F.-H. Wu, W.-Y. Huang / Journal of Fluorine Chemistry 110 (2001) 59–61
61
CH CCl ), 2.60–2.20 (m, 2H, CH ), 1.27 (t, 3H, CH CH ),
2
(2 g), acetonitrile (30 ml) and water (10 ml) was stirred at
40–458C for 20 h. Then 60 ml water was added to dissolve
the solid. The mixture was extracted by ether. The combined
organic layer was washed with saturated aqueous sodium
chloride solution, and dried over anhydrous sodium sulfate.
After removal of the organic solvent, the crude product was
purified over silica gel to give the adduct 8 in yield of 56%.
d (CCl ): 0.90 (3H, t, CH ), 2.30 (2H, m, CH CFCl), 1.30–
3
2
2
3
1
.22 (s, 3H, CH ), 1.10 (s, 3H, CH ) ppm [13].
3 3
1
7: Yield 80%; umax: 1730, 1225, 1220, 1150, 1030, 960,
ꢁ
1
8
CO CH ), 3.40–3.15 (m, 2H, CH CCl ), 2.60 (d, 1H, CH ),
05, 710 cm ; d (CCl ): 4.49 (dd, 1H, CHBr), 4.08 (q, 2H,
H
4
2
2
2
3
2
2
CH ) ppm [13].
.23 (d, 1H, CH ), 1.23 (m, 6H, 2CH ), 1.13 (s, 3H,
2 3
3
H
4
3
2
3.2. The addition reaction of dibromodifluoromethane
with olefins
2.20 (8H, m, other hydrogen atoms) ppm; d (CCl ): 66.8
F
4
(2F, s, CF Cl), 118.8 (1F, m, CFCl) ppm [7].
7
2
: Yield 72%; dH (neat): 2.50–2.1 (2H, m, CH CCl ),
2
2
The mixture of dibromodifluoromethane (2.10 g,
0 mmol), 1-octene (1.68 g, 15 mmol), sodium dithionite
3.69 g, 18 mmol), sodium hydrogencarbonate (1.40 g,
6 mmol), acetonitrile (6 ml) and water (2 ml) was stirred
at 0–58C for 4 h. Dibromodifluoromethane was converted
completely as shown by 19F NMR. The mixture was
extracted with ether (3 ꢀ 20 ml). The ethereal layer sepa-
rated was dried over anhydrous magnesium sulfate. After
evaporation of the solvent, the resultant liquid could be
distilled or chromatographed on a silica gel column using
petroleum ether as eluent to give the adduct 6 (2.83 g, 88%
1.90–0.90 (15H, m, other hydrogen atoms) ppm; d (neat):
F
1
(
1
79.8 (3F, s, CF ) ppm; m/z (%): 267 (0.81), 266 (1.12), 265
þ
3
(4.80), 264 (M , 4.36), 223 (17.15), 221 (26.49), 149
(13.81), 71 (16.96), 57 (100), 55 (20.03), 56 (15.46), 43
(45.45) [7].
9: Yield 70%; d (CCl ): 0.90 (3H, t, CH ), 2.30 (2H, m,
H
4
3
CH CFCl), 1.30–2.20 (10H, m, other hydrogen atoms) ppm;
d (CCl ): 66.8 (1F, s, CFCl ), 109.8 (2F, s, CF ), 114.8 (1F,
2
F
4
2
2
þ
m, CFCl) ppm; m/z (%): 311 (2.66), 330 (M ), 287 (7.45),
211 (21.71), 141 (11.14), 111 (15.34), 97 (20.66), 85
(49.48), 71 (65.11), 69 (32.84), 57 (100), 43 (70.05). Anal.:
C H Cl F (MW 331.5); calc.: C 39.82, H 5.13, F 22.93;
yield). Bp 508C/1 mmHg; d (neat): 4.30 (1H, m, CHBr),
H
11 17
3 4
3
.0 (2H, m, CH CF Br), 0.9–2.10 (13H, m, other hydrogen
found: C 40.00, H 5.42, F 23.10%.
14: Yield 50%; d (CCl ): 3.50 (1H, m, CHCFCl), 1.20–
2
2
atoms) ppm; d (CDCl ): 41.8 (2F, m, CF Br) ppm [11].
