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Supporting Information
An efficient copper-catalyzed N-arylation of NH-containing
heterocycles and sulfonamides with arenediazonium
tetrafluoroborates
Yu-Qing Ouyang, Zhen-Hua Yang, Zhong-Hui Chen and Sheng-Yin Zhao*
Department of Chemistry, Donghua University, No.2999 North Renmin Road,
Shanghai 201620, P. R. China
Tel: +86 21 67792436; Fax: +86 21 67792608-805; E-mail: [email protected]
Table of contents
(1) Experimental Part …………………………………………………………….S2
(2) 1H NMR and 13C NMR spectra of the products....................................................S7
1
(1) EXPERIMENTAL PART
Melting points were uncorrected and were determined with RY-1 apparatus. Infrared (IR)
spectra were determined as KBr pellets on a Shimadzu model 470 spectrophotometer. 1H NMR
and 13C NMR spectra were recorded using a Bruker AV 400 MHz spectrometer in CDCl3with
tetramethylsilane as internal standard. Chemical shifts (δ) are expressed in ppm. EI mass spectra
were recorded on Shimadzu QP-2010 GC-MS system and Waters Micromass GCT system. Silica
gel (100–200 microns) was used for all chromatographic separations. All materials were obtained
from commercial suppliers and were used as received. The purity of substrates and the monitoring
of reactions were performed by TLC on silica gel polygram SILG/UV 254 plates.
General procedure for the synthesis of aryldiazoniumtetrafluoroborates
Aniline (50 mmol) was dissolved in the 40% (V/V) fluoroboric acid (200 mmol). After cooling to
0 , an aqueous solution of sodium nitrite (3.6 g, 51 mmol) in 15 mL H℃ 2O was added dropwise
for 20 min. The mixture was stirred for 3 h and the thick precipitate was collected and washed
with diethyl ether (2×10 mL). The arenediazonium tetrafluoroborate was dried in vacuo (10-3
mbar) for 10 minutes and was then directly used without further purification.
General procedure for the synthesis of N-H containing heterocycles
To a mixture of NH-containing heterocycles (1.0 mmol), K2CO3 (1.0 mmol), CuCl catalyst (0.2
mmol), and 8mL DMSO, arenediazonium tetrafluoroborates (1.2 mmol) was added dropwise for
one hour at 25℃ under air condition. The reaction mixture was stirred for 12 h. After completion
of the reaction, the catalyst was filtered off, and H2O (15mL) was added. The mixture was
extracted with ethyl acetate (3×15mL). The combined extracts were washed with saturated sodium
chloride solution, dried, evaporated to dryness, and chromatographed on silica gel (eluting with
ethyl acetate and petroleum ether=8:1) to yield specified products 4a~4l. All of the products were
known compounds, and the data of mp and 1H NMR were in accord with those reported in the
literature.
1-phenyl-2,5-pyrrolidinedione (4a)1
2
Yield: 93%. White solid, mp156-158℃(lit.[1]156-157℃). IR(KBr,υcm-1):3109,3044,2849,1653,
1457, 1185,812. 1H NMR (400 MHz, CDCl3): δ= 2.93 (s, 4H), 7.31 (d, J = 8.1 Hz, 2H), 7.43 (t, J
= 7.0 Hz, 1H), 7.51 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ= 28.44, 126.48, 128.68,
129.23, 131.88, 176.20. MS(EI):m/z= 175 [M]+, 147, 119, 93, 55, 38.
1-(4-Methoxyphenyl)-2,5-pyrrolidinedione (4b)2
Yield: 95%. White solid, mp162-163℃ (lit.[2] 160-162℃). IR(KBr,υcm-1):3098, 1706, 1516,
1393, 1521,1250,1183. 1H NMR (400 MHz, CDCl3): δ= 2.85 (s, 4H), 3.82 (s, 3H), 6.99 (d, J = 8.9
Hz, 2H), 7.19 (d, J = 8.9 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ=28.36, 55.50, 114.52, 124.52,
127.72, 159.51, 176.57. MS(EI):m/z= 205 [M]+, 162, 134, 123, 78, 55.
