JPS6310157B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (However, X is a halogen atom or an alkoxy group,
R ¹ is an alkyl group having 3 or less carbon atoms, a is an integer of 0 to 2, and n is an integer of 2 or 3) A novel compound 3,9-bis(silylalkyl)-2,
This invention relates to 4,8,10-tetraoxaspiro[5,5]undecane and its production method. The present inventor has been conducting research on the synthesis of various useful functional organosilicon compounds for many years, and discovered a novel compound with the general formula (However, X is a halogen atom or an alkoxy group,
R ¹ is an alkyl group having 3 or less carbon atoms, a is an integer of 0 to 2, and n is an integer of 2 or 3).
By synthesizing -bis(silylalkyl)-2,4,8,10-tetraoxaspiro[5,5]undecane and confirming its structure and uses, the present invention was completed and provided. In the above formula, the halogen atom is preferably a halogen atom such as chlorine, bromine, or the like, the alkoxy group is preferably a methoxy group, ethoxy group, propoxy group, butoxy group, etc., and the lower alkyl group for R ¹ is, for example, methyl. In general, alkyl groups having 3 or less carbon atoms, such as ethyl group, propyl group, etc., are suitable. The 3,9-bis(silylalkyl)-2,4,8,10-tetraoxaspiro[5,5]undecane represented by the above general formula of the present invention is determined by the type of X and the number of a in the formula. Although their properties differ somewhat, they usually exist in the form of a colorless and transparent liquid at room temperature and pressure. Furthermore, the 3,9-bis(silylalkyl)-2,4,8,10-tetraoxaspiro[5,
5] Undecane can generally be confirmed to be each compound of the general formula by the following methods (a) to (d). (b) By measuring the infrared absorption spectrum (IR), two strong absorption lines characteristic of ether bonds appear at 1150 to 1160 cm ^-1 and 1080 to 1090 cm ^-1 . From this, it can be known that the product is an ether compound. In addition, when X in the above general formula is an ethoxy group, Si-
One strong absorption characteristic of O bonds appears near 1110 cm ^-1 . (b) Proton nuclear magnetic resonance spectrum (H-nmr)
By measuring , it is possible to know the type and number of cyclic protons present in the molecule. That is, in H-nmr, a peak of equatorial and axial polarization peculiar to cyclic protons is shown at around 3.2 ppm and 4.7 ppm, and a peak based on the proton of the methylene group adjacent to the silicon atom is shown around 0.7 ppm. Furthermore, since ether bonds exist in the molecule, the proton peak of the carbon atom adjacent to each ether group appears around 3.2 ppm to 4.7 ppm. Also, vinyl group (CH ₂ = CH-)
The complete progress of the hydrosilylation reaction can be determined by the disappearance of the peak around 5.0 ppm to 6.0 ppm. Note that the number of protons in each bonding group can be determined by relatively comparing the respective peak intensities. (c) Determine the type and number of carbons present in the molecule (e.g., quaternary carbon, methine group, and methylene group) and the above general formula by measuring carbon nuclear magnetic resonance spectrum ( ^13C -nmr). In the case where X is an alkoxy group, the number and type of the alkoxy group can be known. That is, in ¹³ C-nmr, there is a peak based on the quaternary carbon atom at around 33 ppm, a peak based on the carbon atom of the methine group bonded to two oxygen atoms with ether at around 105 ppm, and a carbon of the methylene group adjacent to the ether group around 71 ppm. Indicates peaks based on atoms. Note that by relatively comparing the respective peak intensities, it is possible to know the number of each carbon atom in the molecule. (d) Measure the mass spectrum (MS) and each peak observed (generally the mass number expressed as m/e, which is the molecular weight of the ion divided by the number of electron charges e)
By calculating the compositional formula corresponding to , it is possible to estimate the binding mode and ultimately the molecular weight of the sample subjected to measurement. For example, in the above general formula, X is a chlorine atom, a is 0, and n
When is 2, m/e163, 161 has Cl ₃ SiCH ₂ CH ₂
Extremely strong peak corresponding to m/e135, 133
shows a peak corresponding to Cl ₃ Si. Furthermore, if measurements are carried out extremely carefully, a molecular ion peak (M) corresponding to the corresponding molecular weight can be observed, although it is strong in terms of intensity. Furthermore, in the general formula, X is an ethoxy group,
