electronic supplementary information (esi) direct …electronic supplementary information (esi)...

Electronic Supplementary Information (ESI)

Direct N-Alkylation of Amino-azoles with Alcohols Catalyzed by an Iridium Complex/Base System

Feng Li,* Haixia Shan, Lin Chen, Qikai Kang and Po Zou

School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. China

General Experimental Details Infrared spectra were recorded on a Nicolet iS10 FT-IR spectrometer. High-resolution mass spectra (HRMS) were obtained on a HPLC-Q-Tof MS(Micro) spectrometer and are reported as m/z (relative intensity). Accurate masses are reported for the molecular ion [M+H]+. Melting points were measured on a X-6 micro-melting apparatus (Beijing Tech Instrument Co., Ltd). Proton nuclear magnetic resonance (1H NMR) spectra were recorded at 500 MHz using a Bruker Avance 500 spectrometer. Chemical shifts are reported in delta (δ) units, parts per million (ppm) downfield from trimethylsilane or ppm relative to the center of the singlet at 7.26 ppm for CDCl3 and 2.50 ppm for DMSO-d6. Coupling constants J values are reported in Hertz (Hz), and the splitting patterns were designated as follows: s, singlet; d, doublet; t, triplet; m, multiplet; b, broad. Carbon-13 nuclear magnetic resonance (13C NMR) spectra were recorded at 125 MHz using a Bruker Avance 500 spectrometer. Chemical shifts are reported in delta (δ) units, ppm relative to the center of the triplet at 77.0 ppm for CDCl3 and 39.5 ppm for DMSO-d6. 13C NMR spectra were routinely run with broadband decoupling.

[Cp*IrCl2]2 (Cp* = pentamethylcyclopentadienyl) and [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) were prepared according to literature methods.1,2 Commercially unavailable amino-azoles were synthesized according to the previously reported procedures.3,4 Reactions tubes were purchased from Beijing Synthware Glass Inc. All reactions were run under an atmosphere of nitrogen, unless otherwise indicated. Analytical thin-layer chromatography (TLC) was carried out using 0.2-mm commercial silica gel plates.

General Procedure for direct N-alkylation of amino-azoles with alcohols catalyzed by an iridium complex/base system To an oven-dried, nitrogen purged 20 ml Schlenk tube were added amino-azole (1mmol), [Cp*IrCl2]2 (0.002 mmol, 0.2 mol%), base (0.2 mmol, 20 mol%) and alcohol (5 mmol, 500 mol%). The resulting mixture was heated at 150 oC for 12h, followed by the mixture of the reaction was allowed to cool to ambient temperature. The mixture of the reaction was concentrated in vacuo and purified by flash column chromatography with hexane/ethyl acetate to afford the corresponding product.

Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2011

N-butylbenzo[d]thiazol-2-amine (3aa)5

S

NHN

mp 69.6-70.6 oC (lit.5 mp 68 oC); 1H NMR (500 MHz, CDCl3) δ 7.58 (d, J = 7.9 Hz, 1H, ArH), 7.52 (d, J = 8.1 Hz, 1H, ArH), 7.29 (t, J = 7.6 Hz, 1H, ArH), 7.07 (t, J = 7.6 Hz, 1H, ArH), 5.49 (br s, 1H, NH), 3.42 (t, J = 7.1 Hz, 2H, CH2N), 1.68 (quint, J = 7.3 Hz, 2H, CH2), 1.45 (sext, J = 7.4 Hz, 2H, CH2), 0.97 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 168.0, 152.4, 130.2, 125.9, 121.2, 120.7, 118.5, 45.4, 31.6, 20.0, 13.7. N-hexylbenzo[d]thiazol-2-amine (3ab)6

S

NHN

mp 58.5-59.4 oC (lit.6 mp 53.2-55.4 oC); 1H NMR (500 MHz, CDCl3) δ 7.58 (d, J = 7.9 Hz, 1H, ArH), 7.53 (d, J = 8.1 Hz, 1H, ArH), 7.29 (t, J = 7.7 Hz, 1H, ArH), 710 (t, J = 7.5 Hz, 1H, ArH), 5.39 (br s, 1H, NH), 3.41 (t, J = 7.1Hz, 2H, CH2N), 1.68 (quint, J = 7.3 Hz, 2H, CH2), 1.41 (quint, J = 7.2 Hz, 2H, CH2), 1.34-1.30 (m, 4H, 2xCH2), 0.90 (t, J = 7.1Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 168.0, 152.5, 130.2, 125.8, 121.2, 120.7, 118.5, 45.7, 31.4, 29.5, 26.5, 22.5, 13.9. N-octylbenzo[d]thiazol-2-amine (3ac)

S

NHN

mp 43.0-44.3 oC; 1H NMR (500 MHz, CDCl3) δ 7.58 (d, J = 7.7 Hz, 1H, ArH), 7.50 (d, J = 8.1 Hz, 1H, ArH) 7.28 (t, J = 7.8 Hz, 1H, ArH),7.06 (t, J = 7.6 Hz, 1H, ArH), 6.29 (br s, 1H, NH), 3.38 (t, J = 7.1 Hz, 2H, CH2N), 1.67 (quint, J = 7.3 Hz, 2H, CH2), 1.38 (quint, J = 7.3 Hz, 2H, CH2), 1.33-1.23 (m, 8H, 4xCH2), 0.87 (t, J = 7.0 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 168.0, 152.5, 130.2, 125.8, 121.2, 120.7, 118.5, 45.7, 31.4, 29.5, 29.2, 29.1, 26.8, 22.6, 14.0; FTIR (net, cm-1) 3196, 2915, 1606, 1557, 1468, 1125; HRMS-EI (70 eV) m/z calcd for C15H23N2S [M+H]+ 263.1582, found 263.1585. N-isopentylbenzo[d]thiazol-2-amine (3ad)

S

NHN


mp 76.8-77.7 oC; 1H NMR (500 MHz, CDCl3) δ 7.58 (d, J = 8.0 Hz, 1H, ArH), 7.53 (d, J = 8.0 Hz, 1H, ArH), 7.29 (t, J = 7.7 Hz, 1H, ArH), 7.07 (t, J = 7.6 Hz, 1H, ArH), 5.45 (brs, 1H, NH), 3.43 (t, J = 7.4 Hz, 2H, CH2N), 1.72 (m, 1H, CH), 1.58 (quart, J = 7.2 Hz, 2H, CH2), 0.96 (d, J = 6.6 Hz, 6H, 2xCH3); 13C NMR (125MHz, CDCl3) δ 168.0, 152.5, 130.2, 125.8, 121.2, 120.7, 118.5, 44.0, 38.4, 25.7, 22.4; FTIR (net, cm-1) 3194, 2954, 1609, 1557, 1446, 1125; HRMS-EI (70 eV) m/z calcd for C12H17N2S [M+H]+ 221.1112, found 221.1107. N-(2-ethylhexyl)benzo[d]thiazol-2-amine (3ae)

