JP2002088090A - Method for manufacturing organosilicon compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of manufacturing a polyfluoro organosilicon compound efficiently at a low cost on an industrial scale by the hydrosilylation of polyfluoroolefin. SOLUTION: A polyfluoro organosilicon compound is manufactured by reacting polyfluoroolefin with a hydrosilane compound in the presence of a transition metal complex having a polyfluorophosphine compound as the ligand by using supercritical carbon dioxide or liquefied carbon dioxide as a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing a polyfluoroorganosilicon compound by directly reacting a polyfluoroolefin with a hydrosilane compound.

[0002]

2. Description of the Related Art Conventionally, as a method for synthesizing an organosilicon compound, a so-called direct method of reacting simple silicon with an organic halogen compound, a method of reacting a halosilane with a Grignard reagent, a hydrosilylation reaction of reacting an unsaturated organic compound with hydrosilane, and the like. It has been known. Among them, the hydrosilylation reaction is a useful reaction capable of obtaining various organic silicon compounds using inexpensive raw materials such as olefins. Usually, the hydrosilylation reaction is carried out using a transition metal compound containing platinum, rhodium, or the like or a radical generator as a catalyst. Was.

On the other hand, polyfluoro organic compounds have excellent physicochemical properties with respect to heat resistance, acid resistance, base resistance, water repellency, oil repellency and the like, and are used for various functional materials (trade names: Teflon, PEEK, etc.). It has also been reported that certain polyfluoroorganosilicon compounds exhibit interesting properties as silane coupling agents, such as improving the chemical and physical properties of the glass surface. However, its synthesis requires a special fluorinated organic solvent,
Yields are not satisfactory [Bulletin of Japan C
Chemical Society, ”Vol. 66, Nos. 472-476
Page (1993)], it has been desired to establish an industrially advantageous synthesis method that is more efficient and has less environmental impact.

[0004] In recent years, a technique of using supercritical or liquefied carbon dioxide as an alternative to an organic solvent has attracted attention, and research on using it for a reaction surface has been actively conducted. This method is 1) less toxic and flammable in the reaction medium and is environmentally friendly compared to the conventional reaction method using an organic solvent. It has the advantage that it can be separated and removed. Especially when used in combination with a metal complex catalyst,
A case has been reported in which activity and selectivity are significantly improved [Chemical Review, Vol. 99, pp. 353-354].
Page (1999)]. Furthermore, it has been described that supercritical or liquefied carbon dioxide has a high affinity for perfluoroorganic compounds and is an excellent reaction medium [Chemic
al Review Magazine ", Vol. 99, pp. 475-493 (199
9 years)], and no application of polyfluoroolefin to hydrosilylation reaction is known.

[0005]

Under such circumstances, the present invention provides a polyfluoroorganosilicon compound (for example,
It is an object of the present invention to provide a method for efficiently producing a silane coupling agent having a perfluoro group) at a high yield and industrially.

[0006]

The present inventors have conducted intensive studies on hydrosilylation of polyfluoroolefin, and as a result, using supercritical carbon dioxide or liquefied carbon dioxide as a solvent, and converting a polyfluorophosphine compound into a ligand. It has been found that a homogeneous phase is formed by carrying out the reaction in the presence of the transition metal complex described above, and the above object can be achieved, and the present invention has been completed based on this finding. The transition metal complex referred to in the present specification is preferably a Group 8 transition metal complex.

That is, according to the present invention, a polyfluoroolefin is reacted with a hydrosilane compound using supercritical carbon dioxide or liquefied carbon dioxide as a solvent in the presence of a transition metal complex having a polyfluorophosphine compound as a ligand. It is intended to provide a method for producing a polyfluoroorganosilicon compound characterized by the above.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, the polyfluoroolefin used as a raw material has no particular restriction on the number of carbon atoms, but preferably has 2 to 20 carbon atoms, particularly preferably 4 to 12 carbon atoms. If the number of carbon atoms is too large, the starting compound becomes expensive and its reactivity is lowered, which is industrially disadvantageous. The olefin may be substituted with a group inert to the hydrosilylation reaction, such as an alkoxy group, an aryloxy group, a bis (hydrocarbyl) amino group, another halogen atom, and the like. The polyfluoroolefin used in the present invention has two or more fluorine atoms on at least one carbon atom. Preferably, all the hydrogen atoms on the carbon atom are fluorine atoms. (Perfluoro group).

