Drefahl, G. published the artcileAmino alcohols. XX. Preparation of 1-substituted 2-piperidino-1-cyclohexanols, Product Details of C7H16N2, the publication is Journal fuer Praktische Chemie (Leipzig) (1966), 32(1-2), 69-86, database is CAplus.
cf. CA 64, 19600c. A series of cis- and trans-isomers of 1-substituted 2-piperidinocyclohexanols (I) was prepared 2-Chlorocyclohexanone (160 g.) added with stirring to refluxing 205 g. piperidine and 200 cc. MePh, heated 2 hrs. at 140° (bath), cooled, and treated with 300 cc. 5% NH4OH yielded 85-90 g. 2-piperidinocyclohexanone (II), b3 95-7°; II.HCl, m. 202-5° (EtOH-dioxane). II (0.1 mole) in 150 cc. dry Et2O added dropwise with cooling and stirring to 0.7 mole appropriate Grignard reagent in 250 cc. dry Et2O under argon and heated 1-2 hrs. at about 50° yielded the corresponding cis-I. The Grignard derivative from 0.6 mole alkyl or aryl halide and 15 g. Mg in 250 cc. dry Et2O treated under argon with stirring and cooling with 0.4 mole cyclohexanone in an equivalent amount Et2O slowly during about 6-8 hrs. and kept overnight, and the crude product heated 2-3 hrs. at 130-150° in the presence of a few crystals iodine yielded the following 1-substituted cyclohexenes (substituent, b.p./mm., and % yield given): iso-Bu, 169-71°/750, 18; cyclopentyl, 87-9°/ 12, 32; p-cumenyl, 148-52°/13, 35; p-PhC6H4, 180-2°/1.5 [m.p. 145-6° (iso-PrOH-C6H6), greenish blue fluorescence]. The appropriate III in about 2 volumes dry Et2O added with stirring and cooling to 0.5-0.6M o-HO2CC6H4CO2OH gave the corresponding 1-substituted 1,2-epoxycyclohexane (IV). The appropriate III (1 mole) added dropwise with stirring below 20° to 1 mole N-bromosuccinimide in 400 cc. H2O containing 1 cc. AcOH, stirred about 1 hr., and evaporated, and the oily, black-brown residue added dropwise at room temperature to 1 equivalent absolute KOH-MeOH and heated 0.5 hr. at 60° (bath) gave the corresponding IV. By these methods were prepared the following IV (R and b.p./mm. given): H 36-9°/25, Me 37-9°/14, Et 51-3°/14, Pr 62-4°/12, Bu 41-4°/1, Am 75-80°/3, iso-Pr 59-62°/12, iso-Bu 47-51°/2-3, iso-Am 67-71°/2-3, tert-Bu 64-8°/13, cyclopentyl 102-3°/12, cyclohexyl 117-18°/12 (m. 10-11°), Ph 131-3°/12, PhCH2 136-8°/12, PhCH2CH2 151-3°/12, p-MeC6H4 90-5°/0.4, p-cumenyl 102-10°/0.5, o-MeC6H4 79-84°/0.4, 1-C10H7 138-42°/ 0.6 (m. 61-3°). R, b.p./mm., n20D, % yield, m.p. of HCl salt; Me, 83-4°/0.6, 1.4914, 69, 198-200° (EtOH-dioxane); Et, 114-15°/1.3, 1.4933, 46, 189-92° (Me2CO-petroleum ether); Pr, 118-21°/1-1.1, 1.4895, 55, 163-6° (Me2CO-petroleum ether); Bu, 127-8°/0.9, 1.4882, 38, 182-4° (Me2CO); Am, 136-7°/0.8, 1.4871, 59, 191-4°; iso-Pr, 116-17°/1, 1.4944, 55, 208-10°; iso-Bu, 128-30°/1.6, 