958814-81-8Relevant articles and documents
Development of a Scalable Process for the Insecticidal Candidate Tyclopyrazoflor. Part 3. A Scalable Synthesis of Methyl 3-((3,3,3-Trifluoropropyl)thio)propanoate via Thiol-Ene Chemistry
Gray, Kaitlyn C.,Heider, Patrick,McGough, Patrick,Ondari, Mark,Devaraj, Jayachandran,Yang, Qiang,Frycek, George,Graham, Brian,Neuman, Joseph,Lorsbach, Beth A.,Zhang, Yu
, p. 2142 - 2147 (2019)
Optimization of the thiol-ene reaction for the preparation of methyl 3-((3,3,3-trifluoropropyl)thio)propanoate (4), a key intermediate in the synthesis of the sap-feeding insecticidal candidate tyclopyrazoflor (1), is described. The major challenge with the radical thiol-ene chemistry was control of the regioselectivity between the linear and branched products. Reducing the radical initiation temperature was found to be the key variable in controlling the selectivity. Because of the high cost and storage challenges associated with the use of the room-temperature diazo initiator 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70), a two-component initiator system consisting of benzoyl peroxide and N,N-dimethylaniline was developed, allowing for radical initiation at temperatures as low as -15 °C. Application of semibatch operation gave 90:1 selectivity favoring the linear product. The overall yield and selectivity of the radical thiol-ene reaction were improved from 78% yield and 11:1 selectivity with azobis(isobutyronitrile) in batch mode to 91% yield and 90:1 selectivity with the two-component system in semibatch mode, further eliminating the need for a fractional distillation purification step.
LOW TEMPERATURE FREE RADICAL INITIATED PROCESS FOR THE PREPARATION OF 3-((3,3,3-TRIFLUOROPROPYL)THIO)PROPIONIC ACID AND ESTERS THEREOF
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Page/Page column 3; 4, (2016/04/01)
3-((3,3,3-Trifluoropropyl)thio)propionic acid and esters thereof are prepared by a low temperature free radical process involving the free radical coupling of 3-mercaptopropionic acid and esters thereof with 3,3,3-trifluoropropene. The ratio of linear to branched isomer is enhanced.
PROCESSES FOR THE PREPARATION OF PESTICIDAL COMPOUNDS
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Paragraph 0033-0034, (2015/04/28)
The present application provides processes for making pesticidal compounds and compounds useful both as pesticides and in the making of pesticidal compounds.