JPS59148791A - Production of organosilane - Google Patents

Abstract

PURPOSE:The reaction of an organic halide with a Grignard reagent of alkoxysilylmethyl readily gives a difunctional organosilane used in medicine and fine chemicals in high yield. CONSTITUTION:The reaction between 1mol of an organic halide of the formula: R<1>X (R<1> is monovalent organic radical; X is halogen) and 1-2mol of an alkoxysilylmethyl Grignard reagent of the formula: (R<2>O)2CH3 SiCH2MgCl (R<2> is 1-4C alkyl) is conducted, preferably in an organic solvent such as tetrahydrofuran in the presence of a catalyst such as CuI to give an organosilane of the formula: (R<2>O)2CH3SiCH2R<1>.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing organosilanes, and in particular to a method for producing difunctional organosilanes having various # substituents.

Various methods are already known for producing organosilanes, but the present invention aims to provide a method for producing bifunctional silanes useful for pharmaceuticals and other fine chemicals using a special Grignard reagent. This is a Th-1m halogen compound represented by the general formula RX (R is a monovalent organic group or a halogen atom) and the general formula (
R20) 2-OH5iOHMg0t (wherein R2 is an alkyl group having 1 to 4 carbon atoms) is reacted with an alkoxysilylmethyl Grignard reagent to obtain the general formula (R"0)
It is characterized by being an organosilane represented by OH3Si6H2.

To explain this, 1. The present inventors have studied the manufacturing method of special silanes, and found that various special silanes can be easily synthesized by using the alkoxysilylmethyl Grignard reagent newly synthesized by the present inventors. As a result of further investigation, we found that a coupling reaction between this Grignard reagent and an organic halogen compound can easily produce bifunctional organosilane in high yield using the following formula. The present invention was completed after confirming that it could be obtained.

The organic halogen compound used as an initiator in the method of the present invention is represented by the general formula R''X, in which the R1 group is a monovalent PJA group, which includes a methyl group and an ethyl group.

Alkyl groups such as globyl group, butyl group, hegetyl group-ogtyl group, vinyl group, allyl group, phenylallyl group,
Alkenyl groups such as nonenyl groups, aromatic hydrocarbon groups such as phenyl groups and tolyl groups, methoxy groups, cyano groups,
Examples include a group containing an aromatic group substituted with an ester group, and an organic group having a bicyclic ring containing a heteroatom such as a nitrogen atom or a sulfur atom. Examples include iodine.

It also reacts with this organic halogen compound. As mentioned above, the alkoxysilylmethyl Grignard reagent used as a starter has the general formula %, but the R2 group constituting this alkoxy group has a carbon number such as a methyl group, ethyl group, propyl group, or butyl group. This is a novel Grignard reagent created by the present inventors. This Grignard reagent consists of alkoxysilylmethylsilane (R"0) OH, 5iOH2-Ct and magnesium gold in a suitable solvent such as diethyl ether, 4 diptyl ether + tetrahydrofuran (preferably tetrahydrofuranf, etc.). When the alkoxy group is an ethoxy group, the resulting Grignard reagent is unstable and the yield is around 20 yen.If the alkoxy group is an ethoxy group, the resulting Grignard reagent has a weak hydrolyzability and is not useful. However, if this alkoxy group is replaced with an isog-a-boxy group, a stable Grignard reagent can be obtained with a high yield of 95%.This Grignard reagent can be obtained by reacting it with zinc chloride (R0 ) The organic zinc reagent represented by CH3SiOH2ZnCt may be reacted with the organic halide represented by R' X described above.

In the method of the present invention, this alkoxysilylmethyl Grignard reagent is added from 1 to 1 mole of the above-mentioned organic halogen compound.
This is carried out by blending 26 moles and reacting them. Although this reaction proceeds at room temperature, it may be heated up to 50°C.

This may also be cooled to 0°C to -50°C in order to increase the target position of the organic group R1 to be included in alfoxysilylmethyl, that is, summer selectivity.

Moreover, this reaction is often carried out in an organic solvent.
As this organic solvent, one that is inert to the reactant, such as tetrahydrofuran, dimethylformamide, acetonitrile, dioxane, benzene, toluene, xylene, etc., may be used.

As mentioned above, this reaction proceeds even at room temperature, but
This can be carried out in the presence of catalysts, such as copper, nickel, baladium compounds 1, etc.
uI, Ni0t2(dPPP).

