One-pot synthesis of acid chloride from 1,2-diols

Article abstract of DOI:10.1080/00397910600978267

A simple and mild system for 1,2-diol cleavage has been developed using a combination of lead diacetate and tert-butyl hypochlorite at room temperature. Copyright Taylor & Francis Group, LLC.

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One‐Pot Synthesis of Acid Chloride from
1,2‐Diols
Vikas N. Telvekar a , Jaishree K. Mali a & Mahesh G. Dighe a
a Department of Pharmaceutical Sciences and Technology , University
Institute of Chemical Technology, University of Mumbai , Matunga, Mumbai,
India
Published online: 10 Mar 2007.
To cite this article: Vikas N. Telvekar , Jaishree K. Mali & Mahesh G. Dighe (2007) One‐Pot Synthesis of Acid
Chloride from 1,2‐Diols, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 37:5, 865-868, DOI: 10.1080/00397910600978267
To link to this article: http://dx.doi.org/10.1080/00397910600978267
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Synthetic Communicationsw, 37: 865–868, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600978267
One-Pot Synthesis of Acid Chloride
from 1,2-Diols
Vikas N. Telvekar, Jaishree K. Mali, and Mahesh G. Dighe
Department of Pharmaceutical Sciences and Technology,
University Institute of Chemical Technology, University of Mumbai,
Matunga, Mumbai, India
Abstract: A simple and mild system for 1,2-diol cleavage has been developed using a
combination of lead diacetate and tert-butyl hypochlorite at room temperature.
Keywords: acid chlorides, aldehydes, 1,2-diols, lead(II) acetate, tert-butyl hypochlorite
INTRODUCTION
Lead tetraacetate is widely used as an oxidizing agent in organic chemistry,
however, it is moisture sensitive, hazardous to hande, and costly.[1] Thus
our aim was to generate the lead tetraacetate in situ. In connection with our
work on tert-butyl hypohalides,[2,3] we observed that lead(II) acetate reacts
with tert-butyl hypochlorite to generate lead tetraacetate and can be used
for cleavage of 1,2-diols to get the corresponding aldehydes. Further, it was
noticed that with the use of excess tert-butyl hypochlorite, the corresponding
acid chloride was formed.
Phenyl ethylene glycol was chosen for the reaction with lead diacetate
and tert-butyl hypochlorite. A mixture of lead diacetate (2.1 mmol) and
tert-butyl hypochlorite (2.0 mmol) in toluene was stirred at room temperature.
Lead dichloride precipitated in 30 min, at which time phenyl ethylene glycol
Received in India May 15, 2006
Address correspondence to Vikas N. Telvekar, Department of Pharmaceutical
Sciences and Technology, University Institute of Chemical Technology, University
of Mumbai, Matunga, Mumbai, India. E-mail: vikastelvekar@rediffmail.com
865

866
V. N. Telvekar, J. K. Mali, and M. G. Dighe
Scheme 1. Reagents and conditions: a) 1.0 mmol substrate, 2.0 mmol lead(II) acet-
ate, 2.0 mmol tert-butyl hypochlorite; b) 1.0 mmol substrate, 2.0 mmol lead(II) acetate,
4 mmol tert-butyl hypochlorite.
Table 1. Oxidation of 1,2-diols using lead diacetate and tert-butyl hypochloritea
Entry
1
Compound
Productb
Time (min)
45
Yield (%)c
92
2
3
4
5
40
45
45
40
91
90
93
93
6
7
45
40
92
90
8
40
93
aAll reactions were carried out at rt in toluene.
1
bStructures confirmed by IR, H NMR, and mp/bp.
cYields are of the isolated products.

Acid Chloride from 1,2-Diols
867
(1.0 mmol) was added. After workup and purification by silica-gel chromato-
graphy using benzaldehyde, it was isolated in 94% yield (Scheme 1).
When the reaction was repeated with 4.0 mmol of tert-butyl hypochlorite,
benzoyl chloride was formed. Encouraged by this observation, a variety of
diols were subjected to the reaction with lead diacetate and tert-butyl
hypochlorite in toluene, and results are given Tables 1 and 2.
In conclusion, a simple, efficient, and mild one-pot method has been
developed for the preparation of acid chloride from 1,2-diols.
GENERAL PROCEDURE
Preparation of Aldehyde from 1,2-Diol
A mixture of lead acetate (8 g, 21 mmol) and tert-butyl hypochlorite (2.2 g,
20 mmol) in toluene (25 ml) was stirred at room temperature by adding a
Table 2. One pot acid chloride preparation from 1,2-diols using lead diacetate and
excess tert-butyl hypochloritea
Entry
1
Compound
Productb
Time (min)
45
Yield (%)c
92
2
3
40
45
91
93
4
5
40
40
92
90
aAll reactions were carried out at rt in toluene.
1
bStructures confirmed by IR, H NMR, bp.
cYields are of the isolated products.

868
V. N. Telvekar, J. K. Mali, and M. G. Dighe
small quantity of benzoyl peroxide as an initiator. After 30 min, 1,2-octane-
diol (1.45 g, 10 mmol) was added and stirred for 15 min. The reaction
mixture was filtered, the filtrate washed with saturated sodium bicarbonate
and water (2 Â 20 ml), dried on sodium sulfate, and evaporated to get the
heptaldehyde.
One-Pot Preparation of Acid Chloride from 1,2-Diol
A mixture of lead acetate (7.6 g, 20 mmol) and tert-butyl hypochlorite
(4.3 g, 40 mmol) in toluene (25 ml) was stirred at room temperature by
adding a small quantity of benzoyl peroxide as an initiator. After 30 min,
1,2 octanediol (1.45 g, 10 mmol) was added and stirred for 15 min. The
reaction mixture was filtered, and the filtrate was concentrated. The residue
was distilled under vacuum to give heptanoyl chloride.
ACKNOWLEDGMENT
J. K. Mali and M. G. Dighe thank University Grand Commission (UGC), New
Delhi, for the award of junior research fellowships.
REFERENCES
1. Fieser, M.; Fieser, L. F. Reagents for Organic Synthesis; John Wiley & Sons: New
York, 1977; Vol. 6; p. 313.
2. Telvekar, V. N. tert-Butyl hypoiodite for deoximation. Synth. Commun. 2005, 35,
2827.
3. Arote, N. D.; Telvekar, V. N.; Akamanchi, K. G. Rapid method for the ring
expansion of 1,3-dithiolanes and 1,3-dithianes with tert-butyl hypochlorite.
Synlett 2005, 19, 2935.