KR830006318A - Silylation of Organic Compounds Using Special Catalysts - Google Patents

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Silylation of Organic Compounds Using Special Catalysts

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Claims (17)

In trimethylsilylating an organic compound having one or more active hydrogen atoms with hexamethyldisilazane, the catalyst represented by the following general formula is present in the range of 0.001 to 10 mol% in the reaction mixture. Trimethylsilyl of organic compounds using special catalysts X-NH-Y In the formula above, X and Y are the same or different groups and each represents a group of electron withdraw, or X represents a group of electron withdraw and Y represents a hydrogen atom or a trialkylsilyl group, or X and Y are both In addition to the nitrogen atom, the group of electron drags forming a ring series is represented. The method according to claim 1, wherein the group of the electron terminal group is an acyl group, a sulfonyl group, or a phosphoryl group. The method according to claim 1, wherein the group of electron-drawing is selected and displayed in some of the following general formulas. In the above general formula, R ₁ and R ₂ are the same or different groups, and each group is one alkyl group, one or more halogen atoms, alkyl group, alkoxy group, or nitro group which may be substituted by or a halogen atom thereof. One aryl group, one alkoxy group, one halogen atom, one alkyl group or one nitro group which may be substituted by one or more aryloxy groups, or R ₃ and R ₄ are the same or above Each group forms a double ring ring group with a R ₃ R ₄ group and a nitrogen atom representing one hydrogen atom, one trialkylsilyl or one alkyl group, and the general formula is represented by -AZB-, wherein A is And Z is an electron withdrawing group representing one alkylene group, alkenylene group or arylene group which may be substituted by one or more halogen atoms or alkyl groups. The method according to claim 1, wherein the group of the electron draw is based on the following general formula display. Wherein R ₅ represents one alkyl group, which may be substituted by one or more halogen atoms or one aryl group, which may be substituted by one or more alkoxy groups or nitro groups, Wherein R ₆ represents one methyl group or one aryl group which may be substituted by one or more halogen atoms or methyl groups, or R ₆ represents one R ₆ R ₇ represents an N- group wherein R ₇ and R ₈ is the same or different and each group is a group representing one hydrogen atom, one trialkyl silyl group or one alkyl group, Wherein R ₉ and R ₁₀ are the same or different groups, and each group is a aryloxy group which may be substituted by one alkoxy group, one halogen atom or one nitro group, and a ring series together with nitrogen atom. It represents the group of electron drags represented by the following general formula: Wherein Z represents an alkenylene group, which is one arylene group which may be substituted by one or more halogen atoms or an alkyl group, or may be substituted by one or more halogen atoms, X is O or 2, and Z is an alkenylene group or an arylene group. The method according to claim 1, wherein the group of the electron draw is based on the following general formula display. Wherein R ₅ is one dihalomethyl or trihalomethyl group or one phenyl group or naphthyl group in which each group may be substituted by one methoxy group, Wherein R ₆ is one phenyl group, one amino group, one dialkylamino group or one trialkylamino group, which may be substituted by one methyl group, one methyl group or one chlorine atom, Wherein R ₉ and R ₁₀ form a ring system together with one phenyl group, one phenyl group which may be substituted by one methoxy group, ethoxy group or propoxy group or one nitro group or one chlorine atom, and nitrogen atom and Displays the group of electron drags expressed by the formula. Wherein Z is an ethylene group, a phenylene group or a naphthylene group, each of which is optionally substituted with a hyperhalo, X is 0 or 2 here, and represents a Z phenylene group. Amides, sulfonamides, cyclic or cyclic imides, cyclic or highly open sulfonimides, disulfonimides, acylphosphoramidites, sulfonyrosporamidites and imidodiphosphates The method of claim 1 to be selected. Trichloroacetamide, trifluoroacetamide, phthalimide, 3,4,5,6-tetrachloro-talimide, 3,4,5,6-tetrabromophthalimide, 1,8-naph Deimide, maleimide, barbituric acid, saccharin, N-benzoyl-4-toluenesulfonamide, N- (2-methoxybenzoyl) -4-toluenesulfonamide, N- (1-naphthoyl) -4 Toluenesulfonamide, N-benzoylbenzenesulfonamide, N- (2-methoxy-1-naphthoyl) -4-toluenesulfonamide, N- (2-methoxy-1-naphthoyl) methanesulfonamide, di -(4-toluenesulfonyl) amine, dimethyl N (trichloroacetyl) phosphoramidart, di-4-nitrophenyl N (trichloroacetyl) phosphoramidart, di-4-nitrophenyl N (P-toluene Sulfonyl) phosphoramidart, diisophore N- (dichloroacetyl) phosphoramidart, di-0-chlorophenyl N- (4-chlorophenylsulfonyl) phosphoramide, tetraphenylimidodiphosphate, sulfa Meade, N, N-dimethylsulf Pamide, N, N'-mis) trimethylsilyl) sulfamide, 1,2-benzisothiazol-3-2H-one and 4-benzoyloxy-1,2-dihydro-1-oxo-phthalazine The method according to claim 6, wherein the catalyst is selected from the above. Select catalysts from saccharin, di-4-nitrophenyl N (4-tolueneacetyl) phosphoramidart, di-4-nitrophenyl N (4-toluenesulfonyl) phosphoramidart and tetraphenylimido diphosphate The method of claim 7. The method according to claim 1, wherein the compound corresponding to the following general formula is prepared. RS-SiMe ₃ In the above general formula, R is a 5 or 6 membered heterocyclic group having a nitrogen atom or a sulfur atom as a hetero atom, which is one or more alkyl groups, one phenyl group, one trimethylsilyl group, one alkylamino group, or It may also be substituted by one trimethylsilyloxycarbonylmethyl group. In the general formula of claim 9, R is one 1,3,4-thiadiazolyl group, one 1,2,3,4-tetrazolyl group, one 1,2,3-triazolyl Group, one 1,2,4-triazolyl group, one imidazolyl group or one pyrimidyl group, whose groups are one methyl group, one phenyl group, one methylamino group, one trimethylsilyl group Or the method according to claim 9, which may be substituted by one trimethylsilyloxycarbonylmethyl group. The compound prepared was (5-methyl-1,3,4-thiadiazole-2-thio) trimethylsilane, 1-methyl-5-trimethylsilylthiotetrazole, 1-trimethylsilyl-5-trimethylsilylthio- 1,2,3-triazole, 1-methyl-2- (trimethylsilylthio) imidazole, 1-trimethylsilyl-3-trimethylsilylthio-1H-1,2,4-triazole, 1-phenyl-5 -Trimethylsilylthio-1H-tetrazole, 4,6-dimethyl-2- (trimethylsilylthio) pyrimidine, 2-methylamino-5-trimethylsilylthio-1,3,4-thiadiazole, trimethylsilyl 5 The method according to claim 9, wherein the compound is selected from -trimethylsilylthio-1H-pytetrazolylacetate-trimethylsilyl-5-trimethylsilylthio-1,3,4-thiadiazolyl-2-acetate . Trimethylsilylated thiols represented by the following general formula: RS-RiMe ₃ In the above general formula, R is a 5 or 6 membered heterocyclic group having a nitrogen atom or a sulfur atom as a hetero atom, which is one or more alkyl groups, one phenyl group, one trimethylsilyl group, one alkylamino group or It may also be substituted by one trimethylsilylcarbonylmethyl group. In the general formula set forth in claim 12, R is one 1,3,4-thiadiazolyl group, one 1,2,3,4-tetrazolyl group, one 1,2,3-triazole group, One 1,2,4-triazolyl group, one imidazolyl group or one pyrimidyl group, which represent one methyl group, one phenyl group, one methylamino group, one trimethylsilyl group or one trimethyl The trimethylsilylated thiol of Claim 12 which may be substituted by the silylcarbonylmethyl group. (5-methyl-1,3,4-thiadiazole-2-thio) trimethylsilane, 1-methyl-5-trimethylsilylthio tetrazole, 1-trimethylsilyl-5-trimethylsilylthio-1,2,3 -Triazole, 1-methyl-2- (trimethylsilylthio) imidazole, 1-trimethylsilyl-3-trimethylsilylthio-1H-1,2,4-triazole, 1-phenyl-5-trimethylsilylthio- 1H-tetrazole, 4,6-dimethyl-2- (trimethylsilylthio) pyrimidine, 2-methylamino-5-trimethylsilylthio-1,3,4-thiadiazole, trimethylsilyl 5-trimethylsilylthio- 1H-tetrazolyl-1-acetate, trimethylsilyl 5-trimethylsilylthio-1,3,4-thiadiazolyl-2-acetate. Trimethylsilyl 7-phenyl acetamide-3- (1-methyl-1 H-tetrazolyl-1-thio) methyl-3-cepem-4-carboxylat 1-oxide, N, O-bis (trimethylsilyl)- 7-phenylacetamide-3- (1H-1,2,3-triazolyl-5-thio) methyl-3-cepem-4-carboxylic acid 1-oxide, trimethylsilyl-7-trimethylsilyl amino-3- ( 5-methyl-1,3,4-thiadiazolyl-2) -thiomethyl-3-cepem-4-carboxylate, trimethylsilyl 7-trimethylsilylamino-3- (1-trimethylsilyl-1H-1, 2,3-triazolyl-5) thiomethyl-3-cepem-4-carboxylate, trimethylsilyl 7-trimethyl silylamino-3- (1-methyl-1H-tetrazolyl-5) thiomethyl-3-cepem 4-carboxylat, trimethylsilyl 7-phenylacet amido-3- (1-methyl-1H-tetrazolyl-5-thio) methyl-3-cefe-4-carboxylate and trimethylsilyl 7-phenylacet Amido-3- (1-trimethylsilyl-1H-1,2,3-triazolyl-5-thio) methyl-3-cepem 4-carboxylate. The method according to claim 1, wherein the catalyst is added to the reaction mixture in a camouflage form. Claim 16 wherein the gastrointestinal catalyst as defined in claim 16 is a silylated derivative, sodium salt or other catalyst derivative which decomposes in the reaction mixture to form the catalyst of claim 1. Way. ※ Note: The disclosure is based on the initial application.