JPH11217391A - Production of silylenolether compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a silylenolether compounds by reacting a ketone compound with a hydrosilane compound in the presence of a specific transition metal catalyst and a halide compound, capable of simply producing the silylenolether compounds by the method having high generality. SOLUTION: This method for producing silylenolether compounds of the formula: R-(C-OSiR<1> R<2> R<3> )=CR'R" comprises reacting a ketone compound of the formula: R-(C-O)-CHR'R" (R, R' and R" are each hydrogen, an alkyl or an aromatic group) with a hydrosilane compound of the formula: HSiR<1> R<2> R<3> (R<1> -R<3> are each an alkyl or an aromatic group) in the presence of a 7-10 group transition metal catalyst and a halide compound of the formula: R<4> X (X is a halogen; R<4> is hydrogen, ammonium, a halogen or the like) (for example, iodobenzene). The transition metal catalyst is preferably a carried zero-valent transition metal catalyst such as platinum/alumina. It is generally preferable from the viewpoint of yield to add an amine compound as an auxiliary catalyst. The reaction is preferably carried out in a solvent not related to the reaction at a temp. of 50-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a reactant widely used in organic synthesis, and an intermediate for organic synthesis,
The present invention relates to a method for producing silyl enol ethers, which are compounds useful in a wide range of fields, such as various functional materials and their raw materials.

[0002]

2. Description of the Related Art Conventionally, as a method for synthesizing silyl enol ethers that can be synthesized according to the present invention, a ketone as a raw material is treated with a base such as butyllithium or triethylamine to form an enolate, which is then reacted with halosilane. Method of synthesis (eg, HO House, LJ Czub
a, M. Gall, HD Olmstead, J. Org. Chem., 34, 232
4 (1969)) has been mainly used. However, this method has to be employed industrially because halosilanes which are very easily hydrolyzed and which are inconvenient to handle must be used, and a salt equivalent to the obtained silyl enol ether is obtained as a by-product. It has disadvantages.

On the other hand, in recent years, a dehydrosilylation reaction of ketones and hydrosilanes using a transition metal catalyst has been reported as a method for synthesizing silyl enol ethers using starting materials that are easier to handle. Previously reported methods include (1) a method using palladium / carbon as a catalyst in the presence of thiophenol (Yoichiro Nagai, Kazutaka Uetake, Toshio Yoshikawa, Hideyuki Matsumoto, Yuika, 31,
759 (1973)), (2) A method using chlorotris (triphenylphosphine) rhodium as a catalyst in the presence of triethylsilylphenylthioether (I. Ojima, Y.N.
agai, J. Organometal. Chem., 57, C42 (1973)),
(3) A method using cobalt carbonyl as a catalyst in the presence of pyridine (H. Sakurai, K. Miyoshi, Y. Nakadair)
a, Tetrahedron Lett., 18, 2671 (1977)), (4) No. 6
Using group µ hydride complex as catalyst (T. Fuchika
mi, Y. Ubukata, Y. Tanaka, Tetrahedron Lett., 32,
1199 (1991)), (5) A method using a rhodium carbonyl compound as a catalyst (I. Ojima, RJ Donovan, N. Clo
s, Organometallics, 10, 2606 (1991)).
However, the method (1) has to use thiophenol which emits a very bad smell, and has a disadvantage that it is difficult to employ industrially. In the method (2), it is not easy to synthesize the co-catalyst, triethylsilylphenylthioether, and it is difficult to employ it industrially. The method (3) has a drawback that a strongly basic pyridine must be used, and the ketones as a raw material are limited. In the method (4), the only hydrosilane that can be used is diphenylsilane, which has a disadvantage of low versatility. In the method (5), since the hydrosilylation reaction proceeds as a competitive reaction, the yield of silyl enol ether is about 40%, and there is a problem in selectivity.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome many of the drawbacks of the prior art as described above,
An object of the present invention is to provide a simple and versatile method for producing silyl enol ethers.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the various drawbacks of the conventional method as described above, and as a result, have found that ketones in the presence of a Group 7 to 10 transition metal catalyst can be obtained. A simple and highly versatile method for producing a silyl enol ether by reacting the compound with hydrosilanes was found, and the present invention was completed.

That is, the following general formula (I) R- (C = O) -CHR'R "(I) wherein R, R 'and R" each independently represent an alkyl group, an aromatic group, A hydrogen atom, and two of them may form a ring together with the carbon atom to which they are bonded together.)
Hydrosilanes represented by the following general formula (II) H-SiR ¹ R ² R ³ (II) (wherein R ¹ , R ² and R ³ each independently represent an alkyl group or an aromatic group) And a group 7-10 transition metal catalyst, and the following general formula (III) R ⁴ X (III) (wherein X represents a halogen atom. R ⁴ represents a hydrogen atom, an alkyl group, an aromatic group , Ammonium, or a halogen atom.) R- (C-OSiR ¹ R ² R ³ ) = CR′R ″ (IV) IV) (wherein, R, R ', R " , R 1, R 2 and R ³ are a method for producing a silyl enol ethers represented by the same as above.).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The alkyl group in the present invention is
1 to 20 carbon atoms which may have a substituent that does not participate in the reaction
Means a linear, branched or cyclic alkyl group of
The aromatic group represents an aromatic hydrocarbon group and a heterocyclic aromatic group, and may have a substituent that does not participate in the reaction, and may have a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a furyl group, Examples thereof include a thienyl group. Examples of the substituent that does not participate in the above reaction include an alkyl group having 1 to 10 carbon atoms which may be branched, an aromatic group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, and a halogen atom.

In the present invention, the above-mentioned general formulas (I), (II),
The ketones, hydrosilanes and halogen compounds represented by (III) are all industrially easily available compounds.

The amount of the ketone represented by the general formula (I) of the present invention is usually in the range of about 0.5 to 2 equivalents to the hydrosilane represented by the general formula (II). It is preferable to use, but if the ketones used are extremely inexpensive and can also serve as a solvent, they can be used in a large excess.

