Supporting Information

 Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013

Visible-Light-Induced Radical Cyclization of Trifluoroacetimidoyl Chlorides

with Alkynes: Catalytic Synthesis of 2-Trifluoromethyl Quinolines
Xichang Dong, Youwei Xu, Jing Jing Liu, Yumin Hu, Tiebo Xiao, and Lei Zhou*[a]
chem_201303149_sm_miscellaneous_information.pdf

Contents
General.........................................................................................................................S1
Typical procedure for synthesis of 2-trifluoromethyl quinolines ................................S1
Characterization data ...................................................................................................S2
Reference: ..................................................................................................................S13
Scheme S1 and Figure S1......S13
1

H and 13C-NMR Spectra:..........................................................................................S17

S0

General All reactions were performed under argon atmosphere in a 10 mL schlenk

tube. MeCN was dried over CaH2 before use. Photoirradiation was carried out with a
5W blue LED. For chromatography, 200-300 mesh silica gel (Qingdao, China) was
employed. 1H NMR and

13

C NMR spectra were measured in CDCl3 and recorded on

Varian 300 or Brucker ARX 400 spectrometer. Mass spectra were obtained on
Thermo Trace GC Ultra-DCQ, and HRMS were performed on Bruker Daltonics
ESI-Q-TOF at Lenh Insititute of Functional Materials or Thermo MAT95XP mass
spectrometer at analytical center of Sun Yat-Sen University. The IR spectra were
measured on a Nicolet/Nexus 670 FT-IR spectrometer. Compounds described in the
literature were characterized by comparing their 1H NMR and

13

C NMR to the

reported values. Melting points were measured on X4 melting point apparatus

(Beijing Tech. Instrument) and uncorrected. Emission intensities were recorded using
a Hitachi F-4500 fluoresence spectrometer. N-aryl trifluoroacetimidoyl chlorides were
prepared according to the reference.1 Unless otherwise noted, materials obtained from
commercial suppliers were used without further purification.

Typical procedure for synthesis of 2-trifluoromethyl quinolines

A 10 mL snap vial under argon atmosphere was charged with Ru(bpy)3Cl26H2O

catalyst (3 mg, 2 mmol%) in dry acetonitrile (1 mL). N-aryl-trifluoroacetimidoyl
chloride (1, 0.2 mmol), alkyne (2, 0.4 mmol), and (nBu)3N (0.4 mmol) were added via
syringe. The solution was stirred at room temperature with the irradiation of a 5 W
blue LED. After the reaction was completed, as monitored by TLC, the resulting
mixture was filtered through a short path of silica gel, eluting with ethyl acetate. The
volatile compounds were removed in vacuo and the residue was purified by column
chromatography (SiO2) with hexane/ethyl acetate.

S1

Characterization data:
2,2,2-Trifluoro-N-phenylacetimidoyl chloride (1a):[1]
Pale yellow oil; IR (KBr): v (cm-1): 762, 1163, 1195, 1285, 1459,
Cl
N

CF3

1602, 1697, 2856, 2924; 1H-NMR (300MHz, CDCl3): (ppm):

7.47-7.42 (m, 2H), 7.33-7.29 (m, 1H), 7.12-7.10 (m, 2H); 13C-NMR

(75MHz, CDCl3): (ppm): 143.7, 132.1 (q, J = 42.8Hz), 129.3, 127.6, 120.8, 117.1(q,
J = 274.9Hz); 19F-NMR (282MHz, CDCl3): (ppm): -72.32 (s, 3F); MS (EI): m/z (%):
207(46)[M]+, 172 (62), 138(24), 77(100).
2,2,2-Trifluoro-N-(p-tolyl)acetimidoyl chloride (1b): [1]
Pale yellow oil; IR (KBr): v (cm-1): 765, 1161, 1195, 1285, 1460,
1697, 2855, 2924; 1H-NMR (300MHz, CDCl3): (ppm): 7.25 (d,
J = 8.1Hz, 2H), 7.09 (d, J = 7.8Hz, 2H), 2.41(s, 3H); 13C-NMR
(75MHz, CDCl3): (ppm): 140.8, 138.0, 130.7 (q, J= 43.1Hz), 129.9, 121.4, 117.1
(q, J= 274.7Hz), 21.4; 19F-NMR (282MHz, CDCl3): (ppm): -72.21(s, 3F); MS(EI):
m/z (%): 221(56)[M]+, 186(68), 152(24), 91(100).
2,2,2-Trifluoro-N-(4-methoxyphenyl)acetimidoyl chloride (1c): [1]
Pale yellow oil; IR (KBr): v (cm-1): 764, 833, 1033, 1157, 1218,
1252, 1506, 1600, 1680, 2930; 1H-NMR (300 MHz, CDCl3):
(ppm): 7.33 (d, J = 8.7Hz, 2H), 6.97 (d, J = 8.7Hz, 2H), 3.85
(s, 3H);

13

C-NMR (75MHz, CDCl3): (ppm): 159.8, 135.6, 128.2 (q, J = 37.8Hz),

124.5, 117.2 (q, J = 274.3Hz), 114.5, 55.7;

19

F-NMR (282 MHz, CDCl3): (ppm):

-72.00 (s, 3F); MS(EI): m/z (%): 237 (100)[M]+, 222(16), 202(98), 168(22), 107(40).
Ethyl 4-((1-chloro-2,2,2-trifluoroethylidene)amino)benzoate (1d): [2]
Pale yellow oil; IR (KBr): v(cm-1): 774, 945, 1020, 1104,
1165, 1198, 1225, 1276, 1501, 1604, 1722, 2934, 2984;
1

H-NMR (300 MHz, CDCl3): (ppm): 8.09 (d, J= 8.1Hz, 2H),

7.04 (d, J= 7.8Hz, 2H), 4.37 (q, J = 7.1Hz, 2H), 1.39 (t, J =7.1Hz, 3H);

13

C-NMR

(75MHz, CDCl3): (ppm): 165.7, 147.5, 134.1 (q, J = 43.3Hz), 130.9, 129.4, 119.9,
116.8 (q, J = 275.1Hz), 61.4, 14.5;

19

F-NMR (282MHz, CDCl3): (ppm): -72.54 (s,

3F); MS(EI): m/z (%): 279(26)[M]+, 251(30), 234(100).