The hydrosilane compound used in the method of the present invention is represented by the general formula HSiR ¹ R ² R ³ , wherein R ¹ , R ² and R ³ are hydrogen, an alkyl group (preferably having carbon atoms). Is 1 to 20, more preferably 1 to 3, and an alkoxy group (preferably having 1 to 2 carbon atoms)
0, more preferably 1-3), an aryl group (preferably 6-18, more preferably 6-10), etc., which may be the same or different from each other. , R ¹ , R ² , and R ³ are all hydrogen, and those in which R ¹ , R ² , and R ³ are all alkyl groups are excluded. Particularly preferred examples of the hydrosilane compound represented by the above general formula include dimethoxymethylsilane, methoxydimethylsilane, dimethoxyethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, and methoxydiphenylsilane. In the present invention, the reaction mole of the hydrosilane compound per 1 mole of the polyfluoroolefin is preferably 1 to 5 mole, more preferably 1 to 3 mole.

In the method of the present invention, a transition metal complex having a polyfluorophosphine compound as a ligand is used as a catalyst. Examples of the transition metal component in the transition metal complex include ruthenium, rhodium, iridium, nickel, palladium, platinum and the like. Among these, ruthenium and rhodium are preferable, and ruthenium is particularly preferable in consideration of selectivity.

In this transition metal complex, examples of the phosphine compound used as a ligand include a general formula R 1 R 2 R 3 P (I) (wherein R 1, R 2 and R 3 are an aryl group or an aralkyl group aromatic hydrocarbon, respectively) A monophosphine compound represented by the general formula R4R5P-A-, or an alkyl group or an aliphatic hydrocarbon group of a cycloalkyl group, which may be the same or different. PR6R7 (II) (wherein R4, R5, R6 and R7 are an aryl group, an aralkyl group aromatic hydrocarbon group and an alkyl group,
Cycloalkyl groups such as aliphatic hydrocarbon groups, which may be the same or different, and A is an alkylene group, a cycloalkylene group, an arylene group, an aralkylene group or a ferrosenylene group. )).

The polyfluorophosphine compound used as a ligand in the present invention has two or more fluorine atoms on at least one carbon atom, and preferably has a hydrogen atom on the carbon atom. All of the atoms are substituted with fluorine atoms (perfluoro group).
The carbon number of each group represented by R1 to R7 in the general formulas (I) and (II) is not particularly limited, but is usually 20 or less. Further, R1 to R7 are more preferably an aromatic hydrocarbon group such as an aryl group having a fluorine substituent or an aralkyl group than an aromatic hydrocarbon group such as an aryl group or an aralkyl group and an aliphatic hydrocarbon group such as an alkyl group or a cycloalkyl group. Groups and aliphatic hydrocarbon groups such as alkyl groups and cycloalkyl groups are preferred from the viewpoint of catalytic performance. The general formula (I) or (II)
Specifically, the polyfluorophosphine compound represented by
f ₃ ), tri-para-perfluorophenylphosphine, tri-para-perfluorophenyl phosphite R
_{f: -CH 2 CH 2 - (} CF 2) n -CF 3 n = 1~
20 °, tri-para-trifluoromethylphenylphosphine, di-para-trifluoromethylphenyltridecafluorohexylphosphine, para-trifluoromethylphenyldi-trifluorooctylphosphine, bis (di-para-trifluoromethylphenyl) (Phosphine) methane and the like.

In the method of the present invention, the catalyst is used as a catalyst.
The transition metal complex is the above-mentioned polyfluorophos as a ligand.
Any material having at least one fin compound
No particular restrictions. As such a transition metal complex
Is, for example, RhX (R1 (R2) R3P)₃, RhX (C
O) (R1 (R2) R3P)₂, RhX (R4 (R5) P-
A-PR6R7) ₃, RuX₂(R1R2R3P)₃, Ru
X₂(R4R5P-A-PR6R7)₃, RuX₂(CO)
(R1R2R3P)₂, RhX (CH₂= CH₂) (R1
(R2) R3P)₂, [Rh (R1 (R2) R3P)₄]
Y, [Rh (R1 (R2) R3P)₂(CNR)₂] Y,
Cp'RhH₂(R1 (R2) R3P), IrX (R1 (R
2) R3P)₃, IrX (CO) (R1 (R2) R3
P)₂, IrH₅(R1 (R2) R3P)₂, IrH
₃(CO) (R1 (R2) R3P)₂, IrX (CO)
(R4R5P-A-PR6R7), Cp'IrH₂(R1
(R2) R3P), Ni (CO)₄, Ni (R1 (R2) R
3P)₄, NiX₂(R1 (R2) R3P)₂, Ni (CH
₂= CH₂) (R1 (R2) R3P)₂, NiX₂(R4R
5P-A-PR6R7), PdX₂(R1 (R2) R3
P)₂, Pd (CH₂= CH₂) (R1 (R2) R3P)
₂, Pd (CO) (R1 (R2) R3P)₃, Pd (R1
(R2) R3P)₄, PdX₂(R4R5P-A-PR6R
7), PtX₂(R1 (R2) R3P)₂, Pt (CH₂=
CH₂) (R1 (R2) R3P)₂, Pt (CO) (R1
(R2) R3P)₃, Pt (R1 (R2) R3P)₄, Pt
(R1 (R2) R3P)₃, PtHX (R1 (R2) R3P)
₂, PtX₂(R4R5P-A-PR6R7) and the like.
It is. In the above formula, X is a halogen atom, hydroxyl
Group, cyano group, alkoxy group, carboxylate group or
Osianato group, Y is PF₆, B (C₆H₅)₄, B
F ₄, ClO₄, CN is an isonitrile group, R is alkyl
Group or aryl group, Cp 'is pentamethylcyclopenta
Represents a dienyl group, and R1 to R7 and A have the same meaning as described above.
Have.