In the present invention, the group 7-10 transition metal catalyst includes zero-valent metals such as manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum, and / or
Alternatively, an inorganic compound, an organic compound, a complex compound, or the like can be given. These catalysts may be supported on a carrier without any problem. Examples of catalysts that can be preferably used include, for example, manganese carbonyl, carbonyl complexes such as tetriridium dodecacarbonyl,
Zero-valent supported catalysts such as palladium / carbon and platinum / alumina can be used. The amount of the transition metal catalyst used may be a so-called catalytic amount, and is selected from a range of about 0.001 equivalent to 0.1 equivalent relative to the hydrosilane represented by the general formula (II), but is usually 0 equivalent. About 0.01 equivalent may be used.

The halogen compound represented by the general formula (III) of the present invention is not particularly limited, and may be hydrogen iodide; an alkyl halogen compound such as methyl iodide, ethyl iodide or benzyl bromide; iodobenzene; Aromatic halogen compounds of triethylammonium iodide, diethylmethylammonium iodide, diethylphenylammonium iodide, benzyldiethylammonium bromide, t-butylethylammonium iodide, ethylmethylphenylammonium iodide, tetraethylammonium iodide, 1- Ammonium halogen compounds such as ethylpyridinium iodide; and iodine and bromine. The amount of the halogen compound to be used may be a so-called catalytic amount, and is selected from a range of about 0.001 equivalent to 0.1 equivalent relative to the hydrosilane represented by the general formula (II). About 005 to 0.05 equivalents may be used. When R ^{4 of the} halogen compound represented by the general formula (III) is ammonium, it may be prepared in a system from the corresponding amine and halide and used.

In carrying out the present invention, it is generally preferred to add amines as a co-catalyst from the viewpoint of yield. Examples of the amines include, but are not particularly limited to, ammonia; primary amines such as ethylamine, propylamine, butylamine, aniline, and benzylamine; and dimethylamine, diethylamine, dipropylamine, dibutylamine, piperidine, morpholine, N-methylaniline, and the like. Secondary amine;
Tertiary amines such as triethylamine, tributylamine, N, N-dimethylaniline and dimethylbenzylamine;
Examples thereof include heteroaromatic amines such as pyridine, pyrrole, and uracil. The amount of the amine to be used may be a so-called catalytic amount, which is selected from the range of about 0.001 equivalent to 0.1 equivalent relative to the hydrosilane represented by the general formula (II), but is usually 0.005 equivalent. What is necessary is just to use about 0.05 equivalent.

The present invention is preferably carried out in a solvent which does not participate in the reaction, and examples thereof include benzene, toluene, xylene, tetrahydrofuran, dimethoxyethane, n-hexane, cyclohexane and the like.

The reaction temperature can be appropriately selected from a temperature range of 0 ° C. to 150 ° C.
C. is preferred.

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Embodiment 1

[0017]

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Cyclohexanone (0.098 g, 1.00 mmol) and triethylsilane (0.175 g,
1.50 mmol), ethyl iodide (0.002 g, 0.01 mmol),
5% palladium / carbon (0.021 g) and toluene (1 ml) as a solvent were added, and the mixture was reacted at 100 ° C. for 16 hours under an argon atmosphere. The reaction mixture was mixed with n-dodecane as an internal standard and subjected to GLC analysis to find that the conversions of cyclohexanone and triethylsilane were 92.8% and 100%, respectively, and that the desired 1- (1) was obtained in a yield of 87.1%.
It became clear that triethylsiloxycyclohexene was produced. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the desired product was isolated by preparative GLC. 1-triethylsiloxycyclohexene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.65 (6H, q, J = 8.0 Hz),
0.97 (9H, t, J = 8.0 Hz), 1.40-1.58 (2H, m), 1.58 -1.
74 (2H, m), 1.91-2.10 (4H, m), 4.79-4.92 (1H, m) p
pm.

Embodiment 2

[0020]

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Cyclohexanone (0.098 g, 1.00 mmol), triethylsilane (0.175 g,
1.50 mmol), methyl iodide (0.001 g, 0.01 mmol),
5% palladium / carbon (0.021 g) and toluene (1 ml) as a solvent were added, and the mixture was reacted at 100 ° C. for 16 hours under an argon atmosphere. The reaction mixture was mixed with n-dodecane as an internal standard substance and subjected to GLC analysis to find that the conversions of cyclohexanone and triethylsilane were 98.6% and 100%, respectively, and that the desired 1-d was obtained in a yield of 76.6%.
It became clear that triethylsiloxycyclohexene was produced.

Embodiment 3

[0023]

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Cyclohexanone (0.098 g, 1.00 mmol), triethylsilane (0.175 g,
1.50 mmol), iodine (0.003 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 ml) as a solvent were added and reacted at 100 ° C. for 16 hours under an argon atmosphere. N- as an internal standard in the reaction mixture
GLC analysis with dodecane added showed that the conversion of cyclohexanone and triethylsilane was 96.
It was 4% and 100%, indicating that the desired 1-triethylsiloxycyclohexene was produced in a yield of 82.9%.

Embodiment 4

[0026]

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Cyclohexanone (0.098 g, 1.00 mmol), triethylsilane (0.175 g,
1.50 mmol), iodobenzene (0.002 g, 0.01 mmo
l) 5% palladium / carbon (0.021 g), and toluene (1 ml) as a solvent were added under an argon atmosphere.
Reaction was carried out at 16 ° C. for 16 hours. When n-dodecane was added to the reaction mixture as an internal standard substance and GLC analysis was performed,
The conversions of cyclohexanone and triethylsilane were 96.9% and 100%, respectively, and it was revealed that the desired 1-triethylsiloxycyclohexene was produced in a yield of 82.0%.

Embodiment 5

[0029]

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Cyclohexanone (0.098 g, 1.00 mmol) and triethylsilane (0.175 g,
1.50 mmol), ethyl iodide (0.002 g, 0.01 mmol),
Diethylamine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 m
l) was added thereto and reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-dodecane was added as an internal standard substance to the reaction mixture and GLC analysis was performed, the conversion of cyclohexanone and triethylsilane was 100% and 98.
It was 7%, indicating that the desired 1-triethylsiloxycyclohexene was produced in a yield of 95.8%.

