JP2003155258A - Method for producing disilyl acetal and aldehyde - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing disilyl acetals and aldehydes useful as an intermediate for an organic synthesis. SOLUTION: This method for producing the disilyl acetals expressed by the general formula RCH(OSiR<1> R<2> R<3> )2 or RCH(OSiR<1> R<2> R<3> )(OSiR<4> R<5> R<6> ) is provided by performing a reaction of a carboxylic acid expressed by the general formula: RCOOH or a carboxylic acid silyl ester expressed by the general formula: RCOOSiR<4> R<5> R<6> with a hydrosilane expressed by the general formula: HSiR<1> R<2> R<3> in the presence of a ruthenium catalyst. The method for producing the aldehydes expressed by the general formula: RCHO is characterized by performing a reaction of the disilyl acetals in the presence of a transition metal catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing disilyl acetals useful as organic synthetic intermediates and useful aldehydes widely used as raw materials for medical and agricultural chemicals.

[0002]

2. Description of the Related Art Disilyl acetals are compounds which are expected not only to be easily induced into aldehydes but also to become carbon-carbon bond forming agents upon activation.

In the method of partially reducing carboxylic acids to obtain aldehydes, there are many kinds of reducing reagents, and their reactivity is diverse, so that it is possible to obtain the desired aldehyde while leaving other functional groups. As a partial reduction method, Ro
The hydrogenation method represented by the senmund method and the method using a metal hydride are generally used. Especially, in recent years, various metal hydrides are commercially available and the experimental operation is simple. It is used frequently. As a method for synthesizing aldehydes by reduction of carboxylic acids with a metal hydride, (1) a method using an organic borohydride (texylborane, texylhalogenoborane, 9-boranebicyclononane (9-BBN)) (for example, HC Brown, P. H
eim, and NM Yoon, J. Org. Chem., 37, 2942 (197
2), HC Brown, JS Cha, NM Yoon, and B. Na
zer, J. Org. Chem., 52, 5400 (1987), JS Cha,
JE Kim, SY Oh, and JD Kim, Tetrahedron Let
t., 28, 6231 (1987)), (2) Method using aluminum hydride (eg M. Muraki and T. Mukaiyama, Chem.
Lett., 1447 (1974), TD Hubert, DP Eyman and
DF Wiemer, J.Org. Chem. 49, 2279 (1984)),
(3) Method using hydrosilanes (eg RJP Corr
iu, GF Lanneau and M. Perrot, Tetrahedron Let
t., 28, 3941 (1987)) is known. However, the method (1) is applicable to aliphatic carboxylic acids,
When an aromatic carboxylic acid is used, the yield is low and the versatility is low. When this organoborohydride is used, the organometallic partial decomposition product remains in the organic layer even after the reaction is stopped, so that a decrease in the yield due to condensation isomerization of the aldehyde is observed, which is problematic in terms of selectivity and yield. There is.

In the method (2), the reaction is carried out at a low temperature,
N-methylpiperazine is used to make aminoaluminum hydride, and it is necessary to reduce the reactivity, so the versatility is low. When organoaluminum hydride is used, the organic metal partial decomposition product remains in the organic layer even after the reaction is stopped, so that the yield is reduced due to condensation isomerization of aldehydes, which is problematic in terms of selectivity and yield. There is.

In the method (3), a hydrosilane having a dimethylamino group must be used at an appropriate position in the molecule, which is problematic in versatility.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome many of the drawbacks of the prior art described above.
An object is to provide a simple and highly versatile method for producing disilyl acetals and aldehydes.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned various drawbacks of the conventional method, the present inventors have found that carboxylic acids and monohydrosilanes are combined in the presence of a ruthenium catalyst. The present invention has been completed by finding a simple and highly versatile method for producing disilylacetals by reacting them, and a method for producing aldehydes by reacting them in the presence of a transition metal catalyst.

That is, the present invention provides a carboxylic acid represented by the following general formula (I) RCOOH (I) (wherein R represents an alkyl group, an aromatic group or a hydrogen atom), or the following general formula (I) IV) RCOOSiR ⁴ R ⁵ R ⁶ (IV) (wherein R is the same as above, R ⁴ , R ⁵ , and R 4
Each ⁶ independently represents an alkyl group, an aromatic group, an alkoxy group, or a halogen atom. ) And a carboxylic acid silyl ester represented by the following general formula (II) HSiR ¹ R ² R ³ (II) (wherein R ¹ , R ² , and R ³ are each independently an alkyl group, an aromatic group, And a hydrosilane represented by an alkoxy group or a halogen atom) in the presence of a ruthenium catalyst. The following general formula (III) RCH (OSiR ¹ R ² R ³ ) ₂ (III ) (Wherein R, R ¹ , R ² , and R ³ are the same as above), and a method for producing a disilyl acetal, and a compound represented by the following general formula (I) RCH (OSiR ¹ R ² R ³ ) ₂ (I) (wherein R represents an alkyl group, an aromatic group, or a hydrogen atom) is reacted with disilyl acetal in the presence of a transition metal catalyst, The following general formula (VI) RCH (VI) (In the formula, R is the same as above.) A method for producing an aldehyde, the following general formula (I) RCOOH (I) (In the formula, R is an alkyl group, an aromatic group, or And a carboxylic acid represented by the following general formula (I
I) HSiR ¹ R ² R ³ (II) (wherein R ¹ , R ² and R ³ each independently represents an alkyl group, an aromatic group, an alkoxy group or a halogen atom). Are reacted in the presence of a ruthenium catalyst to give the following general formula (III) RCH (OSiR ¹ R ² R ³ ) ₂ (III) (wherein R, R ¹ , R ² and R ³ are the same as those described above). A disilylacetal represented by the formula (1), which is then reacted in the presence of a transition metal catalyst,
A method for producing an aldehyde represented by the following general formula (VI) RCHO (VI) (wherein R is the same as above), and the following general formula (IV) RCOOSiR ⁴ R ⁵ R ⁶ (IV) ( In the formula, R represents an alkyl group, an aromatic group, or a hydrogen atom, and R ⁴ , R ⁵ , and R ⁶ each independently represent an alkyl group, an aromatic group, an alkoxy group, or a halogen atom.) A carboxylic acid silyl ester represented by the following general formula (II) HSiR ¹ R ² R ³ (II) (wherein R ¹ , R ² and R ³ are each independently an alkyl group, an aromatic group or an alkoxy group) , Or a hydrosilane represented by a halogen atom) in the presence of a ruthenium catalyst, RCH (OSiR ¹ R ² R ³ ) (OSiR ⁴ R ⁵ R ⁶⁾ (V ^{(Wherein, R, R 1, R 2} , R 3, R 4, R 5, and R ⁶ are as defined above.) To obtain a di-silyl acetals represented by, then the presence of a transition metal catalyst it The present invention relates to a method for producing an aldehyde represented by the following general formula (VI) RCHO (VI) (wherein R is the same as above), which comprises the following reaction.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The alkyl group in the present invention means
1-20 carbon atoms which may have a substituent that does not participate in the reaction
A straight chain, branched chain or cyclic alkyl group. The aromatic group represents an aromatic hydrocarbon group and a heterocyclic aromatic group, which may have a substituent that does not participate in the reaction phenyl group, naphthyl group, anthryl group, pyridyl group, furyl group, Examples thereof include a thienyl group. The alkoxy group means a group in which an oxygen atom is bonded to the above alkyl group or aromatic group. The substituent that does not participate in the above reaction has 1 carbon atoms which may be branched.
Examples thereof include -10 alkyl groups, aromatic groups, alkoxy groups, phenoxy groups, alkylthio groups, phenylthio groups, carbonyl groups, carboxyl groups, cyano groups, nitro groups, amino groups and halogen atoms.

The carboxylic acids represented by the above general formula (I) of the present invention are industrially easily available compounds. The carboxylic acid silyl ester represented by the general formula (IV) is a compound that can be easily synthesized by a reaction between a carboxylic acid and a halosilane or a reaction between a carboxylic acid and a hydrosilane. Further, a mixture of the carboxylic acid represented by the general formula (I) and the carboxylic acid silyl ester represented by the general formula (IV) may be used as a raw material.

The hydrosilanes represented by the general formula (II) of the present invention are industrially easily available compounds, and include the carboxylic acids represented by the general formula (I) or the general formula (IV). It is usually preferable to use it in the range of about 0.5 to 5 equivalents with respect to the carboxylic acid silyl esters represented by In the present invention, as the ruthenium catalyst, ruthenium dioxide, ruthenium oxide such as ruthenium tetraoxide, ruthenium bromide, ruthenium salt such as ruthenium iodide, dicarbonylcyclopentadienyl ruthenium (I
I) dimer, triruthenium dodecacarbonyl, dichlorotricarbonylruthenium (II) dimer, dichlorodicarbonylbis (triphenylphosphine) ruthenium (II), carbonyldihydridotris (triphenylphosphine) ruthenium (II), Dichlorotris (triphenylphosphine) ruthenium (II), chlorocyclopentadienylbis (triphenylphosphine) ruthenium (II), chloroindenylbis (triphenylphosphine) ruthenium (II), dichlorobis (tricyclohexylphosphine) benzylidene ruthenium (I
V), dichlorobis (tricyclopentylphosphine)
Examples thereof include ruthenium complexes such as benzylidene ruthenium (IV). As a catalyst that can be suitably used, a ruthenium carbonyl complex can be mentioned, and in particular, triruthenium dodecacarbonyl and dichlorotricarbonyl ruthenium (II) dimer are preferable in terms of yield. The amount of these ruthenium catalysts used may be a so-called catalytic amount, and a range of about 0.001-0.1 equivalents relative to the carboxylic acid represented by the general formula (I) is selected, but usually 0.005- It may be used in an amount of about 0.05 equivalent.
In carrying out the production of disilylacetal in the present invention, it is often preferable to add amines or amides as a cocatalyst in terms of yield. The amines are not particularly limited, ammonia; ethylamine, propylamine, butylamine, t-butylamine, aniline,
Primary amines such as benzylamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, piperidine, morpholine, N-methylaniline; triethylamine, tributylamine, N, N-dimethylaniline, dimethylbenzylamine, etc. Examples include tertiary amines; heteroaromatic amines such as pyridine, pyrrole, and uracil. The amides are also not particularly limited, and include N, N, 2-trimethylpropionamide, N, N-diethyl-2-methylpropionamide, N
-T-butyl-2-methylpropionamide, N, N-diethylacetamide, Nt-butylacetamide, N-
Phenyl-N-methylacetamide, N, N-diethylcyclohexanecarboxamide, N, N-diethylpropionamide, N, N-diethyl-2,2-dimethylpropionamide, N, N-diethylphenylacetamide, N, N
-Diethylbenzamide and the like can be exemplified. Particularly, diethylamine, pyridine, morpholine and the like are preferable in terms of yield. The amount of amines or amides used may be a so-called catalytic amount, and a range of about 0.001-0.1 equivalents relative to the carboxylic acid represented by the general formula (I) is selected, but it is usually 0. About 0.01 to 0.05 equivalents may be used. In addition, when a halogen compound is added as a co-catalyst when the disilyl acetal is produced in the present invention, the yield is often improved. The halogen compound that can be used is not particularly limited, and hydrogen iodide; alkyl halogen compounds such as ethyl iodide, benzyl bromide and benzyl chloride; aromatic halogen compounds such as iodobenzene; triethylammonium iodide, diethylmethylammonium Ammonium halogen compounds such as iodide, 1-ethylpyridinium iodide and benzyldiethyl ammonium bromide; iodine, bromine and the like can be mentioned. In the case of ammonium salt, it may be prepared in the system from the corresponding amine and halogen compound and used. The amount of these halogen compounds used may be a so-called catalytic amount, and a range of about 0.001-0.1 equivalents relative to the carboxylic acid represented by the general formula (I) is selected, but usually 0.01 It may be used at about -0.05 equivalent. In addition, it is often preferable to add both the amines or amides and the halogen compound from the viewpoint of yield.

