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

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.

Key words

dimethyl sulfoxide - nitric acid - Strecker reaction - amino nitriles - amino azides - tetrazoles

• References and Notes

• 1a Kazemnejadi M, Sardarian AR. RSC Adv. 2016; 6: 91999
• 1b Wang W, Wang Y, Wu B, Cong R, Gao W, Qin B, Yang T. Catal. Commun. 2015; 58: 174
• 1c Yang T, Bartoszewicz A, Ju J, Sun J, Liu Z, Zou X, Wang Y, Li G, Liao F, Martín-Matute B, Lin J. Angew. Chem. Int. Ed. 2011; 50: 12555
• 2a Dekamin MG, Azimoshan M, Ramezani L. Green Chem. 2013; 15: 811
• 2b Shaabani A, Maleki A, Soudi MR, Mofakham H. Catal. Commun. 2009; 10: 945
• 3a Desai UV, Mitragotri SD, Thopate TS, Pore DM, Wadgaonkar PP. Monatsh. Chem. 2007; 138: 759
• 3b Eslami M, Dekamin MG, Motlagh L, Maleki A. Green Chem. Lett. Rev. 2018; 11: 36
• 3c Maleki A, Haji RF, Ghassemi M, Ghafuri H. J. Chem. Sci. 2017; 129: 457
• 3d Baghery S, Zolfigol MA, Schirhagl R, Hasani M, Stuart MC, Nagl A. Appl. Organomet. Chem. 2017; 31: e3883
• 4 Takahashi E, Fujisawa H, Yanai T, Mukaiyama T. Chem. Lett. 2005; 34: 318
• 5 Yadav JS, Reddy BS, Eeshwaraiah B, Srinivas M. Tetrahedron 2004; 60: 1767
• 6a Khalafi-Nezhad A, Foroughi HO, Panahi F. Heteroat. Chem. 2013; 24: 1
• 6b Kantam ML, Mahendar K, Sreedhar B, Choudary BM. Tetrahedron 2008; 64: 3351
• 7 Pathare SP, Akamanchi KG. Tetrahedron Lett. 2012; 53: 871
• 8 Liu Y, Mo K, Cui Y. Inorg. Chem. 2013; 52: 10286
• 9a Seayad AM, Ramalingam B, Chai CL, Li C, Garland MV, Yoshinaga K. Chem. Eur. J. 2012; 18: 5693
• 9b Rajabi F, Nourian S, Ghiassian S, Balu AM, Saidi MR, Serrano-Ruiz JC, Luque R. Green Chem. 2011; 13: 3282
• 10 Rafiee E, Rashidzadeh S, Joshaghani M, Chalabeh H, Afza K. Synth. Commun. 2008; 38: 2741
• 11 Takamura M, Hamashima Y, Usuda H, Kanai M, Shibasaki MA. Angew. Chem. Int. Ed. 2000; 39: 1650
• 12 Gualtierotti JB, Schumacher X, Wang Q, Zhu J. Synthesis 2013; 45: 1380
• 13 Hajipour AR, Rajaei A, Ruoho AE. Tetrahedron Lett. 2009; 50: 708
• 14 Zarchi MA. K, Escandari Z. J. Appl. Polym. Sci. 2011; 4: 1916
• 15 Bosmani A, Pujari SA, Besnard C, Guénée L, Poblador-Bahamonde AI, Lacour J. Chem. Eur. J. 2017; 23: 8678
• 16a Ren R, Zhao H, Huan L, Zhu C. Angew. Chem. Int. Ed. 2015; 54: 12692
• 16b Sharma A, Hartwig JF. Nature 2015; 517: 600
• 17 Lu M.-Z, Wang C.-Q, Loh T.-P. Org. Lett. 2015; 17: 6110
• 18 Varma RS, Naicker KP, Kumar D. J. Mol. Catal. A: Chem. 1999; 149: 153
• 19 Varadaraji D, Suban SS, Ramasamy VR, Kubendiran K, Raguraman JS. K, Nalilu SK, Pati HN. Org. Commun. 2010; 3: 45
• 20a Malik MA, Al-Thabaiti SA, Malik MA. Int. J. Mol. Sci. 2012; 13: 10880
• 20b May BC, Abell AD. J. Chem. Soc., Perkin Trans. 1 2002; 172
• 21 Kantam ML, Kumar KS, Raja KP. J. Mol. Catal. A: Chem. 2006; 247: 186
• 22 Lang L, Zhou H, Xue M, Wang X, Xu Z. Mater. Lett. 2013; 106: 443
• 23 Frija LM. T, Ismael A, Santos Cristiano ML. Molecules 2010; 15: 3757
• 24 Fischer D, Klapötke TM, Stierstorfer J. Angew. Chem. Int. Ed. 2015; 54: 10299
• 25 Hantzsch VA, Vagt A. Justus Liebigs Ann. Chem. 1901; 314: 339
• 26 Moradi P, Ghorbani-Choghamarani A. Appl. Organomet. Chem. 2017; 31: e3602
• 27 Halder M, Islam MM, Singh P, Singh Roy A, Islam SM, Sen K. ACS Omega 2018; 3: 8169
• 28 Mehraban JA, Azizi K, Jalali MS, Heydari A. ChemistrySelect 2018; 3: 116
• 29 Molaei S, Tamoradi T, Ghadermazi M, Ghorbani-Choghamarani A. Microporous Mesoporous Mater. 2018; 272: 241
• 30 Samanta PK, Biswas R, Das T, Nandi M, Adhikary B, Richards RM, 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(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 9a–j; 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.