S

NHN

mp 80.2-81.2 oC; 1H NMR (500 MHz, CDCl3) δ 7.58 (d, J = 7.8 Hz, 1H, ArH), 7.51 (d, J = 8.2 Hz, 1H, ArH), 7.29 (t, J = 7.3 Hz, 1H, ArH), 7.07 (t, J = 7.1 Hz, 1H, ArH) 5.50 (br s, 1H, NH), 3.32 (d, J = 6.2 Hz, 2H, CH2N), 1.61 (sept, J = 6.1 Hz, 1H, CH), 1.41 (quint, J = 7.2 Hz, 2H, CH2), 1.37-1.26 (m, 6H, 3xCH2), 0.94-0.90 (m, 6H, 2xCH3); 13C NMR (125MHz, CDCl3) δ 168.3, 152.5, 130.3, 125.9, 121.2, 120.7, 118.6, 48.9, 39.5, 30.9, 28.8, 24.2, 22.9, 14.0, 10.9; FTIR (net, cm-1) 3196, 2950, 1623, 1575, 1467, 1124; HRMS-EI (70 eV) m/z calcd for C15H23N2S [M+H]+ 263.1582, found 263.1583. N-(2-methoxyethyl)benzo[d]thiazol-2-amine (3af)

S

NHN

O

Oil; 1H NMR (500 MHz, CDCl3) δ 7.56-7.54 (m, 2H, ArH), 7.28 (t, J = 8.1 Hz, 1H, ArH), 7.07 (t, J = 7.6 Hz, 1H, ArH), 6.13 (br s, 1H, NH), 3.65-3.60 (m, 4H, CH2N, CH2O), 3.37 (d, J = 3.8 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3); δ 167.2, 152.4, 130.4, 125.8, 121.5, 120.7, 118.8, 70.7, 58.7, 44.7; FTIR (net, cm-1) 3218, 2921, 1681, 1597, 1443, 1119; HRMS-EI (70 eV) m/z calcd for C10H13N2OS [M+H]+ 209.0749, found 209.0751. N-(2-(phenylthio)ethyl)benzo[d]thiazol-2-amine (3ag)

S

NHN

SPh

mp 147.5-148.7 oC; 1H NMR (500 MHz, CDCl3) δ 7.57 (d, J = 7.7 Hz, 1H, ArH), 7.54 (d, J = 8.1 Hz, 1H, ArH), 7.42 (d, J = 7.6 Hz, 2H, ArH), 7.32-7.28 (m, 3H, ArH), 7.23 (t, J = 7.4 Hz, 1H, ArH), 7.09 (t, J = 7.6 Hz, 1H, ArH), 5.61 (br s, 1H, NH), 3.67 (t, J = 6.4 Hz, 2H, CH2N), 3.24 (t, J = 6.4 Hz, 2H, CH2S); 13C NMR (125MHz, CDCl3) δ 166.7, 152.3, 134.5, 130.5, 130.2, 129.1, 126.8, 126.0, 121.8,


120.8, 119.0, 43.9, 33.6; FTIR (net, cm-1) 3188, 2903, 1614, 1574, 1436; HRMS-EI (70 eV) m/z calcd for C15H15N2S2 [M+H]+ 287.0677, found 287.0679. N-phenethylbenzo[d]thiazol-2-amine (3ah)

S

NHN

mp 143.6-144.4 oC; 1H NMR (500 MHz, CDCl3) δ 7.59 (d, J = 7.9 Hz, 1H, ArH), 7.53 (d, J = 8.1 Hz, 1H, ArH), 7.34-7.28 (m, 3H, ArH), 7.27-7.23 (m, 4H, ArH), 7.09 (t, J = 7.6 Hz, 1H, ArH), 5.42 (br s, 1H, NH), 3.70 (t, J = 6.9 Hz, 2H, CH2N), 3.01 (t, J = 6.9 Hz, 2H, CH2Ph); 13C NMR (125MHz, CDCl3) δ 167.4, 152.4, 138.3, 130.3, 128.8, 128.7, 126.7, 126.0, 121.5, 120.8, 118.8, 46.6, 35.5; FTIR (net, cm-1) 3199, 2910, 1620, 1573, 1446, 1186; HRMS-EI (70 eV) m/z calcd for C15H15N2S [M+H]+ 255.0956, found 255.0959. N-(3-phenylpropyl)benzo[d]thiazol-2-amine (3ai)7

S

NHN

mp 101.2-102.0 oC; 1H NMR (500 MHz, CDCl3) δ 7.58 (d, J = 7.9 Hz, 1H, ArH), 7.53 (d, J = 8.0 Hz, 1H, ArH), 7.31-7.28 (m, 3H, ArH), 7.23-7.19 (m, 3H, ArH), 7.09 (t, J = 7.6 Hz, 1H, ArH), 5.54 (br s, 1H, NH), 3.45 (t, J = 7.0 Hz, 2H, CH2N), 2.75 (t, J = 7.6 Hz, 2H, CH2Ph), 2.04 (quint, J = 7.3 Hz, 2H, CH2); 13C NMR (125MHz, CDCl3) δ 167.9, 152.3, 141.0, 130.2, 128.5, 128.3, 126.1, 125.9, 121.3, 120.8, 118.6, 45.1, 33.0, 31.0. N-benzylbenzo[d]thiazol-2-amine (3aj)8

S

NHN

1H NMR (500 MHz, DMSO-d6) δ 8.50 (t, J = 5.6 Hz, 1H, NH), 7.67 (d, J = 7.8 Hz, 1H, ArH), 7.39-7.33 (m, 5H, ArH), 7.26 (t, J = 7.1Hz, 1H, ArH), 7.22 (t, J = 7.7 Hz, 1H, ArH), 7.02 (t, J = 7.5 Hz, 1H, ArH), 4.60 (br s, 2H, CH2N); 13C NMR (125MHz, DMSO-d6) δ 166.2, 152.4, 138.9, 130.4, 128.3, 127.3, 127.0, 125.5, 120.95, 120.89, 118.1, 47.2. N-(4-methoxybenzyl)benzo[d]thiazol-2-amine (3ak)8