In the present invention, aldehydes are produced by reacting disilyl acetals in the presence of a transition metal catalyst. There is a method of converting disilyl acetals to aldehydes by hydrolysis (Emiko Hagiwara, Takashi Ueno, Takamasa Fuchigami, Proceedings of the 79th Annual Meeting of the Chemical Society of Japan, II, 1181 (2001)), but an excessive amount of fluorine is used. Tetrabutylammonium chloride in tetrahydrofuran solution must be used and requires cooling. In addition, since complicated operations such as extraction, drying and filtration must be performed, and since tetrahydrofuran easily contains water, it is necessary to thoroughly perform these operations. Furthermore, when it has a hydrolyzable functional group, it must be separately protected prior to the reaction.

In the present invention, when the aldehyde is produced from disilylacetal, the transition metal catalyst is
Examples thereof include zero-valent metal itself such as zirconium, niobium, molybdenum, tungsten, rhenium, iron, ruthenium, osmium, rhodium, cobalt, iridium and zinc, and / or an inorganic compound, an organic compound or a complex compound. These transition metal catalysts may be carried on a carrier without any problem. Examples of catalysts that can be suitably used include zirconium (II) sulfate, zirconium (II) chloride, niobium (III) chloride, molybdenum (II) chloride, 5% rhenium-carbon, ammonium rhenate, and iron sulfate (II). ) Heptahydrate, iron (III) sulfate hydrate, iron (II) chloride, iron (II) chloride tetrahydrate, iron chloride (II
I), iron (III) chloride hexahydrate, 5% ruthenium-alumina, ruthenium (III) chloride hydrate, 5% ruthenium-carbon, cobalt (II) bromide, cobalt (II) chloride, cobalt chloride ( II) hydrate, cobalt (II) sulfate hydrate, rhodium carbonyl, rhodium (III) chloride trihydrate, iridium (III) chloride, iridium (IV) chloride tetrahydrate,
Examples thereof include zinc (II) chloride and zinc (II) sulfate heptahydrate. The amount of these transition metal catalysts used may be a so-called catalytic amount, and a range of about 0.001-0.1 equivalents relative to the disilylacetal represented by the general formula (I) is selected, but usually it is selected. About 0.005-0.05 equivalent may be used.

In carrying out the present invention, it is preferable to carry out in a solvent that does not participate in the reaction, and benzene, toluene, xylene, mesitylene, dimethoxyethane, hexane, cyclohexane and the like can be exemplified. The amount of the solvent used is not particularly limited as long as it can dissolve some or all of the raw materials at the reaction temperature.

The reaction temperature can be appropriately selected from the temperature range of room temperature to 200 ° C., but a temperature of about 100 ° C. is preferable in terms of reaction efficiency.

In carrying out the present invention, when a carboxylic acid derivative having an alkenyl group or an alkynyl group is used as a carboxylic acid derivative as a raw material, disilyl in which a part or all of the unsaturated bond is reduced is used. Acetals are obtained. When the aromatic carboxylic acid is substituted with a nitro group, a disilyl acetal in which a part of the nitro group is reduced can be obtained.

[0017]

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

Example 1

[0019]

[Chemical 1]

Cyclohexanecarboxylic acid (128 mg, 1.00 mmol), triethylsilane (4
80 μL, 0.351 g, 3.02 mmol), diethylamine (5 μL, 3.5 mg, 0.048 mmol, 4.8 mol%) as promoter and ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mol%)
, Triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%,
2.2 mg, [Ru] 1.0 mol%) and dry toluene (1 ml) as a solvent were added in sequence, and under argon atmosphere at 100 ° C.
The mixture was heated and stirred for 30 hours. After the reaction was completed, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. It was revealed that the target cyclohexanecarbaldehyde = bis (triethylsilyl) = acetal was produced in a yield of 100%. Became. Cyclohexanecarbaldehyde = bis (triethylsilyl) = acetal colorless oil: 130-138 ℃ / 1 mmHg .MS (EI): m / z 32
9 (M ⁺ -Et, 12), 275 (100), 115 (43), 87 (66%). ¹ H
-NMR (CDCl ₃ , 200 MHz): δ 0.64 (q, J = 8.0 Hz, 12
H), 0.95 (t, J = 8.0 Hz, 18 H), 1.00-1.80 (m, 11
H), 4.93 (d, J = 3.2 Hz, 1 H).

Example 2

[0022]

[Chemical 2]

Cyclohexanecarboxylic acid (130 mg, 1.02 mmol), triethylsilane (4
80 μL, 351 mg, 3.02 mmol), diethylamine (5 μL, 3.5 mg, 0.048 mmol, 4.8 mol%) as a cocatalyst, triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.2
mg, [Ru] 1.0 mol%), and dry toluene as solvent
(1 mL) was added sequentially, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The target cyclohexanecarbaldehyde = bis (triethylsilyl) = acetal was 100% in yield. It became clear that it is generated in.

Example 3

[0025]

[Chemical 3]

In a test tube with a cap, cyclohexanecarboxylic acid (127 mg, 0.99 mmol) and triethylsilane (48
0 μL, 351 mg, 3.02 mmol), ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mol%) as a cocatalyst, triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.4 mg,
[Ru] 1.1 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was conducted. As a result, the target cyclohexanecarbaldehyde
It was revealed that = bis (triethylsilyl) = acetal was produced in a yield of 100%.

Example 4

[0028]

[Chemical 4]

Cyclohexanecarboxylic acid (133 mg, 1.04 mmol), triethylsilane (4
80 μL, 351 mg, 3.02 mmol), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.5 mg, [Ru] 1.2 mol
%) And dry toluene (1 mL) were sequentially added, and the mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The target cyclohexanecarbaldehyde = bis (triethylsilyl) acetal showed a yield of 94%. It became clear that it is generated in.

Example 5

[0031]

[Chemical 5]

Cyclohexanecarboxylic acid (133 mg, 1.04 mmol) and triethylsilane (480
μL, 351 mg, 3.02 mmol), diethylamine (5 μL, 3.5 mg, 0.048 mmol, 4.8 mol%) as a cocatalyst and ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mol%),
Dichlorotricarbonyl ruthenium dimer ((RuCl ₂ (C
O) ₃ ] ₂ , 98%, 2.7 mg, [Ru] 1.0 mol%) and dry toluene (1 mL) were sequentially added, and then under argon atmosphere, 1
The mixture was heated and stirred at 00 ° C for 30 hours. After the reaction was completed, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The target cyclohexanecarbaldehyde = bis (triethylsilyl) = acetal was 100% in yield. It became clear that it is generated in.

Example 6

[0034]

[Chemical 6]

Cyclohexane cal in a test tube with a cap
Boronic acid (1.29 g, 10.1 mmol), triethylsilane (4.8
mL, 3.51 g, 30.2 mmol), diethylamine as co-catalyst
(52 μL, 36.8 mg, 0.500 mmol, 5.0 mol%) and
Ethyl iodide (40 μL, 78.0 mg, 0.50 mmol, 5.0 mol%)
 , Dichlorotricarbonyl ruthenium dimer ((RuCl ₃
(CO)₃]₂, 98%, 2.7 mg, [Ru] 1.0 mol%), and dry
After sequentially adding dry toluene (1 mL), under an argon atmosphere,
The mixture was heated and stirred at 100 ° C. for 30 hours. After the reaction is complete,
Cool the solution to room temperature and use it as an internal standard in the reaction mixture.
When decane was added and GLC analysis was performed,
Hexanecarbaldehyde = bis (triethylsilyl) = acetate
It is clear that tar is produced at a yield of 100%
Became.

Example 7

[0037]

[Chemical 7]

Butyric acid (88.8 mg, 1.
01 mmol), triethylsilane (480 μL, 351 mg, 3.02 mm
ol), diethylamine as a cocatalyst (5 μL, 3.5 mg, 0.
048 mmol, 4.8 mol%) and ethyl iodide (4 μL, 7.8
mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.5 mg, [Ru] 1.2 mol
%) And dry toluene (1 mL) were sequentially added, and the mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. As a result, the conversion rate of triethylsilane as a raw material was 82%.
It was revealed that the target butyraldehyde = bis (triethylsilyl) = acetal was produced in a yield of 86%.

Butyraldehyde = bis (triethylsilyl) = acetal colorless oil: 105-109 ° C./1.5 mmHg MS (EI): m / z
289 (M ⁺ -Et, 40), 275 (73), 217 (100), 189 (68), 11
5 (48), 87 (80%). MS (CI): m / z 317 (M ⁺ -1) .IR (nea
t): 2959, 2915, 2878, 1155, 1063, 1030, 1001, 741
cm ^-1 .c (Tol.-d ₈ , 250 MHz): δ 0.66 (q, J = 8.0 H
z, 12 H), 0.92 (t, J = 7.4 Hz, 3 H), 1.03 (t, J =
8.0 Hz, 18 H), 1.49 (tq, J = 7.4 and 9.6 Hz, 2
H), 1.59 (dt, J = 9.6 and 5.0 Hz, 2 H), 5.25 (t, J
= 5.0 Hz, 1 H) .HRMS: m / z calcd for C ₁₄ H ₃₃ O ₂ Si ₂
289.2018 (M ⁺ -Et) .found 289.2031.

Example 8

[0041]

[Chemical 8]

In a test tube with a cap, 2-methylbutanoic acid
(126 mg, 1.24 mmol), triethylsilane (480 μL, 35
1 mg, 3.02 mmol), diethylamine (5 μ
L, 3.5 mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.8 mg,
[Ru] 1.4 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 24 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The conversion of the starting material triethylsilane was 9%.
It was 2%, and it was revealed that the target 2-methylbutyraldehyde = bis (triethylsilyl) = acetal was produced in a yield of 87%.