2-Phenyl-1H-isoindole-1,3(2H)-dione (4c)3
Yield: 88%. White solid, mp 209-210℃(lit.[3] 208-210℃). IR(KBr,υcm-1): 3031,1733,
1700,1505,1454,1387, 1111.1H NMR (400 MHz, CDCl3): δ= 7.39–7.48(m,2H), 7.51(s,1H), 7.52-
7.56 (m,2H), 7.82(dd,J=5.4,3.1Hz,2H),7.98(dd,J=5.4,3.1Hz,2H). 13C NMR (101 MHz, CDCl3): δ=
123.76, 126.59, 128.12, 129.13, 131.69, 131.78, 134.41, 167.29. MS(EI):m/z= 223 [M]+, 179, 152,
104, 76, 50, 38.
2-(4-Methoxyphenyl)-1H-isoindole-1,3(2H)-dione (4d)4
Yield: 91%. Yellow solid, mp 160-162℃(lit.[4] 164-166℃). IR(KBr,υcm-1):3020,1710, 1603,
1513, 1384, 1248, 1106, 1024. 1H NMR (400 MHz, CDCl3): δ= 3.86 (s, 3H), 7.04 (d, J = 9.0 Hz,
2H), 7.36 (d, J = 9.0 Hz, 2H), 7.79 (dd, J = 5.5, 3.1 Hz, 2H), 7.95 (dd, J = 5.5, 3.0 Hz, 2H). 13C
NMR (101 MHz, CDCl3): δ= 55.52, 114.48, 123.65, 124.29, 127.95, 131.82, 134.32, 159.25,
167.57.MS(EI):m/z= 253 [M]+, 238, 210, 182, 130, 106, 76, 50, 38.
2-(4-Chlorophenyl)-1H-isoindole-1,3(2H)-dione (4e)5
Yield: 83%. White solid, mp 181-183℃(lit.[5] 182-183℃). IR(KBr,υcm-1): 3017,1710, 1496,
1392, 1118, 1080.1H NMR (400 MHz, CDCl3): δ= 7.43 (d, J = 7.7 Hz, 2H), 7.50 (d, J = 7.7 Hz,
2H), 7.83 (s, 2H), 7.97 (s, 2H). 13C NMR (101 MHz, CDCl3): δ= 123.89, 127.69, 129.33, 130.19,
131.59, 133.81, 134.61, 167.01. MS(EI):m/z= 257 [M]+, 213, 178, 151, 104, 76, 50, 38.
2-(4-Methoxyphenyl)-5-nitro-1H-isoindole-1,3(2H)-dione (4f)6
Yield: 81%. Yellow solid, mp 170-172℃IR(KBr,υcm-1): 3120, 1719, 1535, 1249, 1023. 1H NMR
(400 MHz, CDCl3): δ= 3.89 (s, 3H), 7.07 (d, J = 8.9 Hz, 2H), 7.37 (d, J = 8.9 Hz, 2H), 8.17 (d, J =
8.1 Hz, 1H), 8.69 (d, J = 9.9 Hz, 1H), 8.79 (s, 1H). 13C NMR(101MHz,CDCl3): δ= 55.57, 114.65,
3
119.10, 123.53, 124.92, 127.73, 129.54, 133.20, 136.20, 151.97, 165.20, 165.45. MS(EI):m/z=
298 [M]+, 181, 104, 91, 65, 38.
N-(4-Methoxyphenyl)benzenesulfonamide (4g)7
Yield: 85%. Yellow solid, mp 88-89℃(lit.[7] 91-92℃). IR(KBr,υcm-1):3263,2963,2840,1509,1352,
1148. 1H NMR (400 MHz, CDCl3): δ= 3.77 (s, 3H), 6.77 (d, J = 8.9 Hz,2H), 7.00 (d, J = 8.9 Hz,
2H), 7.45 (t, J = 7.7 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.74 (d, J = 7.6 Hz, 2H). 13C NMR (101
MHz, CDCl3): δ= 55.42, 114.44, 125.55, 127.30, 128.72, 128.95, 132.87, 138.91,
158.03.MS(EI):m/z= 263 [M]+, 122, 95, 51, 38.