S

NHN

OMe

1H NMR (500 MHz, DMSO-d6) δ 8.42 (t, J = 5.6 Hz, 1H, NH), 7.66 (d, J = 7.5 Hz, 1H, ArH), 7.38 (d, J = 8.0 Hz, 1H, ArH), 7.31 (d, J = 8.5 Hz, 2H, ArH ), 7.21 (t, J = 7.6 Hz, 1H, ArH), 7.01 (t, J = 7.5 Hz, 1H, ArH), 6.90 (d, J = 8.5, 2H, ArH), 4.51 (d, J = 5.7 Hz, 2H, CH2N), 3.73 (s, 3H, OCH3); 13C NMR (125 MHz, DMSO-d6) δ 166.1, 158.4, 152.5, 130.7, 130.4, 128.8, 125.5, 120.9, 118.0, 113.7, 55.0, 46.7. N-(2-chlorobenzyl)benzo[d]thiazol-2-amine (3al)8

S

NHN

Cl

1H NMR (500 MHz, DMSO-d6) δ 8.54 (br s, 1H, NH), 7.69 (d, J = 7.8 Hz, 1H, ArH), 7.48 (d, J = 6.7 Hz, 2H, ArH), 7.40 (d, J = 8.0 Hz, 1H, ArH), 7.35-7.30 (m, 2H, ArH), 7.22 (t, J = 7.6 Hz, 1H, ArH), 7.04(t, J = 7.6 Hz, 1H, ArH), 4.68 (br s, 2H, CH2N); 13C NMR (125 MHz, DMSO-d6) δ 166.0, 152.3, 135.9, 132.3, 130.5, 129.3, 129.1, 128.9, 127.2, 125.6, 121.1, 121.0, 118.2, 45.0. N-(1,2,3,4-tetrahydronaphthalen-1-yl)benzo[d]thiazol-2-amine (3am)

S

NHN

mp 131.7-132.3 oC; 1H NMR (500 MHz, CDCl3) δ 7.56 (d, J = 7.5, 1H, ArH), 7.42 (d, J = 7.8 Hz, 1H, ArH), 7.37 (d, J = 8.0 Hz, 1H, ArH), 7.24 (t, J = 7.6 Hz, 1H, ArH), 7.20-7.13 (m, 2H, ArH), 7.10 (d, J = 7.5 Hz, 1H, ArH), 7.06 (t, J = 7.6 Hz, 1H, ArH), 6.04 (br s, 1H, NH), 5.01 (t, J = 5.5 Hz, 1H, CHN), 2.85-2.73 (m, 2H, CH2), 2.19-2.13 (m, 1H, CH), 2.07-2.01 (m, 1H, CH), 1.94-1.81 (m, 2H, CH2); 13C NMR (125 MHz, CDCl3) δ 166.6, 152.4, 137.5, 136.1, 130.2, 129.2, 128.9, 127.6, 126.3, 125.9, 121.5, 120.7, 118.8, 53.9, 29.9, 29.1, 19.9; FTIR (net, cm-1) 3213, 2937, 1722, 1567, 1447, 1155; HRMS-EI (70 eV) m/z calcd for C17H17N2S [M+H]+ 281.1112, found 281.1113. N-butyl-6-methylbenzo[d]thiazol-2-amine (3ba)9

S

NHN

Me


mp 90.7-91.7 oC; 1H NMR (500 MHz, CDCl3) δ 7.41 (d, J = 8.2 Hz, 1H, ArH), 7.38 (s, 1H, ArH), 7.09 (d, J = 8.2 Hz, 2H, ArH), 5.47 (br s, 1H, NH), 3.39 (t, J = 7.0 Hz, 2H, CH2N), 2.39 (s, 3H, CH3Ar), 1.66 (quint, J = 7.3 Hz, 2H), 1.43 (sext, J = 7.5 Hz, 2H), 0.96 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 167.4, 150.2, 130.9, 130.3, 127.0, 120.8, 118.1, 45.4, 31.6, 21.1, 20.0, 13.7. N-butyl-6-phenoxybenzo[d]thiazol-2-amine (3ca)

S

NHN

PhO mp 116.0-116.7 oC; 1H NMR (500 MHz, CDCl3) δ 7.48 (d, J = 8.8 Hz, 1H, ArH), 7.31 (t, J = 8.0 Hz, 2H, ArH), 7.25 (s, 1H, ArH), 7.06 (t, J = 7.4 Hz, 1H, ArH), 7.00 (dd, J = 8.3 Hz and 2.5 Hz, 1H, ArH), 6.98 (d, J = 7.9 Hz, 1H, ArH), 5.23 (br s, 1H, NH), 3.41 (t, J = 7.1 Hz, 2H, CH2N), 1.67 (quint, J = 7.4 Hz, 2H, CH2), 1.45 (sext, J = 7.4 Hz, 2H, CH2), 0.97 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (125 MHz, CDCl3) δ 167.2, 158.3, 151.4, 148.9, 131.3, 129.6, 122.6, 119.2, 118.3, 117.9, 112.0, 45.3, 31.6, 20.0, 13.7; FTIR (net, cm-1) 3165, 2956, 1611, 1593, 1455, 1149. HRMS-EI (70 eV) m/z calcd for C17H19N2OS [M+H]+ 299.1218, found 299.1223. N-butyl-4,6-dimethylbenzo[d]thiazol-2-amine (3da)

S

NHNMe

Me mp 46.0-47.2 oC; 1H NMR (500 MHz, CDCl3) δ 7.24 (s, 1H, ArH), 6.93 (s, 1H, ArH), 5.29 (br s, 1H, NH), 3.34 (quart, J = 5.8 Hz, 2H, CH2N), 2.51 (s, 3H, CH3Ar), 2.35 (s, 3H, CH3Ar), 1.65 (quint, J = 5.8 Hz, 2H, CH2), 1.44 (sext, J = 7.4 Hz, 2H, CH2), 0.96 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 166.7, 149.2, 130.8, 130.1, 128.0, 127.9, 118.3, 45.6, 31.6, 21.1, 19.9, 18.3, 13.7; FTIR (net, cm-1) 3242, 2959, 1606, 1557, 1447, 1145; HRMS-EI (70 eV) m/z calcd for C13H19N2S [M+H]+ 235.1269, found 235.1271. N-butyl-6-fluorobenzo[d]thiazol-2-amine (3ea)

S

NHN

F mp 95.8-96.6 oC; 1H NMR (500 MHz, CDCl3) δ 7.43 (dd, J = 8.7 Hz and 4.8 Hz, 1H, ArH), 7.29 (dd, J = 8.2 Hz and 2.5 Hz, 1H, ArH), 7.00 (td, J = 8.9 Hz and 2.6 Hz, 1H, ArH), 5.40 (br s, 1H, NH), 3.40 (t,