2-Methylbutyraldehyde = bis (triethylsilyl) = acetal colorless oil: 115-120 ° C./1.5-1.6 mmHg MS (E
I): m / z 303 (M ⁺ -Et, 21), 275 (100), 217 (49), 189
(34), 115 (55), 87 (82%). MS (CI): m / z 331 (M ⁺ -
1). IR (neat): 2959, 2913, 2878, 1154, 1086, 1042,
^{. 1001, 741 cm -1 1 H} -NMR (Tol.-d 8, 500 MHz): δ 0.6
0 (q, J = 8.0 Hz, 6 H), 0.62 (q, J = 8.0 Hz, 6 H),
0.89 (t, J = 7.5 Hz, 3 H), 0.97 (t, J = 7.0 Hz,
3 H), 0.97 (t, J = 8.0 Hz, 9 H), 0.98 (t, J = 8.0
Hz, 9 H), 1.17-1.27 (m, 1 H), 1.33-1.41 (m, 1
H), 1.57-1.66 (m, 1 H), 5.14 (d, J = 2.6 Hz, 1 H).
HRMS: m / z calcd for C ₁₅ H ₃₅ O ₂ Si ₂ 303.2173 (M ⁺ -E
t) .found 303.2158.

Example 9

[0045]

[Chemical 9]

In a test tube with a cap, 3,3-dimethylbutanoic acid (123 mg, 1.06 mmol) and triethylsilane (480 μm) were added.
L, 351 mg, 3.02 mmol), diethylamine as a cocatalyst
(5 μL, 3.5 mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mol%),
Triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.
2 mg, [Ru] 1.4 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 24 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, and dodecane was added to the reaction mixture as an internal standard substance.
GLC analysis showed that the target 3,3-dimethylbutyraldehyde = bis (triethylsilyl) = acetal was 91%.
It was revealed that they were produced in a yield of.

3,3-Dimethylbutyraldehyde = bis (triethylsilyl) = acetal colorless oil: 105-110 ° C./0.8 mmHg MS (EI): m /
z 317 (M ⁺ -Et, 15), 275 (87), 217 (56), 115 (36), 57
(100%). MS (CI): m / z 345 (M ⁺ -1). IR (neat): 295
5, 2913, 2878, 1144, 1055, 999, 741 cm -1. 1 H-NMR
(Tol.-d ₈ , 500 MHz): δ 0.51 (q, J = 8.0 Hz, 12 H),
0.84 (s, 9 H), 0.87 (t, J = 8.0 Hz, 18 H), 1.43
(d, J = 5.0 Hz, 2 H), 5.27 (t, J = 5.0 Hz, 1 H).
HRMS: m / zcalcd for C ₁₆ H ₃₇ O ₂ Si ₂ 317.2329 (M ⁺ -E
t) .found 317.2321.

Example 10

[0049]

[Chemical 10]

In a test tube with a cap, add 3-methylpentane.
Acid (121 mg, 1.04 mmol), triethylsilane (480 μL,
351 mg, 3.02 mmol), diethylamine (5
μL, 3.5 mg, 0.048 mmol, 4.8 mol%) and iodide
Chill (4 μL, 7.8 mg, 0.050mmol, 5.0 mol%), tolyl
Thenium dodecacarbonyl (Ru₃(CO)₁₂, 99%, 2.8 mg,
[Ru] 1.3 mol%) and dry toluene (1 mL) are added sequentially.
After heating, heat and stir at 100 ° C. for 24 hours in an argon atmosphere.
I stirred. After the reaction is complete, cool the reaction solution to room temperature
GLC analysis by adding dodecane as an internal standard to the mixture
Then, the desired 3-methylvaleraldehyde = bi
Su (triethylsilyl) = acetal is produced in a yield of 97%
It became clear that it was done. 3-Methylvaleraldehyde = bis (triethylsilyl) = a
Cetal colorless oil: 108-112 ℃ / 0.7-0.8 mmHg MS (E
I): m / z 317 (M⁺-Et, 31), 275 (100), 217 (56), 115
(35%). MS (CI): m / z 345 (M⁺-1). IR (neat): 2957, 2
915, 2878, 1049, 1001, 741 cm^-1.¹H-NMR (Tol.-d₈,
500 MHz): δ 0.52 (m, 12 H), 0.73 (t, J = 7.3 Hz,
3 H), 0.77 (d, J = 6.8 Hz, 3 H), 0.86 (m, 18 H),
0.91-1.06 (m, 1 H), 1.15-1.33 (m, 2 H), 1.47-1.59
(m, 2 H), 5.23 (t, J = 5.0 Hz, 1 H). HRMS: m / z calc
d for C₁₆H₃₇O₂Si₂  317.2329 (M ⁺-Et) .found 317.232
7.

Example 11

[0052]

[Chemical 11]

In a test tube with a cap, add benzoic acid (124 m
g, 1.02 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), diethylamine (5 μL, 3.5
mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μ
L, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.2 mg, [Ru] 1.5
mol%) and dry toluene (1 mL) were added sequentially,
The mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere.
After the reaction was completed, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. As a result, the conversion rate of the starting material triethylsilane was 73%, and the desired benzaldehyde = bis (triethyl Cyril) =
It was revealed that acetal and triethylsilyl benzoate were produced in yields of 82% and 18%, respectively. Benzaldehyde = bis (triethylsilyl) = acetal colorless oil: 145-155 ℃ / 0.3-0.4 mmHg MS (EI): m
/ z 329 (M ⁺ -Et, 12), 275 (100), 115 (43), 87 (66
%). ¹ H-NMR (CDCl ₃ , 250 MHz): δ 0.48 (q, J = 8.0
Hz, 12 H), 0.82 (t, J = 8.0 Hz, 18 H), 5.96 (s, 1
H), 7.18-7.35 (m, 5H).

Example 12

[0055]

[Chemical 12]

In a test tube with a cap, add benzoic acid (123 m
g, 1.01 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), diethylamine (5 μL, 3.5
mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μ
L, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 10.5 mg, [Ru] 4.9
mol%) and dry toluene (1 mL) were added sequentially,
The mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere.
After the reaction was completed, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The conversion of the starting material triethylsilane was 84%, and the desired benzaldehyde = bis (triethyl Cyril) =
It was revealed that acetal and triethylsilyl benzoate were produced in yields of 84% and 15%, respectively.

Example 13

[0058]

[Chemical 13]

In a test tube with a cap, add benzoic acid (123 m
g, 1.01 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), diethylamine (5 μL, 3.5
mg, 0.048 mmol, 4.8 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.8 mg, [Ru] 1.3 mol%)
, And dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed.
The conversion of the starting material, triethylsilane, is 60%, and the target benzaldehyde = bis (triethylsilyl) = acetal and triethylsilyl benzoate are 30% each.
And 70% yield was revealed.

Example 14

[0061]

[Chemical 14] In a test tube with a cap, benzoic acid (122 mg, 1.00 mmol)
, Triethylsilane (480 μL, 351 mg, 3.02 mmol)
, Diethylamine as a co-catalyst (5 μL, 3.5 mg, 0.048
mmol, 4.8 mol%) and ethyl iodide (4 μL, 7.8 mg,
0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 10.7 mg, [Ru] 5.0 mol%),
Then, dry toluene (1 mL) was sequentially added, and the mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed.The target benzaldehyde = bis (triethylsilyl) = acetal and triethylsilyl benzoate were 63% each.
% And 22% yield were revealed.

Example 15

[0063]

[Chemical 15]

In a test tube with a cap, benzoic acid (631 mg,
5.16 mmol), triethylsilane (1.9 mL, 11.6 mmol)
, Diethylamine as a co-catalyst (26 μL, 18.4 mg, 0.2
5 mmol, 4.9 mol%) and ethyl iodide (20 μL, 39.0
mg, 0.25 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 53.5 mg, [Ru] 4.8 mol%)
, And dry toluene (5 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed.
It was revealed that the target benzaldehyde = bis (triethylsilyl) = acetal was produced in a yield of 99%.

Example 16

[0066]

[Chemical 16]

In a test tube with a cap, add benzoic acid (123 m
g, 1.01 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), triruthenium dodecacarbonyl (Ru ₃ (C
O) ₁₂ , 99%, 2.6 mg, [Ru] 1.2 mol%), and dry toluene (1 mL) were sequentially added, and then, under argon atmosphere, 10
The mixture was heated and stirred at 0 ° C for 30 hours. After the reaction was completed, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The conversion of the starting material triethylsilane was 78%, and the target benzaldehyde bis (triethyl It was revealed that silyl) = acetal and triethylsilyl benzoate were produced in yields of 28% and 48%, respectively.

Example 17

[0069]

[Chemical 17]

In a test tube with a cap, add benzoic acid (125 m
g, 1.02 mmol), triethylsilane (350 μL, 256 mg,
2.20 mmol), diethylamine (5 μL, 3.5
mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μ
L, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.5 mg, [Ru] 1.2
mol%) and dry toluene (1 mL) were added sequentially,
The mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere.
After completion of the reaction, the reaction solution was cooled to room temperature, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The target benzaldehyde = bis (triethylsilyl) = acetal and triethylsilyl benzoate were 30% each. % And 66% yield was revealed.

Example 18

[0072]

[Chemical 18]

In a test tube with a cap, p-toluic acid (136
mg, 1.00 mmol), triethylsilane (480 μL, 351 m
g, 3.02 mmol), diethylamine (5 μL,
3.5 mg, 0.048 mmol, 4.8 mol% and ethyl iodide (4 μ
L, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.4 mg, [Ru] 1.0
mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was conducted. As a result, the conversion rate of the starting material triethylsilane was 75%, and the target 4-methylbenzaldehyde = Bis (triethylsilyl) = acetal, triethylsilyl p-toluate,
It was revealed that and 4-methylbenzyloxytriethylsilane were produced in yields of 78, 8 and 10%, respectively.

4-methylbenzaldehyde = bis (triethylsilyl) = acetal colorless oil: 135-138 ° C./0.75 mmHg. MS (EI): m /
z 337 (M ⁺ -Et, 100), 275 (4), 235 (69%). MS (CI):
m / z 365 (M ⁺ -1). IR (neat): 2955, 2913, 2878,1103,
^{. 1053, 1003, 741 cm -1} 1 H-NMR (Tol.-d 8, 500 MHz):
δ 0.64 (q, J = 8.0 Hz, 12 H), 1.01 (t, J = 8.0 Hz,
18 H), 2.11 (s, 3 H), 6.18 (s, 1 H), 6.98 (d, J =
8.0 Hz, 2 H), 7.42 (d, J = 8.0 Hz, 2 H). HRMS: m /
z calcdfor C ₁₈ H ₃₃ O ₂ Si ₂ 337.2017 (M ⁺ -Et) .found 37
7.2020.

Triethylsilyl p-toluate colorless oil: 90-95 ℃ / 0.14-0.15 mmHg MS (E
I): m / z 221 (M⁺-Et, 100), 119 (33), 91 (18%). MS
(CI): m / z 251 (M⁺+1). IR (neat): 2959, 2915,2878,
1701, 1290, 1111, 758, 739 cm^-1.¹H-NMR (Tol.-d₈,
250 MHz): δ 0.89 (q, J = 8.1 Hz, 6 H), 1.08 (t, J =
 8.1 Hz, 9 H), 2.06 (s, 3 H), 6.93 (d, J = 8.1 Hz,
 2 H), 8.11 (d, J = 8.1 Hz, 2 H). HRMS: m / z calcd
 for C₁₂H ₁₇O₂Si 221.0997 (M⁺-Et) .found 221.1007.

