fecl -catalyzed cascade reaction: an efficient approach to ... · s1 supporting information...

S1

Supporting Information

FeCl3-Catalyzed Cascade Reaction: An Efficient Approach to

Functionalized Coumarin Derivatives

Xinwei He, Zhenglei Yan, Xiaoqian Hu, Yin Zuo, Chang Jiang, Lei Jin,

Yongjia Shang*

Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecule-Based

Materials, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, P.R. China

E-mail: [email protected]

Contents: pages

Table of

contents ································································································ S1

Experimental

section··························································································· S2 1H and 13C NMR spectra data of all products ················································· S3-S9 1H and 13C NMR spectra of all products ························································· S10-S29

Crystal data and structure refinement for 3b···················································· S30-S33

S2

Experimental Section

General comments 1H NMR spectra were recorded on a 300 MHz instrument. Chemical shifts for 1H NMR were reported as δ (parts per million) relative to the signal of CHCl3 at 7.26 (s) ppm. Chemical shifts for 13C NMR were reported as δ (parts per million) relative to the CDCl3 triplet at 76.0 ppm. HRMS were obtained using (ESI) mass spectrometer (TOF). IR spectra of liquid compounds were recorded as neat, whereas KBr plates were used for solid compounds. All solvents were purified and dried by following standard procedures unless otherwise stated.

General procedure for the synthesis of substituted coumarin derivatives 3. To a stirred solution of salicyladehyde 1 (1 mmol) and the activated methylene compounds 2 (1.2 mmol) in ethanol (3 mL) was added anhydrous FeCl3 (0.05mmol). The mixture was heated in an oil bath at 80 oC for 24 h and cooled down to room temperature. The solvent was removed under vacuum, and the residue was directly purified by flash column chromatography on silica gel (200-300 mesh) with ethyl acetate and petroleum ester (1:6-1:8, v/v) as eluting solvent to afford the product 3.

S3

1H and 13C NMR spectra data of all products

O O

CN

2-Oxo-2H-chromene-3-carbonitrile (3a) [1]

White solid; Yield: 123 mg, (72%); mp 175-176 oC.

IR (KBr) v: 3107, 3072, 3045, 2924, 2229, 1774, 1728, 1604, 1560, 1446, 1369, 1288, 1257, 1188,

1149, 1051, 972, 763 cm-1.

1H NMR (300 MHz, CDCl3) δ: 8.22 (s, 1H, CH), 7.67 (t, J = 7.5 Hz, 1H, ArH), 7.56 (d, J = 7.4

Hz, 1H, ArH), 7.35 (d, J = 4.6 Hz, 2H, ArH) ppm. 13C NMR (75MHz, CDCl3) δ: 151.9, 135.6, 129.3, 125.8, 117.5, 113.5, 106.8, 101.0 ppm.

HRMS (ESI) calcd for C10H5NO2 (M+H+) 172.0398, found 172.0393.

O O

CNCl

6-Chloro-2-oxo-2H-chromene-3-carbonitrile (3b) [2]

White solid; Yield: 153 mg (75%); mp 194-195 oC.

IR (KBr) v: 3068, 3037, 2378, 2310, 2243, 1735, 1612, 1562, 1479, 1415, 1359, 1247, 1186, 1051,

939, 881, 837, 765, 682 cm-1.

1H NMR (300 MHz, CDCl3) δ: 8.20 (s, 1H, CH), 7.65 (t, J = 8.7 Hz, 1H, ArH), 7.59 (s, 1H, ArH),

7.35 (d, J = 8.7 Hz, 1H, ArH) ppm. 13C NMR (75MHz, CDCl3) δ: 149.5, 134.3, 127.4, 127.2, 117.9, 117.2 ppm.

HRMS (ESI) calcd for C10H4ClNO2 (M+H+) 206.0009, found 206.0010.

