Methane → HCID 15035848, compound

To a mixture of KOH pellets (85%, 3.96 g, 60 mmol) and the ketone (26, 1.0 g, 5 mmol) in triethylene glycol (25 mL) was added hydrazine (95%, 1.69 g, 50 mmol) in one portion in a 70 mL, jacketed flask equipped with a magnetic stirrer, a heating mantle, a standard condenser, a lower take-off condenser with a N2 inlet, and two glass stoppers. A heating temperature of 200°-210° C. for 5 h was produced by boiling tetralin (bp 207° C.) in the jacket. After cooling to RT, the solution was diluted with chilled water (100 mL) and extracted with ether (4×50 mL). Combined extracts were washed with 10% NaOH (50 mL) and saturated NaCl (50 mL), dried (Na2SO4, overnight), filtered, and concentrated to a yellow oil (0.8 g). Dissolution of the oil in ether (50 mL) via magnetic stirring and cooling (5° C.) with an external ice bath was followed by dropwise addition of a solution of HClO4 (60%, 1.08 g, 6.45 mmol) in isopropyl alcohol (3 mL) over 10 min. Stirring of the mixture an additional 10 min, filtering the precipitated salt, and then washing the latter with ether (~50 mL) gave an off-white solid. Dissolving the salt in hot 95% EtOH and decolorizing the solution with Norit, followed by filtering, and cooling, afforded 0.91 g (63.6%) of salt (8) as a white solid; mp 281°-282.5° C. IR (KBr) cm-1 3060 (N--H), 3000, 2960, 2935 (C--H), 1090 (Cl--O); 1H NMR (DMSO-d6) δ1.28 (d, 6H, CH3), 1.76 [d, 1H, H(9), J=13.3 Hz], 1.91 [d, 1H, H(9), J=12.9 Hz], 2.35 [bs, 2H, H(1,5)], 2.78 [bd, 2H, H(2,4)ax, J=12.2 Hz], 3.14 [bd, 2H, H(2,4)eq, J=13.6 Hz], 3.29-3.57 [m, 3H, H(6,8)ax and CH(CH3)2 ], 3.62 [d, 2H, H(6,8)eq, J=12.7 Hz], 9.07 (bs, 1H, N--H); 13C NMR (DMSO-d6) ppm 16.19 (q, CH3), 25.51 [d, C(1,5)], 28.35 [t, C(9)], 30.69 [t, C(2,4)], 52.36 [t, C(6,8)], 58.66 [d, CH(CH3)2 ]; 15N NMR (DMSO-d6) ppm 58.47 [N(7)]. Anal. Calcd. for C10H20ClNO4S: C, 42.03; H, 7.05. Found: C, 42.10; H, 7.18.

1. customequipped with a magnetic stirrer
2. customA heating temperature of 200°-210° C. for 5 h was produced
3. extractionextracted with ether (4×50 mL)
4. washCombined extracts were washed with 10% NaOH (50 mL) and saturated NaCl (50 mL)
5. dry with materialdried (Na2SO4, overnight)
6. filtrationfiltered
7. concentrationconcentrated to a yellow oil (0.8 g)
8. dissolutionDissolution of the oil in ether (50 mL)
9. temperaturecooling (5° C.) with an external ice bath
10. stirringStirring of the mixture an additional 10 min
11. filtrationfiltering the precipitated salt
12. washwashing the latter with ether (~50 mL)
13. customgave an off-white solid
14. filtrationby filtering
15. temperaturecooling

ORD record

ord-059803797ed74304843e849b30b1669e

Source dataset

uspto-grants-1992_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05110933