When a is 0 and n is 2, the peak corresponding to m/e163 is extremely strong (EtO) ₃ SU, m/
In addition to the peak corresponding to (EtO) ₃ SiCH ₂ CH ₂ at e191, a peak corresponding to the corresponding molecular weight (M) is observed, which is considered to be the result of desorption of ethanol, that is, a peak of M-46. Similarly, when X is another alkoxy, a unique peak can be observed. Furthermore, in the general formula, X is a chlorine atom, a
When is 0 and n is 3, m/e177, 175
shows an extremely strong peak corresponding to Cl ₃ SiCH ₂ CH ₂ CH ₂ and a peak corresponding to Cl ₃ Si at m/e 135 and 133. Furthermore, if measurements are carried out extremely carefully, a molecular ion peak (M) corresponding to the corresponding molecular weight can be observed, although the intensity is weak. Furthermore, in the general formula, X is an ethoxy group,
When a is 0 and n is 3, there is a very strong peak corresponding to (EtO) ₃ Si at m/e163, m/e163
In addition to the peak corresponding to e205 (EtO) ₃ SiCH ₂ CH ₂ CH ₂ corresponding to the corresponding molecular weight (M)
From this, a peak considered to be due to desorption of ethanol, that is, a peak of M-46, is observed. (e) The weight percentages of carbon, hydrogen, and silicon can be determined by elemental analysis. 3,9 of the present invention
-bis(silylalkyl)-2,4,8,10-
Tetraoxaspiro[5,5]undecane is
It is a colorless and odorless transparent liquid with a high boiling point, and as will be specifically shown in the examples below, the boiling point tends to increase as the molecular weight increases, just like general organic compounds. 3,9-bis(silylalkyl)-2 of the present invention,
4,8,10-tetraoxaspiro[5,5]undecane can be prepared by using benzene, toluene, ether, chloroform, carbon tetrachloride, acetonitrile, N,N
-Soluble in common organic solvents such as dimethylformamide. In the above general formula, when X is a halogen atom, when added to an alcohol, it reacts with the alcohol to generate hydrogen halide, and at the same time the halogen atom is substituted by an alkoxy group, resulting in an alkoxy group derived from the alcohol. Transforms into silane compounds. In addition, when X is an alkoxy group, when it is dissolved in a different type of alcohol, part of the alkoxy group or, depending on the conditions, all of the alkoxy group may be used as a solvent, depending on the amount of alcohol used as a solvent. It is common for the alkoxy group to change to a different type of alkoxy group. 3,9-bis(silylalkyl)-2 of the present invention,
The method for producing 4,8,10-tetraoxaspiro[5,5]undecane is not particularly limited and may be obtained by any method. A typical manufacturing method that is generally suitably employed will be described below. That is, 3,
9-divinyl (or diallyl)-2,4,8,
10-tetraoxaspiro[5,5]undecane

[Formula] (R is -CH=CH ₂ or -CH ₂ -CH=CH ₂ ) and general formula

[Formula] (where, X is a halogen atom or an alkoxy group, R ¹ is a lower alkyl group, a is 0-2
The desired 3,9-bis(silylalkyl)-2,4,8,10 can be obtained in good yield by reacting a silane compound of halogenosilane or alkoxysilane (integer of ) in the presence of a catalyst. -tetraoxaspiro[5,5]undecane can be obtained. As the above-mentioned halogenosilane or alkoxysilane, known ones such as trihalogenosilane or trialkoxysilane can be used. The catalyst used in the reaction is not particularly limited as long as it is a catalyst commonly used in so-called hydrosilylation reactions. For example, a platinum compound such as chloroplatinic acid is preferable because it is effective in a small amount. . Although the reaction can generally be carried out without a solvent, it is generally carried out in the presence of a solvent. As a solvent,
Any non-aqueous solvent that does not react with the raw material or catalyst can be used without particular limitation; generally, hydrocarbon solvents such as benzene, toluene, and hexane; halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride; dimethyl ether, Ether solvents such as diethyl ether are preferably used. Other reaction conditions are not particularly limited, but may vary depending on the type of raw materials, catalyst type, presence or absence of solvent, etc., so it is preferable to select suitable conditions in advance. . Generally -20~
It is sufficient to select a temperature in the range of several 10 minutes to 40 hours at a temperature of 160°C. Since the reaction proceeds sufficiently under atmospheric pressure, it is usually sufficient to carry out the reaction at normal pressure, but it can also be carried out under increased pressure or reduced pressure if necessary. When the target product of the present invention is 3,9-bis(alkoxysilylalkyl)-2,4,8,10-tetraoxaspiro[5,5]undecane,
