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

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.

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

References and Notes

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The cis-cis configuration was confirmed by using NMR, melting point and comparing with literature. See:

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<A NAME="RD09310ST-7A">7a</A>

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).

<A NAME="RD09310ST-7B">7b</A>

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.

<A NAME="RD09310ST-8">8</A>

(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]⁺.