N-(4-cyanophenyl)-2,2,2-trifluoroacetimidoyl chloride (1e): [2]
S2

Pale yellow oil; IR (KBr): v (cm-1): 764, 796, 1093, 1127, 1156,
1179, 1286, 1380, 1508, 1597, 1641, 2927; 1H-NMR (300MHz,
CDCl3): (ppm): 7.74 (d, J = 8.4Hz, 2H), 7.10 (d, J = 8.4Hz,
13

2H); C-NMR (75MHz, CDCl3): (ppm): 147.5, 135.5 (q, J = 43.4Hz), 133.5, 120.8,
118.2, 116.7 (q, J = 275.6Hz), 111.1; 19F-NMR (282MHz, CDCl3): (ppm): -72.46 (s,
3F); MS(EI): m/z (%): 232(48)[M]+, 197(74), 163(48), 102(100).
2,2,2-Trifluoro-N-(o-tolyl)acetimidoyl chloride (1f):[3]
Pale yellow oil; IR (KBr): v(cm-1): 765, 1163, 1207, 1287, 1694,
2858, 2924; 1H-NMR (300MHz, CDCl3): (ppm): 7.30-7.21 (m,
3H), 6.95 (d, J = 7.5Hz, 1H), 2.22 (s, 3H);

13

C-NMR (75MHz,

CDCl3): (ppm): 142.9, 132.5 (q, J = 42.7Hz), 131.0, 129.4, 127.2,

126.6, 118.6, 117.0 (q, J = 274.8Hz), 17.8;

19

F-NMR (282MHz, CDCl3): (ppm):

-72.11 (s, 3F); MS(EI): m/z (%):221(78)[M]+, 186(92), 166 (40), 152(14), 117(62), 91
(100).
N-(2,4-dichlorophenyl)-2,2,2-trifluoroacetimidoyl chloride (1g):[4]
Pale yellow oil; IR (KBr): v(cm-1): 764, 819, 955, 1167, 1203,
1227, 1289, 1471, 1694; 1H-NMR (300MHz, CDCl3): (ppm):
7.49 (s, 1H), 7.31 (d, J= 8.4Hz, 1H), 6.93 (d, J= 8.4Hz, 1H);
13

C-NMR (75MHz, CDCl3): (ppm): 140.4, 136.8 (q, J= 43.3Hz), 133.0, 130.3,

127.9, 125.8, 121.1, 116.8 (q, J= 275.6Hz);

19

F-NMR (282MHz, CDCl3): (ppm):

-72.30 (s, 3F); MS(EI): m/z (%): 275(56) [M]+, 234(100), 206(46), 171(16), 145(62),
109(38).
N-(2,5-dimethoxyphenyl)-2,2,2-trifluoroacetimidoyl chloride (1h):
Pale yellow oil; IR (KBr): v(cm-1): 706, 802, 952, 1045, 1159, 1224,
1277, 1504, 1612, 1698, 2838, 2956; 1H-NMR (300MHz, CDCl3):
(ppm): 6.92-6.89 (m, 1H), 6.79-6.76 (m, 1H), 6.53-6.52 (m, 1H),
3.79 (s, 3H), 3.78 (s, 3H);

13

C-NMR (75MHz, CDCl3): (ppm):

153.8, 143.3, 134.7 (q, J= 42.3Hz), 134.0, 117.0 (q, J= 275.0Hz), 113.5, 112.7, 106.8,
56.6, 56.1;

19

F-NMR (282MHz, CDCl3): (ppm): -72.09 (s, 3F); MS(EI): m/z (%):

267(100)[M]+, 252(72), 232(36), 217(46), 202(4), 183(26), 163(22), 148(12), 107(14);

HRMS(ESI) calcd. For C10H10ClF3NO2 [M+H]+: 268.0347, found: 268.0350.

S3

N-(2,5-dimethylphenyl)-2,2,2-trifluoroacetimidoyl chloride (1i):[5]

Pale yellow oil; IR (KBr): v (cm-1): 810, 944, 1161, 1212, 1289,
1503, 1695, 2926; 1H-NMR (300MHz, CDCl3): (ppm): 7.15 (d, J=
7.8Hz, 1H), 7.00 (d, J = 7.5Hz, 1H), 6.73 (s, 1H), 2.36 (s, 3H), 2.14
(s, 3H); 13C-NMR (75MHz, CDCl3): (ppm): 142.9, 136.4, 132.3 (q,
J = 42.5Hz), 130.8, 127.9, 126.0, 119.0, 117.1 (q, J = 274.8Hz), 21.3, 17.3; 19F-NMR
(282MHz, CDCl3): (ppm): -72.11 (s, 3F); MS(EI): m/z (%): 235(68)[M]+, 200(100),
180(24), 166(8), 131(50), 105(48);
N-(2,5-dichlorophenyl)-2,2,2-trifluoroacetimidoyl chloride (1j):
Pale yellow oil; IR (KBr): v (cm-1): 748, 810, 954, 1167, 1202,
1290, 1465, 1692; 1H-NMR (300MHz, CDCl3): (ppm): 7.40 (d,
J= 8.7Hz, 1H), 7.19 (d, J= 8.4Hz, 1H), 6.97 (s, 1H);

13

C-NMR

(75MHz, CDCl3): (ppm): 142.6, 137.6 (q, J= 43.5Hz), 133.3,

131.3, 127.7, 122.9, 120.2, 116.7 (q, J= 275.5Hz);

19

F-NMR (282MHz, CDCl3):

(ppm): -72.34 (s, 3F); MS(EI): m/z (%): 275(56)[M]+, 234(100), 206(44), 171(16),
145(68), 109(36); HRMS(EI) calcd. For C8H3NCl3F3 [M]+: 274.9278, found:
274.9279.
2,2,3,3,3-pentafluoro-N-phenylpropanimidoyl chloride (1k):[3]
Pale yellow oil; IR (KBr): v (cm-1): 690, 763, 1067, 1144, 1204,
1346, 1488, 1594, 1683; 1H-NMR (300MHz, CDCl3): (ppm):
7.48-7.43 (m, 2H), 7.35-7.30 (m, 1H), 7.15-7.12 (m, 2H);
13

