JPH03261789A - Silylamine manufacturing method - Google Patents

Abstract

PURPOSE:To produce the subject compound useful as a silylating agent, etc., for alcohols in good yield and simultaneously facilitate isolation with hardly any formation of by-products by reacting an amine compound with a hydrosilane in the presence of a specific catalyst. CONSTITUTION:(A) An amine compound expressed by the formula R<1>NH2 (R<1> is alkyl, alkenyl, etc.) is reacted with (B) a hydrosilane expressed by the formula HSiR<2>R<3>R<4> (R<2> to R<4> are R<1>) in the presence of a catalyst composed of (C) a halide of Ru and/or halide of Rh (preferably RuCl3 or RhCl3) and (D) a phosphine expressed by the formula P(R<5>)3 (R<5> is alkyl, aryl, etc.) so as to provide preferably 0.5-2 molar ratio of the components (A)/(B) to afford the objective compound expressed by the formula. Furthermore, the reaction is preferably carried out at 50-200 deg.C. The catalyst is used in a molar amount of preferably 0.01-0.5 based on the component (B) and the component (D) is used in a molar amount of preferably 0.1-10 times based on the component (C).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing silylamines. More specifically, the present invention relates to an amine compound represented by the general formula R'N H* and a silylamine represented by the general formula RINH3iR"R"R' from a hydrosilane represented by the general formula) (However, R1, Rt.

Hs%R' is an alkyl group, an alkenyl group, or an aryl group, and may contain functional groups such as COOH, C1, 0H1COOR, etc.).

BACKGROUND OF THE INVENTION Silylamines are frequently used as protecting compounds for amines or silylating agents such as alcohols.

The most common method for producing aminosilanes is to react amines with chlorosilanes, for example, J, AtC
hew, Soc, + Ko! , 4.5699 (19
52').

2 (CH3) 5sicl +4 R'NHz=
2 R'NH3Cl +2 (CHs) 5siNH
R' However, Rh is an alkyl group.

However, this method has problems such as: (1) it uses rolosilane, which is easily hydrolyzed and unstable, (2) it requires complicated separation operations, and (2) there is corrosion in the process. On the other hand, there are very few reports regarding the reaction between hydrosilane and amine according to the present invention.
hCl (PCJs) s- to snow (IrC1a),
WOCla, Cot(CO)*, Rh4(CO)+z
, a method using Pd/C as a catalyst has been proposed (B
ull, Chew, Soc, Jpn,, g,
2111 (1989); Zh, 0bshch,
Khim, 454 (10), 2257 (
1978);J, Organos+et, Che
m, 41+142 (1977); He1v.

Chin, ^cta,,,Ll (4)+1
408 (1966), ).

However, these methods have low yields of the desired silylamine and are still insufficient.

Problems to be Solved by the Invention An object of the present invention is to provide an industrial method for producing silylamine using hydrosilane as a raw material.

Means for Solving the Problems As a result of intensive studies to achieve the above problems, the present inventors have discovered that silylamine can be produced in good yield by reacting an amine compound and hydrosilane in the presence of a specific catalyst. They discovered this and completed the present invention.

That is, the present invention is based on the general formula R'NHz (where R' is an alkyl group, an alkenyl group, or an aryl group, and C0OH, Cj!,
○An amine compound represented by (which may contain a functional group such as H or COOR) and the general formula H3iR"R'R'
(However, R1, R3, and R4 are an alkyl group, an alkenyl group, or an atomyl group, and are C0OH, Cf, OH, C
), which may contain a functional group such as OOR, and a halide of Ru and/or Rh with the general formula P (R') z (R' is an alkyl group,
It is an alkenyl group or an aryl group. ) is a method for producing a silylamine represented by the general formula R1NHSiR2R'R'i'', which is characterized by carrying out the reaction in the presence of a phosphine represented by the following formula.

The reaction formula of the present invention is as follows.

R’NH1+H3iRtomiR1R4 The present invention will be explained in more detail below.

The following are exemplified as the amine compounds used in the present invention.

CH, NH,, C5HyNHz, C5HyNHz, t-C5HyNHz.

n −Cs Hr t N Ht , CHz = CH
-NHt, CHx-CH-CHxNHg The following are exemplified as hydrosilanes used in the present invention.

HSi(CHsh, HSi(Cz)is)z, HSi
(C1Ht)s, HSi(t-C4H9)z, HSi
(CHz)z(t-CaH,), H5i(CR2)(C
H=CHz)z, H5iCCH=CHt)s, The compositional ratio of these raw materials is not particularly limited and can be arbitrarily changed depending on the reaction mode.

Preferred charging composition ratio (amine compound/hydrosilane)
is 0.5 to 2 (molar ratio). Moreover, two or more types of each can be used simultaneously as raw materials if necessary.

