JPH03258789A - N,1-bissilylenamine derivative and production thereof - Google Patents

Abstract

PURPOSE:To obtain under mild condition the title compound useful as an intermediate for synthesizing medicines and pesticides etc., using inexpensive raw materials available in large quantities by reaction between each specific hydrosilane and nitrile in the presence of a transition metal complex catalyst. CONSTITUTION:The objective compound of formula II can be obtained by reaction at pref. 0-150 deg.C between (A) a hydrosilane of formula I (Y is divalent organic group, O, etc.; R<1>-R<4> are each monovalent organic group, halogen, etc.) [e.g. Obis(dimethylsilyl)benzene] and (B) a nitrile of formula R<5>R<6>CHCN (R<5> is H or monovalent organic group; R<6> is aryl) (e.g. phenylacetonitrile) in the presence of a transition metal complex catalyst (said metal being selected from platinum, palladium and nickel) [pref. tetrakis(diphenylmethylphosphine) platinum]. Among the objective compounds, a compound of formula III (R<7>-R<14> are each H, halogen, etc.; R<15> is 1-5C organic group or H; R<16> is 6-15C aryl) is a new material.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing N,1-bisilylenamine derivatives by reacting hydrosilanes and nitriles.

N,l-bissilyl enamine derivatives are useful as synthetic intermediates for fine chemicals such as medicines and agricultural chemicals.

[Conventional technique #I] (However, in the formula, R", R", R', R', R',
R'' and Y are respectively as described above),
No industrially advantageous method for producing 1-bissilyl enamine derivatives is known.

[Problems to be Solved by the Invention] The present invention provides a method for industrially advantageously producing N,1-bissilyl enamine derivatives using raw materials that are inexpensive and available in large quantities under mild conditions. That is the issue.

Another object of the present invention is to provide a novel N,1-bissilyl enamine derivative obtained thereby.

[Means for Solving the Problems] As a result of intensive research by the present inventors to solve the above problems, (a) General formula HRlR"5L-Y-3iR3R'H (
(b) Hydrosilanes represented by the general formula R5R6CHCN (wherein, R1, RZ, R3, R4 and Y are each as described above); and (b) a nitrile represented by the general formula R5R6CHCN (wherein, Rs and R6 are each as described above). (c) react rapidly under mild conditions in the presence of a transition metal complex selected from platinum, palladium, and nickel to form N
, a novel fact that provides a 1-bissilyl enamine derivative was discovered, and the present invention was completed based on this discovery.

That is, according to the present invention, ((in formula 1, R", R", R', R', R',
R' and HY are each represented by (as described above)
, a method for producing a 1-bissilyl enamine derivative is provided.

The method of the present invention proceeds by a reaction represented by the following formula.

HRlR"5i-Y-5iR3R'H+ R'R"C)
IcN→(in the formula, R', R", R", R', R',
(R' and Y are as described above) The hydrosilanes (a) used in the present invention have the general formula H
R″R″ 5i-Y-SiR3R' H (However, in the formula R
1, R1, R3, R4 and Y are as described above)
* R", R", R" and R4 represented by include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a bis(hydrocarbyl)amino group, a halogen atom, a hydrogen atom, etc. They may be the same or different.

In the general formula, Y is a divalent organic group, an oxygen atom, a nitrogen atom, a sulfur atom, and the divalent organic group is specifically (A) a divalent organic group having an aromatic ring structure. Group (B) Alkylene group (C) A divalent organic group containing a typical element as a hetero atom (D) A divalent organic group containing a transition metal as a hetero atom.

Examples of (A) include the following, and examples of (B) include -Cl, -, -CH2CO, -, -CH3CO, CH2
-, -HC=CH-.

etc. are listed.

(C) is 1 example.

-0-CH2-, -C)+2-0-CH,-, -CH2
-N(CH,)-CH2-.

(D) is 1, for example, etc. can be mentioned.

Moreover, various substituents can be included as substituents on the carbon atoms of the divalent organic group. Specific examples of such substituents include alkoxy groups, aryloxy groups, acyloxy groups, alkoxycarbonyl groups, acyl groups, bis(hydrocarbyl)amino groups, halogen atoms, and hydrogen atoms.

More specific examples of hydrosilanes used in the present invention include 0-bis(dimethylsilyl)benzene, 0-bis(
diphenylsilyl)benzene, 0-bis(dimethoxysilyl)benzene, O-bis(diphenoxysilyl)benzene, 0-(bis(dimethylamino)silyl)(dimethylsilyl)3.4-bis(dimethylsilyl)pyridine,
2゜3-bis(dimethylsilyl)thiophene, 2,3-
Bis(dimethylsilyl)furan, 1,2-bis(dimethylsilyl)naphthalene, 1,2-bis(dimethylsilyl)anthracene, 1,2-bis(dimethylsilyl)-4
-methoxybenzene, 3゜4-bis(dimethylsilyl)
Phenylethyl ether, 1,2-bis(dimethylsilyl)-4-chlorobenzene, 1,2-bis(dimethylsilyl)ethane, 1. 1,3,3-tetramethyldisiloxane, 1,1,3,3-tetramethyldisilazane.