In the method of the present invention, these transition metal complexes may be used alone or in combination of two or more. It is not necessary to prepare and use the transition metal complex in advance, and the phosphine compound and an appropriate transition metal compound are allowed to coexist in the reaction system, and the transition metal complex is used in the reaction system (in situ).
In u), a desired transition metal complex may be formed.

The transition metal compound used for such a purpose is not particularly limited, but examples of the case where the transition metal is rhodium include RhX ₃ , RhX (DE) ₂ ,
hX (EN) _{2 and the} like. In the above formula, DE represents norbornadiene, 1,5-cyclooctadiene or 1,5-hexadiene, EN represents ethylene or cyclooctene, and X has the same meaning as described above.

In the method of the present invention, supercritical carbon dioxide or liquefied carbon dioxide is used as a solvent, and a polyfluoroolefin is reacted with a hydrosilane compound in the presence of the transition metal complex to directly form a polyfluoroorganosilicon compound. can get. The phosphine metal complex with a polyfluoro substituent results in a homogeneous solution in a CO ₂ solvent under the reaction conditions, but the well-known metal complex does not dissolve completely. A phase change occurs depending on the reaction pressure. At 60 atm, the gas phase is a gas phase and a liquid phase. However, as the CO ₂ pressure increases, the gas phase decreases, and at around 300 atm, the reaction mixture becomes a completely uniform phase.

In the method of the present invention, the amount of the transition metal complex to be used is not particularly limited and may be arbitrarily selected. It is advantageous to choose a range. The raw material polyfluoroolefin may be initially charged all at once in the reaction system, or may be sequentially added to the reaction system. The reaction temperature and the reaction pressure are not particularly limited as long as they are in a supercritical region or a liquefaction region of carbon dioxide. Separation of the product after completion of the reaction can be easily carried out by subjecting the product to a normal separation operation such as distillation, recrystallization or chromatography after depressurization. Thus, a polyfluoroorganosilicon compound can be obtained efficiently by hydrosilylation of a polyfluoroolefin.

[0018]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The product was confirmed by the retention time of gas chromatography (GC) and the fragmentation pattern of GC-MS. Example 1 5 mg (0.005 mmol) of dichlorotris (tri-para-trifluoromethylphenylphosphine) ruthenium was placed in a 20 ml stainless steel autoclave.
And 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-
0.35 g (1 mmol) of octene and 0.22 g (1.2 mmol) of dimethoxymethylsilane were charged at room temperature. Next, liquefied carbon dioxide gas is charged from a carbon dioxide gas cylinder and the internal pressure is 60 kg.
/ cm ² . Thereafter, the autoclave was heated to 90 ° C. in an oil bath while stirring, the internal pressure was raised to 300 atm, and the reaction was carried out for 24 hours. After cooling the obtained reaction solution, the remaining carbon dioxide gas was released, and the reaction mixture was analyzed by gas chromatography. The overall yield of polyfluoroorganosilicon compound was 74% based on the charged 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene. there were.
The result is shown as No. 1 in Table 1. The reaction formula is as follows.

