Supporting Information

 Wiley-VCH 2010
69451 Weinheim, Germany

Gold-Catalyzed Halogenation of Aromatics by N-Halosuccinimides**

Fanyang Mo, Jerry Mingtao Yan, Di Qiu, Fei Li, Yan Zhang, and Jianbo Wang*

anie_200906699_sm_miscellaneous_information.pdf
CONTENTS

1. General................................................................................................................................................................ 2
2. AuCl3-catalyzed chlorination and iodination...................................................................................................... 2
3. General experimental procedure.......................................................................................................................... 3
3.1 Typical procedure for the AuCl3-catalyzed bromination with NBS.............................................................. 3
3.2 Experiment with 0.01 mol% catalyst loading............................................................................................... 3
3.3 Converting arenes into aniline derivatives.................................................................................................... 3
3.4 Suzuki coupling as the sequential reaction.................................................................................................... 3
3.5 Miyaura borylation as the sequential reaction............................................................................................... 4
3.6 Sonogashira coupling as the sequential reaction............................................................................................ 4
4. Kinetic isotopic effect experiment....................................................................................................................... 4
5. Spectral data for selected compounds.................................................................................................................. 6
6. References............................................................................................................................................................ 9

1
1. General

All reactions were performed under a nitrogen atmosphere in a flame-dried reaction flask. All solvents were
distilled prior to use. 1,2-Dichloroethane (DCE) was distilled over calcium hydride, THF and toluene were
distilled over sodium. For chromatography, 200-300 mesh silica gel (Qindao, China) was employed. 1H and 13C
NMR spectra were recorded at 300/200 MHz and 75/50 MHz with Varian Mercury 300/200 spectrometer, 400
MHz and 100 MHz with Bruker 400 spectrometer. Chemical shifts are reported in ppm using tetramethylsilane
as internal standard. IR spectra were recorded with a Nicolet Avatar 330 FT-IR infrared spectrometer. A CEM
Discover microwave was used.

2. AuCl3-Catalyzed Chlorination and Iodination

The success of bromination with AuCl3 catalysis leads to the further extension of this method to chlorination and
iodination with NCS and NIS, respectively. NCS is less reactive than NBS, which limits its application as a
chlorinating agent in the current catalytic system. In some cases, increasing catalyst loading or adding additional
Lewis acid is needed for the reaction to complete (Table 4, entries 1, 2). NIS is more reactive than NBS,
however, it is not very stable and side reaction occurs during the prolonged reaction. Moreover, poly iodination
became a significant side reaction, which needs the adjustment of the reaction conditions by carrying out the
reaction at lower temperature (entry 4).

Table 4. AuCl3-Catalyzed reaction of aromatics by NCS or NIS.[a]

cat. AuCl 3
ArH + NXS ArX
DCE
1d,f,p,j (X = Cl, I) 7a-c; 8a,b

AuCl3
Entry ArH T (oC) t (h) ArX Yield[b]
(mol%)

Cl
1[c] 1 80 15 >99%
1d 7a

2 3 RT 24 Cl 83%

1f 7b
OMe OMe
Cl
>99%
3 1 RT 24
(96%)
MeO MeO
1p 7c

I
>99%
4 1 0 40
(96%)
1f 8a
MeO2C MeO2C
>99%
5 MeO 1 RT 24 MeO I
(96%)
1j 8b

[a] Reaction conditions: substrate (1 mmol), NXS (1 mmol), DCE (2 mL). [b] GC MS yields using n-dodecane
as internal standard. Isolated yield in parentheses. [c] 40% BF3·OEt2 was added.

2
3. General experimental procedure

3.1 Typical procedure for the AuCl3-catalyzed bromination with NBS

NBS (3 mmol, 540 mg), AuCl3 (0.003 mmol, 0.1 mol%, 1 mg) were weighted in a 25 mL round bottom flask.
DCE (6 mL), methyl 2-methoxybenzoate 1j (3 mmol, 498 mg) were then added in succession. The resulting
reaction mixture was allowed to stir for about 23 h at 80 oC (monitored by GC-MS). The solution was then
concentrated under reduced pressure and the residue was purified by flash column chromatography (petroleum
ether/EtOAc 20:1) to give methyl 5-bromo-2-methoxybenzoate 2j (703 mg, yield 96%).