Examples include bis-η5-((dimethylsilyl)cyclopentadienyl)iron, bis-η5-((dimethylsilyl)cyclopentagenyl)ruthenium, and the like.

The nitriles (b) used in the present invention have the general formula R”
@R' represented by R'CHCN (wherein R5 and R" are each as described above) includes an alkyl group, ary-8&1, an alkoxymethyl group, an aryloxymethyl group, etc.R" Examples include aryl groups.6 More specifically, examples of nitriles used in the present invention include phenylacetonitrile.

0-1 m-1 or p-tolylacetonitrile.

2-13-1 or 4-chlorophenylacetonitrile, 2-3-, or 4-acetoxyphenylacetonitrile, 2-3-. 4-(N,N-dimethylamino)
Examples include phenylacetonitrile.

The molar ratio of hydrosilanes and nitriles is usually in the range of 1/100 to 100, preferably in the range of 1/10 to 10.

According to the present invention, a novel N, 1-
Bissilyl enamine derivatives are provided.

"1-In the formula, R', R', R' and R" baffle lL
It represents a z group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, a bis(hydrocarbyl)amino group, a halogen atom, a hydrogen atom, and the like. R'', R12, R13 and R'' represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a bis(hydrocarbyl)amino group, a halogen atom, a hydrogen atom, etc. R" represents an alkyl group, an aryl group, an alkoxymethyl group, an aryloxymethyl group, etc.

R'' represents an aryl group. Examples of the alkyl group, alkoxy group, and acyl group include lower alkyl groups, alkoxy groups, and acyl groups having 1 to 10 carbon atoms, and examples of the aryl group and aryloxy group include Carbon number 6-15
Examples of the acyloxy group, alkoxycarbonyl group, and bis(hydrocarbyl)amino group, such as phenyl group, tolyl group, and phenoxy group, include acyloxy group, alkoxycarbonyl group, and bis(hydrocarbyl)amino group having 1 to 10 carbon atoms. can give. As a halogen atom,
Examples include fluorine, chlorine, bromine, and iodine atoms.

In the transition metal complex catalyst (C) used in the present invention, examples of the transition metal component include platinum, palladium, and nickel, and use of platinum is particularly preferred. Various conventionally known transition metal complexes can be used, but from the viewpoint of reaction rate it is preferable to use compounds that are at least partially soluble in the reaction system. Complexes containing carbon monoxide or carbon monoxide are particularly preferably used. To give a concrete example of these, (η−
ethylene)bis(triphenylphosphine)platinum, tetrakis(diphenylmethylphosphine)platinum, dichlorobis(phenyldimethylphosphine)platinum, chlorohydridobis(tributylphosphine)platinum, dichloro(tetramethylethylenediamine)platinum, dibromobis(triethylphosphite) Platinum, dichlorobis(benzonitrile)platinum, bis(η-1,5-cyclooctadiene)platinum, dichloro(η-1,5-cyclooctadiene)platinum, carbonatobis(tricyclohexylphosphine)platinum, diphenylacetylene bis (triphenylphosphine)platinum, bis(dibenzylideneacetone)bis(triphenylphosphine)platinum, (η-ethylene)bis(triphenylphosphine)palladium, tetrakis(diphenylmethylphosphine)palladium, dichlorobis(phenyldimethylphosphine)palladium , tris(dibenzylideneacetone)nipalladium, dichloro(η-1,5-cyclooctadiene)palladium, bis(η-allyl)palladium, (η-ethylene)bis(triphenylphosphine)nickel, tricarbonyl(diphenylmethyl) phosphine) nickel, dibromobis(
Examples include triethylphosphine) nickel, tetrakis(phenyldimethylphosphine) nickel, bromotris(tributylphosphine) nickel, bis(η5-cyclopentadienyl) nickel, bis(acetylacetonato)nickel, etc. The transition metal compound may be used not only alone, but also in the coexistence of two or more types. Furthermore, the process may be carried out by adding an organic ligand that is the same as or different from that contained in the transition metal compound together with the transition metal compound. are also included in the advantageous embodiments of the invention. Examples of such organic ligands include phosphine, phosphonite, phosphinite, phosphite, olefin,
Examples include acetylene, β-diketone, and amine. Examples of these include trimethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(p-
Chain phosphine such as tolyl)phosphine, tri(p-anilyl)phosphine, diphenylmethylphosphine, phenyldimethylphosphine, P-methylphosphine, p
- Cyclic phosphines such as methylphosphole, 9-methyl-9-phosphabicyclo[4,2,11 nonane, 1,2-
Bis(dimethylphosphino)ethane, 1,3-bis(dimethylphosphino)propane, 1,4-bis(dimethylphosphino)butane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis( diphenylphosphino)
Propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(dimethylphosphino)ferrocene, 1,1'-bis(diphenylphosphino)ferrocene, α,α'-bis(dimethylphosphino) )-〇-xylene, bisphosphine such as 1,2-bis(dimethylphosphino)benzene, phosphonite such as dimethylmethylphosphonite, dimethylphenylphosphonite, phosphinite such as methyldimethylphosphinite, diphenylphosphinite, and triethyl Phosphites such as phosphite, triphenyl phosphite, trimethylolpropane phosphite, ethylene, propene, cyclooctene, 1,5-hexadiene, 1,5-cyclooctadiene, 1,3-cyclopentadiene, norbornadiene,
Olefins such as 1,3,5.7-cyclooctatetraene, aceQ such as phenylacetylene, diphenylacetylene, etc. (β-diketones such as hydrogen chloride, acetylacetone, etc., amines such as ethylenediamine, 2,2'-bipyridyl, etc.) It will be done.

