JPH03258792A - 1-siloxy-1-silylmethane derivative and production thereof - Google Patents

Abstract

PURPOSE:To obtain under mild condition the objective derivative useful as an intermediate for synthesizing medicines and pesticides etc., using inexpensive raw materials available in large quantities by reaction between a hydrosilane and an aldehyde in the presence of a catalyst. CONSTITUTION:The objective compound of formula II can be obtained by reaction between (A) a hydrosilane of formula I (Y is divalent organic group, O, N or S; R<1>-R<4> are each monovalent organic group, halogen or H) and (B) an aldehyde of formula R<5>CHO (R<5> is monovalent organic group) in the presence of (C) a transition metal complex catalyst (said metal being selected from platinum, palladium and nickel). It is preferable that the objective compound be a compound of formula III (R<7>-R<14> are each 1-15C organic group, H or halogen; R<15> is 1-15C organic group).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing 1-siloxy-1-silylmethane derivatives by reacting hydrosilanes and aldehydes.

1-Siloxy-1-silylmethane derivatives are useful as synthetic intermediates for fine chemicals such as medicines and agricultural chemicals.

[Prior art] 1-siloxy- represented by (wherein R1, R'', R', R', R'' and Y are each as described above)
No industrially advantageous method for producing 1-silylmethane derivatives is known.

[Problems to be Solved by the Invention] The present invention provides an industrially advantageous method for producing 1-siloxy-1-silylmethane derivatives under mild conditions using raw materials that are inexpensive and available in large quantities. That is the issue.

Another object of the present invention is to provide a novel 1-siloxy-1-silylmethane 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 HR1R2Si-Y-5iR3R'H (
(b) hydrosilanes represented by the general formula RsCHO (wherein R1, R'', R', R' and Y are as described above); (c) Acetylenes react rapidly under mild conditions in the presence of a transition metal complex selected from platinum, palladium, and nickel.
-Siloxy-1-silylmethane derivatives were discovered, and the present invention was completed based on this discovery.

That is, according to the present invention, there is provided a method for producing a 1-siloxy-1-silylmethane derivative represented by (wherein R1, R2, R3, R4, R5 and Y are each as described above).

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

HRlR"5L-Y-5iR'R')I + Rs
CHO→(In the formula, R1, R", R3, R', R
' and Y are as described above) The hydrosilanes (a) used in the present invention have the general formula H
R1R2Si-Y-5iR3R'H (wherein, R1,
R'', R', R' and Y are each as described above)
It is expressed as Examples of R1, R', R' and R4 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, and even if they are the same as each other, , may be different.

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

Examples of (A) include the following, examples of (B) include the following, and examples of (C) include -0-CI(2-, -CH, -0-CH2- , -CH2
-N(CFl,)-CH2-.

(D) may include, for example, o-0. Additionally, various substituents can be included as substituents on the carbon atom of the divalent organic group. Specific examples of such substituents include an alkoxy group, an aryloxy group, an acyloxy group, a dialkoxycarbonyl group, an acyl group, a bis(hydrocarbyl)amino group, a halogen atom, and a hydrogen atom.

More specific examples of hydrosilanes used in the present invention include 0-bis(dimethylsilyl)benzene, 0-bis(diphenylsilyl)benzene, 0-bis(dimethoxysilyl)benzene, 0-bis(diphenoxysilyl)benzene. , 0-(bis(dimethylamino)silyl)(dimethylsilyl)benzene, 0-bis(dichlorosilyl)benzene, 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-tetra Methyldisiloxane, 1,1,3.3-tetramethyldisilazane, bis-
Examples include η5-((dimethylsilyl)cyclopentagenyl)iron, bis-η5-((dimethylsilyl)cyclopentagenyl)ruthenium, and the like.

The aldehyde (b) used in the present invention has the general formula R'
It is represented by CHO (wherein R5 is as described above). Examples of R5 include an alkyl group, an aryl group, an alkoxymethyl group, and an aryloxymethyl group.

More specific examples of aldehydes used in the present invention include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, isovaleraldehyde, 2-methylbutanal, 2-methylpropanal, 2- ethyl hexanal,
1-hexanal, 1-undecanal, citronellal, 2-ethylcrotonaldehyde, 3-acetoxy-
1-butanal, 2-methyl-3-acetoxy-1-pentanal, cyclohexanecarbaldehyde, benzaldehyde, 0-1m-1 or p-tolualdehyde,
0-1 m-1 or p-chlorobenzaldehyde, 0-
1m-1 or P-acetoxybenzaldehyde o-1
m-1 or P-(N,N-dimethylamino)benzaldehyde.

Examples include furfural.