4-Methylbenzyloxytriethylsilane colorless oil: 80-85 ° C./0.2 mmHg MS (EI): m / z 236
(M ⁺ , 2), 207 (M ⁺ -Et, 100), 177 (11), 149 (3), 105
(30%). MS (CI): m / z 235 (M ⁺ -1). IR (neat): 2955, 2
913, 2878, 1090, 1015, 822, 795, 741 cm -1. 1 H-NMR
(Tol.-d ₈ , 250MHz): δ 0.66 (q, J = 8.0Hz, 9H),
1.04 (t, J = 8.0 Hz, 6 H), 2.18 (s, 3 H), 4.66 (s,
2 H), 7.04 (d, J = 8.5 Hz, 2 H), 7.27 (d, J = 8.5 H
z, 2 H) .HRMS: m / z calcd for C ₁₂ H ₁₉ OSi 207.1204
(M ⁺ -Et) .found 207.1219.

Example 19

[0078]

[Chemical 19]

In a test tube with a cap, p-toluic acid (137
mg, 1.00 mmol), triethylsilane (480 μL, 351 m
g, 3.02 mmol), diethylamine (5 μL,
3.5 mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4
μL, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.7 mg, [Ru]
1.3 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 68%.
It was revealed that the target 4-methylbenzaldehyde = bis (triethylsilyl) = acetal and triethylsilyl p-toluate were produced in yields of 74 and 26%, respectively.

Example 20

[0081]

[Chemical 20]

In a test tube with a cap, p-toluic acid (137
mg, 1.01 mmol), triethylsilane (480 μL, 351 m
g, 3.02 mmol), diethylamine (3 μL,
2.1 mg, 0.029 mmol, 2.9 mol%) and ethyl iodide
(0.002 mL, 3.9 mg, 0.025 mmol, 2.5 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.7 mg,
[Ru] 1.7 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed.
1% of the desired 4-methylbenzaldehyde bis (triethylsilyl) acetal, triethylsilyl p-toluate, and 4-methylbenzyloxytriethylsilane were produced in yields of 78, 16 and 3% respectively. It became clear.

Example 21

[0084]

[Chemical 21] In a test tube with a cap, p-toluic acid (138 mg, 1.00 mm
ol), triethylsilane (480 μL, 351 mg, 3.02 mmol)
, Diethylamine as co-catalyst (3 μL, 2.1 mg, 0.029
mmol, 2.9 mol%) and ethyl iodide (2 μL, 3.6 mg,
0.025 mmol, 2.5 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.4 mg, [Ru] 1.6 mol%),
Then, dry xylene (1 mL) was sequentially added, and the mixture was heated with stirring at 100 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed.
The conversion of the starting material, triethylsilane, is 70%, and the target 4-methylbenzaldehyde = bis (triethylsilyl) =
Acetal, triethylsilyl p-toluate, and 4
-Methylbenzyloxytriethylsilane is 7,
It was revealed that the yield was 63 and 17%.

Example 22

[0086]

[Chemical formula 22]

In a test tube with a cap, p-toluic acid (68.
0 mg, 0.499 mmol), triethylsilyl p-toluate (1
34 mg, 0.536 mmol), and triethylsilane (480 μ
L, 351 mg, 3.02 mmol), diethylamine as a cocatalyst
(5 μL, 3.5 mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.2)
mg, [Ru] 1.0 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction is completed, the reaction solution is cooled to room temperature,
Dodecane was added to the reaction mixture as an internal standard and GLC
The analysis showed that the conversion rate of the starting material triethylsilane was 60%, and the target 4-methylbenzaldehyde = bis (triethylsilyl) = acetal, triethylsilyl p-toluate, and 4-methylbenzyloxytriethylsilane were , 84, 10 and 2% yield, respectively.

Example 23

[0089]

[Chemical formula 23] In a test tube with a cap, p-toluic acid (68.2 mg, 0.499
mmol), triethylsilyl p-toluate (131 mg, 0.536
mmol) and triethylsilane (480 μL, 351 mg,
3.02 mmol), diethylamine (5 μL, 3.5
mg, 0.048 mmol, 4.8 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.7 mg, [Ru] 1.3 mol
%) And dry toluene (1 mL) were sequentially added, and the mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 45%.
The target 4-methylbenzaldehyde bis (triethylsilyl) = acetal, triethylsilyl p-toluate, and 4-methylbenzyloxytriethylsilane are each 2
It was revealed that the yields were 4, 70 and 4%.

Example 24

[0091]

[Chemical formula 24]

In a test tube with a cap, p-toluic acid (341
mg, 2.50 mmol), triethylsilyl p-toluate (637
mg, 2.54 mmol), and triethylsilane (2.4 mL, 1
5.1 mmol), diethylamine (26 μL, 0.25
mmol, 5.0 mol%) and ethyl iodide (20 μL, 0.25 m
mol, 5.0 mol%), triruthenium dodecacarbonyl (R
u ₃ (CO) ₁₂ , 99%, 12.0 mg, [Ru] 1.1 mol%) and dry toluene (5 mL) were sequentially added, and then heated and stirred at 100 ° C. for 30 hours under an argon atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature, and the reaction solvent and unreacted triethylsilane were distilled off under reduced pressure. The precipitate of the reaction mixture was quickly filtered off with glass wool under an atmosphere of argon. The resulting crude product was Kugelrohr distilled.
(0.25 mmHg) to separate and purify the desired 4-methylbenzaldehyde = bis (triethylsilyl) = acetal (1.393
g, 3.80 mmol, 75%) was obtained as a colorless oil.

Example 25

[0094]

[Chemical 25]

In a test tube with a cap, p-toluic acid (137
mg, 1.00 mmol), triethylsilane (480 μL, 351 m
g, 3.02 mmol), diethylamine (3 μL,
2.1 mg, 0.029 mmol, 2.9 mol%) and ethyl iodide (2
μL, 3.9 mg, 0.025 mmol, 2.5 mol%), dichlorotricarbonyl ruthenium dimer ([RuCl ₂ (CO) ₃ ] ₂ , 98
%, 3.6 mg, [Ru] 1.4 mol%) and dry toluene (1
(mL), and then add 3 mL at 100 ° C under an argon atmosphere.
The mixture was heated and stirred for 0 hours. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. As a result, the conversion rate of the starting material triethylsilane was 86%, and the desired 4-methylbenzaldehyde = It was revealed that bis (triethylsilyl) = acetal, triethylsilyl p-toluate, and 4-methylbenzyloxytriethylsila were produced in yields of 37, 25, and 9%, respectively.

Example 26

[0097]

[Chemical formula 26]

In a test tube with a cap, p-anisic acid (153 m
g, 1.01 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), diethylamine (5 μL, 3.5
mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μ
L, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.0 mg, [Ru] 1.4 m
ol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion of the starting material triethylsilane was 65%, and the target 4-methoxybenzaldehyde = Bis (triethylsilyl) = acetal, triethylsilyl p-anisate,
And 4-methoxybenzyloxytriethylsilane is
It was revealed that they were produced in yields of 51, 43 and 4%, respectively.

4-methoxybenzaldehyde = bis (triethylsilyl) = acetal colorless oil: ¹ H-NMR (Tol.-d ₈ , 500 MHz): δ 0.58
(q, J = 7.9 Hz, 12 H), 0.95 (t, J = 7.9 Hz, 18 H),
3.23 (s, 3 H), 6.11 (s, 1 H), 6.67 (d, J = 8.7 Hz,
2 H), 7.35 (d, J = 8.7 Hz, 2 H) .triethylsilyl p-anisate colorless oil: 133-135 ℃ / 0.9 mmHg MS (EI): m / z 2
37 (M ⁺ -Et, 100%). MS (CI): m / z 267 (M ⁺ +1). IR (ne
at): 2959, 2913, 2880, 1694, 1607, 1510, 1294, 125
8, 1167, 1121, 775 cm -1. 1 H-NMR (Tol.-d 8, 250 MH
z): δ 0.91 (q, J = 7.5 Hz, 9 H), 1.10 (t, J = 7.5 H
z, 6 H), 3.25 (s, 3 H), 6.64 (d, J = 8.9 Hz, 2 H),
8.15 (d, J = 8.9 Hz, 2 H) .HRMS: m / z calcd for C
₁₄ H ₂₂ O ₂ Si266.1337 (M ⁺ -Et) .found 266.1339.

4-methoxybenzyloxytriethylsila
The colorless oil: 115-125 ℃ / 0.4 mmHg MS (EI): m / z 2
52 (M⁺, 29), 223 (91), 121 (100%). IR (neat): 295
5, 2911, 2878, 1514, 1246, 1088, 820, 741 cm ^-1.¹
H-NMR (Tol.-d₈, 250 MHz): δ 0.66 (q, J = 7.9 Hz, 6
 H), 1.05 (t, J = 7.9 Hz, 9 H), 3.38 (s, 3 H), 4.63
 (s, 2 H), 6.80 (d, J = 8.0 Hz, 2 H), 7.25 (d, J =
8.0 Hz, 2 H). HRMS: m / z calcd for C₁₄H_{twenty four}O₂Si 25
2.1544.found 252.1568.

Example 27

[0102]

[Chemical 27]

In a test tube with a cap, p-anisic acid (153 m
g, 1.00 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), diethylamine (5 μL, 3.5
mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μ
L, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.4 mg, [Ru] 1.0 m
ol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was conducted. The conversion of the starting material triethylsilane was 61%, and the target 4-methoxybenzaldehyde = Bis (triethylsilyl) = acetal, triethylsilyl p-anisate,
And 4-methoxybenzyloxytriethylsilane is
It was revealed that the yields were 32, 56 and 9%, respectively.

Example 28

[0105]

[Chemical 28]

In a test tube with a cap, p-anisic acid (153 m
g, 1.00 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), t-butylamine (5 μL, 0.0
48 mmol, 4.8 mol%) and ethyl iodide (4 μL, 7.8 m
g, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.8 mg, [Ru] 1.3 mol
%) And dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The conversion rate of triethylsilane as a raw material was 75%.
The desired 4-methoxybenzaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane were found to be produced in yields of 62, 20 and 17%, respectively. Became.

Example 29

[0108]

[Chemical 29]

In a test tube with a cap, p-anisic acid (152 m
g, 0.997 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), cyclohexylamine (6
μL, 0.052 mmol, 5.2 mol%) and ethyl iodide (4 μ
L, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.2 mg, 1.5 mol
%) And dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 84%.
It was revealed that the desired 4-methoxybenzaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane were produced in yields of 60, 25, and 11%, respectively. Became.

