The dealkylation of tertiary aliphatic amines with phenyl chlorothionoformate

Tetrahedron Letters

Volumn 39, Issue 24, 1998, Pages 4387-4390

  Millan, David S ^a   Prager, Rolf H ^a  

^a FLINDERS UNIVERSITY   (Australia)

Author keywords

[No Author keywords available]

Indexed keywords

ALIPHATIC AMINE; CHLORIDE; URETHAN DERIVATIVE;

ARTICLE; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; DEALKYLATION; HYDROLYSIS;

EID: 0032507916     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)00743-6     Document Type: Article

References (22)

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3. 2. Gadamer, J.; Knoch., F. Arch. Pharm. 1921, 259, 135-135; Flynn, E.H.; Murphy, H.W.; McMahon, R.E. J. Am. Chem. Soc. 1955, 77, 3104-3106; Campbell, J.A. J. Org. Chem. 1957, 22, 1259-1260.
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8. 5. Vinyl chloroformate: Olofson, R.A.; Schnur, R.C.; Bunes, L.; Pepe, J.P. Tetrahedron Lett. 1977, 1567-1570.
9. 6. 2,2,2-Trichloroethyl chloroformate: Montzka, T.A.; Matiskella, J.D.; Partyka, R.A. Tetrahedron Lett. 1974, 1325-1327.
10. 7. Potassium permanganate: Willstatter, R. Ber. Dtsch. Chem. Ges. 1896, 29, 1575-1584; Werner, G.; Hackel, R.; Mohammad, N.; Seiler, N.; Stoor, K.-H. Liebigs Ann. Chem. 1967, 708, 210-217. Potassium ferricyanate: Findlay, S.P. J. Am. Chem. Soc. 1953, 75, 3204-3208. Oxygen: Beckwith, A.L.J.; Eichinger, P.H.; Mooney, B.A.; Prager, R.H. Aust. J. Chem. 1983, 36, 719-739; Kovtum, G.A.; Aleksandrov, A.L. Izv. Akad. Nauk. SSSR, Ser. Chim. 1974, 1274-1279; (Chem . Abstr. 1974, 81, 177130r). Nitrous acid: Wegler, R.; Frank, W. Ber. Dtsch. Chem. Ges. 1936, 69, 2071-2077; Ber. Dtsch. Chem. Ges. 1937, 70, 1279-1287.
11. 7. Potassium permanganate: Willstatter, R. Ber. Dtsch. Chem. Ges. 1896, 29, 1575-1584; Werner, G.; Hackel, R.; Mohammad, N.; Seiler, N.; Stoor, K.-H. Liebigs Ann. Chem. 1967, 708, 210-217. Potassium ferricyanate: Findlay, S.P. J. Am. Chem. Soc. 1953, 75, 3204-3208. Oxygen: Beckwith, A.L.J.; Eichinger, P.H.; Mooney, B.A.; Prager, R.H. Aust. J. Chem. 1983, 36, 719-739; Kovtum, G.A.; Aleksandrov, A.L. Izv. Akad. Nauk. SSSR, Ser. Chim. 1974, 1274-1279; (Chem . Abstr. 1974, 81, 177130r). Nitrous acid: Wegler, R.; Frank, W. Ber. Dtsch. Chem. Ges. 1936, 69, 2071-2077; Ber. Dtsch. Chem. Ges. 1937, 70, 1279-1287.
12. 7. Potassium permanganate: Willstatter, R. Ber. Dtsch. Chem. Ges. 1896, 29, 1575-1584; Werner, G.; Hackel, R.; Mohammad, N.; Seiler, N.; Stoor, K.-H. Liebigs Ann. Chem. 1967, 708, 210-217. Potassium ferricyanate: Findlay, S.P. J. Am. Chem. Soc. 1953, 75, 3204-3208. Oxygen: Beckwith, A.L.J.; Eichinger, P.H.; Mooney, B.A.; Prager, R.H. Aust. J. Chem. 1983, 36, 719-739; Kovtum, G.A.; Aleksandrov, A.L. Izv. Akad. Nauk. SSSR, Ser. Chim. 1974, 1274-1279; (Chem . Abstr. 1974, 81, 177130r). Nitrous acid: Wegler, R.; Frank, W. Ber. Dtsch. Chem. Ges. 1936, 69, 2071-2077; Ber. Dtsch. Chem. Ges. 1937, 70, 1279-1287.
13. 7. Potassium permanganate: Willstatter, R. Ber. Dtsch. Chem. Ges. 1896, 29, 1575-1584; Werner, G.; Hackel, R.; Mohammad, N.; Seiler, N.; Stoor, K.-H. Liebigs Ann. Chem. 1967, 708, 210-217. Potassium ferricyanate: Findlay, S.P. J. Am. Chem. Soc. 1953, 75, 3204-3208. Oxygen: Beckwith, A.L.J.; Eichinger, P.H.; Mooney, B.A.; Prager, R.H. Aust. J. Chem. 1983, 36, 719-739; Kovtum, G.A.; Aleksandrov, A.L. Izv. Akad. Nauk. SSSR, Ser. Chim. 1974, 1274-1279; (Chem . Abstr. 1974, 81, 177130r). Nitrous acid: Wegler, R.; Frank, W. Ber. Dtsch. Chem. Ges. 1936, 69, 2071-2077; Ber. Dtsch. Chem. Ges. 1937, 70, 1279-1287.