O O

CNBr

6-Bromo-2-oxo-2H-chromene-3-carbonitrile (3c) [1]


IR (KBr) v: 3089, 3068, 2972, 2897, 2372, 1753, 1705, 1616, 1598, 1558, 1471, 1411, 1352, 1290,

1240, 1209, 1134, 1070, 1024, 995, 837, 794, 653 cm-1.

1H NMR (300 MHz, CDCl3) δ: 8.19 (s, 1H, CH), 7.78 (d, J = 9.0 Hz, 1H, ArH), 7.59 (s, 1H, ArH),

7.28 (d, J = 8.7 Hz, 1H, ArH) ppm. 13C NMR (75MHz, CDCl3) δ: 149.4, 137.1, 130.2, 118.0, 117.4 ppm.

HRMS (ESI) calcd for C10H4BrNO2 (M+H+) 249.9503, found 249.9503.

O O

CN(H3C)3

(CH3)3 6,8-Di-tert-butyl-2-oxo-2H-chromene-3-carbonitrile (3d) [3]

S4


IR (KBr) v:2970, 2910, 2875, 2320, 2233, 1745, 1614, 1577, 1465, 1452, 1394, 1369, 1330, 1244,

1201, 1176, 1041, 945, 761 cm-1.

1H NMR (300 MHz, CDCl3) δ: 8.24 (s, 1H, CH), 7.74 (s, 1H, ArH), 7.36 (s, 1H, ArH), 1.48 (s,

9H, t-Bu), 1.35 (s, 9H, t-Bu) ppm. 13C NMR (75MHz, CDCl3) δ: 152.3, 147.3, 137.3, 130.3, 122.9, 116.3, 113.0, 100.9, 34.3, 33.9,

30.3, 28.8 ppm.


7-Methoxy-2-oxo-2H-chromene-3-carbonitrile (3e) [4]

Yellow solid; Yield: 160 mg (80%); mp 127-128 oC.

IR (KBr) v: 3053, 2956, 2922, 2848, 2372, 2229, 1751, 1608, 1560, 1506, 1473, 1444, 1381,

1294, 1215, 1172, 1114, 1020, 829, 798 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.49 (s, 1H, CH), 7.48 (d, J = 8.4 Hz, 1H, ArH), 6.87 (d, J = 8.7

Hz, 1H, ArH), 6.80 (s, 1H, ArH), 3.89 (s, 3H, OCH3) ppm. 13C NMR (75MHz, CDCl3) δ: 165.2, 163.5, 151.3, 148.9, 130.6, 130.2, 114.4, 113.6, 111.6, 101.1,

101.0, 100.3, 55.9 ppm.


Ethyl 2-oxo-2H-chromene-3-carboxylate (3f) [5]


IR (KBr) v: 3469, 3062, 2978, 1776, 1766, 1606, 1564, 1450, 1375, 1296, 1247, 1207, 1132, 1033,

985, 962, 920, 866, 775 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.37 (s, 1H, CH), 7.49 (d, J = 7.3 Hz, 2H, ArH), 7.11-7.19 (m, 2H,

ArH), 4.23 (q, J = 6.7 Hz, 2H, CH2), 1.23 (t, J = 6.9 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 162.7, 156.5, 154.8, 134.3, 129.6, 124.8, 117.8, 117.6, 116.4, 61.7,

14.1 ppm.

HRMS (ESI) calcd for C12H10O4 (M+H+) 219.0657, found 219.0657.

Ethyl 6-chloro-2-oxo-2H-chromene-3-carboxylate (3g) [6]


IR (KBr) v: 3070, 2976, 2899, 2372, 1755, 1705, 1616, 1560, 1473, 1415, 1367, 1290, 1244, 1211,

1083, 1024, 997, 840, 794, 663, 605 cm-1.