Embodiment 6

[0032]

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Cyclohexanone (0.098 g, 1.00 mmol), triethylsilane (0.175 g,
1.50 mmol), methyl iodide (0.001 g, 0.01 mmol),
Diethylamine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 m
l) was added thereto and reacted at 100 ° C. for 16 hours under an argon atmosphere. N-dodecane was added to the reaction mixture as an internal standard, and GLC analysis was performed.The conversion of cyclohexanone and triethylsilane was 100% and 96.
It was 0%, indicating that the desired 1-triethylsiloxycyclohexene was produced in a yield of 94.8%.

Embodiment 7

[0035]

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Cyclohexanone (0.098 g, 1.00 mmol), triethylsilane (0.175 g,
1.50 mmol), iodine (0.003 g, 0.01 mmol), diethylamine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 ml) as a solvent. The reaction was performed for 16 hours. When n-dodecane was added to the reaction mixture as an internal standard and GLC analysis was performed, the conversions of cyclohexanone and triethylsilane were 100% and 99.3%, respectively.
It was found that the desired 1-triethylsiloxycyclohexene was produced in a yield of 94.0%.

Embodiment 8

[0038]

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Cyclohexanone (0.098 g, 1.00 mmol) and triethylsilane (0.175 g,
1.50 mmol), iodobenzene (0.002 g, 0.01 mmo
l), diethylamine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 ml) as a solvent were added, and the reaction was carried out at 100 ° C. for 16 hours under an argon atmosphere. N- as an internal standard in the reaction mixture
Dodecane was added and GLC analysis showed that the conversions of cyclohexanone and triethylsilane were 100% each.
% And 96.0%, which revealed that the desired 1-triethylsiloxycyclohexene was produced in a yield of 96.1%.

Embodiment 9

[0041]

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In a test tube with a cap, cyclohexanone (0.098 g, 1.00 mmol), triethylsilane (0.175 g,
1.50 mmol), benzyl bromide (0.002 g, 0.01 mmol),
Diethylamine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 m
l) was added thereto and reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-dodecane was added as an internal standard substance to the reaction mixture and GLC analysis was performed, the conversions of cyclohexanone and triethylsilane were 54.4% and 6%, respectively.
It was 8.7%, indicating that the desired 1-triethylsiloxycyclohexene was produced with a conversion yield of 80.3%.

Embodiment 10

[0044]

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In a test tube with a cap, cyclohexanone (0.098 g, 1.00 mmol) and triethylsilane (0.175 g,
1.50 mmol), ethyl iodide (0.002 g, 0.01 mmol),
t-butylamine (0.001 g, 0.01 mmol), 5% palladium on carbon (0.021 g), and toluene (1
ml), and reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-undecane was added as an internal standard to the reaction mixture and GLC analysis was performed, the conversion of cyclohexanone and triethylsilane was 100% each.
% And 97.6%, which revealed that the desired 1-triethylsiloxycyclohexene was produced in a yield of 99.4%.

Embodiment 11

[0047]

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In a test tube with a cap, cyclohexanone (0.098 g, 1.00 mmol) and triethylsilane (0.175 g,
1.50 mmol), ethyl iodide (0.002 g, 0.01 mmol),
N-methylaniline (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 ml) were added as a solvent, and the mixture was reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-undecane was added as an internal standard substance to the reaction mixture and GLC analysis was performed, the conversion of cyclohexanone and triethylsilane was 96.
It was 5% and 100%, indicating that the desired 1-triethylsiloxycyclohexene was produced in a yield of 94.9%.

Embodiment 12

[0050]

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Cyclohexanone (0.098 g, 1.00 mmol) and triethylsilane (0.175 g,
1.50 mmol), ethyl iodide (0.002 g, 0.01 mmol),
Triethylamine (0.001 g, 0.01 mmol), 5% palladium on carbon (0.021 g), and toluene (1
ml), and reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-undecane was added as an internal standard to the reaction mixture and GLC analysis was performed, the conversion of cyclohexanone and triethylsilane was 100% each.
% And 96.3%, which revealed that the desired 1-triethylsiloxycyclohexene was produced in a yield of 95.9%.

Embodiment 13

[0053]

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In a test tube with a cap, cyclohexanone (0.098 g, 1.00 mmol), triethylsilane (0.175 g,
1.50 mmol), ethyl iodide (0.002 g, 0.01 mmol),
Pyridine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 ml) as a solvent were added, and the mixture was reacted at 100 ° C. for 16 hours under an argon atmosphere. The reaction mixture was mixed with n-undecane as an internal standard and subjected to GLC analysis to find that the conversions of cyclohexanone and triethylsilane were 100% and 97.8%, respectively.
It was found that the desired 1-triethylsiloxycyclohexene was produced in a yield of 99.0%.

Embodiment 14

[0056]

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In a test tube with a cap, cyclohexanone (0.098 g, 1.00 mmol) and triethylsilane (0.140 g,
1.20 mmol), ethyl iodide (0.008 g, 0.05 mmol),
Diethylamine (0.004 g, 0.05 mmol), tetriiridium dodecacarbonyl (0.003 g), and toluene (1 ml) were added as a solvent, and the mixture was heated at 100 ° C under an argon atmosphere.
The reaction was performed for 6 hours. N-dodecane was added to the reaction mixture as an internal standard, and the GLC analysis was performed. The conversions of cyclohexanone and triethylsilane were respectively reduced.
It was 77.2% and 72.3%, indicating that the desired 1-triethylsiloxycyclohexene was produced with a conversion yield of 66.4%.

Embodiment 15

[0059]

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Cyclohexanone (0.098 g, 1.00 mmol) and triethylsilane (0.175 g,
1.50 mmol), ethyl iodide (0.008 g, 0.05 mmol),
Diethylamine (0.004 g, 0.05 mmol), manganese carbonyl (0.002 g), and toluene (1 m
l) was added thereto and reacted at 100 ° C. for 40 hours under an argon atmosphere. When n-dodecane was added as an internal standard substance to the reaction mixture and GLC analysis was performed, the conversions of cyclohexanone and triethylsilane were 100% and 8%, respectively.
6.0%, indicating that the desired 1-triethylsiloxycyclohexene was produced in a yield of 55.3%.

