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M. A. Nasseri et al.
Letter
Synlett
(17) Lu, M.-Z.; Wang, C.-Q.; Loh, T.-P. Org. Lett. 2015, 17, 6110.
(18) Varma, R. S.; Naicker, K. P.; Kumar, D. J. Mol. Catal. A: Chem.
1999, 149, 153.
(19) Varadaraji, D.; Suban, S. S.; Ramasamy, V. R.; Kubendiran, K.;
Raguraman, J. S. K.; Nalilu, S. K.; Pati, H. N. Org. Commun. 2010,
3, 45.
(20) (a) Malik, M. A.; Al-Thabaiti, S. A.; Malik, M. A. Int. J. Mol. Sci.
2012, 13, 10880. (b) May, B. C.; Abell, A. D. J. Chem. Soc., Perkin
Trans. 1 2002, 172.
(21) Kantam, M. L.; Kumar, K. S.; Raja, K. P. J. Mol. Catal. A: Chem.
2006, 247, 186.
or swallowing. A 14:1 mixture of DMSO and HNO3 (5 mL) was
stirred for 20 min at 40 °C. Then, KCN or NaN3 (1 mmol), PhCHO
(1 mmol), PhNH2, (1 mmol), and H2O (2 mL) were simultane-
ously added to the mixture. Upon completion of reaction (TLC),
the mixture was neutralized with 01. M aq NaOH and extracted
with CH2Cl2 (2 × 20 mL). The solvent was removed, and the
crude product was purified by chromatography.
7a White solid; yield: 9.3 mg (90%); mp 74–76 °C. 1H NMR (250
MHz, CDCl3): = 4.07 (br s, 1 H, N–H), 5.48 (s, 1 H, C–H), 6.77–
6.80 (m, 2 H, Ar–H), 6.92 (t, J = 7.50 Hz, 1 H, Ar–H), 7.22–7.28
(m, 2 H, Ar–H), 7.46 (d, J = 7.50 Hz, 3 H, Ar–H), 7.55–7.59 (m, 2
H, Ar–H). 13C NMR (62.9 MHz, CDCl3): = 50.1, 114.1, 118.1,
120.2, 127.3, 129.3, 129.5, 133.9, 144.7. Anal. Calcd for
(22) Lang, L.; Zhou, H.; Xue, M.; Wang, X.; Xu, Z. Mater. Lett. 2013,
106, 443.
(23) Frija, L. M. T.; Ismael, A.; Santos Cristiano, M. L. Molecules 2010,
15, 3757.
(24) Fischer, D.; Klapötke, T. M.; Stierstorfer, J. Angew. Chem. Int. Ed.
2015, 54, 10299.
(25) Hantzsch, V. A.; Vagt, A. Justus Liebigs Ann. Chem. 1901, 314,
339.
(26) Moradi, P.; Ghorbani-Choghamarani, A. Appl. Organomet. Chem.
2017, 31, e3602.
C14H12N2: C, 80.74; H, 5.81; N, 13.45. Found: C, 80.67; H, 5.71; N,
13.47.
8a White solid; yield: 10.2 mg (91%); mp 82 °C. 1H NMR (250
MHz, CDCl3): = 4.03 (d, J = 5.00 Hz, 1 H, N–H), 5.44 (d, J = 5.00
Hz, 1 H, C–H), 6.77–6.88 (m, 2 H, Ar–H), 6.92 (d, J = 7.00 Hz, 1 H,
Ar–H), 7.25–7.27 (m, 2 H, Ar–H), 7.29 (d, J = 7.00 Hz, 3 H, Ar–H),
7.45–7.61 (m, 2 H, Ar–H). 13C NMR (62.9 MHz, CDCl3): = 62.3,
114.6, 120.5, 125.3, 129.2, 130.0, 131.0, 146.1, 146.6. MS: m/z =
224 [M+]. Anal. Calcd for C13H12N4: C, 69.62; H, 5.39; N, 24.98.
Found: C, 69.66; H, 5.33; N, 25.07.
(27) Halder, M.; Islam, M. M.; Singh, P.; Singh Roy, A.; Islam, S. M.;
Sen, K. ACS Omega 2018, 3, 8169.
(28) Mehraban, J. A.; Azizi, K.; Jalali, M. S.; Heydari, A. ChemistrySe-
lect 2018, 3, 116.
(35) 5-Substituted 1H-Tetrazoles 9a–j; General Procedure
CAUTION: Due to the formation of HN3 during the preparation
of 5-substituted 1H-tetrazoles, the reactions should be per-
formed in a well-ventilated fume hood and behind a blast
shield. A 14:1 mixture of DMSO and HNO3 (5 mL) was stirred for
20 min at 40 °C. PhCHO (1.0 mmol), NH2OH·HCl (1.2 mmol), and
H2O (2 mL) were added, the mixture was stirred for 20 min at
40 °C, and NaN3 (1.2 mmol) was added. Upon completion of
reaction (TLC), the mixture was neutralized with 0.1 M aq
NaOH and extracted with CH2Cl2 (2 × 20 mL). The solvent was
removed, and the crude product was purified by chromatogra-
phy. 5-Phenyl-1H-tetrazole (9a) White solid; yield: 6.8 mg
(94%); mp 214–215 °C (Lit.7 214–215 °C). 1H NMR (250 MHz,
DMSO-d6): = 3.38 (s, 1 H), 7.59–7.61 (m, 3 H), 8.02–8.06 (m, 2
H). 13C NMR (62.9 MHz, DMSO-d6): = 121.1, 126.8, 129.9,
141.2, 155.0. Anal. Calcd for C7H6N4; C, 57.53; H, 4.14; N, 38.34.
Found: C, 57.57; H, 4.34; N, 38.44.
(29) Molaei, S.; Tamoradi, T.; Ghadermazi, M.; Ghorbani-Choghama-
rani, A. Microporous Mesoporous Mater. 2018, 272, 241.
(30) Samanta, P. K.; Biswas, R.; Das, T.; Nandi, M.; Adhikary, B.;
Richards, R. M.; Biswas, P. J. Porous Mater. 2019, 26, 145.
(31) Salahshournia, B.; Hamadi, H.; Nobakht, V. Appl. Organomet.
Chem. 2018, 32, e4416.
(32) De Luca, L.; Giacomelli, G.; Porcheddu, A. J. Org. Chem. 2002, 67,
6272.
(33) Goheen, D.; Bennett, C. J. Org. Chem. 1961, 26, 1331.
(34) Phenyl(phenylamino)acetonitrile (7a) and N-[Azido(phe-
nyl)methyl]aniline (8a); Typical Procedure
CAUTION: Due to the formation of HN3 during the preparation
of -amino azides, the reactions should be performed in a well-
ventilated fume hood and behind a blast shield. Cyanides
present a serious risk of poisoning by inhalation, skin contact,
© 2019. Thieme. All rights reserved. Synlett 2019, 30, A–E