general formula (However, Y is a halogen atom, R ² is a lower alkyl group, b is an integer of 0 to 2, and n is an integer of 2 or 3) 3,9-bis(halosilylalkyl)-2,4 , 8,10-tetraoxaspiro[5,5]undecane and an alcohol represented by the general formula R ³ OH (wherein R ³ is an alkyl group). In addition, in the above reaction, a base, such as ammonia,
It is effective to coexist a primary to tertiary lower alkylamine, and it is also effective to flow an inert gas such as nitrogen or argon gas into the reaction system. 3,9-bis(silylalkyl)-2 of the present invention,
As is clear from the above general formula, 4,8,10-tetraoxaspiro[5,5]undecane is a compound containing quaternary carbon at the center of two rings and silicon at both ends. This compound has strong water repellency due to the silicon content, so it has uses as a water repellent. In this case, 3,9-bis(2-silylalkyl)-2,4,8,10-tetraoxaspiro[5,
5] Undecane can be partially or completely hydrolyzed to form a strong crosslinked film, so it can be used for various inorganic materials such as glass, cement, mortar, etc.; paper, wood, cellulose, nylon, etc. By coating the surface of a shaped workpiece, water repellency can be imparted to the workpiece. In addition, the strong film crosslinked by this hydrolysis has a strong network structure due to the quaternary carbon, and can be dyed with disperse dyes, so it can also be used as a coding agent for plastic lenses, etc. . EXAMPLES In order to explain the present invention more specifically, examples and application examples will be described below, but the present invention is not limited to these examples. Example 1 3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5]undecane

[Formula] (21.2 g, 0.1 mol), trichlorosilane (32.5 g, 0.24
Chloroplatinic acid hexahydrate (25.1 mg) was added to a mixture of anhydrous n-hexane (70 ml) and heated under reflux for 5 hours under magnetic stirring (reaction temperature: 65°C to 68°C). After removing low-boiling components from the reaction mixture by atmospheric distillation, high-boiling components were carefully distilled off in vacuo (about 2 mmHg) while heating at about 80° C. on an oil bath. Furthermore, the residue is vacuum distilled (2 mmHg,
A colorless and transparent highly viscous liquid (29.0 g) was obtained by heating the mixture (bp 196-198°C). When the IR spectrum was measured, it showed two strong absorption lines at 1150 cm ^-1 and 1080 cm ^-1 that are characteristic of ether bonds. Its elemental analysis values are C27.58%, H3.95%, and C ₁₁ H ₁₈ O ₄ Cl ₆ Si ₂
C27.33%, H3.73, which is the calculated value for (482.99)
% was in very good agreement. In addition, when mass spectra were measured, molecular ion peaks (M) corresponding to molecular weight, although weak in intensity, were observed at m/e485, 483, and 481; peaks corresponding to Cl ₃ SiCH ₂ CH ₂ were found at m/e163 and 161; Peaks corresponding to Cl ₃ Si were shown at e135 and 133. When proton nuclear magnetic resonance spectra were measured, the presence of cyclic protons was revealed by the equatorial and axially polarized peaks of cyclic protons. Furthermore ( ¹³ C
-nmr), the analysis results of each peak (chemical shift value: δppm: based on tetramethylsilane) were as follows. From the above results, the isolated product indicates that two vinyl groups in the raw material 3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5]undecane have been trichlorosilylated. 3,9-bis(2
-trichlorosilylethyl)-2,4,8,10-
It became clear that it was tetraoxaspiro[5,5]undecane. The yield was 60.0% based on the 3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5]undecane used. Example 2 3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5]undecane (21.2 g, 0.1
mol), methyldichlorosilane (27.6 g, 0.24 mol), anhydrous n-hexane (70 ml), chloroplatinic acid 6
A mixture of hydrate (25.1 mg) was reacted and post-treated in the same manner as in Example 1, and the residue was vacuum distilled (2 mmHg, bp 186-188°C) to obtain a colorless and transparent highly viscous liquid (31.2 g). I got it. When the infrared absorption spectrum was measured, it was 1150 cm ^-1 and 1080 cm
^-1 showed two strong absorptions characteristic of ether bonds. The elemental _analysis values were C35.7% and H5.62%, which agreed very well with the calculated values _{for C13H24O4Cl4Si2} ( _441.98 ), _which were C35.30% and H5.43%. .