N-(4-Chlorophenyl)-4-methylbenzenesulfonamide (4h)8
Yield:76%.White solid, mp 115-117℃ (lit.[8] 115-118℃). IR(KBr,υcm-1): 3230, 1482, 1344, 1195,
1160, 1087, 1005, 883.1HNMR (400 MHz, CDCl3): δ= 2.51 (s, 3H, CH3), 7.43 (d, J= 8.0 Hz, 2H,
Ar-H),7.50 (d, J= 8.8 Hz, 2H),7.80 (d, J= 8.8 Hz, 2H), 7.88 (d, J= 8.3 Hz, 2H).13CNMR (101
MHz, CDCl3): δ= 21.82, 125.72, 129.85, 129.89, 129.94,130.42, 141.26, 146.15, 147.51.
MS(EI):m/z= 282 [M]+, 155, 139, 91, 65.
N-(4-Nitrophenyl)-4-methylbenzenesulfonamide (4i)8
Yield:72%. Yellow solid, mp 188-190℃(lit.[8] 192-193℃). IR(KBr,υcm-1): 3270, 1524, 1334,
1170, 1004, 852. 1HNMR (400 MHz, CDCl3): δ= 2.523(d, J= 9.3 Hz, 3H), 7.46 (d, J= 8.3 Hz,
2H), 7.88–7.93 (m, 2H),7.97-8.01 (m, 2H), 8.36– 8.41 (m, 2H). 13C NMR (101 MHz, CDCl3): δ=
21.88, 124.93, 125.03, 129.07, 130.13, 130.62, 146.72, 150.76, 152.08. MS(EI):m/z= 292 [M]
+,155, 91, 65.
N-(3-Trifluoromethyl-4-chlorophenyl)-4-methylbenzenesulfonamide (4j)
Yield:67%. Yellow solid,mp 198-200℃. IR(KBr,υcm-1): 3268, 1597, 1484, 1353, 1249, 1166,
1128, 1028.1HNMR (400 MHz, CDCl3): δ= 2.52 (s, 3H, CH3), 7.29 (s, 1H, NH), 7.45 (d, J = 8.2
Hz, 2H, Ar-H ), 7.69 (d, J= 8.6 Hz, 1H, Ar-H), 7.89 (d, J= 8.2 Hz, 2H, Ar-H), 7.97 (dd, J = 8.6, 2.2
Hz, 1H, Ar-H), 8.17 (d, J= 2.1 Hz, 1H, Ar-H ). 13CNMR (101 MHz, CDCl3): δ= 21.87, 120.62,
124.35, 124.40(q, J = 10.1, 5.1 Hz), 127.29, 129.29, 130.11, 130.52, 132.91, 138.76, 146.58,
147.07. MS(EI):m/z= 349 [M]+, 207, 179, 91, 65.
1,2-Benzisothiazol-3(2H)-one, 2-phenyl-1,1-dioxide (4k)9
Yield: 67%. White solid, mp 189-191℃(lit.[9]187-189℃). IR(KBr,υcm-1):3084, 2917, 1733,
1653,1490, 1310, 1179. 1H NMR (400 MHz, CDCl3): δ= 7.58 (s, 5H), 7.93 (dd, J = 14.9, 7.4 Hz,
4
2H), 8.03(d, J = 7.4 Hz, 1H), 8.18 (d, J = 7.3 Hz, 1H). 13C NMR (101 MHz, CDCl3): δ= 121.28,
125.67, 127.18, 128.70, 128.78, 129.97, 130.17, 134.52, 135.15, 137.57, 158.43. MS(EI):m/z=
259 [M]+, 195, 179, 152, 119, 91, 64, 38.