C-NMR (75MHz, CDCl3): (ppm): 143.6, 132.5 (q, J = 32.8Hz), 129.3, 127.8,

121.0, 118.3 (qt, J = 284.6Hz, 34.8Hz), 108.1 (qt, J= 37.8Hz, 257.8Hz);

19

F-NMR

(282MHz, CDCl3): (ppm): -81.88 (s, 3F), -114.41 (s, 2F); MS(EI): m/z(%):
257(38)[M]+, 222(46), 138(38), 77(100).
4-Phenyl-2-(trifluoromethyl)quinoline (3aa):[6]
Pale yellow solid, m.p. 60-61oC; IR (KBr): v (cm-1): 703, 770, 884,
1093, 1132, 1187, 1262, 1383, 1493, 1509, 2870, 2929; 1H-NMR
(300MHz, CDCl3): (ppm): 8.29 (d, J = 8.7Hz, 1H), 7.99 (d, J =
8.4Hz, 1H), 7.85-7.80 (m, 1H), 7.68 (s, 1H), 7.64-7.59 (m, 1H),
7.55-7.54 (m, 5H);

13

C-NMR (75MHz, CDCl3): 151.0, 148.0, 147.7 (q, J= 34.2Hz),

137.3, 130.7, 129.7, 129.2, 129.0, 128.7, 127.6, 126.1, 121.9 (q, J= 273.2Hz), 117.2,
S4

117.2;

19

F-NMR (282MHz, CDCl3): (ppm): -68.15 (s, 3F); MS(EI): m/z(%):

273(100)[M]+, 252(30), 232(6), 204(52), 176(16), 151(6), 127(10), 101(14).

4-(p-Tolyl)-2-(trifluoromethyl)quinoline (3ab):
White solid, m.p. 61-63 oC; IR (KBr): v(cm-1): 768, 819, 880, 1090,
1133, 1185, 1261, 1383, 1463, 1502, 1587, 2859, 2923; 1H-NMR
(300MHz, CDCl3): (ppm): 8.28 (d, J= 8.4Hz, 1H), 8.02 (d, J=
8.4Hz, 1H), 7.83-7.78 (m, 1H), 7.67(s, 1H), 7.63-7.58 (m, 1H), 7.42
(d, J= 8.1Hz, 2H), 7.36 (d, J= 7.8Hz, 2H), 2.49 (s, 3H);

13

C-NMR

(75MHz, CDCl3): (ppm): 151.1, 148.0, 147.7 (q, J= 34.3Hz), 139.2, 134.4, 130.7,
130.6, 129.7, 129.6, 128.6, 127.7, 126.1, 121.9 (q, J= 273.3Hz), 117.1, 21.6; 19F-NMR
(282MHz, CDCl3): (ppm): -68.16 (s, 3F); MS(EI): m/z (%): 287(100)[M]+, 272(32),
252(20), 232(2), 218(22), 202(12), 107(14); HRMS(ESI) calcd. For C17H13F3N
[M+H]+: 288.0995, found: 288.0999.
4-(m-Tolyl)-2-(trifluoromethyl)quinoline (3ac):
Pale yellow oil; IR (KBr): v (cm-1): 706, 764, 894, 1093, 1127, 1155,
1178, 1286, 1380, 1596, 2926; 1H-NMR (300MHz, CDCl3): (ppm):
8.29 (d, J = 8.4Hz, 1H), 8.01 (d, J = 8.4Hz, 1H), 7.84-7.79 (m, 1H),
7.68 (s, 1H), 7.64-7.59 (m, 1H), 7.47-7.42 (m, 1H), 7.36-7.31 (m,
3H), 2.49 (s, 3H); 13C-NMR (75MHz, CDCl3): (ppm): 151.3, 147.9,
147.7 (q, J = 34.2Hz), 138.8, 137.3, 130.7, 130.3, 129.9, 128.8, 128.7, 127.7, 126.8,
126.2, 121.9 (q, J = 273.2Hz), 117.1, 117.1, 21.8; 19F-NMR (282MHz, CDCl3):
(ppm): -68.13 (s, 3F); MS(EI): m/z (%): 287 [M]+(100), 272(40), 252(28), 232(4),
218(22), 202(16), 142(4), 133(18); HRMS(ESI) calcd. For C17H13F3N [M+H]+:
288.0995, found: 288.1000.
4-(2,4-Dimethylphenyl)-2-(trifluoromethyl)quinoline (3ad):
Yellow oil; IR (KBr): v (cm-1): 769, 824, 889, 1089, 1137, 1190,
1265, 1379, 1499, 1614, 2866, 2925; 1H-NMR (300MHz, CDCl3):
(ppm): 8.30 (d, J = 8.4Hz, 1H), 7.84-7.79 (m, 1H), 7.63-7.54 (m,
3H), 7.21 (s, 1H), 7.18-7.16 (m, 1H), 7.14-7.11 (m, 1H), 2.46 (s, 3H),
2.04 (s, 3H); 13C-NMR (75MHz, CDCl3): (ppm): 151.4, 147.7 (q, J
= 34.2Hz), 147.7, 139.0, 135.9, 133.9, 131.3, 130.7, 130.6, 129.6, 128.7, 128.4, 126.9,
126.3, 121.9 (q, J = 273.3Hz), 117.6, 21.5, 20.2;
S5

19

F-NMR (282MHz, CDCl3):

(ppm): -68.08 (s, 3F); MS(EI): m/z (%): 301 [M]+(100), 286(34), 266(14), 232(30),
216(14), 189(8), 133(14), 108(10); HRMS(ESI) calcd. For C18H15F3N [M+H]+:
302.1151, found: 302.1155.
4-(4-Methoxyphenyl)-2-(trifluoromethyl)quinoline (3ae):
White solid, m.p. 66-69 oC; IR (KBr): v (cm-1): 770, 834, 1093, 1111,
1126, 1248, 1267, 1384, 1505, 1609; 1H-NMR (300MHz, CDCl3):
(ppm): 8.27 (d, J = 8.4Hz, 1H), 8.03 (d, J = 8.4Hz, 1H), 7.82-7.77
(m, 1H), 7.65 (s, 1H), 7.63-7.58 (m, 1H), 7.46 (d, J = 8.7Hz, 2H),
7.08 (d, J = 8.7Hz, 2H), 3.92 (s, 3H); 13C-NMR (75MHz, CDCl3):
(ppm): 160.5, 150.8, 148.0, 147.7 (q, J = 34.2Hz), 131.0, 130.7, 130.6, 129.6, 128.6,
127.8, 126.1, 121.9 (q, J = 273.3Hz), 117.1, 114.5, 55.7; 19F-NMR (282MHz, CDCl3):
(ppm): -68.15 (s, 3F); MS(EI): m/z (%): 303(100)[M]+, 288(10), 272(8), 219(4),
190(26); HRMS(ESI) calcd. For C17H13F3NO [M+H]+: 305.0944, found: 305.0948.
Methyl 4-(2-(trifluoromethyl)quinolin-4-yl)benzoate (3af):
Dark brown solid; m.p. 82-85 oC; IR (KBr): v (cm-1): 710, 772, 862,
1018, 1093, 1129, 1190, 1283, 1465, 1593, 1724, 2958, 3064;
1

