Preparation method of deuterated diphenyl dimethoxysilane
The one-pot method for preparing deuterated diphenyldimethoxysilane solves the problems of complex synthesis and low purity in existing technologies, and realizes the industrial production of deuterated diphenyldimethoxysilane with high purity and high yield.
Patent Information
- Application Number
- CN202510690870.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-27
- Publication Date
- 2025-11-07
AI Technical Summary
The existing synthesis process of deuterated diphenyldimethoxysilane is complex and unsuitable for mass production. Furthermore, deuterated dichlorodiphenylsilane is difficult to synthesize, resulting in low product purity and yield.
Using tetrahydrofuran as the reaction solvent, deuterated bromobenzene was added dropwise to a reactor containing magnesium shavings, tetramethoxysilane, and I2 particles under inert gas protection. Deuterated diphenyl dimethoxysilane was prepared in a one-pot process via Grignardization and substitution reactions, simplifying the reaction steps and optimizing the reaction conditions.
The preparation of deuterated diphenyldimethoxysilane products with a deuteration rate of ≥99%, purity of ≥98%, and yield of >60% has been achieved, which is suitable for industrial production and avoids the use of high temperature, high pressure and expensive catalysts.
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Figure CN120904236A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of fine chemical industry, and particularly relates to a preparation method of deuterated diphenyl dimethoxysilane. BACKGROUND
[0002] Deuterated compounds are widely used in nuclear magnetic resonance (NMR), medicine, OLED and other fields. In the pharmaceutical industry, replacing one or more carbon-hydrogen bonds (C-H) in a specific part of a drug molecule with carbon-deuterium bonds (C-D) can prolong the drug metabolism cycle, reduce the production of toxic metabolites, thereby reducing the drug dosage, improving safety and obtaining better efficacy. Although the current demand for deuterated diphenyl dimethoxysilane is small, with the development of deuterated chemicals, deuterated diphenyl dimethoxysilane will have great application prospects in the future.
[0003] In the prior art, diphenyl dimethoxysilane is mainly prepared by the ROCHOW method through a copper catalyst from silicon powder and chlorobenzene to generate diphenyl dichlorosilane, and then esterification is performed on the diphenyl dichlorosilane and methanol to obtain diphenyl dimethoxysilane. However, since deuterated dichlorodiphenylsilane is difficult to synthesize, the process for synthesizing deuterated diphenyl dimethoxysilane is complex and is not suitable for batch production. SUMMARY
[0004] In view of the deficiencies in the prior art, the application provides a preparation method of deuterated diphenyl dimethoxysilane, which has a simple reaction process, mild reaction conditions, high deuterium substitution rate and purity, and a yield of more than 60%, and is very beneficial to industrial production.
[0005] Specifically, the application provides the following technical solutions:
[0006] A preparation method of deuterated diphenyl dimethoxysilane, in which tetrahydrofuran (THF) is used as a reaction solvent, and deuterated bromobenzene is added dropwise into a reactor containing magnesium turnings, tetramethoxysilane and I2 particles under the protection of an inert gas, so as to simultaneously perform Grignard reaction and substitution reaction, and deuterated diphenyl dimethoxysilane is obtained by one-pot method without multiple reactions.
[0007] Preferably, the mass ratio of the tetramethoxysilane to the deuterated bromobenzene is 1:1-1:4.
[0008] Preferably, the mass ratio of the magnesium turnings to the deuterated bromobenzene is 1:4-1:6.
[0009] Preferably, the method comprises the following steps:
[0010] A. Mix tetramethoxysilane, magnesium chips, I2 particles and tetrahydrofuran under inert gas protection, stir, heat to 30-90℃, drop the mixture of deuterated bromobenzene and tetrahydrofuran, after dropping, reflux for a period of time;
[0011] B. Filter the reaction solution obtained in step A, remove the solvent in the filtrate, and further separate deuterated diphenyldimethoxysilane product by vacuum distillation.
[0012] Further preferably, in step A, the temperature is raised to 40-70℃.
[0013] Further preferably, in step A, after dropping, reflux for 0.5-6h.
