Cyclopropanes. XXX. Haller-Bauer cleavage of phenyl cyclopropyl ketones

Abstract

based on starting dione lb) of 4b-7-di after triturating the initial residue with 2-methylbutane, separating, distilling, and combining distillates. A 5.03-g portion of deuterated dienone was reduced with lithium aluminum deuteride, using the procedure described for the undeuterated case, and afforded 5.0 g (98%) of 5-l,7-d2, mp 75-77.5°. This was converted to 6.4 g (70%) of 5-l,7-d2 p-nitrobenzoate, mp 73-78°, which was solvolyzed in buffered acetic acid for 19 hr at room temperature. Work-up gave 4.09 g of product which yielded 0.36 g (5.6%) of dideuterated 8b after addition of 2-methylbutane and filtration. The remaining oil was subjected to preparative tic (development with 1:9 ether-hexane), giving 1.53 g of dideuterated 7 and 2.20 g of cloudy yellow oil which afforded 2.0 g of dideuterated acetate 8a as a clear oil after treatment with Norit in 2-methylbutane (<1% p-nitrobenzoate present). Pyrolysis of a 0.528-g portion of acetate yielded 0.279 g (72%) of a mixture of dienes which was separated by preparative glpc on column 2 (120°) into two fractions, the second of which (69 mg) was, by analytical glpc, a 90:10 mixture of 9b and dideuterated 7, respectively: nmr (CC14) 7.47 (triplet of septuplets, J = 5.8 and 1.3 Hz) and 4.56 (triplet of quartets, J = 5.8 and 1.4 Hz).

Structure, Synthesis, and Chemical Reactions of Fluorinated Cyclopropanes and Cyclopropenes

“…Not so commonly utilized, but nevertheless quite effective to their purpose, are reactions of carbenes, carbenoids, or diazo compounds with fluoroalkenes to form fluorocyclopropanes. Haszeldine's addition of dichlorocarbene to vinyl fluoride was the first reported example of such a reaction, and shortly thereafter, Walborsky made 1-fluorocyclopropanecarboxylic esters by a then-novel addition of a diphenyldiazomethane to ethyl α-fluoroacrylate …”

“…Haszeldine's addition of dichlorocarbene to vinyl fluoride was the first reported example of such a reaction, 64 and shortly thereafter, Walborsky made 1-fluorocyclopropanecarboxylic esters by a then-novel addition of a diphenyldiazomethane to ethyl R-fluoroacrylate. 65 In recent years, such additions have become more common. Taguchi has carried out chiral Simmon-Smith-type chemistry on functionalized fluoroalkenes, 66,67 Kirk has used diazomethane for a similar cyclopropanation of a β-fluoro-R,β-unsaturated ester, 68 and Haufe has used transition metal catalysis to add diazo esters to R-fluorostyrene, with the reaction exhibiting good diastereo-and enantioselectivity when chiral ligands were used with copper(I) triflate.…”

Cyclopropanes. 39. The configurational stability of the 1-isocyano-2,2-diphenylcyclopropyl anion

“…Triglyme (1.1 g, 6 mmol) dissolved in 1 mL of THF was added and the reaction mixture was stirred for 30 min at -72 °C. Excess of D20 was added and the crude product was purified to yield 184 mg (84%) of (+)-(S)-l-deuterio-2,2-diphenylcyclopropyl isocyanide (8), mp 128-129 °C, optical purity 99% (90% deuterium incorporation). IR and NMR spectra were identical with those of an authentic sample.…”

“…The reaction mixture was stirred for 30 min at -72 °C and quenched with an excess of MeOD. Purification of the crude product gave 210 mg (80% yield) of (-)-(R)-l-deuterio-2,2-diphenylcyclopropyl isocyanide (8) (90% deuterium incorporation), mp 128-130 °C, optical purity >99%. IR and NMR spectra were identical with those of an authentic sample.…”

Novel synthesis of primary arylamides from aryl methyl ketone oxidations using iodine in aqueous ammonia

“…On the other hand, this process represents a new variant of the Haller-Bauer reaction, [17][18][19] which allows the direct conversion of nonenolizable ketones to primary amides, with the advantage that strong bases such as sodium amide are not required.…”