JPH0739424B2 - N, 1-bissilylenamine derivative, N, 1-bissilylimine derivative and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to N, 1-bissilylenamine derivatives and N, 1-bissilylimine derivatives useful as synthetic intermediates for fine chemicals such as pharmaceuticals and agricultural chemicals, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Silylimines are known to be silylketone equivalents [see, for example, J. Am. Che
m. Soc. , 109, 7889 (1987)], silylketones are easily converted into silylninol ethers and substituted ketones [eg, Synthesis, 6].
47 (1989)]. Further, it is known that silyl enamines are easily converted into imines, amides, pyridine derivatives and the like [eg, J. Org. Chem. ，
55, 2878 (1990)]. Therefore, the N, 1-bissilylenamine derivative and the N, 1-bissilylimine derivative are useful as synthetic intermediates for fine chemicals such as pharmaceuticals and agricultural chemicals.

[0003]

Therefore, the inventors of the present invention have used the N, 1-bissilylenamine derivative and the cyclic N, 1-
The present invention has been made for the purpose of providing a method for industrially advantageously producing a bissilylimine derivative, particularly a novel compound.

[0004]

The present inventors have previously reacted a cyclic N, 1-bissilylenamine derivative with a hydrosilane and a nitrile having an aryl group at the α-position to the nitrile group. Then, a method for producing the same was proposed (Japanese Patent Application No. 2-57278). According to this method, an N, 1-bissilylimine derivative is first produced by double silylation of nitriles accompanied by dehydrogenation, and N =
N, 1 via the transition from C—C bond to N—C═C bond
-Bissilyl enamine derivative is generated,
It is considered that this transfer reaction proceeds due to conjugation stabilization (generation of N—C═C—Ar) by a C═C bond and an aryl group, and when an aryl group is present at the α-position carbon with respect to the nitrile group. It was limited.

Then, as a result of examining various reactivities of other nitriles, the present inventors have found that certain nitriles are effective, and have completed the present invention based on these findings.

That is, the present invention has the general formula (I)

[Chemical 7] (Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different alkyl groups or hydrogen atoms) and the general formula (II) R ⁵ R ⁶ CHCN (wherein R ⁵ and R ⁶ are the same or different alkyl groups or hydrogen atoms), and a nitrile represented by the formula (III), which is characterized by reacting in the presence of a platinum compound.

[Chemical 8] (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as described above), and a method for producing an N, 1-bissilylenamine derivative represented by the general formula (I ) And a nitrile represented by the general formula (IV) R ⁷ CN (wherein R ⁷ is an aryl group) are reacted in the presence of a platinum compound. Formula (V)

[Chemical 9] (Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁷ have the same meanings as described above), and a method for producing the N, 1-bissilylimine derivative represented by The present invention provides novel compounds represented by the general formulas (III) and (V).

In the method of the present invention, R ¹ , R ² , R ³ and R ⁴ in the hydrosilanes represented by the general formula (I) used as one of the reaction components are methyl group, ethyl group and propyl group, respectively. An alkyl group such as a butyl group or a hydrogen atom, which may be the same or different from each other. Further, the benzene ring in the general formula (I) may be substituted with a substituent inert to the reaction. Therefore,
Examples of the compound of general formula (I) include o-disilylbenzene, o-bis (dimethylsilyl) benzene, o-bis (diethylsilyl) benzene, o-bis (dipropylsilyl) benzene, o-bis ( Methylethylsilyl) benzene, o-bis (methylpropylsilyl) benzene, 1
-Dimethylsilyl-2-diethylsilylbenzene, 1-
Methyl-2,3-bis (dimethylsilyl) benzene, 1
-Ethyl-3,4-bis (dimethylsilyl) benzene,
1-chloro-3,4-bis (dimethylsilyl) benzene and the like can be mentioned.