[0014] The present application has at least the following beneficial effects:
[0015] (1) The present application provides a preparation method of deuterated diphenyldimethoxysilane, which can prepare deuterated diphenyldimethoxysilane product with deuterium substitution rate ≥ 99%, purity ≥ 98% and yield > 60% through one-pot method without multiple reactions, which meets market demand;
[0016] (2) The present application provides a preparation method of deuterated diphenyldimethoxysilane, which further improves the purity and yield of the obtained deuterated diphenyldimethoxysilane product by optimizing the reaction conditions;
[0017] (3) The present application provides a preparation method of deuterated diphenyldimethoxysilane, which does not require high temperature and high pressure or use of expensive transition metal catalysts, the reaction process is simple, the reaction conditions are mild, and it is very suitable for industrial production. BRIEF DESCRIPTION OF DRAWINGS
[0018] Figure 1 A flowchart of a preparation method of deuterated diphenyldimethoxysilane according to the present application is shown. DETAILED DESCRIPTION
[0019] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. The following embodiments are used to illustrate the present application, but not to limit the scope of the present application. If the specific technology or condition is not specified in the embodiments, it is carried out according to the technology or condition described in the literature in the art, or according to the product manual.
[0020] Example 1
[0021] Into a 500 mL dry three-necked flask with reflux condenser, dropping funnel, magnetic stirrer and thermometer, 1.91 g of magnesium turnings, 45 mL of THF and 5 g of tetramethoxysilane were added under N2protection, and 3 I2pellets were added as initiators, and the stirring was started, and the oil bath temperature was set to 60 °C. 10.64 g of deuterated bromobenzene was diluted with 90 mL of THF to form a solution to be added dropwise. After the oil bath temperature was stabilized at 60 °C for 0.5 h, the deuterated bromobenzene dilution was added dropwise, and the reaction temperature was controlled at 60 °C, and the solution was added dropwise within 2 h, and the reaction was heated and maintained for 2 h.
[0022] After the reaction was completed, 5 mL of anhydrous methanol was added dropwise to quench the reaction, and the mixture was cooled and filtered, and the filter cake was washed with THF, and the solvent in the filtrate was evaporated, and the target product was collected by vacuum distillation, and deuterium substitution rate of 99.43% and purity of 98.14% of deuterated diphenyldimethoxysilane were obtained, and the yield reached 65.43%.
[0023] Example 2
[0024] Into a 500 mL dry three-necked flask with reflux condenser, dropping funnel, magnetic stirrer and thermometer, 1.91 g of magnesium turnings, 45 mL of THF and 5 g of tetramethoxysilane were added under N2protection, and 3 I2pellets were added as initiators, and the stirring was started, and the oil bath temperature was set to 40 °C. 10.64 g of deuterated bromobenzene was diluted with 90 mL of THF to form a solution to be added dropwise. After the oil bath temperature was stabilized at 40 °C for 0.5 h, the deuterated bromobenzene dilution was added dropwise, and the reaction temperature was controlled at 40 °C, and the solution was added dropwise within 2 h, and the reaction was heated and maintained for 2 h.
[0025] After the reaction was completed, 5 mL of anhydrous methanol was added dropwise to quench the reaction, and the mixture was cooled and filtered, and the filter cake was washed with THF, and the solvent in the filtrate was evaporated, and the target product was collected by vacuum distillation, and deuterium substitution rate of 99.43% and purity of 98.14% of deuterated diphenyldimethoxysilane were obtained, and the yield reached 65.43%.
[0026] Example 3
[0027] Into a 500 mL dry three-necked flask with reflux condenser, dropping funnel, magnetic stirrer and thermometer, 1.91 g of magnesium turnings, 45 mL of THF and 5 g of tetramethoxysilane were added under N2protection, and 3 I2pellets were added as initiators, and the stirring was started, and the oil bath temperature was set to 80 °C. 10.64 g of deuterated bromobenzene was diluted with 90 mL of THF to form a solution to be added dropwise. After the oil bath temperature was stabilized at 80 °C for 0.5 h, the deuterated bromobenzene dilution was added dropwise, and the reaction temperature was controlled at 80 °C, and the solution was added dropwise within 2 h, and the reaction was heated and maintained for 2 h.
[0028] After the reaction is completed, 5 mL of anhydrous methanol is added dropwise to quench the reaction, and the mixture is cooled and filtered. The filter cake is washed with THF, and the solvent in the filtrate is evaporated. The target product is collected by distillation under reduced pressure. The deuterium substitution rate is 99.41%, the purity is 98.02%, and the yield is 53.66%.
