Cyclopropyl amine rearrangement

Abstract

signal above 2.4 ppm; mass spectrum m/e 460 (M+), 445 (M+ -CHS), 432 (M+ -CO), 400 (M+ -COS), 316 (M+ -144).

Synthesis of some 4-substituted pentacyclo[4.3.0.02,403,805,7]nonane derivatives and their reactions. Cyclopropane ring expansion and cleavage

“…Primary cyclopropylamine has recently been shown to rearrange with base, similar to the well-known cyclopropanol rearrangement. 15 For example, l-methyl-2,2-diphenylcyclopropylamine gives 4,4-diphenyl-2-butanone on treatment with aqueous sodium bicarbonate at room temperature. 15 The present pentacyclic system was converted to appropriate cyclopropylamine derivatives [19][20][21][22] and their base-catalyzed rearrangement was examined (Scheme II).…”

Ring-opening reactions of certain 2-carbonyl-substituted cyclopropylamines

“…Excess SOCl2 was removed by distillation and residual portions were azeotroped with anhydrous benzene. Distillation of the residue gave 12.2 g (85%) of product: bp 52-53°(0.35 mm); ir (film) 1790 (acyl chloride C=0), 1730 cm-1 (ester C=0); nmr (CCI4) 1.20-2.80 (m, 4 H, ring H), 3.73 (s, 3 H, OCH3).…”

“…The reaction mixture was extracted with four 50-ml portions of Et20. The combined extracts were dried (MgS04), and filtered, and the Et20 was removed to leave an oil which distilled at 89-92°(0.05 mm) to yield 1.15 g (48%) of product: ir (film) 2730 (CHO), 1730-10 cm"1 (ester, aldehyde C=0); nmr (CDClg) 2.72 (t, 4 H, CH2 CH2), 5.13 (s, 2 H, CH2Ph), 7.37 (s, 5 H, ArH), 9.78 Concentration of the aqueous solution from the Et20 extraction and addition of anhydrous EtOH to the residue afforded 0.55 g (78%) of a white solid which gave a positive test for chloride with AgNOg and which liberated NHg upon addition of NaOH; nmr (D20) revealed no C-H signals.…”