The nitriles used as the other reaction component in the present invention are represented by the general formula (II) or the general formula (I
V), in which R ⁵ and R ⁶ are each a methyl group, an ethyl group, an isopropyl group, a propyl group,
An alkyl group such as a butyl group, a hexyl group, a dodecyl group, or a hydrogen atom, which may be the same or different from each other, and R ⁷ is an aryl group; , Phenyl group, tolyl group, 1
Examples include -naphthyl group, 2-naphthyl group, and 2-anthryl group.

The alkyl group and the aryl group may be substituted with a substituent inert to the reaction, such as an alkyl group, an alkoxy group, a halogen atom and the like.

Illustrative examples of these nitriles include those represented by the general formula (I
Examples of the compound represented by I) include acetonitrile, propionitrile, 2-methylpropionitrile, 3-ethoxypropionitrile, dodecanonitrile, and the like, and those represented by the general formula (IV) are benzonitrile,
p-tolylnitrile, p-hexylbenzonitrile, p
-Chlorobenzonitrile, m-methoxybenzonitrile, p-fluorobenzonitrile, 1-naphthonitrile, 2-naphthonitrile and the like can be mentioned.

In the method of the present invention, the ratio of hydrosilanes to nitriles is usually in the range of 1: 100 to 100: 1 by molar ratio of hydrosilanes to nitriles, preferably 1: 5 to 1: 1. It is a range.

In the method of the present invention, the platinum compound acts as a catalyst and various conventionally known compounds can be used, but it is preferable in terms of reaction rate to use a compound which is at least partially soluble in the reaction system. . Complexes are particularly preferably used as these compounds. Examples of the ligand of such a complex include phosphine, phosphonite, phosphinite, phosphite, olefin, acetylene, β-
Examples include diketonato ligands, conjugated ketones, amines, carbon monoxide, and the like. Specific examples thereof include trimethylphosphine, tributylphosphine, triethylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (p-tolyl) phosphine, tri (p
-Anisyl) phosphine, diphenylmethylphosphine, chain phosphine such as phenyldimethylphosphine,
Cyclic phosphines such as P-methylphosphorene, P-methylphosphole, 9-methyl-9-phosphabicyclo [4.2.1] 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 Bisphosphines such as'-bis (diphenylphosphino) ferrocene, α, α'-bis (dimethylphosphino) -o-xylene, 1,2-bis (dimethylphosphino) benzene, dimethyl methylphosphonite, dimethyl phenylphosphon Phosphonites such as night, phosphinites such as methyl dimethylphosphinite, phenyldiphenylphosphinite, and triethylphosphite, triphenylphosphite, 1-phospha-2,6,7-trioxa-4-ethylbicyclo [2.2 .2] phosphite such as octane, ethylene, pro Amine, cyclooctene, maleic anhydride, 1,5-hexadiene, 1,5-cyclooctadiene, 1,3-cyclopentadiene, 2,5-norbornadiene, 1,3,5,7-cyclooctatetraene, etc. Olefins and dienes, acetylene such as phenylacetylene and diphenylacetylene, β-diketonato ligands such as acetylacetonato, conjugated ketones such as dibenzylideneacetone, and ethylenediamine, 2,2′-
Examples include amines such as bipyridyl, and carbon monoxide.

Therefore, specific examples of the platinum compound used in this reaction include (η-ethylene) bis (triphenylphosphine) platinum, tetrakis (diphenylmethylphosphine) platinum, dichlorobis (phenyldimethylphosphine) platinum and chlorohydridobis. (Tributylphosphine) platinum, dichloro (tetramethylethylenediamine) platinum, dibromobis (triethylphosphite) platinum, bis (η-1,5-cyclooctadiene) platinum, dichloro (η-1,5-cyclooctadiene) platinum, Dicarbonylbis (tributylphosphine) platinum, carbonatobis (tricyclohexylphosphine) platinum, diphenylacetylenebis (triphenylphosphine) platinum,
Examples thereof include, but are not limited to, bis (dibenzylideneacetone) bis (triphenylphosphine) platinum and bis (dibenzylideneacetone) platinum.

