Record Details

Novel Synthetic Strategies towards Acetylenic Biscarbamates/Biscarbonates and Organochalcogen Derivatives

Electronic Theses of Indian Institute of Science

View Archive Info
 
 
Field Value
 
Title Novel Synthetic Strategies towards Acetylenic Biscarbamates/Biscarbonates and Organochalcogen Derivatives
 
Creator Cheerladinne, Venkateshwarlu
 
Subject Acetylenic Biscarbamates - Synthesis
Acetylenic Biscarbonates - Synthesis
Organochalcogen Derivatives
Hydrochalcogenation
Amino Sulfides/Selenides
Aminobenzothioate Derivatives
Butadiynes
Thioglycosides
Selenoglycosides
Glycosyl Disulfides/Selenenylsulfides
Isatoic Anhydrides
Rongalite
Organic Chemistry
 
Description Bisacetylenic cabamates/carbonates are most useful compounds in finger mark development, for the synthesis of polymeric gels and other material applications. Organochalogen derivatives are the organic compounds containing chalcogen (S, Se) atoms. They have been used as chiral ligands for enatioselective catalysis, glycosyl donors and in the synthesis of heterocyclic compounds etc. This thesis describes our efforts towards synthesis of bisacetylenic cabamates/carbonates and development new synthetic strategies using rongalite (Na+HOCH2SO2-) and benzyltriethyl ammonium tetrathiomolybate [BnEt3N]2MoS4 as a reducing agents led to obtain various organochalcogen derivatives.
We developed a new reagent, hexa-2,4-diyne-1,6-bisoxycarbonyl chloride [Hbc Cl] for the synthesis of symmetrical diacetylenic biscarbamates/biscarbonates and further studied the solid state structures using X-ray crystallography. Later we described a stereoselective method for the hydrothiolation of buta-1,3-diynes derivatives using diaryldichalcogenides in the presence of rongalite and K2CO3. The buta-1,3-diynes underwent stereoselective addition reaction with in situ generated chalocgenate anion from diaryl dichalcogenides which afforded the corresponding (Z)-chalcogenynes. The reactivity of buta-1,3-diynes with diaryl dichalcogenides was further studied at higher temperature led to a mixture of mono chalcogenated and bischalcogenated products. Then an efficient method was developed for the synthesis of enatiopure β-amino sulfides/selenides via ring opening of sulfamidates using diarylchalcogenides with rongalite as reducing agent. Further we synthesized chalcogeno derivatives of sugars from glycosyl halides and diaryl dichalcogenides in the presence rongalite. In addition, the synthesis of mixed glycosyl dichalcogenides has been demonstrated using [BnEt3N]2MoS4 as sulfur transfer agent as well as reducing agent. Finally the reactivity of [BnEt3N]2MoS4 was studied in detail with various isatioc anhydrides which led to the formation of S-benzyl 2-aminobenzothioate derivatives. Further we synthesized S-alkyl/aryl 2-aminobenzothioate derivatives via ring opening of isatoic anhydrides and diaryl/dialkyl chalcogenides by mean of [BnEt3N]2MoS4 as a reducing agent. We extended this method in a one-pot, tandem fashion with various alkyl halides. In this thesis, details of all of the above studies have been described.
 
Contributor Chandrasekaran, S
 
Date 2018-05-01T06:30:05Z
2018-05-01T06:30:05Z
2018-05-01
2013
 
Type Thesis
 
Identifier http://etd.iisc.ernet.in/2005/3466
http://etd.iisc.ernet.in/abstracts/4333/G25882-Abs.pdf
 
Language en_US
 
Relation G25882