3.2 For 0.01 mol% catalyst loading

NBS (3 mmol, 540 mg) was weighted in a 25 mL round bottom flask. DCE (6 mL), anisole 1h (3 mmol, 324
mg) were then added in succession. AuCl3 (0.003 mmol, 1 mg) was dissolved in another 1 mL DCE. 0.1 mL of
this AuCl3 solution was added to the reaction mixture via syringe. The resulting mixture was allowed to stir for
about 20 h at 80 oC (monitored by GC-MS). The solution was then concentrated under reduced pressure and the
residue was purified by flash column chromatography (petroleum ether/EtOAc 20:1) to give methyl 4-
bromoanisole 2h (550 mg, yield 98%).

3.3 Converting arenes into aniline derivatives

NBS (1 mmol, 180 mg), AuCl3 (0.003 mmol, 0.5 mol%, 1.5 mg) were weighted in a 25 mL round bottom flask.
DCE (2 mL), benzo[d][1,3]dioxole 1o (1 mmol, 122 mg) were then added in succession. The resulting reaction
mixture was allowed to stir for about 4 h at room temperature (monitored by GC-MS). Upon completion of
bromination, the solvent was removed under reduced pressure. This residue was then dissolved in DMF (1 mL).
Newly prepared active copper (5 mmol, 320 mg) was added. The resulting mixture was irradiated by Microwave
(150 W, 150 oC, 30 min). The resulting solution was filtrated though celite and concentrated under reduced
pressure and the residue was purified by flash column chromatography (petroleum ether/EtOAc 1:1) to give 1-
(benzo[d][1,3]dioxol-5-yl)pyrrolidine-2,5-dione 3d (142 mg, 65% yield).

Preparation of active copper[1]:

HCl
CuSO4 5H2O + Zn Active Cu
H2O, rt

Zinc powder (650 mg, 10 mmol) was added to a solution of CuSO4 · 5H2O (3.25 g, 13 mmol), 4 drops of
concentrated HCl and 10 mL H2O at 0 oC. Then the resulting mixture was allowed to stir for 30 min at room
temperature. The precipitated copper was collected, washed with 10 mL H2O and 20 mL dry acetone, and dried
at 100 oC under vacuum for 1 h. The yield ranged 80~90 %. The fresh prepared active copper should be used
immediately. Otherwise, the copper may lose its catalytic activity.

3.4 Suzuki coupling as the sequential reaction

Ar'B(OH)2
cat. AuCl3 Pd(PPh3)4 (3 mol%)
ArH + NBS Ar-Ar'
DCE Na2CO3 (2 eq.)
THF/H2O, 80 oC

Upon completion of bromination (m-xylene 1d, 1 mmol scale), the solvent was removed under reduced pressure.
3-Nitrophenylboronic acid (200 mg, 1.2 eq., 1.2 mmol), Pd(PPh3)4 (35 mg, 3 mol%, 0.03 mmol) , Na2CO3 (212
mg, 2 eq., 2 mmol) and THF (1 mL)/H2O (1 mL) were added to the residue in succession. The reaction was
degassed 4 times and protected in nitrogen atmosphere and stirred at 80 oC for 12h. When the reaction was
completed, organic phase was separated and aqueous phase was washed with EtOAc (5 mL×2). The combined
organic phase was dried over Na2SO4. After concentration, the residue was purified by column chromatography
(petroleum ether/EtOAc 20:1) to give 2,4-dimethyl-3'-nitrobiphenyl 4a (215 mg, 95% yield).

3
3.5 Miyaura borylation as the sequential reaction

B2pin2 (1.1 eq.)

cat. AuCl3 PdCl2(dppf) (3 mol%) O
ArH + NBS Ar B
DCE KOAc (3 eq.), DMSO, 80 oC O

Upon completion of bromination (anisole 1h, 1 mmol scale), the solvent was removed under reduced pressure.
Bis(pinacolato)diboron (B2pin2) (280 mg, 1.1 eq., 1.1 mmol), PdCl2(dppf) [dppf = 1,1'-
bis(diphenylphosphino)ferrocene] (22 mg, 3 mol%, 0.03 mmol), KOAc (294 mg, 3 eq., 3 mmol) and DMSO (6
mL) were added to the residue in succession. The reaction was degassed 4 times and protected in nitrogen
atmosphere and carried out at 80 oC for 24 h. The resulting solution was extracted with benzene, washed with
water, and dried over anhydrous magnesium sulfate. After concentration, the residue was purified by column
chromatography (petroleum ether/EtOAc 20:1) to give 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-
dioxaborolane 5b (159 mg, 68% yield).

