Thioglycoluril as a novel organocatalyst: Rapid and efficient α-monobromination of 1,3-dicarbonyl compounds

Article abstract of DOI:10.1055/s-0029-1216746

Thioglycoluril as a novel hydrogen-bonding organocatalyst, combined with NBS, in MeOH provided rapid and efficient α-monobromination of 1,3-dicarbonyl compounds in excellent yields at room temperature. A bifunctional catalytic mechanism was proposed from

Full text of DOI:10.1055/s-0029-1216746

Accounts and
Rapid Communications in
Synthetic Organic Chemistry
SYNLETT
SUPPORTING INFORMATION
Supporting Information
for DOI: 10.1055/s-0029-1216746
© Georg Thieme Verlag KG Stuttgart · New York 2009
Thieme

Supporting Information
Thioglycoluril as a Novel Organocatalyst: Rapid and
Efficient α-Monobromination of 1,3-Dicarbonyl Compounds
By Liping Cao, Jiaoyang Ding, Guodong Yin, Meng Gao, Yitao Li, Anxin Wu*
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, Central China Normal
University, Wuhan 430079, People’s Republic of China
chwuax@mail.ccnu.edu.cn
Table of Contents
Pages
General experimental----------------------------------------------------------------S2
Synthesis of the catalyst 1b–f ------------------------------------------------------S2-S3
Table S1. α-bromination of methyl ketones using NBS/1d --------------------S3
General procedure of α-bromination reaction and date of 6c–6m-------------S4–S7
Spectra of all new compounds------------------------------------------------------S8–S22
S1

General experimental
Catalyst 1a and other reagents were obtained from commercial suppliers and used
without further purification. Catalysts 1b-d were prepared according to the literature
procedures. TLC analysis was performed using pre-coated glass plates. Column
chromatography was performed using silica gel (200-300 mesh). IR spectra were
recorded on a PE-983 spectrophotometer as KBr pellets and were reported in cm-1. 1H
and 13C NMR spectra were recorded on a Varian Mercury 600 spectrometer operating
at 600 MHz and 150 MHz, respectively. Chemical shifts are reported in ppm, relative
to the internal standard of tetramethylsilane (TMS). Electron impact (EI) mass spectra
were acquired using a Finnegan Trace MS spectrometer. HRMS were obtained on a
Bruker 7-tesla FT-ICR MS equipped with an electrospray source (Billelica, MA,
USA). The X-ray crystal-structure determinations of 1d were obtained on a Bruker
SMART APEX CCD system.
Synthesis of the catalyst 1b–f
3a,6a-Bis(diethoxycarbonyl)tetrahydroidazo[4,5d]imidazole-2,5-dione(1b). This
compound was synthesized according to a literature procedure.1
3a,6a-Bis(diphenyl)tetrahydroidazo[4,5d]imidazole-2,5-dione(1c). This compound
was synthesized according to a literature procedure.2
3a,6a-Bis(diphenyl)tetrahydroidazo[4,5d]imidazole-2,5-dithione(1d).
This
compound was synthesized according to a literature procedure.3
S2