H-NMR (300MHz, CDCl3): (ppm): 8.27 (d, J = 8.4Hz, 1H),

8.22-8.20 (m, 2H), 7.88 (d, J = 8.4Hz, 1H), 7.84-7.79 (m, 1H), 7.67
(s, 1H), 7.64-7.59 (m, 3H), 3.98 (s, 3H);

13

C-NMR (100MHz,

CDCl3): (ppm): 161.9, 151.1, 149.1, 148.9 (q, J = 34.7Hz), 143.0,

132.1, 132.0, 131.4, 131.0, 130.3, 128.4, 126.8, 122.9 (q, J = 276.4Hz), 122.0, 118.2,
53.7;

19

F-NMR (282MHz, CDCl3): (ppm): -68.16 (s, 3F); MS(EI): m/z (%):

331(78)[M]+, 312(4), 300(100), 272(12), 252(26), 232(10), 202(38), 175(10), 150(26),

101(30); HRMS(ESI) calcd. For C18H13F3NO2 [M+H]+: 332.0893, found: 332.0896.
1-(4-(2-(Trifluoromethyl)quinolin-4-yl)phenyl)ethanone (3ag):
Pale yellow solid, m.p.154-157 oC; IR (KBr): v (cm-1): 768, 844,
1094, 1128, 1183, 1291, 1681; 1H-NMR (300MHz, CDCl3):
(ppm): 8.23 (d, J = 8.7Hz, 1H), 8.11 (d, J = 8.1Hz, 2H), 7.87 (d, J =
8.4Hz, 1H), 7.81-7.76 (m, 1H), 7.64 (s, 1H), 7.61-7.59 (m, 3H),
2.68 (s, 3H);

13

C-NMR (75MHz, CDCl3): (ppm): 197.3, 149.7,

147.9, 147.6 (q, J= 34.3Hz), 141.8, 137.6, 130.9, 130.8, 130.0,

129.1, 128.8, 127.1, 125.6, 121.7 (q, J= 273.2Hz), 117.0, 27.0;
S6

19

F-NMR (282MHz,

CDCl3): (ppm): -68.15 (s, 3F); MS(EI): m/z (%): 315 (50)[M]+, 300(100), 272(4),
252(20), 232(6), 202(24), 175(6), 150(14), 123(24), 110(36); HRMS(ESI) calcd. For
C18H13F3NO [M+H]+: 316.0944, found: 316.0944.
4-(4-Fluorophenyl)-2-(trifluoromethyl)quinoline (3ah):
White solid, m.p. 72-75; IR (KBr): v (cm-1): 768, 842, 1093, 1130,
1158, 1185, 1383, 1504, 1605; 1H-NMR (300MHz, CDCl3): (ppm):
8.19 (d, J = 8.7Hz, 1H), 7.84 (d, J = 8.4Hz, 1H), 7.75-7.70 (m, 1H),
7.56-7.51 (m, 2H), 7.43-7.39 (m, 2H), 7.19-7.13 (m, 2H);

13

C-NMR

(75MHz, CDCl3): (ppm): 163.4 (d, J = 274.6Hz), 149.9, 148.0,

147.7 (q, J = 33.2Hz), 133.3 (d, J = 3.4Hz), 131.4 (d, J = 8.1Hz), 130.8, 130.8, 128.9,
127.6, 125.7, 121.8 (q, J = 273.1Hz), 117.2, 116.1 (d, J = 21.7Hz);

19

F-NMR

(282MHz, CDCl3): (ppm): -68.21 (s, 3F), -112.5(s, 1F); MS(EI): m/z (%):
291(100)[M]+, 270(24), 250(6), 222(44), 194(10), 175(8); HRMS(ESI) calcd. For
C16H10F4N [M+H]+: 292.0744, found: 292.0742.
4-(4-Chlorophenyl)-2-(trifluoromethyl)quinoline (3ai):
Pale yellow solid, m.p. 85-87 oC; IR(KBr): v (cm-1): 725, 769, 834,

Cl

890, 1089, 1138, 1184, 1382, 1488, 1596; 1H-NMR (300MHz,

CDCl3): (ppm): 8.27 (d, J = 8.4Hz, 1H), 7.92 (d, J = 8.7Hz, 1H),
7.84-7.79 (m, 1H), 7.65-7.60 (m, 2H), 7.57 (d, J = 8.4Hz, 2H), 7.46
N

CF3

(d, J = 8.4Hz, 2H);

13

C-NMR (75MHz, CDCl3): (ppm): 149.7,

147.9, 147.8 (q, J= 34.3Hz), 135.7, 135.5, 131.0, 130.8, 130.8, 129.3, 129.0, 127.4,
125.7, 121.8 (q, J= 273.2Hz), 117.1; 19F-NMR (282MHz, CDCl3): (ppm): -68.14 (s,
3F); MS(EI): m/z(%): 307[M]+ (100), 288(4), 272 (28), 252(52), 232(10), 212(2),
202(36), 176(16), 150(4), 126(34), 101(16); HRMS(ESI) calcd. For C16H10ClF3N
[M+H]+: 306.0448, found: 306.0449.
4-(4-Bromophenyl)-2-(trifluoromethyl)quinoline (3aj):
Pale yellow solid, m.p. 82-84 oC; IR (KBr): v (cm-1): 557, 768, 841,
1093, 1129, 1158, 1269, 1383, 1504, 1606; 1H-NMR (300MHz,
CDCl3): (ppm): 8.27 (d, J = 8.4Hz, 1H), 7.91 (d, J = 8.4Hz, 1H),
7.84-7.78 (m, 1H), 7.68 (d, J = 8.1Hz, 2H), 7.64-7.59 (m, 2H), 7.39
(d, J = 8.4Hz, 2H);