S5

1H NMR (300 MHz, CDCl3) δ: 8.43 (s, 1H, CH), 7.60 (s, 1H, ArH), 7.26-7.33 (m, 2H, ArH), 4.43

(q, J = 6.9 Hz, 2H, CH2), 1.41 (t, J = 6.9 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 146.2, 133.2, 127.5, 117.9, 117.4, 61.3, 13.3 ppm.

HRMS (ESI) calcd for C12H9ClO4 (M+H+) 253.0267, found 253.0267.

Ethyl 6-bromo-2-oxo-2H-chromene-3-carboxylate (3h) [7]


IR (KBr) v: 3070, 2972, 2899, 2360, 1753, 1705, 1616, 1598, 1558, 1477, 1411, 1367, 1290, 1242,

1211, 1024, 995, 837, 794 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.44 (s, 1H, CH), 7.24 (s, 1H, ArH), 7.70-7.78 (m, 2H, ArH), 4.43

(q, J = 7.0 Hz, 2H, CH2), 1.41 (t, J = 7.2 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 161.7, 155.1, 153.0, 149.6, 146.2, 137.2, 136.0, 130.6, 130.5, 118.5,

118.4, 118.2, 117.6, 116.4, 61.3, 13.3 ppm.

HRMS (ESI) calcd for C12H9BrO4 (M+H+) 296.9762, found 296.9765.

Ethyl 7-methoxy-2-oxo-2H-chromene-3-carboxylate (3i) [8]

Yellow solid; Yield: 198 mg (80%); 132-134 oC.

IR (KBr) v: 3053, 2985, 2926, 2848, 2229, 1753, 1726, 1714, 1620, 1606, 1558, 1506, 1381,

1294, 1217, 1172, 1118, 1031, 829, 798, 761 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.48 (s, 1H, CH), 7.47 (d, J = 8.7 Hz, 1H, ArH), 6.87 (d, J = 8.7

Hz, 1H, ArH), 6.78 (s, 1H, ArH), 4.38 (q, J = 7.0 Hz, 2H, CH2), 3.87 (s, 3H, OCH3), 1.37 (t, J =

7.1 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 164.2, 162.5, 156.6, 156.2, 148.1, 129.8, 113.1, 112.7, 110.7, 99.4,

60.8, 55.1, 28.8, 13.4 ppm.


Ethyl 6-nitro-2-oxo-2H-chromene-3-carboxylate (3j) [9]


IR (KBr) v: 3088, 3055, 2993, 2922, 2372, 1780, 1757, 1691, 1618, 1570, 1527, 1497, 1348,

1305, 1257, 1219, 1095, 1018, 985, 848, 794, 752 cm-1.

1H NMR (300 MHz, CDCl3) δ: 8.56 (s, 1H, CH), 8.48 (d, J = 6.9 Hz, 1H, ArH), 7.48 (d, J = 9.0

Hz, 1H, ArH), 4.44 (q, J = 6.9 Hz, 2H, CH2), 1.41 (t, J = 6.9 Hz, 3H, CH3) ppm.

S6

13C NMR (75MHz, CDCl3) δ: 146.0, 127.7, 124.3, 117.2, 61.6, 13.3 ppm.

HRMS (ESI) calcd for C12H9NO6 (M+Na+) 286.0322, found 286.0324.

O O

O

O

N

Ethyl 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylate (3k) [10]

Pale brown solid; Yield: 231 mg (80%); mp 172-173 oC.

IR (KBr) v: 3525, 3446, 3354, 2976, 2922, 2872, 2700, 2376, 2322, 2220, 1732, 1699, 1622,

1589, 1514, 1477, 1446, 1423, 1354, 1311, 1222, 1186, 1141, 1103, 1028, 819, 792, 684, 638

cm-1.

