аЯрЁБс>ўџ ,.ўџџџ+џџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџьЅС7 №ПоbjbjUU 7|7|ТџџџџџџlЄђђђ8*> Є `VV(~~~‘‘‘!!!!!!$  „E‘‘‘‘Em~~Zmmm‘~~~m‘mŽmћћ~J 0§Jn}ПЄNђvћћ$p0 ћЄ…шЄћmЄЄйSynthesis of trans-2-(1-Aryl-1-methylethyl)cyclohexylamines Wen-yee Lee, James M. Salvador*, Kalavathi Bodige Department of Chemistry, University of Texas at El Paso, El Paso, Texas 79968 james@salvador.chemistry.utep.edu Supporting Information: Synthesis of N-(Diphenylphosphinoyl)-7-azabicyclo[4.1.0]heptane (1).6 trans-2-Aminocyclohexanol (5.75 g, 50 mmol) and triethylamine (15.17 g, 20.90 mL, 150 mmol) were mixed in tetrahydrofuran (THF, 200 mL). The solution was cooled to 0 (C under a nitrogen atmosphere before diphenylphosphinic chloride (23.66 g, 19.08 mL, 100 mmol) was added dropwise. The mixture was stirred at room temperature for twenty hours. Excess sodium hydride (6.20 g, 258 mmol, > 5 equivalents) was then added and the mixture was stirred overnight. The reaction was cooled in an ice bath and carefully quenched with water. A yellowish crude material was obtained after filtration. Recrystallization from hexanes and ethyl acetate gave the product as a white solid (mp 161-162 (C) in seventy five percent yield. Elemental analysis calculated for C18H20NOP: C, 72.71; H, 6.78; N, 4.71; Found: C, 72.24; H, 6.88; N, 4.56. 1H NMR (CDCl3): ( 7.96-7.88 (m, 4H), 7.48-7.42 (m, 6H), 2.98 (t, 1H, J = 1.26 Hz), 2.86 (t, 1H, J = 1.26 Hz), 2.04-1.77 (m, 4H), 1.65-1.57 (m, 2H), 1.55-1.28 (m, 2H). 13C NMR: 134.70, 132.69, 131.49, 128.40, 128.20, 34.66, 23.92, 19.84. IR (KBr): 3046, 2994, 2923, 2861, 1438, 1244, 1194((P=O), 1122, 1112, 1044, 1011, 938, 850, 727, 700, 550, 505 cm-1. MS (Direct Laser Desorption/Ionization): 297.681, 154.074, 95.96, 55.98, 38.98, 23.02. Synthesis of trans-2-(1-Methyl-1-phenylethyl)-N-(diphenylphosphinoyl) cyclohexylamine (2a).4,5 To an oven-dried 100 mL flask with nitrogen atmosphere was added cumene (2.404 g, 2.78 mL, 20 mmol), potassium tert-pentoxide (18 wt % in cyclohexane, 5.5 mL, 6 mmol) and n-butyllithium (2.5 M solution in hexane, 2 mL, 5 mmol) dropwise. After the resulting purple suspension was stirred for two days at room temperature, aziridine 1 (0.297 g, 1 mmol) was added into the flask and the mixture was stirred for five days. The reaction was quenched with saturated ammonium chloride. The organic layer was washed with saturated ammonium chloride (3(50 mL) and the aqueous layer was back-extracted with ethyl acetate (3(20 mL). The combined organic layers were dried over anhydrous potassium carbonate and filtered. The solvent was removed at reduced pressure and unreacted cumene was removed by bulb-to-bulb distillation. 2a was obtained as a white solid (mp 171-172 (C) in seventy percent yield by recrystallization from hexanes and ethyl acetate. Elemental analysis calculated for C27H32NOP: C, 77.66; H, 7.73; N, 3.36; Found: C, 77.36; H, 7.86; N, 3.23. 1H NMR (CDCl3): ( 7.53-6.91 (m, 15H), 3.20 (td, 1H, J = 6.32, 3.86 Hz), 2.47 (t, 1H, J = 6.62 Hz), 2.04-1.97 (m, 4H), 1.68-1.38 (m, 4H), 1.38 (s, 3H), 1.08 (s, 3H). 13C NMR: 152.09, 135.36, 134.14, 133.31, 131.89, 131.74, 131.31, 131.15, 128.48, 128.31, 128.11, 127.92, 125.36, 125.24, 54.01, 51.60, 39.85, 37.54, 32.10, 27.25, 26.33, 25.03, 21.02. IR (KBr): 3365((NH), 3057, 2951, 2932, 2855, 1437, 1197((P=O), 1120, 1086, 899, 750, 721, 687, 544 cm-1. Preparation of trans-2-(1-Methyl-1-phenylethyl)cyclohexylamine (3a).4 To 2a (0.834 g, 2 mmol) dissolved in dichloromethane (5 mL) was added trifluoroacetic acid (1 mL) dissolved in dichloromethane (1 mL). The mixture was stirred for three hours before the removal of solvent at reduced pressure. Anhydrous potassium carbonate (3 g) and diethyl ether (10 mL) were then added and stirred for another five hours. The mixture was filtered and washed with diethyl ether (30 mL) to give the resulting colorless amine (3a, oil) in ninety percent yield without further purification. 1H NMR (CDCl3) ( 7.41-7.13 (m, 5H), 2.63 (td, 1H, J = 9.99, 3.87 Hz), 1.86-1.03 (m, 15H, including 1.38 (s, 3H) and 1.21(s, 3H)). 13C NMR ( 152.65, 128.46, 125.52, 125.37, 54.15, 53.56, 40.05, 37.32, 30.61, 27.10, 26.55, 25.56, 22.50. 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