14. 7. Potassium permanganate: Willstatter, R. Ber. Dtsch. Chem. Ges. 1896, 29, 1575-1584; Werner, G.; Hackel, R.; Mohammad, N.; Seiler, N.; Stoor, K.-H. Liebigs Ann. Chem. 1967, 708, 210-217. Potassium ferricyanate: Findlay, S.P. J. Am. Chem. Soc. 1953, 75, 3204-3208. Oxygen: Beckwith, A.L.J.; Eichinger, P.H.; Mooney, B.A.; Prager, R.H. Aust. J. Chem. 1983, 36, 719-739; Kovtum, G.A.; Aleksandrov, A.L. Izv. Akad. Nauk. SSSR, Ser. Chim. 1974, 1274-1279; (Chem . Abstr. 1974, 81, 177130r). Nitrous acid: Wegler, R.; Frank, W. Ber. Dtsch. Chem. Ges. 1936, 69, 2071-2077; Ber. Dtsch. Chem. Ges. 1937, 70, 1279-1287.
15. 7. Potassium permanganate: Willstatter, R. Ber. Dtsch. Chem. Ges. 1896, 29, 1575-1584; Werner, G.; Hackel, R.; Mohammad, N.; Seiler, N.; Stoor, K.-H. Liebigs Ann. Chem. 1967, 708, 210-217. Potassium ferricyanate: Findlay, S.P. J. Am. Chem. Soc. 1953, 75, 3204-3208. Oxygen: Beckwith, A.L.J.; Eichinger, P.H.; Mooney, B.A.; Prager, R.H. Aust. J. Chem. 1983, 36, 719-739; Kovtum, G.A.; Aleksandrov, A.L. Izv. Akad. Nauk. SSSR, Ser. Chim. 1974, 1274-1279; (Chem . Abstr. 1974, 81, 177130r). Nitrous acid: Wegler, R.; Frank, W. Ber. Dtsch. Chem. Ges. 1936, 69, 2071-2077; Ber. Dtsch. Chem. Ges. 1937, 70, 1279-1287.
16. 7. Potassium permanganate: Willstatter, R. Ber. Dtsch. Chem. Ges. 1896, 29, 1575-1584; Werner, G.; Hackel, R.; Mohammad, N.; Seiler, N.; Stoor, K.-H. Liebigs Ann. Chem. 1967, 708, 210-217. Potassium ferricyanate: Findlay, S.P. J. Am. Chem. Soc. 1953, 75, 3204-3208. Oxygen: Beckwith, A.L.J.; Eichinger, P.H.; Mooney, B.A.; Prager, R.H. Aust. J. Chem. 1983, 36, 719-739; Kovtum, G.A.; Aleksandrov, A.L. Izv. Akad. Nauk. SSSR, Ser. Chim. 1974, 1274-1279; (Chem . Abstr. 1974, 81, 177130r). Nitrous acid: Wegler, R.; Frank, W. Ber. Dtsch. Chem. Ges. 1936, 69, 2071-2077; Ber. Dtsch. Chem. Ges. 1937, 70, 1279-1287.
17. 7. Potassium permanganate: Willstatter, R. Ber. Dtsch. Chem. Ges. 1896, 29, 1575-1584; Werner, G.; Hackel, R.; Mohammad, N.; Seiler, N.; Stoor, K.-H. Liebigs Ann. Chem. 1967, 708, 210-217. Potassium ferricyanate: Findlay, S.P. J. Am. Chem. Soc. 1953, 75, 3204-3208. Oxygen: Beckwith, A.L.J.; Eichinger, P.H.; Mooney, B.A.; Prager, R.H. Aust. J. Chem. 1983, 36, 719-739; Kovtum, G.A.; Aleksandrov, A.L. Izv. Akad. Nauk. SSSR, Ser. Chim. 1974, 1274-1279; (Chem . Abstr. 1974, 81, 177130r). Nitrous acid: Wegler, R.; Frank, W. Ber. Dtsch. Chem. Ges. 1936, 69, 2071-2077; Ber. Dtsch. Chem. Ges. 1937, 70, 1279-1287.
18. 8. Dealkylation procedure: To a solution of triethylamine (0.12g; 0.17mL; 1.19mmol) in dichloromethane (10mL) was added phenyl chlorothionoformate (0.20g; 0.16mL; 1.19mmol) and the solution was stirred under nitrogen for 1 h. The solvent was removed under reduced pressure to give a colourless oil which was chromatographed on silica to give O-phenyl diethylthiocarbamate, 5 (0.23g; 93%). Satisfactory analytical and spectral data were obtained for all new compounds.
19. 9. Von Braun, J.; Kohler, Z. Ber. Dtsch. Chem. Ges. 1918, 51, 255-265.
20. 10. Kraiss, G.; Nador, K. Tetrahedron Lett. 1971, 57-58.
21. 11. Klotzer, W., Teitel, S., Brossi, A. Helv. Chim. Acta. 1972, 55, 2228-2232.
22. 12. Hydrolysis procedure: The thiourethane 5 (0.2g; 0.96mmol) and dimethyl sulfate (0.24g; 0.18mL; 1.91mmol) were refluxed under nitrogen for 2 h. in dichloromethane (10mL). The solvent was removed under reduced pressure affording the imminium salt 14. The salt 14 (0.1g; 0.28mmol) was dissolved in water (5mL) and the solution refluxed for 2 h. Excess water was evaporated under reduced pressure to give diethylamine hydrogen sulfate as a spectroscopically pure orange oil (0.038g; >95%).