A suspension of thioglycoluril (1.63 g, 5 mmol) in anhydrous formaldehyde (0.3 g, 10
mmol) and MeOH (150 ml) was brought to reflux under magnetic stirring. A solution
of ethyl amine (7.5 mmol) in MeOH (10 ml) was added dropwise (over 1 h) to the
mixture. Then refluxing was continued for 10–12 h, monitored by TLC. The solvent
was removed under reduced pressure. The products 1e and 1f were separated by
column chromatography (silica gel) in 32% and 58% isolated yield, respectively.
1
1e: Yield 32%; white solid; H NMR (600 MHz, DMSO-d6): δ = 10.56 (s, 2H),
7.15-7.08 (m, 6H), 7.03 (d, 2H, J = 6.6 Hz), 6.88 (d, 2H, J = 6.6 Hz), 5.35 (d, 2H, J =
13.8 Hz), 4.04 (d, 2H, J = 13.2 Hz), 2.65 (q, 2H, J = 7.2 Hz), 1.12 (t,3H, J = 6.6 Hz);
13C NMR (150 MHz, DMSO-d6): δ =182.4, 134.9, 132.8, 128.9, 128.7, 128.6, 127.7,
127.3, 126.9, 88.7, 85.8, 60.9, 44.1, 13.1; IR (KBr, cm-1): 3403w, 3110m, 2966m,
2941m, 1504m, 1457s, 1345m, 1325m, 1299m, 1219s, 1192m, 1157m, 1103m,
1962m, 1045m, 1001m, 979s, 955m, 828m; HRMS (ESI): m/z [M + Na]+ calcd for
C20H21N5NaS2: 418.1131; found: 418.3326.
1
1f: Yield 58%; white solid; H NMR (600 MHz, CDCl3): δ = 7.12-7.10 (m, 8H),
7.05-7.04 (m, 2H), 5.60 (d, 2H, J = 13.8 Hz), 4.35 (d, 2H, J = 13.8 Hz), 3.11 (q, 2H, J
13
= 7.2 Hz), 1.23 (t,3H, J = 7.2 Hz); C NMR (150 MHz, CDCl3): δ = 185.9, 132.6,
129.3, 128.8, 127.6, 88.25, 61.8, 46.5, 13.6; IR (KBr, cm-1): 3440w, 3031w, 2965w,
2935w, 2858w, 1454s, 1415s, 1375m, 1324s, 1239s, 1195w, 1146w, 1083m, 1032w,
1002m, 966m, 953m, 929w, 861s; HRMS (ESI): m/z [M + H]+ calcd for C24H29N6S2:
465.1890; found: 465.1881; [M + Na]+ calcd for C24H28N6NaS2: 487.1709; found:
487.1698.
Table S1. α-bromination of methyl ketones using NBS/1d.a
Entry
Substrate
Product
Time(h)
Yieldb
54%
1
3
2
3
2
2
58%
42%
4
2
36%
a
Reaction conditions: 1 mmol of substrate, 2 mmol NBS and 20 mol % catalyst 1d in MeOH at
room temperature. b Isolated yield.
S3