2-(4-Methoxyphenyl)-1,1-dioxide-1,2-benzisothiazol-3(2H)-one (4l)10
Yield:73%. White solid, mp 210-212℃.IR(KBr,υcm-1): 3078, 2838, 1733, 1508, 1326, 1251,
1178, 1014. 1H NMR (400 MHz, CDCl3): δ= 3.89 (s, 3H), 7.08 (d, J = 8.4 Hz, 2H), 7.46 (d, J =
8.4 Hz, 2H), 7.99 – 7.87 (m, 2H), 8.02 (d, J = 7.3 Hz, 1H), 8.18 (d, J = 7.2 Hz, 1H). 13C NMR
(101 MHz, CDCl3): δ= 55.61, 115.31, 120.46, 121.31, 125.61, 127.29, 130.50, 134.42, 135.02,
137.59, 158.68, 160.99.MS(EI):m/z= 289 [M]+,192, 165, 89, 51, 38.
2-(4-Chloro-3-trifluoromethyl-phenyl)-1,1-dioxide-1,2-benzisothiazol-3(2H)-one (4m)
Yield: 56%. Yellow solid, mp 232-234℃. IR(KBr,υcm-1):3057, 2852, 1736, 1476, 1320, 1183,
1134. 1H NMR (400 MHz, CDCl3): δ= 7.73 (s, 2H), 7.92 (s, 1H), 7.98 (dt, J = 19.6, 7.3 Hz, 2H),
8.05 (d,J = 7.4 Hz, 1H), 8.21 (d, J = 7.5 Hz, 1H).13C NMR (101 MHz, CDCl3): δ= 120.69, 121.46,
125.95, 126.69, 127.71, 127.75, 127.80 (q, J = 10.1, 4.6 Hz), 132.65, 133.13, 134.31, 134.87,
135.60, 137.32, 158.11. HRMS (EI):m/zcalcd for C14H7ClF3NO3S: 361.99; found:361.9859
1-(4-Chlorophenyl)-1H-pyrazole (4n)11
Yield: 71%. White solid, mp52-54℃(lit.[11] 53-54℃). IR(KBr,υcm-1):3020, 1716, 1597, 1436,
1120, 880.1H NMR (400 MHz, CDCl3): δ= 6.51 (s, 1H), 7.44 (d, J = 8.8 Hz, 2H), 7.67 (d, J = 8.8
Hz, 2H), 7.75 (s, 1H), 7.92 (s, 1H).13C NMR (101 MHz, CDCl3): δ=108.00, 120.34, 126.76,
129.52, 131.94, 138.71, 141.34.MS(EI):m/z=178 [M]+,143, 111, 75, 63, 38.
1-(4-nitrophenyl)-1H-pyrazole (4o)12
Yield:63%. Yellow solid, mp 167-169℃(lit.[12] 170-172℃). IR(KBr,υcm-1): 3037,1596, 1333,
1234, 969. 1H NMR (400 MHz, CDCl3): δ= 6.60 (s, 1H), 7.83 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H),
8.08 (s, 1H), 8.37 (d, J = 8.2 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ= 109.43, 118.61, 125.42,
127.12, 142.83, 144.41, 145.42.MS(EI):m/z= 189 [M]+, 159, 142, 116, 89, 63, 38.
1-(3-Bromophenyl)-1H-tetrazole (4p)13
Yield:51%. White solid, mp 75-78℃(lit.[13] 80-82℃). IR(KBr,υcm-1):3125, 3110, 1583, 1490,
1458, 1211, 1179. 1H NMR (400 MHz, CDCl3): δ= 7.51 (t, J = 8.0 Hz, 1H), 7.71 (d, J = 8.0 Hz,
2H), 7.95 (s, 1H), 9.04 (s, 1H). 13C NMR (101 MHz, CDCl3): δ= 119.73, 123.78, 124.36, 131.54,
133.20, 134.71, 140.44. MS(EI):m/z= 225 [M]+, 196, 169, 117, 90, 63, 38.