13

C-NMR (75MHz, CDCl3): (ppm): 149.7,

147.9, 147.7 (q, J = 34.4Hz), 136.2, 132.2, 131.2, 130.9, 130.8, 129.0, 127.3, 125.6,
S7

123.7, 121.8 (q, J = 273.3Hz), 117.0; 19F-NMR (282MHz, CDCl3): (ppm): -68.12 (s,
3F); MS(EI): m/z (%): 351[M]+(100), 332(4), 273(22), 252(64), 232(16), 202(66),
176(20), 126(34), 101(38); HRMS(ESI) calcd. For C16H10BrF3N [M+H]+: 351.9943,
found: 351.9944.
4-(Thiophen-3-yl)-2-(trifluoromethyl)quinoline (3ak):
White solid, m.p. 59-62 oC; IR (KBr): v (cm-1): 679, 769, 1097, 1126,

1178, 1258, 1348, 1422, 1506, 1587, 2958, 3094;

H-NMR

(300MHz, CDCl3): (ppm): 8.26 (d, J = 8.4Hz, 1H), 8.13 (d, J =

N

CF3

8.4Hz, 1H), 7.83-7.78 (m, 1H), 7.71 (s, 1H), 7.65-7.60 (m, 1H),
7.57-7.53 (m, 2H), 7.36-7.35 (m, 1H); 13C-NMR (75MHz, CDCl3):

(ppm): 148.0, 147.8 (q, J = 34.1Hz), 145.7, 137.8, 130.7, 128.8, 128.8, 127.6, 127.0,
125.9, 125.9, 121.8 (q, J = 273.1Hz), 116.9; 19F-NMR (282MHz, CDCl3): (ppm):
-68.12 (s, 3F); MS(EI): m/z (%): 279 (100)[M]+, 258(22), 234(16), 210(26), 184(6),
164(8), 107(10); HRMS(ESI) calcd. For C14H9F3NS [M+H]+: 280.0402, found:
280.0407.
Ethyl 3-phenyl-2-(trifluoromethyl)quinoline-4-carboxylate (3al):
Pale yellow oil; IR (KBr): v (cm-1): 706, 763, 1033, 1133, 1197,
1225, 1377, 1564, 1743, 2934, 2978; 1H-NMR (300MHz, CDCl3):
(ppm): 8.28 (d, J =8.4Hz, 1H), 7.87-7.82 (m, 1H), 7.67-7.58 (m,
2H), 7.51 (m, 3H), 7.38 (m, 2H), 4.09 (q, J = 7.2Hz, 2H), 1.03 (t, J
= 7.2Hz, 3H); 13C-NMR (75MHz, CDCl3): (ppm): 165.9, 148.9, 146.7, 143.5 (q, J =
34.3Hz), 134.6, 131.5, 130.5, 129.6, 129.4, 129.2, 128.5, 127.6, 126.8, 124.8, 121.5 (q,
J = 274.3Hz), 62.3, 13.9;

19

F-NMR (282MHz, CDCl3): (ppm): -65.10(s, 3F);

MS(EI): m/z (%): 345(46)[M] , 317(20), 300(100), 280(18), 252(32), 232(8), 202(24),
176(16); HRMS(EI) calcd. For C19H14F3NO2 [M]+: 345.0971, found: 345.0975.
6-Methyl-4-phenyl-2-(trifluoromethyl)quinoline (3ba) and 7-Methyl-4-phenyl2-(trifluoromethyl) quinoline (3ba):[7]

These compounds were obtained as a pale yellow oil (7: 3 mixture of 3ba and 3ba);
S8

IR (KBr): v (cm-1): 704, 768, 827, 886, 1094, 1131, 1184, 1263, 1384, 1500, 1586,
2867, 2924; 1H-NMR (300MHz, CDCl3) (ppm): 8.18 (d, J= 8.7Hz, 0.7H), 8.08 (s,
0.3H), 7.88 (d, J = 8.7 Hz, 0.3H), 7.74 (s, 0.7H), 7.65-7.63 (m, 1.8H), 7.55-7.53 (m,
4.9H), 7.43 (d, J = 8.7Hz, 0.3H), 2.60 (s, 0.8H), 2.51 (s, 2.2H);

13

C-NMR (75MHz,

CDCl3): (ppm): 150.7, 150.1, 148.2, 147.1 (q, J = 33.8Hz), 146.8(q, J = 34.7Hz),
146.6, 141.2, 139.1, 137.6, 137.5, 133.0, 131.0, 130.4, 129.6, 129.1, 129.0, 128.9,
127.6, 125.7, 124.7, 122.0 (q, J = 273.1Hz), 117.2, 116.4, 22.3, 22.0;

19

F-NMR

(282MHz, CDCl3) for (ppm): -67.96 (s, 2.2F), -68.10 (s, 0.8F); MS(ESI): m/z(%):
287(100) [M]+, 272(28), 252(20), 218(14), 202(8), 133(10), 107 (10)
6-Methoxy-4-phenyl-2-(trifluoromethyl)quinoline (3ca) and 7-Methoxy-4-phenyl2-(trifluoromethyl)quinoline (3ca): [7]

These compounds were obtained as a yellow oil (4: 1 mixture of 3ca and 3ca); IR
(KBr): v (cm-1): 707, 829, 1029, 1095, 1127, 1179, 1225, 1385, 1478, 1622, 2934,
2965; 1H-NMR (300MHz, CDCl3): (ppm): 8.16 (d, J = 9.3Hz, 0.8H), 7.85 (d, J
=9.3Hz, 0.2H), 7.62 (s, 0.8H), 7.58-7.43 (m, 6.2H), 7.27-7.21 (m, 1H), 3.98 (s, 0.6H),
3.81 (s, 2.4H); 13C-NMR (75MHz, CDCl3): (ppm): 161.6, 159.6, 150.7, 150.0, 149.2,
147.9 (q, J= 33.7Hz), 145.3 (q, J= 34.3Hz), 144.1, 137.7, 137.5, 132.1, 129.6, 129.4,
129.0, 128.9, 127.1, 123.5, 122.1 (q, J= 272.6Hz), 117.6, 115.3, 114.2, 108.2, 103.7,
56.0, 55.8; 19F-NMR (282MHz, CDCl3) (ppm): -67.83 (s, 2.4F), (ppm): -68.19 (s,
0.6F); MS(EI): m/z (%): 303(100)[M]+, 288(6), 272(10), 268(28), 218(10), 190(14).
Ethyl 4-phenyl-2-(trifluoromethyl)quinoline-6-carboxylate (3da) and Ethyl
4-phenyl-2- (trifluoromethyl)quinoline-7-carboxylate (3da):
Ph