In mass spectrometry, in addition to the molecular ion peak (M),

【formula】

Each peak of [Formula] was observed. When proton nuclear magnetic resonance spectra were measured, the presence of cyclic protons was revealed by the equatorial and axial polarization peaks of cyclic protons. Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C-nmr)
was measured. Each peak (chemical shift value: δppm:
The analysis results (based on tetramethylsilane) were as follows. From the above results, it is clear that the isolated product is 3,9-bis(2-methyldichlorosilylethyl)-2,4,
It was revealed that it was 8,10-tetraoxaspiro[5,5]undecane. The yield was 71.2% based on the 3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5]undecane used.
It was hot. Example 3 3,9-bis(2-trichlorosilylethyl)
-2,4,8,10-tetraoxaspiro[5,
5] While undecane (48.3 g, 0.1 mol) was cooled in a cryogen bath using sodium chloride/ice, a mixture of anhydrous ethanol (60 ml) and anhydrous benzene (60 ml) was slowly added dropwise with stirring. After continuing cooling and stirring for 2 hours after the addition, dry ammonia gas was further bubbled under the same conditions until no white precipitate of ammonium chloride was formed, and excess ammonia gas was removed by bubbling nitrogen gas. Excluded. After removing the formed ammonium chloride precipitate by suction filtration and further removing the low-boiling components contained in the filtrate by distillation, the high-boiling components were further removed while heating at approximately 80°C in an oil bath. Carefully evaporate under vacuum (approximately 2 mmHg). Further, the residue was vacuum distilled (2 mmHg, bd. 206-208°C) to obtain a colorless and transparent highly viscous liquid (41.5 g).
When the infrared absorption spectrum was measured, it was 1150 cm ^-1
Two strong absorption lines characteristic of ether bonds were observed at 1080 cm ^-1 . Its elemental analysis values are C51.32%, H8.92
%, which agreed very well with the calculated values for C 51.10% and H 8.89% for C ₂₃ H ₄₈ O ₁₀ Si ₂ (540.17). Also, when we measured the mass spectrum, we found that m/
At e494, a peak considered to be due to the desorption of ethanol from the molecular ion peak (M) corresponding to the molecular weight, that is, a peak of M-46 was observed. Furthermore, a peak corresponding to (EtO) ₃ SiCH ₂ CH ₂ was shown at m/e191, and a peak corresponding to (EtO) ₃ Si was shown at m/e163. Through proton nuclear magnetic resonance spectroscopy, we discovered the existence of cyclic protons, and further discovered that ¹³ C−
nmr was measured. The analysis results for each Peter were as follows. From the above results, the product is 3,9-bis(2-
triethoxysilylethyl)-2,4,8,10-
It became clear that it was tetraoxaspiro[5,5]undecane. The yield was 76.8%. Example 4 3,9-bis(2-methyldichlorosilylethyl)-2,4,8,10-tetraoxaspiro[5,
5] An almost colorless and transparent highly viscous liquid was obtained using undecane (44.2 g, 0.1 mol) in the same manner as in Example 3, except that anhydrous methanol was used instead of anhydrous ethanol. The residue was vacuum distilled (2 mmHg, 182-184°C) to obtain a colorless and transparent highly viscous liquid (33.2 g). Measurement of the infrared absorption spectrum showed two strong absorption lines at 1150 cm ^-1 and 1080 cm ^-1 that are characteristic of ether bonds.
