Pegolotti, J. A. published the artcileAllylic rearrangements. L. Reactions of α- and γ-trifluoromethylallyl alcohols with thionyl chloride and thermal decomposition of the chlorosulfinate intermediates, Synthetic Route of 83706-94-9, the publication is Journal of the American Chemical Society (1961), 3251-8, database is CAplus.
The reactions of α-(trifluoromethyl)allyl alc. (I) and γ-(trifluoromethyl)allyl alc. (II) with SOCl2 in Et2O and SOCl2 were investigated. In the absence of amines, I in either solvent yielded α-(trifluoromethyl)allyl chlorosulfinate (III) only. With I, Bu3N, and SOCl2 (equimolar in ether) the products were 68% III and 32% γ-(trifluoromethyl)allyl chloride (IV) after 1 hr. The presence of Bu3NHCl in the mixture gave small amounts of IV. II and SOCl2 in ether yielded γ-(trifluoromethyl)allyl chlorosulfinate (V), which slowly gave IV on standing. In the presence of Bu3N, II and SOCl2 gave IV exclusively. III and V, the first isolable allylic chlorosulfinates outside of allyl chlorosulfinate itself, were thermally decomposed with no solvent and in n-decane and nitrobenzene and the rates of decomposition measured by the rate of evolution of SO2 [compound, solvent, decompn, temperature, and rate (105k. sec.-1, extrapolated to 100°) given]: III, none (3 runs), 108-110° (103°, 105-106°), 6.5 (6.2, 7.3); III, nitrobenzene, 106-108°, 10.0; III, n-decane, 124°, 1.5; V, none (2 runs), 105° (139-142°), 126 (0.27); V, nitrobenzene (2 runs), 115-116° (118-120°), 5.1 (8.8). The insensitivity of the decomposition to solvent was explained in terms of a concerted reaction with predominant covalent character maintained in the intermediate through the rearrangement sequence. II was prepared by the procedure of McBee (CA 49, 10171b). I was prepared by addition of CF3CHO to the Grignard reagent from vinyl bromide and Mg in tetrahydrofuran; I formed an azeotrope, b. 102-3°, with the solvent. Chromatography of the azeotrope gave I, b. 91.5°, n25D 1.3450. The α-napthylurethan of I m. 121-3°. Adding 8.9 g. SOCl2 to 9.4 g. II and 13.9 g. Bu3N over 30 min. at 0°, stirring 1 hr., then flash distilling gave IV, b. 82.5-83°, n25D 1.3610. γ-(Trifluoromethyl)allyl n-amyl sulfite (VI) was prepared by adding dropwise over 30 min. a mixture of 3.0 g. II and 1.9 g. anhydrous pyridine to a cooled (-20 to -30°) solution of 5.12 g. n-amyl chlorosulfinate in ether. H2O was added after 45 min., the layers separated, the ether layer washed, dried, and distilled to yield 2.05 g. VI, b4 100-102°, n25D 1.4099. α-(Trifluoromethyl)allyl n-amyl sulfite (VII) was prepared similarly, b5 80-2°, n25D 1.4030. Addition of 4.86 g. SOCl2 in ether to a stirred solution of 3.57 g. II in 60 ml. ether at 0° and distillation gave 1.23 g. V, b6 55°, n25D 1.4089. Reaction of V with n-amyl alc. gave VI. Addition of 3.1 g. I to 14.3 g. SOCl2 and 5.3 g. Bu3N over 45 min. at 0°, with stirring continued 1 hr., and distillation gave 2.78 g. III, b39 52°, n25D 1.4088. Reaction of III with n-amyl alc. gave VII. The refractive indexes of III and V did not change during 5 min. in the refractometer.
Journal of the American Chemical Society published new progress about 83706-94-9. 83706-94-9 belongs to alcohols-buliding-blocks, auxiliary class Trifluoromethylated Building Blocks, name is (E)-4,4,4-Trifluorobut-2-en-1-ol, and the molecular formula is C4H5F3O, Synthetic Route of 83706-94-9.
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