Embodiment 16

[0062]

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In a test tube with a cap, cyclohexanone (0.098 g, 1.00 mmol), triethylsilane (0.175 g,
1.50 mmol), ethyl iodide (0.008 g, 0.05 mmol),
Diethylamine (0.004 g, 0.05 mmol), 5% platinum / alumina (0.039 g), and toluene (1 m
l) was added thereto and reacted at 100 ° C. for 40 hours under an argon atmosphere. When n-dodecane was added as an internal standard substance to the reaction mixture and GLC analysis was performed, the conversions of cyclohexanone and triethylsilane were 86.0% and 86.0%, respectively.
8.7%, indicating that the desired 1-triethylsiloxycyclohexene was produced with a conversion yield of 75.0%.

Embodiment 17

[0065]

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In a test tube with a cap, cyclohexanone (0.098 g, 1.00 mmol) and phenyldimethylsilane (0.
204 g, 1.50 mmol), ethyl iodide (0.002 g, 0.01 mm)
ol), diethylamine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 ml) as a solvent were reacted at 100 ° C. for 16 hours under an argon atmosphere. N- as an internal standard in the reaction mixture
Dodecane was added, and GLC analysis was performed. The conversions of cyclohexanone and dimethylphenylsilane were 100% and 82.0%, respectively, and the desired 1-
It was found that phenyldimethylsiloxycyclohexene was formed. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. GLC
Thus, the desired product was isolated. 1-phenyldimethylsiloxycyclohexene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.43 (6H, s), 1.35-1.55
(2H, m), 1.55 -1.73 (2H, m), 1.88-2.08 (4H, m), 4.
78-4.90 (1H, m), 7.29-7.44 (3H, m), 7.51-7.78 (2H,
m) ppm.

Embodiment 18

[0068]

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In a test tube with a cap, cyclohexanone (0.098 g, 1.00 mmol), t-butyldimethylsilane (0.175 g, 1.50 mmol), and ethyl iodide (0.002 g, 0.0
1 mmol), diethylamine (0.001 g, 0.01 mmol), 5
% Palladium / carbon (0.021 g) and toluene (1 ml) as a solvent were added at 100 ° C under an argon atmosphere.
The reaction was performed for 6 hours. The reaction mixture was mixed with n-dodecane as an internal standard substance and subjected to GLC analysis to find that the conversions of cyclohexanone and t-butyldimethylsilane were 90.1% and 92.7%, respectively, and that the desired 1-methylaniline was obtained in a yield of 89.4%. It became clear that (t-butyldimethylsiloxy) cyclohexene was produced. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the desired product was isolated by preparative GLC. 1- (t-butyldimethylsiloxy) cyclohexene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.12 (6H, s), 0.92 (9H,
s), 1.41-1.58 (2H, m), 1.58 -1.73 (2H, m), 1.89-2.0
8 (4H, m), 4.80-4.91 (1H, m) ppm.

Embodiment 19

[0071]

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In a test tube with a cap, cycloheptanone (0.112 g, 1.00 mmol), triethylsilane (0.175 g,
1.50 mmol), ethyl iodide (0.002 g, 0.01 mmol),
Diethylamine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 m
l) was added thereto and reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-dodecane was added to the reaction mixture as an internal standard substance and GLC analysis was performed, the conversions of cycloheptanone and triethylsilane were 100% and 99.
It was 3%, indicating that the desired 1-triethylsiloxycycloheptene was produced in a yield of 86.0%. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. 1-triethylsiloxycycloheptene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.65 (6H, q, J = 8.0 Hz),
0.97 (9H, t, J = 8.0 Hz), 1.42-1.77 (6H, m), 1.91-2.
07 (2H, m), 2.16-2.30 (2H, m), 5.01 (1H, t, J = 8.3 H
z) ppm.

Embodiment 20

[0074]

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In a test tube with a cap, cyclooctanone (0.126 g, 1.00 mmol) and triethylsilane (0.175 g,
1.50 mmol), ethyl iodide (0.002 g, 0.01 mmol),
Diethylamine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 m
l) was added thereto and reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-dodecane was added as an internal standard substance to the reaction mixture and GLC analysis was performed, the conversions of cyclooctanone and triethylsilane were 100% and 95%, respectively.
It was 3%, indicating that the desired 1-triethylsiloxycyclooctene was produced in a yield of 97.7%. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. 1-triethylsiloxycyclooctene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.66 (6H, q, J = 8.0 Hz),
0.97 (9H, t, J = 8.0 Hz), 1.46-1.70 (8H, m), 1.85-2.0
8 (2H, m), 2.10-2.27 (2H, m), 4.72 (1H, t, J = 8.3 H
z) ppm.

Embodiment 21

[0077]

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In a test tube with a cap, 2-methylcyclohexanone (0.112 g, 1.00 mmol), triethylsilane (0.175 g, 1.50 mmol), ethyl iodide (0.002 g, 0.0
1 mmol), diethylamine (0.001 g, 0.01 mmol), 5
% Palladium / carbon (0.021 g) and toluene (1 ml) as a solvent were added at 100 ° C under an argon atmosphere.
The reaction was performed for 6 hours. The reaction mixture was mixed with n-dodecane as an internal standard and subjected to GLC analysis to find that the conversions of 2-methylcyclohexanone and triethylsilane were 100% and 96.7%, respectively, and that the desired 1-mer was obtained in a yield of 98.4%. It became clear that triethylsiloxy-2-methylcyclohexene was produced. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. 1-triethylsiloxy-2-methylcyclohexene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.65 (6H, q, J = 7.7 Hz),
0.99 (9H, t, J = 7.7 Hz), 1.45-1.72 (4H, m), 1.58 (3
H, s), 1.85-2.08 (4H, m) ppm.

Embodiment 22

[0080]

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In a test tube with a cap, acetophenone (0.
120 g, 1.00 mmol), triethylsilane (0.140 g, 1.2
0 mmol), ethyl iodide (0.008 g, 0.05 mmol), diethylamine (0.004 g, 0.05 mmol), tetriridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent. At 16
A time reaction was performed. N was added to the reaction mixture as an internal standard.
Addition of dodecane and GLC analysis showed that the conversion of acetophenone and triethylsilane was 98.
It was 5% and 98.7%, indicating that the desired α-triethylsiloxystyrene was produced in a yield of 74.0%. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. α-triethylsiloxystyrene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.76 (6H, q, J = 7.7 Hz),
1.01 (9H, t, J = 7.7 Hz), 4.42 (1H, d, J = 1.7 Hz), 4.8
7 (1H, d, J = 1.7 Hz), 7.20-7.36 (3H, m), 7.50-7.65
(2H, m) ppm.