1H NMR (300 MHz, CDCl3) δ: 8.38 (s, 1H, CH), 7.32 (d, J = 8.9 Hz, 1H, ArH), 6.57 (d, J = 8.7

Hz, 1H, ArH), 6.40 (s, 1H, ArH), 4.35 (q, J = 6.9 Hz, 2H, OCH2), 3.42 (q, J = 6.8 Hz, 2H, NCH2),

1.35 (t, J = 7.0 Hz, 3H, CH3), 1.20 (t, J = 6.7 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 163.3, 157.5, 152.0, 149.7, 148.2, 130.1, 129.8, 109.2, 108.6, 107.9,

106.7, 96.2, 95.7, 60.2, 44.3, 44.2, 13.5, 11.5 ppm.


O O

CN

CH3

4-Methyl-2-oxo-2H-chromene-3-carbonitrile (3l) [11]


IR (KBr) v: 3344, 3226, 2962, 2922, 2850, 2378, 2349, 2320, 2204, 1720, 1602, 1564, 1450,

1386, 1261, 1226, 1085, 1022, 804, 758 cm-1.

1H NMR (300 MHz, CDCl3) δ: 7.76 (d, J = 7.8 Hz, 1H, CH), 7.48 (t, J = 7.4 Hz, 1H, ArH), 6.98

(d, J = 8.4 Hz, 1H, ArH), 6.91 (t, J = 7.4 Hz, 1H, ArH), 2.64 (s, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 162.2, 156.7, 136.5, 130.7, 118.9, 118.4, 26.7 ppm.


O O

CH3

NH2

O

4-Methyl-2-oxo-2H-chromene-3-carboxamide (3m) [12]

Pale brown solid; Yield: 83 mg (41%).

IR (KBr) v: 3523, 3435, 3263, 3078, 2983, 2918, 2351, 2320, 1778, 1716, 1606, 1566, 1446,

1386, 1367, 1267, 1184, 1151, 1070, 925, 848, 752, 704, 576, 509 cm-1. 1H NMR (300 MHz, CDCl3) δ: 7.62 (d, J = 7.8 Hz, 1H, CH), 7.54 (t, J = 7.5 Hz, 1H, ArH), 7.33

(t, J = 7.7 Hz, 1H, ArH), 7.27 (d, J = 7.3 Hz, 1H, ArH), 6.31(s, 2H, NH2), 2.45 (s, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 165.3, 130.9, 123.6, 123.3, 116.2, 114.2, 17.7 ppm.

S7


O O

NH2

O

N

7-(Diethylamino)-2-oxo-2H-chromene-3-carboxamide (3n) [13]

Yellow solid; Yield: 150 mg (58%).

IR (KBr) v: 3392, 3319, 3151, 2964, 2926, 2868, 2351, 1691, 1666, 1620, 1566, 1514, 1423,

1355, 1251, 1188, 1136, 1080, 974, 806, 578 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.69 (s, 1H, CH), 8.55 (s, 1H, NH2), 7.40 (d, J = 8.9 Hz, 1H, ArH),

6.43 (d, J = 7.5 Hz, 1H, ArH), 6.48 (s, 1H, ArH), 5.88 (s, 2H, NH2), 3.46 (q, J = 6.9 Hz, 4H, CH2),

1.23 (t, J = 6.9 Hz, 6H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 164.1, 161.6, 157.0, 151.9, 147.9, 130.4, 109.1, 108.7, 107.4, 95.6,

44.2, 11.5 ppm.

HRMS (ESI) calcd for C14H16N2O3 (M+H+) 261.1239, found 261.1239.

3-Oxo-3H-benzo[f]chromene-2-carbonitrile (3o) [14]


IR (KBr) v: 2954, 2924, 2852, 2376, 2349, 2310, 1743, 1629, 1602, 1514, 1465, 1379, 1278,


Hz, 1H, ArH), 7.91 (d, J = 7.8 Hz, 1H, ArH), 7.74 (d, J = 7.2 Hz, 1H, ArH), 7.62 (d, J = 6.9 Hz,

1H, ArH), 7.46 (d, J = 8.7 Hz, 1H, ArH) ppm. 13C NMR (75MHz, CDCl3) δ: 162.7, 156.0, 155.0, 143.6, 135.2, 129.3, 128.9, 128.5, 128.3, 128.2,

125.7, 120.6, 115.7, 115.5, 111.3, 28.8 ppm.