Ph
EtOOC
and
N
3da

EtOOC

CF3

N
3da'

CF3

These compounds were obtained as a yellow oil (3: 1 mixture of 3da and 3da); IR
(KBr): v (cm-1): 706, 756, 1110, 1140, 1187, 1384, 1441, 1584, 1722, 2925; 1H-NMR
(300MHz, CDCl3) (ppm): 8.99 (s, 0.7H), 8.74 (s, 0.2H), 8.38 (d, J = 8.7Hz, 0.24H),
8.30 (d, J= 8.7Hz, 0.25H), 8.19 (d, J = 8.4Hz, 0.74H), 8.03 (d, J = 8.7Hz, 0.78H),
S9

7.74 (s, 1H), 7.55-7.53 (m, 5H), 4.50-4.32 (m, 2H), 1.49-1.38 (m, 3H);

13

C-NMR

(75MHz, CDCl3): (ppm): 165.8, 152.6, 151.1, 149.7, 149.2, 148.7 (q, J = 34.5Hz),
147.4, 136.8, 136.7, 133.0, 132.6, 131.3, 131.1, 131.0, 130.6, 130.1, 129.8, 129.7,
129.6, 129.5, 129.2, 129.1, 129.1, 128.1, 127.1, 126.4, 121.5 (q, J = 273.5Hz), 118.7,
117.8, 61.9, 14.6, 14.6; 19F-NMR (282MHz, CDCl3) (ppm): -68.39 (s, 2.2F); -68.48
(s, 0.8F); MS(EI): m/z (%): 345(66)[M]+, 317(34), 300(100), 272(28), 252(34),
232(14), 202(36), 176(10), 150(12), 101(8); HRMS(ESI) calcd. For C19H15F3NO2
[M+H]+: 346.1049, found: 346.1052;
4-Phenyl-2-(trifluoromethyl)quinoline-6-carbonitrile (3ea) and 4-phenyl-2(trifluoromethyl) quinoline-7-carbonitrile (3ea):

These compounds were obtained as a white solid (9: 1 mixture of 3ea: 3ea), m.p.
77-80 oC; IR (KBr): v (cm-1): 707, 778, 836, 1097, 1125, 1267, 1383, 1597, 2229,
2924; 1H-NMR (300MHz, CDCl3): (ppm): 8.61 (s, 0.9H), 8.38 (s, 0.1H), 8.14-8.11
(m, 0.9H), 7.95 (d, J = 8.4Hz, 0.1H), 7.80 (s, 1H), 7.77-7.74 (m, 1H), 7.59 (m, 3H),
7.52(m, 2H);

13

C-NMR (75MHz, CDCl3): (ppm): 152.1, 151.6, 150.3 (q, J =

35.3Hz), 149.6 (q, J= 35.2Hz), 148.8, 146.8, 136.4, 136.0, 132.7, 132.2, 131.2, 130.1,
129.9, 129.6, 129.5, 129.3, 129.2, 127.9, 127.1, 126.8, 121.3 (q, J = 276.1Hz), 119.5,
118.7, 118.3, 118.0, 115.9, 114.5, 112.7; 19F-NMR (282MHz, CDCl3) (ppm): -68.39
(s, 2.7F), -68.48 (s, 0.3F); MS(ESI): m/z (%): 298(100)[M]+, 277(24), 229(54), 207
(22), 175(10); HRMS(ESI) cald. For C17H10F3N2 [M+H]+: 299.0791, found:
299.0790.
8-Methyl-4-phenyl-2-(trifluoromethyl)quinoline (3fa):
Pale yellow oil; IR (KBr): v (cm-1): 735, 777, 885, 1138, 1186,
1266, 1449, 1491, 1584, 2867, 2931, 2269; 1H-NMR (300MHz,
CDCl3): (ppm): 8.16 (d, J = 8.4Hz, 1H), 7.71-7.66 (m, 1H), 7.55
(s, 1H), 7.48-7.46 (m, 3H), 7.39 (d, J = 6.9Hz, 1H), 7.35-7.33 (m,
2H), 2.06 (s, 3H);

13

C-NMR (75MHz, CDCl3): (ppm): 151.4, 149.1, 146.3 (q, J =

34.1Hz), 141.7, 136.0, 131.9, 130.3, 129.5, 128.8, 128.5, 128.3, 127.2, 121.8 (q, J =
273.2Hz), 119.3, 24.7; 19F-NMR (282MHz, CDCl3): (ppm): -68.20 (s, 3F); MS(EI):
S10

m/z (%): 287[M] +(100), 267(20), 252(6), 216(12), 189(12), 163(2), 132(14), 107(12),
93(8); HRMS(ESI) calcd. For C17H13F3N [M+H]+: 288.0995, found: 288.1000.
5-Methyl-4-phenyl-2-(trifluoromethyl)quinoline (3fa):
Pale yellow oil; IR (KBr): v (cm-1) : 701, 771, 888, 1112, 1137, 1173,
1200, 1260, 1492, 1593, 2853, 2925, 2956. 1H-NMR (300MHz,
CDCl3): (ppm): 7.82-7.79 (m, 1H), 7.66 (m, 2H), 7.52 (m, 6H),
2.91 (s, 3H);