Embodiment 23

[0083]

Embedded image

In a test tube with a cap, acetophenone (0.
120 g, 1.00 mmol), triethylsilane (0.140 g, 1.2
0 mmol), ethyl iodide (0.008 g, 0.05 mmol), t-
Butylamine (0.004 g, 0.05 mmol), tetriridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent were added, and the mixture was heated at 100 ° C under an argon atmosphere.
A time reaction was performed. N was added to the reaction mixture as an internal standard.
-GLC analysis with addition of decane showed that the conversion of acetophenone and triethylsilane was 100% each.
%, 90.9%, and it was clear that the desired α-triethylsiloxystyrene was produced in a yield of 59.2%.

Embodiment 24

[0086]

Embedded image

In a test tube with a cap, acetophenone (0.
120 g, 1.00 mmol), triethylsilane (0.140 g, 1.2
0 mmol), ethyl iodide (0.008 g, 0.05 mmol), N-
Methylaniline (0.005 g, 0.05 mmol), tetriridium dodecacarbonyl (0.003 g), and toluene (1 ml) were added as a solvent, and the mixture was reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-decane was added to the reaction mixture as an internal standard substance and GLC analysis was performed, the conversion of acetophenone and triethylsilane was 9% each.
It was 2.9% and 93.0%, and it was clear that the desired α-triethylsiloxystyrene was produced in a yield of 43.2%.

Embodiment 25

[0089]

Embedded image

In a test tube with a cap, acetophenone (0.
120 g, 1.00 mmol), triethylsilane (0.140 g, 1.2
0 mmol), ethyl iodide (0.008 g, 0.05 mmol), triethylamine (0.005 g, 0.05 mmol), tetriridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent. At 16
A time reaction was performed. N was added to the reaction mixture as an internal standard.
GLC analysis with the addition of decane showed that the conversions of acetophenone and triethylsilane were each 60.3.
% And 61.5%, and it became clear that the target α-triethylsiloxystyrene was produced with a conversion yield of 98.0%.

Embodiment 26

[0092]

Embedded image

In a test tube with a cap, acetophenone (0.
120 g, 1.00 mmol), triethylsilane (0.140 g, 1.2
0 mmol), ethyl iodide (0.008 g, 0.05 mmol), pyridine (0.004 g, 0.05 mmol), tetriiridium dodecacarbonyl (0.003 g), and toluene (1
ml), and reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-decane was added to the reaction mixture as an internal standard substance and GLC analysis was performed, the conversions of acetophenone and triethylsilane were 100% and 92.4%, respectively.
%, Indicating that the desired α-triethylsiloxystyrene was produced in a yield of 87.9%.

Embodiment 27

[0095]

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In a test tube with a cap, 3,3-dimethyl-
2-butanone (0.100 g, 1.00 mmol), triethylsilane (0.140 g, 1.20 mmol), ethyl iodide (0.008 g,
0.05 mmol), diethylamine (0.004 g, 0.05 mmol),
Tetrairidium dodecacarbonyl (0.003 g) and toluene (1 ml) as a solvent were added, and the reaction was carried out at 100 ° C. for 16 hours under an argon atmosphere. When n-decane was added as an internal standard substance to the reaction mixture and GLC analysis was performed, the conversions of 3,3-dimethyl-2-butanone and triethylsilane were 78.8% and 73.6%, respectively.
70.3% yield of the desired 2-triethylsiloxy-3,
It became clear that 3-dimethyl-1-butene was produced. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. 2-triethylsiloxy-3,3-dimethyl- ¹ -butene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.70 (6H, q, J = 8.0 Hz),
0.99 (9H, t, J = 8.0 Hz), 1.06 (9H, s), 3.89 (1H, d,
J = 1.3 Hz), 4.02 (1H, d, J = 1.3 Hz) ppm.

Embodiment 28

[0098]

Embedded image

In a test tube with a cap, 3,3-dimethyl-
2-butanone (0.100 g, 1.00 mmol), triethylsilane (0.175 g, 1.50 mmol), ethyl iodide (0.002 g,
0.01 mmol), diethylamine (0.001 g, 0.01 mmol),
5% palladium / carbon (0.021 g) and toluene (1 ml) as a solvent were added, and the mixture was reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-decane was added to the reaction mixture as an internal standard and GLC analysis was performed,
The conversion of dimethyl-2-butanone and triethylsilane was 85.1% and 100%, respectively, and the desired 2-triethylsiloxy-3,3-dimethyl- was obtained at a yield of 72.8%.
It became clear that 1-butene was produced.

Embodiment 29

[0101]

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In a test tube with a cap, 3-methyl-2-butanone (0.086 g, 1.00 mmol) and triethylsilane (0.
140 g, 1.20 mmol), ethyl iodide (0.008 g, 0.05 mm)
ol), diethylamine (0.004 g, 0.05 mmol), tetriridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent.
The reaction was performed at 0 ° C. for 16 hours. When n-decane was added to the reaction mixture as an internal standard, and subjected to GLC analysis,
The conversions of 3-methyl-2-butanone and triethylsilane were 83.4% and 76.9%, respectively, and the desired 2-triethylsiloxy-3-methyl- conversion was obtained at a conversion yield of 59.0%.
It became clear that 2-butene was produced. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. 2-triethylsiloxy-3-methyl-2-butene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.65 (6H, q, J = 8.0 Hz),
0.99 (9H, t, J = 8.0 Hz), 1.58 (3H, s), 1.60 (3H, s),
1.79 (3H, s) ppm.

