N,N-(dimethylamino)-2-pyrrolidinones from the rearrangement of N-allyl-N ',N '-dimethyl-2,2-dichlorohydrazides promoted by CuCl-N,N,N ',N '-tetramethylethylendiamine

Treatment of N-allyl-N¢,N¢-dimethyl-2,2-dichlorohydrazides with CuCl/TMEDA in ethyl acetate35is a mild and easy method for preparing N-(dimethylamino)-2-pyrrolidinones. As the N-N bond in the lactamproducts can be easily and efficiently cleaved, this makesN-dimethylamino protection an attractive alternative toN-benzylic protection

2,2-Dichloroaldehydes and 2,2-dichlorocarboxylic acids from 2-picoline center dot HCl catalyzed chlorination of aldehydes

An efficient preparation of 2,2-dichloroaldehydes and 2,2-dichlorocarboxylic acids has been achieved by chlorination of aldehydes using 2-picoline hydrochloride as recoverable catalyst.An efficient preparation of 2,2-dichloroaldehydes and 2,2- dichlorocarboxylic acids has been achieved by chlorination of aldehydes using 2-picoline hydrochloride as recoverable catalyst

TRIMETHYLCHLOROSILANE-MEDIATED FORMATION OF 2-CHLOROCYCLOHEXYL SULPHIDES BY SULPHOXIDES

The title 2-chlorocyclohexyl sulfides, e.g. I (R = Me, Et, Me2CH, Bu) were prepd. by treating cyclohexene with the corresponding alkyl sulfoxides RSOR in the presence of Me3SiCl. Unsym. sulfoxides, e.g. EtSOBu gave a mixt. of products I (R = Et, Bu). Tetramethylene sulfoxide (II) gave aldehyde I (R = CH2CH2CH2CHO) as the major product. A mechanism is presented in which 2 mol. of sulfoxide form an intermediates S-alkoxysulfonium salt

ON THE INTERMEDIATES OF THE REACTION OF KETONES WITH MNO2-CHLOROTRIMETHYLSILANE

The chlorination of ketones with MnO2-chlorotrimethylsilane occurs through an enolization catalyzed by an Mn(IV) species, which is also involved in the halogenation of alkenes

Base-promoted rearrangement of 2,3-epoxycyclohexanones to phenols

The reactions were examd. of ten 2,3-epoxycyclohexanones with NaH in (MeOCH2)2; the products were trapped by treatment with Me3CSiMe2Cl and Et3N. Generally, the main reaction products were the corresponding silylated phenols. E.g., carvone epoxide gave 66% 3,4-Me3CSiMe2O(Me)C6H3CMe:CH2. This aromatization proceeds by deprotonation at the α'-C atom followed by O-silylation, β'-proton removal, olefinic bond shift, oxirane ring cleavage, and 1,2-elimination

THE REACTION OF STYRENES WITH CHLOROTRIMETHYLSILANE DIMETHYL-SULFOXIDE

The chlorotrimethylsilane-dimethyl sulphoxide reagent system gives rise to smooth and high yield transformations of: i) beta-alkyl- and beta,beta-dialkyl-styrenes into vicinal dichlorides, ii) alpha,beta-dialkyl- and alpha,beta,beta-trialkyl-styrenes into allyl chlorides

THE REACTION OF BENZYLIC ALCOHOLS WITH CHLOROTRIMETHYLSILANE/DIMETHYL SULFOXIDE

With catalytic amounts of chlorotrimethylsilane/dimethyl sulphoxide (CTMSO/DMSO) in acetonitrile benzylic alcohols have been found to give high yields of styrenes. By using stoicheiometric amounts of reagents, different reaction pathways are observed: an elimination-addition sequence occurs with secondary and tertiary alcohols affording vicinal dichloro derivatives, beta-chloro thioethers and allyl chlorides, whereas a nucleophilic substitution to the corresponding monochlorides occurs star-ting from primary and sterically hindered substrates

The chlorination of ketones with manganese(IV) chloride

In situ formation of MnCl4 by reaction of MnO2 with ClSiMe3 or AcCl followed by reaction with a ketone gives the α-chloro ketone. A CH2 group is attacked in preference to a Me group; steric factors limit the chlorination of CH groups