3.6 Sonogashira coupling as the sequential reaction

Ph H
cat. AuCl3 Pd(PPh3)4 (3 mol%)
ArH + NBS Ar Ph
DCE CuI (5 mol%), Et3N (2 eq.)
PhMe, 90 oC

Upon completion of bromination (naphthalene 1g, 1 mmol scale), the solvent was removed under reduced
pressure. Pd(PPh3)4 (35 mg, 3 mol%, 0.03 mmol), CuI (9 mg, 5 mol%, 0.05 mmol), PhMe (5 mL),
phenylacetylene (112 mg, 1.1 eq., 1.1 mmol) and Et3N (202 mg, 2 eq., 2 mmol) were added to the residue in
succession. The reaction was degassed 4 times and was protected in nitrogen atmosphere. The reaction was
carried out at 90 oC for 12 h. After concentration, the residue was purified by column chromatography
(petroleum ether/EtOAc 30:1) to give 1-(phenylethynyl)naphthalene 6a (164 mg, 72% yield).

4. Kinetic isotopic effect experiment

Br

Catalyst
1 eq. + NBS
DCE, 80 oC
1 eq. Br
d6 8h
d5

1 eq.

Catalyst loading: AuCl3 1 mol%; for other Lewis acids 20 mol%.

NBS (1 mmol, 178 mg), catalyst were weighted in a 25 mL round bottom flask. DCE (2 mL), benzene (78 mg, 1
mmol) and benzene-d6 (84 mg, 1 mmol) were then added in succession. The resulting solution was allowed to
stir for 8 h at 80 oC. Then the reaction mixture was subjected to GC analysis. When brominations were catalyzed
by BF3•OEt2, FeBr3, and ZrCl4, the kH/kD values were between 0.91 and 1.13. The kH/kD value is 1.66 in the case
of AuCl3-catalyzed bromination.

4
 Catalyzed by AuCl3
kH/kD ~ 1.66
Br Br
d5

37.6% 62.4%

Catalyzed by BF3·OEt2
kH/kD ~ 0.91
Br Br
d5

52.5% 47.5%

Catalyzed by FeBr3
Br Br kH/kD ~ 1.05
d5

51.3%
48.7%

Br
Catalyzed by ZrCl4
Br
kH/kD ~ 1.13
d5

47.0% 53.0%

5
5. Spectral data for selected compounds

2-Bromo-1,3,5-trimethylbenzene (2f). 1H NMR (300 MHz, CDCl3) δ 6.88 (s, 2H), 2.36 (s,
Br 6H), 2.23 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 137.9, 136.2, 129.0, 124.2, 23.7, 20.6; IR
film: 3353, 2950, 2922, 1464, 1377, 1028, 950, 848, 825, 697 cm-1; EI-MS (m/z, relative
intensity): 200 (M+, 59) 198 (61), 185 (6), 183 (6), 119 (100), 103 (14), 91 (31), 77 (12), 63
(7), 51 (8).
2f

Br 1-Bromonaphthalene (2g). 1H NMR (200 MHz, CDCl3) δ 8.23(d, J = 8.1 Hz, 1H),
7.86~7.75 (m, 3H), 7.62~7.44 (m, 2H), 7.33~7.22 (m, 1H); 13C NMR (50 MHz, CDCl3) δ
134.6, 131.9, 129.8, 128.2, 127.8, 127.2, 127.0, 126.6, 126.1, 122.8; IR film: 3054, 1590,
1561, 1501, 1252, 1199, 1135, 1021, 956, 788, 763 cm-1; EI-MS (m/z, relative intensity):
2g 208 (M+, 95), 207 (11), 206 (100), 128 (10), 127 (91), 126 (26), 101 (7), 77 (9), 63 (11).