Embodiment 30

[0104]

Embedded image

In a test tube with a cap, 3-methyl-2-butanone (0.086 g, 1.00 mmol) and triethylsilane (0.
175 g, 1.50 mmol), ethyl iodide (0.002 g, 0.01 mm)
ol), diethylamine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 ml) as a solvent were reacted at 100 ° C. for 16 hours under an argon atmosphere. N- as an internal standard in the reaction mixture
When decane was added and GLC analysis was performed, 3-methyl-
The conversion rates of 2-butanone and triethylsilane were 87.2% and 100%, respectively, and it was clear that the desired 2-triethylsiloxy-3-methyl-2-butene was produced at a conversion yield of 78.2%. Was.

Embodiment 31

[0107]

Embedded image

In a test tube with a cap, add 2-butanone (0.07
2 g, 1.00 mmol), triethylsilane (0.140 g, 1.20
mmol), ethyl iodide (0.008 g, 0.05 mmol), diethylamine (0.004 g, 0.05 mmol), tetriiridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent. The reaction was performed for 16 hours. N- as an internal standard in the reaction mixture
When decane was added and GLC analysis was performed, the conversions of 2-butanone and triethylsilane were 100% and 8%, respectively.
4.3%, indicating that the desired 2-triethylsiloxy-2-butene was produced in a yield of 69.8%. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. 1H-NMR of this crude product was measured, and it was found that the ratio of the E-form to the Z-form of 2-triethylsiloxy-2-butene was 39:61. From now on
By GLC, 2-triethylsiloxy-2-butene was isolated as a mixture of E-form and Z-form. (E) -2-Triethylsiloxy-2-butene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.65 (6H, q, J = 8.0 Hz),
0.97 (9H, t, J = 8.0 Hz), 1.49 (3H, d, J = 6.8 Hz), 1.7
3 (3H, s), 4.67 (1H, q, J = 6.8 Hz) ppm. (Z) -2-triethylsiloxy-2-butene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.69 (6H, q , J = 8.0 Hz),
1.00 (9H, t, J = 8.0 Hz), 1.49 (3H, d, J = 6.6 Hz), 1.7
7 (3H, s), 4.44 (1H, q, J = 6.6 Hz) ppm.

Embodiment 32

[0110]

Embedded image

In a test tube with a cap, 2-butanone (0.07
2 g, 1.00 mmol), triethylsilane (0.175 g, 1.50
mmol), ethyl iodide (0.002 g, 0.01 mmol), diethylamine (0.001 g, 0.01 mmol), 5% palladium / carbon (0.021 g), and toluene (1 ml) as a solvent. For 16 hours. GLC analysis was performed by adding n-decane as an internal standard substance to the reaction mixture, and the conversion rates of 2-butanone and triethylsilane were 100% and 88.5%, respectively. It became clear that triethylsiloxy-2-butene was produced.
The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. 1H-NMR of the crude product was measured.
It was found that the ratio of the E-form to the Z-form of -triethylsiloxy-2-butene was 34:66.

Embodiment 33

[0113]

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In a test tube with a cap, add 3-pentanone (0.
086 g, 1.00 mmol), triethylsilane (0.140 g, 1.2
0 mmol), ethyl iodide (0.008 g, 0.05 mmol), diethylamine (0.004 g, 0.05 mmol), tetriridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent. At 40
A time reaction was performed. N was added to the reaction mixture as an internal standard.
When decane was added and GLC analysis was performed, the conversion of 3-pentanone and triethylsilane was 100% each.
% And 88.6%, which revealed that the desired 3-triethylsiloxy-2-pentene was produced in a yield of 73.2%. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. When 1 H-NMR of the crude product was measured, the E of 3-triethylsiloxy-2-pentene was determined.
The ratio of isomer to Z-isomer was found to be 24:76. From now on, by preparative GLC, 3-triethylsiloxy-2
-Pentene was isolated as a mixture of E and Z forms. (E) -3-Triethylsiloxy-2-pentene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.66 (6H, q, J = 7.9 Hz),
0.96 (3H, t, J = 7.5 Hz), 0.99 (9H, t, J = 7.9 Hz), 1.5
5 (3H, d, J = 6.6 Hz), 2.04 (2H, q, J = 7.5 Hz), 4.58
(1H, q, J = 6.8 Hz) ppm. (Z) -2-triethylsiloxy-2-pentene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.67 (6H, q, J = 7.9 Hz),
0.96 (3H, t, J = 7.5 Hz), 0.99 (9H, t, J = 7.9 Hz), 1.5
2 (3H, d, J = 6.6 Hz), 2.04 (2H, q, J = 7.5 Hz), 4.47
(1H, q, J = 6.6 Hz) ppm.

Embodiment 34

[0116]

Embedded image

In a test tube with a cap, add 3-pentanone (0.
086 g, 1.00 mmol), triethylsilane (0.175 g, 1.5
0 mmol), ethyl iodide (0.002 g, 0.01 mmol), diethylamine (0.001 g, 0.01 mmol), 5% palladium /
Carbon (0.021 g) and toluene (1 ml) as solvent
And reacted at 100 ° C. for 16 hours under an argon atmosphere. The reaction mixture was mixed with n-decane as an internal standard and subjected to GLC analysis. The conversions of 3-pentanone and triethylsilane were 73.8% and 86.9%, respectively, and the desired 3-triethyl was obtained in a yield of 66.4%. It became clear that siloxy-2-pentene was produced.
The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. 1H-NMR of the crude product was measured.
It was found that the ratio of the E-form to the Z-form of -triethylsiloxy-2-pentene was 21:79.

Embodiment 35

[0119]

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In a test tube with a cap, cyclohexyl methyl ketone (0.126 g, 1.00 mmol), triethylsilane (0.140 g, 1.20 mmol), and ethyl iodide (0.008 g, 0.08 g) were added.
5 mmol), diethylamine (0.004 g, 0.05 mmol), tetriridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent were reacted at 100 ° C. for 40 hours under an argon atmosphere. GLC analysis was carried out by adding n-decane as an internal standard substance to the reaction mixture, and the conversions of cyclohexylmethyl ketone and triethylsilane were 100% and 96.3%, respectively.
% Of the desired (1-cyclohexylideneethoxy)
It became clear that triethylsilane was produced. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. (1-cyclohexylideneethoxy) triethylsilane ¹ H-NMR (CDCl ₃ , TMS): δ = 0.65 (6H, q, J = 7.4 Hz),
0.99 (9H, t, J = 7.4 Hz), 1.38-1.61 (6H, m), 1.80 (3
H, s), 1.99-2.09 (2H, m), 2.09-2.22 (2H, m) ppm.