Ethyl 3-oxo-3H-benzo[f]chromene-2-carboxylate (3p) [15]


IR (KBr) v: 3080, 2974, 2902, 2349, 1745, 1697, 1627, 1604, 1568, 1517, 1463, 1396, 1296,


Hz, 1H, ArH), 7.92 (d, J = 7.8 Hz, 1H, ArH), 7.74 (t, J = 7.5 Hz, 1H, ArH), 7.60 (t, J = 7.5 Hz,

S8

1H, ArH), 7.44 (d, J = 9.0 Hz, 1H, ArH), 4.47 (q, J = 10.5 Hz, 2H, CH2), 1.45 (t, J = 10.5 Hz, 3H,

CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 162.7, 155.0, 143.6, 135.2, 129.3, 128.5, 128.3, 128.2, 125.6, 120.6,

115.7, 115.5, 111.4, 61.2, 13.4 ppm.


O O

O

O

N

Methyl 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylate (3q)[16]


IR (KBr) v:3425, 3118, 2966, 2924, 2870, 1724, 1664, 1614, 1570, 1508, 1477, 1423, 1361, 1344,

1274, 1215, 1188, 1138, 1078, 817, 759, 621 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.45 (s, 1H, CH), 7.35 (d, J = 9.0 Hz, 1H, ArH), 6.61 (d, J = 9.0

Hz, 1H, ArH), 6.46 (s, 1H, ArH), 3.91 (s, 3H, CH3), 3.45 (q, J = 6.8 Hz, 4H, NCH2), 1.23 (t, J =

4.6 Hz, 6H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 163.5, 157.2, 152.0, 148.8, 130.2, 108.7, 106.8, 95.8, 51.5, 44.2,

28.8, 11.5 ppm.


O O

O

Br

3-Acetyl-6-bromo-2H-chromen-2-one (3r) [17]


IR (KBr) v: 2962, 2922, 2378, 2351, 2310, 1687, 1625, 1566, 1508, 1489, 1423, 1355, 1321,

1267, 1234, 1213, 1076, 1020, 813, 794 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.14 (s, 1H, CH), 7.57 (d, J = 8.7 Hz, 1H, ArH), 7.35 (s, 1H, ArH),

6.95 (s, 1H, ArH), 2.50 (s, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 172.8, 162.5, 148.4, 132.7, 132.3, 125.2, 118.5, 117.2, 116.9, 112.4,

21.7 ppm.

HRMS (ESI) calcd for C11H7BrO3 (M+H+) 266.9657, found 266.9655.

O O

O

N

3-Acetyl-7-(diethylamino)-2H-chromen-2-one (3s) [18]

Yellow solid; Yield: 98 mg (38%).

S9

IR (KBr) v: 3086, 2976, 2933, 2872, 2719, 2351, 2220, 1753, 1701, 1616, 1583, 1512, 1454,

1417, 1355, 1311, 1220, 1201, 1134, 1080, 1016, 970, 837, 796, 692 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.44 (s, 1H, CH), 7.39 (d, J = 7.5 Hz, 1H, ArH), 7.25 (d, J = 7.5

Hz, 1H, ArH), 6.61 (s, 1H, ArH) 3.45 (q, J = 6.7 Hz, 4H, NCH2), 2.69 (s, 3H, CH3), 1.23 (t, J =

6.9 Hz, 6H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 159.9, 152.1, 147.0, 131.0, 126.7, 116.2, 108.9, 95.7, 44.2, 11.5

ppm.


O

O

O

O2N

O

Ethyl 2-ethoxy-2-methyl-6-nitro-2H-chromene-3-carboxylate (3t)

Faint yellow solid; Yield: 291 mg (95%); mp 76-77 oC.

