JPH0826046B2 - Method for producing 1-silyl-1-siloxymethanes - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to 1-silyl-1- by reacting an aldehyde with a chain disilane.
The present invention relates to a method for producing siloxymethanes. 1-
It is known that silyl-1-siloxymethanes are easily hydrolyzed under acidic conditions and converted into 1-silylmethanols (for example, Journal of Organic Chemist
ry, 48, 912 (1983)). In addition, 1-aryl-1-silyl-1-siloxymethanes are known to easily react with aldehydes in the presence of a base to be converted into asymmetric ethylenediols (Chemistry Letters, 1223 (198
Five)). Therefore, 1-silyl-1-siloxymethanes are useful as synthetic intermediates for fine chemicals such as medical and agricultural chemicals.

[0002]

2. Description of the Related Art Conventionally, several methods are known as methods for producing 1-silyl-1-siloxymethanes. As a method for producing 1-silyl-1-siloxyalkanes, a method in which an aliphatic aldehyde and a disilane are reacted in a hexamethylphosphoric triamide (HMPA) solvent in the presence of a catalytic amount of tributylammonium fluoride (Journal of Organic Chemistry, 48, 912
(1983)) is known. However, this method requires the use of HMPA, which has extremely high toxicity such as carcinogenicity, as a solvent, and is not an industrially satisfactory method. Further, as a method for producing 1-phenyl-1-silyl-1-siloxymethanes, a method of reacting benzyloxysilanes with butyllithium and then reacting this with chlorosilanes (Journal of the American Chemical Society, 96, 321).
4 (1974)), but this method is not an industrially advantageous method because a large amount of salt is by-produced. As another method, aldehydes and a highly strained four-membered ring disilane are heated to a high temperature (Organometallics, 1
0, 3173 (1991)) and irradiate with ultraviolet light (Organometallic
s, 11, 2580 (1992)), in the presence of a nickel complex (Orga
nometallics, 12, 87 (1993)) or in the presence of a platinum complex (Organometallics, 12, 4987 (1993), Chemistry
Letters, 985 (1993)) are known, but those produced by these methods are limited to 6-membered cyclic 1-silyl-1-siloxymethanes. As yet another method, a method of reacting a bis (hydrosilyl) compound with an aldehyde in a dehydrogenative manner in the presence of a platinum complex (Orga
nometallics, 11, 2639 (1992)) is known, but since one of the raw materials is a bis (hydrosilyl) compound,
The 1-silyl-1-siloxymethanes produced by this method are also limited to those whose skeleton forms a ring.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides 1-silyl-1-, under mild conditions, without producing by-products such as salts.
It is an object to provide a method capable of efficiently producing siloxymethanes.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that aldehydes and chain disilanes react rapidly in the presence of palladium, platinum, or nickel complex. However, the inventors have discovered the novel fact that 1-silyl-1-siloxymethanes are produced, and have completed the present invention based on these findings. That is, the present invention includes (a) an aldehyde represented by the general formula (I) R ¹ CHO (wherein R ¹ represents a monovalent organic group or a hydrogen atom), and (b) a general formula (II) R ² (R ³ ) (R ⁴ ) Si-Si (R ⁵ ) (R ⁶ ) R ⁷ (in the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are an alkyl group, an aryl group, An aralkyl group, an alkoxy group, an aryloxy group, a fluorine atom, a chlorine atom or a bromine atom, which may be the same or different from each other.) (C) Palladium, platinum or nickel complex Of the general formula (III) R ¹ ((R ² ) (R ³ ) (R ⁴ ) Si) CH-O-Si (R ⁵ ) (R ⁶ ) R ⁷ ( In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each have the same meaning as described above.) And a method for producing 1-silyl-1-siloxymethanes To do.

The aldehydes used in the present invention are represented by the above general formula (I), wherein R ¹ is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group or a monovalent heterocycle. Groups, hydrogen atoms and the like. More specifically, examples of aldehydes used in the present invention include acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pivalaldehyde, valeraldehyde, isovaleraldehyde, 2-
Methyl butanal, hexanal, undecanol, 7
-Methoxy-3,7-dimethyloctanal, cyclohexanecarbaldehyde, 3-methyl-2-butena-
Le, benzaldehyde, 2-naphthalaldehyde, o-,
m- or p-tolualdehyde, o-, m-, or p-chlorobenzaldehyde, o-, m-, or p-
Anisaldehyde, o-, m-, or p-acetoxybenzaldehyde, o-, m-, or p- (N, N-
Examples thereof include dimethylamino) benzaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, furfural, 2-thiophenecarbaldehyde, nicotinaldehyde and formaldehyde.