Pd0t, (dPPf) (Tarishi dPPP is (06H
s) 2P(OH2)3P(C,H,), -dPPf means i,i'-his-diphenylphosphine ferrocene] and the like are preferred - these are 1 NlO mol tiq of reactants for OuI. .

NIOZZ (d P P P ), P d OZ
2 (d P P f ) may be used at about 0.1 to 5 molar ratio.

In summary, the present invention is a method for producing organosilane by the reaction of an organic halogen compound and an alkoxysilylmethyl Grignard reagent, and according to this,
The 2-bifunctional silane represented by OH5iOHR can be obtained easily and in high yield.
This bifunctional silane can be easily made into various special silanes by introducing various substituents into it, and it can also be hydrolyzed under appropriate conditions and copolymerized with dimethylsiloxitin. Since it is possible to provide various new polysiloxanes if
It is said to be useful in the synthesis of V-loxane.

Next, examples of the present invention will be given.In one example, Me is a methyl group, Et is an ethyl group, -1-Pr is an isograhylic group, and P
h represents a phenyl group.

Glue example (synthesis of alkoxysilylmethyl Grignard reagent) A 50t/50 t/m unit equipped with a cooling tube, 1 isobaric dropping funnel, and a magnetic rotor.
74 square meters of magnesium powder was weighed out into a 20 flask, heated and dried under reduced pressure over direct fire, and after being allowed to cool, 2 d of dried tetrahydrofuran was added thereto.

Next, add (i-Pro)2MeSiOH2 to the dropping funnel.
A mixture of 4.74 g (22.5 mol) of Tochitrahydrofuran and 1/4 t of it was added to the magnesium powder at room temperature, and when heated, violent reflux occurred due to self-heating accompanying the start of the reaction. At this point, I added tetrahydrofuran l□n/ and started dropping o-
) was added dropwise at 0°C, and stirring was continued for 2 hours after the completion of the drop to complete the reaction, resulting in formula 1 (i -P r
An alkoxysilylmethyl Grignard reagent represented by O)2Me S i OH2Mg0L was obtained.

Example 1゜5011 equipped with cooling tube 1 isobaric dropping roll and magnetic rotor
1.33 g of n-ogtyl bromide in 20 flasks of
(7,0 mmol) and 141 mg of OuI as catalyst
After adding (0.74 mmol) and 12 rrrl of tetrahydrofuran, 9.0 mmol of the alkoxysilylmethyl Grignard reagent obtained in Example 4 was added dropwise from the dropping funnel at -60°C to -50°C. After stirring for 3 hours, the temperature was raised to 0°C over 2 hours.

Next, an aqueous solution of NH4O is added to the mixture to hydrolyze it, ether is added, and ether extraction is performed.

After washing with water, drying with -NH4So4 and distilling off the ether, single distillation was carried out using a Kugelrohr.

Analysis of the obtained product revealed that it was (ip
ro), MeSiOH, ('c, H,,), and the yield was 92 mm.

Note that the same treatment was performed using this organic halogen chemistry instead of n-octyl bromide≦2 in the above.

Luganosilane could be obtained in yields of 91% and 96%, respectively.

Example 2 2.67 g (14
, 6 mmol) and Ni072 (dPPP) as a catalyst.
After adding 80m9 (0.15 mmol) of tetrahydrofuran and 20a of tetrahydrofuran, 18 mmol of the alkoxysilylmethyl Grignard reagent obtained in Reference Example was added dropwise to the mixture at room temperature, and the mixture was stirred at 50°C for 18 hours.

Next, after confirming the disappearance of the original i[II halogen compound using a gas chromatograph, the entire aqueous NH4ClH4Cl solution was extracted at 0°C, dried over Na25O4, the ether was distilled off, and the remaining liquid was distilled using Gugelmiel. As a result, an organosilane represented by PhN to SiMe(i-Pro)2 was obtained, and the yield was 100%.

In addition, the same treatment was performed using the organic halogen compound shown by the formula in place of β-bromostyrene ζ in the above.

The organosilane represented by the formula has a yield of 85% and 90%, respectively.
%, I was able to get it with 88 sections.

Rimol, PdO22 (dPPf) as a catalyst 0,03
5 mmol and 12 ml of tetrahydrofuran were added, and 19.0 mmol of isoglopoxymethylsilyl Grignard sample ff was added dropwise from the dropping funnel at room temperature.
The mixture was stirred at 50°C for 18 hours.

Next, after confirming the disappearance of organic halides using a gas chromatograph, 10 rnl of an aqueous NH4at solution was added dropwise at 0°C, followed by extraction three times with ether, and Na
After drying with 2 SO 4 - the ether was distilled off.

