Download PDF
Synlett 2011(12): 1745-1747  
DOI: 10.1055/s-0030-1260802
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Copper(I) Iodide Catalyzed Formation of Aryl Hydrazides from a Mitsunobo Reagent and Aryl Halides

Issa Yavari*, Majid Ghazanfarpour-Darjani, Yazdan Solgi, Salome Ahmadian
Chemistry Department, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran
Fax: +98(21)82883455; e-Mail: yavarisa@modares.ac.ir;
Further Information

Publication History

Received 10 February 2011
Publication Date:
21 June 2011 (online)

   Permissions and Reprints All articles of this category
Preview

Abstract

The Mitsonubo reagent (triphenylphosphine and dialkyl azodicarboxylates) was employed as a potential anionic nucleophile in a reaction involving aryl halides to produce aryl hydrazides. Aryl iodides and bromides, with electron-withdrawing as well as electron-releasing groups on the aromatic ring, undergo coupling reactions in good yields. The optimized conditions are developed for aryl iodides at room temperature and for aryl bromides at 60-75 ˚C.

Key words

aryl iodide - aryl bromide - Mitsonubo reagent - aryl ­hydrazide - copper(I) iodide

    References and Notes

  • 1a Enders E. In Methoden der Organischen Chemie   Vol. 10/2:  Stroh R. Thieme; Stuttgart: 1967.  p.546 
    Search in Google Scholar
  • 1b Dekeyser M. McDonald PT. Angle GW.
    J. Agric. Food Chem.  1994,  42:  1358 
    Search in Google Scholar
  • 1c Reich MF. Fabio PF. Lee VJ. Kuck NA. Testa RT. J. Med. Chem.  1989,  32:  2474 
    Search in Google Scholar
  • 2a Gribble GW. J. Chem. Soc., Perkin Trans. 1  2000,  1045 
  • 2b Oliva A. Ellis M. Fiocchi L. Menta E. Krapcho AP. J. Heterocycl. Chem.  2000,  37:  47 
    Search in Google Scholar
  • 2c Hughes DL. Org. Prep. Proced. Int.  1993,  25:  607 
    Search in Google Scholar
  • 2d Yavari I. Khalili G. Mirzaei A. Helv. Chim. Acta  2010,  93:  277 
    Search in Google Scholar
  • 3a Duthale RO. Angew. Chem. Int. Ed.  2003,  42:  975 
    Search in Google Scholar
  • 3b Waser J. Carreira EM. J. Am. Chem. Soc.  2004,  126:  5676 
    Search in Google Scholar
  • 3c Saaby S. Bella M. Jorgensen KA. J. Am. Chem. Soc.  2004,  126:  8120 
    Search in Google Scholar
  • 4 Ragnarsson U. Chem. Soc. Rev.  2001,  30:  205 
    CrossrefSearch in Google Scholar
  • 5 Demers JP. Klaubert DH. Tetrahedron Lett.  1987,  28:  4933 
    CrossrefSearch in Google Scholar
  • 6 Metallinos C. Nerdinger S. Snieckus V. Org. Lett.  1999,  1:  1183 
    CrossrefSearch in Google Scholar
  • 7 Velarde-Ortiz R. Guijarro A. Rieke RD. Tetrahedron Lett.  1998,  39:  9157 
    CrossrefSearch in Google Scholar
  • 8a Bombek S. Lenarsic R. Kocevar M. Saint-Jalmes L. Desmurs J.-R. Polanc S. Chem. Commun.  2002,  1494 
  • 8b Kinart WJ. Kinart CM. J. Organomet. Chem.  2003,  665:  233 
    Search in Google Scholar
  • 9 Wolter M. Klapars A. Buchwald SL. Org. Lett.  2001,  3:  3803 
    CrossrefPubMedSearch in Google Scholar
  • 10 Uemura T. Chatani N. J. Org. Chem.  2005,  70:  8631 
    CrossrefPubMedSearch in Google Scholar
  • 11 Typical Procedure for the Preparation of Aryl Hydrazides 3a-i To a stirred solution of aryl iodide (1 mmol) and Ph3P (0.263 g, 1 mmol) in THF (2 mL), was added CuI (9 mg, 0.05 mmol) in one portion. The mixture was stirred at r.t. for 30 min under N2. Then, the DAAD (1.2 mmol) was added to the reaction mixture, which was stirred at r.t. for 18 h under nitrogen. After removal of the solvent, the residue was purified by chromatography (silica gel, hexane-EtOAc = 5:1) to give hydrazides 3a-i. Representative Analytical DataDiethyl 1-Phenyl-hydrazine-1,2-dicarboxylate (3a) Colorless solid, mp 81-83 ˚C; yield 0.23 g (91%). IR (KBr): νmax = 3280, 1599, 1518, 1340, 1100 cm-¹. ¹H NMR (500.1 MHz, CDCl3): δ = 1.27 (3 H, t, ³ J = 7.0 Hz, Me), 1.28 (3 H, t, ³ J = 7.0 Hz, Me), 4.22 (4 H, m, 2 CH2O), 7.09 and 7.19 (1 H, br s, NH), 7.20 (1 H, t, ³ J = 7.1 Hz), 7.33 (2 H, t, ³ J = 7.6 Hz), 7.42 (2 H, d, ³ J = 7.4 Hz). ¹³C NMR (125.7 MHz, CDCl3): δ = 14.4 (Me), 14.5 (Me), 62.3 (CH2O), 63.0 (CH2O), 124.3 (2 CH, br), 126.3 (2 CH), 128.6 (CH), 141.7 (C), 155.0 (C=O), 156.4 (C=O). MS: m/z (%) = 252 (1) [M+], 180 (10), 152 (100), 134 (16), 108 (22), 107 (69), 106 (14), 91 (17), 77 (32). Anal. Calcd (%) for C12H16N2O4 (252.27): C, 57.13; H, 6.39; N, 11.10. Found: C, 57.59; H, 6.44; N, 11.23. Diisopropyl 1-Phenyl-hydrazine-1,2-dicarboxylate (3b) Colorless solid, mp 90-92 ˚C; yield 0.25 g (92%). IR (KBr); νmax = 3241, 1569, 1500, 1325, 1110 cm-¹. ¹H NMR (500.1 MHz, CDCl3): δ = 1.26 (6 H, t, ³ J = 6.6 Hz, 2 Me), 1.29 (6 H, t, ³ J = 6.8 Hz, 2 Me), 5.08-5.10 (2 H, m, CHO), 6.96 and 7.12 (1 H, br s, NH), 7.20 (1 H, t, ³ J = 7.1 Hz), 7.36 (2 H, t, ³ J = 7.1 Hz), 7.46 (2 H, d, ³ J = 7.4 Hz). ¹³C NMR (125.7 MHz, CDCl3): δ = 21.0 (2 Me), 21.7 (2 Me), 70.0 (CHO), 70.7 (CHO), 121.2 (2 CH, br), 125.9 (2 CH), 128.9 (CH), 139.3 (C), 154.7 (C=O), 156.0 (C=O). MS: m/z (%) = 280 (1) [M+], 194 (16), 152 (100), 134 (11), 108 (19), 107 (65), 106 (12), 91 (14), 77 (25). Anal. Calcd (%) for C14H20N2O4 (280.32): C, 59.99; H, 7.19; N, 9.99. Found: C, 59.69; H, 7.24; N, 9.93.
12

