3570
H. Liu et al. / Tetrahedron 62 (2006) 3564–3572
chromatography (10% CH2Cl2 in hexane). 49.1% yield;
1578 (m), 1451 (s), 1428 (s), 1346 (w), 1297 (m), 1214
(m), 1113 (w), 1078 (m), 1060 (m), 710 (s), 701 (s), 684
(s) cmK1. Anal. Calcd for C6HOBr3F2 C: C, 19.65; H, 0.27.
Found: C, 19.50; H, 0.26.
1
98.8% purity (GLC); H NMR(300 MHz, CDCl3): d 7.29
(dd, JZ8.3, 1.6 Hz, 2H, H5 and H50), 6.83 (ddt, JZ8.3,
2–7, 0.8 Hz, 2H, H6, H60), 6.81 (dd, JZ8.3, 2.2 Hz, 2H, H4,
H40), 6.73 (dt, JZ10.0, 2.3 Hz, 2H, H2, H20); 13C NMR
1
(75 MHz, CDCl3): d 163.9 (d, JCFZ247.1 Hz, C3, C30),
4.1.15. 3,30,4,40-Tetrabromodiphenyliodonium chloride
(22).12,16,25 The title compound was prepared from 1,2-
dibromobenzene by Method A and characterised according
to literature.25
3
3
158.3 (d, JCFZ11.0 Hz, C1, C10) 131.1 (d, JCFZ9.4 Hz,
C5, C50), 115.0 (d, 4JCFZ2.8 Hz, C6, C60), 111.1 (d, 2JCF
Z
2
21.0 Hz, C4, C40), 107.2 (d, JCFZ24.3 Hz, C2, C20); MS:
m/z 206 (M, 100%), 178 (40), 177 (57), 112 (38), 95 (28); IR
(KBr) nmax: 3076 (m), 1606 (s), 1480 (s), 1450 (s), 1309 (s),
1276 (s), 1164 (s), 1135 (s), 1071 (m), 975 (s), 853 (s), 773
4.1.16. 2,4,40,6-Tetrabromodiphenyl ether (BDE 75).12,16
The title compound was prepared from (2) and 2,4,6-
tribromophenol (3) by Method B; 21% yield, 98.4% purity
(GLC) (lit.16 23% yield); mp 149–150 8C (lit.16 134–
135 8C); 1H and 13C NMR was in accordance with literature
data;16 MS: m/z 490 (M, 14%), 488 (M, 61), 486 (M, 100),
484 (M, 64), 482 (M,15), 328 (34) 326 (75), 324 (34); IR
(KBr) nmax: 2063 (w), 1879 (w), 1730 (w), 1580 (w), 1547
(m), 1483 (s), 1440 (s), 1399 (w), 1372 (m), 1354 (w), 1282
(m), 1253 (s), 1202 (s), 1163 (m), 1070 (m), 1006 (m), 860
(s), 679 (s) cmK1
.
4.1.12. 2,3,4-Tribromo-5,6-difluorophenol (19). The title
compound was prepared from 2,3-difluorophenol (16) by
Method C (Fe 0.6 equiv, Br2 5.8 equiv) to afford beige
crystals; 78.8% yield; 99.2% purity (GLC); mp 114–116 8C;
1H NMR (300 MHz, CDCl3): d 5.78 (s, 1H, OH); 13C NMR
1
2
(75 MHz, CDCl3): d 148.4 (dd, JCFZ249.9 Hz, JCF
Z
2
3
13 Hz, C5), 142.8 (dd, JCFZ11.0 Hz, JCFZ3.3 Hz, C1),
(s), 822 (s), 809 (m), 748 (m), 739 (m) cmK1
.
1
2
139.1 (dd, JCFZ252.6 Hz, JCFZ16.5 Hz, C6), 121.9 (d,
3JCFZ4.8 Hz, C3), 109.8 (dd, 3JCFZ3.7 Hz, 4JCFZ1.1 Hz,
4.1.17. 2,20,3,4,40-Pentabromodiphenyl ether (BDE
85).21,25 The title compound was prepared from 5a and 8
by Method B to give white crystals; 49.2% yield; 99.3%
purity (GLC); mp 123–124 8C; 1H NMR were in accordance
with literature data;21 13C NMR (75 MHz, CDCl3): d 153.8
(C1), 152.3 (C10), 136.8 (C30), 132.8 (C5), 132.3 (C50),
129.9 (C30), 1201.5 (C60, C6 or C4), 120.7 (C60, C60 or C4),
119.3 (C6 0, C6 or C4), 118.5 (C40or C2), 118.1 (C4 or C2),
115.9 (C2 ); MS: m/z 570 (M, 9%), 568 (M, 46), 566 (M,
95), 564 (M, 100), 562 (M, 49), 560 (M, 10), 408 (26), 406
C2), 104.9 (d, JCFZ20.5 Hz, C4); 19F NMR (376 MHz,
2
CDCl3/hexafluorobenzene): d K120.4 (d, JZ21.1 Hz, F5),
K153.4 (d, JZ21.1 Hz, F6); MS: m/z 370 (M, 29%), 368
(M, 100), 366 (M, 100), 364 (M, 30), 288 (6), 286 (11), 284
(5), 259 (8), 257 (8), 179 (12), 177 (12). IR (KBr nmax):
3673 (w), 3528 (m, br), 1605 (m), 1575 (m), 1480 (s), 1405
(m), 1332 (w), 1299 (m), 1240 (m), 1199 (m), 1072 (m), 926
(m), 804 (s) cmK1. HRMS calcd for C6 Br3F2HO (MC):
363.7546. Found: 363.7545.
(81), 404 (83), 402 (27), 203 (19), 202 (19). IR (KBr) nmax
:
4.1.13. 2,4,5-Tribromo-3,6-difluorophenol (20). The title
compound was prepared from 3,6-difluorophenol (17) by
Method C (Fe 0.5 equiv; Br2 5.5 equiv) to afford beige
crystals; 66.3% yield; 99.0% purity (GLC); mp 78–79.5 8C;
1H NMR (300 MHz, CDCl3): d 5.86 (s, 1H, OH); 13C NMR
ca 3100 (w), 1573 (w), 1556 (m), 1463 (s), 1427 (s), 1374
(m), 1356 (m), 1256 (s), 1247 (s), 1215 (m), 1076 (w), 1049
(m), 953 (w), 906 (m), 842 (m), 803 (m), 721 (m) cmK1
.
