ChemInform Abstract: CHEMISTRY OF DIFLUOROCYCLOPROPYL ACETATES. APPLICATION OF DIFLUOROCARBENE CHEMISTRY TO HOMOLOGATION REACTIONS

Abstract

Das aus dem Chlordifluoracetat (II) in siedendem Diglyme freigesetzte Difluorcarben addiert sich an das Enolacetat (I) zum Addukt (III), dessen Hydrolyse in Gegenwart von Base in wäßrigem tert.‐Butanol ein Gemisch des cis‐ und trans‐Ketons (lV′ liefert.

Fatty acids containing photoactivable carbene precursors. Synthesis and photochemical properties of 3,3-bis(1,1-difluorohexyl)diazirine and 3-(1,1-difluorooctyl)-3H-diazirine

“…A yellow liquid (29 g, 85%) was thus obtained which on being distilled through a 15-cm Vigreux column yielded 93% pure , -difiuoro ketone 19 (20 g, 60%), bp 55-59 °C (0.5 mmHg), and a fraction (6 g, bp 62-75 °C) containing 65% irans-7-fluorododec-8-en-6-one (18).…”

“…Sodium chlorodifluoroacetate (20 g, 0.128 mol) in diglyme (50 mL) was added to a stirred solution of the trimethylsilyl enol ether 20 (18.7 g, 0.064 mol) in diglyme (100 mL) exactly as described for 16. Distillation through a 15-cm Vigreux column gave difiuoro ketone 18 (3 g) and the difluorocarbene adduct 21 (11.7 g, 58%, bp 71-78 °C (0.1 mmHg)) of 85% purity.…”

“…C6H13COCl latter, the , -difluoro ketone 19 was generated by solvolytic ring opening in cold methanolic potassium hydroxide. It was separated from the side product, 6-fluorododec-5,6-en-7-one (18), by distillation and was obtained in 40% yield.…”

The synthesis and photochemical behaviour of some annelated tropones

“…H, dd, J7.8 and 1 8. Hz,4-H),8.83 (1 H, dd, J4.6 and 1 8. Hz, 2-H); miz 317, 319, and 321 ((a).-A mixture of the dibromoketone (47) (4.0 g) and lithium carbonate (3 g) in dimethylformamide (500 ml) was stirred and boiled under nitrogen (5 h).…”

“…(7).-This compound was prepared as reported by reduction of the acid (6), in virtually quantitative yield; 6 (2 H, s). (8).-This compound was prepared by decarboxylation of the acid (7) (80%), b.p. 142-143 "ClO.17 mmHg (lit.," b.p.…”