Embodiment 36

[0122]

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In a test tube with a cap, cyclohexyl methyl ketone (0.126 g, 1.00 mmol), triethylsilane (0.175 g, 1.50 mmol), ethyl iodide (0.002 g, 0.0
1 mmol), diethylamine (0.001 g, 0.01 mmol), 5
% Palladium / carbon (0.021 g) and toluene (1 ml) as a solvent were added at 100 ° C under an argon atmosphere.
The reaction was performed for 6 hours. GLC analysis was performed by adding n-decane as an internal standard substance to the reaction mixture, and the conversions of cyclohexylmethyl ketone and triethylsilane were 100% and 100%, respectively, and the desired (1- It was found that (cyclohexylideneethoxy) triethylsilane was formed.

Embodiment 37

[0125]

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In a test tube with a cap, diisopropyl ketone (0.114 g, 1.00 mmol) and triethylsilane (0.140 g) were added.
g, 1.20 mmol), ethyl iodide (0.008 g, 0.05 mmo
l), diethylamine (0.004 g, 0.05 mmol), tetriiridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent.
The reaction was performed at 0 ° C. for 40 hours. When n-decane was added to the reaction mixture as an internal standard, and subjected to GLC analysis,
The conversion of triethylsilane was 89.6%, revealing that the desired 3-triethylsiloxy-2,4-dimethyl-2-pentene was produced in a yield of 73.4%. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. 3-triethylsiloxy-2,4-dimethyl-2-pentene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.69 (6H, q, J = 7.9 Hz),
0.94 (6H, d, J = 6.9 Hz), 1.00 (9H, t, J = 7.9 Hz), 1.5
7 (3H, s), 1.60 (3H, s), 2.79 (1H, sep, J = 6.9 Hz)
ppm.

Embodiment 38

[0128]

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In a test tube with a cap, phenylisopropyl ketone (0.148 g, 1.00 mmol), triethylsilane (0.140 g, 1.20 mmol), and ethyl iodide (0.008 g, 0.0
5 mmol), diethylamine (0.004 g, 0.05 mmol), tetriridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent were reacted at 100 ° C. for 40 hours under an argon atmosphere. When n-decane was added to the reaction mixture as an internal standard and subjected to GLC analysis, the conversion of triethylsilane was 65.9%.
The desired [(1-phenyl-2-methyl-
[1-Propenyl) oxy] triethylsilane was found to be produced. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. GLC
Thus, the desired product was isolated. [(1-Phenyl-2-methyl-1-propenyl) oxy] triethylsilane ¹ H-NMR (CDCl ₃ , TMS): δ = 0.44 (6H, q, J = 8.0 Hz),
0.86 (9H, t, J = 8.0 Hz), 1.63 (3H, s), 1.80 (3H, s),
7.15-7.35 (5H, m) ppm.

Embodiment 39

[0131]

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In a test tube with a cap, 4'-iodoacetophenone (0.246 g, 1.00 mmol), triethylsilane (0.140 g, 1.20 mmol), and ethyl iodide (0.008 g, 0.0
5 mmol), diethylamine (0.004 g, 0.05 mmol), tetriridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent, and the mixture was reacted at 100 ° C. for 16 hours under an argon atmosphere. N-decane was added to the reaction mixture as an internal standard, and GLC analysis was performed.The conversion rates of 4′-iodoacetophenone and triethylsilane were 90.9% and 100%, respectively, and 83.9%.
It was found that the desired α-triethylsiloxy-4-iodostyrene was produced at a% yield. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. α-triethylsiloxy-4-iodostyrene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.70 (6H, q, J = 7.3 Hz),
0.99 (9H, t, J = 7.3 Hz), 4.43 (1H, d, J = 1.8 Hz), 4.8
7 (1H, d, J = 1.8 Hz), 7.34 (2H, d, J = 8.5 Hz), 7.64
(2H, d, J = 8.5 Hz) ppm.

Embodiment 40

[0134]

Embedded image

In a test tube with a cap, 3,4-dihydro-
1 (2H) -naphthalenone (0.146 g, 1.00 mmol), triethylsilane (0.140 g, 1.20 mmol), ethyl iodide (0.008 g, 0.05 mmol), diethylamine (0.004 g,
0.05 mmol), tetriiridium dodecacarbonyl (0.0
03 g) and toluene (1 ml) as a solvent were added and reacted at 100 ° C. for 16 hours under an argon atmosphere. The reaction mixture was mixed with n-decane as an internal standard and subjected to GLC analysis to find that the conversions of 3,4-dihydro-1 (2H) -naphthalenone and triethylsilane were respectively
The yields were 93.3% and 91.5%, and it was revealed that the desired 4-triethylsiloxy-1,2-dihydronaphthalene was produced in a yield of 55.3%. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From now on
The desired product was isolated by GLC. 4-triethylsiloxy-1,2-dihydronaphthalene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.72 (6H, q, J = 7.9 Hz),
0.99 (9H, t, J = 7.9 Hz), 2.25 (2H, td, J = 6.0, 4.6 H
z), 2.69 (2H, t, J = 6.0 Hz), 5.18 (1H, t, J = 4.6 H
z), 7.02-7.61 (4H, m) ppm.

Embodiment 41

[0137]

Embedded image

A 2-acetylfuran (0.110 g, 1.00 mmol) and triethylsilane (0.140 g,
1.20 mmol), ethyl iodide (0.008 g, 0.05 mmol),
Diethylamine (0.004 g, 0.05 mmol), tetriridium dodecacarbonyl (0.003 g), and toluene (1 ml) as a solvent were added, and the mixture was reacted at 100 ° C. for 16 hours under an argon atmosphere. When n-undecane was added to the reaction mixture as an internal standard, and subjected to GLC analysis,
The conversion rates of -acetylfuran and triethylsilane were 100% and 100%, respectively, and it was revealed that the desired 2- (1-triethylsiloxyvinyl) furan was produced in a yield of 73.5%. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From now on G
The desired product was isolated by LC. 2- (1-triethylsiloxyvinyl) furan ¹ H-NMR (CDCl ₃ , TMS): δ = 0.74 (6H, q, J = 7.9 Hz),
0.99 (9H, t, J = 7.9 Hz), 4.36 (1H, d, J = 1.6 Hz), 4.8
5 (1H, d, J = 1.6 Hz), 6.54 (1H, dd, J = 3.5, 1.7 Hz),
7.18 (1H, dd, J = 3.5 0.6 Hz), 7.58 (1H, dd, J = 1.7,
(0.6 Hz) ppm.