General procedure of α-bromination reaction
1, 3-dicarbonyl compound 5a–o (1 mmol) reacted with NBS (1.5 mmol) and 1d
(0.2 mmol) in MeOH at room temperature. After total consumption of the starting
material (determination by TLC), the solvent was removed in vacuo, and the residue
was isolated by column chromatography on silica gel to get the pure product 6a–o as
solid or oil.
2-bromo-1,3-diphenylpropane-1,3-dione (6a)4
O
O
1H NMR (600 MHz, CDCl3): δ = 7.99 (d, 4H, J = 7.2 Hz), 7.60
(t, 2H, J = 7.2 Hz), 7.48 (t, 4H, J = 7.8 Hz), 6.55 (s, 1H);
EI-MS: m/z 301.2 ([M-1]+, 4), 300.2 ([M-2]+, 4), 105.1 (65),
Br
77.2 (100).
2-bromo-1-phenylbutane-1,3-dione (6b)5
O
O
1H NMR (600 MHz, CDCl3): δ = 7.98 (d, 2H, J = 7.8 Hz), 7.64 (t,
1H, J = 7.2 Hz), 7.51 (t, 2H, J = 7.8 Hz), 5.63 (s, 1H), 2.46 (s, 3H);
EI-MS: m/z 242.2 ([M+2]+, 2), 241.2 ([M+1]+, 5), 240.2 (M+, 2),
Br
105.2 (100).
2-bromo-1-(furan-2-yl)-3-(4-methoxyphenyl)propane-
O
O
1,3-dione (6c)
O
1H NMR (600 MHz, CDCl3): δ = 8.00 (d, 2H, J = 8.4 Hz),
6.95 (d, 2H, J = 9.0 Hz), 7.56 (s, 1H), 7.38 (d, 2H, J = 3.6
Br
MeO
13
Hz), 6.56 (s, 1H), 6.40 (s, 1H), 3.86 (s, 3H); C NMR
(150 MHz, CDCl3): δ = 187.2, 177.5, 164.3, 149.6, 147.4, 131.6, 126.4, 119.8, 114.1,
112.9, 55.5, 51.6; IR (KBr, cm-1): 3429w, 3134w, 2970w, 2936w, 1695s, 1668s, 1600s,
1571s, 1511m, 1463s, 1423w, 1391w, 1317m, 1298m, 1265s, 1218w, 1176s, 1116w,
1083w, 1025m, 989w, 914w, 884w; EI-MS: m/z 322.0 (M+, 13), 135.1(20), 95.0
(100).
2-bromo-1-(4-tert-butylphenyl)-3-(4-methoxyphen
O
O
yl)propane-1,3-dione (6d)
1H NMR (600 MHz, CDCl3): δ = 7.99 (d, 2H, J = 9.0
Hz), 7.93 (d, 2H, J = 7.8 Hz), 7.46 (d, 2H, J = 9.0 Hz),
6.93 (d, 2H, J = 8.4 Hz), 6.48 (s, 1H), 3.86 (s, 3H),
Br
MeO
13
1.32 (s, 9H); C NMR (150 MHz, CDCl3): δ = 188.5, 187.5, 164.2, 158.0, 131.7,
131.1, 129.1, 126.5, 125.9, 114.1, 55.5, 53.1, 35.1, 30.9; IR (KBr, cm-1): 3395w,
2965s, 1701s, 1671s, 1601s, 1573s, 1511s, 1462m, 1422m, 1409m, 1365m, 1319s,
1292s, 1262s, 1174s, 1109m, 1027m, 998m, 872m, 848m; EI-MS: m/z 388.6 (M+, 18),
161.2 (25), 135.1 (100).
2-bromo-1-(4-methoxyphenyl)-3-phenylpropane-1,3-di
O
O
one (6e)
Br
MeO
S4

