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Nikishin et al.
2,3ꢀDibromohexanꢀ1ꢀol (2d) (see Ref. 21). 1H NMR (CDCl3),
: 0.95 (t, 3 H, CH3, J = 7.5 Hz); 1.47 (m, 2 H, CH3CH2); 1.62
(m, 2 H, CH3CH2CH2); 3.93 (m, 2 H, CH2OH); 4.08 (m, 1 H,
BrCHCH2OH); 4.13 (m, 1 H, CH3CH2CH2CHBr). 13C NMR
(CDCl3), : 13.94, 18.92, 36.66, 54.82, 60.87, 64.58.
2,3ꢀDibromoꢀ3ꢀmethylbutanꢀ1ꢀol (2e) (see Ref. 22).
1H NMR (CDCl3), : 1.42 (s, 3 H, CH3); 1.44 (s, 3 H, CH3);
3.65 (d, 1 H, CHBr, J = 8.7 Hz); 4.04 (m, 2 H, CH2OH).
13C NMR (CDCl3), : 27.00, 27.16, 34.32, 67.05, 73.08.
3,4ꢀDibromobutanꢀ1ꢀol (2f) (see Ref. 23). 1H NMR (CDCl3),
: 2.31 (m, 2 H, CH2CH2OH); 3.98 (m, 2 H, CH2OH); 4.02
(m, 2 H, CH2Br); 4.45 (m, 1 H, CHBr). 13C (CDCl3), : 37.22,
37.76, 49.45, 60.21.
3,4ꢀDibromobutanꢀ2ꢀol (2g) (see Ref. 24). 1H NMR (CDCl3),
: 1.38 (d, 3 H, CH3, J = 7.0 Hz); 3.77 (m, 2 H, CH2Br); 4.02
(m, 1 H, CHBr); 4.48 (m, 1 H, CHOH). 13C NMR (CDCl3), :
22.56, 32.77, 60.81, 65.75.
3,4ꢀDibromoꢀ2ꢀmethylbutanꢀ2ꢀol (2h) (see Ref. 19). 1H NMR
(CDCl3), : 1.40 (s, 3 H, CH3); 1.42 (s, 3 H, CH3); 3.99 (m, 2 H,
CH2Br); 4.20 (d, 1 H, CHBr, J = 6.8 Hz). 13C NMR (CDCl3), :
27.13, 27.32, 34.30, 67.13, 73.06.
bromine from LiBr under the action of CeIV and oxidation
of CeIII with hydrogen peroxide to CeIV
.
Experimental
GLC analysis was performed on a LKhMꢀ80 chromatograph
with the flameꢀionization detector and 2000×3 mm analytical
metal columns with 5% SEꢀ30 and 5% FFAP on Chromaton
NꢀAWꢀHMDS (0.16—0.20 mm). The product yields were deꢀ
termined by an internal standard method with the empirical corꢀ
relation coefficients. 1H and 13C NMR spectra were run on Brukꢀ
er ACꢀ200 and Bruker AMꢀ300 instruments in CDCl3. The
GCꢀMS analysis was carried out on a Finnigan MAT ITDꢀ700
spectrometer (EI, 70 eV, the source of ionꢀionic trap system
temperature was 220 C) connected with Carlo Erba 4200
chromatograph with a 25 m×0.2 mm Ultraꢀ1 column (Hewꢀ
lett—Packard), the stationary phase (polymethylsiloxane) thickꢀ
ness 0.33 m, helium was used as a carrier gas. The reaction
products were isolated by column chromatography (silica gel,
L 40/100 m, elution with heptane—ethyl acetate). The starting
alkenols (propꢀ2ꢀenꢀ1ꢀol (1a), hexꢀ5ꢀenꢀ1ꢀol (1b), hexꢀ3ꢀenꢀ1ꢀ
ol (1c), hexꢀ2ꢀenꢀ1ꢀol (1d), 3ꢀmethylbutꢀ2ꢀenꢀ1ꢀol (1e), butꢀ3ꢀ
enꢀ1ꢀol (1f), butꢀ3ꢀenꢀ2ꢀol (2g), 2ꢀmethylbutꢀ3ꢀenꢀ2ꢀol (2h)
(Acros)) were distilled prior to use. Lithium bromide, cerium
ammonium nitrate (Ce(NH4)2(NO3)6), cerium(III) nitrate
(Ce(NO3)3•6H2O), hydrogen peroxide (35% aqueous solution)
(Acros) were used as purchased.
Bromination of alkenols with the H2O2—LiBr—CeIII/CeIV
system (general procedure). To a vigorously stirred solution of
alcohol 1a—h (1 mmol), LiBr, and the CeIII or CeIV salts in
water (10 mL), a solution of 35% H2O2 in water (10 mL) was
added by portions of 0.5—0.7 mL within ~4—5 h at 65—70 C
(reagent ratios are given in Tables 1 and 2). After addition
of the first portion of the H2O2 solution, the reaction mixꢀ
ture turns pale yellow, the color disappeared after 20—30 min.