Example 30

[0111]

[Chemical 30]

In a test tube with a cap, p-anisic acid (152 m
g, 1.00 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), di-i-propylamine (7 μ
L, 0.050 mmol, 5.0 mol%) and ethyl iodide (4 μL,
7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.3 mg, [Ru] 1.0 m
ol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion of the starting material triethylsilane was 65%, and the target 4-methoxybenzaldehyde = Bis (triethylsilyl) = acetal, triethylsilyl p-anisate,
And 4-methoxybenzyloxytriethylsilane is
It was revealed that the yields were 46, 31 and 19%, respectively.

Example 31

[0114]

[Chemical 31]

In a test tube with a cap, p-anisic acid (152 m
g, 1.00 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), dibutylamine (8 μL, 0.0
47 mmol, 4.7 mol%) and ethyl iodide (4 μL, 7.8 m
g, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.3 mg, [Ru] 1.1 mol
%) And dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 65%.
It is clear that the desired 4-methoxybenzaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane were produced in yields of 48, 38, and 8%, respectively. Became.

Example 32

[0117]

[Chemical 32]

In a test tube with a cap, p-anisic acid (153 m
g, 1.01 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), didecylamine (14.9 mg,
0.050 mmol, 5.0 mol%) and ethyl iodide (4 μL, 7.8
mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.0 mg, [Ru] 1.4 mol
%) And dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 65%.
It was revealed that the desired 4-methoxybenzaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane were produced in yields of 51, 43, and 4%, respectively. Became.

Example 33

[0120]

[Chemical 33]

In a test tube with a cap, p-anisic acid (152 m
g, 1.00 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), triethylamine (7 μL,
0.050 mmol, 5.0 mol%) and ethyl iodide (4 μL, 7.8
mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.2 mg, [Ru] 1.0 mol
%) And dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 53%
It was revealed that the desired 4-methoxybenzaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane were produced in yields of 19, 76 and 1%, respectively. Became.

Example 34

[0123]

[Chemical 34]

In a test tube with a cap, p-anisic acid (152 m
g, 1.00 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), ethyldiisopropylamine (8 μL, 0.052 mmol, 5.2 mol%) as promoter and ethyl iodide
(4 μL, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.5 mg, [Ru]
1.6 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out.
And the desired 4-methoxybenzaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane are produced in yields of 33, 53, and 12%, respectively. It became clear.

Example 35

[0126]

[Chemical 35]

In a test tube with a cap, p-anisic acid (153 m
g, 1.01 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), pyridine as a co-catalyst (4 μL, 0.049 mmo
l, 4.9 mol%) and ethyl iodide (4 μL, 7.8 mg, 0.0
50 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.5 mg, [Ru] 1.2 mol%), and dry toluene (1 mL) were added sequentially, and then under argon atmosphere. The mixture was heated and stirred at 100 ° C. for 30 hours. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was conducted. The conversion of the starting material triethylsilane was 63%, and the desired 4-methoxybenzaldehyde = Bis (triethylsilyl) = acetal, p-anisate triethylsilyl, and 4-methoxybenzyloxytriethylsilane are 50 and 44, respectively.
And it was revealed that the yield was 4%.

Example 36

[0129]

[Chemical 36]

In a test tube with a cap, p-anisic acid (152 m
g, 1.00 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), diethylaminotrimethylsilane (8 μL, 0.051 mmol, 5.1 mol%) as a co-catalyst, ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO)) ₁₂ , 99%, 2.7 mg, [R
u] 1.3 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 66.
%, The desired 4-methoxybenzaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane were produced in yields of 56, 36 and 6%, respectively. It became clear.

Example 37

[0132]

[Chemical 37]

In a test tube with a cap, p-anisic acid (152 m
g, 1.00 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), di-t-butylamine (9 μL,
0.053 mmol, 5.3 mol%) and ethyl iodide (4 μL,
7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.2 mg, [Ru] 1.0 mol
%) And dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 71%.
The target 4-anisaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate and 4-methoxybenzyloxytriethylsilane were 71 and 18 respectively.
And 7% yield was revealed.

Example 38

[0135]

[Chemical 38]

In a test tube with a cap, p-anisic acid (137 m
g, 1.01 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), morpholine as a co-catalyst (4.5 μL, 0.052 m
mol, 5.2 mol%) and ethyl iodide (4 μL, 7.8 mg, 0.
050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.5 mg, [Ru] 1.6 mol%), and dry toluene (1 mL) were added sequentially, and then under an argon atmosphere. The mixture was heated and stirred at 100 ° C. for 30 hours. After the reaction,
The reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 76%.
It was revealed that anisaldehyde = bis (triethylsilyl) = acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane were produced in yields of 80, 11 and 7%, respectively.

Example 39

[0138]

[Chemical Formula 39]

In a test tube with a cap, p-anisic acid (153 m
g, 1.01 mmol), and triethylsilane (480 μL, 351
mg, 3.02 mmol), 2,6-lutidine (6 μL,
5.5 mg, 0.052 mmol, 5.2 mol%) and ethyl iodide (4
μL, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.3 mg, [Ru]
1.1 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out.
And the desired 4-anisaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane are produced in yields of 66, 28 and 5%, respectively. It became clear.

Example 40

[0141]

[Chemical 40]

In a test tube with a cap, p-anisic acid (152 m
g, 1.00 mmol), and triethylsilane (480 μL, 351
mg, 3.02 mmol), 2,4,6-collidine (7 μL,
0.053 mmol, 5.3 mol%) and ethyl iodide (4 μL,
7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.5 mg, [Ru] 1.2mo
1%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. As a result, the conversion rate of the starting material triethylsilane was 61%, and the desired 4-anisaldehyde = Bis (triethylsilyl) = acetal, triethylsilyl p-anisate, and
4-methoxybenzyloxytriethylsilane is 5 each
It was revealed that the yields were 9, 32 and 4%.

Example 41

[0144]

[Chemical 41]

In a test tube with a cap, p-anisic acid (153 m
g, 1.00 mmol), and triethylsilane (480 μL, 351
mg, 3.02 mmol), pyrrolidine (4 μL, 0.
048 mmol, 4.8 mol%) and ethyl iodide (4 μL, 7.8 m
g, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.4 mg, [Ru] 1.1 mol%)
, And dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, n-dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 57%.
The target 4-anisaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane are 50 and 4, respectively.
It was revealed that the yield was 5 and 2%.

Example 42

[0147]

[Chemical 42]

In a test tube with a cap, p-anisic acid (153 m
g, 1.00 mmol), and triethylsilane (480 μL, 35
0.8 mg, 3.02 mmol), piperidine (5 μL,
0.051 mmol, 5.1 mol%) and ethyl iodide (4 μL, 7.
8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.6 mg, [Ru] 1.2 mol
%) And dry toluene (1 mL) were sequentially added, and the mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 69%.
The desired 4-anisaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane are 64 and 2 respectively.
It was revealed that they were produced in yields of 8 and 5%.

Example 43

[0150]

[Chemical 43]

In a test tube with a cap, p-anisic acid (153 m
g, 1.00 mmol), and triethylsilane (480 μL, 351
mg, 3.02 mmol), piperazine (4.3 mg, 0.
050 mmol, 5.0 mol%) and ethyl iodide (4 μL, 7.8 m
g, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.1 mg, [Ru] 1.0 mol%)
, And dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the completion of the reaction, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The conversion rate of triethylsilane as a raw material was 67%.
The desired 4-anisaldehyde bis (triethylsilyl) acetal, triethylsilyl p-anisate, and 4-methoxybenzyloxytriethylsilane were 47 and 4 respectively.
It was revealed that they were produced in yields of 4 and 6%.

Example 44

[0153]

[Chemical 44]

In a test tube with a cap, p-anisic acid (153 m
g, 1.00 mmol), and triethylsilane (480 μL, 351
mg, 3.02 mmol), diethylamine (5 μL,
3.5 mg, 0.048 mmol, 4.8 mol%) and benzene iodide (5 μL, 0.045 mmol, 4.5 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.3 mg, [Ru] 1.1 m
ol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was conducted. The conversion of the starting material triethylsilane was 66%, and the target 4-anisaldehyde = Bis (triethylsilyl) = acetal, triethylsilyl p-anisate, and
4-methoxybenzyloxytriethylsilane is 5 each
It was revealed that the yields were 5, 36 and 9%.

Example 45

[0156]

[Chemical formula 45]

In a test tube with a cap, p-anisic acid (153 m
g, 1.01 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), diethylamine (5 μL, 3.5
 mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μ
L, 7.8 mg, 0.050 mmol, 5.0 mol%), dichlorotrica
Rubonyl ruthenium dimer ((RuCl₂(CO) ₃]₂, 98%, 3.
0 mg, [Ru] 1.1 mol%) and dry toluene (1 mL)
After adding sequentially, under argon atmosphere at 100 ℃ for 30 hours
Heated and stirred. After the reaction is complete, cool the reaction solution to room temperature
And added dodecane as an internal standard to the reaction mixture,
GLC analysis showed that the conversion of the raw material triethylsilane
The conversion rate is 70%, and the desired 4-methoxybenzaldehyde
De bis (triethylsilyl) acetal, p-anisic acid
Liethylsilyl, and 4-methoxybenzyloxytri
Ethylsilane has yields of 50, 35 and 11% respectively.
It has become clear that they are being generated.

Example 46

[0159]

[Chemical formula 46]

Under an argon atmosphere, 4-methylbenzaldehyde = bis (triethylsilyl) = acetal (200 mg, 0.
545 mmol) in dry toluene (1 mL) was cooled to 0 ° C,
A tetrahydrofuran solution of tetrabutylammonium fluoride (1.0 M in THF, 2.3 mL) was slowly added dropwise. 0 ° C
After stirring for 2 hours at room temperature, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, water and toluene were added to the reaction solution, the organic layer was separated, and dried over anhydrous magnesium sulfate. After removing the desiccant and evaporating the solvent under reduced pressure, crude p-tolualdehyde was obtained. 1,3-Dioxolane was added to the obtained crude product and ¹ H-NMR spectrum was measured in a deuterated toluene solvent.
It was revealed that the target p-tolualdehyde was produced at a conversion yield of 7%.

Example 47

[0162]

[Chemical 47]

In a test tube with a cap, add 2-ethylbutanoic acid.
(124 mg, 1.06 mmol), triethylsilane (480 μL, 35
1 mg, 3.02 mmol), diethylamine (5 μ
L, 3.5 mg, 0.048 mmol, 4.5 mol%) and ethyl iodide (4
μL, 7.8 mg, 0.050 mmol, 4.7 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.5 mg, [Ru] 1.
1 mol%) and dry toluene (1 mL) were added sequentially,
The mixture was heated and stirred at 100 ° C. for 24 hours under an argon atmosphere.
After completion of the reaction, the reaction solution was cooled to room temperature, 1.3-dioxolane as an internal standard substance was added to the reaction mixture, GLC analysis and NMR measurement were performed to calculate the conversion rate of the raw material and the yield of the product. -Ethyl butyraldehyde =
Bis (triethylsilyl) = acetal and triethylsilyl 2-ethylbutanoate are 67 and 29, respectively.
It was revealed that the product was produced in a yield of%. 2-Ethylbutyraldehyde = bis (triethylsilyl) = acetal colorless oil: 95 ℃ / 0.65 mmHg. MS (EI): m / z 317
(M ⁺ -Et, 20), 275 (100), 217 (16), 189 (8), 115
(5), 87 (4%). MS (CI): m / z 345 (M ⁺ -1). IR (neat):
2959, 2733, 1092, 1001, 741 cm -1. 1 H-NMR (Tol.-d
₈ , 250 MHz): δ 0.51 (q, J = 7.9 Hz, 12 H), 0.83
(t, J = 7.5 Hz, 6 H), 0.88 (t, J = 7.9 Hz, 18 H),
1.02-1.11 (m, 1 H), 1.19-1.33 (m, 2 H), 1.43-1.57
(m, 2 H), 5.21 (d, J = 5.0 Hz, 1 H).

