Synlett 2012; 23(18): 2663-2666
DOI: 10.1055/s-0032-1317345
letter
© Georg Thieme Verlag Stuttgart · New York

Simple and Practical Method for Preparation of [(Diacetoxy)iodo]arenes with Iodoarenes and m-Chloroperoxybenzoic Acid

Masataka Iinuma
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan   Fax: +81(43)2902792   Email: togo@faculty.chiba-u.jp
,
Katsuhiko Moriyama
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan   Fax: +81(43)2902792   Email: togo@faculty.chiba-u.jp
,
Hideo Togo*
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan   Fax: +81(43)2902792   Email: togo@faculty.chiba-u.jp
› Author Affiliations
Further Information

Publication History

Received: 23 August 2012

Accepted after revision: 11 September 2012

Publication Date:
09 October 2012 (online)


Abstract

Various [(diacetoxy)iodo]arenes bearing 4-methylphenyl, phenyl, 4-nitrophenyl, 3-nitrophenyl, 4-cyanophenyl, 4-bromophenyl, 4-methoxycarbonyphenyl, 3,5-bis(trifluoromethyl)phenyl, and 4-(N,N,N-trimethylammonium)methylphenyl groups were efficiently prepared by the treatment of iodoarenes with m-chloroperoxybenzoic acid in acetic acid. The great advantage of the present method is the easy preparation and isolation of [(diacetoxy)-­iodo]arenes bearing electron-withdrawing groups, such as 4-nitro, 4-cyano, 4-methoxycarbonyl, and 3,5-bis(trifluoromethyl) groups, on the aromatic ring.