J = 7.1 Hz, 2H, CH2N), 1.67 (quint, J = 7.3 Hz, 2H, CH2), 1.44 (sext, J = 7.5 Hz, 2H, CH2), 0.96 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 167.4, 158.1 (d, JC-F = 238.3 Hz), 148.9, 131.0 (d, JC-F = 10.7 Hz), 118.9, 113.5 (d, JC-F = 23.6 Hz), 107.5 (d, JC-F = 26.2), 45.4, 31.6, 20.0, 13.7; FTIR (net, cm-

1) 3214, 2972, 1621, 1569, 1461, 1137; HRMS-EI (70 eV) m/z calcd for C11H14N2FS [M+H]+ 225.0862, found 225.0863 N-butyl-6-chlorobenzo[d]thiazol-2-amine (3fa)10

S

NHN

Cl mp 109.5-110.6 oC; 1H NMR (500 MHz, CDCl3) δ 7.54 (d, J = 2.1 Hz, 1H, ArH), 7.41 (d, J = 8.7 Hz, 1H, ArH), 7.24 (dd, J = 8.7 Hz and 2.4 Hz, 1H, ArH), 5.44 (br s, 1H, NH), 3.41 (t, J = 7.1 Hz, 2H, CH2N), 1.67 (quint, J = 7.3 Hz, 2H, CH2), 1.44 (sext, J = 7.5 Hz, 2H, CH2), 0.97 (t, J = 7.3 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 168.0, 151.1, 131.5, 126.4, 126.3, 120.4, 119.2, 45.4, 31.5, 20.0, 13.7. N-butyl-6-chloro-4-methylbenzo[d]thiazol-2-amine (3ga)

S

NHN

Cl

Me

mp 70.1-71.4 oC; 1H NMR (500 MHz, CDCl3) δ 7.40 (s, 1H, ArH), 7.08 (s, 1H, ArH), 5.32 (br s, 1H, NH), 3.36 (quart, J = 6.1 Hz, CH2N), 2.51 (s, 3H, CH3Ar), 1.66 (quint, J = 7.3 Hz, 2H, CH2), 1.44 (sext, J = 7.4 Hz, 2H, CH2), 0.97 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 167.2, 150.1, 131.0, 129.6, 126.9, 126.0, 117.8, 45.5, 31.6, 19.9, 18.2, 13.6; FTIR (net, cm-1) 3219, 2958, 1600, 1553, 1435, 1138; HRMS-EI (70 eV) m/z calcd for C12H16N2SCl [M+H]+ 255.0723, found 255.0722. N-butyl-6-(trifluoromethoxy)benzo[d]thiazol-2-amine (3ha)

S

NHN

F3CO

mp 76.4-77.4 oC; 1H NMR (500 MHz, CDCl3) δ 7.48-7.45 (m, 2H, ArH), 7.15 (d, J = 8.7 Hz, 1H, ArH), 5.47 (br s, 1H, NH), 3.42 (t, J = 7.0 Hz, 2H, CH2N), 1.68 (quint, J = 7.3 Hz, 2H, CH2), 1.45 (sext, J = 7.5 Hz, 2H, CH2), 0.97 (t, J = 7.4 Hz, 3H, CH3); 3C NMR (125MHz, CDCl3) δ 168.2, 151.3, 143.5, 131.0, 120.6 (q, JC-F = 254.8 Hz), 119.6, 118.9, 114.0, 45.4, 31.6, 20.0, 13.7; FTIR (net, cm-1) 3223,


3094, 1619, 1574, 1455, 1143; HRMS-EI (70 eV) m/z calcd for C12H14N2OF3S [M+H]+ 291.0779, found 291.0775. N-butyl-5-methyl-4-phenylthiazol-2-amine (3ia)11

Ph

Me

S

NHN

mp 55.4-56.8 oC; 1H NMR (500 MHz, CDCl3) δ 7.57 (d, J = 7.8 Hz, 2H, ArH), 7.38 (t, J = 7.7 Hz, 2H, ArH), 7.28 (t, J = 7.4 Hz, 1H, ArH), 5.26 (br s, 1H, NH), 3.20 (quart, J = 6.0 Hz, 2H, CH2N), 3.40 (s, 3H, CH3), 1.59 (quint, J = 7.3 Hz, 2H, CH2), 1.39 (sext, J = 7.4 Hz, 2H, CH2), 0.94 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 166.2, 146.3, 135.4, 128.4, 128.2, 127.1, 115.3, 45.9, 31.6, 20.0, 13.7, 12.4. N-butyl-4,5-diphenylthiazol-2-amine (3ja)11

S

NHN

Ph

Ph mp 116.2-117.0 (lit.12 mp 117-118 oC); 1H NMR (500 MHz, CDCl3) δ 7.47 (dd, J = 7.9 Hz and 2.2 Hz, 2H, ArH), 7.27-7.17 (m, 8H, ArH), 6.15 (br s 1H, NH), 3.14 (quart, J = 6.2 Hz, 2H, CH2N), 1.51 (quint，J = 7.4 Hz, 2H, CH2) 1.33 (sext, J = 7.4 Hz, 2H, CH2), 0.90 (t, J = 7.3 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 168.0, 146.1, 135.6, 133.0, 129.2, 129.0, 128.4, 128.1, 127.4, 126.8, 119.9, 46.0, 31.3, 20.0, 13.7. N-butyl-4,5-dihydronaphtho[1,2-d]thiazol-2-amine (3ka)

S

NHN

mp 89.8-90.6 oC; 1H NMR (500 MHz, CDCl3) δ 7.70 (d, J = 7.6 Hz, 1H, ArH), 7.23 (t, J = 7.3 Hz, 1H, ArH), 7.17-7.11 (m, 3H, ArH), 5.1 (br s, 1H, NH), 3.27 (quart, J = 6.5 Hz, 2H, CH2N), 3.02 (t, J = 7.8 Hz, 2H, CH2), 2.85 (t, J = 7.8 Hz, 2H, CH2), 1.65 (quint, J = 7.3 Hz, 2H, CH2), 1.43 (sext, J = 7.5 Hz, 2H, CH2), 0.96 (t, J = 7.3 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 168.3, 145.4, 134.4, 131.8, 127.5, 126.8, 126.5, 122.7, 117.7, 45.8, 31.5, 29.2, 21.8, 20.0, 13.7; FTIR (net, cm-1) 3201, 2958, 1600, 1553, 1435, 1138; HRMS-EI (70 eV) m/z calcd for C15H19N2S [M+H]+ 259.1269, found 259.1274. N-butyl-5-chlorobenzo[d]oxazol-2-amine (3la)12