4.1.18. 2,20,3,4,40,50-Hexabromodiphenyl ether (BDE
138).21 The title compound was prepared from 5a and 9
by Method B; white crystals; 54.0% yield; 99.8% purity
(GLC); mp 135–136 8C; (lit.21 134.2 8C); 1H NMR were in
accordance with literature data;21 13C NMR (75 MHz,
CDCl3): d 152.7 (C1 or C10), 152.4 (C1 or C10), 137.5 (C30),
132.7 0(C5), 129.8 (C3), 124.3 (C50), 123.4 (C60), 121.2 (C4
or C4 ) 120.3 (C4 or C40), 119.4 (C6), 119.0 (C2), 113.4
(C20); MS: m/z 649 (M, 4%), 647 (M, 25), 645 (M, 70), 643
(M, 100), 641 (M, 74), 639 (M, 28), 637 (M, 5), 488 (14),
486 (63), 484 (100), 482 (64), 480 (15), 242 (19), 74 (23). IR
(KBr) nmax: 3076 (w), 1572 (w), 1552 (m), 1454 (m), 1426
(s), 1358 (w), 1332 (m), 1265 (m), 1248 (m), 1208 (w), 1107
1
4
(75 MHz, CDCl3): d 153.1 (dd, JCFZ244.3 Hz, JCF
Z
3.9 Hz, C3), 145.4 (dd, 1JCFZ242.6 Hz, 4JCFZ4.5 Hz, C6),
2
3
142.1 (dd, JCFZ17.1 Hz, JCFZ3.8 Hz, C1), 112.6 (dd,
3
2
2JCFZ21.5 Hz, JCFZ1.6 Hz, C5), 103.6 (d, JCF
Z
2
3
26.0 Hz, C4), 98.6 (dd, JCFZ27.1 Hz, JCFZ2.4 Hz, C2);
19F NMR (376 MHz, CDCl3/hexafluorobenzene): d K96.5
(d, JZ9.8 Hz, F3), K125.2 (d/JZ9.8 Hz, F6), MS: m/z 370
(M, 28%), 368 (M, 99), 366 (M, 100), 364 (M, 29), 98 (15);
IR (KBr) nmax: 3506 (m, br), 3403 (w, br), 3126 (m, br),
1583 (w), 1439 (s), 1350 (m), 1325 (m), 1247 (w), 1175 (w),
1078 (m), 1070 (m), 912 (m), 838 (s) cmK1. Anal. Calcd for
C6Br3F2HO: C, 19.65; H, 0.27. Found: C, 19.45; H, 0.18.
(m), 1049 (m), 931 (m), 884 (m), 842 (w), 798 (m) cmK1
.
4.1.14. 2,4,6-Tribromo-3,5-difluorophenol (21). The title
compound was prepared from 3,5-difluorophenol (18) by
Method C (Fe 0.5 equiv; Br2 5 equiv) to afford beige
crystals; 83.0% yield; 98.4% purity (GLC); mp 110–111 8C;
1H NMR (300 MHz, CDCl3): d 6.16 (s, 1H, OH); 13C NMR
4.1.19. 2,20,3,4,40,50,6-Heptabromodiphenyl ether (BDE
183).22,25 The title compound was prepared from 9 and 7 by
Method B to afford white crystals; 54.0% yield; 99.4%
purity (GLC); mp 174–174.5 8C; 1H NMR were in
accordance with literature data;25 13C NMR (75 MHz,
CDCl3): d 151.7 (s, C1), 148.6 (s, C10) 137.5 (s, C30), 136.1
(s, C3), 128.8 (s, C5), 124.0 (s, C50), 123.6 (s, C4), 123.0 (s,
C60), 118.7 (s, C40or C2) 118.4 (s, C40 or C2), 117.0 (s, C6),
111.4 (s, C20); MS: m/z 729 (M, 3%), 727 (M, 17), 725 (M,
55), 723 (M, 98), 721 (M, 100), 719 (M, 58), 717 (M, 18),
715 (M, 3), 567 (8), 565 (40), 563 (91), 561 (92), 559 (43),
1
3
(75 MHz, CDCl3): d 156.4 (dd, JCFZ246.5 Hz, JCF
Z
3
5.8 Hz, C3,C5), 150.9 (t, JCFZ4.8 Hz, C1), 94.1 (dd,
4
2
2JCFZ26.5 Hz, JCFZ4.4 Hz, 2C, C2, C6), 90.2 (t, JCF
Z
27.0 Hz, 1C, C4); 19F NMR (376 MHz, CDCl3/hexafluoro-
benzene): d K96.7 (s, 2F); MS: m/z 370 (M, 33%), 368 (M,
97), 366 (M, 100), 364 (M, 35), 290 (6), 288 (12), 286 (10).
IR (KBr) nmax: 3482 (m, br), 1762 (w), 1685 (w), 1591 (m),