2352
Russian Chemical Bulletin, International Edition, Vol. 53, No. 10, p. 2352, October, 2004
SOCl2ꢀ and POCl3ꢀactivated βꢀchloroselenenation of alkenes
ꢀ
N. V. Zyk, E. K. Beloglazkina, and R. L. Antipin
Department of Chemistry, M. V. Lomonosov Moscow State University,
Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (095) 939 0290. Eꢀmail: antipin@org.chem.msu.ru
Addition of diethylbenzeneselenenamide (1) to olefins in the
At present, selenenamides PhSeNR2 find a limited
application as electrophilic agents. Only very reactive oleꢀ
fins such as enamines and enol silyl ethers react with
nonactivated selenenamides.1 Earlier,2 electrophilic adꢀ
dition of selenenamides activated by sulfur trioxide to
olefins was studied; the reaction products were βꢀphenylꢀ
selenenylsulfamates.
Recently, we have proposed phosphorus and sulfur
oxyhalides (Refs 3 and 4, respectively) as activating agents
in the electrophilic addition of sulfenamides to unsaturꢀ
ated compounds. In the present work, we studied the
reaction of diethylbenzeneselenenamide 1 with olefins in
the presence of sulfur(IV) and phosphorus(V) oxychlorides.
The сorresponding βꢀchloro selenides were obtained in
73—99% yields (Scheme 1).
presence of phosphorus(V) or sulfur(IV) oxychloride (general proꢀ
cedure). A solution of POCl3 or SOCl2 (2.5 mmol) in 10 mL of
dry CH2Cl2 was added at –30 °C to a stirred solution of comꢀ
pound 1 (2.5 mmol) in 10 mL of anhydrous CH2Cl2. The reacꢀ
tion mixture was kept for 10 min and then a solution of an olefin
(2.5 mmol) in 10 mL of CH2Cl2 was added. After 30 min, the
reaction mixture was warmed to ~20 °C and passed through a
5ꢀcm layer of silica gel. The solvent was removed to give yellow
oily products.
transꢀ1ꢀChloroꢀ2ꢀphenylselenenylcyclohexane (2). 1H NMR,
δ: 1.4, 1.6, 1.7, 2.3 (all m, 2 H each, H(5), H(4), H(6), H(3));
3.5 (dd, 1 H, HCSe, J = 6.0 Hz, J = 10.1 Hz); 4.15 (dd, 1 H,
HCCl, J = 7.0 Hz, J = 10.1 Hz); 7.4 (m, 5 H, H arom.).
13C NMR, δ: 22.95, 25.30, 32.67, 34.15, 50.32 (CSe), 64.10
(CCl), 127.85, 129.78, 136.30. MS (EI, 70 eV), m/z (Irel (%)):
274 [M]+ (35), 276 [M + 2]+ (32).
2ꢀChloroꢀ1ꢀphenylselenenylhexane (3). 1H NMR, δ: 0.86 (t,
3 H, Me, J = 7.3 Hz); 1.3 (m, 4 H, CH2); 1.7, 2.0 (both m,
1 H each, H(3)); 3.17 (dd, 1 H, HCSe, J = 8.5 Hz, J = 12.4 Hz);
3.26 (dd, 1 H, HCSe, J = 5.2 Hz, J = 12.4 Hz); 4.0 (m, 1 H,
HCCl); 7.4 (m, 5 H, H arom.). 13C NMR, δ: 15.25, 22.85,
29.10, 35.95, 38.50 (CSe), 63.40 (CCl), 127.36, 129.25, 136.65.
MS (EI, 70 eV), m/z (Irel (%)): 276 [M]+ (43), 278 [M + 2]+ (39).
Scheme 1
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 00ꢀ03ꢀ
32888a), the Foundation "Russian Universities" (Grant
No. 05.03.046), and the Presidium of the Russian Acadꢀ
emy of Sciences (Program "Theoretical and Experimental
Investigation of the Nature of Chemical Bonding and the
Mechanisms of Chemical Reactions and Processes").
References
The reaction with cyclohexene is transꢀstereospecific.
The chloroselenenation of the terminal olefin, namely,
hexꢀ1ꢀene, affords a Markovnikov adduct. Apparently,
the reaction mechanism is analogous to that reported
earlier.3
This reaction affords quantitative yields with the use
of SOCl2 and thus can serve as a convenient alternative to
direct chloroselenenation with selenenyl chlorides.
1. P. Lerouge and C. Paulimer, Bull. Soc. Chim. Fr., 1985, 1219.
2. N. V. Zyk, I. V. Alabugin, A. G. Kutateladze, J. L. Kice, and
N. S. Zefirov, Dokl. Akad. Nauk, 1994, 337, 208 [Dokl. Chem.,
1994 (Engl. Transl.)].
3. N. V. Zyk, E. K. Beloglazkina, R. A. Gazzaeva, V. S. Tyurin,
and I. D. Titanyuk, Phosphorus, Sulfur and Silicon, 1999,
155, 33.
4. N. V. Zyk, E. K. Beloglazkina, and I. D. Titanyuk, Izv. Akad.
Nauk, Ser. Khim., 1998, 2516 [Russ. Chem. Bull., 1998, 47,
2434 (Engl. Transl.)].
1
H and 13C NMR spectra were recorded on a Varian
VXRꢀ400 instrument (400 and 100 MHz, respectively) in CDCl3.
N,NꢀDiethylbenzeneselenenamide (1) was prepared accordꢀ
ing to a known procedure.2
Received May 12, 2004;
in revised form July 13, 2004
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2250—2251, October, 2004.
1066ꢀ5285/04/5310ꢀ2352 © 2004 Springer Science+Business Media, Inc.
Zyk
