Synlett 2019; 30(20): 2290-2294
DOI: 10.1055/s-0039-1690742
letter
© Georg Thieme Verlag Stuttgart · New York

A Facile Approach to Catalyst-Free Cyanation and Azidation of ­Organic Compounds and a One-Pot Preparation of 5-Substituted 1H-Tetrazoles by Using a Dimethyl Sulfoxide–Nitric Acid Combination

Mohammad Ali Nasseri
a  Department of Chemistry, Faculty of Science, University of Birjand, P. O. Box 97175-615, Birjand, Iran   Email: miladkazemnejadi@birjand.ac.ir
,
Seyyedeh Ameneh Alavi
a  Department of Chemistry, Faculty of Science, University of Birjand, P. O. Box 97175-615, Birjand, Iran   Email: miladkazemnejadi@birjand.ac.ir
,
Boshra Mahmoudi
b  Research Center, Sulaimani Polytechnic University, Sulaimani 46001, Kurdistan Region, Iraq
,
Milad Kazemnejadi
a  Department of Chemistry, Faculty of Science, University of Birjand, P. O. Box 97175-615, Birjand, Iran   Email: miladkazemnejadi@birjand.ac.ir
› Author Affiliations
The authors gratefully acknowledge the financial support of this work by the Research Council of the University of Birjand.
Further Information

Publication History

Received: 06 September 2019

Accepted after revision: 23 October 2019

Publication Date:
31 October 2019 (online)


Abstract

In this study, cyanations or azidations of imines were performed by using hydroxy(dimethyl)-λ4-sulfanecarbonitrile or azido(dimethyl)-λ4-sulfanol, respectively, prepared in situ by treatment of potassium cyanide or sodium azide with a dimethyl sulfoxide–nitric acid combination. Furthermore, a one-pot preparation of 5-substituted 1H-tetrazole derivatives was carried out by using this reagent combination in the presence of an aldehyde, hydroxylamine hydrochloride, and sodium azide under mild conditions.

Supporting Information

 
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  • 34 Phenyl(phenylamino)acetonitrile (7a) and N-[Azido(phenyl)methyl]aniline (8a); Typical Procedure CAUTION: Due to the formation of HN3 during the preparation of α-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, 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 simultaneously 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): δ = 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): δ = 50.1, 114.1, 118.1, 120.2, 127.3, 129.3, 129.5, 133.9, 144.7. Anal. Calcd for 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): δ = 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): δ = 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.
  • 35 5-Substituted 1H-Tetrazoles 9aj; General Procedure CAUTION: Due to the formation of HN3 during the preparation of 5-substituted 1H-tetrazoles, the reactions should be performed 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 chromatography. 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): δ = 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): δ = 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.