The chain disilane used in the present invention is represented by the above general formula (II), and specific examples thereof include hexamethyldisilane, 1,2-diethyl-1,1,2,2-tetramethyldisilane, 1,2-dihexyl-1,1,
2,2-tetramethyldisilane, 1,2-diphenyl-
1,1,2,2-tetramethyldisilane, 1,2-dimethyl-1,1,2,2-tetraphenyldisilane, 1,
2-dibenzyl-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethyl-1,1,2,2-tetramethoxy Disilane, 1,2-diphenoxy-1,1,
2,2-tetramethyldisilane, 1-fluoro-1,
1,2,2,2-pentamethyldisilane, 1,2-difluoro-1,1,2,2-tetramethyldisilane, 1,
1,1-trifluoro-2,2,2-trimethyldisilane, 1,2-dimethyl-1,1,2,2-tetrafluorodisilane, 1,2-dichloro-1,1,2,2-tetramethyl Disilane, 1,2-dimethyl-1,1,2,2
-Tetrachlorodisilane, 1,2-dibromo-1,1,
2,2-tetramethyldisilane and the like can be mentioned.

The reaction of the present invention is usually carried out in a molar ratio of aldehyde to linear disilane of 1/100 to 100, preferably 1/10 to 10.

As the palladium, platinum or nickel complex used as a catalyst in the present invention, various conventionally known compounds can be used, but it is preferable to use a compound which is at least partially soluble in the reaction system. It is preferable in terms of speed. A complex containing an organic ligand is particularly preferably used as these compounds. Examples of such organic ligands include phosphine, phosphinite, phosphonite,
Phosphite, olefin, β-diketonato ligand, conjugated ketone, nitrile, amine, carboxylato ligand,
Examples thereof include carbon monoxide. Further specific examples of these organic ligands include trimethylphosphine, tributylphosphine, triethylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (p
-Chain phosphines such as -tolyl) phosphine, tri (p-anisyl) phosphine, diphenylmethylphosphine and phenyldimethylphosphine, p-methylphosphorene,
Cyclic phosphines such as p-methylphosphole, 9-methyl-9-phosphabicyclo [4.2.1] nonane, 1,2
-Bis (dimethylphosphino) ethane, 1,2-bis (diethylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'- Such as bis (dimethylphosphino) ferrocene, 1,1′-bis (diphenylphosphino) ferrocene, α, α′-bis (dimethylphosphino) -o-xylene, 1,2-bis (dimethylphosphino) benzene. Phosphinites such as bisphosphine, methyl dimethyl phosphinite, phenyl diphenyl phosphinite, phosphonite such as dimethyl methyl phosphonite, dimethyl phenyl phosphonite, triethyl phosphite, triphenyl phosphite, 1-
Phospha-2,6,7-trioxa-4-ethylbicyclo [2.2.2] octane and other phosphites, ethylene, propene, cyclooctene, maleic anhydride, 1,
5-hexadiene, 1,5-cyclooctadiene, 1,
3-cyclopentadiene, 2,5-norbornadiene,
Olefins such as 1,3,5,7-cyclooctatetraene and dienes, β-diketonato ligands such as acetylacetonato, conjugated ketones such as dibenzylideneacetone, nitriles such as acetonitrile and benzonitrile, ethylenediamine, 2, Examples include amines such as 2'-bipyridyl, and carboxylato ligands such as acetonato. Specific examples of the palladium complex, platinum complex, and nickel complex used in the present invention are tetrakis (triphenylphosphine) palladium, tetrakis (diphenylmethylphosphine) palladium, dichlorobis (trimethylphosphine) palladium, dichlorobis (triethylphosphine) palladium. , Dichlorobis (triphenylphosphine) palladium, dichlorobis (phenyldimethylphosphine) palladium, dichloro (1,2-bis (dimethylphosphino) ethane) palladium, dichloro (1,3-bis (diphenylphosphino) propane)
Palladium, dichloro (1,4-bis (diphenylphosphino) butane) palladium, dichloro (1,2-bis (diethylphosphino) ethane) palladium, dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium , Bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichloro (η-1,5-cyclooctadiene) palladium, bis (η-allyl) palladium, (η-ethylene) bis (triphenylphosphine ) Palladium, dichlorobis (benzonitrile) palladium, dichloroethylenediaminepalladium, palladium acetate, (η-ethylene) bis (triphenylphosphine) platinum, tetrakis (triphenylphosphine) platinum, tetrakis (diphenylmethylphosphine) Gold, tetrakis (triethylphosphine) platinum, dichlorobis (triphenylphosphine) platinum, dibromobis (triethylphosphite) platinum, bis (η-1,5-cyclooctadiene) platinum, dichloro (η-1,5-cyclooctadiene) ) Platinum, dicarbonylbis (tributylphosphine) platinum,
Carbonato bis (tricyclohexylphosphine) platinum, bis (dibenzylideneacetone) bis (triphenylphosphine) platinum, tris (dibenzylideneacetone) diplatinum, dichlorobis (benzonitrile) platinum, dichlorobis (acetonitrile) platinum, tetrakis (triphenylphosphine) Nickel, tetrakis (diphenylmethylphosphine) nickel, tetrakis (triethylphosphine) nickel, dichlorobis (trimethylphosphine) nickel, dichlorobis (triethylphosphine) nickel, dichlorobis (triphenylphosphine) nickel, dichlorobis (phenyldimethylphosphine) nickel, dichloro (1 , 2-bis (dimethylphosphino) ethane) nickel, dichloro (1,3-bis (diphenylphosphine) ) Propane) nickel, dichloro (1,4-bis (diphenylphosphino) butane) nickel, dichloro (1,2-bis (diethylphosphino) ethane) nickel, dichloro (1,1'-bis (diphenylphosphino)) Ferrocene) nickel, bis (η
-1,5-Cyclooctadiene) nickel, dimethylbis (trimethylphosphine) nickel, diethyl (2,
Examples thereof include 2'-bipyridyl) nickel, bis (η-allyl) nickel, (η-ethylene) bis (triphenylphosphine) nickel, and bis (acetylacetonato) nickel, but are not limited thereto.