The molar ratio of hydrosilanes and aldehydes 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 1-siloxy-1-silylmethane derivative represented by the following general formula is provided.

In the above formula, R7, R', R' and R'' are alkyl groups,
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, etc., and R11, R12, R'' and R'' are an alkyl group or an aryl group. , an alkoxy group, an aryloxy group, an acyloxy group, a bis(hydrocarbyl)amino group, a halogen atom, a hydrogen atom, etc., and R'' represents an alkyl group, an aryl group, an alkoxymethyl group, an aryloxymethyl group, etc.

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 6 to 15 carbon atoms, such as phenyl group and tolyl group. basis,
Indicates a phenoxy group, etc. Acyloxy group, alkoxycarbonyl group, biggy' (1:130ka2.bi2.)a, t group, -C is an acyloxy group, alkoxycarbonyl group, bis(hydrocarbyl)amino having 1 to 10 carbon atoms. The basics are given. Examples of halogen atoms 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.

As the transition metal complex, various conventionally known ones can be used, but from the viewpoint of reaction rate, it is preferable to use a compound that is at least partially soluble in the reaction system. As these compounds, complexes containing organic ligands or carbon monoxide are particularly preferably used. Specific examples of these are:
(η-ethylene)bis(triphenylphosphine)platinum, tetrakis(diphenylmethylphosphine)platinum, dichlorobis(phenyldimethylphosphinechlorohydridobis(tributylphosphine)platinum, dichloro(tetramethylethylenediamine)%.dibromobis(triethylphosphine) Platinum, dichlorobis(benzonitrile)platinum, bis(η-1,5-cyclooctadiene)platinum, dichloro(η-1,5-cyclooctadiene)platinum, dicarbonylbis(tributylphosphine)platinum, carbonatobis(tricyclohexyl) phosphine) 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(diphenylmethylphosphine)nickel, dibromobis(triethylphosphine)nickel, tetrakis(phenyldimethylphosphine)nickel ) nickel, bromotris(tributylphosphine)nickel, bis(η5-cyclopentagenyl)nickel, bis(acetylacetonato)nickel, etc., but are not limited thereto.

In addition, these transition metal compounds may be used not only alone, but also in combination of two or more, and in addition, an organic ligand that is the same as or different from that contained in the transition metal compound is added together with the transition metal compound. It is also included in an advantageous aspect of the invention.

Examples of such organic ligands include phosphine, phosphonite, phosphinite, phosphite, olefin, β-diketone, amine, and nitrile. Examples of these include trimethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(p
- Chain phosphine such as tolyl)phosphine, tri(p-anisyl)phosphine, diphenylmethylphosphine, phenyldimethylphosphine, p-methylphosphole, p-methylphosphole, 9-methyl-9-phosphabicyclo[4 .2.11 Cyclic phosphine such as 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)-0-xylene, 1,2-bis( Bisphosphines such as dimethylphosphino)benzene, phosphonites such as dimethylmethylphosphonite and dimethylphenylphosphonite, phosphinites such as methyldimethylphosphinite and diphenylphosphinite, and triethylphosphite, triphenylphosphite, and trimethylolpropane phosphite. Phosphites such as phyto, ethylene, propene, cyclooctene, 1,5-hexadiene, 1,5-cyclooctadiene, 1,3-cyclopentadiene, norbornadiene, 1,3,5,7-cyclooctadienine olefins such as, β-diketones such as acetylacetone, 2,2'
- Amines such as bipyridyl and ethylenediamine, and nitriles such as benzonitrile.

The amount of transition metal complex catalyst used may be a so-called catalytic amount, expressed as a molar ratio to hydrosilane.

It is used in the range of 0.00001 to 0.5.

The reaction of the present invention can be easily carried out without using any particular solvent by using a mixture of hydrosilanes and aldehydes 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 aldehydes, etc.

Although the reaction of the present invention proceeds below 0°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 post-reaction product is easily carried out by separating unreacted raw materials etc. 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, 1-siloxy-1-silylmethane derivatives can be easily obtained from hydrosilanes and aldehydes,
Its industrial significance is enormous.

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

Example I Pt (CH2=CH2) (PPh, ), 0.0
05 mmol and 0.25 mmol of 〇-bis(dimethylsilyl)benzene in 2 mQ of a benzene solution at 80°C.
Benzene solution 2 containing 0.25 mmol of benzaldehyde
mA was added and the reaction was carried out at 80°C. After reacting for 40 hours, the mixture was concentrated and distilled to obtain 1,1,4,4-tetramethyl-3-phenyl-2,1,4-benzoxadisilane in a yield of 40%.

This compound is a new compound that has not been described in any literature.