Typical Procedure for the Preparation of Aryl Hydrazides 3j-s
To a stirred solution of aryl bromide (1 mmol), Ph3P (0.263 g, 1 mmol), and Phen (0.036 g, 20 mol%) in MeCN (2 mL) was added CuI (9 mg, 0.05 mmol) in one portion. The mixture was stirred at r.t. for 30 min under N2. Then, the DAAD (1 mmol) was added to the reaction mixture, which was stirred at 60-75 ˚C for 16 h under N2. After removal of the solvent, the residue was purified by chromatography (silica gel, hexane-EtOAc = 5:1) to give hydrazides 3j-s.
Representative Analytical DataDiethyl 1-(3-Methylphenyl)-hydrazine-1,2-dicarboxylate (3j) Yellow oil; yield 0.22 g (83%). IR (KBr): νmax = 3310, 1539, 1510, 1321, 1132 cm-¹. ¹H NMR (500.1 MHz, CDCl3): δ = 1.27 (3 H, t, ³ J = 7.2 Hz, Me), 1.30 (3 H, t, ³ J = 7.1 Hz, Me), 2.32 (3 H, s, Me), 4.20 (4 H, m, 2 CH2O), 6.96 and 7.07 (1 H, br s, NH), 7.12 (1 H, d, ³ J = 7.2 Hz, CH), 7.20 (1 H, d, ³ J = 7.3 Hz, CH), 7.26 (1 H, s, CH), 7.45 (1 H, t, ³ J = 7.2 Hz, CH). ¹³C NMR (125.7 MHz, CDCl3): δ = 19.6 (Me), 19.9 (Me), 26.6 (Me), 67.6 (CH2O), 68.2 (CH2O), 125.4 (CH, br), 130.3 (CH, br), 133.6 (CH), 136.3 (CH), 141.2 (C), 143.8 (C), 156.5 (C=O), 161.5 (C=O). MS: m/z (%) = 266 (1) [M+], 194 (13), 166 (100), 148 (16), 122 (14), 120 (68), 105 (17), 91 (8). Anal. Calcd (%) for C13H18N2O4 (266.29): C, 58.63; H, 6.81; N, 10.52. Found: C, 58.83; H, 6.88; N, 10.69.
Diisopropyl 1-(3-Methylphenyl)-hydrazine-1,2-dicarboxylate (3k) Yellow oil; yield 0.24 g (81%). IR (KBr): νmax = 3291, 1527, 1524, 1314, 1112 cm-¹. ¹H NMR (500.1 MHz, CDCl3): δ = 1.17 (6 H, d, ³ J = 7.2 Hz, Me), 1.28 (6 H, t, ³ J = 7.1 Hz, Me), 2.32 (3 H, s, Me), 4.97-4.99 (2 H, m, 2 CHO), 6.67 and 6.71 (1 H, br s, NH), 6.90 (1 H, d, ³ J = 7.2 Hz, CH), 6.97
(1 H, d, ³ J = 7.3 Hz, CH), 7.20 (1 H, s, CH), 7.28 (1 H, t, ³ J = 7.2 Hz, CH). ¹³C NMR (125.7 MHz, CDCl3): δ = 21.6 (2 Me), 21.9 (2 Me), 29.6 (Me), 70.6 (CHO), 70.8 (CHO), 121.4 (CH, br), 124.3 (CH, br), 126.6 (CH), 128.3 (CH), 138.2 (C), 141.8 (C), 154.5 (C=O), 156.5 (C=O). MS: m/z (%) = 294 (1) [M+], 208 (13), 166 (100), 148 (16), 122 (14), 120 (68), 105 (17). Anal. Calcd (%) for C15H22N2O4 (294.35): C, 61.21; H, 7.53; N, 9.52. Found: C, 61.42; H, 7.62; N, 9.60.

13

The reaction of aryl bromides was improved in the presence of Phen.