O

NHN

Cl

mp 109.5-110.6 oC; 1H NMR (500 MHz, CDCl3) δ 7.31 (s, 1H, ArH), 7.13 (d, J = 8.3 Hz, 1H, ArH), 6.98 (d, J = 8.1 Hz, 1H, ArH), 5.18 (br s, 1H, NH), 3.48 (quart, J = 6.4 Hz, 2H, CH2N), 1.67 (quint, J = 7.2 Hz, 2H, CH2), 1.44 (sext, J = 7.5 Hz, 2H, CH2), 0.97 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 163.2, 147.1, 144.4, 129.2, 120.4, 116.2, 109.1, 42.8, 31.8, 19.9, 13.7. N-butyl-5-phenylbenzo[d]oxazol-2-amine (3ma)

O

NHN

Ph

mp 132.3-133.6 oC; 1H NMR (500 MHz, CDCl3) δ 7.59-7.58 (m, 3H, ArH), 7.43 (t, J = 7.7 Hz, 2H, ArH), 7.33 (t, J = 7.4, 1H, ArH), 7.29-7.26 (m, 2H, ArH), 5.10 (br s, 1H, NH), 3.51 (t, J = 6.6 Hz, 2H, CH2N), 1.68 (quint, J = 7.4 Hz, 2H, CH2), 1.45 (sext, J = 7.5 Hz, 2H, CH2), 0.97 (t, J = 7.4 Hz, 3H, CH3); 13C NMR (125MHz, CDCl3) δ 162.7, 148.1, 143.6, 141.6, 137.7, 128.7, 127.3, 126.9, 120.1, 114.8, 108.6, 42.9, 31.8, 19.9, 13.7; FTIR (net, cm-1) 3157, 2953, 1690, 1592, 1467, 1181; HRMS-EI (70 eV) m/z calcd for C17H19N2O [M+H]+ 267.1497, found 267.1499. Procedure for the condensation of 4,5-diphenylthiazol-2-amine with benzaldehyde To an oven-dried, nitrogen purged 20 ml Schlenk tube were added 4,5-diphenylthiazol-2-amine (1 mmol), base (0.2 mmol, 20 mol%) and benzaldehyde (5 mmol, 500 mol%). The resulting mixture was heated at 150 oC for 12h, followed by the mixture of the reaction was allowed to cool to ambient temperature. The mixture of the reaction was concentrated in vacuo and purified by flash column chromatography with hexane/ethyl acetate to afford the corresponding product. (E)-N-benzylidene-4,5-diphenylthiazol-2-amine13

Ph

Ph

S

N N Ph

mp 109.4-110.2 oC; 1H NMR (500 MHz, CDCl3) δ 9.09 (s, 1H, CH=N), 8.01 (d, J = 7.1 Hz, 2H, ArH), 7.58-7.56 (m, 2H, ArH), 7.54 (d, J = 7.1 Hz, 1H, ArH), 7.50 (t, J = 7.3 Hz, 2H, ArH), 7.39-7.37 (m, 2H, ArH), 7.34-7.32 (m, 3H, ArH), 7.30-7.29 (m, 3H, ArH); 13C NMR (125MHz, CDCl3) δ 169.8, 163.1, 148.5, 135.1, 134.8, 132.6, 132.2, 132.1, 129.9, 129.6, 129.2, 128.9, 128.7, 128.24, 128.17, 127.9. Procedure for the reaction of (E)-N-benzylidene-4,5-diphenylthiazol-2-amine with benzyl alcohol


To an oven-dried, nitrogen purged 20 ml Schlenk tube were added (E)-N-benzylidene-4,5-diphenylthiazol-2-amine (1mmol), [Cp*IrCl2]2 (0.002 mmol, 0.2 mol%), NaOH (0.2 mmol, 20 mol%) and benzyl alcohol (5 mmol, 500 mol%). The resulting mixture was heated at 150 oC for 12h, followed by the mixture of the reaction was allowed to cool to ambient temperature. The mixture of the reaction was concentrated in vacuo and purified by flash column chromatography with hexane/ethyl acetate to afford the corresponding product. The yield of N-benzyl-4,5-diphenylthiazol-2-amine is isolated yield, and the yield of benzaldehyde is determined by the 1H NMR integration. N-benzyl-4,5-diphenylthiazol-2-amine11

Ph

Ph

S

NHN Ph

mp 142.1-143.2 oC; 1H NMR (500 MHz, CDCl3) δ 7.48-7.47 (m, 2H, ArH), 7.38-7.33 (m, 4H, ArH), 7.31-7.28 (m, 1H, ArH), 7.25-7.19 (m, 8H, ArH), 6.13 (br s, 1H, NH), 4.42 (s, 2H, CH2); 13C NMR (125MHz, CDCl3) δ 167.3, 146.0, 137.7, 135.5, 132.8, 129.3, 129.0, 128.7, 128.5, 128.1, 127.7, 127.6, 127.5, 127.0, 120.8, 49.8


References 1 R. G. Ball, W. A. G. Graham, D. M. Heinekey, J. K. Hoyano, A. D. McMaster, B. M. Mattson and S.

T. Michel, Inorg. Chem., 1990, 29, 2023. 2 R. Walter, S. Kirchner and R. Franz, US6399804, 2002. 3 P. Jimonet, F. Audiau, M. Barreau, J. C. Blanchard, A. Boireau, Y. Bour, M. A. Coleno, A. Doble, G.

Doerflinger, C. D. Huu, M. H. Donat, J. M. Duchesne, P. Ganil, C. Gueremy, E. Honore, B. Just, R. Kerphirique, S. Gontier, P. Hubert, P. M. Laduron, J. L. Blevec, M. Meunier, J. M. Miquet, C. Nemecek, M. Pasquet, O. Piot, J. Pratt, J. Rataud, M. Reibaud, J. M. Stutzmann and S. Mignani, J. Med. Chem., 1999, 42, 2828.