Triethylsilyl 2-ethylbutanoate colorless oil: 65 ° C./0.8 mmHg MS (EI): m / z 201 (M
⁺ -Et, 100%). MS (CI): m / z 231 (M ⁺ +1). IR (neat): 2
961, 2880, 1717, 1192, 1007, 741 cm -1. 1 H-NMR (To
l.-d ₈ , 250 MHz): δ 0.60 (q, J = 7.5 Hz, 6 H), 0.7
3 (t, J = 7.5 Hz, 6 H), 0.84 (t, J = 7.5 Hz, 9 H),
1.18-1.32 (m, 2 H), 1.41-1.53 (m, 2 H), 1.93-1.99
(m, 1 H).

Example 48

[0166]

[Chemical 48] Add 4-pentenoic acid (114 mg, 1.13 mm) to a capped test tube.
ol), triethylsilane (480 μL, 351 mg, 3.02 mmol)
, Diethylamine as co-catalyst (5 μL, 3.5 mg, 0.048
mmol, 4.3 mol%) and ethyl iodide (4 μL, 7.8 mg, 0.0
50 mmol, 4.4 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.3 mg, [Ru] 1.0 mol%), and dry toluene (1 mL) were added sequentially, and then under argon atmosphere. The mixture was heated and stirred at 100 ° C. for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was conducted. As a result, the conversion of the starting material triethylsilane was 100%, and the desired pentane aldehyde = bis ( It was revealed that triethylsilyl) = acetal was produced in a yield of 83%. Pentane aldehyde = bis (triethylsilyl) = acetal colorless oil: 87-97 ℃ / 0.5-0.6 mmHg. MS (EI): m
/ z 303 (M ⁺ -Et, 28), 275 (100), 217 (83), 115 (45),
87 (68%). MS (CI): m / z 331 (M ⁺ -1). IR (neat): 2
957, 2915, 2878, 1154, 1046, 1001, 741 cm -1. 1 HN
MR (Tol.-d ₈ , 250MHz): δ 0.52 (q, J = 7.9 Hz, 12
H), 0.76 (t, J = 7.3 Hz, 3 H), 0.89 (t, J = 7.9 Hz,
18 H), 1.11-1.23 (m, 2 H), 1.26-1.35 (m, 2 H), 1.
43-1.53 (m, 2 H), 5.10 (t, J = 5.0 Hz, 1 H). HRM
S: m / z calcd for C ₁₇ H ₄₀ O ₂ Si ₂ 303.2174 (M ⁺ -Et) .fo
und 303.2176.

Example 49

[0168]

[Chemical 49]

Cyclopentyl ether was added to the test tube with the cap.
Tanoic acid (144 mg, 1.12 mmol), triethylsilane (480
μL, 351 mg, 3.02 mmol), diethylamine as a promoter
Solution (5 μL, 3.5 mg, 0.048 mmol, 4.3 mol%) and iodide
Chill (4 μL, 7.8 mg, 0.050 mmol, 4.5 mol%), tri
Ruthenium Dodecacarbonyl (Ru₃(CO)₁₂, 99%, 2.3 m
g, [Ru] 1.0 mol%), and dry toluene (1 mL) sequentially
After adding, heat at 100 ° C for 24 hours under argon atmosphere
It was stirred. After the reaction is complete, cool the reaction solution to room temperature and
Dodecane was added to the reaction mixture as an internal standard substance, and GLC
As a result of the analysis, the conversion of the starting material triethylsilane was found to be
85%, the desired cyclopentylethane aldehyde
= Bis (triethylsilyl) = acetal, 96% yield
It became clear that it is generated in. Cyclopentylethane aldehyde = bis (triethylsilyl)
Le) = acetal colorless oil: 108-113 ℃ / 0.3 mmHg. MS (EI): m / z
 329 (M⁺-Et, 25), 275 (100), 217 (47), 189 (27), 11
5 (24), 87 (36%). MS (CI): m / z 357 (M⁺-1) .IR (nea
t): 2955, 2913, 2878, 1142, 1047, 1003, 741 cm^-1.
 ¹H-NMR (Tol.-d ₈, 250 MHz): δ 0.48 (q, J = 7.9 Hz,
 12 H), 0.84 (t, J = 7.9 Hz, 18 H), 0.89-1.00 (m, 2
 H), 1.23-1.43 (m, 4 H), 1.47-1.53 (m, 2 H), 1.57-
1.70 (m, 2 H), 1.80-1.90 (m, 1 H), 5.12 (t, J = 5.
0 Hz, 1 H). HRMS: m / z calcdfor C₁₉H₄₂O₂Si₂  329.2
330 (M⁺-Et) .found 329.2336.

Example 50

[0171]

[Chemical 50]

In a test tube with a cap, decanoic acid (174 mg,
 1.01 mmol), triethylsilane (480 μL, 351 mg, 3.
02 mmol), diethylamine (5 μL, 3.5 m
g, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μL, 7.8
 mg, 0.050 mmol, 5.0 mol%), triruthenium dodeca
Carbonyl (Ru₃(CO)₁₂, 99%, 3.3 mg, [Ru] 1.5 mol
%) And dry toluene (1 mL) were added sequentially, and
The mixture was heated and stirred at 100 ° C. for 24 hours under a gon atmosphere. reaction
After the completion, cool the reaction solution to room temperature and put it inside the reaction mixture.
Dodecane was added as a standard substance and GLC analysis was performed.
The conversion rate of the raw material triethylsilane is 78%,
Desired decane aldehyde = bis (triethylsilyl) = ace
It was revealed that tar was produced in a yield of 89%.
became. Decane aldehyde = bis (triethylsilyl) = acetal colorless oil: 116-126 ℃ / 0.6 mmHg. MS (EI): m / z
 373 (M⁺-Et, 28), 275 (100), 217 (59), 189 (28), 11
5 (21), 87 (30%). MS (CI): m / z 401 (M⁺-1) .IR (nea
t): 2955, 2924, 2878, 1150, 1053, 1001, 741 cm^-1.
 ¹H-NMR (Tol.-d ₈, 250 MHz): δ 0.50 (q, J = 7.9 Hz,
 12 H), 0.72 (t, J = 7.5 Hz, 3 H), 0.87 (t, J = 7.
9 Hz, 18 H), 1.04-1.18 (m, 12 H), 1.27-1.38 (m, 2
H), 1.44-1.53 (m, 2 H), 5.10 (t, J = 5.0 Hz, 1 H).
  HRMS: m / z calcd for C_{twenty two}H₅₀O₂Si₂  373.2955 (M⁺-E
t) .found 373.2949.

Example 51

[0174]

[Chemical 51]

A test tube with a cap was charged with 4-t-butylbenzenecarboxylic acid (179 mg, 1.00 mmol) and triethylsilane.
(480 μL, 351 mg, 3.02 mmol), diethylamine (5 μL, 3.5 mg, 0.048 mmol, 4.8 mol%) as a cocatalyst and ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mol%),
Triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.0
mg, [Ru] 1.4 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction is completed, the reaction solution is cooled to room temperature,
Dodecane was added to the reaction mixture as an internal standard and GLC
Analysis showed that the conversion of the starting material, triethylsilane, was 76%, and the target 4-t-butylbenzaldehyde =
It was revealed that bis (triethylsilyl) = acetal was produced in a yield of 93%. 4-t-butylbenzaldehyde = bis (triethylsilyl) =
Acetal colorless oil: 165-175 ℃ / 0.2 mmHg. MS (EI): m / z
379 (M ⁺ -Et, 100), 277 (57), 217 (25), 189 (28), 87
(41%). MS (CI): m / z 407 (M ⁺ -1). IR (neat): 2957,
2878, 1111, 1053, 1003, 743 cm -1. 1 H-NMR (Tol.-
d ₈ , 250 MHz): δ 0.52 (q, J = 7.8 Hz, 12 H), 0.87
(t, J = 7.8 Hz, 18 H), 1.08 (s, 9 H), 6.08 (s, 1
H), 7.12 (d, J = 8.4 Hz, 2 H), 7.35 (d, J = 8.4 H
z, 2 H) .HRMS: m / z calcd for C ₂₃ H ₄₄ O ₂ Si ₂ 379.248
6 (M ⁺ -Et) .found 379.2478.

Example 52

[0177]

[Chemical 52]

In a test tube with a cap, put 3-pentenoic acid (108
mg, 1.07 mmol), triethylsilane (480 μL, 351 m
g, 3.02 mmol), diethylamine (5 μL,
3.5 mg, 0.048 mmol, 4.5 mol%) and ethyl iodide (4 μ
L, 7.8 mg, 0.050 mmol, 4.7 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.3 mg, [Ru] 1.0
mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 24 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. As a result, the conversion of the starting material triethylsilane was 100%, and the target pentanal = bis (triethyl) was obtained. It was revealed that silyl) = acetal was produced in a yield of 87%. Example 53

[0179]

[Chemical 53]

In a test tube with a cap, phenoxyethanoic acid (152 mg, 1.00 mmol) and triethylsilane (480 μL,
351 mg, 3.02 mmol), diethylamine (5
μL, 3.5 mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4
μL, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.2 mg, [Ru]
1.5 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 24 hours under an argon atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion of triethylsilane as a raw material was 78%.
It was revealed that the target phenoxyacetal dehydrate = bis (triethylsilyl) = acetal was produced in a yield of 94%. Phenoxyacetal dehydrate = bis (triethylsilyl) = acetal pale yellow oil: 133-138 ℃ / 0.8 mmHg. MS (EI): m
/ z 353 (M ⁺ -Et, 6), 275 (100%). MS (CI): m / z 383 (M
⁺ +1). IR (neat): 2955, 2913, 2878, 1248, 1154, 109
^{0, 745 cm -1. 1 H} -NMR (Tol.-d 8, 250 MHz) δ0.76 (q,
J = 7.8 Hz, 12H), 1.09 (t, J = 7.8 Hz, 18 H), 3.86
(d, J = 4.8 Hz, 2 H), 5.58 (t, J = 4.8 Hz, 1 H),
6.81-6.86 (m, 2 H), 7.07-7.18 (m, 3 H). HRMS: m /
z calcdfor C ₂₀ H ₃₈ O ₃ Si ₂ 353.1967 (M ⁺ -Et) .found 35
3.1992.