Embodiment 42

[0140]

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In a test tube with a cap, 2,5-dimethylcyclopentanone (0.112 g, 1.00 mmol), triethylsilane (0.140 g, 1.20 mmol), ethyl iodide (0.008 g,
0.05 mmol), diethylamine (0.004 g, 0.05 mmo)
l), tetriridium dodecacarbonyl (0.003 g),
And toluene (1 ml) was added as a solvent, and the reaction was carried out at 100 ° C. for 16 hours under an argon atmosphere. The reaction mixture was mixed with n-decane as an internal standard and subjected to GLC analysis.The conversions of 2,5-dimethylcyclopentanone and triethylsilane were 86.6% and 89.8%, respectively, with a yield of 70.1%. It became clear that the desired 1-triethylsiloxy-2,5-dimethylcyclopentene was formed. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. 1-triethylsiloxy-2,5-dimethylcyclopentene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.69 (6H, q, J = 7.9 Hz),
0.99 (9H, t, J = 7.9 Hz), 1.03 (3H, d, J = 6.8 Hz), 1.3
1-1.40 (1H, m), 1.55 (3H, s), 1.96-2.04 (1H, m), 2.
04-2.12 (1H, m), 2.12-2.22 (1H, m), 2.45-2.54 (1H, m
m) ppm.

Embodiment 43

[0143]

Embedded image

In a test tube with a cap, 2,5-dimethylcyclopentanone (0.112 g, 1.00 mmol), triethylsilane (0.175 g, 1.50 mmol), ethyl iodide (0.001 g,
0.01 mmol), diethylamine (0.001 g, 0.01 mmo
l) 5% palladium / carbon (0.021 g), and toluene (1 ml) as a solvent were added under an argon atmosphere.
Reaction was carried out at 16 ° C. for 16 hours. When n-decane was added to the reaction mixture as an internal standard, and subjected to GLC analysis,
The conversions of 2,5-dimethylcyclopentanone and triethylsilane were 90.1% and 100%, respectively,
It was found that the desired 1-triethylsiloxy-2,5-dimethylcyclopentene was produced in a yield of%.

Embodiment 44

[0146]

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In a test tube with a cap, 2,2-dimethylcyclohexanone (0.126 g, 1.00 mmol), triethylsilane (0.140 g, 1.20 mmol), ethyl iodide (0.008 g,
0.05 mmol), diethylamine (0.004 g, 0.05 mmo)
l), tetriridium dodecacarbonyl (0.003 g),
And toluene (1 ml) was added as a solvent, and the reaction was carried out at 100 ° C. for 16 hours under an argon atmosphere. N-decane was added to the reaction mixture as an internal standard, and GLC analysis was performed.The conversions of 2,2-dimethylcyclohexanone and triethylsilane were 75.2% and 79.7%, respectively, and the target conversion yield was 80.2%. 1-triethylsiloxy-6,6-dimethylcyclohexene. The solvent was distilled off from the reaction mixture by heating under reduced pressure to obtain a crude product. From this, the target product was isolated by preparative GLC. 1-triethylsiloxy-6,6-dimethylcyclohexene ¹ H-NMR (CDCl ₃ , TMS): δ = 0.67 (6H, q, J = 8.0 Hz),
0.98 (9H, t, J = 8.0 Hz), 1.03 (6H, s), 1.42-1.64 (4
H, m), 1.88-2.04 (2H, m), 4.61 (1H, t, J = 3.9Hz) pp
m.

Embodiment 45

[0149]

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In a test tube with a cap, 2,2-dimethylcyclohexanone (0.126 g, 1.00 mmol), triethylsilane (0.175 g, 1.50 mmol), ethyl iodide (0.001 g,
0.01 mmol), diethylamine (0.001 g, 0.01 mmo
l) 5% palladium / carbon (0.021 g), and toluene (1 ml) as a solvent were added under an argon atmosphere.
Reaction was carried out at 16 ° C. for 16 hours. When n-decane was added to the reaction mixture as an internal standard, and subjected to GLC analysis,
The conversions of 2,2-dimethylcyclohexanone and triethylsilane were 88.3% and 100%, respectively,
It was found that the desired 1-triethylsiloxy-6,6-dimethylcyclohexene was produced at a yield of%.

[0151]

Industrial Applicability The present invention is a simple reaction of silyl enol ethers, which are compounds widely used in organic synthesis and useful in a wide range of fields such as organic synthesis intermediates and various functional materials. To provide a highly versatile manufacturing method.

Claims (2)

[Claims] (1) The following general formula (I) R- (C = O) -CHR'R "(I) wherein R, R 'and R" each independently represent an alkyl group, an aromatic group, Or a hydrogen atom, two of which may form a ring together with the carbon atom to which they are bonded together) and a ketone represented by the following general formula (II) A group 7-10 transition with a hydrosilane represented by SiR ¹ R ² R ³ (II) (wherein R ¹ , R ² and R ³ each independently represent an alkyl group or an aromatic group). A metal catalyst, and the following general formula (III) R ⁴ X (III) (wherein X represents a halogen atom, and R ⁴ represents a hydrogen atom, an alkyl group, an aromatic group, ammonium, or a halogen atom. Wherein the reaction is carried out in the presence of a halogen compound represented by the formula: And the following general formula (IV): R- (C-OSiR ¹ R ² R ³ ) = CR′R ″ (IV) (where R, R ′, R ″, R ¹ , R ² and R ³ are as defined above) The same applies to the production of silyl enol ethers. 2. The method according to claim 1, which is carried out in the coexistence of an amine.