[0019]

Embedded image

Example 2 The procedure of Example 1 was repeated except that the internal pressure of the autoclave was raised to 230 atm and then reacted. The overall yield of polyfluoroorganosilicon compound was 70% based on the charged polyfluoroolefin. The result is shown in No. 2 of Table 1. Comparative Example 1 (organic solvent: hexane) 5 mg (0.005 mmol) of dichlorotris (tri-para-trifluoromethylphenylphosphine) ruthenium and 3,3,
0.35 g (1 mmol) of 4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene and 0.22 g (1.2 mmol) of dimethoxymethylsilane are added to 5 ml of hexane. Melted and charged. Thereafter, the inside of the autoclave was heated to 90 ° C. while stirring, and reacted for 24 hours. After cooling the obtained reaction solution,
The reaction mixture was analyzed by gas chromatography.
The overall yield of the polyfluoroorganosilicon compound was 3,3,
It was 5% based on 4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene. The results are shown in Table 1, No. 3. Comparative Example 2 8 mg (0.005 mmol) of dichlorotris (triphenylphosphine) ruthenium and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene 0.35 g (1 mmol) and 0.22 g (1.2 mmol) of dimethoxymethylsilane were charged. Then, liquefied carbon dioxide gas was filled from a carbon dioxide gas cylinder to adjust the internal pressure to 60 kg / cm ² . Thereafter, the inside of the autoclave was heated to 90 ° C. while stirring, the internal pressure was raised to 300 atm, and the reaction was carried out for 24 hours. After cooling the obtained reaction solution,
Residual carbon dioxide was released and the reaction mixture was analyzed by gas chromatography. The overall yield of the polyfluoroorganosilicon compound was 3,3,4,4,5,5,6,6,7,7,8,8,8-
It was 11% based on tridecafluoro-1-octene. The results are shown in Table 1, No. 4.

Example 3 8 mg (0.005 mmol) of chlorotris (tri-para-trifluoromethylphenylphosphine) rhodium and 3,3,4,4,
0.35 g (1 mmol) of 5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene and 0.1 g of dimethoxymethylsilane.
22 g (1.2 mmol) were charged. Then, liquefied carbon dioxide gas was filled from a carbon dioxide gas cylinder to adjust the internal pressure to 60 kg / cm ² . Then, while stirring the inside of the autoclave, 9
After heating to 0 ° C. and raising the internal pressure to 300 atm, the reaction was carried out for 24 hours. After cooling the obtained reaction solution, the remaining carbon dioxide gas was released, and the reaction mixture was analyzed by gas chromatography. The overall yield of the polyfluoroorganosilicon compound was 72% based on the charged 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene. there were. The results are shown in Table 1, No. 5.

Comparative Example 3 5 mg of chlorotris (triphenylphosphine) rhodium
(0.005 mmol), 0.35 g (1 mmol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene and 0.1 g of dimethoxymethylsilane. 22 g (1.2 mmol) were charged. Then, liquefied carbon dioxide gas was filled from a carbon dioxide gas cylinder to adjust the internal pressure to 60 kg / cm ² . Thereafter, the autoclave was heated to 90 ° C. while stirring, and the internal pressure was increased to 300 atm.
The reaction was performed for 24 hours. After cooling the obtained reaction solution, the remaining carbon dioxide gas was released, and the reaction mixture was analyzed by gas chromatography. The total yield of the polyfluoroorganosilicon compound is 1% based on the charged 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene. there were. The results are shown in Table 1, number 6. Example 4 Example 4 was carried out in the same manner as in Example 3 except that 0.005 mmol of carbonylchlorobis (tri-tdecafluorooctylphosphine) rhodium was used as a catalyst. The overall yield of polyfluoroorganosilicon compound was 50% based on the charged polyfluoroolefin. The results are shown in Table 1, number 7. Comparing Example 1 with Comparative Example 2, and Example 3 with Comparative Example 3, it is surprising that a complex having a phosphine compound containing a polyfluoro moiety as a ligand exhibits excellent catalytic activity. is there.

[0023]

[Table 1]

[0024]

According to the method of the present invention, various polyfluoroolefins can be prepared by reacting a polyfluoroolefin with a hydrosilane compound in the presence of a transition metal complex using inexpensive and easily available carbon dioxide as a solvent. An organosilicon compound can be efficiently produced at a high yield.

Claims (3)

[Claims] 1. A method comprising reacting a polyfluoroolefin with a hydrosilane compound using supercritical carbon dioxide or liquefied carbon dioxide as a solvent in the presence of a transition metal complex having a polyfluorophosphine compound as a ligand. A method for producing a polyfluoroorganosilicon compound. 2. The method according to claim 1, wherein the transition metal complex is ruthenium, rhodium,
The method according to claim 1, which is a complex of iridium, nickel, palladium or platinum. 3. The method according to claim 1, wherein the transition metal complex is a ruthenium or rhodium complex.