1H NMR (600 MHz, CDCl3): δ = 7.99 (d, 2H, J = 9.0 Hz), 7.98 (d, 2H, J = 8.4 Hz),
7.59 (t, 1H, J = 7.2 Hz), 7.44 (t, 2H, J = 7.8 Hz), 6.94 (d, 2H, J = 8.4 Hz), 6.49 (s, 1H),
13
3.87 (s, 3H); C NMR (150 MHz, CDCl3): δ = 188.9, 187.5, 164.4, 134.1, 133.8,
131.7, 129.2, 128.9, 126.5, 114.2, 55.6, 52.9; IR (KBr, cm-1): 3424w, 1694s, 1668s,
1601s, 1573s, 1510m, 1447w, 1421m, 1315m, 1291s, 1260s, 1180s, 1152m, 1119w,
1077w, 1025m, 998m, 933w, 867w, 844m, 808w; EI-MS: m/z 333.5 ([M+1]+, 2),
332.4 (M+, 8), 77.2 (100).
2-bromo-1-(4-fluorophenyl)-3-(furan-2-yl)propane-1,3
-dione (6f)
O
O
O
1H NMR (600 MHz, CDCl3): δ = 8.07 (dd, 2H, J = 8.4
and 5.4 Hz), 7.58 (d, 1H, J = 1.2 Hz), 7.41 (d, 1H, J = 3.6
Br
F
Hz), 7.17 (t, 2H, J = 8.4 Hz), 6.59 (dd, 1H, J = 3.6 and 1.2
13
19
Hz), 6.34 (s, 1H); C NMR (150 MHz, CDCl3): δ = 187.3, 177.2, 166.2 (d, JC-
=
=
F
19
19
255.5 Hz), 149.7, 147.5, 132.1 (d, JC- = 9.5 Hz), 130.1, 120.1, 116.2 (d, JC-
F
F
22.4 Hz), 113.2, 51.5; IR (KBr, cm-1): 3448w, 1701s, 1675s, 1566m, 1545w, 1509m,
1463s, 1431w, 1411w, 1392w, 1296m, 1272m, 1238m, 1160s, 1130w, 1084w, 1022w,
917w, 884w, 851m; EI-MS: m/z 312.5 ([M+2]+, 8), 310.3 (M+, 8), 95.2 (100).
2-bromo-1-(4-tert-butylphenyl)-3-(4-fluorophenyl)
O
O
propane-1,3-dione (6g)
1H NMR (600 MHz, CDCl3): δ = 8.04 (dd, 2H, J =
8.4 and 5.4 Hz), 7.94 (d, 2H, J = 8.4 Hz), 7.49 (d, 2H,
Br
F
J = 8.4 Hz), 7.14 (t, 2H, J = 7.8 Hz), 6.46 (s, 1H),
19
1.33 (s, 9H); 13C NMR (150 MHz, CDCl3): δ = 188.4, 187.6, 166.1 (d, JC- F = 256.2
19
19
Hz), 158.4, 132.1 (d, JC- = 9.6 Hz), 130.1, 130.2, 129.2, 125.9, 116.1 (d, JC-
=
F
F
21.8 Hz), 52.7, 35.2, 30.9; IR (KBr, cm-1): 3400w, 2966s, 1704s, 1675s, 1601s,
1565m, 1508s, 1463m, 1410s, 1365m, 1290s, 1258s, 1241s, 1197s, 1160s, 1107m,
1003m, 910w, 874m, 852s, 821m; EI-MS: m/z 378.3 ([M+2]+, 9), 377.2 ([M+1]+, 6),
123.1 (100).
2-bromo-1-(4-fluorophenyl)-3-phenylpropane-1,3-dione
O
O
(6h)
1H NMR (600 MHz, CDCl3): δ = 8.04 (dd, 2H, J = 8.4 and
Br
F
5.4 Hz), 7.99 (d, 2H, J = 7.2 Hz), 7.61 (t, 1H, J = 7.8 Hz),
13
7.48 (t, 2H, J = 7.8 Hz), 7.14 (t, 2H, J = 7.8 Hz), 6.47 (s, 1H); C NMR (150 MHz,
19
19
CDCl3): δ = 188.9, 187.5, 166.2 (d, JC- F = 256.1 Hz), 134.4, 133.7, 132.1 (d, JC-
=
F
9.5 Hz), 130.1, 129.2, 129.0, 116.3 (d, JC- F = 21.8 Hz), 52.7; IR (KBr, cm-1): 3448w,
1703s, 1675s, 1597s, 1544w, 1506m, 1446m, 1410w, 1287m, 1240m, 1191m, 1160m,
1103w, 1074w, 999m, 931w, 876m, 852m, 842m, 815m; EI-MS: m/z 322.5 ([M+2]+,
30), 321.3 ([M+1]+, 33), 320.6 (M+, 30), 105.2 (90), 77.2 (100).
19
1-(biphenyl-4-yl)-2-bromo-3-(furan-2-yl)propane-1,3
-dione (6i)
O
O
O
Br
S5