Its physical property values and spectral data were as follows. 1H-NMR (CDCI, ): 6 7.6-7.1 (m, 9H).

(S, IH), 0.43 (S, 3H)t(s
, 3H), 0.29 (s, 3H).

(s, 3H).

δ 144.6, 143.7° 133.4, 132.5, 128.64° 128.1
(2C).

124.5 (2C), 69.8° -0,62,-4,98,-5,03 298 (M”, 39).

283 (16), 193 (100) IR (
Figure 1)

[Brief explanation of drawings]

Figure 1 shows 1°1.4,
The infrared absorption spectrum of 4-tetramethyl-3-phenyl-2゜1.4-benzoxadisilane was measured by the Nujol method, the vertical axis is the transmittance (%), and the horizontal axis is the wave number (all -1). 5.0 0.37 0.00 "C-NMR (CDCI, ): 142.6° 128.60° 125.5° 0.21° GC-MS (EI, 70eV); 1. Indication of incident 20 inventions Written amendment to the name (procedural amendment) 3 Kagiken No. 605 1990 Patent Application No. 57276 1-Siloxy-1-silylmethane derivative and its manufacturing method 3, person making the amendment Patent related to the case Address of applicant 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo Name (1)
14) Ken Sugiura, Director of the Agency of Industrial Science and Technology8, Contents of the amendment The following amendments will be made to the specification of this application. (1) In the 6th line of page 17, the line next to ``It was as follows.'' ``Melting point: 80.5-81.0℃
”. (2) In the line next to "rIR (Figure 1)" in the second line of page 18, "Elemental analysis value: Actual value C68,09%, H7,4
8% theoretical value C68, 40%, H7, 43% Example 2 Toluene was used as a solvent instead of benzene, and the temperature was set to 110
The reaction was carried out in the same manner as in Example 1. 6 hours later, 1
,1,4,4-tetramethyl-3-phenyl-2,1,
4-Benzoxadisilane was obtained with a yield of 77%. ”. 6. Procedure for increasing the number of claims due to amendment (spontaneous) June 4, 1991 1. Indication of the case 1990 Patent Application No. 57276 2. Name of the invention 1-Siloxy-1-silylmethane Derivatives and their manufacturing method 3, relationship with the amended person case Patent applicant address 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo Name (11
4) Director of the Agency of Industrial Science and Technology Ken Sugiura 5, date of amendment order
Voluntary action 6, "Detailed description of the invention" column of the specification to be amended, "Brief of drawings 7,
Contents of the amendment (1) "Acetylene" on page 4, lines 5-6 of the specification will be amended to "aldehyde". (2) On page 8, line 13 of the same book, after “alkyl group,” “
Add an alkenyl group, j. (3) Add "cinnamaldehyde," next to "-ethylcrotonaldehyde," on page 9, line 3 of the same book. (4) Add "alkenyl group," next to "alkyl group," in the eighth line from the bottom of page 10 of the same book. (5) “Bis(dibenzylideneacetone)bis(triphenylphosphine)platinum,” on page 12, lines 8-9 of the same book.
Next, add "bis(dibenzylideneacetone) platinum." (6) The following description of “Example 2” on page 18, line 2 of the same book (
(Added by procedural amendment submitted on April 4, 1991), add the following on a new line. “Example 3 Pt(CH2=CH*) (PPh3) P in place of 2
A reaction was carried out at 80° C. for 1 hour in the same manner as in Example 1 using t(dba)z (bis(dibenzylideneacetone)platinum). After reaction 1. 1,4,4-tetramethyl-3-phenyl-2,1,4-benzoxadisilane was obtained with a yield of 91%. Example 4 Using n-heptanal instead of benzaldehyde,
The temperature was set to 80° C., and the reaction was carried out for 600 hours in the same manner as in Example 1. After the reaction, the reaction mixture was concentrated and distilled to obtain 1,1,4.4-tetramethyl-3-hexyl-2,1,4-benzoxadisilane in a yield of 47%. This compound is a new compound that has not been described in any literature, and its spectral data were as follows. 1.1,4.4-tetramethyl-3-hexyl-21,
4-Benzoxadisilane boiling point 95-105℃/0.5mmHg (Kugerrohr)'H-NMR (CDCIm): 67.55-
7.34 (4H, ml, 3.80-3.70(1)
1. m), 1.8-1.5 (4H, m), 1.5