The amount of transition metal complex catalyst used may be a so-called catalytic amount, and the molar ratio to hydrosilane is 0.00001 to 0.5.
used within the range.

The reaction of the present invention can be easily carried out without using any particular solvent by using a mixture of hydrosilanes and nitriles to be subjected to the reaction. However, the use of a solvent is not an obstacle to the occurrence of this reaction, and the reaction can be carried out in a solvent if necessary.

These solvents are preferably selected from commonly used solvents, such as hydrocarbon-based or ether-based solvents, taking into consideration the reactivity and boiling point of the hydrosilanes to be reacted, the boiling point of the nitriles, etc.

Although the reaction of the present invention proceeds below O"C, it can be heated to temperatures up to 250°C to achieve the desired rate. Depending on the structure of the raw material, - the preferred temperature range for boat fishing is The temperature is 0 to 150°C.

Separation of the product after the reaction is easily carried out by separating unreacted raw materials by distillation or the like, and then subjecting the product to rectification, recrystallization, chromatography, or the like.

[Effects of the Invention] According to the present invention, N,1-bisilylenamine derivatives can be easily obtained from hydrosilanes and nitriles, and the industrial significance thereof is great.

[Example] Next, the present invention will be explained in more detail with reference to Examples.

Example I Pt (CH2=CH,) (PPh, )z is 0.0
05 mmol and 0.25 mmol of 〇-bis(dimethylsilyl)benzene in 2 mQ of a benzene solution at 80°C.
2 mQ of a benzene solution containing 0.25 mmol of phenylacetonitrile was added and reacted at 80°C.

After reacting for 19 hours, it was concentrated and distilled to give 1.1°4.
4-tetramethyl-3-benzylidene-2H-2,1,
4-Penzazadicillin was obtained quantitatively. This compound is a new compound that has not been described in any literature, and its physical property values and spectral data were as follows.

1H-NMR (CDC1,): δ 7.6-7.
1 (m, 9H).

5.60 (s, LH), 4.69 (br s
, LH).

0.45 (s, 6H), 0.37 (s, 6H)
)”C-NMR (CDC13): δ 145.
2.143.8°143.3.137.7.133.1
．． 132.4°128.73 (2G), 128.6
8.128.4゜127.8 (2C), 125.1
．． 111.0゜1.54 (2C), -0,98 (2
C) GC-MS (EI, 70eV); 309
(M”, 44), 192 (100) IR (Fig. 1)

[Brief explanation of drawings]

FIG. 1 shows 1°1.4.
4-tetramethyl-3-penzylidene-yelement = 2.1.
The infrared absorption spectrum of 4-penzazadicillin was measured by a liquid film method, where the vertical axis is transmittance (%) and the horizontal axis is wave number (=n-1).

Claims (2)

[Claims] (1) (a) General formula HR^1R^2Si-Y-SiR^
3R^4H (wherein, Y is a divalent organic group, an oxygen atom,
Hydrosilanes represented by a nitrogen atom, a sulfur atom, and R^1, R^2, R^3, and R^4 represent a monovalent organic group, a halogen atom, or a hydrogen atom; and (b) Nitriles represented by the general formula R^5R^6CHCN (wherein, R^5 represents a monovalent organic group or a hydrogen atom, and R^6 represents an aryl group), There are general formulas▲mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R^1, R^2, R^ 3, R^4, R^5
, R^6 and Y are respectively as described above).
, a method for producing a 1-bissilyl enamine derivative. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^7, R^8, R^9, R^1^0, R
^1^1, R^1^2, R^1^3, and R^1^4 are organic groups with 1 to 15 carbon atoms, hydrogen atoms, and halogen atoms, and R^1^5 is an organic group with 1 carbon number. -15 organic groups and hydrogen atoms, R^1^6 can be selected from aryl groups having 6 to 15 carbon atoms).