5
1-(4-Methoxyphenyl)-5-phenyl-1H-tetrazole (4q)14
Yield:43%. White solid, mp 215-218℃. IR(KBr,υcm-1): 3027, 1610, 1578, 1474, 1398, 1250,
1192, 1103, 1020. 1H NMR (400 MHz, CDCl3):δ= 3.91 (s, 3H), 7.03 (d, J = 8.1 Hz, 2H), 7.33 (d,
J = 8.0 Hz, 2H), 7.43 (t, J = 7.4 Hz, 2H), 7.54 – 7.48 (m, 1H), 7.60 (d, J = 7.7 Hz, 2H). 13C NMR
(101 MHz, CDCl3): δ= 55.69, 114.98, 123.69, 126.76, 127.27, 128.87, 128.97, 131.21,153.59,
160.87. MS(EI):m/z= 252 [M]+,196, 119, 91, 63, 51, 38 .
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[3] Hsieh, J.C.; Cheng, C.H. Chem. Commun. 2005, 4554-4556.
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2905-2910.
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4552-4563.
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[13] Aridoss, G.; Laali, K.K. Eur. J. Org. Chem. 2011, (15), 2827-2835.
[14] Artamonova, T.V.; Zhivich, A.B.; Dubinskii, M.Y.; Koldobskii, G.I. Synthesis. 1996, 1428-
1430.
6
(2) 1H NMR and 13C NMR spectra1H NMR and 13C NMR spectra were recorded using a Bruker AV 400MHz spectrometer in CDCl3
with tetramethylsilane as internal standard.
7
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 1-phenyl-2,5-pyrrolidinedione (4a) in
CDCl3.
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 1-(4-methoxyphenyl)-2,5-
pyrrolidinedione(4b) in CDCl3.
8
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 2-phenyl-1H-isoindole-1,3(2H)-dione(4c)
in CDCl3.
9
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 2-(4-methoxyphenyl)-1H-isoindole-
10
1,3(2H)-dione in(4d) CDCl3.
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 2-(4-chlorophenyl)-1H-isoindole-
11
1,3(2H)-dione (4e) in CDCl3.
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 2-(4-methoxyphenyl)-5-nitro-1H-
12
isoindole-1,3(2H)-dione (4f) in CDCl3.
1H NMR (400MHz) and 13C NMR (101MHz) spectra of N-(4-
13
methoxyphenyl)benzenesulfonamide in (4g) CDCl3.
14
1H NMR (400MHz) and 13C NMR (101MHz) spectra ofN-(4-chlorophenyl)-4-methylbenzenesulfonamide(4h)in CDCl3.
15
1H NMR (400MHz) and 13C NMR (101MHz) spectra of N-(4-nitrophenyl)-4-
methylbenzenesulfonamide(4i)in CDCl3.
16
1H NMR (400MHz) and 13C NMR (101MHz) spectra of N-(3-trifluoromethyl-4-chlorophenyl)-4-
methylbenzenesulfonamide (4j) in CDCl3.
17
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 2-phenyl-1,1-dioxide -1,2-benzisothiazol-3(2H)-one(4k) in CDCl3.
18
1H NMR (400MHz) and 13C NMR (101MHz) spectra of, 2-(4-methoxyphenyl)-1,1-dioxide-1,2-benzisothiazol-3(2H)-one(4l) in CDCl3.
19
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 2-(4-Chloro-3-trifluoromethylphenyl)-
1,1-dioxide-1,2-benzisothiazol-3(2H)-one(4m) in CDCl3.
20
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 1-(4-chlorophenyl)-1H-pyrazole(4n) in
CDCl3.
21
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 1-(4-nitrophenyl)-1H-pyrazole (4o) in
CDCl3.
22
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 1-(3-bromophenyl)-1H-tetrazole (4p) in
CDCl3.
23
1H NMR (400MHz) and 13C NMR (101MHz) spectra of 1-(4-methoxyphenyl)-5-phenyl-1H-
tetrazole(4q) in CDCl3.
24