V. I. Rakhlin

Acyl iodides in organic synthesis: XI. Unusual N-C bond cleavage in tertiary amines

Acyl iodides reacted with excess primary and secondary amines in a way similar to acyl chlorides, yielding the corresponding carboxylic acid amide and initial amine hydroiodide. Reactions of tertiary amines with acyl iodides were accompanied by cleavage of the N-C bond with formation of the corresponding N,N-di(hydrocarbyl)carboxamide and alkyl iodide. In the presence of excess tertiary amine the latter was converted into quaternary tetra(hydrocarbyl)ammonium iodide.

An investigation of the mechanism of the reation of allyltriethylstannane with bromotrichloromethane by radiofrequency probing and chemically induced dynamic nuclear polarization (CIDNP)

Abstract The methods of radiofrequency probing (RFP) and chemically induced dynamic nuclear polarization (CIDNP) have been used to study the mechanism of the reaction of allyltriethylstannane with bromotrichloromethane. The CIDNP effects which have been detected prove the presence of radical stages in this reaction. An assumption has been made about a possible radical pathway for the β-decomposition of elementorganic compounds.

Acyl iodides in organic synthesis: XII. Reactions with organosilicon amines

Reactions were investigated between acyl iodides RCOI (R = Me, Ph) and organosilicon amines of two classes: trimethyl(diethylamino)silane, dimethyl-bis(diethylamino)silane, and hexamethyldisilazane on the one hand, and 3-aminopropyl(triorganyl)silanes H2N(CH2)3SiX3 (X = Et, EtO) on the other hand. The reaction of RCOI with trimethyl(diethylamino)silane Me3SiNEt2 occurred with a cleavage of the Si-N bond and the formation of N,N-diethylacet- or -benzamides and trimethyliodosilane separated in a mixture with hexamethyldisiloxane. At the reaction of acyl iodides RCOI (R = Me, Ph) with dimethyl-bis(diethylamino)silane in the ratio 2:1 in benzene solution both Si-N were ruptured leading to the diethylamide of the corresponding acid and dimethyldiiodosilane. The main product of the reaction of acetyl iodide with hexamethyldisilazane at the molar ratio 2:1 was diacetylimide (MeCO)2NH. This reaction can be recommended as a simple and convenient preparation procedure for diacylimides. The exothermal reaction of the acetyl iodide with 3-aminopropyl(triethyl)- and -(triethoxy)silanes at the molar ratio of the reagents 1:1 without solvent resulted in quaternary ammonium salts, hydroiodides of the corresponding acetylamides I−MeCON+H2(CH2)3SiX3 (X = Et, OEt).

Photoinitiated reactions of allyltriorgano-silanes and -germanes with polyhaloidalkanes: study of the mechanisms of the reactions by means of the 1H CIDNP method

Abstract The radical stages in the photolysis reactions of various allyltriorgano-silanes and -germanes (R 3 MCH 2 CHCH 2 ; M = Si, Ge) with polyhaloidalkanes have been studied using the 1 H CIDNP method. It has been shown that the mechanism of the photochemical reaction for M = Sn, Ge is different from the case when M = Sn. Some rather stable R 3 MCH 2 CH(Hal)CH 2 R′ (M = Si, Ge) derivatives were isolated and characterized.

Acyl iodides in organic synthesis. Reaction of acyl iodides with triphenylethoxy- and triphenylhydroxysilane

The reaction of triphenylethoxysilane with acetyl or benzoyl iodide led to the formation of triphenyliodosilane and ethyl ester of the corresponding carboxylic acid. Triphenyliodosilane formed also in the reaction of triphenylsilanol with benzoyl iodide. These reactions comprise the new simplest method of preparation of the triphenyliodosilane (yield over 60%). The reaction product of triphenylhydroxysilane and acetyl iodide is triphenylacetoxysilane. The reactions of the studied acyl iodides with triphenylhydroxysilane is the first example of different regioselectivity of acetyl iodide and benzoyl iodide in reactions with organic and organoelemental compounds.

Reaction of a stable silylene with tetrahydrofuran

Reduction of 1,3-di-tert-butyl-2,2-dichloro-2,3-dihydro-1H-1,3,2-diazasilole with metallic potassium gave, instead of a stable silylene, 1,3-di-tert-butyl-2,3-dihydro-1H-1,3,2λ2-diazasilylolene, a product of insertion of the latter into the carbon-oxygen bond of tetrahydrofuran, 1,4-di-tert-butyl-6-oxa-1,4-diaza-5-silaspiro[4,5]dec-2-ene.

(Organylsulfanyl)chloroacetylenes: VIII. Reaction with (diethylamino)trimethylsilane

Abstract(Alkylsulfanyl)chloroacetylenes react with (diethylamino)trimethylsilane in diethyl ether (20–22°C) to form dialkyl(alkylsulfanylethynyl)amines (19–29%) and 1,3-bis(alkylsulfanyl)-4-chloro-4-(diethylamino)but-3-en-1-ynes (17–42%). The yield depends on the reagent ratio.

Reaction of Alkylsulfanylchloroacetylenes with 1,1-Dimethylhydrazine

Alkylsulfanylchloroacetylenes react with 1,1-dimethylhydrazine in diethyl ether at 20–22°C to give, depending on the reactant ratio, 3,6-bis(alkylsulfanylmethyl)-1,1,4,4-tetramethyl-1,4-dihydro-1,2,4,5- tetrazine-1,4-diium dichlorides (yield 67–80%) or 1-[2-(alkylsulfanyl)-1-(2,2-dimethylhydrazono)ethyl]-1,1-dimethylhydrazinium chlorides. The latter readily undergo dequaternization to the corresponding 2-alkylsulfanyl-N1,N2,N4-trimethylethanohydrazide hydrazones (yield up to 53%).

Deep purification of hexamethyldisilazane

We considered a deep cleaning of 1,1,1,3,3,3-hexamethyldisilazane used in microelectronics and organoelement synthesis from a series of homogeneous and heterogeneous admixtures by various physicochemical methods.

Homolytic reactions of N-bromohexamethyldisilazane with trialkyl(phenylalkoxy) derivatives of silicon and tin

The main product of the photoinduced reaction of N-bromohexamethyldisilazane with trialkyl-(benzyloxy)derivatives of silicon and tin R3MO(CH2)nPh (R = Me, Et; M = Si, Sn; n = 1) is N,N-dibenzylidene-C-phenylmethanediamine (hydrobenzamide). For M = Si, with increase of the length of the methylene chain between the oxygen atom and the phenyl group (n = 2, 3), the similar reaction affords the product of bromination of the benzylic carbon atom R3MO(CH2)n−1CHBrPh. For M = Sn, the reaction results in the formation of 2-phenyloxacycloalkanes PhCHO(CH2)n−1.