FULL PAPERS
Mild and General Access to Diverse 1H-Benzotriazoles
(
150 mg, 0.76 mmol), para-anisidine (280 mg, 2.28 mmol), t-
BuONa (73 mg, 1.52 mmol), Pd (dba) (69.5 mg,
.076 mmol), and (t-Bu) P (23.0 mg, 0.114 mmol) in 1,4-diox-
of Health Grant G12MD007603 from the National Institute
on Minority Health and Health Disparities.
2
3
0
3
ane (0.85 mL) over 6 h at 1008C. Work-up of the reaction
mixture and chromatography of the crude material on
a silica gel column by gradient elution with EtOAc in hex-
anes gave compound 27 as a pale brown solid; yield: 127 mg
References
(
70%); R (SiO /50% EtOAc in hexanes)=0.31. IR (KBr):
f 2
1 1
ꢀ
[1] a) X.-M. Peng, G.-X. Cai, C.-H. Zhou, Curr. Top. Med.
Chem. 2013, 13, 1963–2010; b) B. V. Suma, N. N.
Natesh, V. Madhavan, J. Chem. Pharm. Res. 2011, 3,
375–381.
n=3467, 3391, 1510, 804 cm ; H NMR (400 MHz, DMSO-
d6): d=14.92 (br s, NH, 1H), 8.18 (s, NH, 1H), 7.79 (s, Ar-
H, 1H), 7.14–6.94 (m, Ar-H, 6H), 3.74 (s, CH 3H);
3
,
13
C NMR (100 MHz, DMSO-d ): d=154.5, 145.3, 138.9,
6
˙
[
2] a) K. Kopa n´ ska, A. Najda, J. Zebrowska, L. Chomicz,
1
35.3, 134.5, 121.8, 119.1, 116.0, 114.6, 89.5, 55.2; HR-MS
+
J. Piekarczyk, P. Myjak, M. Bretner, Bioorg. Med.
Chem. 2004, 12, 2617–2624; b) G. Caliendo, G. Greco,
P. Grieco, E. Novellino, E. Perissutti, V. Santagada, D.
Barbarulo, E. Esposito, A. De Blasi, Eur. J. Med.
Chem. 1996, 31, 207–213; c) G. Caliendo, R. Di Carlo,
G. Greco, R. Meli, E. Novellino, E. Perissutti, V. Santa-
gada, Eur. J. Med. Chem. 1995, 30, 77–84.
(
ESI/TOF): m/z=241.1086, calcd, for C H N O [M+H] :
1
3
13
4
2
41.1084.
N-(1H-Benzo[d][1,2,3]triazol-6-yl)isoquinolin-5-amine
28): Synthesized using 6-bromo-1H-benzo[d][1,2,3]triazole
200 mg, 1.01 mmol), isoquinolin-5-amine (436 mg,
.03 mmol), t-BuONa (193 mg, 2.02 mmol), Pd (dba)
(
(
3
2
3
(
92.4 mg, 0.101 mmol), and (t-Bu) P (30 mg, 0.151 mmol) in
3
[
3] a) K. H. G. Verschueren, K. Pumpor, S. Anemꢂller, S.
anhydrous 1,4-dioxane (1 mL) over 6 h at 1008C. Work-up
of the reaction mixture and chromatography of the crude
material on a silica gel column by gradient elution with
EtOAc in hexanes gave compound 28 as a brown solid;
yield: 178 mg (68%); R (SiO /10% MeOH in CH Cl )=
Chen, J. R. Mesters, R. Hilgenfeld, Chem. Biol. 2008,
1
5, 597–606; b) C.-Y. Wu, K.-Y. King, C.-J. Kuo, J.-M.
Fang, Y.-T. Wu, M.-Y. Ho, C.-L. Liao, J.-J. Shie, P.-H.
Liang, C.-H. Wong, Chem. Biol. 2006, 13, 261–268;
c) M. Bretner, A. Baier, K. Kopa n´ ska, A. Najda, A.
Schoof, M. Reinholz, A. Lipniacki, A. Piasek, T. Kuli-
kowski, P. Borowski, Antiviral Chem. Chemother. 2005,
f
2
2
2
ꢀ
1
0
.54. IR (KBr): n=3437, 3272, 1518, 1387, 824 cm ;
1
H NMR (400 MHz, DMSO-d +1drop TFA-d): d=9.91 (s,
6
Ar-H, 1H), 8.73 (s, Ar-H, 2H), 8.12 (d, J=7.8 Hz, Ar-H,
1
6, 315–326; d) K.-L. Yu, Y. Zhang, R. L. Civiello, K. F.
1
H), 7.97–7.89 (m, Ar-H, 3H), 7.45 (s, Ar-H, 1H), 7.37 (d,
13
Kadow, C. Cianci, M. Krystal, N. A. Meanwell, Bioorg.