Its elemental analysis values are C48.19% and H8.54%.
This is the calculated value for C ₁₇ H ₃₆ O ₈ Si ₂ (424.17)
It matched extremely well with C48.09% and H8.49%. In addition, when the mass spectrum was measured, there was a peak at m/e392 that was considered to be the desorption of methanol from the molecular ion peak (M) corresponding to the molecular weight, that is, M
-32 peak at m/e133

A peak corresponding to [formula], m/e105

A peak corresponding to [Formula] was observed. By measuring the proton nuclear magnetic resonance spectrum, we were able to find out the existence of cyclic protons. Furthermore, ¹³ C-nmr was measured. The analysis results for each peak were as follows. From the above results, the product is 3,9-bis(2-
methyldimethoxysilylethyl)-2,4,8,
It was revealed that it was 10-tetraoxaspiro[5,5]undecane. The yield was 78.3%. Example 5 3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5]undecane (21.2 g, 0.1
A mixture of triethoxysilane (39.3 g, 0.24 mol), anhydrous benzene (100 ml), and platinum black (8 mg) was heated to reflux on an oil bath (reaction temperature was 78-80 mol).
℃) for 3 hours. After removing low-boiling components from the reaction mixture by atmospheric distillation, high-boiling components were further distilled on an oil bath at 80 to 150°C under vacuum (approximately 2 mmHg).
Distilled away. Furthermore, the remaining pot residue is vacuum distilled (approximately 2 mm
A colorless and transparent highly viscous liquid (46.2 g) was obtained. Measurement of the infrared absorption spectrum showed two strong absorption lines at 1150 cm ^-1 and 1080 cm ^-1 that are characteristic of ether bonds. Its elemental analysis values are C51.38% and H8.84%.
This is the calculated value for C ₂₃ H ₄₈ O ₁₀ Si ₂ (540.17)
It matched extremely well with C51.10% and H8.89%. In addition, when we measured the mass spectrum, m/e494
A peak considered to be the desorption of ethanol from the molecular ion peak (M) corresponding to the molecular weight, that is, a peak of M-46 was observed. Also m/e191
The peak corresponding to (EtO) ₃ SiCH ₂ CH ₂ , m/
A peak corresponding to (EtO) ₃ Si was shown at e163.
The existence of cyclic protons was discovered by proton nuclear magnetic resonance spectroscopy, and ¹³ C-nmr was also measured. The analysis results for each peak were the same as in Example 3. From the above results, the product is 3,9-bis(2-triethoxysilylethyl)-2,4,8,
It was revealed that it was 10-tetraoxaspiro[5,5]undecane. The yield was 85.5%. Example 6 3,9-divinyl-2,4,8,10-tetraoxaspiro[5,5]undecane (21.2 g, 0.1
mol), methyldiethoxysilane (32.2g, 0.24
mole), anhydrous benzene (100ml), Shirogane black (8mg)
The mixture was subjected to the same operation as in Example 5, and the residue was vacuum distilled (approximately 2 mmHg, 197-199°C) to obtain a colorless and transparent highly viscous liquid (40.8 g). The infrared absorption spectrum was measured at 1150 cm.
It showed two strong absorption lines at ^-1 and 1080 cm ^-1 that are characteristic of ether bonds. Its elemental analysis value is C52.73%,
The H content was 9.26%, which agreed extremely well with the calculated values for C 52.48% and H 9.16% for C ₂₁ H ₄₄ O ₈ Si ₂ (480.17). In addition, when the mass spectrum was measured, a peak at m/e 434, which is considered to be the result of desorption of ethanol from the molecular ion peak (M) corresponding to the molecular weight, was observed, that is, a peak of M-46.