IR (KBr) v: 3089, 2981, 2939, 2906, 2351, 2310, 1942, 1716, 1618, 1577, 1521, 1477, 1373,

1344, 1273, 1215, 1161, 1095, 1043, 948, 885, 831, 750, 719 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.20 (d, J = 2.5 Hz, 1H, ArH), 8.17 (s, 1H, ArH), 7.70 (s, 1H, CH),

7.02 (d, J = 8.5 Hz, 1H, ArH), 4.32 (q, J = 7.1 Hz, 2H, CH2), 3.54 (q, J = 7.0 Hz, 2H, CH2), 1.98

(s, 3H, CH3), 1.37 (t, J = 7.1 Hz, 3H, CH3), 1.13 (t, J = 7.0 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 162.8, 157.7, 140.9, 132.6, 126.5, 125.9, 123.5, 117.5, 115.6, 101.9,

60.4, 58.0, 25.2, 14.2, 13.1 ppm.


References

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[2] Yuan, H.-J.; Wang, M.; Liu, Y.-J.; Wang, L.-L. Liu, J.; Liu, Q. Chem. Eur. J. 2010, 16, 13450-13457.

[3] Fringuelli, F.; Piermatti, O.; Pizzo, F. Synthesis 2003, 2331-2334.

[4] Valizadeh, H.; Mahmoodian, M.; Gholipour, H. J. Heterocyclic Chem. 2011, 48, 799-802.

[5] Diaz, U.; Garcia, T.; Velty, A.; Corma, A. Chem. Eur. J. 2012, 18, 8659-8672.

[6] Liu, J.-B.; Wu, F.-Y.; Zhao, L.-Z.; Zhao, Z.-B.; Wang, M.; Lei, S.-L. Chen, L.-J. Food Chem. 2012, 135,

2872-2878.

[7] Starcevic, S.; Turk, S.; Cesar, J.; Gobec, S.; Brozic, P.; Lanisnik Rizner, T. J. Med. Chem. 2011, 54, 248-261.

[8] Robert, S.; Bertolla, C.; Masereel, B.; Dogne, J.-M.; Pochet, L. J. Med. Chem. 2008, 51, 3077-3080.

[9] Martinez-Martinez, F. J.; Razo-Hernandez, R. S.; Peraza-Campos, A. L.; Cano, D. J.; Gomez-Sandoval, Z.;

Villanueva-Garcia, M.; Sumaya-Martinez, M. Molecules 2012, 17, 14882-14898.

[10] Kim, T.-H.; Swager, T. M. Angew. Chem, Int. Ed. 2003, 42, 4803-4806.

[11] Ranjith, C.; Vijayan, K. K.; Paul, N. Asian J. Chem. 2011, 23, 235-238.

[12] Jana, R.; Partridge, J. J.; Tunge, J. A. Angew. Chem, Int. Ed. 2011, 50, 5157-5161.

[13] Takechi, H.; Oda, Y.; Nishizono, N.i; Oda, K.; Machida, M. Chem. Pharm. Bull. 2000, 48, 1702-1710.

[14] Kumar, B. V.; Naik, H. S. B.; Girija, D.; Kumar, B. V. J. Chem. Sci. (Bangalore) 2011, 123, 615-621.

[15] Posakony, J.; Hirao, M.; Stevens, S.; Simon, J. A.; Bedalov, A. J. Med. Chem. 2004, 47, 2635-2644.

[16] Simonin, J.; Lochner, M.; Vernekar, S. K. V.; Thompson, A. J.; Lummis, S. C. R.; Hothersall, J. D.; Connolly,

S10

C. N. Bioorg. Med. Chem. Lett. 2012, 22, 1151-1155.

[17] Secci, D.; Carradori, S.; Bolasco, A.; Chimenti, P.; Yanez, M.; Ortuso, F.; Alcaro, S. Eur. J. Med. Chem. 2011,

46, 4846-4852.

