Pyrolysis of difluorocyclopropanes
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 3, March, 2015
663
2.31 (m, 3 H, Me); 1.83 (m, 3 H, Me). 13C NMR (CDCl3,
50.3 MHz), 17.3 (CH3), 25.4 (CH3), 125.2 (C=C), 145.2
(C=C), 199.3 (C=O). MS, m/z (Irel (%)): 84 [M]+ (83), 69 (76),
43 (100), 41 (87), 39 (30).
3ꢀMethylbutanꢀ2ꢀone (8)29. 1H NMR (CDCl3, 300.1 MHz),
2.60 (m, 1 H, CH); 2.15 (s, 3 H, Me); 1.10 (d, 6 H, 2 Me,
J =7.0 Hz). 13C (CDCl3, 50.3 MHz), 17.6 (CH3), 26.8 (CH3),
40.9 (CH), 211.2 (C=O). MS, m/z (Irel (%)): 86 [M]+ (27),
71(5), 43(100), 41 (15), 39(5).
A. A. Ivashenko, Bull. Acad. Sci. USSR, Div. Chem.Sci.
(Engl. Transl.), 1968, 17, 1346 [Izv. Akad. Nauk SSSR, Ser.
Khim., 1968, 1417]; (c) N. V. Volchkov, A. V. Zabolotskikh,
A. V. Ignatenko, O. M. Nefedov, Bull. Acad. Sci. USSR, Div.
Chem. Sci. (Engl. Transl.), 1990, 39, 1458 [Izv. Akad. Nauk
SSSR, Ser. Khim., 1990, 1609]; (d) N. V. Volchkov, A. V.
Zabolotskikh, M. B. Lipkind, O. M. Nefedov, Bull. Acad.
Sci. USSR, Div. Chem.Sci. (Engl. Transl.), 1989, 38, 1782
[Izv. Akad. Nauk SSSR, Ser. Khim., 1989, 1935].
11. W. E. Parham, R. R. Twelves, J. Org. Chem., 1957, 22, 730.
12. M. Christl, M. Braun, H. Fischer, S. Groetsch, G. Muller,
D. Leusser, S. Deuerlein, D. Stalke, M. Arnone, B. Engels,
Eur. J. Org. Chem., 2006, 5045.
13. W. R. Dolbier, Jr., J. J. Keaffaber, C. R. Burkholder,
H. Koroniac, J. Pradhan, Tetrahedron, 1992, 48, 9649.
14. (a) W. R. Dolbier, Jr., Acc. Chem. Res., 1981, 14, 195;
(b) W. R. Dolbier, Jr., S. F. Sellers, J. Am. Soc. Chem.,1982,
104, 2494; (c) W. R. Dolbier, Jr., S. F. Sellers, J. Org. Chem.,
1982, 47, 1; (d) J. C. Ferrero, E. A. R. De Staricco, E. H.
Staricco. J. Phys. Chem., 1975, 79, 1242.
This work was financially supported by the Division of
Chemistry and Material Sciences of the Russian Academy
of Sciences (Program for Basic Research "Theoretical and
Experimental Studies of the Chemical Bond Nature and
Mechanisms of Principal Chemical Reactions and Proꢀ
cesses") and the President of the Russian Federation Counꢀ
cil for Grants (Program for State Support of Leading
Scientific Schools of the Russian Federation, Grant
NShꢀ1310.2014.3).
15. W. R. Dolbier, Jr., H. O. Enoch, J. Am. Soc. Chem., 1977,
99, 4532—4533.
16. J. M. Birchall, R. N. Haszeidine, D. W. Roberts, J. Chem.
Soc., Chem. Commun., 1967, 287.
References
1. (a) H. Jendralla, Cyclopropyl to allyl rearrengement, in Methods
of Organic Chemistry (HoubenꢀWeyl), Ed. A. de Meijere, Thiꢀ
eme, Stuttgart, 1997, Vol. E17c, 2313; (b) R. R. Kostikov,
A. P. Molchanov, H. Hopf, Top. Curr. Chem., 1990, 155, 41;
(c) M. Fedorynski, Chem. Rev., 2003, 103, 1099; (d) W. R.
Dolbier, Jr., M. A. Battiste, Chem. Rev., 2003, 103, 1071;
(e) R. Bartlet, Y. Quang, Bull. Soc. Chim. Fr., 1969, 3729;
(f) M. Schlosser, Tetrahedron, 1978, 34, 3.