1H NMR (600 MHz, CDCl3): δ = 8.10 (d, 2H, J = 9.0 Hz), 7.71 (d, 2H, J = 8.4 Hz),
7.62 (d, 2H, J = 7.2 Hz), 7.58 (d, 1H, J = 1.2 Hz), 7.48 (t, 2H, J = 7.2 Hz), 7.43-7.41
(m, 2H), 6.59 (dd, 1H, J = 3.6 and 1.6 Hz), 6.42 (s, 1H); 13C NMR (150 MHz, CDCl3):
δ = 188.3, 177.5, 149.9, 147.4, 146.9, 139.4, 132.4, 129.9, 129.0, 128,6, 127.6, 127.3,
120.0, 113.1, 51.8; IR (KBr, cm-1): 3397w, 1708s, 1653s, 1603m, 1580w, 1560m,
1486w, 1461s, 1395m, 1313m, 1275w, 1200m, 1161m, 1086w, 1043m, 1001m, 919m,
871w, 828w; EI-MS: m/z 369.5 ([M+1]+, 5), 368.2 (M+, 10), 289.1 (M+-Br, 40), 181.4
(100).
1-(biphenyl-4-yl)-2-bromo-3-(4-tert-butylphenyl)
O
O
propane-1,3-dione (6j)
1H NMR (600 MHz, CDCl3): δ = 8.07 (d, 2H, J =
9.0 Hz), 7.96 (d, 2H, J = 8.4 Hz), 7.68 (d, 2H, J =
8.4 Hz), 7.60 (d, 2H, J = 9.0 Hz), 7.50-7.40 (m, 5H),
Br
13
6.57 (s, 1H), 1.33 (s, 9H); C NMR (150 MHz, CDCl3): δ = 188.6, 188.5, 158.3,
146.8, 139.3, 132.4, 131.0, 129.8, 129.3, 128.9, 128.5, 127.5, 127.2, 125.9, 52.9, 35.2
(17 resonances expected, 16 observed); IR (KBr, cm-1): 3379w, 2961s, 1698s, 1668s,
1562m, 1512w, 1484m, 1463m, 1407s, 1365m, 1320s, 1290s, 1261s, 1192s, 1153m,
1107m, 1079w, 1023m, 1101s, 877m; EI-MS: m/z 434 (M+, 8), 181.6 (38), 161.2
(100).
1-(biphenyl-4-yl)-2-bromo-3-phenylpropane-1,3-dion
O
O
e (6k)
1H NMR (600 MHz, CDCl3): δ = 8.07 (d, 2H, J = 9.0
Hz), 8.02 (d, 2H, J = 8.4 Hz), 7.69 (d, 2H, J = 8.4 Hz),
7.56 (d, 2H, J = 9.6 Hz), 7.50-7.40 (m, 6H), 6.58 (s, 1H);
Br
13C NMR (150 MHz, CDCl3): δ = 188.9, 188.5, 146.9, 139.3, 134.2, 133.8, 132.3,
129.8, 129.2, 128.9, 128.6, 127.6, 127.2, 127.2, 52.8; IR (KBr, cm-1):3448w, 2924w,
1694s, 1672s, 1599s, 1579m, 1561m, 1485m, 1447m, 1404m, 1341w, 1319m, 1291s,
1259m, 1191m, 1158m, 1121w, 1075w, 1024w, 998m, 936w, 916w, 875w; EI-MS:
m/z 379.4 ([M+1]+, 13), 378.4 (M+, 21), 105.1 (42), 77.2 (100).
2-bromo-1-(4-tert-butylphenyl)-3-(naphthalen-2-
O
O
yl)propane-1,3-dione (6l)
1H NMR (600 MHz, CDCl3): δ = 8.55 (s, 1H), 8.01
(d, 1H, J = 9.0 Hz), 7.95 (d, 2H, J = 8.4 Hz), 7.93 (d,
1H, J = 8.4 Hz), 7.87 (d, 1H, J = 8.4 Hz), 7.84 (d,
Br
1H, J = 8.4 Hz), 7.60 (t, 1H, J = 7.2 Hz), 7.54 (t, 1H, J = 7.2 Hz), 7.45 (d, 3H, J = 7.2
Hz), 6.71 (s, 1H), 1.30 (s, 9H); 13C NMR (150 MHz, CDCl3): δ = 189.1, 188.5, 158.2,
135.9, 132.3, 131.4, 131.1, 129.8, 129.2, 128.9, 127.8, 127.1, 125.9, 124.3, 53.0, 35.2,
30.9 (19 resonances expected, 17 observed); IR (KBr, cm-1): 3424w, 1701s, 1668s,
1623s, 1597m, 1579w, 1545w, 1505w, 1485m, 1448m, 1418w, 1392w, 1340w, 1320w,
1296s, 1273s, 1226m, 1174s, 1147m, 1029m, 992w, 845m; EI-MS: m/z 410.1 ([M+2]+,
15), 409.2 ([M+1]+, 20), 408.1 (M+, 18), 303.1 ([M-Br] +, 30), 161.2 (8), 155.1 (37),
S6