4 M. D. Chordia, L. J. Murphree, T. L. Macdonald, J. Linden and R. A. Olsson, Bioorg. Med. Chem. Lett., 2002, 12, 1563.

5 P. Saha, T. Ramana, N. Purkait, M. A. Ali, R. Paul and T. Punniyamurthy, J. Org. Chem., 2009, 74, 8719.

6 J. W. Qiu, X. G. Zhang, R. Y. Tang, P. Zhong and J. H. Li, Adv. Synth. Catal., 2009, 351, 2319. 7 D. J. Thiele, D. W. Neef and J. S. Mendoza, US 20110112073, 2011. 8 F. Li, H. Shan, Q. Kang and L. Chen, Chem. Commun., 2011, 47, 5058. 9 A. V. Pande, S. R. Lokhande, M. R. Patel and B. G. Khadse, Indian Drugs, 1982, 19, 342. 10 A. S. Bobade, S. R. Lokhande, M. R. Patel and B. G. Khadse, Bulletin of Haffkine Institute, 1981, 9,

76. 11 T. Aoyama, S. Murata, I. Arai, N. Araki, T. Takido, Y. Suzuki and M. Kodomari, Tetrahedron, 2006,

62, 3201. 12 M. Yamato, Y. Takeuchi, K. Hattori and K. Hashigaki, Chem. Pharm. Bull., 1984, 32, 3053. 13 B. Dash, M. Potza and P. K. Mohapatra, J. Indian. Chem. Soc., 1985, 62, 460.


8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.000

0.951

0.966

0.980

1.409

1.424

1.438

1.454

1.469

1.484

1.646

1.660

1.675

1.690

1.704

3.401

3.415

3.430

5.494

7.059

7.074

7.090

7.260

7.273

7.288

7.303

7.516

7.532

7.574

7.590

2.95

1.99

2.07

2.00

0.91

0.96

0.98

0.96

0.94

Proton CDCl3N−butylbenzo[d]thazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.680

19.994

31.581

45.436

77.000

118.533

120.736

121.228

125.865

130.218

152.405

167.990

C13CPD CDCl3N−butylbenzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.881

0.895

0.909

1.304

1.311

1.318

1.325

1.332

1.340

1.382

1.396

1.411

1.427

1.440

1.653

1.668

1.682

1.697

1.711

3.393

3.407

3.421

5.389

7.059

7.074

7.089

7.260

7.272

7.287

7.303

7.518

7.534

7.576

7.592

3.00

4.49

2.24

2.73

2.00

0.86

0.88

0.99

0.88

0.89

Proton CDCl3N−hexylbenzo[d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.937

22.490

26.491

29.482

31.389

45.743

77.000

118.537

120.733

121.199

125.848

130.239

152.459

168.019

C13CPD CDCl3N−hexylbenzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.857

0.871

0.885

1.228

1.245

1.260

1.273

1.285

1.299

1.313

1.328

1.351

1.366

1.382

1.397

1.410

1.641

1.656

1.671

1.685

1.699

3.364

3.378

3.392

6.293

7.044

7.059

7.074

7.252

7.261

7.276

7.292

7.494

7.510

7.568

7.584

3.54

9.18

2.18

2.04

2.00

0.91

1.02

1.14

1.01

1.00

Proton CDCl3N−octylbenzo[d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

14.031

22.576

26.824

29.128

29.172

29.518

31.722

45.750

77.000

118.529

120.725

121.188

125.847

130.235

152.459

168.036

C13CPD CDCl3N−octylbenzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.953

0.966

1.557

1.571

1.586

1.601

1.671

1.684

1.698

1.711

1.724

1.738

1.751

1.765

1.778

3.412

3.427

3.441

5.450

7.058

7.074

7.089

7.260

7.272

7.288

7.303

7.519

7.535

7.576

7.592

5.82

2.00

1.18

2.00

0.92

1.00

1.02

0.97

0.96

Proton CDCl3N−isopentylbenzo[d]thiazol−2−amine


li

图章

30405060708090100110120130140150160170 ppm

22.381

25.719

38.353

43.973

77.000

118.515

120.733

121.184

125.840

130.225

152.452

168.027

C13CPD CDCl3N−isopentylbenzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.895

0.912

0.927

0.942

1.255

1.286

1.295

1.310

1.335

1.346

1.360

1.373

1.385

1.399

1.413

1.428

1.442

1.578

1.590

1.603

1.615

1.627

1.639

1.652

3.316

3.328

5.495

7.055

7.070

7.085

7.260

7.270

7.286

7.301

7.505

7.521

7.577

7.593

6.12

6.20

1.86

1.04

2.00

0.91

0.91

0.83

0.95

0.84

Proton CDCl3N−(2−ethylhexyl)benzo[d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

10.859

13.995

22.945

24.245

28.832

30.985

39.494

48.943

77.000

118.602

120.718

121.202

125.876

130.254

152.488

168.251

C13CPD CDCl3N−(2−ethylhexyl)benzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

3.366

3.373

3.600

3.605

3.608

3.616

3.624

3.633

3.641

3.649

6.132

7.051

7.066

7.081

7.258

7.276

7.291

7.537

7.546

7.553

7.561

3.01

4.00

0.89

1.01

1.09

2.00

Proton CDCl3N−(2−methoxyethyl)benzo[d]thiazol−2−amine


li

图章

5060708090100110120130140150160170 ppm

44.667

58.724

70.701

77.000

118.804

120.668

121.498

125.811

130.405

152.358

167.181

C13CPD CDCl3N−(2−methoxyethyl)benzo[d]thiazol−2−amine


Owner

附注

“Owner”设置的“Marked”