In addition, these platinum compounds are not used alone but in 2
It may be carried out in the presence of one or more species, and it is also included in an advantageous embodiment of the present invention that the same or different ligand as that contained in the platinum compound is added together with the platinum compound.

The amount of these platinum compounds used may be a so-called catalytic amount, which is 0.00001 per mol of hydrosilanes.
Used in the range of 0.5 mol. The ligand is used in a molar ratio with respect to platinum atom of 1 to 20, preferably 1 to 4.

The reaction of the present invention is easily carried out without using a solvent, by using a mixture of hydrosilanes and nitriles to be subjected to the reaction. However, the use of a solvent does not hinder the occurrence of the reaction of the present invention, and is carried out in a solvent, if necessary. These solvents are selected from commonly used solvents, for example, hydrocarbon-based or ether-based solvents in consideration of the reactivity and boiling point of hydrosilanes to be reacted, the boiling point of nitriles, and the like. preferable.

Although the reaction of the present invention proceeds at 0 ° C. or lower,
It is also possible to heat to a temperature up to 250 ° C. from the reaction rate. Although it depends on the structure of the raw material, a generally preferable temperature range is 0 to 150 ° C.

The product after the reaction can be easily separated by separating unreacted raw materials by distillation or the like and then subjecting it to rectification, recrystallization, chromatography and the like.

[0019]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 0.02 mmol of Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ (where Ph is a phenyl group), 0.5 mmol of o-bis (dimethylsilyl) benzene, and 8 ml of a benzene solution containing 0.5 mmol of propionitrile
The mixture was heated to 0 ° C. and reacted for 20 hours. After concentration and distillation, 1,1,4,4-tetramethyl-3-ethylidene-
2H-2,1,4-benzazadicillin

[0021]

[Chemical 10]

Was obtained with a yield of 92%. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows. Boiling point: 90 ° C./0.2 mmHg (Kugelroll) ¹ H-NMR (CDCl ₃ ): δ 7.5-7.3
(M, 4H), 4.7 (q, J = 6.5Hz, 1H),
3.4 (br s, 1H), 1.6 (d, J = 6.5H)
z, 3H), 0.35 (s, 6H), 0.34 (s, 6)
H) ¹³ C-NMR (CDCl ₃ ): δ 144.3, 14
3.7, 143.0, 132.9, 132.3, 12
8.4, 128.1, 106.7, 10.0, 1.7
(2C), -0.94 (2C) IR (liquid film): ν 1600,1270 cm ^-1 GC-MS (EI, 70 eV): 247 (M ⁺ , 3)
8), 192 (100) HRMS (EI, 70 eV):
C ₁₃ H ₂₁ Si ₂ N theoretical value 247.1213, measured value 247.1220

EXAMPLE 2 Toluene containing 0.02 mmol of Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ , 0.5 mmol of o-bis (dimethylsilyl) benzene and 0.5 mmol of p-tolunitrile. 8 ml of the solution was heated to 110 ° C. and reacted for 6 hours. After concentration and distillation, 1,1,4,4-tetramethyl-3- (4-methylphenyl) -2,1,4-benzazadisicillin

[0024]

[Chemical 11]

Was obtained with a yield of 93%. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows. Boiling point: 130 ° C./0.003 mmHg (Kugelroll) ¹ H-NMR (CDCl ₃ ): δ 7.6-7.1
(M, 8H), 2.38 (s, 3H), 0.54 (s,
6H), 0.52 (s, 6H) ¹³ C-NMR (CDCl ₃ ): δ 144.9, 14
3.2, 142.6, 139.9, 133.2, 13
2.6, 129.0 (2C), 128.9, 128.
5, 128.3, 126.3 (2C), 21.4, 0.
22 (2C), -0.02 (2C) IR (liquid film): ν 1640, 1610, 1260 c
m ^-1 GC-MS (EI, 70 eV): 309 (M ⁺ , 1
6), 294 (M ⁺ -CH ₃ , 20), 193 (10
0) HRMS (EI, 70 eV): C ₁₈ H ₂₃ Si ₂ N
Theoretical value 309.1369, measured value 309.1364

