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Reduction of 1,2-benzoquinones to give catechols; 4-methylsulfanyl-1,2-dihydroxybenzene

SyntheticPage 440
DOI: 10.1039/SP440
Submitted Jul 20, 2010, published Jul 20, 2010
Christopher Cooksey (rsc@chriscooksey.demon.co.uk)
A contribution from QUINTOX group


			Reaction Scheme: Reduction of 1,2-benzoquinones to give catechols

Chemicals Used

4-(Methylsulfanyl)-1,2-benzoquinone Page 439

Sodium dithionite (BDH)

Na2HPO4

Procedure

A solution of 4-(methylsulfanyl)-1,2-benzoquinone (prepared by nitrosodisulfonate oxidation of 4-(methylmercapto)phenol, 1.0 g, 7.1 mmol) in CHCl3 (150 cm3) was shaken with a solution of Na2S2O4 (6 g) and Na2HPO4 (2.2 g) in water (30 cm3). The red quinone was rapidly decolourised. The CHCl3 was separated, dried (MgSO4) and evaporated to give a residue which was flash chromatographed on silica gel 60 (50 g) eluting with ethyl acetatecyclohexane. Evaporation of the appropriate fractions gave the product as a cream solid (42% based on 4-(methylmercapto)phenol).

Author's Comments

Using the same method (no attempt was made to optimise yields), the following 4-substituted catechols were prepared (yield):

CH3O (34%)

CH3CH2CH2O (72%)

CH3CH2CH2CH2O (58%)

CH3CH2CH2S (55%)

CH3CH2CH2CH2S (87%)

HOCH2CH2S (47%)

 

The reaction failed (recovered starting material) with 4-CH3Se-  and 4-Br phenols.

Data

mp 56.8 ºC (lit Winker A, Ger. Offen. 1978, DE 2644591, p. 30, 50-52 ºC)

δH (CDCl3) 6.88d (1H, 1.2), 6.80m (2H), 5.22brs (1H), 5.08brs (1H), 2.44s (3H).

δC (CDCl3) 143.76s, 141.79s, 129.30s, 121.21d, 116.20d, 115.75d, 17.41q.

MS(EI) m/z (%), 156 (100), 141 (64).

Lead Reference

Cooksey CJ, Land EJ, Riley PA, Org. Prep. Proced. Int., 1996, 28(4), 463-467

DOI: 10.1080/00304949609356553

Other References

Winker A, Ger. Offen. 1978, DE 2644591, p. 30.

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Get structure file (.cdx, .sk2, .mol)

Keywords: catechol, quinone, reduction

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