Issue in Honor of Prof. Oleg N. Chupakhin ARKIVOC 2004 (xi) 9-15
benzene–ethyl acetate, 2:1. Compound 1 was obtained by a known method.3 “Ether” refers to diethyl ether.
General procedures for compounds 2a–d A mixture of compound 1 (3.91 g, 0.03 mole), acyl hydrazine (0.025 mole), and several drops of acetic acid in methanol (25 ml) was maintained at 25 °C for three days. After removal of the solvent under reduced pressure the residue was washed with ether, and recrystallized from a 2:1 hexane–ethyl acetate mixture, or purified on the column. 5-(2-Acetylhydrazine)-3,3,5-trimethylisoxazolidine (2a). (51%), m.p. 137–140 oC. 1H NMR (CDCl3) d/ppm: Z’-A form, (90%): 1.20, 1.22 (2s, 6H, 2CH3C(3)), 1.39 (s, 3H, CH3C(5)), 1.74,
1.96 (AB-system, JAB = 13 Hz, 2H, H-4), 1.95 (s, 3H, CH3CO), 4.82 (br. s, 1H, NH), 6.21 (br. s, 1H, NH), 8.37 (br. s, 1H, NHCO), E’-A form, (10%): 1.17 (s, 3H, CH3C(3)), 1.36 (s, 3H, CH3C(5)), 1.92 (s, 3H, CH3CO), 2.05 (s, 2H, H-4), 7.41 (br. s, 1H, NH). 13C NMR (CDCl3) dC/ppm: Z’-A form: 21.8 (CH3C=O), 22.8, 25.1 (2CH3C(3)), 28.6 (CH3C(5)), 52.8 (C(4)), 62.5 (C(3)), 100.1 (C(5)), 168.5 (C=O), E’-A form: 28.2 (CH3C(5)), 52.2 (C(4)), 60.7 (C(3)), 99.7 (C(5)), 175.8 (C=O). 13C NMR (solid phase) dC/ppm: Z’-A form, (100%): 22.3 (CH3C=O), 23.5 (2CH3C(3)), 29.1 (CH3C(5)), 53.1 (C(4)), 61.8 (C(3)), 99.8 (C(5)), 170.3 (C=O). Anal.: Calcd for C8H17N3O2 (187.24): C, 51.32; H, 9.15; N, 22.44. Found: C, 51.27; H, 9.20; N, 22.49%. 5-(2-Isopropanoylhydrazine)-3,3,5-trimethylisoxazolidine (2b). (55%), m.p. 123–125 oC. 1H NMR (DMSO-d6) d/ppm: Z’-A form, (100%): 1.01 (s, 6H, 2CH3C(3)); 1.14 (d, 6H, 2CH3CH); 1.79 (s, 3H, CH3C(5)); 2.16 (s, 2H, H-4); 2.37 (m, 1H, CH); 3.38 (br. s, 1H, NH); 8.03 (br. s, 1H, NH); 10.41 (br. s, 1H, NHCO). 13C NMR (DMSO-d6) dC/ppm: 20.5 (2CH3CH); 23.1; 24.6 (2CH3C(3)); 28.7 (CH3C(5)); 33.1 (CH); 53.0 (C(4)); 62.6 (C(3)); 100.4 (C(5)); 170.3 (C=O). 13C NMR (solid phase) dC/ppm: 21.2 (2CH3CH); 22.8 (2CH3C(3)); 28.3 (CH3C(5)); 33.5 (CH); 52.9 (C(4)); 62.0 (C(3)); 100.2 (C(5)); 172.6 (C=O). Anal. Calcd for C10H21N3O2 (215.29): C, 55.79; H, 9.83; N 19.52. Found: C, 55.83; H, 9.78; N, 19.47%. 4-Methyl-4-hydroxylaminopentan-2-one 2-thiobenzoylhydrazone (2c). (60%), m.p. 144–146oC. 1H NMR (CDCl3) d: A form, (10%): 1.15 (s, 6H, 2CH3C(3)), 1.53 (s, 3H, CH3C(5)), 1.81, 2.08 (AB-system, JAB = 12 Hz, 2H, H-4), E-B form, (60%), 1.28 (s, 6H, 2CH3), 1.98 (s, 3H, CH3C=N), 2.45 (s, 2H, CH2), 8.33 (br. s, 2H, NHOH), 10.11 (br. s, 1H, NHCO), Z-B form, (30%): 1.34 (s, 6H, 2CH3C–N), 1.97 (s, 3H, CH3C=N), 2.58 (s, 2H, CH2), 8.45 (br. s, 2H, NHOH), 7.38–7.74 (m, 5., C6H5 of A and E,Z-B forms). 1H NMR (CF3COOD) d: E-B form, (65%): 1.56 (s, 6H, 2CH3C–N), 2.29 (s, 3H, CH3C=N), 3.03 (s, 2H, CH2), Z-B form, (35%), 1.61 (s, 6H, 2CH3C–N), 2.20 (s, 3H, CH3C=N), 3.23 (s, 2H, CH2), 7.35–7.78 (m, 5., C6H5 of E-B and Z-B forms). 13C NMR (CF3COOD) dC E-B form, 16.5 (CH3C=N), 22.1 (2CH3C–N), 41.6 (CH2), 65.5 (C–N), 163.2 (C=N), 202.1 (C=S). Z-B form: 20.7 (CH3C=N), 22.4 (2CH3), 38.3 (CH2), 67.4 (C–N), 127.3–137.7 (C6H5 of E-B and Z-B forms), 163.9 (C=N), 201.5 (C=S). 13C NMR (solid phase) dC, E-B form, (100%): 18.6 (CH3C=N), 23.9, 25.4 (2CH3C–N), 44.4 (CH2), 59.7 (C–N), 124.2–138.3 (C6H5), 157.3 (C=N), 195.2 (C=S). Anal. Calcd for C13H19N3OS (265.38): C, 58.84; H, 7.22; N, 15.83. Found: C, 58.80; H, 7.27; N, 15.78%. ISSN 1424-6376 Page 13 ©ARKAT USA, Inc