li

图章

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

3.229

3.241

3.254

3.656

3.669

3.682

5.612

7.079

7.094

7.109

7.215

7.230

7.245

7.259

7.279

7.293

7.307

7.322

7.413

7.428

7.532

7.549

7.566

7.582

2.01

2.00

0.95

0.99

1.08

3.05

1.97

0.96

0.98

Proton CDCl3N−(2−phenylthio)ethyl0benzo[d]thiazol−2−amine


li

图章

405060708090100110120130140150160170 ppm

33.610

43.883

77.000

119.017

120.779

121.751

125.959

126.778

129.137

130.206

130.488

134.519

152.289

166.701

C13CPD CDCl3N−(2−(phenylthio)ethyl)benzo[d]thiazol−2−amine


li

图章

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

2.991

3.005

3.019

3.688

3.701

3.715

5.423

7.078

7.093

7.108

7.234

7.250

7.258

7.266

7.285

7.300

7.315

7.329

7.344

7.526

7.542

7.579

7.595

1.99

2.00

0.89

0.97

3.71

2.86

0.97

0.92

Proton CDCl3N−phenethylbenzo[d]thiazol−2−amine


li

图章

405060708090100110120130140150160170 ppm

35.543

46.581

77.000

118.775

120.769

121.462

125.923

126.678

128.700

128.780

130.333

138.286

152.372

167.376

C13CPD CDCl3N−phenethylbenzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

2.009

2.023

2.038

2.052

2.067

2.738

2.753

2.768

3.437

3.451

3.465

5.544

7.074

7.089

7.104

7.192

7.207

7.225

7.259

7.284

7.298

7.313

7.520

7.536

7.576

1.98

2.00

2.00

0.96

0.89

2.58

2.61

0.89

0.89

Proton CDCl3N−(3−phenylpropyl)benzo[d]thiazol−2−amine


li

图章

405060708090100110120130140150160170 ppm

30.999

33.000

45.067

77.000

118.609

120.779

121.347

125.934

126.064

128.339

128.469

130.224

140.988

152.315

167.875

C13CPD CDCl3N−(3−phenylpropyl)benzo[d]thiazol−2−amine


li

图章

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.000

2.503

4.596

7.004

7.019

7.034

7.201

7.217

7.232

7.248

7.263

7.277

7.331

7.346

7.361

7.376

7.392

7.659

7.674

2.00

0.93

0.96

0.94

4.70

1.00

0.44Proton DMSO−d6N−benzylbenzo[d]thiazol−2−amine


li

图章

405060708090100110120130140150160170 ppm

39.501

47.200

118.078

120.888

120.946

125.504

126.985

127.345

128.336

130.387

138.894

152.420

166.224

Proton DMSO−d6N−benzylbenzo[d]thiazol−2−amine


li

图章

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

2.502

3.727

4.503

4.514

6.899

6.916

6.995

7.010

7.025

7.197

7.213

7.228

7.298

7.314

7.374

7.390

7.651

7.666

8.412

8.423

8.434

3.00

2.00

1.88

1.07

1.01

1.90

1.13

1.07

0.97Proton DMSO−d6N−(4−methoxybenzyl)benzo[d]thiazol−2−amine


li

图章

405060708090100110120130140150160170 ppm

39.500

46.724

55.017

113.739

118.019

120.868

125.477

128.768

130.361

130.747

152.472

158.381

166.118

C13CPD DMSO−d6N−(4−methoxybenzyl)benzo[d]thiazol−2−amine


li

图章

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.000

4.681

7.021

7.036

7.051

7.207

7.223

7.238

7.301

7.327

7.351

7.392

7.408

7.473

7.486

7.680

7.696

8.548

2.00

0.94

0.96

1.86

0.99

1.96

1.04

0.53Proton DMSO−d6N−(2−chlorobenzyl)benzo[d]thiazol−2−amine


li

图章

405060708090100110120130140150160170 ppm

39.500

44.998

118.243

120.977

121.129

125.557

127.240

128.879

129.060

129.252

130.487

132.318

135.901

152.291

165.985

C13CPD DMSO−d6N−(2−chlorobenzyl)benzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

1.811

1.939

2.009

2.071

2.134

2.195

2.733

2.848

4.997

5.009

5.019

6.038

7.046

7.061

7.077

7.094

7.109

7.128

7.200

7.227

7.241

7.258

7.357

7.373

7.410

7.425

7.551

7.567

2.47

1.10

1.05

2.09

1.00

0.95

0.99

0.96

2.13

1.21

0.99

1.03

0.97

Proton CDCl3N−(1,2,3,4−tetrahydronaphthalen−1−yl)benzo[d]thiazol−2−amine


Administrator

图章

2030405060708090100110120130140150160170 ppm

19.860

29.135

29.937

53.935

77.000

118.789

120.675

121.477

125.897

126.309

127.617

128.867

129.213

130.181

136.141

137.506

152.438

166.603

C13CPD CDCl3N−(1,2,3,4−tetrahydronaphthalen−1−yl)benzo[d]thiazol−2−amine


Administrator

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.943

0.958

0.973

1.399

1.414

1.429

1.444

1.459

1.474

1.631

1.646

1.661

1.676

1.690

2.387

3.380

3.394

3.408

5.465

7.084

7.100

7.260

7.385

7.400

7.417

3.15

2.12

2.12

3.21

2.00

0.94

0.95

0.87

0.95

Proton CDCl3N−butyl−6−methylbenzo[d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.684

19.986

21.124

31.599

45.374

77.000

118.139

120.808

126.974

130.275

130.904

150.249

167.376

C13CPD CDCl3N−butyl−6−methylbenzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.955

0.970

0.984

1.410

1.424

1.439

1.454

1.469

1.484

1.642

1.657

1.672

1.686

1.701

3.398

3.412

3.426

5.231

6.972

6.988

6.997

7.002

7.014

7.019

7.047

7.062

7.076

7.253

7.260

7.294

7.310

7.326

7.472

7.489

2.91

1.96

2.04

2.00

0.87

1.80

1.03

0.96

1.80

1.89

0.96

Proton CDCl3N−butyl−6−phenoxybenzo[d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.698

19.990

31.613

45.338

77.000

111.956

117.923

118.327

119.172

122.647

129.625

131.258

148.912

151.376

158.346

167.238

C13CPD CDCl3N−butyl−6−phenoxybenzo[d]thiazol−2−amine


li

图章

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.944

0.959

0.974

1.400

1.414

1.429

1.444

1.460

1.474

1.622

1.637

1.652

1.666

1.681

2.351

2.511

3.324

3.338

3.345

3.359

5.286

6.927

7.242

7.259

3.00

2.11

2.18

3.11

3.05

2.00

1.00

0.95

0.92

Proton CDCl3N−butyl−4,6−dimethylbenzo[d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.662

18.278

19.940

21.095

31.649

45.559

77.000

118.255

127.942

128.029

130.080

130.781

149.194

166.733

C13CPD CDCl3N−butyl−4,6−dimethylbenzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.950

0.964

0.979

1.404

1.418

1.433

1.448

1.463

1.478

1.637

1.651

1.667

1.681

1.696

3.389

3.403

3.417

5.399

6.984

6.989

7.002

7.007

7.019

7.025

7.261

7.277

7.282

7.294

7.299

7.419

7.428

2.84

1.95

2.46

2.00

0.94

0.90

0.86

0.91

Proton CDCl3N−butyl−6−fluorobenzo[d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.666

19.983

31.577

45.360

77.000

107.405

107.615

113.361

113.549

118.928

130.912

130.998

148.905

157.119

159.025

167.411

C13CPD CDCl3N−butyl−6−fluorobenzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.952

0.966

0.981

1.404

1.419

1.433

1.449

1.464

1.479

1.640

1.655

1.669

1.684

1.698

3.391

3.406

3.420

5.441

7.227

7.231

7.244

7.248

7.262

7.403

7.421

7.541

7.545

3.07

2.05

2.68

2.00

0.90

0.95

0.95

0.88

Proton CDCl3N−butyl−6−chlorobenzo[d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.662

