Research On Synthesis Of Spirodiclofen And Clodinafop-propargyl

Based on the literature researched,The reported preparation of a new acaricide Spirodiclofen and optical activity herbicide Clodinafop-propargyl were introduced in detail through two parts in this article.In the firstly part,adopting the cyclohexanone for the main beginning raw material, the spirodiclofen is given by the cyanic reaction,the ester reaction,the phenyl-acetyl reaction,the condensation,the acyl reaction.The total yield reaches to 56.0%.There is not any literature report about its parts of synthesis technical routes and the best conditions, and not broad produce in our country now.This part mainly discussion about the preparation of spirodiclofen,1-hydroxycyclohexanecarbonitrile,3-(2,4-dichlorophenyl)2-oxo-1-oxa-spiro[4,5]-decyl-3-en-4-ol. Through the comparison experimentation,the optimum one is ascertained.During the preparation of 1-hydroxycyclohexanecarbonitrile, the different proton acids,the molar ratio,and the solvents are all discussed.The yield was heightened to 98.5%by using TEBA as a phase-trasfer catalysts,and it exceeds literature to a 22.0%,which possess a vast innovation.During the preparation of ethyl 1-hydroxycyclohexanecarboxylate,the quantity of hydrochloric gas and ethanol,the rection time,the extraction reagents are discussed,which improves the product content to 92.2%.Compare to synthesis method of two steps,the yield increases abouts 40%. During the preparation of 3-(2,4-dichlorophenyl)-2-oxo-1-oxa-spiro[4,5]-decyl-3-en-4-ol, the cyclization reaction was processed by using unpurified liquid of ethyl 1-(2-(2,4-dichlorophenyl)acetoxy)cyclohexane carboxylate,the quantity of alkali,the solvents and its recycle,the reaction pressure,the temperature,the drop speed and the conditions of purification are discussed,which reduces the work intensity,increases the yield to 99.1%,resolves the crux problem on synthesis of spirodiclofen and obtains a more great innovation.The two steps total yield reaches to 79.2%.During the preparation of spirodiclofen,the quantity of solvents,the catalysts are discussed,the product yield reaches to 92.6%,the product purity reaches 97%above,and reaches internal advanced level,accords with export standard.By the creative method above,the synthesis technical routes and conditions fit to industrialized production,its cost also reduces to about each don of 25 thousands yuan,the market rate reaches to 60 thousands yuan now, so it possesses the biggest economic benefit.The secondly part mainly discussion about the preparation of clodinafop-propargyl, the important intermediate R-(+)-2-(4-hydrophenoxy)propionic acid.During the preparation of R-(+)-2-(4-hydrophenoxy)propionic acid,Adopting the L-methyl lactate for the main beginning raw material,the different routs and conditions of purification are comp- areed to confirm synthesis technics which fit to industrialized production.During the preparation of Clodinafop-propargyl,the molar ratio,the solvents,the reaction temperature, the alkalis are all discussed.The total yield reaches to 86%based on R-(+)-2-(4-hyd rophenoxy)propionic acid,and the product purity reaches 97%,the product ee value reaches 93%.The ultimate product and its important intermediates were proveded to be consilient with the molecule constructure of by nuclear magnetic resonance spectra and mass spectroscopic.