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Synthetic Communications: An
International Journal for Rapid
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Organic Chemistry
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Iodine Catalyzed Chlorination

of Naphthoquinones Using
Metal (II) Chlorides
a
Prakash Chander Thapliyal
a
Department of Chemistry , University of Delhi ,
Delhi, 110007, India
Published online: 15 Aug 2006.

To cite this article: Prakash Chander Thapliyal (1998) Iodine Catalyzed Chlorination
of Naphthoquinones Using Metal (II) Chlorides, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 28:7,
1123-1126, DOI: 10.1080/00397919808005952

To link to this article: http://dx.doi.org/10.1080/00397919808005952

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 SYNTHETIC COMMUNICATIONS,28(7), 1123-1126 (19%)

IODINE CATALYZED CHLORINATION OF

NAPHTHOQUINONES USING METAL (11) CHLORIDES
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Prakash Chander Thapliyal

Department of Chemistry, University of Delhi,Delhi-l10007, India

Abstract : The active quinonoid position of various naphthoquinones is

chlorinated by metal(I1) chloride (Cu/Hg) and iodine in acetic acid in single step
reaction with excellent yields.

The complex metal salts are of great synthetic utility and they have been

employed in various reactions in olefins’-’ i.e. halogenation (particularly for the

synthesis of vicinal dibromo, chloro iodo, chloro bromo), nitration, cyclization,

iodo-alkoxylation, oxymercuration etc. In continuation of our studies6-*on metal

salts-quinone reactions, I report in the present communication a simple

versatile reaction for the chlorination at quinonoid position in 1,4-

naphthoquinone and its derivatives giving fair to good yield of the products.

When a solution of 1,Cnaphthoquinone (1)(0.1 mole) in acetic acid (30 ml) was

stirred at 6OoC in the presence of mercury(I1) chloriddcopper(1I) chloride (0.1

mole) and iodine (0.01 mole), 2-chloro-l,Cnaphthoquinone ( I ) was obtained in

98% yield. Similarly other naphthoquinones (2. to 5) on reaction gave

corresponding chloroquinones (8 to 2).

1123

Copyright 0 1998 by Marcel Dekker, Inc.

 1124 THAPLIYAL

Chlorination does not occur in the absence of any one of the reagents i.e.

copper@) chloride/mercury(II) chloride and iodine. The reaction is fast at

elevated temperature rather than at room temperature. The chlorination

reactions are not quenched on the addition of radical quencher implying the

involvement of ionic mechanism. It has been reported6 that the molecular iodine
Downloaded by [University of California Santa Cruz] at 08:08 16 November 2014

is activated by the complexation with the metal salts facilitating an electrophilic

attack. So the initial step in this mechanism is the electrophilic attack of iodine

ori the quinonoid double bond, thus leading to iodonium intermediate, there is

transfer of chloride ion from the metal complex to iodonium intermediate

resulting in the product formation.

EXPERIMENTAL
Melting points recorded are uncorrected. 'I-INMR spectrum was recorded on 6

scale on Perkin-Elmer R-32 spectrophotometer (90 MHz) with T M S as internal

standard using CDCh as solvent. The notations used are s for singlet, for

multiplet and & for aromatic. IR spectrum was recorded on Perkin-Elmer

spectrophotometer model 599-B in nujol and v- is in cm-'.

General procedure : A solution of naphthoquinone (0.1 mole) in acetic acid (30

ml) is stirred vigourously at 60°C. To this metal salt (0.1 mole) and iodine

(0.01 mole) are added with continuous stirring. The reaction is monitored on

TLC (silica gel, pet ether) for the completion of the reaction. When the

composition of the product remain unaltered on TLC, the reaction mixture is

 N APHTHOQUINONES 1125

Table : Reaction of naphthoquinoneswith HgC12/CuC12

and iodine in CH3COOH
Reactant Time Product Yield m.p. Spectral Data-
ms.1 (%) ("C)
-1 3.0 7
- 98'
2
- 3.O 8
- 808
-3 3.0 9
- 858
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4 3.0 -
10 95*
5
- 2.5 11
- 98 205 'HNMR: 6 3.9 (s,lH,
Mz),7.6-8.2
(m,4H,Ar-Hs).
IR : 1320, 1680,
3300 cm-'
6
- 2.5 -
12 50 190 'HNMR: 6 3.7 (s,lH,
OCH3),7.5-8.1
(m,4H&-Hs).
IR :1625,168Ocm-'
* SatisfactoryCHN data found.

filtered and solvent is evaporated on rotary vaccum evaporator. The residual

mixture is extracted with ether (3 X 100 ml) and the ethereal layer is washed

thoroughly with water and dried over ignited sodium sulphate and the ether is

evaporated and the reaction mixture is subjected to preparative TLC (silica gel;
 1 I26 THAPLIYAL

pet. ether : benzene :: 9:l) to isolate the various chlorination products. The

identification of products has been done by physical as well as chemical

methods and also by comparing with the authentic samples.

Acknowledgement : The author is grateful to the CSIR, New Delhi for the
Downloaded by [University of California Santa Cruz] at 08:08 16 November 2014

award of SRF and the financial assistance rendered thereof.

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(Received in the U K 16th A p r i l , 1997)