides, alkali metal amides, triethylamine, N,N-dimethylaniline, and pyridine.

The amount of the base to be used can be appropriately selected within the range of 1 to 5 equivalents relative to the compound represented by the general formula (II).

The polyfluoroalkyl iodide represented by the general formula (II), which is a raw material of the present invention, is a compound that is easily available industrially, and includes, for example, iodofluoromethane, 1-iodopentafluoroethane, 1-iodo Hebutafluoropropane, 1-"?-)' nonafluorobutane, l-iodoperfluorohebutane, 1-iodoperfluorooctane, 1-iodoperfluorodecane,
2-iodohebutafluoropropane, 2-promo 1-
iodotetrafluoroethane, 1,2-dichloro-1-
Iodorifluoroethane, 1,2-short tetrafluoroethane, l-chloro-2-iodo-1,1,2-
) Lifluoroethane, 1.4-short perfluorobutane, 1.6-') iodoperfluorohexane, 1.
8-Short perfluorooctane, 2-nonafluorobutyl-1゜1-difluoro-1-iodoethane, 1,
3.3°3-Tetrafluoro-1-iodopropane, iodoperfluorotoluene, etc. can be used.

As the terminal acetylene represented by the general formula (II), which is another raw material of the present invention, various compounds can be used, such as acetylene, propylene,
-butyl, 1-pentyne, 1-hexyne, l-heptyne, 1-octyne, 1-decyne, 3-methyl-1-butyne, 3.3-dimethyl-1-butyne, 4-methyl-1-pentyne, trifluoro Lopropine, pentafluoro-1-
Butyne, heptafluoro-1-pentyne, 3-trifluoromethyl-3,4,4,4-tetrafluoro-1-butyne, 1-H-perfluorohexine-1,1-H-perfluoroheptine-1, 1-H-perfluorooctin-1, propargyl alcohol, propargyl acetate, 3-methyl-1-butyn-3-ol, 4-methyl-3-hebuten-3-yne, phenylacetylene, naphthylacetylene, 3-phenyl- Examples include 1-propyne, trimethy;'IIv=, +IIv π7cetylene, phenyldimethy)aγcetylene, t-butyldimethylsilylacetylene, chlorodimethylsilylacetylene, methoxydimethylsilylacetylene, jetoxymethylsilylacetylene, etc. . The amount of terminal acetylene used is determined by the above general formula (II).
A range of 2 to 10 equivalents can be selected as appropriate for the compound represented by.

In carrying out the present invention, it is not a problem to use solvents (e.g., hydrocarbon solvents, alcoholic solvents, ethereal solvents, halogenated solvents such as acetonitrile, dimethylsulfoxide, N,N-dimethylformamide, etc.). Protic and protic scratching solvents can be used alone or in appropriate combinations.

The reaction proceeds at a temperature ranging from room temperature to 200°C, but from the viewpoint of reaction efficiency and economy, a temperature range of 50°C to 120°C is preferred.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 C, F, 7I + 21 hair C = Mi CC4H
2-11---In a micro test tube, dichlorobis(triphenylphosphine) palladium 5■ (7, IX 1
(I'm-mo 1), iodide 1142* (
1,1x 10-”m-mol), potassium carbonate 40w
(0.29 mmo 1), add 0.3 ml of chloroform and 60 μi of ethanol, and add 86 u of l-hexyne.
1 (0.75 mmol) and 5 μl (0.242 mmol) of perfluorooctyl yoshitro were added, capped and stirred at room temperature for 30 minutes, then heated and stirred at 50°C for 17 hours. It was quantitatively determined by gas chromatography, and 2-butyl-1-perfluorooctyl-1-octen-3-yne was 74% (isomer ratio 10:
It was obtained in a yield of 90). The product was separated using a gas chromatograph, and its structure was determined from the spectrum shown below.

2-Butyl-1-perfluorooctyl-1-octen-3-yne'HNMR (CDCIs, TMS) 60.93 (t, 6
1 (, J-7Hz), 1.3-1.6 (m, 8H), 2
．． 3-2.4 (m, 4H).

5.58or5.71 (t, IH, J=15Hz)
.

I″F-NMR (CDCIS, CFCIs) δ-81,
3 (t, 3F, J-9, 6Hz).

-105,5 (m, 2F), -122,2 (m.

6F), -123,1 (m, 2F).

-123,6 (m, 2F), -126,5 (m.

2F).

IR (KBr plate) 2230°16301
-1゜MS (m/z) 582 (M”, 7%), 540
(51%), 525 (39%), 163 (
7%), 107 (100%).