[18] Wu, J.-S.; Sheng, R.-L.; Liu, W.-M.; Wang, P.-F.; Zhang, H.-Y.; Ma, J.-J. Tetrahedron 2012, 68, 5458-5463.

S11

1H and 13C NMR spectra of all products

3a O O

CN

3a

S12

3b O O

CNCl

3b

S13

3c O O

CNBr

3c

S14

3d

O O

CN(H3C)3

(CH3)3

3d

S15

3e

3e

S16

3f

3f

S17

3g

3g

S18

3h

3h

S19

3i

3i

S20

3j

3j

S21

3k

O O

O

O

N

3k

S22

3l O O

CN

CH3

3l

S23

3m O O

CH3

NH2

O

3m

S24

3n

O O

NH2

O

N

3n

S25

3o

3o

S26

3p

3p

S27

3q

O O

O

O

N

3q

S28

3r O O

O

Br

3r

S29

3s

O O

O

N

3s

S30

3t

O

O

O

O2N

O

3t

S31

Crystal data and structure refinement for 3b

X-ray Crystallography

The diffraction data for 3b were collected on a Bruker SMART APEX diffractometer using Mo K

α (λ = 0.71073 Å). The crystallographic data are listed in Table S1. The CIF deposition number:

CCDC-850126.

Table S1. Crystal data and structure refinement for 3b.

Identification code h0521_0m

Empirical formula C20 H8 Cl2 N2 O4

Formula weight 411.18

Temperature 293(2) K

Wavelength 0.71073 A

Crystal system, space group Monoclinic, P2(1)/c

Unit cell dimensions a = 9.3655(13) A alpha = 90 deg.

b = 11.4888(16) A beta = 105.226(2) deg.

c = 16.559(2) A gamma = 90 deg.

Volume 1719.2(4) A^3

Z, Calculated density 4, 1.589 Mg/m^3

Absorption coefficient 0.410 mm^-1

F(000) 832

Crystal size 0.30 x 0.25 x 0.23 mm

Theta range for data collection 2.18 to 27.55 deg.

Limiting indices -12<=h<=12, -14<=k<=14, -20<=l<=21

Reflections collected / unique 14389 / 3951 [R(int) = 0.0268]

Completeness to theta = 27.55 99.5 %

Absorption correction Semi-empirical from equivalents

Max. and min. transmission 0.9117 and 0.8870

Refinement method Full-matrix least-squares on F^2

Data / restraints / parameters 3951 / 0 / 253

Goodness-of-fit on F^2 1.000

Final R indices [I>2sigma(I)] R1 = 0.0351, wR2 = 0.0986

R indices (all data) R1 = 0.0409, wR2 = 0.1059

Largest diff. peak and hole 0.231 and -0.316 e.A^-3

Table S2. Selected Bond lengths [Å] and angles [°] for 3b.

C(1)-O(1) 1.3741(16)

C(1)-C(2) 1.3807(19)

C(1)-C(6) 1.3973(17)

C(2)-C(3) 1.376(2)

C(2)-H(2) 0.9300

C(3)-C(4) 1.395(2)

C(3)-H(3) 0.9300

C(4)-C(5) 1.372(2)

S32

C(4)-Cl(1) 1.7357(14)

C(5)-C(6) 1.4018(19)

C(5)-H(5) 0.9300

C(6)-C(7) 1.4285(18)

C(7)-C(8) 1.3495(18)

C(7)-H(7) 0.9300

C(8)-C(10) 1.4342(18)

C(8)-C(9) 1.4619(18)

C(9)-O(2) 1.1953(18)

C(9)-O(1) 1.3739(17)

C(10)-N(1) 1.1361(19)

C(11)-O(4) 1.3749(15)

C(11)-C(12) 1.3818(19)