 
  • References and Notes

  • 4 Zagulyaeva AA, Yusubov MS, Zhdankin VV. J. Org. Chem. 2010; 75: 2119
  • 7 Preparation of [(Diacetoxy)iodo]benzene (2b; Non-Electron-Deficient Iodoarene)To a solution of 4-iodobenzene (0.61g, 3 mmol) in AcOH (3 mL) was added MCPBA (ca. 65%, 0.88 g, 3.3 mmol). The mixture was stirred at r.t. for 2 h. Then, H2O (30 mL) was added to the reaction mixture and then it was extracted with CHCl3 (3 × 20 mL). After being dried over Na2SO4, filteration, and removal of the solvent (residue ca. 3 mL), Et2O (20 mL) and hexane (20 mL) were added to the residue, and the mixture was cooled to 0 °C to induce precipitation (method A). After filtration, the solids were washed with a mixture of Et2O and hexane to provide [(diacetoxy)iodo]benzene in 83% yield.Preparation of 4-Nitro[(diacetoxy)iodo]benzene (2c; Electron-Deficient Iodoarene)To a solution of 4-iodonitrobenzene (0.75g, 3 mmol) in AcOH (20 mL) was added MCPBA (ca. 65%, 0.88 g, 3.3 mmol). The mixture was stirred for 48 h at 55 °C. Then, H2O (30 mL) was added to the reaction mixture and then it was extracted with CHCl3 (3 × 20 mL). After being dried over Na2SO4, filteration, and removal of the solvent (residue ca. 3 mL), Et2O (20 mL) and hexane (20 mL) were added to the residue, and the mixture was cooled to –78 °C to induce precipitation (method B). After filtration, the solids were washed with a mixture of Et2O and hexane to provide 4-nitro[(diacetoxy)iodo]benzene in 81% yield.Conditions for the Precipitation of (Diacetoxyiodo)arenesMethod AEt2O (20 mL) and hexane (20 mL) were added to the residue, and the mixture was cooled at 0 °C for (diacetoxy­-iodo)benzene, 4-cyano(diacetoxyiodo)benzene, and 1-acetoxy-1,2-benziodoxole-3(1H)-one.Method BEt2O (20 mL) and hexane (20 mL) were added to the residue, and the mixture was cooled at –78 °C for 4-nitro[(diacet­-oxy)iodo]benzene and 3-nitro[(diacetoxy)iodo]benzene.Method CEt2O (20 mL) and hexane (40 mL) were added to the residue, and the mixture was cooled at –78 °C for 4-bromo[(diacet­-oxy)iodo]benzene, 4-methoxycarbonyl[(diacet­-oxy)iodo]benzene, (diacetoxy)iodotoluene, and 3,5-bis(trifluoromethyl)-1-[(diacetoxy)iodo]benzene.Method DEt2O (30 mL) was added to the residue for 4-[(diacetoxy)iodo]benzyl-N,N,N-trimethylammonium tosylate.(Diacetoxyiodo)tolueneMp 102–103 °C (lit.3c mp 106–108 °C). IR (KBr): 663, 1267, 1410, 1567, 1649 cm–1. 1H NMR (500 MHz, CDCl3 TMS): δ = 2.00 (s, 6 H), 2.45 (s, 3 H), 7.30 (d, 2 H, J = 8.3 Hz), 7.97 (d, 2 H, J = 8.3 Hz). 13C NMR (125 MHz, CDCl3, TMS): δ = 20.27, 21.43, 118.27, 131.65, 134.88, 142.57, 176.26.(Diacetoxyiodo)benzeneMp 156–158 °C (lit.9 mp 161–162 °C). IR (KBr): 666, 743, 1271, 1644 cm–1. 1H NMR (500 MHz,CDCl3, TMS): δ = 2.01 (s, 6 H), 7.49 (d, 2 H, J = 7.3 Hz), 7.60 (t, 1 H, J = 7.4 Hz), 8.10 (d, 2 H, J = 7.5 Hz). 13C NMR (125 MHz, CDCl3, TMS): δ = 20.32, 121.57, 130.92, 131.69, 134.90, 176.37.4-Nitro(diacetoxyiodo)benzeneMp 103–104 °C (lit.3c mp 104–105 °C). IR (KBr): 673, 734, 849, 1274, 1348, 1414, 1515, 1570, 1644 cm–1. 1H NMR (500 MHz, CDCl3, TMS): δ = 2.03 (s, 6 H), 8.28 (d, 2 H, J = 9.1 Hz), 8.32 (d, 2 H, J = 9.3 Hz). 