Furthermore, the C2 residual liquid was distilled using a Kugelrohr.

An organosilane represented by e λso\OH 2 S i -( 1-Pro)2 was obtained in a yield of 63%.

Examples 4 to 8 The isoglopoxymethylsilyl Grignard reagent obtained in the reference example was mixed with an equivalent amount of zinc chloride (Zn0Lz) and reacted to form M2O3 of this Grignard reagent.
Organozinc reagents were made in which the groups were substituted with Z n Ot groups.

Next, in the same reaction vessel as in Example 1, 7.0i! of the organic halogen compound shown in the first column below was added. I mole and P as catalyst
0.035 mmol of dO22 (dPPf) and 12 ml of tetrahydrofuran were added, and to this was added 90 mmol of the above organozinc reagent having an isopropoxymethylsilyl group from the dropping funnel at room temperature, and the mixture was heated to 18 ml at 50°C.
Stir for hours.

After confirming the disappearance of organic halides using a gas chromatograph, 10 ml of an aqueous solution of NH4O was added dropwise at 0°C, followed by extraction three times with ether.
After drying with 2 SO a, the ether was distilled off (
When this residual liquid was distilled using a Gugelrohr, the organosilanes listed in Table 1 were obtained.

Procedural amendment 1. Indication of the case 1982 Patent Application No. 23591 2, Name of the invention: Process for producing organonlan 3, Person making the amendment”; Relationship to the case Name of patent applicant (206) Shin-Etsu Chemical Co., Ltd. 4, Agent Address: Nagai Building, 4-9 Nihonbashi Honmachi, Chuo-ku, Tokyo 103 [TL story Tokyo <270) O858,0859]
Voluntary action 6. "Claims column" and "Detailed description of the invention column" in the specification subject to amendment 7. Contents of amendment 1) Claims from line 104 to page S2, line 3 of the specification Correct as shown in the attached sheet.

2) r(R”O on page 3, line 1 and page 7, line 10 of the specification)
) 0H3slOH2R”J Y r(R20)20H
Correct with 3SiOH2R1J.

3) Mei 11 (book page 5, lines 2-3 Kei Kei siege ship±koreko's ``(R2
0) OH3S10H2-CJ, J as “(R20)2CH
Correct as 3SICH2-C1J.

4) "I'll give you something" in line 8 of the detailed boat, "I'll give you something."
” he corrected.

5) [NH45Od on page 9, line 16 of the specification] [Na25
Correct as o4J.

6) "Organohalogen chemistry" on page 10, line 5 of the specification is corrected to "organohalogen compound."

7) Statement yi, line 11@12 "phゝ\?be, 8x
Me (1-Pro) 2J [Ph\/\/ SIMe
Correct as (1-Pro)2J.

8) Correct ``Organic halide J'' in page 13, line 3 of Bright 14fl i'l to read ``1 organic halogen compound''.

10) "Organic halide" on page 14, line 8 of the specification is replaced with "
Corrected to ``Wataru halogen compounds''.

11 r (R2o)ca, page 5, line 15 of the specification, 5
ica2Zn(J J r(R20), aH, 5iCH
Correct as 2” lnU l.

The above claims and the general formula (R20)OH5ICHMgC1 (here 2
3 2 ζ 2 R 2 is an alkyl group having 1 to 4 carbon atoms) is reacted with an alkoxysilylmethyl Grignard reagent to form an organo 2 3 2 silane represented by the general formula (R20) OH5ICHR' A method for producing an organosilane 2. A method for producing an organosilane according to claim 1, which uses a compound of Ou, N1, and Pd as a catalyst. A patent in which the alkoxysilylmethyl Grignard reagent is an isopropoxysilylmethyl Grignard reagent. Method for producing organosilane according to claim 1 or 2

Claims (1)

[Claims] 1. An organic halide represented by the general formula R"X (where R1 is a monovalent organic group, and X is a halogen atom) and m general formula (
R20) 2CH3s1cH2Mg at (where R is an alkyl group having 1 to 4 carbon atoms) is reacted with an alkoxysilylmethyl Grignard reagent to form an organosilane represented by the general formula '(RO)CH,5iOH2R. Characteristic method for producing organosilane 2. Method 3 for producing organosilane according to claim 1 using a compound of 0'u-Ni-Pd as a catalyst. Alkoxysilylmethyl Grignard reagent Kaisoge a boxysilyl A method for producing an organosilane according to claim 1 or m2, which is a methyl Grignard reagent.