13

C-NMR (75MHz, CDCl3): (ppm): 150.9, 147.0,

146.3 (q, J = 34.4Hz), 138.9, 137.9, 130.6, 129.7, 128.9, 128.8, 128.3, 127.6, 123.9,
122.0 (q, J = 273.2Hz), 117.0, 18.5; 19F-NMR (282MHz, CDCl3): (ppm): -68.14 (s,
3F); MS(EI): m/z (%): 287(100)[M]+, 267(20), 252(8), 216(12), 189(12), 107(10);
HRMS(ESI) calcd. For C17H13F3N [M+H]+: 288.0995, found: 288.0988.
6,8-Dichloro-4-phenyl-2-(trifluoromethyl)quinoline (3ga) and 5,7-dichloro-4phenyl-2- (trifluoromethyl)quinoline (3ga):

These compounds were obtained as a pale yellow solid (9: 1 mixture of 3ga and 3ga),
m.p. 90-93oC; IR (KBr): v(cm-1): 697, 764, 869, 1103, 1135, 1184, 1267, 1496, 1592,
2925; 1H-NMR (300MHz, CDCl3) (ppm): 8.24 (s, 0.9H), 7.91 (s, 0.1H), 7.86 (s,
0.1H), 7.75 (s, 0.1H), 7.66 (s, 0.9H), 7.62 (s, 0.9H), 7.47-7.46 (m, 3H), 7.34-7.32 (m,
2H); 13C-NMR (75MHz, CDCl3): (ppm): 151.4, 151.0, 149.4, 148.5 (q, J = 35.2Hz),
147.9 (q, J = 34.5Hz), 143.0, 139.5, 136.4, 136.1, 134.3, 132.3, 132.1, 131.6, 129.7,
129.6, 129.3, 129.3, 128.9, 128.8, 128.2, 124.0, 121.3 (q, J = 273.5Hz), 120.8, 119.0;
19

F-NMR (282MHz, CDCl3) (ppm): -68.57 (s, 2.7F), -68.21 (s, 0.3F); MS(EI): m/z

(%): 341(66)[M]+, 306(100), 286(68), 271(34), 236(34), 201(54), 175(16), 142(20);

HRMS(ESI) calcd. For C16H9Cl2F3N [M+H]+: 342.0059, found: 342.0061.
5,8-Dimethoxy-4-phenyl-2-(trifluoromethyl)quinoline (3ha):
White solid, m.p. 98-101 oC; IR (KBr): v (cm-1): 777, 803, 876,
1008, 1095, 1130, 1263, 1478, 1614, 2841, 2960, 3003; 1H-NMR
(300MHz, CDCl3): (ppm): 7.55 (s, 1H), 7.37 (m, 3H), 7.30 (m,
2H), 7.06 (d, J = 8.4Hz, 1H), 6.85 (d, J = 8.4Hz, 1H), 4.05 (s, 3H),
S11

3.45 (s, 3H); 13C-NMR (75MHz, CDCl3): (ppm): 150.5, 150.3, 149.8, 146.1 (q, J =
34.4Hz), 141.8, 140.8, 128.2, 127.6, 127.3, 121.8 (q, J = 273.3Hz), 120.8, 119.7,
109.1, 108.4, 56.8, 56.1;

19

F-NMR (282MHz, CDCl3): (ppm): -67.71 (s, 3F);

MS(EI): m/z (%): 333(48)[M]+, 318(100), 304(20), 288(12), 268(6), 190(5), 151(8),
126(4); HRMS(ESI) calcd. For C18H15F3NO2 [M+H]+: 334.1049, found: 334.1053.
5,8-Dimethyl-4-phenyl-2-(trifluoromethyl)quinoline (3ia):
Pale yellow oil; IR (KBr): v (cm-1): 735, 763, 1092, 1122, 1169,
1343, 1463, 1599, 2923; 1H-NMR (300MHz, CDCl3): (ppm):
7.57-7.53 (m, 2H), 7.47 (m, 3H), 7.34-7.27 (m, 3H), 2.87 (s, 3H),
2.01 (s, 3H)13C-NMR (75MHz, CDCl3): (ppm): 151.3, 148.0,
144.9 (q, J =34.3Hz), 142.1, 137.1, 133.4, 131.6, 130.4, 128.9, 128.3, 128.3, 127.2,
122.0 (q, J = 272.9Hz), 119.0, 24.7, 18.9;

19

F-NMR (282MHz, CDCl3): (ppm):

-68.13 (s, 3F); MS(EI): m/z(%): 301(100)[M]+, 286(26), 266(14), 216(8), 133(12);
HRMS(ESI) calcd. For C18H15F3N [M+H]+: 302.1151, found: 302.1151.
5,8-Dichloro-4-phenyl-2-(trifluoromethyl)quinoline (3ja):
Yellow oil; IR (KBr): v (cm-1): 700, 734, 769, 802, 832, 1094, 1128,
1265, 1488, 1590, 1663, 2855, 2926; 1H-NMR (300MHz, CDCl3):
(ppm): 7.85 (d, J = 8.1Hz, 1H), 7.71 (s, 1H), 7.59 (d, J= 8.1Hz, 1H),
7.48-7.46 (m, 3H), 7.34-7.33 (m, 2H); 13C-NMR (75MHz, CDCl3):
(ppm): 151.9, 147.7 (q, J = 35.2Hz), 145.5, 139.5, 134.8, 131.2, 130.3, 130.0,
129.0, 128.7, 128.2, 121.6, 121.5, 121.3 (q, J = 273.5Hz);

19

F-NMR (282MHz,

CDCl3): (ppm): -68.29 (s, 3F); MS(EI): m/z (%): 341(66)[M]+,

306(100),

286(72), 271(40), 236(35), 201(52); HRMS(ESI) calcd. For C16H9Cl2F3N [M+H]+:

342.0059, found: 342.0057.
2-(Perfluoroethyl)-4-phenylquinoline (3ka):
Pale yellow solid, m.p. 67-69 oC; IR (KBr): v(cm-1): 699, 769,
844, 1109, 1158,1207, 1510, 1582, 2960. 1H-NMR (300MHz,
CDCl3): (ppm): 8.32 (d, J= 8.4Hz, 1H), 8.01 (d, J= 8.7Hz, 1H),
7.85-7.80 (m, 1H), 7.71 (s, 1H), 7.65-7.60 (m, 1H), 7.55 (m, 5H);
13