19.976

31.519

45.432

77.000

119.158

120.429

126.316

126.360

131.460

151.094

168.048

C13CPD CDCl3N−butyl−6−chlorobenzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.951

0.966

0.981

1.404

1.419

1.434

1.449

1.464

1.479

1.631

1.646

1.661

1.676

1.690

2.509

3.343

3.356

3.368

3.380

5.316

7.084

7.260

7.400

3.14

2.10

2.98

3.00

2.00

0.93

0.94

0.90

Proton CDCl3N−butyl−6−chloro−4−methylbenzo[d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.637

18.231

19.921

31.551

45.515

77.000

117.832

126.024

126.949

129.571

130.994

150.122

167.196

C13CPD CDCl3N−butyl−6−chloro−4−methylbenzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.954

0.969

0.984

1.409

1.423

1.438

1.453

1.468

1.483

1.646

1.661

1.676

1.691

1.705

3.404

3.418

3.432

5.467

7.144

7.161

7.261

7.454

7.466

7.484

2.78

2.00

2.77

2.00

0.96

0.92

1.90

Proton CDCl3N−butyl−6−(trifluoromethoxy)benzo[d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170180 ppm

13.669

19.983

31.563

45.396

77.000

113.978

117.583

118.927

119.642

121.657

123.698

131.027

143.502

151.311

168.207

C13CPD CDCl3N−butyl−6−(trifluoromethoxy)benzo[d]thiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.922

0.936

0.951

1.356

1.371

1.386

1.401

1.416

1.431

1.565

1.579

1.594

1.609

1.623

2.396

3.179

3.193

3.201

3.215

5.261

7.266

7.281

7.296

7.366

7.382

7.397

7.561

7.577

3.23

2.15

2.10

3.02

2.00

0.89

0.95

1.99

1.92

Proton CDCl3N−butyl−5−methyl−4−phenylthiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

12.409

13.724

20.019

31.552

45.869

77.000

115.333

127.068

128.170

128.408

135.444

146.308

166.239

C13CPD CDCl3N−butyl−5−methyl−4−phenylthiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.880

0.895

0.910

1.289

1.304

1.318

1.333

1.349

1.363

1.485

1.500

1.514

1.529

1.544

3.119

3.133

3.143

3.156

6.154

7.169

7.183

7.197

7.212

7.227

7.239

7.252

7.266

7.270

7.465

7.468

7.471

7.479

7.484

3.09

2.05

1.98

2.00

0.96

7.83

1.89

Proton CDCl3N−butyl−4,5−diphenylthiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.677

19.983

31.332

46.003

77.000

119.880

126.801

127.422

128.094

128.426

128.997

129.163

133.006

135.643

146.081

168.019

C13CPD CDCl3N−butyl−4,5−diphenylthiazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.943

0.957

0.972

1.396

1.411

1.426

1.441

1.456

1.471

1.617

1.632

1.646

1.661

1.675

2.840

2.855

2.872

3.003

3.019

3.034

3.251

3.264

3.276

3.290

5.098

7.114

7.128

7.143

7.152

7.165

7.220

7.235

7.249

7.258

7.697

7.712

3.22

2.15

2.09

2.16

2.06

2.00

0.87

1.88

1.02

0.88

Proton CDCl3N−butyl−4,5−dihydronaphtho[1,2−d]thiazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.691

20.005

21.789

29.164

31.505

45.822

77.000

117.720

122.690

126.451

126.786

127.523

131.756

134.443

145.382

168.286

C13CPD CDCl3N−butyl−4,5−dihydronaphtho[1,2−d]thiazol−2−amine


li

图章

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.954

0.969

0.984

1.402

1.417

1.431

1.446

1.460

1.476

1.637

1.651

1.665

1.681

1.694

3.461

3.474

3.487

3.499

5.184

6.975

6.992

7.120

7.137

7.263

7.313

3.30

2.25

2.23

2.00

0.99

0.98

0.97

0.97

Proton CDCl3N−butyl−5−chlorobenzo[d]oxazol−2−amine


li

图章

2030405060708090100110120130140150160170 ppm

13.655

19.875

31.750

42.824

77.000

109.131

116.171

120.400

129.184

144.415

147.063

163.150

C13CPD CDCl3N−butyl−5−chlorobenzo[d]oxazol−2−amine


li

图章

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

0.960

0.975

0.990

1.414

1.429

1.444

1.459

1.474

1.489

1.654

1.669

1.684

1.699

1.713

3.494

3.507

3.520

5.103

7.255

7.258

7.276

7.292

7.311

7.326

7.341

7.413

7.428

7.444

7.577

7.592

3.12

2.26

2.54

2.00

1.06

2.82

1.18

2.33

2.99

Proton CDCl3N−butyl−5−phenylbenzo[d]oxazol−2−amine


Administrator

图章

2030405060708090100110120130140150160170 ppm

13.691

19.889

31.794

42.897

77.000

108.604

114.845

120.068

126.851

127.284

128.686

137.705

141.602

143.567

148.074

162.688

C13CPD CDCl3N−butyl−5−phenylbenzo[d]oxazol−2−amine


Administrator

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.000

7.256

7.286

7.290

7.300

7.319

7.324

7.329

7.333

7.340

7.373

7.377

7.384

7.393

7.483

7.497

7.512

7.532

7.546

7.561

7.564

7.575

7.580

8.002

8.016

9.090

2.96

3.11

2.01

2.08

0.96

2.09

2.05

1.00

Proton CDCl3(E)−N−benzylidene−4,5−diphenylthiazol−2−amine


li

图章

7580859095100105110115120125130135140145150155160165170 ppm

77.000

127.870

128.166

128.238

128.722

128.903

129.155

129.567

129.878

132.125

132.218

132.637

134.804

135.093

148.522

163.057

169.818

C13CPD CDCl3(E)−N−benzylidene−4,5−diphenylthiazol−2−amine


li

图章

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.000

4.424

6.134

7.190

7.214

7.218

7.226

7.239

7.250

7.279

7.292

7.306

7.335

7.350

7.364

7.379

7.465

7.468

7.476

7.484

2.00

0.96

7.97

1.21

4.05

2.11

Proton CDCl3N−benzyl−4,5−diphenylthiazol−2−amine


li

图章

5060708090100110120130140150160170 ppm

49.773

77.000

120.769

127.017

127.487

127.588

127.668

128.137

128.476

128.701

128.975

129.297

132.840

135.491

137.697

146.001

167.297

C13CPD CDCl3N−benzyl−4,5−diphenylthiazol−2−amine


li

图章

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