Further, these palladium, platinum, or nickel complexes may be used in combination of two or more types, not alone. Furthermore, it is also included in an advantageous aspect of the present invention to carry out by adding a ligand which is the same as or different from those contained in the complex together with these complexes. Alternatively, the metal of the catalyst and the ligand may be separately added to the reaction system to form the complex catalyst in the reaction system.

The palladium, platinum, or nickel complex may be used in a so-called catalytic amount, and the molar ratio to the aldehyde is 0.00001 to 0.5. The ligand is used in a molar ratio of 1 to 20 with respect to palladium, platinum or nickel atoms.

The present invention can be easily carried out without using a solvent. However, the use of the solvent does not hinder the occurrence of the reaction, and is carried out in the solvent if necessary. The selection of these solvents is carried out in consideration of the reactivity of the aldehyde to be reacted and the chain disilane, and commonly used solvents such as aromatic hydrocarbons, saturated hydrocarbons,
Alternatively, it is preferable to select from alkyl ether type solvents.

Although the reaction of the present invention proceeds at 0 ° C. or lower,
It is also possible to heat to temperatures up to 250 ° C. to reach the desired rate. Although it depends on the structure of the raw material, a generally preferable temperature range is 0 to 200 ° C.

Separation of the product after the reaction is easily carried out by means generally used in organic chemistry such as distillation, recrystallization, chromatography and the like.

[0014]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 Tetrakis (triphenylphosphine) palladium (0.01 mmol), benzaldehyde (0.5 mm)
ol), 1,2-difluoro-1,1,2,2, -tetramethyldisilane (0.5 mmol), deuterated benzene (C ₆
D _6, a mixture of 0.1 ml), under nitrogen, was charged in a glass sealed tube for NMR, it was heated 20 h to 120 ° C.. NMR
As a result of analysis, it was shown that dimethylfluoro [phenyl (dimethylfluorosilyl) methoxy] silane was produced in a yield of 95%. The spectral data and elemental analysis values of this compound are as follows. ¹ H-NMR (C ₆ D ₆ ); δ 7.23-7.12.
(M, 3H), 7.05-6.95 (m, 3H),
4.77 (s, 1H), 0.18 (d, J = 7.1H
z, 3H), 0.08 (d, J = 6.0Hz, 3H),
0.01 (d, J = 7.0 Hz, 3H), -0.05
(D, J = 6.2 Hz, 3H) ¹³ C-NMR (C ₆ D ₆ ); δ 141.2, 12
8.6 (2C), 126.6, 125.1 (2C),
69.4 (d, J = 16.9 Hz), -2.8 (d,
J = 18.3 Hz), -3.1 (d, J = 19.0H)
z), -4.3 (d, J = 14.0 Hz), -4.
7 (d, J = 14.0 Hz) ²⁹ Si-NMR (C ₆ D ₆ ); δ 22.2 (d, J =
292 Hz), 3.4 (d, J = 287 Hz) GC-MS (EI, 70 eV); 260 (M ⁺ , 1)
9), 217 (M ⁺ -SiMe ₃ , 15), 183 (8
6), 164 (15), 163 (12), 149 (1
7), 105 (20), 90 (100), 77 (69) Elemental analysis; C ₁₁ H ₁₈ F ₂ OSi ₂ Theoretical value: C50.73, H6.97% Actual value: C51.07, H7.13%

Examples 2 to 7 The results of the reaction were carried out in the same manner as in Example 1 except that the catalyst was changed and benzene (C ₆ H ₆ ) was used instead of heavy benzene (C ₆ D ₆ ). Shown in 1.