Med. Chem. Lett. 2003, 13, 2141–2144; e) P. Borowski,
J. Deinert, S. Schalinski, M. Bretner, K. Ginalski, T.
Kulikowski, D. Shugar, Eur. J. Biochem. 2003, 270,
1645–1653.
J=8.8 Hz, Ar-H, 1H); C NMR (100 MHz, DMSO-d +
6
1
1
drop TFA-d): d=147.5, 141.6, 140.3, 138.0, 137.3, 131.6,
31.1, 130.7, 128.6, 122.6, 121.2, 120.7, 119.5, 117.8, 99.7;
HR-MS (ESI/TOF): m/z=262.1099, calcd. for C H N
1
5
12
5
+
[
M+H] : 262.1087.
-(1H-Benzo[d][1,2,3]triazol-6-ylamino)benzonitrile (29):
Synthesized using 6-bromo-1H-benzo[d][1,2,3]triazole
150 mg, 0.76 mmol), para-aminobenzonitrile (269 mg,
[
4] a) M. Fin sˇ gar, I. Milo sˇ ev, Corros. Sci. 2010, 52, 2737–
4
2
749; b) N. K. Allam, A. A. Nazeer, E. A. Ashour, J.
Appl. Electrochem. 2009, 39, 961–969; c) M. M. Antoni-
jevic, M. B. Petrovic, Int. J. Electrochem. Sci. 2008, 3,
(
2
.28 mmol), t-BuONa (73 mg, 1.52 mmol), Pd (dba)
2 3
1
–28.
(
69.5 mg, 0.076 mmol), and (t-Bu) P (23 mg, 0.114 mmol) in
3
[
[
5] H. Janna, M. D. Scrimshaw, R. J. Williams, J. Churchley,
anhydrous 1,4-dioxane (0.85 mL) over 6 h at 1008C. Work-
up of the reaction mixture and chromatography of the crude
material on a silica gel column by gradient elution with
MeOH in CH Cl gave compound 29 as a pale brown solid;
J. P. Sumpter, Environ. Sci. Technol. 2011, 45, 3858–
3
864.
6] S. Weiss, J. Jakobs, T. Reemtsma, Environ. Sci. Technol.
006, 40, 7193–7199.
2
2
2
yield: 116 mg (65%); R (SiO /70% EtOAc in hexanes)=
f
2
ꢀ
1
[7] R. D. Theys, G. Sosnovsky, Chem. Rev. 1997, 97, 83–
0
.40. IR (KBr): n=3436, 3338, 2212, 1606, 805 cm ;
1
132.
H NMR (400 MHz, DMSO-d +1 drop of TFA-d): d=7.94
6
[
8] a) R. R. Kale, V. Prasad, P. P. Mohapatra, V. K. Tiwari,
Monatsh. Chem. 2010, 141, 1159–1182; b) A. R. Katritz-
ky, K. Suzuki, Z. Wang, Synlett 2005, 1656–1665;
c) A. R. Katritzky, B. V. Rogovoy, Chem. Eur. J. 2003,
(
7
d, J=8.7 Hz, Ar-H, 1H), 7.65 (d, J=8.7 Hz, Ar-H, 2H),
.56 (d, J=1.5 Hz, Ar-H, 1H), 7.28 (dd, J=1.8, 8.8 Hz, Ar-
1
3
H, 1H), 7.22 (d, J=8.8 Hz, Ar-H, 2H); C NMR (100 MHz,
DMSO-d +1 drop of TFA-d): d=148.1, 139.6, 137.9, 137.2,
6
9
, 4586–4593; d) A. Paio, A. Zaramella, R. Ferritto, N.
Conti, C. Marchioro, P. Seneci, J. Comb. Chem. 1999, 1,
17–325; e) A. R. Katritzky, S. Rachwal, G. J. Hitchings,
1
33.8, 120.0, 119.9, 117.7, 115.2, 100.6, 100.2; HR-MS (ESI/
+
TOF): m/z=236.0933, calcd. for C H N [M+H] :
1
3
10
5
3
236.0931.
Tetrahedron 1991, 47, 2683–2732.
[
9] For examples see: a) S. S. Panda, C. D. Hall, E. Scriven,
A. R. Katritzky, Aldrichimica Acta 2013, 46, 43–55;
b) S. Liaqat, S. S. Panda, A. Rauf, A. O. Al-Youbi,
A. R. Katritzky, Synthesis 2014, 46, 67–72; c) A. Abdel-
majeid, S. R. Tala, M. S. Amine, A. R. Katritzky, Syn-
thesis 2011, 2995–3005; d) A. R. Katritzky, P. Angrish,
E. Todadze, Synlett 2009, 2392–2411; e) A. R. Katritzky,
P. Angrish, K. Suzuki, Synthesis 2006, 411–424; f) A. R.
Katritzky, P. Angrish, D. Hur, K. Suzuki, Synthesis
Acknowledgements
Support of this work by NSF Grant CHE-1265687 (MKL)
and GVKBIO (NP) is gratefully acknowledged. Infrastruc-
tural support at CCNY was provided by National Institutes
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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