[0029] Example 4
[0030] In a 500 mL dry three-necked flask equipped with a reflux condenser, an addition funnel, a magnetic stirrer, and a thermometer, 1.72 g of magnesium turnings, 45 mL of THF, and 5 g of tetramethoxysilane are added under N2protection. Three I2pellets are added as initiators, and stirring is started. The oil bath temperature is set to 60°C. 9.58 g of deuterated bromobenzene is diluted with 90 mL of THF to form a solution to be added dropwise. After the oil bath temperature is stabilized at 60°C for 0.5 h, the deuterated bromobenzene solution is added dropwise. The reaction temperature is controlled at 60°C, and the addition is completed within 2 h. The reaction is heated and maintained for 2 h.
[0031] After the reaction is completed, 5 mL of anhydrous methanol is added dropwise to quench the reaction, and the mixture is cooled and filtered. The filter cake is washed with THF, and the solvent in the filtrate is evaporated. The target product is collected by distillation under reduced pressure. The deuterium substitution rate is 99.39%, the purity is 98.11%, and the yield is 58.89%.
[0032] Example 5
[0033] In a 500 mL dry three-necked flask equipped with a reflux condenser, an addition funnel, a magnetic stirrer, and a thermometer, 2.1 g of magnesium turnings, 45 mL of THF, and 5 g of tetramethoxysilane are added under N2protection. Three I2pellets are added as initiators, and stirring is started. The oil bath temperature is set to 60°C. 11.7 g of deuterated bromobenzene is diluted with 90 mL of THF to form a solution to be added dropwise. After the oil bath temperature is stabilized at 60°C for 0.5 h, the deuterated bromobenzene solution is added dropwise. The reaction temperature is controlled at 60°C, and the addition is completed within 2 h. The reaction is heated and maintained for 2 h.
[0034] After the reaction is completed, 5 mL of anhydrous methanol is added dropwise to quench the reaction, and the mixture is cooled and filtered. The filter cake is washed with THF, and the solvent in the filtrate is evaporated. The target product is collected by distillation under reduced pressure. The deuterium substitution rate is 99.44%, the purity is 97.87%, and the yield is 60.1%.
[0035] It should be pointed out finally that the above embodiments are only used to illustrate the technical solutions of the present application, but not to limit the same; and although the present application has been described in detail with reference to the foregoing embodiments, it should be appreciated by those skilled in the art that the technical solutions recorded in the foregoing embodiments can be modified, or some technical features thereof can be replaced equivalently; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.
Claims
1. A method for preparing a deuterated diphenyldimethoxysilane, characterized by, The deuterated bromobenzene is added dropwise into a reactor containing magnesium chips, tetramethoxysilane and I2 particles under inert gas protection, so as to carry out Grignard reaction and substitution reaction, and deuterated diphenyldimethoxysilane is obtained.
2. The method of claim 1, wherein the deuterated diphenyldimethoxysilane is prepared by the reaction of a deuterated diphenylamine with a deuterated chlorosilane. The mass ratio of the tetramethoxysilane to the deuterated bromobenzene is 1:1-1:
4.
3. The method for preparing deuterated diphenyldimethoxysilane according to claim 1, characterized in that, The mass ratio of the magnesium chips to the deuterated bromobenzene is 1:4-1:
6.
4. Process for the preparation of deuterated diphenyldimethoxysilane according to any one of claims 1 to 3, characterized in that, The method comprises the following steps: A. The tetramethoxysilane, magnesium chips, I2 particles and tetrahydrofuran are mixed under inert gas protection, and the mixture is heated to 30-90 ℃, and the mixture of deuterated bromobenzene and tetrahydrofuran is added dropwise, and after the dropwise addition is completed, the reaction is carried out under reflux for a period of time; B. The reaction solution obtained in step A is filtered, the solvent in the filtrate is removed, and the deuterated diphenyldimethoxysilane product is separated by further vacuum rectification.
5. The method of claim 4, wherein the deuterated diphenyldimethoxysilane is prepared by the reaction of a deuterated diphenylamine with a deuterated chlorosilane. In step A, the temperature is increased to 40-70 ℃.
6. The method of claim 4, wherein the deuterated diphenyldimethoxysilane is prepared by the reaction of a deuterated diphenylamine with a deuterated chlorosilane. In step A, after the dropwise addition is completed, the reaction is carried out under reflux for 0.5-6 h. In step A, after the dropwise addition is completed, the reaction is carried out under reflux for 0.5-6 h.