5718-75-2Relevant articles and documents
Synthesis process of isothiocineole
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Paragraph 0022; 0033; 0040-0041; 0042; 0049-0050; 0051; 0058, (2019/10/23)
The invention discloses a synthesis process of isothiocineole, and relates to the technical field of synthesis of isothiocineole. Alpha-terpineol is taken as an initial raw material, and is sequentially subjected to halogenation reaction, nucleophilic substitution reaction, elimination reaction and Michael addition reaction to prepare a crude isothiocineole product, and the crude isothiocineole product is rectified to obtain a pure isothiocineole product. The synthesis process has the advantages of high yield, low cost, simple operation, suitability for industrial production and the like.
Practical and highly selective sulfur ylide-mediated asymmetric epoxidations and aziridinations using a cheap and readily available chiral sulfide: Extensive studies to map out scope, limitations, and rationalization of diastereo- and enantioselectivities
Illa, Ona,Namutebi, Mariam,Saha, Chandreyee,Ostovar, Mehrnoosh,Chen, C. Chun,Haddow, Mairi F.,Nocquet-Thibault, Sophie,Lusi, Matteo,McGarrigle, Eoghan M.,Aggarwal, Varinder K.
supporting information, p. 11951 - 11966 (2013/09/02)
The chiral sulfide, isothiocineole, has been synthesized in one step from elemental sulfur, γ-terpinene, and limonene in 61% yield. A mechanism involving radical intermediates for this reaction is proposed based on experimental evidence. The application of isothiocineole to the asymmetric epoxidation of aldehydes and the aziridination of imines is described. Excellent enantioselectivities and diastereoselectivities have been obtained over a wide range of aromatic, aliphatic, and α,β-unsaturated aldehydes using simple protocols. In aziridinations, excellent enantioselectivities and good diastereoselectivities were obtained for a wide range of imines. Mechanistic models have been put forward to rationalize the high selectivities observed, which should enable the sulfide to be used with confidence in synthesis. In epoxidations, the degree of reversibility in betaine formation dominates both the diastereoselectivity and the enantioselectivity. Appropriate tuning of reaction conditions based on understanding the reaction mechanism enables high selectivities to be obtained in most cases. In aziridinations, betaine formation is nonreversible with semistabilized ylides and diastereoselectivities are determined in the betaine forming step and are more variable as a result.
REACTION OF SULFUR HALIDES WITH UNSATURATED COMPOUNDS. XX. REACTION OF SULFUR DICHLORIDE WITH 1-METHYL-4-ISOPROPENYL- AND 1,4-DIMETHYL-4-VINYL-1-CYCLOHEXENES. SYNTHESIS OF THIABICYCLOOCTANES AND THIABICYCLONONANES
Tolstikov, G. A.,Lerman, B. M.,Komissarova, N. G.,Zelenova, L. M.
, p. 283 - 291 (2007/10/02)
The reaction of 1-methyl-4-isopropenyl- and 1,4-dimethyl-4-vinyl-1-cyclohexenes with sulfur dichloride gave the corresponding methyl-substituted dichlorothiabicyclononanes.Reductive dechlorination of the latter led to mixtures of isomeric thiabicyclanes, from which dimethyl- and trimethyl-substituted 2-thiabicyclo- and 6-thiabicyclooctanes and 2-thiabicyclo- and 2-thiabicyclononanes were isolated; the effect of the nature of the reducing agent and the conditions on the isomeric composition of the thiabicyclanes was demonstrated.Acetolysis of 4,8-dichloro-5,8-dimethyl-2-thiabicyclononane is accompanied by the formation of two isomeric thiabicyclononadienes in addition to the corresponding hydroxy and acetoxy derivatives.