C-NMR (75MHz, CDCl3): (ppm): 150.8, 148.1, 147.3 (t, J= 25.1Hz), 137.3, 130.9,

130.6, 129.7, 129.2, 129.0, 128.8, 127.5, 126.0, 119.4 (qt, J= 37.1Hz, 284.6Hz), 118.2,
111.7 (qt, J= 37.8Hz, 253.3Hz); 19F-NMR (282MHz, CDCl3): (ppm): -83.29 (s, 3F),
S12

-116.89 (s, 2F); MS(EI): m/z (%): 323(100)[M]+, 254(34), 234(14), 204(65), 176(20),
151(8), 127(50), 102(10), 87(14); HRMS(ESI) calcd. For C17H11F5N [M+H]+:
324.0806, found: 324.0805.
5,8-Dimethoxy-2-(trifluoromethyl)-4-(trimethylsilyl)quinoline (3hm):
Pale yellow oil; IR (KBr): v(cm-1): 809, 842, 1018, 1125, 1266,
OMe TMS
1346, 1476, 1614, 2950; 1H-NMR (300MHz, CDCl3): (ppm): 7.94
N

CF3

OMe

(s, 1H), 7.03 (d, J= 8.7Hz, 1H), 6.87 (d, J= 8.4Hz, 1H), 4.05 (s, 3H),
3.94 (s, 3H), 0.41 (s, 9H);

13

C-NMR (101MHz, CDCl3): (ppm):

150.5, 150.1, 149.3, 146.1 (q, J= 34.2Hz), 139.4, 126.6, 124.0, 121.2 (q, J= 276.7Hz),
108.2, 105.6, 56.8, 54.6, 1.2;

19

F-NMR (282MHz, CDCl3): (ppm): -67.65 (s, 3F);

MS(EI): m/z(%): 329(68)[M] , 314(84), 299(82), 270(100), 256(26), 149(16);

HRMS(EI) calcd. For C15H18F3NO2Si [M]+: 329.1053, found: 329.1051.
5,8-Dimethoxy-4-phenethyl-2-(trifluoromethyl)quinoline (3hn):
OMe

Ph

Pale yellow solid, m.p. 121-123 oC; IR (KBr): v(cm-1): 727, 809,
843, 1125, 1176, 1477, 1614, 2843, 3080; 1H-NMR (300MHz,

N
OMe

CF3

CDCl3): (ppm): 7.41 (s, 1H), 7.33-7.17 (m, 5H), 7.05 (d, J= 8.4Hz,
1H), 6.94 (d, J= 8.4Hz, 1H), 4.06 (s, 3H), 4.00 (s, 3H), 3.64 (t, J=

7.8Hz, 2H), 2.99 (t, J= 7.8Hz, 2H);

13

C-NMR (101MHz, CDCl3): (ppm): 153.0,

151.7, 147.9 (q, J= 34.6Hz), 142.7, 142.3, 129.8, 129.8, 127.6, 123.2, 123.0 (q, J=
276.4Hz), 120.6, 109.7, 108.3, 57.9, 57.2, 40.9, 39.5; 19F-NMR (282MHz, CDCl3):
(ppm): -67.97 (s, 3F); MS(EI): m/z(%): 361(55)[M]+, 346(66), 332(14), 270(20),
91(100); HRMS(EI) calcd. For C20H18F3NO2 [M]+: 361.1284, found: 361.1287.

S13

Reference:
[1] K. Tamura, H. Mizukami, K. Maeda, H. Watanabe, K. Uneyama, J. Org.Chem.
1993, 58, 32.
[2] J. Zhu, Z. Chen, H. Xie, S. Li, Y. Wu, Org. Lett. 2010, 12, 2434.
[3] S. Li, Z. Li, Y. Yuan, D. Peng, Y. Li, L. Zhang, Y. Wu, Org. Lett. 2012, 14, 1130.
[4] T. Kuragano, S. Nakamura, K. Minami, I. Minamida, T. Okauchi, Patent, JP
08295663 A 19961112, 1996.
[5] W. Maringgele, A. Meller, Monatsh. Chem. 1979, 110, 63.
[6] M. Zhu, W. Fu, G. Zou, C. Xun, D. Deng, B. Ji. J. Fluorine Chem. 2012, 135, 195.
[7] Y. Dan-oh, H. Matta, J. Uemura, H. Watanabe, K. Uneyama, Bull. Chem. Soc. Jpn.
1995, 68, 1497.

S14

Scheme S1. Radical trapping experiment with TEMPO.

The reaction was carried out under standart condition with the addition of 1 equiv. of
TEMPO. It was found that the reaction was completely suppressed and large amounts
of 1a and 2a remained unreacted.

When the reaction was quenched by 2 equiv of TEMPO after the mixture was
irradiated by 5 W blue LED for a period of 40 min, trace amount of
TEMPO-intermediate B adduct was detected by the GC-MS.

N
O
Ph
N

CF3

TEMPO-intermediate B adduct

[M+]

S15

Figure S1. Luminescence quenching by substrates 1a and Bu3N.

A Hitachi F-4500 fluoresence spectrometer was used to record the emission
intensities. All the solutions were excited at 465nm and the emission intensity at
595nm was observed. In a typical procedure, the emission spectrum of
Ru(bpy)3Cl26H2O solution (510-5M in 3 mL MeCN) was recorded after degassing
with a stream of argon for 30 min. Then appropriate amount of (n-Bu)3N or 1a was
added to the measured solution under the protection of argon. Here I and I0 represent
the intensities of the emission with or without the quenchers, respectively.

1. Luminescence quenching by substrates 1a.

I0/I

1a (mol/L)

2. Luminescence quenching by substrates (nBu)3N.

I0/I

n-Bu3N (mol/L)

S16

H and 13C NMR Spectra:

S17

S18

S19

S20

S21

S22

S23

S24

Me
Cl
N
Me

CF3

1i

Me
Cl
N
Me

CF3

1i

S25

S26

S27

S28

S29

S30

S31

S32

S33

S34

S35

S36

S37

S38

S39

S40

S41

S42

S43

S44

S45

S46

S47

S48

Ph

Cl

N
Cl

Cl

3ja

Ph

N
Cl

CF3

CF3

3ja

S49

S50

OMe TMS

CF3

OMe
3hm

OMe TMS

N
OMe
3hm

CF3

S51

OMe

Ph

N
OMe
3hn

CF3

OMe

Ph

N
OMe
3hn

CF3

S52