F
3
2
H
4
19
1
2: Yield 75%; (E)/ðZÞ ¼ 1:0 (estimated by F NMR);
2.50 (10H, m, other hydrogen atoms) ppm; d (CCl ): 61.8
F
4
ꢁ
1
umax: 2800–3000 (C–H). 1460, 1300, 1200 (C–F) cm ; dH
(2F, s, CF Cl), 116.8 (1F, m, CFCl) ppm [7]. Anal.:
C H Cl F (MW 235.08) calc.: C 40.87, H 4.72, F
2
(
CDCl ): (E): 4.18 (1H, td, JHH ¼ 9 Hz, J ¼ 4 Hz, CHBr),
3
HH
8
11
2 3
(Z): 4.72 (1H, br, s, CHBr) ðEÞ þ ðZÞ: 1.0–2.6 (9H, m, other
24.24; found: C 40.90, H 4.68, F 24.32%.
hydrogen atoms) ppm; d (CDCl ): (E): 41.23 (AB system),
F
3
(
(
(
(
Z): 48.50 (d, AB system), (m, 2F, CF Br) ppm; m/z (%): 294
þ
2
þ
0.04), 292 (0.11), 290 (M , 0.04), 211 (M ꢁ Br, 3.92), 131
Acknowledgements
þ
M ꢁ Br2, 100), 111 (27.06), 91 (12.07), 77 (29.84), 52
53.93) [11].
1
We thank the National Natural Science Foundation of
China (NSF Grant No. 29902001) and the Department of
Education of China for financial support.
3: Yield 80%; d (CDCl ): 4.50 (1H, m, CHBr), 1.0–2.6
H
3
(
13H, m, other hydrogen atoms) ppm; d (CDCl ): 47.3 (m,
F
3
þ
2
1
1
3
1
F, CF Br) ppm; m/z (%): 240 (M ꢁ Br, 5.05), 238 (6.36),
2
þ
60(M ꢁ Br2, 54.36), 159(54.13), 138(45.80), 117(34.82),
16 (21.18), 77 (64.14), 44 (100). Anal.: C H Br F (MW
9
References
14
2 2
20);calc.: C33.75, H4.38,F11.88;found:C34.16,H4.24, F
2.20%.
[1] W.-Y. Huang, B.-N. Huang, C.-M. Hu, Acta Chim. Sinica 37 (1981)
4
81.
1
CO CH ), 3.50 (1H, m, CH), 2.90 (2H, m, CH CF Br),
9: Yield 80%; dH (CCl ): 4.10 (5H, m, CHBr þ
2 2 2
4
[
[
2] W.-Y. Huang, J. Fluorine Chem. 58 (1992) 1, and references cited
therein.
2
2
.20 (2H, m CH ), 1.20 (6H, t, 2CH ) ppm; d (CCl ): 41.8
2
3
F
4
3] F.-H. Wu, B.-N. Huang, W.-Y. Huang, J. Chem. 39 (1999) 167.
(
(
(
2F, s, CF Br) ppm; m/z (%): 413 (1.73), 411 (3.43), 409
þ
2
[4] F.-H. Wu, B.-N. Huang, W.-Y. Huang, Youji Huaxue 13 (1993)
449.
þ
M þ 1, 1.79), 329 (M ꢁ Br, 9.78), 311 (9.77), 257
[
[
[
[
5] N.O. Brace, J. Fluorine Chem. 93 (1999) 1.
17.07), 255 (18.59), 175 (39.00), 160 (100), 133 (25.89),
03 (17.10), 101 (20.93), 73 (18.15). Anal.: C H Br F O
11 16 2 2 4
6] F.-H. Wu, W.-Y. Huang, J. Fluorine Chem. 92 (1998) 85.
7] C.M. Hu, F.L. Qing, Tetrahedron Lett. 31 (1990) 1307.
8] F.-H. Wu, B.-N. Huang, L. Lu, W.-Y. Huang, J. Fluorine Chem. 80
1
(
3
MW 410); calc.: C 32.20, H 3.90, F 9.27; found: C 32.46, H
.50, F 9.60%.
(
1996) 91.
[
9] D. Arlt, M. Jautelat, R. Lantzsch, Angew. Chem. 20 (1981) 703.
[
[
[
10] D.J. Burton, L. Kohoe, J. Org. Chem. 35 (1970) 1339.
11] W.Y. Huang, H.Z. Zhuang, Chin. J. Chem. 10 (1992) 274.
12] J. Tsuji, K. Sato, H. Nagashima, Tetrahedron Lett. 41 (1985)
3.3. The addition reaction of halocarbons with CFCl2
group with alkenes
3
93.
The mixture of F113 (3.75 g, 20 mmol), 1-hexene (0.84 g,
0 mmol), sodium dithionite (4 g), sodium bicarbonate
[
13] Y. Nakada, R. Endo, S. Muramatsu, J. Ido, Y. Yura, Bull. Chem. Soc.
Jpn. 52 (1979) 1511.
1