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Synlett 2010(14): 2059-2062  
DOI: 10.1055/s-0030-1258511
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Novel Application of (Diacetoxyiodo)benzene for Carbon-Carbon Cleavage of Aryl Diamines and Synthesis of Quinones

Vikas N. Telvekar*, Harshal M. Bachhav
Department of Pharmaceutical Sciences & Technology, Institute of Chemical Technology, Matunga, Mumbai 400 019, India
Fax: +91(22)24145614; e-Mail: vikastelvekar@rediffmail.com;
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Received 13 April 2010
Publikationsdatum:
22. Juli 2010 (online)

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Abstract

A novel synthetic utility of hypervalent iodine reagent, (diacetoxyiodo)benzene for diamino aryl carbon-carbon cleavage is described. 1,2-Diamino aryl compounds were successfully converted into the corresponding nitriles, while the developed method was also useful for the preparation of quinones from corresponding 1,4-diamino aryl compounds. The advantages of this protocol are shorter reaction times and mild reaction conditions to obtain moderate to good yields.

Key words

(diacetoxyiodo)benzene - 1,2-diamino aryl - carbon-carbon cleavage - nitirle - quinone

    References and Notes

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  • 7a

    General Procedure for the Cleavage of 1,2-Diamino-benzene (Table 1, Entry 1)
    To a stirred solution of(diacetoxyiodo)benzene (3g, 9.2 mmol) in acetone (15 mL) was added 1,2-diaminobenzene (0.5 g, 4.6 mmol). The reaction mixture was stirred at r.t. until the starting material was completely consumed (TLC). After completion of reaction, the reaction mixture was quenched with H2O (20 mL) and further diluted with EtOAc (30 mL). The organic layer was separated and washed successively with 10% NaHSO4 solution (2 × 20 mL), 10% NaHCO3 (2 × 15 mL), and H2O (2 × 20 mL). The organic layer was dried over anhyd Na2SO4, filtered, and concentrated under reduced pressure to give crude product. Pure mucononitrile was obtained as a colorless solid after silica gel column chromatography (10% EtOAc-hexane).

  • 7b

    General Procedure for the Oxidation of 1,4-Diaminobenzene (Table 1, Entry 10)
    To a stirred solution of(diacetoxyiodo)benzene (3g, 9.2 mmol) in acetone (15 mL) was added 1,4-diaminobenzene (0.5 g, 4.6 mmol). The reaction mixture was stirred at r.t. and after completion of reaction (TLC) the reaction mixture was quenched in H2O and the above workup procedure was followed to obtain benzoquinone.

8

(2 E ,4 Z )-3-Chlorohexa-2,4-dienedinitrile (Entry 2) Mp 90 ˚C (lit.4 mp 89-90 ˚C). IR (KBr): 3050, 2220, 1640, 1111, 784 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 5.83-5.85 (d, J = 6.0 Hz, 1 H), 5.89 (s, 1 H), 7.32-7.31 (d, J = 6.0 Hz, 2 H). ¹³C NMR (75 MHz, CDCl3): δ = 105.6, 105.9, 135.7, 138.1, 147.9, 162.7. ESI-MS: m/z = 137 [M+].
(2 E ,4 Z )-3-Methylhexa-2,4-dienedinitrile (Entry 3) Mp 57 ˚C (lit.4 mp 56.5-57.5 ˚C). IR (KBr): 3071, 2214, 1640, 1261, 1031, 797 cm-¹. ¹H NMR (300 MHz, CDCl3):
δ = 2.41 (s, 3 H), 5.51 (s, 1 H), 5.68-5.70 (d, J = 5.4 Hz, 1 H), 7.24-7.26 (d, J = 5.4 Hz, 1 H). ¹³C NMR (75 MHz, CDCl3): δ = 20.6, 102.4,105.2, 115.0, 115.7, 143.5, 153.1. ESI-MS: m/z = 118 [M+].
(2 E ,4 Z )-3-Methoxyhexa-2,4-dienedinitrile (Entry 4) Mp 116 ˚C(lit.4 mp 116-117 ˚C). IR (KBr): 3061, 2214, 1710, 1627, 1210, 803 cm-¹. ¹H NMR (300 MHz, CDCl3):
δ = 3.86 (s, 3 H), 4.80 (s, 1 H), 5.67-5.71 (d, J = 12.0 Hz, 1 H), 7.05-7.09 (d, J = 12.0 Hz, 1 H). ¹³C NMR (75 MHz, CDCl3): δ = 29.6, 101.6, 105.9, 113.4, 113.9, 138.1, 148.0. ESI-MS: m/z = 134 [M+].
(2 E ,4 Z )-3-Benzoylhexa-2,4-dienedinitrile (Entry 6) Mp 95 ˚C. IR (KBr): 3019, 2214, 1638, 1401, 1319 cm-¹. ¹H-NMR (300 MHz, CDCl3): δ = 5.75-5.78 (d, J = 10.8 Hz, 1 H), 5.82 (s, 1 H), 7.27-7.30 (d, J = 10.8 Hz, 1 H), 7.48-7.79 (m, 5 H). ¹³C NMR (75 MHz, CDCl3): δ = 106.3, 108.4, 113.8, 114.0, 129.1, 130.0, 134.5, 135.0, 140.3, 153.1, 191.2. ESI-MS: m/z = 208 [M+].
1-Chloroanthracene-9,10-dione (Entry 15) Mp 162 ˚C. IR (KBr): 3082, 1669, 1574, 1318, 1264, 702 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 7.69-8.30 (m, 7 H). ¹³C NMR (75 MHz, CDCl3): δ = 127.54, 128.3, 130.3, 133.1, 134.4, 134.7, 135.3, 135.8, 138.5, 182.6, 183.0. ESI-MS: m/z = 242 [M+].
2-Aminoanthracene-9,10-dione (Entry 16) Mp 303-306 ˚C. IR (KBr): 3434, 3331, 1673, 1625, 1588, 1337, 714 cm-¹. ¹H NMR (300 MHz, DMSO): δ = 6.68 (s, 2 H), 6.92-8.10 (m, 7 H). ¹³C NMR (75 MHz, DMSO): δ = 109.8, 118.2, 126.5, 129.7, 133.4, 133.5, 134.4, 135.0, 154.8, 180.2. ESI-MS: m/z = 224 [M + H]+.