OMe 1-Bromo-4-methoxybenzene (2h). 1H NMR (300 MHz, CDCl3) δ 7.37 (d, J = 8.8 Hz, 2H),
6.78 (d, J = 8.8 Hz, 2H), 3.78 (s, 3H); 13C NMR (50 MHz, CDCl3) δ 158.6, 132.1, 115.6,
112.7, 55.3; IR film: 2955, 2836, 1578, 1488, 1460, 1289, 1453, 1180, 1170, 1072, 1032,
1002, 821 cm-1; EI-MS (m/z, relative intensity): 188 (M+, 98), 186 (100), 173 (46), 171 (48),
145 (42), 143 (42), 92 (15), 77 (22), 63 (38), 50 (17).
Br 2h

OMe 2-Bromo-1,4-dimethoxybenzene (2i). 1H NMR (200 MHz, CDCl3) δ 7.13~7.10 (m, 1H),
Br 6.83~6.80 (s, 2H), 3.84 (s, 3H), 3.76 (s, 3H); 13C NMR (50 MHz, CDCl3) δ 154.0, 150.3,
118.9, 113.6, 112.9, 111.9, 56.8, 55.8; IR film: 2942, 2834, 1575, 1493, 1461, 1436, 1271,
1217, 1180, 1039, 863, 199, 731 cm-1; EI-MS (m/z, relative intensity): 218 (M+, 80), 216
(83), 203 (98), 201 (100), 175 (18), 173 (19), 107 (25), 79 (32), 63 (25).
OMe
2i

Methyl 5-bromo-2-methoxybenzoate (2j).[2] 1H NMR (200 MHz, CDCl3) δ 7.90

COOMe
(d, J = 2.6 Hz, 1H), 7.55 (dd, J = 8.9, 2.6 Hz, 1H), 6.87 (d, J = 8.9 Hz, 1H), 3.89 (s,
OMe 6H); 13C NMR (50 MHz, CDCl3) δ 165.1, 158.1, 135.9, 134.1, 121.6, 113.8, 112.1,
56.1, 52.1; IR film: 2945, 2842, 1732, 1487, 1462, 1395, 1298, 1274, 1242, 1181,
Br 1098, 1082, 1023, 968, 850, 811, 782, 676 cm-1; EI-MS (m/z, relative intensity):
2j 246 (M+, 29), 244 (31), 215 (70), 213 (100), 211 (40), 200 (7), 198 (8), 185 (11),
183 (10), 172 (17), 170 (17), 155 (15), 153 (15), 63 (29).

Br 5-Bromobenzo[d][1,3]dioxole (2o). 1H NMR (200 MHz, CDCl3) δ 6.98~6.92 (m, 2H),

O
6.69 (d, J = 8.7 Hz, 1H), 5.97 (s, 2H); 13C NMR (50 MHz, CDCl3) δ 146.9, 124.3,
113.0, 112.2, 110.3, 109.5, 101.5; IR film: 1711, 1607, 1500, 1473, 1233, 1038, 875,
O
757, 701 cm-1; EI-MS (m/z, relative intensity): 202 (M+, 93), 201 (83), 200 (100), 199
2o (81), 65 (21), 63 (68), 62 (26).

6
 O 1-Phenylpyrrolidine-2,5-dione (3a). 1H NMR (200 MHz, CDCl3) δ 7.52~7.35 (m, 3H),
7.30~7.25 (m, 2H), 2.86 (s, 4H); 13C NMR (50 MHz, CDCl3) δ 176.1, 131.8, 129.0,
N 128.5, 126.3, 28.3; IR film: 2957, 1706, 1595, 1505, 1394, 1189, 1148, 926, 766, 699cm-
1
; EI-MS (m/z, relative intensity):175 (M+, 100), 146 (9), 119 (48), 93 (31), 77 (17), 55
O (20).
3a

1-(4-Methoxyphenyl)pyrrolidine-2,5-dione (3b).[4] 1H NMR (200 MHz,

O CDCl3) δ 7.19 (d, J = 8.7 Hz, 2H), 6.98 (d, J = 8.7 Hz, 2H), 3.82 (s, 3H), 2.86 (s,
4H); 13C NMR (50 MHz, CDCl3) δ 176.3, 159.4, 127.6, 124.4, 114.4, 55.4,
MeO N 28.2; IR film: 2938, 1701, 1517, 1396, 1303, 1251, 1186, 1028, 822 cm-1.