13C NMR (125 MHz, CDCl3, TMS): δ = 20.27, 125.59, 126.72, 136.03, 149.40, 176.66.3-Nitro(diacetoxyiodo)benzeneMp 144–146 °C (lit.3b mp 148–150 °C). IR (KBr): 714, 815, 1346, 1569, 1647 cm–1. 1H NMR (500 MHz, CDCl3, TMS): δ = 2.04 (s, 6 H), 7.73 (t, 1 H, J = 8.2 Hz), 8.40 (d, 1 H, J = 9.7 Hz), 8.45 (d, 1 H, J = 9.3 Hz), 8.95 (s, 1 H). 13C NMR (125 MHz, CDCl3, TMS): δ = 20.28, 120.60, 126.31, 130.07, 131.50, 140.37, 148.65, 176.78.4-Cyano(diacetoxyiodo)benzeneMp 168–170 °C (lit.3b mp 172–173 °C). IR (KBr): 673, 821, 1009, 1270, 1650, 2227 cm–1. 1H NMR (500 MHz, CDCl3, TMS): δ = 2.03 (s, 6 H), 7.78 (d, 2 H, J = 8.9 Hz), 8.20 (d, 2 H, J = 8.6 Hz). 13C NMR (125 MHz, CDCl3, TMS): δ = 20.26, 115.65, 117.05, 125.20, 134.01, 135.54, 176.61.4-Bromo(diacetoxyiodo)benzeneMp 116–118 °C (lit.3b mp 120–122 °C). IR (KBr): 669, 746, 804, 1380, 1411, 1644 cm–1. 1H NMR (500 MHz, CDCl3, TMS): δ = 2.01 (s, 6 H), 7.62 (d, 2 H, J = 8.6 Hz), 7.95 (d, 2 H, J = 8.6 Hz). 13C NMR (125 MHz, CDCl3, TMS): δ = 20.31, 119.58, 126.80, 134.15, 136.41, 176.50.4-Bromo(diacetoxyiodo)benzeneMp 116–118 °C (lit.3b mp 120–122 °C). IR (KBr): 669, 746, 804, 1380, 1411, 1644 cm–1. 1H NMR (500 MHz, CDCl3, TMS): δ = 2.01 (s, 6 H), 7.62 (d, 2 H, J = 8.6 Hz), 7.95 (d, 2 H, J = 8.6 Hz). 13C NMR (125 MHz, CDCl3, TMS): δ = 20.31, 119.58, 126.80, 134.15, 136.41, 176.50.4-Methoxycarbonyl(diacetoxyiodo)benzeneMp 127–130 °C. IR (KBr): 670, 755, 826, 1284, 1410, 1566, 1642, 1716 cm–1. 1H NMR (500 MHz, CDCl3, TMS): δ = 2.02 (s, 6 H), 3.97 (s, 3 H), 8.13 (d, 2 H, J = 8.9 Hz), 8.17 (d, 2 H, J = 8.6 Hz). 13C NMR (125 MHz, CDCl3, TMS): δ = 20.25, 52.65, 125.67, 131.74, 133.00, 134.84, 165.45, 176.45. ESI-HRMS: m/z [M + Na]+ calcd for C12H13O6INa: 402.9649; found: 402.9639.3,5-Bis(trifluoromethyl)-1-(diacetoxyiodo)benzeneMp 102–104 °C (lit.3c mp 108–110 °C). IR (KBr): 670, 1131, 1185, 1278, 1349, 1369, 1649 cm–1. 1H NMR (125 MHz, CDCl3, TMS): δ = 2.05 (s, 6 H), 8.09 (s, 1 H), 8.51(s, 2 H). 13C NMR (500 MHz, CDCl3, TMS): δ = 20.24, 129.03, 123.21, 125.49, 133.73 (q, J = 34.4 Hz), 134.95, 176.97. 19F NMR (500 MHz, CDCl3, TMS): δ = –62.72 (CF3).4-[(Diacetoxy)iodo]benzyltrimethylammonium TosylateOil. IR (neat): 566, 684, 1009, 1034, 1123, 1186, 1267, 1482, 1646 cm–1. 1H NMR (500 MHz, DMSO-d 6): δ = 1.90 (s, 6 H), 2.28 (s, 3 H), 3.04 (s, 9 H), 4.60 (s, 2 H), 7.12 (d, 2 H, J = 7.8 Hz), 7.50 (d, 2 H, J = 7.7 Hz), 7.73 (d, 2 H J = 8.0 Hz), 8.07 (d, 2 H, J = 8.0 Hz). 13C NMR (125 MHz, DMSO-d 6): δ = 20.82, 21.11, 51.94, 67.05, 97.85, 125.52, 127.17, 128.16, 133.31, 134.86, 137.81, 145.59, 172.08. ESI-HRMS (+): m/z calcd for C14H21O4NI: 394.0510; found: 394.0497. ESI-HRMS (anion): m/z calcd for C7H7O3S: 171.0110; found: 171.0113.1-Acetoxy-1,2-benziodoxole-3-(1H)-oneMp 168–170 °C (lit.10 mp 164–168 °C). IR (KBr): 743, 1563, 1613 cm–1. 1H NMR (500 MHz, DMSO-d 6): δ = 1.90 (s, 3 H), 7.70 (t, 1 H, J = 7.2 Hz), 7.84 (d, 1 H, J = 8.0 Hz), 7.96 (t, 1 H, J = 7.6 Hz), 8.01 (d, 1 H, J = 7.5 Hz). 13C NMR(500 MHz, DMSO-d 6): δ = 21.08, 120.45, 126.31, 130.40, 131.13, 131.52, 134.52, 167.77, 172.07.
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