Intermediate 14d was obtained in 50% yield after chromatography. Hydrogenation yielded a foam, which gave 1.4 g (88%) of crystalline 15d, mp 195-198 °C, on trituration with EtOH.Recrystallization from EtOH gave pure 15d, mp 210-213 °C. AnaL (CzgH^NOa) C, , N. Intermediate 14e was obtained in 44% yield after chromatography. Hydrogenation of crude material containing 14e gave a 36% yield of 15e. The HC1 salt was obtained in crystalline form, mp 77-80 °C, from EtOH. After drying under high vacuum at room temperature overnight, 15e-HCl gave a mp of 105-115 °C.Anal. (C23H31N03-HC1) C, , N. Intermediate 14f was not purified but directly reduced to 15f, which was obtained in 50% yield after chromatography. The HC1 salt, mp 191-195 °C, was obtained as the EtOH solvate from EtOH-EtaO. Analysis, after drying at 80 °C under high vacuum, fashion to give a light yellow foam (2.0 g), which was shown by TLC to be an -9:1 mixture of 6a/60 20.7-(2-Oxopropyl)dihydrocodeine ( 21). The foam obtained above was dissolved in MeOH (20 mL), and 1 N HC1 (8 mL) was added. The solution was stirred for 20 min and then made basic with concentrated NH4OH, and the mixture was evaporated. Processing in the usual fashion gave 1.84 gofa foam, which showed one major spot on TLC. The foam was dissolved in 95% EtOH (25 mL), 1 N HC1 (8 mL) and 10% Pd/C (0.3 g) were added, and the mixture was hydrogenated at 50 psi for 1 h. Workup in the usual fashion gave a foam, which was chromatographed to give 838 mg (45%) of 21. Two crystallizations from EtOH gave pure 21: mp 71-73 °C; NMR 4.62 (d, 1 , H-5, J = 6 Hz). Anal.(C21H27N04) C, H, N.7-(2-Hydroxy-2-methylpropyl)dihydrocodeine ( 22). A solution of 21 (1.07 g, 3.0 mmol) in toluene (15 mL) was added dropwise to a 0 °C solution of MeLi (7.5 mmol) in EtgO (30 mL) under argon. Stirring was continued for 20 min and the mixture was quenched with water and processed in the usual manner to give a foam, which was chromatographed. Pure fractions were combined to give 824 mg (74%) of 22 as a foam. The tartrate salt of 22 could not be obtained in crystalline form. Anal.(C22H31N04.C4H606.H20) c, h, n.JV-(Cycloalkylmethyl)-7a-methyl-14-hydroxydihydromorphinone (26). A mixture of 23 (10 mmol) and DMF-DMA (10 mL) was refluxed in an oil bath for 3-4 h. The crystals which formed on cooling the mixture in ice were collected and washed with EtaO to give 25 (37% yield), mp 253-258 °C dec, or 25P (40% yield), mp 223-226 °C. 25B was not isolated from the mixture but directly hydrogenated. Intermediates 25 were hydrogenated in 95% EtOH as above to give 26 directly in 95% yield as impure crystals, mp 220-226 °C. Chromatography, followed by crystallization from EtOH, gave 26 •0.5 2 , mp 230-233 °C dec (lit.6 mp 226-228 °C). Anal. (C19H23N04-0.5H20) C, , N. 26P was obtained in 62% yield after chromatography and obtained as crystals, mp 113-114 °C, from EtOH. Anal.(C22H27N04) C, , N. 26B was obtained in 24% overall yield from 23B and was converted to the d-tartrate monohydrate, mp 200-203 °C. Anal. ( ^ ^ ,-, -, ) C, , N. Compo...