O
3b

1-(3-Chloro-4-methylphenyl)pyrrolidine-2,5-dione (3c). 1H NMR (400 MHz,

Cl O CDCl3) δ 7.43 (d, J = 8.5 Hz, 1H), 7.16 (d, J = 2.4 Hz, 1H), 7.11~7.05 (m, 1H), 2.87
(s, 4H), 2.39 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 175.8, 137.2, 134.6, 131.1,
N 129.6, 128.6, 125.0, 28.3, 20.1; IR film: 1708, 1482, 1412, 1381, 1177, 1051, 819,
731, 710, 664 cm-1. EI-MS (m/z, relative intensity): 225 (M+, 34), 223 (100), 195
(12), 167 (30), 160 (34), 141 (49), 132 (30), 77 (28), 55 (83), 27 (51).
3c O

1-(Benzo[d][1,3]dioxol-5-yl)pyrrolidine-2,5-dione (3d). 1H NMR (400 MHz,

O
CDCl3) δ 6.90~6.88 (m, 1H), 6.74~6.72 (m, 2H), 6.02 (s, 2H), 2.88 (s, 4H); 13C
NMR (100 MHz, CDCl3) δ 176.2, 148.1, 147.8, 125.3, 120.3, 108.4, 107.6, 101.7,
O N
28.3; IR film: 2917, 1705, 1504, 1489, 1394, 1352, 1239, 1182, 1036, 930, 818, 729,
O 672 cm-1; EI-MS (m/z, relative intensity): 219 (M+, 100), 191 (15), 163 (20), 137
O (60), 77 (11), 55 (18), 27 (21). HRMS (ESI): calcd for C11H10NO4 [(M+H)+]
3d 220.0604, found 220.0600.

NO2 2,4-Dimethyl-3'-nitrobiphenyl (4a). 1H NMR (400 MHz, CDCl3) δ 8.20~8.17 (m, 2H),
7.65 (dt, J = 7.6, 1.3 Hz, 1H), 7.59~7.55 (m, 1H), 7.14~7.08 (m, 3H), 2.38 (s, 3H), 2.25
(s, 3H); 13C NMR (100 MHz, CDCl3) δ 148.0, 143.5, 138.1, 136.4, 135.3, 134.9, 131.4,
129.5, 128.9, 126.8, 124.1, 121.6, 21.0, 20.2; IR film: 2917, 1530, 1505, 1350, 1097, 906,
807, 752, 741, 692 cm-1; EI-MS (m/z, relative intensity): 227 (M+, 100), 212 (7), 181
(17), 165 (43), 152 (8), 89 (7), 39 (3). HRMS (ESI): calcd for C14H14NO2 [(M+H)+]
4a 228.1019, found 228.1015.

4-Methoxybiphenyl (4b). 1H NMR (400 MHz, CDCl3) δ 7.56~7.51 (m, 4H),

7.43~7.39 (m, 2H), 7.31~7.28 (m, 1H), 6.99~ 6.96 (m, 2H), 3.84(s, 3H); 13C
MeO NMR (100 MHz, CDCl3) δ 159.1, 140.8, 133.7, 128.7, 128.1, 126.7, 126.6,
114.2, 55.3; IR film: 3003, 1607, 1520, 1487, 1270, 1249, 1201, 1035, 908, 833,
4b 760, 732, 689 cm-1; EI-MS (m/z, relative intensity):184 (M+, 100), 169 (46), 141
(38), 115 (26), 76 (5), 63 (5).

7
 4,4,5,5-Tetramethyl-2-(naphthalen-1-yl)-1,3,2-dioxaborolane (5a). 1H NMR (400
O MHz, CDCl3) δ 8.76 (d, J = 8.3 Hz, 1H), 8.07 (d, J = 6.7 Hz, 1H), 7.92 (d, J = 8.3 Hz,
B 1H), 7.82 (d, J = 7.8 Hz, 1H), 7.53 (t, J = 7.8 Hz, 1H), 7.48~7.44 (m, 2H), 1.42 (s,
O 12H); 13C NMR (100 MHz, CDCl3) δ 136.9, 135.6, 133.2, 131.5, 128.4, 128.3, 126.3,
125.4, 124.9, 83.7, 24.9; IR film: 2978, 1508, 1337, 1257, 1147, 1134, 1059, 989, 867,
846, 804, 780, 738 cm-1; EI-MS (m/z, relative intensity): 254 (M+, 54), 168 (23), 155
5a (50), 154 (100), 153 (37).

