Preparation of acyl phosphates on the surface of magnesia

Article abstract of DOI:10.1081/SCC-120002412

Phosphorylation of carboxylic acids with diethyl chlorophosphate on the surface of magnesia is an easy, rapid, safe and good yielding reaction.

Full text of DOI:10.1081/SCC-120002412

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PREPARATION OF ACYL PHOSPHATES ON THE
SURFACE OF MAGNESIA
Babak Kaboudin
Published online: 16 Aug 2006.
To cite this article: Babak Kaboudin (2002) PREPARATION OF ACYL PHOSPHATES ON THE SURFACE OF MAGNESIA, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:4, 637-640, DOI:
10.1081/SCC-120002412
To link to this article: http://dx.doi.org/10.1081/SCC-120002412
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SYNTHETIC COMMUNICATIONS, 32(4), 637–640 (2002)
PREPARATION OF ACYL PHOSPHATES
ON THE SURFACE OF MAGNESIA
Babak Kaboudin
Institute for Advanced Studies in Basic Sciences
(IASBS), Gava Zang, Zanjan, 45195-159, Iran
E-mail: kaboudin@iasbs.ac.ir
ABSTRACT
Phosphorylation of carboxylic acids with diethyl chlorophos-
phate on the surface of magnesia is an easy, rapid, safe and
good yielding reaction.
Organophosphorus compounds have found a wide range of applica-
tion in the areas of industrial, agricultural, and medicinal chemistry owing
to their biological and physical properties as well as their utility as synthetic
intermediates.1 The synthesis of phosphate esters is an important objective
in organic synthesis, since they have found use in the preparation of biolo-
gical active molecules, and also versatile intermediate in synthesis of amides
and esters.2,3 Owing to their synthetic and biological values, the chemistry of
phosphates has stimulated an increasing interest and the development of
new methodologies for their preparation still remains of great interest.4
Surface-mediated solid phase reactions are of growing interest5
because of their ease of set up and work-up, mild reaction conditions,
rate of the reaction, selectivity, high yields, lack of solvent and the low
cost of the reactions in comparison with their homogeneous counterparts.
As a part of our efforts to explore the utility of surface-mediated reactions,
637
Copyright & 2002 by MarcelDekker, Inc.
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KABOUDIN
for synthesis of organophosphorus compounds,6–10 herein I wish to report a
new method for the preparation of acylphosphates by reaction of car-
boxylic acids on the solid surface. It is found magnesia under solvent-free
conditions was capable of producing high yields of acyl phosphates from
phosphorylation of carboxylic acids with diethyl chlorophosphate under
mild reaction conditions (Scheme 1 and Table 1).
Scheme 1.
As shown in Table 1, o-, m- and p-substituted benzoic acid afforded
the desired products in excellent yields (2a–2h). The reaction also proceeded
in high yields for naphthalene carboxylic acid in the presence of magnesia
(2i). Aliphatic carboxylic acids gave desired products in good yields. The
reaction also proceeded in high yields for 1-hydroxyfurfuryl, a-naphthyl,
and b-naphthylphosphonates ( 2p–r).
The reactions are clean with no tar formation, and interestingly, no
cleavage of the C–O–P bond is observed. Indeed a wide range of carboxylic
acids was converted to corresponding acylphosphates under this condition.
Table 1. The Preparation of AcylPhosphates ( 2) Under Solvent-Free Condition
Product 2
R-
Time (min)
Yielda (%)
a
b
c
d
e
f
g
h
i
Ph-
5
20
5
10
5
30
5
5
90
85
85
90
90
80
90
90
p-CH3C6H4-
p-ClC6H4-
p-FC6H4-
p-O2NC6H4-
m-CH3C6H4-
m-ClC6H4-
o-ClC6H4-
a-Naphthyl25
CH3-
85
30
15
j
k
76
80
PhCH2-
aIsolated yields.

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PREPARATION OF ACYL PHOSPHATES
639
Acidic, neutral, and basic alumina is not as effective as magnesia and
usually give low yields of the corresponding esters.
In summary, simple work-up, low consumption of solvent, relatively
fast reaction rates, mild reaction condition, good yields, and selectivity of
the reaction make this method an attractive and a usefulcontribution to
present methodologies.
EXPERIMENTAL SECTION
General
All chemicals were commercial products and distilled or recrystallized
before use. A kitchen type microwave at 2450 MHz (900 W) was used.
1
The infrared (IR) spectra were determined neat using a FTIR. H NMR
(at 90 MHz) spectra were obtained as solutions in deuteriochloroform
(CDCl3).
General Procedure for Phosphorylation of Carboxylic Acids
with DiethylChol rophosphonate on the Surface of Magnesia
This solvent-free method is operationally simple. Magnesia (0.3 g) was
added to a mixture of diethyl chlorophosphate (0.86 ml, 0.006 mol) and the
carboxylic acid (0.005 mol). This mixture was stirred at room temperature
for 5–30 min (Table 1). The solid mixture was washed with dichloromethane
(4 ꢀ 25). The solution was then washed with saturated NaHCO3 solution
and saturated sodium chloride solution and dried over MgSO4. After
evaporating of solvent, the crude product was isolated in a pure state by
distillation under vacuum in 76–90% yield.
Acyl phosphates 2: All products gave satisfactory spectral data in
1
accord with the assigned structures. [e.g. for 2a H NMR (CDCl3, TMS)
d: 1.22 (t, 3H, J ¼ 6 Hz, -OCH2CH3), 1.28 (t, 3H, J ¼ 6 Hz, -OCH2CH3),
4.05–4.72 (m, 4H, -OCH2CH3), 7.20 (t, 2H, J ¼ 7.3 Hz), 7.44 (t, 1H,
J ¼ 7.3 Hz), 8.18 (d, 2H, J ¼ 7.3 Hz); IR (neat): n 1795, 1735 (C¼O), 1590
(Ar), 1242 (P¼O), 1103–978 (P-O-Et) cmꢁ1].
ACKNOWLEDGMENT
The Institute for Advanced Studies in Basic Sciences (IASBS) is
thanked for supporting this work.

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KABOUDIN
REFERENCES
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publication.
Received in Japan January 31, 2001

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