Elemental analysis C*IHI9Fl? calcd:C,41,25:1(,3,29fou
nd: C, 41, 29; , Verfuquoorooctyl rhodide 65 μl (0,242 mmo 1)
, l-hexane 86 ttl (0,75 mmol) and triethylamine 70 μJ (0,50 mmol)
The reaction solution was capped and continued to be heated and stirred at 80°C for 3 hours, then subjected to gas chromatography for quantitative determination, and transferred to a 2-butyl Example 3C,J",I+2HC3C8iMe5->micro test tube. , dichlorobis(triphenylphosphine)
Palladium 5■ (7,IX 10-'m-mol),
Iodide-3M2m (1,1x10-”m-mol)
, potassium carbonate 40s (0,29 mmol), chloroform 0.3 ml, ethanol 60 μj, )limethylsilylacetylene 100 #1 (0,71 mmol), perfluorobrobyl iodide 36 μj (0,249 m
mol) was added, the cap was capped, and stirring was continued for 30 minutes at room temperature.The 0 reaction solution was heated and stirred at 50°C for 17 hours, and then subjected to gas chromatography to quantify l-perfluoropropyl-2,4. -ditrimethylsilyl-1-buten-3-yne was obtained in a yield of 70% (isomer ratio 70:30). The product is separated by gas chromatography,
The structure was determined from the spectrum below.

1-Perfluoropropyl-2,4-ditrimethylsilyl-1-buten-3-yne'H-NMR (CDCIs, TMS) lj O,23o
r0.18 (s, 9H), 0.26or0.20(s
, 9H), 6.57or5.88 (t, IH.

Jw-15H2o r 12Hz).

"F-NMR (CDCl2.CFCIs) δ-80
,9or-81,1(t, 3F, J-9,4
o r 9.5 Hz), 108.4 o r-1
10,5 (m, 2F), -127,6or-1
28,2 (s, 2F).

IR (KBr plate) 2130°1580,
840om-'.

MS (m/z)364 CM”, 2%or1
%).

157 (35or8%), 133 (18o
r6%), ? ? (100or93%), 73(
99orlOO%).

Example 4 Dichlorobis(triphenylphosphine)palladium IO (1,4X IQ-''m-mol
), 130μIl perfluorooctyl iosite (
0,484 mmo 1), trimethylsilylacetylene 212 μ! (1,5mmo 1) and triethylamine l O5,! f 1 (0.75 mmo 1) was added and camped, and the 0 reaction solution was heated and stirred at 80°C for 3 hours. The 0 reaction solution was directly subjected to gas chromatography and quantitatively determined. -Buten-3-yne was obtained in a yield of 21% (isomer ratio 30 near 0).

The product was separated using a gas chromatograph, and its structure was determined from the spectrum shown below.

1-Perfluorooctyl-2,4-ditrimethylsilyl-1-buten-3-yne'HNMR (CDC1s, TMS) 60.22 (
s, 9H), 0.26 (t, 9H, J-1, 4Hz)
, 6.56 (t, LH, J-16)Iz).

"F-NMR (CDCIs, CFCIs) δ-80
, 6 (t, 3F, J=10Hz).

-106,5 (q, 2F, J=15Hz).

-121,1 (m, 6F), -121,5
(n.

4F), -125,3 (m, 2F).

IR (KBr plate) 2130°1580,
845<! l-'.

MS (m/z) 614 (M”, )
, 483°407, 383. 157. 77
(100%).

Elemental analysis C+sHt*F+tS 1lcalcd:C
,35,18;H,3,12found+c, 35
．． 19; H, 2,92 Example 5 08F, 7I + HCmi C04H7 --- ÷ In a micro test tube, palladium chloride 1.3 (7,3X10°" mm
l) ,) Riphenylphosphine 4.1w (1,6
X 10-”mmo 1), 1-hexine 86 μl
-(0,75mmol), Bell 7) LtO.

Octyl Yositro 5 tll (0,242 mmo 1
), triethylamine? 0uj (0,50mmo
1) was added, the mixture was capped, and the mixture was heated and stirred at 80° C. for 3 hours. After cooling, the reaction solution was directly transferred to a gas chromatograph to obtain 2-butyl-1-belfluoroctyl-
39% 1-octen-3-yne (isomer ratio 10:90
) with a yield of

Claims (2)

[Claims] (1) In the presence of a palladium catalyst and a base, the general formula ▲ includes a mathematical formula, a chemical formula, a table, etc. ▼ [In the formula, R^1 and R^2 are a hydrogen atom, a halogen atom, or a polyfluorocarbon group. ] and a polyfluoroalkyl iodide represented by the general formula R^3C≡CH (wherein R^3 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a silyl group.)
General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1, R^2 and R^3 are the same as above. ] A method for producing a fluorine-containing unsaturated carbon compound. (2) The method according to claim (1), which comprises using a copper compound as a promoter.