The Ru halide used in the present invention is Ru
The three Rh halides used in the present invention, such as F x, RuC1z, RuBrx, and Ru13, are Rh
F3, RhCl s, RhBrx, Rhl! etc. Among these, RuCl3 and RhCl are particularly preferred.

As the phosphine used in the present invention, P (C
Hz)z, P (CzHs)i, P (t-CaHJ
s, P (cyclo-C,H,)s, P (CHz
CH'CHz)s, P (CH3)(C4H9)z, P (ChH5)3
Examples include.

In the present invention, 211 or more Ru halides or Rh halides can be used.

Similarly, two or more types of phosphine can be used.

The amount of these catalysts used is 0 based on the raw material hydrosilane.
．． 001 to 10 times the mole, preferably 0.01 to 0.5 times the mole. The amount of phosphine used is 0.01 to 100 times the mole of Ru halide or Rh halide, preferably 0.1 to 10 times mole. Using more than these ranges results in a large amount of by-product acids and is not economical. If the amount is less than these ranges, the catalytic action will be insufficient and the yield of silylapolymer will be low.

There is no particular reaction mode, and the reaction can be carried out in either liquid phase or gas phase. When conducting in a liquid phase, hydrocarbons such as benzene, toluene, xylene, heptane, hexane, ether, tetrahydrofuran, and dioxane are used as solvents.

The reaction temperature ranges from 0 to 300°C, preferably from 50 to 200°C.

After the reaction, the product is usually separated by distillation.

Example The present invention will be specifically explained by the following examples.

Example 1 50-Hensylamine (
3,1)+5ol), t-butyldimethylsilane (
3,:3-mol), RuCl3 (0,1 mm
ol), P (t-C4HJs (0,3ms+
ol), benzene (3, Ommol) and reacted at 120 °C for 6 hours under Ar. The reaction product was isolated by vacuum distillation, 'H-NMR, "C-NMRlI
R.

Identification was performed by QC-MS and quantification was performed by GC.

The conversion rate of benzylamine was 93 mol%, and the main product was N.
-(t-butyldimethylsilyl)benzylamine (CiHsCHzNHSi(CHs)z (t-C4
H9)) (yield 84 mol%).

In this case, dibenzylamine was observed as a by-product acid.

Examples 2 to 5 In Example 1, RuC11/P (t-CaHq)
sRuCIs /P (CtHJs, RuC1z
/P (cyclo-CaH++)3, RhC
l3 /P (t-caH*)i, RhCl1
An experiment was conducted in the same manner as in Example 1 except that /P (ClH5)3 was used.

The results are shown in Table 1.

Comparative Examples 1 to 5 RuC11/P (t-CnHq) in Example 1
RuC1:+, RuC1z CP (C4H6)l ) instead of 3, respectively.
, RhCxz, RhCl(P(C,H5)3)3
, Cot(Co)s was used, but the experiment was conducted in the same manner as in Example 1.

The results are shown in Table 1. In both cases, the yield was lower than in the examples.

Examples 6-7 Experiments were conducted in the same manner as in Example 1 except that octylamine or aniline was used instead of benzylamine.

dimethylsilyl)octylamine (CsH+tNHSi(CHs)z (t-CaHq
)) and N-(t-butyldimethylsilyl) phenylamine (CaHsNH3i(CHs)z (t-C4HJ)
The yields were 76 mol% and 80 mol%, respectively.

Table *l Bu: n-C4H9, Et: CzHs, Cy
: cyclo -C&HII, Ph:C1Hs *2 Conversion rate of benzylamine *3 Yield of N -(t-j'nt dimethylsilyl)benzylamine Effect of the invention The present invention is a novel method for producing silylamine from hydrosilane and an amine compound. This is a great method. According to the present invention, the desired silylamine can be obtained in high yield. In this case, it is easy to isolate the silylamine with few by-product acids.

Claims (3)

[Claims] (1) An amine represented by the general formula R^1NH_2 (where R^1 is an alkyl group, alkenyl group, or aryl group, and may contain a functional group such as COOH, Cl, OH, COOR, etc.) Compound and general formula HS
iR^2R^3R^4 (However, R^2, R^3, R^4
is an alkyl group, an alkenyl group, or an aryl group, and may contain a functional group such as COOH, Cl, OH, or COOR. ), Ru and/or Rh halide and general formula P(R^5)
_3 (R^5 is an alkyl group, alkenyl group or aryl group.) General formula R^1NHSiR^2R^ characterized by being reacted in the presence of a phosphine represented by
A method for producing silylamine represented by 3R^4. (2) The method according to claim 1, wherein the Ru halide is a Ru chloride. (3) The method according to claim 1, wherein the Rh halide is a Rh chloride.