Toward a New Direct Process: Synthesis of Methylmethoxysilanes from Dimethyl Carbonate and Pentacopper Silicide

We disclose the direct synthesis of methylmethoxysilanes from pentacopper silicide, Cu5Si, and dimethyl carbonate, DMC, affording high levels of dimethylsilyl products without the use of halide catalysts. When Cu5Si powder (99.5%) was reacted with DMC at 350 °C, Me2Si­(OMe)2 was the major silane pro...

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Published inIndustrial & engineering chemistry research Vol. 59; no. 16; pp. 7457 - 7465
Main Authors Roberts, John M, Pushkarev, Vladimir V, Sturm, Jason J, Katsoulis, Dimitris E
Format Journal Article
LanguageEnglish
Published American Chemical Society 22.04.2020
Subjects
carbonates
catalysts
organosilicon compounds
oxidation
silane
tin
X-ray photoelectron spectroscopy
Online AccessGet full text
ISSN0888-5885
1520-5045
1520-5045
DOI10.1021/acs.iecr.0c00505

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Abstract We disclose the direct synthesis of methylmethoxysilanes from pentacopper silicide, Cu5Si, and dimethyl carbonate, DMC, affording high levels of dimethylsilyl products without the use of halide catalysts. When Cu5Si powder (99.5%) was reacted with DMC at 350 °C, Me2Si­(OMe)2 was the major silane product at >70% selectivity. In contrast, when a high purity Cu5Si (99.99%) was used, the reaction afforded mainly permethoxylated silanes. ICP-OES identified several impurity elements in the low purity Cu5Si. By synthesizing materials that contained the individual impurity elements and reacting them with DMC, tin was revealed as being a crucial promoter. XPS revealed that tin segregates to the surface under reaction conditions, and elevated tin levels have a significant impact on DMC reactivity with the surface. XPS also suggests that tin is in the zero oxidation state at the surface, which provides some insight to its role in the direct synthesis of methylmethoxysilanes.
AbstractList We disclose the direct synthesis of methylmethoxysilanes from pentacopper silicide, Cu5Si, and dimethyl carbonate, DMC, affording high levels of dimethylsilyl products without the use of halide catalysts. When Cu5Si powder (99.5%) was reacted with DMC at 350 °C, Me2Si­(OMe)2 was the major silane product at >70% selectivity. In contrast, when a high purity Cu5Si (99.99%) was used, the reaction afforded mainly permethoxylated silanes. ICP-OES identified several impurity elements in the low purity Cu5Si. By synthesizing materials that contained the individual impurity elements and reacting them with DMC, tin was revealed as being a crucial promoter. XPS revealed that tin segregates to the surface under reaction conditions, and elevated tin levels have a significant impact on DMC reactivity with the surface. XPS also suggests that tin is in the zero oxidation state at the surface, which provides some insight to its role in the direct synthesis of methylmethoxysilanes.
We disclose the direct synthesis of methylmethoxysilanes from pentacopper silicide, Cu₅Si, and dimethyl carbonate, DMC, affording high levels of dimethylsilyl products without the use of halide catalysts. When Cu₅Si powder (99.5%) was reacted with DMC at 350 °C, Me₂Si(OMe)₂ was the major silane product at >70% selectivity. In contrast, when a high purity Cu₅Si (99.99%) was used, the reaction afforded mainly permethoxylated silanes. ICP-OES identified several impurity elements in the low purity Cu₅Si. By synthesizing materials that contained the individual impurity elements and reacting them with DMC, tin was revealed as being a crucial promoter. XPS revealed that tin segregates to the surface under reaction conditions, and elevated tin levels have a significant impact on DMC reactivity with the surface. XPS also suggests that tin is in the zero oxidation state at the surface, which provides some insight to its role in the direct synthesis of methylmethoxysilanes.
Author Roberts, John M
Pushkarev, Vladimir V
Katsoulis, Dimitris E
Sturm, Jason J
AuthorAffiliation Dow Silicones Corporation
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Snippet We disclose the direct synthesis of methylmethoxysilanes from pentacopper silicide, Cu5Si, and dimethyl carbonate, DMC, affording high levels of dimethylsilyl...
We disclose the direct synthesis of methylmethoxysilanes from pentacopper silicide, Cu₅Si, and dimethyl carbonate, DMC, affording high levels of dimethylsilyl...
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SubjectTerms carbonates
catalysts
organosilicon compounds
oxidation
silane
tin
X-ray photoelectron spectroscopy
Title Toward a New Direct Process: Synthesis of Methylmethoxysilanes from Dimethyl Carbonate and Pentacopper Silicide
URI http://dx.doi.org/10.1021/acs.iecr.0c00505
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