2. (a) R. Fields, R. N. Haszeldine, D. Peter, J. Chem.Soc. (C),
1969, 165—172; (b) K. A. Holbrook, K. A. W. Parry, J. Chem.
Soc. (B), 1970, 1019.
3. (a) N. V. Volchkov, M. A. Novikov, M. B. Lipkind, O. M.
Nefedov, Mendeleev Commun., 2013, 19; (b) M. A. Novikov,
N. V. Volchkov, M. B. Lipkind, O. M. Nefedov, Russ. Chem.
Bull. (Int. Ed.), 2013, 62, 71 [Izv. Akad. Nauk, Ser. Khim.,
2013, 71].
4. (a) G. C. Robinson, J. Org. Chem., 1968, 33, 607; (b) M. S.
Baird, B. S. Mahli, L. Sheppard, J. Chem. Soc., Perkin Trans.
1, 1990, 1881; (c) R. P. Clifford, K. A. Holbrook, J. Chem.
Soc., Perkin Trans. 2, 1972, 1972.
5. N. V. Volchkov, M. B. Lipkind, A. V. Zabolotskikh, A. V.
Ignatenko, O. M. Nefedov, Mendeleev Commun., 2006, 153.
6. P. Weyerstahl, D. Klamann, C. Finger, M. Fligge, F. Nerꢀ
del, J. Buddrus, Chem. Ber., 1968, 101, 1303.
7. E. V. Guseva, N. V. Volchkov, Yu. V. Tomilov, O. M. Nefeꢀ
dov, Eur. J. Org. Chem., 2004, 14, 3136.
8. T. B. Patrick, J. Rogers, K. Gorrell, Org. Lett., 2002, 4, 3155.
9. O. M. Nefedov, N. V. Volchkov, Mendeleev Commun.,
2006, 121.
17. B. Atkinson, D. McKeagan. J. Chem. Soc., Chem. Commun.,
1966, 287.
18. N. V. Volchkov, M. B. Lipkind, A. V. Zabolotskikh, O. M.
Nefedov, Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.),
1990, 39, 211 [Izv. Akad. Nauk SSSR, Ser. Khim., 1990, 228].
19. N. V. Volchkov, M. B. Lipkind, A. V. Zabolotskikh, O. M.
Nefedov, Russ. Chem. Bull. (Int. Ed.), 2014, 63, 2250
[Izv. Akad. Nauk, Ser. Khim., 2014, 2250].
20. (a) I. V. Kozhernikov, Chem. Rev., 1998, 98, 171; (b) R. Mello,
A. AlcaldeꢀAragones, M. E. GonzalezꢀNunez, Tetrahedron
Lett., 2010, 51, 4281.
21. M. Kamel, W. Kimpenhaus, J. Buddrus, Chem. Ber., 1976,
109, 2351.
22. R. A. Mitsch, J. Am. Chem. Soc., 1965, 87, 758.
23. M. L. Brewitz, J. Llaverid, A. Yada, A. Fürstner, Chemisꢀ
try—A European J., 2013, 19, 4532.
24. R. Vestin, A. Borg, T. Lindblom, Acta Chem. Scand., 1968,
22, 687.
25. E. Defranq, T. Zesiger, R. Tabacchi. Helv. Chim. Acta, 1993,
76, 425.
26. W. S. Trahanovsky, S. L. Emeis, J. Am. Chem. Soc., 1975,
97, 3773.
27. R. Mello, A. AlcaldeꢀAragones, M. E. GonzalezꢀNunez,
Tetrahedron Lett., 2010, 51, 4281.
28. C. Delseth, T. T.ꢀT. Nguyen, J.ꢀP. Kintzinger, Helv. Chim.
Acta., 1980, 63, 498.
29. D. Derouet, L. Cauret, J.ꢀC. Brosse, J. Org. Chem., 2001,
66, 3767.
10. (a) O. M. Nefedov, A. A. Ivashenko, Bull. Acad. Sci. USSR,
Div. Chem. Sci. (Engl. Transl.), 1968, 17, 445 [Izv. Akad.
Nauk SSSR, Ser. Khim., 1968, 446]; (b) O. M. Nefedov,
Received February 2, 2015