Investigation In The Methodology For Construction Of Carbon-Carbon Multiple-Bond On The Basis Of One-pot Elimination Protocol

Carbon-Carbon multiple-bond compounds is playing an important role in organic chemistry, applied chemistry and related fields. So it is academic and practical significance to explored new methods for constructing carbon-carbon multiple-bond. By taking advantage of simplified process, higher total yield and economical operation, one-pot synthesis process acts a procedure with resource-saving and environment friendly, which have caught the eyes of synthesis chemists thus be used to synthesize various compounds. In this dissertation, elimination protocol was employed as a basal route, so a new strategy was developed to construct multiple-bond (including multiple-bond with functional group) via one-pot process by examineing some sulfones reaction with aldehydes. And the application of some Carbon-Carbon multiple-bond compounds with especial structure was explored.This dissertation consists of six parts and is described in below contents.Chapter 1, Various reactions for construction of multiple-bond compounds and the application of some target moleculars were firstly subjected to review.Chapter 2, Based on nucleophilic addition, nucleophilic substitution and elimination reaction, one-pot procedure for synthesizing Methylthio aromatic acetylenes was presented. And reaction with methylthiomethyl phenyl sulfone(MP-S) and aryl aldehyde then through double elimination procedure have furnished an array of methylthio aromatic acetylenes in good yield. By capturing and identifying the structures of intermediates which generated from reaction process, the postulated mechanism of one-pot double elimination protocol was examined. The results showed one-pot procedure contained the formation of intermediate which borne two leaving groups and double elimination process of these two leaving groups. The advantages of present protocol are facile availability of starting materials, easy operation and higher yield, besides of fewer byproduct and efficient purification of the target products.Chapter 3, the extended application of several methylthio aromatic acetylenes obtained by one-pot procedure was discussed here. Multidentate thioether molecules with different size, shape, functional groups andπ-conjugated bone were designed and synthesized. So their application in the evolution to mediate the assembly with gold nanoparticle and then appeared special property were examined.Chapter 4, a new protocol for synthesis of (1-propynyl)arenes was discussed. The synthesis methodology to (1-propynyl)arenes through one-pot double elimination procedure was developed based on detailed exploration of the reaction condition of each step. So reaction with methyl phenyl sulfone and aryl aldehyde then through a double elimination procedure have afforded an array of (1-propynyl)arenes in moderate to excellent yield. The virtues of present protocol are facile available starting materials, easy operation. And some products with a variety of functional groups such as halogen, ether, heteroaromatic and some compounds borne two 1-propynyl groups were synthesized via this protocol.Chapter 5, a new process for synthesis of enynes was presented here. Firstly, the idea of one-pot elimination procedure was presented and then the synthesis route to enynes via one-pot elimination procedure was established. Employment of N,N-dimethyl-propyleneurea(DMPU) as additive agent, several enynes have been synthesized via one-pot procedure which consisted of reaction of (1-propynyl)arenes which were obtained in the chart 4 with aldehyde, formation of intermediate of new leaving group and elimination process of the leaving group, and the preliminary spectral examination of these compounds was presented here.Chapter 6, a new protocol for construction of double-bond was presented here. Benzyl sulfones undergo the process of intermolecular nucleophilic substitution and elimination reaction to give double-bond compounds. On the basis of this protocol, helical cyclophane was prepared via the designed one-pot protocol. And the structure of helical cyclophane was identified by spectral examination.In conclusion, elimination reaction was employed as the basic protocol and the idea of one-pot synthesis procedure to prepare some multiple-bond compounds with important structure. Some important were synthesized via this protocol based on the modification by redesigning synthesis route, exploring reaction conditions and reagents, capturing and identifying the intermediates, so one-pot elimination protocol was developed to construct Carbon-Carbon multiple-bond. This protocol for synthesis of multiple-bond compound will enrich the contents of organic chemistry and it is significance of the application of compounds in material chemistry and applied chemistry.