Example 54

[0182]

[Chemical 54]

In a test tube with a cap, 2-propylpentanoic acid (147 mg, 1.02 mmol) and triethylsilane (480 μm) were added.
L, 351 mg, 3.02 mmol), diethylamine as a cocatalyst
(5 μL, 3.5 mg, 0.048 mmol, 4.7 mol%) and ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 4.9 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.0 mg ,
[Ru] 1.4 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 24 hours under an argon atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature, 1.3-dioxolane as an internal standard substance was added to the reaction mixture,
The conversion rate of the raw material and the yield of the product were calculated by GLC analysis and NMR measurement, and the desired 2-propylvaleraldehyde = bis (triethylsilyl) = acetal, and 2-
Triethylsilyl propylpentanoate is 35
And the yield was 58%. 2-Propylvaleraldehyde = bis (triethylsilyl) =
Acetal pale yellow oil: 95-103 ℃ / 1.0 mmHg. MS (EI): m /
z 345 (M ⁺ -Et, 12), 275 (100), 217 (18), 189 (12), 1
15 (25), 87 (32%). MS (CI): m / z 373 (M ⁺ -1). IR (n
eat):. 2957, 2878, 1040, 1001, 741 cm -1 1 H-NMR (To
l.-d ₈ , 250 MHz): δ 0.52 (q, J = 7.9 Hz, 12 H), 0.
80 (t, J = 6.9 Hz, 6 H), 0.88 (t, J = 7.9 Hz, 18
H), 1.18-1.30 (m, 7 H), 1.42-1.54 (m, 2 H), 5.18
(s, 1 H).

Tripropylsilyl 2-propylpentanoate pale yellow oil: 70 ° C./1.0 mmHg MS (EI): m / z 229
(M ⁺ -Et, 100%). MS (CI): m / z 259 (M ⁺ +1). IR (nea
t):. 2959, 2878, 1717, 1186, 1007, 741 cm -1 1 H-NM
R (Tol.-d ₈ , 250 MHz): δ 0.60 (q, J = 7.9 Hz, 6 H),
0.71 (t, J = 7.0Hz, 6 H), 0.83 (t, J = 7.9 Hz, 9
H), 1.08-1.24 (m, 6 H), 1.43-1.53 (m, 2H), 2.12-2.
23 (m, 1 H).

Example 55

[0186]

[Chemical 55]

[0187] Glutaric acid (134 m
g, 1.02 mmol), triethylsilane (960 μL, 702 mg,
6.04 mmol), diethylamine (10 μL, 7.
0 mg, 0.097 mmol, 9.4 mol%) and ethyl iodide (8 μL,
15.6 mg, 0.10 mmol, 9.8 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 4.5 mg, [Ru] 2.0mo
(1%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 24 hours under an argon atmosphere. After completion of the reaction, the reaction solution was cooled to room temperature, 1.3-dioxolane as an internal standard substance was added to the reaction mixture, GLC analysis and NMR measurement were performed to calculate the conversion rate of the raw materials and the yield of the product. It was revealed that dialdehyde = bis (triethylsilyl) = acetal was produced in a yield of 81%. Pentanedialdehyde = bis (triethylsilyl) = acetal MS (EI): m / z 563 (M ⁺ -Et, 4), 275 (100), 189 (18), 1
71 (71), 115 (25), 87 (28%). ¹ H-NMR (CDCl ₃ , 500 MH
z): δ 0.62 (q, J = 7.5 Hz, 24 H), 0.90-0.95 (m, 6
H), 0.96 (t, J = 7.5 Hz, 36 H), 5.18 (t, J = 4.9
Hz, 2 H).

Example 56

[0189]

[Chemical 56]

In a test tube with a cap, p-toluic acid (137
mg, 1.0 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), diethylamine (5 μL, 3.
5 mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4
μL, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.0 mg, [Ru] 1.
39 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated with stirring at 100 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. The conversion rate of triethylsilane as a raw material was 65%.
And the target p-tolualdehyde = bis (triethylsilyl) = acetal, triethylsilyl 4-toluate, and 4-methylbenzyloxytriethylsilane are each 7
It was revealed that the yields were 6, 8 and 11%. Unreacted triethylsilane was distilled off from this reaction mixture under reduced pressure to obtain a crude product. Then, the toluene solution of the obtained crude product was cooled to 0 ° C. under an argon atmosphere, and a tetrahydrofuran solution of tetrabutylammonium fluoride (1.0 M in THF, 4.3 mL) was slowly added dropwise. After stirring at 0 ° C for 2 hours, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, water and toluene were added to the reaction solution, the organic layer was separated, and dried over anhydrous magnesium sulfate. After removing the desiccant and evaporating the solvent under reduced pressure, crude p-tolualdehyde was obtained. 1,3-Dioxolane was added to the obtained crude product, and the ¹ H-NMR spectrum was measured in a deuterated toluene solvent to confirm that the target p-tolualdehyde was produced at a conversion yield of 88%. Became clear.

Example 57

[0192]

[Chemical 57]

In a test tube with a cap, 3-hydroxybutanoic acid (105 mg, 1.01 mmol) and triethylsilane (640 μm) were added.
L, 468 mg, 4.02 mmol), diethylamine as a cocatalyst
(5 μL, 3.5 mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 2.4 mg) ,
[Ru] 1.1 mol%) and dry toluene (1 mL) were sequentially added, and the mixture was heated and stirred at 100 ° C. for 24 hours under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed to calculate the conversion rate of the raw material and the yield of the product, and the target 3-triethylsiloxybutyraldehyde = Bis (triethylsilyl) = acetal was found to be produced in a yield of 93%. 3-triethylsiloxybutyraldehyde = bis (triethylsilyl) = acetal colorlesss oil: 115-118 ℃ / 0.6 mmHg. MS (CI): m /
z 447 (M ⁺ -1). ¹ H-NMR (Tol.-d8, 250 MHz): δ 0.52 (q,
J = 8.0 Hz, 18 H), 0.88 (t, J = 8.0 Hz, 18H), 0.9
2 (t, J = 8.0 Hz, 9 H), 1.02 (d, J = 6.0 Hz, 2 H),
1.51-1.61 (m, 1 H), 1.67-1.77 (m, 1 H), 3.97 (tq,
J = 6.0 and 5.0 Hz, 1 H), 5.30 (m, 1H).

Example 58

[0195]

[Chemical 58]

In a test tube with a cap, diethylamine (5 μL, 3.5 mg, 0.048 mmol, 4.8 mol%) as a cocatalyst and ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mo) were added.
l%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99
%, 3.9 mg, [Ru] 1.7 mol%), and dry toluene (1
(mL) and then 1 at 100 ° C under an argon atmosphere.
The mixture was heated and stirred for an hour. After preparing the catalyst, the reaction solution was cooled to room temperature and triethylsilyl 4-toluate (255 mg, 1.0 mmo
l) and triethylsilane (320 μL, 233 mg, 2.0 mmol) were added, and the mixture was heated with stirring at 100 ° C. for 15 hours. After the reaction,
The reaction solution was cooled to room temperature, dodecane was added to the reaction mixture as an internal standard substance, and the product yield was calculated by GLC analysis. The yield of 4-methylbenzaldehyde = bis (triethylsilyl) = acetal was 95%. It has been revealed that they are generated at a rate.

Example 59

[0198]

[Chemical 59]

Butyraldehyde in a test tube with a cap =
Bis (triethylsilyl) = acetal (155 mg, 0.49 mmo
l), zirconium (IV) sulfate tetrahydrate _{(Zr (SO 4) 2 ·} 4H 2 O,
4.0 mg, [Zr] 2.3 mol%) and dry toluene (1 ml) as a solvent were sequentially added, and the mixture was heated and stirred at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The conversion of the starting material butyraldehyde = bis (triethylsilyl) = acetal was 100%, and the target butyraldehyde was 100%. It was revealed that the product was produced in a yield of%. This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra. Example 60

[0200]

[Chemical 60]

Butyl aldehyde = in test tube with cap
Bis (triethylsilyl) = acetal (153 mg, 0.48 mmo
l) 5% rhenium / carbon (5% Re / C, 4.7 mg, [Re] 0.3
mol%) and dry toluene (1 ml) as a solvent were sequentially added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was conducted. As a result, the conversion of the starting material butyraldehyde = bis (triethylsilyl) = acetal was 100%, and the target butyraldehyde was
It was revealed that the product was produced in a yield of 00%. Example 61

[0202]

[Chemical formula 61]

Butyl aldehyde = in test tube with cap
Bis (triethylsilyl) = acetal (159 mg, 0.50 mmo
l), molybdenum (II) chloride (MoCl ₂ , 1.7 mg, [Mo] 2.0 m
ol%) and dry toluene (1 ml) as a solvent were sequentially added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was conducted. The conversion of the starting material butyraldehyde = bis (triethylsilyl) = acetal was 100%, and the target butyraldehyde was 93%.
It was revealed that the product was produced in a yield of%. Example 62

[0204]

[Chemical formula 62]

Butyl aldehyde = in test tube with cap
Bis (triethylsilyl) = acetal (153 mg, 0.48 mmo
l), cobalt (II) bromide (CoBr ₂ , 5.0 mg, [Co] 4.8 mol
%) And dry toluene (1 ml) as a solvent were sequentially added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The conversion of the starting material butyraldehyde = bis (triethylsilyl) = acetal was 100%, and the target butyraldehyde was 100%.
It was revealed that the product was produced in a yield of%. Example 63

[0206]

[Chemical formula 63]

Butyraldehyde in a test tube with a cap =
Bis (triethylsilyl) = acetal (153 mg, 0.48 mmo
l), ruthenium (III) chloride (RuCl ₃ nH ₂ O, 2.1 mg, [R
u] 2.1 mol%) and dry toluene (1 ml) as a solvent were sequentially added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. The conversion of the starting material butyraldehyde = bis (triethylsilyl) = acetal was 100%, and the target butyraldehyde was
It was revealed that the product was produced in a yield of 92%.

Example 64

[0209]

[Chemical 64]

In a test tube with a cap, cyclohexanecarbaldehyde = bis (triethylsilyl) = acetal (183 m
g, 0.51 mmol), ruthenium chloride (III) (RuCl ₃ nH ₂ O,
6.0 mg, [Ru] 5.7 mol%) and dry toluene (1 ml) as a solvent were added successively, and the mixture was heated at 110 ° C. under an argon atmosphere for 3 times.
The mixture was heated and stirred for 0 hours. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. It was revealed that the product was produced in a yield of 57%. This compound is a Mass
And ¹ H-NMR spectrum confirmed the above compound.