[0017]

[Table 1]

Example 8 p-anisaldehyde was used in place of benzaldehyde, benzene (C ₆ H ₆ ) was used in place of heavy benzene (C ₆ D ₆ ) as a solvent, and the heating time was 5 hours. The reaction was carried out in the same manner as in Example 1 and analyzed by gas chromatography to find that dimethylfluoro [(4-anisyl) (dimethylfluorosilyl) methoxy] silane was found to be 9
It was produced in a yield of 5%.

Example 9 p-Chlorobenzaldehyde was used in place of benzaldehyde, benzene (C ₆ H ₆ ) was used in place of heavy benzene (C ₆ D ₆ ) as a solvent, and the heating time was 2.5 hours. Others were reacted in the same manner as in Example 1 and analyzed by gas chromatography to find that dimethylfluoro [(4-chlorophenyl) (dimethylfluorosilyl)
Methoxy] silane was produced in a yield of 50%.

Example 10 2-thiophenecarbaldehyde was used instead of benzaldehyde, benzene (C ₆ H ₆ ) was used instead of heavy benzene (C ₆ D ₆ ) as a solvent, and the heating time was 5 hours. Was reacted in the same manner as in Example 1 and analyzed by gas chromatography to find that dimethylfluoro [(2-thienyl) (dimethylfluorosilyl) methoxy] silane was produced in a yield of 80%.

Example 11 Using 2-furfural instead of benzaldehyde,
Benzene instead of heavy benzene as the solvent _{(C 6 D 6) (C} 6
Example 1 except that H ₆ ) is used and the heating time is 5 hours.
The reaction was carried out in the same manner as in Example 1 and was analyzed by gas chromatography.
50% of (dimethylfluorosilyl) methoxy] silane
Produced in a yield of

[0022] Hekisana instead of Example 12 benzaldehyde - using Le benzene instead of heavy benzene as the solvent _{(C 6 D 6) (C} 6 H 6)
Was used and the reaction was carried out in the same manner as in Example 1 except that the heating time was 40 hours. Gas chromatography analysis revealed that dimethylfluoro [1- (dimethylfluorosilyl) hexyloxy] silane was 2%. Produced in yield.

Example 13 Tris (dibenzylideneacetone) diplatinum (0.01 mmol as platinum), 1-phospha-2,6,7-trioxa-4-ethylbicyclo [2.2.2] octane (0.016 mmol) ), Benzaldehyde (0.5m
mol), hexamethyldisilane (0.5 mmol) and benzene (C ₆ H ₆ , 0.1 ml) were charged into a glass sealed tube under nitrogen, heated to 120 ° C. for 20 hours, and then analyzed by gas chromatography. When analyzed, trimethyl [phenyl (trimethylsilyl) methoxy] silane was produced in a yield of 9%.

Example 14 Except that the heating temperature was 160 ° C., the reaction was carried out in the same manner as in Example 13 and analyzed by gas chromatography. As a result, the yield of trimethyl [phenyl (trimethylsilyl) methoxy] silane was 50%. Generated by.

Example 15 The reaction was carried out in the same manner as in Example 14 except that p-anisaldehyde was used instead of benzaldehyde, and gas chromatography analysis revealed that trimethyl [(4
-Anisyl) (trimethylsilyl) methoxy] silane was produced in a yield of 40%.

[0026]

According to the present invention, 1-silyl-1-siloxymethanes can be efficiently produced from easily available aldehydes and chain disilanes. Therefore, the industrial significance of the present invention is great.

Claims (1)

[Claims] 1. An aldehyde represented by the general formula (I) R ¹ CHO (wherein R ¹ represents a monovalent organic group or a hydrogen atom) and (b) the general formula (II) R ² (R ³ ) (R ⁴ ) Si-Si (R ⁵ ) (R ⁶ ) R ⁷ (in the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are an alkyl group, an aryl group, Aralkyl group, alkoxy group, aryloxy group,
It represents a fluorine atom, a chlorine atom, or a bromine atom, which may be the same or different. ) With a chain disilane represented by the formula (c) in the presence of (c) palladium, platinum or nickel complex, represented by the general formula (III) R ¹ ((R ² ) (R ³ ) (R ⁴ ) Si) CH-O-Si (R ⁵ ) (R ⁶ ) R ⁷ (in the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each have the same meaning as described above. A method for producing 1-silyl-1-siloxymethanes represented by the formula (1).