Dicyclic Hydrocarbons. III. Diphenyl- and Dicyclohexylalkanes through C₁₅

Abstract

were used for determination of infrared spectra which were obtained with a Perkin-Elmer infrared spectrometer, Model 12-c. 3a-Hydroxy-11,20-diketo- Alb-pregnene (II).--111 a solution of 30 ml. of acetic acid and 10 ml. of water, 3.065 g. of 3a-hydroxy-21-acetoxy -11,aO-diketo-12a -bromo -AI6-pregnene (I) was stirred for ten minutes a t 15" with 6 g. of zinc dust. The suspended material was removed by filtration, washed \+ith methanol and the combined filtrates were evaporated under reduced pressure nearly to dryness. Addition of water precipitated material which weighed 1.9 g. Crystallization four times fr?m methanol-water gave material which melted a t 220-222 , [cY]'~"D S91' (CHCla), Xms, 235 mp, e 7,400. Sinety-eight per cent. of the theoretical amount of hromide ion was present in the aciii~ous ph:tse.ilnal. Calcd. for CLiH1~O1: C, 76.34; 13, 9.15. Fomtl: C' , 76.10; €1, 9.07. LYhen treatment with zinc was carried out a t 15" for three minutes a 71% yield of I1 was obtained, n1.p. 208-3~~,2Oa-Dihydroxy-ll-keto-Al@-pregnene (III).-The combined mother liquors from the preceding experiment (I1 from 3.065 g. of I ) were concentrated under reduced pressure and yielded 800 mg. of crystalline solid. Recrystallization from ethyl acetate gave a product m-hich melted at 1&3-185", [ ( Y ]~~" D +61' (CHC13). When treatment with zinc was extended to 130 minutes at 30-38", the yield of crude material, m.p. 178-1XOo, [ a ] 2 4~ +60° (CHCld), was 43%. Recrystallization several times from ethyl acetate raised the melting point to 189-190°, [ a ] z 4~ +57" (CEfC13j. This compound did not have an absorption maximum between 225 and 250 m p and did not show an acetate band in the infrared spectrum. It gave a negative a-keto1 test with alkaline 2,3,5-triphenyltetrazolium chloride reagent and a positive test for unsaturation with tetranitromethane. a solution of 990 mg. of 3a-hydroxy-l1,20diketo-~~~-pregnene in 4 ml. of chloroform and 1 rnl. of acetic acid was added 0.33 ml. (130%) of 28.7 N aqueous chromic acid. After vigorous stirring for 15 minutes a t O", 0.33 ml. of 18 N sulfuric acid was added and the mixture was stirred for one hour a t 0". Water and chloroform were added and the organic phase was washed with dilute hydrochloric acid, a 5% solution of sodium carbonate, and with water, dried and evaporated under reduced pressure. Crystallization from mrthanol afforded 446 mg. of product which melted at 196-). 198". Addition of water to the methanol gave 306 mg. as a second crop, m.p. 180-185°. Recrystallization of the firzt crop from methanol raised the melting point to 20*5-210 , Anal. Calcd. for CaH&: C, 76.80; H, 8.39. liound: C, 76.97; H, 8.57.da-Hydroxy-l1,2O-diketopregnane (V) .-Hydrogenation of 500 mg. of 3~~-hydroxy-ll,20-diketo-A~~-pregnene was carried out in 10 ml. of methanol with 1.5 g. of 2% palladium hydroxide on calcium carbonate at room temperature and atmospheric pressure. After 11 minutes the catalyst mas filtered out, the solution was concentrated under reduced pressure, the product was precipitated wit...

Carbon‐13 NMR relaxation studies of some dicyclohexyl compounds at high pressure

“…DCP and DCE were synthesized by the high-pressure hydrogenation of the aromatic analogues. 26 The 13C NMR spectra of all four compounds showed no trace of impurities; the spectral assignments have been given elsewhere.4…”

Kinetic Resolution of Isoxazolidines by a Pd−BINAP Complex

“…Commercially available compounds were used without further purification. N-(2-Ethoxy-2-oxoethylidene)methylamine N-oxide, [9] N-(2-ethoxy-2-oxoethylidene)benzylamine N-oxide, [9] N-(benzylidene)methylamine N-oxide, [10] N-(2-isopropoxy-2-oxoethylidene)methylamine N-oxide, [9] N-(2-benzyloxy-2-oxoethylidene)methylamine N-oxide, [9] 1,1-diphenylpropene, [11] [Pd{(S)-BINAP}(CH 3 CN) 2 ](BF 4 ) 2 (3), [4c] [Ru{(S)-BINAP}(OTf) 2 ], [12] and [Pd{(S)-TolBINAP}(CH 3 -CN) 2 ](BF 4 ) 2 (4) [4c] were prepared by literature methods. Isoxazolidines 1aϪ1i were prepared by treatment of the corresponding N-(alkylidene)methylamine N-oxides with the corresponding olefins.…”

Oxidation of Aryl- and Diarylcyclopropanes in a Pentasil Zeolite: Ring Opening with Deprotonation or Net Hydrogen Migration

“…cis-and trans-1,3-Diphenylpropene (3): A mixture of these compounds was prepared by dehydration of 1,3-diphenylpropan-2-ol [32] or, in better yields, by base-catalyzed aldol condensation of phenylacetaldehyde. [33] trans-1-Methyl-2-phenylcyclopropane (trans-5): trans-5 was prepared by a modified Simmons-Smith [25] addition of methylene (from CH 2 I 2 ) to trans-1-phenylpropene in 1,4-dioxane.…”