-1.15 (6H, br s), 0.9 (3H, t
1ike), 0.35 (3H,s), 0.31
(3H,s), 0.28(3H,s), 0.2
5 (3H,s)13cmNMTh(cpcl,+:
δ144.9.144.1.133.2.132.3
゜128.44.128.38.66.6.33.2.
31.9.29.1.26.6゜22.7.14.1.
0.2. -0.7. -4.1. -4.8GC-MS:3
06 (M′″0.1), 291 (M-15,0,1
), 193 (100) Engineering R: Figure 2 Example 5 Pt(CH2=CH-) (PPh-) Using Pt(dba)2 instead of 2, the same procedure as in Example 4 was carried out at 80°C for 1 hour. The reaction was carried out. After the reaction, 1.1,4.4-tetramethyl-3-hexyl-2°1.4-benzoxadisilane was obtained with a yield of 91%. Example 6 Using n-hexanal instead of benzaldehyde,
The temperature was raised to 80° C., and the reaction was carried out for 17 hours in the same manner as in Example 1. After the reaction, the reaction mixture was concentrated and distilled to obtain 1.1,4.4-tetramethyl-3-benzo-2.1.4-benzoxadisilane in a yield of 52%. This compound is a new compound that has not been described in any literature, and its spectral data were as follows. 1.1,4.4-tetramethyl-3-benzene 2゜1
．． 4-Benzoxadisilane'H-NMR (CDC1a): δ 7.55-7.3
4 (4H, m), 3.80-3.70 (LH, m)
, 1.8-1.5 (4N, m), 1.5-1.1
5 (4H,br s)0.9 (3H,t 1ik
e), 0.35 (3H,s), 0.31
(3H,s)0.28 (3H,s), 0.2
5 (3H,s) Example 7 Pt(CH2=CHi) (PPhs) P instead of z
1 at 80°C in the same manner as in Example 6 using t(dba)z.
The reaction was carried out for 6 hours. After the reaction, 1.1,4.4-tetramethyl-3-hexyl-2°1.4-benzoxadisilane was obtained with a yield of 71%. Example 8 1 was prepared in the same manner as in Example 1 using trans-cinnamaldehyde in place of benzaldehyde and at a temperature of 110°C.
The reaction was carried out for 2 hours. After the reaction, it is concentrated and distilled to 1°1
．． 4.4-tetramethyl-3-(trans-2-phenylethynyl)-2,1,4-benzoxadisilane is 8
Obtained with a yield of 0%. This compound is a new compound that has not been described in any literature, and its spectral data were as follows. 1.1,4.4-tetramethyl-3-(trans-2-
phenylethynyl)-2,1,4-benzoxadisilane boiling point 145-150°C 70.4 mmHg (Kugerrohr) H-NMR ((:DC13): 67.46-
7.11 (9H, m), 6.53 (IH,
dd. J=15.8. 1.4Hz), 6.25(LH,
dd, J:15.8. 5.5Hz) 4.56(I
H, dd, J=5.5. 1.4Hz), 0.34
(3H,s), 0.30(3H,s), 0.
27 (3H,s), 0.13 (3H,s)3
C-NMR (CDC1g): 6144.5.
143.5. 137.7°133.2. 132.5
．． 129.7. 128.7. 128.6. 12
8.4126.7. 126, l, 126.0.
68.9. 0.2. -0.5. -4.8GC-M
S; 324 (M”, 51), 193 (37),
115 (100) Engineering R; Figure 3 Example 9 Pt(C:H*=CH2) (PPhs) 110°C in the same manner as in Example 6 using Pt(dba)z instead of 2.
The reaction was carried out for 12 hours. After reaction 1,1,4.4-tetramethyl-3-(trans-2-phenylethynyl)
-2,1,4-benzoxadisilane was obtained with a yield of 8%. (7) Add the following statement on a new line after the 9th line of page 18 of the same book. "Figure 2 was synthesized according to the embodiment of the present invention. 1,14
．． The infrared absorption spectrum of 4-tetramethyl-3-hexyl-2,1,4-benzoxadisilane was measured using the liquid film method, where the vertical axis is the transmittance (%) and the horizontal axis is the wave number. (cm-'). FIG. 3 shows 1,1°4. synthesized according to an example of the present invention.
The infrared absorption spectrum of 4-tetramethyl-3-(trans-2-phenylethynyl)-2,1,4-benzoxadisilane was measured using the liquid film method, and the vertical axis is the transmittance (%). The horizontal axis is the wave number (cm-'). ](
8) Add Figures 2 and 3 as drawings.

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) (c) An aldehyde represented by the general formula R^5CHO (where R^5 represents a monovalent organic group) in the presence of (c) a transition metal complex selected from platinum, palladium, and nickel. , characterized by reacting with the general formula R^1R^2Si-R^5CH-O-SiR^3
R^4-Y (However, in the formula, R^1, R^2, R^3, R^
4, R^5 and Y are each as described above). (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. 1-siloxy-1-silylmethane derivatives represented by