127 (100).
2-bromo-1-(6-methoxynaphthalen-2-yl)-3-phen
ylpropane-1,3-dione (6m)
O
O
1H NMR (600 MHz, CDCl3): δ = 8.48 (s, 1H),
8.01 (d, 1H, J = 8.4 Hz), 8.00 (t, 2H, J = 9.6 Hz),
Br
MeO
7.84 (d, 1H, J = 9.0 Hz), 7.77 (d, 1H, J = 8.4 Hz), 7.59 (t, 1H, J = 7.2 Hz), 7.46 (t, 2H,
13
J = 7.2 Hz), 7.21 (d, 1H, J = 9.0 Hz), 7.14 (s, 1H), 6.66 (s, 1H), 3.95 (s, 3H); C
NMR (150 MHz, CDCl3): δ = 188.9, 188.7, 160.4, 137.8, 134.1, 133.9, 131.5, 131.3,
129.2, 129.0, 128.9, 127.7, 127.6, 125.1, 120.2, 105.8, 55.5, 53.0; IR (KBr, cm-1):
3424w, 1701s, 1668s, 1623s, 1597m, 1579w, 1545w, 1505w, 1485m, 1448m, 1418w,
1392w, 1340w, 1320w, 1296s, 1273s, 1226m, 1174s, 1147m, 1029m, 992w, 845m;
EI-MS: m/z 384.4 ([M+2]+, 23), 382.0 (M+, 40), 303.1 ([M-Br] +, 30), 185.5 (100),
105.0 (50).
ethyl 2-bromo-3-oxo-3-phenylpropanoate (6n)4
O
O
1H NMR (600 MHz, CDCl3): δ = 8.00 (d, 2H, J = 7.2 Hz), 7.64
(t, 1H, J = 7.2 Hz), 7.51 (t, 2H, J = 7.8 Hz), 5.67 (s, 1H), 4.29
(q, 2H, J = 7.2 Hz), 1.25 (t, 3H, J = 7.2 Hz); EI-MS: m/z 270.6
OEt
Br
(M+, 20), 105.2 (100).
ethyl 2-bromo-3-(4-nitrophenyl)-3-oxopropanoate (6o)6
O
O
1H NMR (600 MHz, CDCl3): δ = 8.35 (d, 2H, J = 9.0 Hz),
OEt
8.17 (d, 2H, J = 9.0 Hz), 5.61 (s, 1H), 4.32 (q, 2H, J = 7.2
Hz), 1.28 (t, 3H, J = 7.2 Hz); EI-MS: m/z 317.9 ([M+1]+,
Br
O2N
18), 315.7 (M+, 17), 150.3 (100).
References:
1. Branda, N.; Grotzfeld, R. M.; Valdés, C.; Rebek, J. Jr. J. Am. Chem. Soc. 1995, 117, 85-88.
2. Niele, F. G. M.; Nolte, R. J. M. J. Am. Chem. Soc. 1988, 110, 172-177.
3. Broan, C. J.; Butler, A. R. J. Chem. Soc., Perkin Trans. 2, 1991, 1501-1504.
4. Meshram, H. M.; Reddy, P. N.; Vishnu, P.; Sadashiv, K.; Yadav, J. S. Tetrahedron Lett. 2006, 47,
991-995.
5. Khan, A. T.; Ali, M. A.; Goswami, P.; Choudhury, L. H. J. Org. Chem. 2006, 71, 8961-8963.
6. Klosa, J. Archiv der Pharmazie 1953, 286, 391-397.
S7

