Synthesis of Diazonaphthoquinones from Naphthols by Diazo-Transfer Reaction with 2-Azido-1,3-dimethylimidazolinium Chloride

Abstract

An efficient synthetic method for the synthesis of diazo­naphthoquinones from naphthols is described. A variety of diazo­naphthoquinones were synthesized from the corresponding naphthols by the diazo transfer with 2-azido-1,3-dimethylimidazolinium chloride prepared by the reaction of 2-chloro-1,3-dimethylimidazorinium chloride and sodium azide.

Key words

azides - diazo compounds - diazonaphthoquinone - diazo transfer - quinone diazide

References and Notes

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12

Typical Procedure for the Preparation of 1-Diazo-2(1 H )naphthalenone (3)
[Caution: Although we have never had any trouble with azidoimidazolinium salt 4, it is potentially explosive.]
To a solution of 2-chloro-1,3-dimethylimidazolinium chloride (228 mg, 1.35 mmol) in MeCN (2 mL), NaN₃ (99.4 mg, 1.5 mmol), and 15-crown-5 ether (0.06 mL, 0.3 mmol) was added at -20 ˚C, and the mixture was stirred for 30 min. 2-Naphthol (130 mg, 0.90 mmol) and Et₃N (0.25 mL, 1.8 mmol) in THF (4 mL) was added to the mixture, which was stirred for 20 min. The reaction was quenched with H₂O, and organic materials were extracted three times with CH₂Cl₂. The combined extracts were washed with H₂O and brine, and then, dried over anhyd Na₂SO₄. The solvent was removed in vacuo to afford crude compounds. The crude materials were purified by flash column chromatography (silica gel: hexane-EtOAc = 4:1) to give diazonaphthoquinone 3 in 86% yield.

13

Spectral Data for 3
IR (ATR): 2333, 2221, 2084, 1616, 1558, 1479, 1452, 1394, 1346, 1304, 1251, 1203, 819, 613 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 7.62 (d, 1 H, J = 9.8 Hz) 7.57 (dd, 1 H, J = 7.8, 1.2 Hz) 7.51 (ddd, 1 H, J = 7.8, 7.8, 1.2 Hz), 7.28 (br d, 1 H, J = 7.8 Hz), 7.27 (ddd, J = 7.8, 7.8, 1.2 Hz), 6.65 (d, 1 H, J = 9.8 Hz). ^¹³C NMR (100 MHz, CDCl₃): δ = 180.2, 140.2, 130.0, 129.7, 127.1, 125.9, 125.6, 124.7, 119.6, 77.2. Anal. Calcd (%) for C₁₀H₆N₂O: C, 70.58; H, 3.55; N, 16.46. Found: C, 70.76; H, 3.70; N, 16.39. Mp 74-75 ˚C (dec.).

14

Spectral Data for 5
IR (ATR): 2917, 2850, 2348, 2113, 1689, 1619, 1562 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 8.33 (d, 1 H, J = 8.0 Hz) 7.59 (ddd, 1 H, J = 8.0, 7.2, 1.4 Hz), 7.49 (d, 1 H, J = 7.2 Hz), 7.47 (ddd, 1 H, J = 8.0, 7.2, 1.4 Hz), 6.89 (d, 1 H, J = 9.3 Hz), 6.58 (d, 1 H, J = 9.3 Hz). ^¹³C NMR (100 MHz, CDCl₃): δ = 180.2, 137.47, 132.6, 129.5, 128.2, 127.2, 125.3, 117.3, 116.2, 74.2. Anal. Calcd (%) for C₁₀H₆N₂O: C, 70.58; H, 3.55; N, 16.46. Found: C, 70.20; H, 3.68; N, 16.74. Mp 73.5-74 ˚C (dec.).