Example 3 0.02 mmol of Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ , 0.5 mmol of o-bis (dimethylsilyl) benzene and 0.5 mmol of 1-naphthonitrile. 8 ml of a toluene solution was heated to 110 ° C. and reacted for 16 hours. After concentration and distillation, 1,1,4,4-tetramethyl-3- (1-naphthyl) -2,1,4-benzazadisicillin

[0027]

[Chemical 12]

Was obtained with a yield of 90%. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows. Boiling point 155 ° C / 0.001 mmHg (Kugelroll) ¹ H-NMR (CDCl ₃ ): δ 7.9-7.2
(M, 11H), 0.34 (s, 6H), 0.33
(S, 6H) IR (liquid film): ν 1620, 1250 cm ^-1

Example 4 0.02 mmol of Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ , 0.5 mmol of o-bis (dimethylsilyl) benzene and 0.5 mmol of 2-naphthonitrile. 8 ml of a benzene solution was heated to 110 ° C. and reacted for 15 hours. After concentration and distillation, 1,1,4,4-tetramethyl-3- (2-naphthyl) -2,1,4-benzazadisicillin

[0030]

[Chemical 13]

Was obtained with a yield of 73%. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows. Boiling point 160 ° C./0.001 mmHg (Kugelroll) ¹ H-NMR (CDCl ₃ ): δ 7.8-7.3
(M, 11H), 0.55 (s, 6H), 0.52
(S, 6H) IR (liquid film): ν 1630, 1600, 1260 c
m ^-1

Example 5 A benzene solution containing 0.02 mmol of Pt (CH ₂ ═CH ₂ ) (PPh ₃ ) ₂ , 0.5 mmol of o-bis (dimethylsilyl) benzene and 0.5 mmol of benzonitrile. 8 ml was heated to 80 ° C. and reacted for 6 hours. After concentration and distillation, 1,1,4,4-tetramethyl-3-phenyl-2,1,4-benzazadicillin

[0033]

[Chemical 14]

Was obtained with a yield of 90%. This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows. Boiling point 115 ° C./0.004 mmHg (Kugelroll) ¹ H-NMR (CDCl ₃ ): δ 7.8-7.3
(M, 9H), 0.55 (s, 6H), 0.52 (s,
6H) IR (liquid film): ν 1630, 1260 cm ^-1

[0035]

INDUSTRIAL APPLICABILITY According to the present invention, a cyclic N, 1-bissilylenamine derivative and N, 1-bissilylimine derivative are obtained by a one-step reaction from readily available hydrosilanes and nitriles, and their separation Purification is also easy. Therefore, its industrial significance is great.

Claims (4)

[Claims] 1. A general formula: (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different alkyl groups or hydrogen atoms) and are N, 1-bissilylenamine derivatives. 2. A general formula: (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different alkyl groups or hydrogen atoms, and R ⁷ is an aryl group.) An N, 1-bissilylimine derivative. 3. A general formula: (Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different alkyl groups or hydrogen atoms) and the general formula R ⁵ R ⁶ CHCN (wherein R ⁵ and R ^{And 6} are the same or different alkyl groups or hydrogen atoms), and nitriles represented by the formulas are reacted in the presence of a platinum compound. (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as described above), and a method for producing an N, 1-bissilylenamine derivative. 4. A general formula: (Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different alkyl groups or hydrogen atoms) and the general formula R ⁷ CN (wherein R ⁷ is an aryl group) A nitrile represented by the formula) is reacted in the presence of a platinum compound. (Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁷ have the same meanings as described above), and a method for producing an N, 1-bissilylimine derivative.