2202-56-4

Upstream product

• 3735-91-9 ethyl N,N-dimethylthiocarbamate 
• 325809-14-1 2-(benzo[d]oxazol-2-ylthio)-1-phenylpropan-1-one 
• 343332-34-3 2-phenyl-4-methyl-1,3-oxathiolan-5-one 
• 343332-73-0 2-methyl-4-phenyl-1,3-oxathiolan-5-one 
• 75-15-0 carbon disulfide 
• 4436-22-0 1-phenylpropylene oxide 
• 82797-31-7 1-hydroxy-1-phenyl-2-propyl N,N-dimethylthiocarbamate 

Downstream Products

• 873-66-5 1-propenylbenzene 
• 766-90-5 cis-1-phenyl-1-propylene 
• 4475-55-2 1-phenylpropane-2-thiol 

Relevant academic research and scientific papers

Atom economical synthesis of di- and trithiocarbonates by the lithium: Tert -butoxide catalyzed addition of carbon disulfide to epoxides and thiiranes

Alkali metal alkoxides were studied as catalysts for the addition of CS2 to epoxides. A screening of several commercially available alkoxides revealed lithium tert-butoxide as an active and selective catalyst for this reaction. The influence of different reaction parameters as well as the substrate scope under optimized reaction conditions has been studied. Terminal and highly substituted epoxides as well as thiiranes were converted. In total 28 products were prepared and isolated in yields up to 95%. Notably, the reactions were performed under mild conditions without additional solvents. The regio- and stereoselectivity of the reaction has been studied e.g. by converting (R)-styrene and (R)-propylene oxide. Moreover, the test reaction was monitored by 13C NMR and a plausible mechanism for the conversion of terminal and internal epoxides is given. This proposal is in agreement with the observed regio- and stereoselectivity of the reaction.

A facile and efficient one-pot synthesis of thiirans by the reaction of benzoxazolyl β-ketosulfides with NaBH4/NaOH

Convenient and efficient procedures for thiirans have been developed via a one-pot reaction of benzoxazolyl β-ketosulfides with NaBH4 and NaOH in MeOH and THF. The reaction is considered to proceed via the spiro intermediate by the ipso-additio

A convenient synthesis of episulfides and their conversion into alkenes

A convenient and stereoselective synthesis of episulfides based on the reaction of readily available S-(β-oxoalkyl) thiophosphate with sodium borohydride and their conversion into alkenes is described.

Glycosylsulfenyl and (Glycosylthio)sulfenyl Halides (Halogeno and Halogenothio 1-Thioglycosides, Resp.): Preparation and Reaction with Alkenes

The disulfides 11-17 and 20 were prepared from 7, 9, and 18 via the dithiocarbonates 8, 10, and 19, respectively (Scheme 2).The structure of 11 and of 13 was established by X-ray analysis.Chlorolysis (SO2Cl2) of 11 gave mostly the sulfenyl chloride 24, characterized as the sulfenamide 26, a small amount of 21, characterized as the (glycosylthio)sulfenamide 23, and the glycosyl chloride 27 (Scheme 3).Bromolysis of 11 followed by treatment of the crude with PhNH2 yielded only 28.Chlorolysis of the diglycosyl disulfide 13, however, gave mostly the (glycosylthio)sulfenyl chloride 21 and 27, besides 24.Bromolysis of 13 (-> 22 and traces of 25) followed by treatment with PhNH2 gave an even higher proportion of 23.Similarly, 20 led to 29 and hence to 30.In solution (CH2Cl2) the sulfenyl chloride 24 decomposes faster than the (thio)sulfenyl chloride 21, and both interconvert.Addition of crude 24 to styrene (-78 deg C) yielded the chloro-sulfide 31 and some 37, both in low yields.The product of the addition of 24 to 1-methylcyclohexene was transformed into the triol 32.Silyl ethers of allylic alcohols reacted with 24 only at room temperature, yielding, after desilylation, isomer mixtures 33 and 34, and pure 35.Much higher yields were achieved for the addition of (thio)sulfenyl halides yielding halogeno-disulfides.Good diastereoselectivities were only obtained with 21, its cyclohexylidene-protected analogue, and 22, and this only in the addition to styrene (-> 36, 37, 38), to (E)-disubstituted alkenes (-> 46, 48, 49a,b, 50a,b, 53), and to trisubstituted alkenes (-> 47, 51, 52, 54, 55).Other monosubstituted alkenes (-> 41-45) and (Z)-hex-2-ene (-> 49c,d, 50c,d) reacted with low diastereoselectivities.Where structurally possible, a stereospecific trans-addition was observed: regioselectivity was observed in the addition to mono- and trisubstituted alkenes and to derivatives of allyl alcohols.The absolute configuration of the 2-chloro-disulfides was either established by X-ray analysis (47a) or determined by transforming (LiAlH4) the chloro-disulfides into known thiiranes (Scheme 5).Thus, 37, 48, and the mixtures of 49a/b and 50a/b gave the thiiranes 56, 61, and 64, respectively, in good-to-acceptable yields (Scheme 5).Harsher conditions transformed 56 into the thiols 57 and 58.Similarly, 61 gave 62.The enantiomeric excesses of these thiols were determined by GC analysis of their esters obtained with (-)-camphanoyl chloride.Addition of 21 to trimethylsilane, followed by LiAlH4 reduction and desilylation, gave the known 66 (63percent, e.e. 74percent).The diastereoselectivity of the addition of 21 to trans-disubstituted and trisubstituted alkenes is rationalized by assuming a preferred conformation of the (thio)sulfenyl chloride and destabilizing steric interactions with one of the alkene substituents, . . .

Dipole-Stabilized Carbanions from Thioesters. Secondary α'-Lithio Carbamates and Tertiary α'-Lithio Thioesters

The formation of 5 and 17, synthetic equivalents of the α-lithioalkylthio and α-lithiodialkylthio functions, respectively, by deprotonations of the corresponding carbamate 4 and thioester 16 are reported.The reactions of these formally dipole-stabilized carbanions with a variety of electrophiles and their use in synthese of 2,3-substituted thiiranes are demonstrated.The rearrangement of 17 to an α-thiol ketone is shown to be intramolecular by a double labeling experiment.Potentially chiral or conformationally isomeric α'-lithio thioesters are found to be racemized and equilibrated.Formations of secondary α'-lithio thioesters in medium chain, β'-dimethylamino, and allyl systems are reported while β'-alkoxy groups are shown to eliminate to give vinyl thio esters which undergo further metalation.The kinetic acidity of a methyl thioester is shown to be comparable to a propenyl thioester and greater then an ethyl thioester.

Flash Vacuum Pyrolysis of 1,3-Oxathiolan-5-ones

Flash vacuum pyrolysis of 1,3-oxathiolan-5-ones causes loss of carbon dioxide with the concominant formation of the corresponding thiiranes in nearly quantitative yield.The reaction is stereospecific and proceeds by clean inversion of configuration.This suggests a concerted loss of carbon dioxide.Furthermore, substituent effects strongly support the intermediacy of thiocarbonyl ylides.Consequently, this method becomes one of the simplest ways of generating these species.