Example 65

[0212]

[Chemical 65]

In a test tube with a cap, cyclohexanecarbaldehyde = bis (triethylsilyl) = acetal (189 m
g, 0.53 mmol), 5% rhenium / carbon (5% Re / C, [Re]
2.0 mol%) and dry toluene (1 ml) as a solvent were sequentially added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. As a result, starting material cyclohexanecarbaldehyde = bis (triethylsilyl) =
It was revealed that the conversion of acetal was 100% and the target cyclohexanecarbaldehyde was produced in a yield of 98%.

Example 66

[0215]

[Chemical formula 66]

In a test tube with a cap, cyclohexanecarbaldehyde = bis (triethylsilyl) = acetal (181 m
g, 0.50 mmol), molybdenum (II) chloride (MoCl ₂ , 3.4 mg,
[Mo] 4.1 mol%) and dry toluene (1 m
l) were sequentially added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. It was revealed that the product was produced in a yield of 99%.

Example 67

[0218]

[Chemical formula 67] 4-methylbenzaldehyde = bis in test tube with cap
(Triethylsilyl) = acetal (191 mg, 0.52 mmol),
Ruthenium (III) chloride (RuCl ₃ · nH ₂ O, 3.9 mg, [Ru] 3.6
mol%) and dry toluene (1 ml) as a solvent were sequentially added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, dodecane was added as an internal standard substance to the reaction mixture, and GLC analysis was performed. The conversion rate of 4-methylbenzaldehyde = bis (triethylsilyl) = acetal as a raw material was 44%, and the target p-tolualdehyde Was found to be produced in a yield of 44%. This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.

Example 68

[0220]

[Chemical 68]

In a test tube with a cap, 4-methylbenzaldehyde = bis (triethylsilyl) = acetal (153 mg,
0.48 mmol), 5% rhenium / carbon (5% Re / C, [Re] 2.
0 mol%) and dry toluene (1 ml) as a solvent were sequentially added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. As a result, the conversion rate of 4-methylbenzaldehyde = bis (triethylsilyl) = acetal, which was a raw material, was 100%. Was found to have been produced in a yield of 88%.

Example 69

[0223]

[Chemical 69] In a test tube with a cap, 4-t-butylbenzaldehyde = bis (triethylsilyl) = acetal (128 mg, 0.31 mmo
l) 5% rhenium / carbon (5% Re / C, [Re] 2.0 mol
%) And dry toluene (1 ml) as a solvent were sequentially added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, decane was added to the reaction mixture as an internal standard substance, and GLC analysis was carried out. As a result, the conversion rate of 4-t-butylbenzaldehyde = bis (triethylsilyl) = acetal, which was the starting material, was 100%. It was revealed that tert-butylbenzaldehyde was produced in a yield of 76%. This compound was confirmed to be the above compound by Mass and ¹ H-NMR spectra.

Example 70

[0225]

[Chemical 70]

In a test tube with a cap, 4-t-butylbenzaldehyde = bis (triethylsilyl) = acetal (22 mg,
0.054 mmol), molybdenum (II) chloride (MoCl ₂ , 1.2 mg,
[Mo] 13.3 mol%) and dry toluene (1 m
l) were sequentially added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. As a result, the conversion rate of 4-t-butylbenzaldehyde = bis (triethylsilyl) = acetal as a raw material was 100%. tert
-Butylbenzaldehyde was found to be produced in a yield of 75%.

Example 71

[0228]

[Chemical 71]

Phenoxyacetal dehydrate bis (triethylsilyl) acetal (191 mg,
0.52 mmol), ruthenium chloride (III) (RuCl ₃ nH ₂ O, 3.9
mg, [Ru] 3.6 mol%) and dry toluene as solvent
(1 ml) was added sequentially, and the mixture was heated at 110 ° C under argon atmosphere for 30 minutes.
The mixture was heated and stirred for an hour. After the reaction was completed, dodecane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. Was found to have been produced in a yield of 76%. colorless oil: MS (EI): m / z 136 (M ⁺ , 49), 107 (62),
77 (100%). ¹ H-NMR (CDCl ₃ , 250 MHz): δ 4.50 (d, J
= 1.1 Hz, 2 H), 6.70-7.00 (m, 3 H), 7.15-7.28 (m,
2 H), 9.80 (t, J = 1.1 Hz, 1 H) .HRMS: m / z calcd
for C ₈ H ₈ O ₂ 136.0523.found 136.0522.

Example 72

[0231]

[Chemical 72]

In a test tube with a cap, p-toluic acid (137
mg, 1.0 mmol), triethylsilane (480 μL, 351 mg,
3.02 mmol), diethylamine (5 μL, 3.
5 mg, 0.048 mmol, 4.8 mol%) and ethyl iodide (4
μL, 7.8 mg, 0.050 mmol, 5.0 mol%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99%, 3.6 mg, [Ru] 1.
7 mol%) and dry toluene (1 mL) were added sequentially,
The mixture was heated and stirred at 100 ° C. for 30 hours under an argon atmosphere.
After completion of the reaction, the reaction solution was cooled to room temperature and unreacted triethylsilane was distilled off under reduced pressure to obtain a crude product. Decane was added to the reaction mixture as an internal standard substance, and GLC analysis was performed. , 12 and 11% yield was revealed. Then, in a toluene solution of the obtained crude product, 5% rhenium / carbon (5% Re / C, [Re]
2.0 mol%), and at 30 ° C. under an argon atmosphere at 110 ° C.
The mixture was heated and stirred for an hour. After completion of the reaction, GLC analysis was conducted, and the conversion rate of 4-methylbenzaldehyde = bis (triethylsilyl) = acetal as a raw material was 100%.
It was revealed that p-tolualdehyde was produced in a yield of 82%.

Example 73

[0234]

[Chemical formula 73]

In a test tube with a cap, diethylamine (5 μL, 3.5 mg, 0.048 mmol, 4.8 mol%) as a cocatalyst and ethyl iodide (4 μL, 7.8 mg, 0.050 mmol, 5.0 mo) were added.
l%), triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ , 99
%, 3.9 mg, [Ru] 1.7 mol%), and dry toluene (1
(mL) and then 1 at 100 ° C under an argon atmosphere.
The mixture was heated and stirred for an hour. After catalyst preparation, triethylsilyl 4-toluate (261 mg, 1.0 mmol), triethylsilane (320
μL, 233 mg, 2.0 mmol) was added and the mixture was heated with stirring at 100 ° C. for 30 hours. After completion of the reaction, the reaction solution was cooled to room temperature and unreacted triethylsilane was distilled off under reduced pressure to obtain a crude product. Decane was added to the reaction mixture as an internal standard substance, and GLC analysis revealed that 4-methylbenzaldehyde = bis (triethylsilyl) = acetal was produced in a yield of 99%. Then, add 5% rhenium / carbon to the toluene solution of the obtained crude product.
(5% Re / C, [Re] 2.0 mol%) was added, and the mixture was heated with stirring at 110 ° C. for 30 hours under an argon atmosphere. After the reaction, G
An LC analysis showed that the conversion rate of 4-methylbenzaldehyde = bis (triethylsilyl) = acetal as a raw material was 1
It was revealed that the target p-tolualdehyde was produced at a yield of 85% at a yield of 85%.

[0236]

The present invention uses carboxylic acids as a raw material,
Provided is a simple and versatile method for producing disilyl acetals and aldehydes, which are compounds useful as organic synthetic intermediates.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI theme code (reference) C07F 7/18 C07F 7/18 BD // C07B 61/00 300 C07B 61/00 300

Claims (8)

[Claims] 1. A carboxylic acid represented by the following general formula (I) RCOOH (I) (wherein R represents an alkyl group, an aromatic group or a hydrogen atom) and the following general formula (I)
I) HSiR ¹ R ² R ³ (II) (wherein R ¹ , R ² and R ³ each independently represents an alkyl group, an aromatic group, an alkoxy group or a halogen atom). And R in the presence of a ruthenium catalyst, the following general formula (III) RCH (OSiR ¹ R ² R ³ ) ₂ (III) (wherein R, R ¹ , R ² , and R ³ is the same as above.) A method for producing a disilyl acetal. 2. The following general formula (IV) RCOOSiR ⁴ R ⁵ R ⁶ (IV) (wherein R represents an alkyl group, an aromatic group, or a hydrogen atom, and R ⁴ , R ⁵ , and R ⁶ are A carboxylic acid silyl ester represented by each independently an alkyl group, an aromatic group, an alkoxy group, or a halogen atom) and the following general formula (II) HSiR ¹ R ² R ³ (II) (wherein R is ¹ , R ² , and R ³ each independently represent an alkyl group, an aromatic group, an alkoxy group, or a halogen atom) in the presence of a ruthenium catalyst. , RCH (OSiR ¹ R ² R ³ ) (OSiR ⁴ R ⁵ R ⁶ ) (V) (wherein R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are indicated by the same as above.) Jishirirua Manufacturing method of tars. 3. A disilyl represented by the following general formula (II) RCH (OSiR ¹ R ² R ³ ) ₂ (II) (wherein R represents an alkyl group, an aromatic group, or a hydrogen atom). A method for producing an aldehyde represented by the following general formula (VI) RCHO (VI) (wherein R is the same as above), which comprises reacting an acetal in the presence of a transition metal catalyst. . 4. A carboxylic acid represented by the following general formula (I) RCOOH (I) (wherein R represents an alkyl group, an aromatic group or a hydrogen atom) and the following general formula (I)
I) HSiR ¹ R ² R ³ (II) (wherein R ¹ , R ² and R ³ each independently represents an alkyl group, an aromatic group, an alkoxy group or a halogen atom). Are reacted in the presence of a ruthenium catalyst to give the following general formula (III) RCH (OSiR ¹ R ² R ³ ) ₂ (III) (wherein R, R ¹ , R ² and R ³ are the same as those described above). A disilylacetal represented by the formula (1), which is then reacted in the presence of a transition metal catalyst,
A method for producing an aldehyde represented by the following general formula (VI) RCHO (VI) (wherein R is the same as above). 5. The following general formula (IV) RCOOSiR ⁴ R ⁵ R ⁶ (IV) (wherein R represents an alkyl group, an aromatic group or a hydrogen atom, and R ⁴ , R ⁵ and R ⁶ are A carboxylic acid silyl ester represented by each independently an alkyl group, an aromatic group, an alkoxy group, or a halogen atom) and the following general formula (II) HSiR ¹ R ² R ³ (II) (wherein R is ¹ , R ² , and R ³ each independently represent an alkyl group, an aromatic group, an alkoxy group, or a halogen atom) in the presence of a ruthenium catalyst. , RCH (OSiR ¹ R ² R ³ ) (OSiR ⁴ R ⁵ R ⁶ ) (V) (wherein R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are indicated by the same as above.) Jishirirua Of the aldehydes represented by the following general formula (VI) RCHO (VI) (wherein R is the same as the above), which comprises reacting tars in the presence of a transition metal catalyst. Production method. 6. The method according to claim 1, which is carried out in the presence of amines or amides. 7. The method according to claim 1, which is performed in the coexistence of a halogen compound. 8. The method according to any one of claims 1 and 2, which is carried out in the coexistence of amines or amides and a halogen compound.
The method according to 4 or 5.