Surface-mediated solid phase reactions: Microwave assisted Arbuzov rearrangement on the solid surface

Article abstract of DOI:10.1081/SCC-100105324

Microwave assisted Arbuzov rearrangement under solvent-free condition was found to be an efficient method for the preparation of dialkyl alkylphosphonates of alkyl halides. This method is an easy, rapid, and high-yielding reaction for the Arbuzov rearrangement.

Full text of DOI:10.1081/SCC-100105324

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SURFACE-MEDIATED SOLID PHASE REACTIONS:
MICROWAVE ASSISTED ARBUZOV REARRANGEMENT ON
THE SOLID SURFACE
B. Kaboudin a & M. S. Balakrishna b
a Institute for Advanced Studies in Basis Sciences (IASBS), Gava Zang, Zanjan, 45195-159,
Iran
b Department of Chemistry, Indian Institute of Technology (IIT), Powai, Mumbai, 400 076,
India
Version of record first published: 15 Aug 2006.
To cite this article: B. Kaboudin & M. S. Balakrishna (2001): SURFACE-MEDIATED SOLID PHASE REACTIONS: MICROWAVE
ASSISTED ARBUZOV REARRANGEMENT ON THE SOLID SURFACE, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 31:18, 2773-2776
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SYNTHETIC COMMUNICATIONS, 31(18), 2773–2776 (2001)
SURFACE-MEDIATED SOLID PHASE
REACTIONS: MICROWAVE ASSISTED
ARBUZOV REARRANGEMENT ON
THE SOLID SURFACE
B. Kaboudin1,* and M. S. Balakrishna2
1Institute for Advanced Studies in Basis Sciences
(IASBS), Gava Zang, Zanjan 45195-159, Iran
2Department of Chemistry, Indian Institute of
Technology (IIT), Powai, Mumbai 400 076, India
ABSTRACT
Microwave assisted Arbuzov rearrangement under solvent-
free condition was found to be an efficient method for the
preparation of dialkyl alkylphosphonates of alkyl halides. This
method is an easy, rapid, and high-yielding reaction for the
Arbuzov rearrangement.
Although phosphorus compounds containing the phosphorus–carbon
bond are not particularly abundant in nature, their diverse biological activ-
ity,1,2 has for a long time attracted considerable synthetic3 and pharmacolo-
gical interest.4 The Michaelies–Arbuzov rearrangement, also known as the
Arbuzov reaction, is a very versatile way to create a phosphorus–carbon bond
from a trialkyl phosphite and an alkyl halide.5 This reaction is one of the most
*Corresponding author. Fax: (þ98) 241 449023, E-mail: kaboudin@iasbs.ac.ir
2773
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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KABOUDIN AND BALAKRISHNA
extensively investigated in organophosphorus chemistry and is widely used to
prepare phosphonates, phosphinates and phosphine oxides.6 Basically, the
trialkyl phosphites usually used are (EtO)3P, and (MeO)3P. The rearrange-
ment involves the formation of the corresponding alkyl halide (EtX, and
MeX) that is volatile in the general experiment conditions of the Arbuzov
reaction. There is no doubt that microwave can be used to great effect in
organic synthesis; the in situ generation of heat is very efficient and can be
used to significantly reduce reaction times of numerous synthetically useful
organic transformations.7 To our knowledge, there is no report in the litera-
ture on a Michaelies–Arbuzov reaction on the solid surface that assisted by
microwave. As a part of our efforts to explore the novel utilities of surface-
mediated reaction for the synthesis of organophosphorus compounds,8–11 we
report here a new method for the Arbuzov rearrangement on the solid
surface. It is found that alumina (neutral) under solvent-free conditions
was capable of producing high yields of dialkyl alkylphosphonates from
alkyl chloride and trialkyl phosphite under microwave irradiation (Scheme 1)
(Table 1).
Scheme 1.
Table 1. The Arbuzov Reaction for the Preparation of Dialkyl Alkylphosphonates
(3) Under Solvent-Free Condition Using Microwave Irradiation
Product
3
Time
(min)
Yielda
(%)
R-
PhCH2-
CCl3-
CH2¼CH-CH2-
PhCOCH2-CH2-
t-butyl-
PhCH2-
CCl3-
CH2¼CH-CH2-
PhCOCH2-CH2-
t-butyl-
R0
a
b
c
d
e
f
g
h
i
Et-
Et-
Et-
Et-
10
5
5
85
78
73
90
–
80
76
70
90
–
5
Et-
15
10
5
5
5
15
Me-
Me-
Me-
Me-
Me-
f
aIsolated Yields.

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ARBUZOV REARRANGEMENT
2775
As shown in Table 1, benzyl chloride, tetrachloride carbon, allyl
chloride, and also 3-chloro-1-phenyl-1-propanone with triethyl phosphite
and trimethyl phosphite in the presence of alumina (n), afford the desired
products in excellent yields with microwave irradiation. The t-butyl chloride
is failed in this condition and no Arbuzov rearrangement product was
detected.
The other types of alumina (acidic and basic) are not as effective as
neutral alumina and usually give relatively low yields of the corresponding
products.
Simple work-up, low consumption of solvent, fast reaction rates, mild
reaction condition, and good yields of the reaction make this method an
attractive and useful contribution to the 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 in all experiments. The infrared (IR) spectra were determined neat
1
using a FTIR. H NMR (at 60 MHz) spectra were obtained as solutions in
deuteriochloroform (CDCl3).
General Procedure for the Preparation of Dialkyl
Alkylphosphonates (3) on the Solid Surface
Alumina (Al2O3, neutral, 2 g) was added to a mixture of trialkyl phos-
phite (0.0025 mol) and the alkyl chloride (0.002 mol). This mixture was
irradiated by microwave for 5–10 min (Table 1). The reaction mixture was
washed with CH2Cl2 (200 mL), dried (CaCl2), and the solvent evaporated to
give the crude products. Pure product was obtained by distillation under
reduced pressure in 73–90% yields.
ACKNOWLEDGMENTS
We thank the Department of Atomic Energy (DAE), Bombay for the
financial support of this work done at the Indian Institute of Technology,
Bombay. BK also thanks Institute for Advanced Studies in Basic Sciences
(IASBS) for supporting this work.

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KABOUDIN AND BALAKRISHNA
REFERENCES
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Received in Japan October 2, 2000

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