Spectra of all new compounds
d4-2u 600MHz 1h-nmr
S
N
N
NH
Ph
NH
N
Ph
S
1e
11.0
ppm (f1)
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
d4-2u 150MHz 13c-nmr
S
N
N
NH
Ph
NH
N
Ph
S
1e
200
150
100
50
0
ppm (f1)
S8

a.i.
4.5e+06
4.0e+06
3.5e+06
3.0e+06
2.5e+06
2.0e+06
1.5e+06
1.0e+06
5.0e+05
0.0e+00
S
PULPROG se__curr_pp
TD
NS
DS
SW
524288
N
N
NH
Ph
NH
8
0
N
1878794.600 ppm
Ph
S
1e
410
415
420
425
430
m/z
/Data/pyj/080924/2U-S/pdata/1
Administrator
Mon Oct
6 21:17:35 2008
d4a 1h-nmr 600MHz
S
N
N
N
N
N
Ph
Ph
N
S
1f
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
S9

S
N
N
N
N
N
Ph
Ph
N
S
1f
200
ppm (f1)
150
100
50
0
a.i.
4.5e+06
4.0e+06
3.5e+06
3.0e+06
2.5e+06
2.0e+06
1.5e+06
1.0e+06
5.0e+05
0.0e+00
S
N
N
N
N
N
Ph
Ph
N
S
1f
PULPROG se__curr_pp
TD
NS
DS
SW
524288
8
0
1878794.600 ppm
462
467
472
477
482
487
m/z
/Data/pyj/080924/3U-S/pdata/1
Administrator
Mon Oct
6
21:19:28 2008
S10

d34 h1 nmr 600HMz cdcl3
O
O
O
Br
6c
MeO
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
d34 c13-nmr 150MHz cdcl3
O
O
O
Br
6c
MeO
200
150
100
50
0
ppm (t1)
S11

d33 h1-nmr 600MHz cdcl3
O
O
Br
6d
MeO
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
D33 13C-NMR150MHz CDCL3
O
O
Br
6d
MeO
200
150
100
50
0
ppm (t1)
S12

d31 h1-nmr 600MHz cdcl3
O
O
Br
6e
MeO
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
d31 c13-nmr150MHz cdcl3
O
O
Br
6e
MeO
200
ppm (t1)
150
100
50
0
S13

c174 h1-nmr 600MHz cdcl3
O
O
O
Br
6f
F
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
c174 c13-nmr 150MHz cdcl3
O
O
O
Br
6f
F
200
ppm (f1)
150
100
50
0
S14

c173 h1-nmr 600MHz cdcl3
O
O
Br
6g
F
10.0
ppm (f1)
5.0
0.0
c173 h1-nmr 150MHz cdcl3
O
O
Br
6g
F
200
ppm (f1)
150
100
50
0
S15

d28 h1-nmr 600MHz cdcl3
O
O
Br
6h
F
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
d28 c13-nmr 150MHz cdcl3
O
O
Br
6h
F
200
ppm (f1)
150
100
50
0
S16

d29 h1-nmr 600HMz cdcl3
O
O
O
Br
6i
10.0
ppm (f1)
5.0
0.0
d29 c13-nmr 150MHz cdcl3
O
O
O
Br
6i
200
150
100
50
0
ppm (f1)
S17

c175 h1-nmr 600MHz cdcl3
O
O
Br
6j
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
c175 c13-nmr 150MHz cdcl3
O
O
Br
6j
200
ppm (f1)
150
100
50
0
S18

d32 h1-nmr 600HMz cdcl3
O
O
Br
6k
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
d32 c13-nmr 150MHz cdcl3
O
O
Br
6k
200
150
100
50
0
ppm (f1)
S19

c177 h1-nmr 600MHz cdcl3
O
O
Br
6l
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
c177 c13-nmr 150MHz cdcl3
O
O
Br
6l
200
ppm (f1)
150
100
50
0
S20

d36a h1-nmr 600MHz cdcl3
O
O
Br
6m
MeO
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
d36a c13-nmr 150MHz cdcl3
O
O
Br
6m
MeO
200
150
100
50
0
ppm (f1)
S21