The Hydrolytic Cleavage of Methyl and Chloromethyl Siloxanes

Krieble, Robert H.; Elliott, James R.

doi:10.1021/ja01215a049

Cited by 43 publications

(12 citation statements)

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“…This is in agreement with literature data that substitution of trimethylsiloxy groups by chlorine does not take place [15]. This is in agreement with literature data that substitution of trimethylsiloxy groups by chlorine does not take place [15].…”

Section: Model Compoundssupporting

confidence: 93%

“…Toluene and dichloromethane were used as solvents for acylations with triethylamine as hydrogen chloride scavenger and the reaction temperature was kept below 50 8C in order to avoid formation of free hydrogen chloride which is known to cleave Si1O bonds [15]. Dimethylaminopyridine (DMAP) was used as catalyst in some cases [16].…”

Section: Acylation At Room Temperature In the Presence Of An Acid Accmentioning

confidence: 99%

“…[15] where chlorotrimethylsilane is obtained from the reaction of a siloxy group with hydrogen chloride. During acylation of 1,3-bis(trimethylsiloxy)-2-propanol (2) 39% of the primary trimethylsiloxy groups and 5% of secondary hydroxy groups are chlorinated (ratio 8: 1).…”

Section: Model Compoundsmentioning

confidence: 99%

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Selectivity in the acylation of partially silylated hydroxy polymers - a study with trimethylsilyl cellulose and model compounds

Mörmann¹,

Demeter

Wagner

1999

Acta Polym.

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Acylation of partially trimethylsilylated cellulose, glycerol (1), 1,3‐bis(trimethylsiloxy)‐2‐propanol (2), methyl‐2,3,4,6‐tetrakis‐O‐trimethylsilyl‐α‐D‐glucopyranoside (10) and methyl‐2,3,4‐tris‐O‐trimethylsilyl‐α‐D‐glucopyranoside (11) either with acyl chlorides/triethylamine at room temperature or with acyl chlorides at elevated temperature in the absence of an acid scavenger has been studied. Selective acylation of free hydroxy groups has been found with acyl chloride/amine, though complete conversion of free hydroxy groups of cellulose could not be achieved under these conditions. High temperature acylation, however, results in an unselective reaction of free hydroxy groups and trimethylsilyloxy groups. Trans‐silylation takes place and chlorination is found in the reaction of 1 and 2. Carbohydrates were not chlorinated under these conditions, silyl cellulose, however, is strongly depolymerized.

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Section: Model Compoundssupporting

confidence: 93%

Section: Acylation At Room Temperature In the Presence Of An Acid Accmentioning

confidence: 99%

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Selectivity in the acylation of partially silylated hydroxy polymers - a study with trimethylsilyl cellulose and model compounds

Mörmann¹,

Demeter

Wagner

1999

Acta Polym.

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“…For example, Krieble and Elliott have pointed out that, in compounds of the type X3C-AY3, where A is a carbon or silicon atom attacked by base, cleavage of the C-A rather than the X-C bond occurs in the carbon analog only if all three X atoms are halogen and a t least two of the Y positions are occupied by oxygen. When A is silicon, only one X need be a halogen atom and only one Y an oxygen atom in order to get cleavage of the C-A bond (122). In the case of trichloro( trichloromethyl)silane, cold water alone cleaves the carbon-silicon bond readily (37).…”

Section: A Silicon-carbon Single Bondsmentioning

confidence: 99%

Relationships between Analgous Organic Compounds of Silicon and Carbon.

Gilman¹,

Dunn²

1953

Chem. Rev.

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“…This proves that under these conditions too, the free hydroxy groups are more reactive than siloxy groups. The results also suggest that hydrogen chloride at least partly causes desilylation via a nucleophilic attack at the silicon atom [15].…”

Section: Model Compoundsmentioning

confidence: 75%

Selectivity in the acylation of partially silylated hydroxy polymers – a study with trimethylsilyl cellulose and model compounds

Mormann¹,

Demeter²,

Wagner³

1999

Acta Polym.

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Acylation of partially trimethylsilylated cellulose, glycerol (1), 1,3-bis(trimethylsiloxy)-2-propanol (2), methyl-2,3,4,6-tetrakis-O-trimethylsilyl-a-D-glucopyranoside (10) and methyl-2,3,4-tris-O-trimethylsilyl-a-D-glucopyranoside (11) either with acyl chlorides/triethylamine at room temperature or with acyl chlorides at elevated temperature in the absence of an acid scavenger has been studied. Selective acylation of free hydroxy groups has been found with acyl chloride/amine, though complete conversion of free hydroxy groups of cellulose could not be achieved under these conditions. High temperature acylation, however, results in an unselective reaction of free hydroxy groups and trimethylsilyloxy groups. Trans-silylation takes place and chlorination is found in the reaction of 1 and 2. Carbohydrates were not chlorinated under these conditions, silyl cellulose, however, is strongly depolymerized.

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The Hydrolytic Cleavage of Methyl and Chloromethyl Siloxanes

Cited by 43 publications

References 1 publication

Selectivity in the acylation of partially silylated hydroxy polymers - a study with trimethylsilyl cellulose and model compounds

Selectivity in the acylation of partially silylated hydroxy polymers - a study with trimethylsilyl cellulose and model compounds

Relationships between Analgous Organic Compounds of Silicon and Carbon.

Selectivity in the acylation of partially silylated hydroxy polymers – a study with trimethylsilyl cellulose and model compounds

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