The reaction mixture was cooled, extracted with diethyl
ether (3×15 mL), the combined organic layers were washed
with water, and dried with MgSO4. The solvent was removed
in vacuo, the yields of the products 2a—h, 3, 4 and the conꢀ
version of alcohol 1a—h were determined by GLC with the inꢀ
ternal standard. The products were isolated by column chromaꢀ
tography.
3ꢀBromotetrahydrofuran (3) (see Ref. 25). 1H NMR (CDCl3),
: 2.08 (m, 2 H, CH2CH2CHBr); 3.71 (m, 2 H, CH2CHBrCH2);
3.99 (m, 2 H, CH2CH2CHBr); 4.18 (m, 1 H, CHBr). 13C NMR
(CDCl3), : 38.75, 46.56, 66.97, 76.37.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 09ꢀ03ꢀ
00292a) and the Council for Grants at the President of the
Russian Federation (the Program for the State Support of
Leading Scientific Schools of the Russian Federation,
Grant NShꢀ4945.2010.3).
References
1. B. S. Chhikara, R. Chandra, V. Tandon, Synlett, 2005, 872.
2. J. Wang, L. Yan, G. Li, X. Wang, Y. Ding, J. Suo, Tetraꢀ
hedron Lett., 2005, 46, 7023.
3. C. Venturello, M. Gambaro, J. Org. Chem., 1991, 56, 5924.
4. S. Das, T. Punniyamurthy, Tetrahedron Lett., 2003, 44, 6033.
5. R. Anderson, K. Griffin, P. Johnston, P. L. Alsters, Adv.
Synth. Catal., 2003, 345.
The structures of the synthesized compounds were evaluated
6. J. Liu, F. Wang, K. Sun, X. Xu, Catal. Commun., 2008,
9, 386.aa
1
from H and 13C NMR spectra, GCꢀMS data, and IR spectroꢀ
scopic data.
7. Y. Kon, Y. Usui, K. Sato, Chem. Commun., 2007, 4399.
8. T. Hori, K. B. Sharpless, J. Org. Chem., 1978, 43, 1689.
9. P. Kumar, R. Kumar, B. Pandey, Synlett, 1995, 289.
10. A. Amati, G. Dosualdo, L. Zhao, A. Bravo, F. Fontana,
F. Minisci, Org. Proc. Res. Dev., 1998, 2, 261.
2,3ꢀDibromopropanꢀ1ꢀol (2a) (see Ref. 18). 1H NMR (CDCl3),
: 3.78 (m, 2 H, CH2Br); 3.95 (d, 2 H, CH2OH, J = 8.7 Hz);
4.35 (m, 1 H, CHBr). 13C NMR (CDCl3), : 31.57, 53.36, 64.04.
MS, m/z: 217 [M]+ 79Br); 219 [M]+ 81Br).
( (
5,6ꢀDibromohexanꢀ1ꢀol (2b) (see Ref. 19). 1H NMR (CDCl3),
: 1.62 (m, 4 H, CH2CH2CH2OH); 1.84 (m, 2 H, CHBr—
CH2CH2CH2CH2OH); 3.61 (t, 2 H, CH2OH, J = 6.6 Hz); 3.89
(m, 2 H, CH2Br); 4.28 (m, 1 H, CHBr). 13C NMR (CDCl3), :
23.29, 29.41, 35.91, 36.26, 52.56, 62.69.
3,4ꢀDibromohexanꢀ1ꢀol (2c) (see Ref. 20). 1H NMR (CDCl3),
: 1.02 (m, 3 H, CH3, J = 7.2 Hz); 1.87 (m, 2 H, CH3CH2);
2.16 (m, 2 H, CH2CH2OH); 3.76 (t, 2 H, CH2OH, J =
= 6.1 Hz); 3.92 (m, 1 H, BrCHCH2CH2OH); 4.08 (m, 1 H,
CH3CH2CHBr). 13C NMR (CDCl3), : 10.42, 26.53, 36.86,
49.45, 60.09, 65.90.aaa
11. G. I. Nikishin, L. L. Sokova, N. I. Kapustina, Izv. Akad.
Nauk, Ser. Khim., 2011, 303 [Russ. Chem. Bull., Int. Ed.,
2011, 60, 310].
12. N. I. Kapustina, L. L. Sokova, G. I. Nikishin, Izv. Akad.
Nauk, Ser. Khim., 2010, 1255 [Russ. Chem. Bull., Int. Ed.,
2010, 59, 1284].
13. N. I. Kapustina, L. L. Sokova, R. G. Gasanov, G. I. Nikiꢀ
shin, Izv. Akad. Nauk, Ser. Khim., 2007, 1445 [Russ. Chem.
Bull., Int. Ed., 2007, 56, 1501].
14. V. Nair, S. B. Panieker, A. Augustine, T. G. George,
S. Thomas, M. Vairamani, Tetrahedron, 2001, 57, 7417.