1 · Web viewTo a mixture of NH-containing heterocycles (1.0 mmol), K 2 CO 3 (1.0 mmol), CuCl...

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: syzhao8@dhu.edu.cn

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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[4] Begouin, A.; Queiroz, M. P. Eur. J. Org. Chem. 2009, 2820-2827.

[5] Prey, V.; Kerres, B.; Berbalk, H. Monatsh. Chem. 1960, 91, 319-330.

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[7] GarciaRuano, J.L.; Parra, A.; Marzo, L.; Yuste, F.; Mastranzo, V.M. Tetrahedron. 2011, 67,

2905-2910. 

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4552-4563.

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5193-5200.

[11] Correa, A.; Bolm, C. Angew. Chem. Int. Ed. 2007, 46, 8862-8865.

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[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