Also on m/e161

Equivalent to [formula] peak at m/e133

A peak corresponding to [Formula] was shown. We learned the existence of cyclic protons by proton nuclear magnetic resonance spectra, and further discovered that ¹³ C
-nmr was measured. The analysis results for each peak were as follows. From the above results, the product is 3,9-bis(2-
The product was found to be ethoxysilylethyl-2,4,8,10-tetraoxaspiro[5,5]undecane. The yield was 85.0%. Example 7 3,9-diallyl-2,4,8,10-tetraoxaspiro[5,5]undecane (24.0 g, 0.1
mol), trichlorosilane (32.5g, 0.24 mol),
A mixture of anhydrous n-hexane (70 ml) and chloroplatinic acid hexahydrate (25.1 mg) was reacted and post-treated in the same manner as in Example 1, and the residue was vacuum distilled (2
mmHg, bp. 208-210°C) to obtain a colorless and transparent highly viscous liquid (32.5 g). Measurement of the infrared absorption spectrum showed two strong absorption lines at 1150 cm ^-1 and 1080 cm ^-1 that are characteristic of ether bonds.
Its elemental analysis values are C30.47% and H4.45%.
This is the calculated value for C ₁₃ H ₂₂ O ₄ Cl ₆ Si ₂ (510.99)
It matched extremely well with C30.53% and H4.31%. Furthermore, in mass spectrometry, in addition to the molecular ion peak (M), Cl ₃ SiCH ₂ CH ₂ CH ₂ and Cl ₃ Si peaks were observed. When we measured the proton nuclear magnetic resonance spectrum, we found that due to the equatorial and axial polarization peaks of the cyclic proton,
We learned about the existence of cyclic protons. moreover
¹³ C-nmr was measured. The analysis results for each peak were as follows. From the above results, the product is 3,9-bis(3-
trichlorosilylpropyl)-2,4,8,10-
It became clear that it was tetraoxaspiro[5,5]undecane. The yield was 61.2%. Example 8 3,9-diallyl-2,4,8,10-tetraoxaspiro[5,5]undecane (24.0 g, 0.1
mol), dimethylchlorosilane (22.7 g, 0.24 mol), anhydrous n-hexane (70 ml), chloroplatinic acid 6
A mixture of hydrates (25.1 mg) was reacted and post-treated in the same manner as in Example 1, and the residue was vacuum distilled (2 mmHg, bp. 180-182°C) to form a colorless and transparent highly viscous liquid (32.8 mg). g) was obtained. When the infrared absorption spectrum was measured, it was 1150 cm ^-1 and 1080 cm
^-1 showed two strong absorptions characteristic of ether bonds. The elemental _analysis values were C47.41% and H7.88%, which agreed very well with the calculated values _{for C17H34O4Cl2Si2} ( _429.19 ), _which were C47.53% and H7.92%. In mass spectrometry, in addition to the molecular ion peak (M), ClSi(CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ , ClSi
(CH ₃ ) ₂ peaks were observed. When proton nuclear magnetic resonance spectra were measured, the presence of cyclic protons was revealed by the equatorial and axial polarization peaks of cyclic protons. In addition, ¹³ C-nuclear magnetic resonance spectrum (
¹³ C-nmr) was measured. The analysis results for each peak were as follows. From the above results, the product is 3,9-bis(3-
dimethylchlorosilylpropyl)-2,4,8,
It was revealed that it was 10-tetraoxaspiro[5,5]undecane. The yield was 76.4%. Example 9 3,9-bis(3-dimethylchlorosilylpropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (30.2 g, 0.07 mol) in a mixture of anhydrous ethanol and anhydrous benzene was slowly added dropwise in the same manner as in Example 3, followed by post-treatment. As a result, an almost colorless and transparent highly viscous liquid was obtained. Vacuum distillation (2 mmHg,
A colorless and transparent highly viscous liquid (26.5 g) was obtained. When the infrared absorption spectrum was measured, it showed two strong absorption lines at 1150 cm ^-1 and 1080 cm ^-1 that are characteristic of ether bonds. Its elemental analysis values are C56.13% and H9.78%.