2-(4-Methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5b). 1H
O NMR (400 MHz, CDCl3) δ 7.75 (d, J = 8.7 Hz, 2H), 6.89 (d, J = 8.7 Hz, 2H),
MeO B 3.82 (s, 3H), 1.33 (s, 12H); 13C NMR (100 MHz, CDCl3) δ 162.1, 136.4,
O 113.2, 83.5, 55.0, 24.8; IR film: 2978, 1604, 1396, 1360, 1318, 1277, 1247,
1175, 1143, 1091, 1030, 962, 860, 831, 736 cm-1; EI-MS (m/z, relative
5b
intensity): 234 (M+, 62), 219 (27), 148 (39), 135 (86), 134 (100), 133 (22), 43
(30), 41 (33).

1-(Phenylethynyl)naphthalene (6a).[5] 1H NMR (400 MHz, CDCl3) δ 8.40 (d,

J = 8.2 Hz, 1H), 7.82~7.71 (m, 3H), 7.62~7.26 (m, 8H); 13C NMR (100 MHz,
CDCl3) δ 133.3, 133.2, 131.6, 130.3, 128.7, 128.4, 128.4, 128.3, 126.7, 126.4,
126.2, 125.2, 123.4, 120.9, 94.3, 87.5; IR film: 3057, 1720, 1597, 1489, 1442,
6a 1396, 1175, 1069, 908, 798, 772, 754, 732, 689 cm-1.

5-(Phenylethynyl)benzo[d][1,3]dioxole (6b).[5] 1H NMR (400 MHz, CDCl3) δ

Ph
7.51~7.48 (m, 2H), 7.34~7.29 (m, 3H), 7.05 (dd, J = 8.0, 1.6 Hz, 1H,), 6.97 (d, J =
O 1.6 Hz, 1H), 6.77 (d, J = 8.0 Hz, 1H), 5.96 (s, 2H); 13C NMR (100 MHz, CDCl3) δ
147.8, 147.4, 131.4, 128.2, 128.0, 126.2, 123.3, 116.5, 111.5, 108.4, 101.2, 89.3,
O 87.7; IR film: 1596, 1501, 1483, 1442, 1338, 1228, 1115, 1087, 1039, 941, 927,
6b 908, 812, 735, 732, 789 cm-1.

OMe 1-Chloro-2,4-dimethoxybenzene (7c). 1H NMR (200 MHz, CDCl3) δ 7.24 (d, J =

8.6 Hz, 1H), 6.50 (d, J = 2.7 Hz, 1H), 6.43 (dd, J = 8.6, 2.7 Hz, 1H), 3.87 (s, 3H),
Cl
3.79 (s, 3H); 13C NMR (50 MHz, CDCl3) δ 159.4, 155.6, 130.0, 114.1, 105.1, 100.0,
56.0, 55.5; IR film: 2935, 2836, 1585, 1492, 1455, 1437, 1308, 1282, 1209, 1163,
MeO 1073, 1031, 823, 790, 660 cm-1; EI-MS (m/z, relative intensity): 174 (M+, 33), 172
7c (100), 157 (11), 142 (8), 131 (15), 129 (47), 114 (8), 107 (7), 99 (5), 86 (5), 79 (11),
63 (15), 51 (8).

2-Iodo-1,3,5-trimethylbenzene (8a). 1H NMR (300 MHz, CDCl3) δ 6.88 (s, 2H), 2.43 (s, 6H),
I 2.23 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 141.7, 137.3, 127.9, 104.2, 29.4, 20.6; IR film:
2919, 1571, 1460, 1376, 1299, 1176, 1130, 1003, 948, 846, 693 cm-1; EI-MS (m/z, relative
intensity): 246 (M+, 100), 127 (19), 119 (79), 103 (21), 91 (65), 77 (23), 63 (11), 51 (12).
8a

8
 Methyl 5-iodo-2-methoxybenzoate (8b).[3] 1H NMR (300MHz, CDCl3) δ 8.06 (d, J =
COOMe
2.3 Hz, 1H), 7.72 (dd, J = 8.7, 2.4 Hz, 1H), 6.75 (d, J = 8.8 Hz, 1H), 3.88 (s, 3H), 3.87
OMe (s, 3H); 13C NMR (50 MHz, CDCl3) δ 164.9, 158.8, 141.8, 139.8, 122.0, 114.2, 81.5,
56.0, 52.1; IR film: 2948, 1730, 1485, 1434, 1297, 1277, 1257, 1241, 1085, 1022, 810
I cm-1; EI-MS (m/z, relative intensity): 292 (M+, 100), 261 (100), 259 (58), 246 (10),
8b 231 (16), 218 (26), 203 (23), 134 (16), 76 (25), 63 (33).

6. References

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