1.4874, 72, 193-5°; iso-Am, 132-3°/0.8, 1.4864, 73, 198-200°; tert-Bu, 118-19°/0.6, 1.4981, 21, 182-3°; cyclopentyl, 142-3°/0.7, 1.5111, 24, 220-2° (iso-PrOH); cyclohexyl, 151-2°/0.7 (m. 51-3°), 1.5103, 33, 231-3° (iso-PrOH); Ph, 158-60°/0.7 (m. 65-6°), 1.5423, 39, 237-9° (Bu2O-EtOH); PhCH2, 166-7°/0.6, 1.5432, 85, 234-6° (iso-PrOH); PhCH2CH2, 172-3°/0.5, 1.5362, 89, 210-12° (EtOH-dioxane); p-MeC6H4, 160-1°/0.8 (m. 54-5°), 1.5400, -, 247-9°; p-cumenyl, 168-9°/0.6, 1.5300, 66, 202-5° (iso-PrOH); p-PhC6H4, 214-18°/0.4 (m. 105-7°), -, 70, 231-4° (absolute EtOH); o-MeC6H4, 155-6°/0.6, 1.5398, 79, 265-6°; 1-C10H7, 204-5°/0.8 (m. 106-7°), -, 50, 220-3° (EtOH-Et2O) The appropriate IV and excess piperidine in 95% EtOH heated in a sealed tube or in an autoclave gave the corresponding trans-I. The crude cis- or traus-I in the 8-10 fold amount dry Et2O treated dropwise at 0-5° with the equivalent amount HCl-Et2O yielded the I.HCl. II in EtOH hydrogenated 3 hrs. at 65°/65 atm. yielded 66% cis-I (R = H), m. 93-4° (50% EtOH); HCl salt, m. 287-8° (iso-PrOH). R, b.p./mm., m.p., n20D, % yield, m.p. of HCl salt, moles piperidine used/mole IV, reaction time (hrs.), temperature; H, 82-5°/0.5, 35-6°, 1.4890, 46, 263-6°, 5, 5-6, 130°; Me, 97-8°/1, 43-4°, 1.4887, 37, 263-4°, 5, 6-8, 150°; Et, 110-12°/1.3, -, 1.4886, 59, 233-4°, 5, 6-8, 150°; Pr, 122-5°/1-1.2, 63-4°, 1.4886, 45, 217-18°, 5, 6-8, 150°; Bu, 131-3°/1, 52-3°, 1.4875, 40, 225-7°, 5, 6-8, 150°; Am, 146-8°/1.3, 37-9°, 1.4862, 19, 232-3°, 5, 6-8, 150°; iso-Pr, 116-17°/1, -, 1.4944, 55, 211-13°, 5, 8-9, 150°; iso-Bu, 113-14°/0.6, -1.4857, 12, 230-2°, 5, 10-11, 150°; iso-Am, 127-8°/0.6, 48-50°, 1.4843, 56, -, 5, 6-8, 150°; tert-Bu, 132-4°/1.3, -, 1.5072, 3.5, 178-80°, 8, 11-12, 150°; cyclopentyl, 140-1°/0.5, -, 1.5108, 40, 168-71°, 5, 7-9, 160°; cyclohexyl, 150-1°/0.6, -, 1.5140, 55, 218-19°, 5, 11-12, 180°; Ph, 158-9°/0.8, -, 1.5471, 30, 216-18°, 5, 5-6, 150°; PhCH2, -, 121-2°, -, 25, -, 5, 6-7, 150°; PhCH2CH2, -, 103-5°, -, 38, 239-41°, 5, 7-8, 160°; p-MeC6H4, 163-9°/0.4, 106-9°, -, 2.4, 284-6°, 8, 10-11, 175°; p-cumenyl, 150-3°/0.4, -, -, 2, 277-9°, 8, 10-11, 175°; o-MeC5H4, 135-6°/0.2, -, 1.5532, 3.7, 196-9°, 8, 9-10, 190°; 1-C10H7, 196-8°/0.3, 96-8°, -, 14, 166-9°, 15, 9-10, 220° By the general method described were prepared the cis-I listed in the 1st table. By the general method were prepared the trans-I listed in the 2nd table.
Journal fuer Praktische Chemie (Leipzig) published new progress about 14613-37-7. 14613-37-7 belongs to piperidines, auxiliary class Piperidine,Amine, name is (1-Methylpiperidin-3-yl)methanamine, and the molecular formula is C7H16N2, Product Details of C7H16N2.
Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem