Small-Ring Compounds. XXXIII. A Study by Nuclear Magnetic Resonance of the Extent of Isotope-position Rearrangement in the Vapor-phase Photochlorination of methyl-¹³C-Cyclopropane¹

Alkoxycarbonyl‐ and Carboxylate‐Group Migrations in the Benzilic Acid Rearrangement of Ethyl Cyclopropane‐2, 3‐dioxopropionate

“…We prepared C3H,-CO-CO-COOEt (lb), a yellow oil, according to [ 5 ] ; the I3C-labelled substrate [3-13C]-lb (lb") was prepared in the same way, starting from C3H5-13COOH [6]. In aqueous solution l b is colourless, owing to hydration of the a-carbonyl group; this is borne out by the NMR.…”

“…-Cyclopropyl methyl [2-13C/ketone (method: 11 I]). A solution of methyllithium (150 mmol) in 100 ml dry ether was added dropwise under an atmosphere of dry N2 to a solution of 8.0 g (92 mmol) of cy~lopropane['~C] acid (90% I3C, prepared from cyclopropylmagnesium bromide and 13C02, following [6]) in 100 mi dry ether. The mixture was decomposed by the addition of a sat.…”

Reactions involving electron transfer. VII. Use of intramolecular reactions as a test for anion radical intermediates

“…The same reaction procedure was repeated with 1.25 mmol of Me2CuLi and 236 mg (1.0 mmol) of the dienone 11 in 10 ml of Et20 to yield 237 mg (94%) of the crude ketone 23c (NMR analyses) which exhibited one major GLC peak (ret time 25.2 min) on a GLC column (Apiezon L on Chromosorb P) where the dienone 11 has a retention time of 14.1 min. A collected (GLC) sample of the pure ketones 23c was obtained as a colorless liquid: rr25D 1.4572; ir (CC14) 1705 cm-1 (C=0); NMR (CC14) 5.08 (1 H, t, J = 7 Hz, further partially resolved splitting apparent, vinyl CH), 1.2-2.5 (13 H, m, aliphatic CH including broad singlets at 1.59 and 1.67 attributable to the allylic CH3 groups), 1.10 (9 H, s, r-Bu), 0.84 (6 H, s, CH3), and 0.73 (3 H, d, J = 7 Hz, CH3); mass spectrum, m/e (rel intensity) 252 (M+, 1), 195 (32), 128 (83), 123 (65), 95 (28), 83 (25), 69 (100), 57 (73), 55 (20), 43 (54), and 41 (50).…”

Platinum Complexes of Bicyclopropylidene and Related Ligands

“…While the literature method reported yields of 82% for the synthesis of c PrCOOH, it was not possible to obtain yields of greater than 30%. 88 Br i) Mg, THF ii) Ba 13…”

“…Synthesis of Cyclopropanecarboxylic-carboxyl -13 C{ 1 H} Acid 88 Magnesium turnings (1.7 g, 0.070 mol) was placed in a 2-neck 100 mL RB flask equipped with a double surface condenser and a dropping funnel and dry stirred overnight. THF (25 mL) was added and bromocyclopropane (5.0 g, 0.413 mol) placed in the dropping funnel.…”