This is the calculated value for C ₂₁ H ₄₄ O ₆ Si ₂ (448.29)
It matched extremely well with C56.21% and H9.82%. In addition, when the mass spectrum was measured, there was a peak at m/e402 that was considered to be the desorption of ethanol from the molecular ion peak (M) corresponding to the molecular weight, that is, M
A peak of −46 was observed. Further, a peak corresponding to (EtO)Si(CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ was shown at m/e163, and a peak corresponding to (EtO)Si(CH ₃ ) ₂ was shown at m/e103. We learned the existence of cyclic protons by proton nuclear magnetic resonance spectroscopy, and further discovered that ¹³ C
-nmr was measured. The analysis results for each peak were as follows. From the above results, the product is 3,9-bis(3-
dimethyltoxysilylpropyl)2,4,8,10
-Tetraoxaspiro[5,5]undecane. The yield was 84.4%. Example 10 3,9-diallyl-2,4,8,10-tetraoxaspiro[5,5]undecane (24.0 g, 0.1
mol), dimethylethoxysilane (25.0g, 0.24
mole), anhydrous benzene (100ml), Shirogane black (8mg)
The mixture was subjected to reaction and post-treatment in the same manner as in Example 5, and the residue was vacuum distilled (2 mmHg, 182-184
℃) to obtain a colorless and transparent highly viscous liquid (27.8 g). Measurement of the infrared absorption spectrum showed two strong absorption lines at 1150 cm ^-1 and 1080 cm ^-1 that are characteristic of ether bonds. _Its elemental analysis values are C56.37%, _H9.76 % _, and _C21H44O6Si2
C56.21%, H9.82, which is the calculated value for (448.29)
% was in very good agreement. Further, when the mass spectrum was measured, a peak at m/e402, which is considered to be the result of desorption of ethanol from the molecular ion peak (M) corresponding to the molecular weight, was observed, that is, a peak of M-46. Also, (EtO)Si at m/e163
(CH ₃ ) ₂ CH ₂ CH ₂ Peak corresponding to CH ₂ , m/
A peak corresponding to (EtO)Si(CH ₃ ) ₂ was shown at e103. By proton nuclear magnetic resonance spectrum,
After learning about the existence of cyclic protons, we also measured ¹³ C-nmr. The analysis results were the same as in Example 9.
From the above results, the product is 3,9-bis(3-
dimethylethoxysilylpropyl)-2,4,8,
It was revealed that it was 10-tetraoxaspiro[5,5]undecane. The yield was 62.0%.

Claims (1)

[Claims] 1 General formula, (However, X is a halogen atom or an alkoxy group,
3,9-bis(silylalkyl)-2,4,8,10-tetraoxaspiro[5 ^, 5] Undecan. 2 General formula, [Formula] (R is -CH=CH ₂ or -CH ₂ -CH=CH ₂ ) 3,9-divinyl (or diallyl)
-2,4,8,10-tetraoxaspiro[5,
5] Undecane and general formula [Formula] (However, X is a halogen atom or an alkoxy group,
A general formula characterized by reacting a silane compound represented by R ¹ with a lower alkyl group and a with an integer of 0 to 2 in the presence of a catalyst. (However, X is a halogen atom or an alkoxy group,
3,9-bis(silylalkyl)-2,4,8,10-tetraoxaspiro[5 ^, 5] Method for producing undecane. 3 general formula, (However, Y is a halogen atom, R ² is a lower alkyl group, b is an integer of 0 to 2, and n is an integer of 2 or 3) 3,9-bis(silylalkyl)
-2,4,8,10-tetraoxaspiro [5,
5] 3,9-bis(alkoxysilylalkyl)-2,4,8,10-, which is characterized by reacting undecane with an alcohol represented by the general formula R ³ OH (where R ³ is an alkyl group) A method for producing tetraoxaspiro[5,5]undecane.