C(11)-C(16) 1.3982(17)

C(12)-C(13) 1.380(2)

C(12)-H(12) 0.9300

C(13)-C(14) 1.397(2)

C(13)-H(13) 0.9300

C(14)-C(15) 1.3691(19)

C(14)-Cl(2) 1.7336(13)

C(15)-C(16) 1.4065(18)

C(15)-H(15) 0.9300

C(16)-C(17) 1.4298(18)

C(17)-C(18) 1.3469(18)

C(17)-H(17) 0.9300

C(18)-C(20) 1.4307(19)

C(18)-C(19) 1.4629(17)

C(19)-O(5) 1.2008(16)

C(19)-O(4) 1.3664(16)

C(20)-N(2) 1.137(2)

O(1)-C(1)-C(2) 117.16(11)

O(1)-C(1)-C(6) 121.19(11)

C(2)-C(1)-C(6) 121.64(12)

C(3)-C(2)-C(1) 119.24(13)

C(3)-C(2)-H(2) 120.4

C(1)-C(2)-H(2) 120.4

C(2)-C(3)-C(4) 119.72(13)

C(2)-C(3)-H(3) 120.1

C(4)-C(3)-H(3) 120.1

C(5)-C(4)-C(3) 121.49(13)

C(5)-C(4)-Cl(1) 120.29(11)

C(3)-C(4)-Cl(1) 118.20(11)

C(4)-C(5)-C(6) 119.25(12)

S33

C(4)-C(5)-H(5) 120.4

C(6)-C(5)-H(5) 120.4

C(1)-C(6)-C(5) 118.65(12)

C(1)-C(6)-C(7) 117.91(12)

C(5)-C(6)-C(7) 123.41(12)

C(8)-C(7)-C(6) 120.16(12)

C(8)-C(7)-H(7) 119.9

C(6)-C(7)-H(7) 119.9

C(7)-C(8)-C(10) 121.59(12)

C(7)-C(8)-C(9) 121.90(12)

C(10)-C(8)-C(9) 116.49(12)

O(2)-C(9)-O(1) 118.21(13)

O(2)-C(9)-C(8) 125.77(13)

O(1)-C(9)-C(8) 116.01(12)

N(1)-C(10)-C(8) 178.06(16)

O(4)-C(11)-C(12) 117.27(11)

O(4)-C(11)-C(16) 120.95(11)

C(12)-C(11)-C(16) 121.78(12)

C(13)-C(12)-C(11) 118.89(13)

C(13)-C(12)-H(12) 120.6

C(11)-C(12)-H(12) 120.6

C(12)-C(13)-C(14) 119.95(13)

C(12)-C(13)-H(13) 120.0

C(14)-C(13)-H(13) 120.0

C(15)-C(14)-C(13) 121.50(12)

C(15)-C(14)-Cl(2) 119.99(11)

C(13)-C(14)-Cl(2) 118.51(11)

C(14)-C(15)-C(16) 119.19(12)

C(14)-C(15)-H(15) 120.4

C(16)-C(15)-H(15) 120.4

C(11)-C(16)-C(15) 118.67(12)

C(11)-C(16)-C(17) 118.13(11)

C(15)-C(16)-C(17) 123.20(12)

C(18)-C(17)-C(16) 119.96(12)

C(18)-C(17)-H(17) 120.0

C(16)-C(17)-H(17) 120.0

C(17)-C(18)-C(20) 122.00(12)

C(17)-C(18)-C(19) 121.87(12)

C(20)-C(18)-C(19) 116.09(11)

O(5)-C(19)-O(4) 118.23(12)

O(5)-C(19)-C(18) 125.50(13)

O(4)-C(19)-C(18) 116.28(11)

N(2)-C(20)-C(18) 178.83(18)

C(1)-O(1)-C(9) 122.58(10)

S34

C(19)-O(4)-C(11) 122.73(10)

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