Preparation of α-ketophosphonates by oxidation of α-hydroxyphosphonates with Pyridinium Chlorochromate (PCC)

Article abstract of DOI:10.1080/10426500490463925

Various types of diethyl α-hydroxyphosphonates were converted efficiently to their corresponding diethyl α-ketophosphonates by pyridiinum chlorochromate (PCC) without cleavage of C(O) - P bond in the absence of solvent or in solution in high yields.

Full text of DOI:10.1080/10426500490463925

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Phosphorus, Sulfur, and Silicon and the Related
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PREPARATION OF α-KETOPHOSPHONATES BY OXIDATION
OF α-HYDROXYPHOSPHONATES WITH PYRIDINIUM
CHLOROCHROMATE (PCC)
a
a
a
Habib Firouzabadi , Nasser Iranpoor & Sara Sobhani
a
Department of Chemistry, College of Sciences, Shiraz University, Shiraz, Iran
Published online: 16 Aug 2010.
To cite this article: Habib Firouzabadi , Nasser Iranpoor & Sara Sobhani (2004) PREPARATION OF α-KETOPHOSPHONATES BY
OXIDATION OF α-HYDROXYPHOSPHONATES WITH PYRIDINIUM CHLOROCHROMATE (PCC), Phosphorus, Sulfur, and Silicon and the
Related Elements, 179:8, 1483-1491, DOI: 10.1080/10426500490463925
To link to this article: http://dx.doi.org/10.1080/10426500490463925
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Phosphorus, Sulfur, and Silicon, 179:1483–1491, 2004
Copyright ꢀC Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490463925
PREPARATION OF α-KETOPHOSPHONATES
BY OXIDATION OF α-HYDROXYPHOSPHONATES
WITH PYRIDINIUM CHLOROCHROMATE (PCC)
Habib Firouzabadi, Nasser Iranpoor, and Sara Sobhani
Department of Chemistry, College of Sciences,
Shiraz University, Shiraz, Iran
(
Received December 18, 2003; accepted December 18, 2003)
Various types of diethyl α-hydroxyphosphonates were converted effi-
ciently to their corresponding diethyl α-ketophosphonates by pyridi-
inum chlorochromate (PCC) without cleavage of C(O) P bond in the
absence of solvent or in solution in high yields.
Keywords: α-Hydroxyphosphonates; α-ketophosphonates; chlorochro-
mates; oxidation
INTRODUCTION
Organophosphorus compounds have found wide applications in chem-
istry, medicinal chemistry, and biology. Phosphonates, as a class of
organophosphorus compounds, are interesting complements to phos-
phates in terms of biological activity and have been well documented
1
in the literature. α-Ketophosphonates are an important subdivision
of this class of compounds. The adjacent phosphorus substituents and
carbonyl functional groups in α-ketophosphonates are the main reason
2
that makes them interesting compounds in organic synthesis. For in-
3
4
stance, it is possible to prepare α,α-difluorophosphonates and oximes
from their carbonyl functional groups, to reduce enantioselectively
5
α-ketophosphonates to their corresponding α-hydroxyphosphonates,
6
7
and use them in hetero Diels Alder and Wittig reactions. For several
years it has been known that the carbonyl of a α-ketophosphonate is ac-
tivated towards attack by nucleophiles and that the carbon-phosphorus
8
bond is readily cleaved. This property makes α-ketophosphonates
The authors are thankful to the Shiraz University Research Council for the partial
support of this work.
Address correspondence to Habib Firouzabadi, Department of Chemistry, College of
Sciences, Shiraz University, Shiraz 71454, Iran. E-mail: firouzabadi@chem.susc.ac.ir
1
483

1
484
H. Firouzabadi et al.
potentially useful acylating agents but also susceptible to hydrolysis
and difficult to handle.8
The Michael-Arbuzov reaction is a general method for the prepara-
9
tion of these compounds from acyl chlorides and trialkylphosphites.
This method works well for the less-complex acyl chlorides but shows
less success in the preparation of α-keto-β,γ -unsaturated phospho-
9
nates, where multiple addition products are often observed. An
alternative method for the preparation of α-ketophosphonates is the
1
0
oxidation of easily prepared and stable α-hydroxyphosphonates.
A
literature survey indicates that in contrast to the existing methods
for the conversion of alcohols to carbonyl compounds, few methods are
known for the preparation of diethyl α-ketophosphonates from their cor-
responding diethyl α-hydroxysphonates. Oxidation by known reagents
requires long reaction times, high molar ratios of the oxidant/substrate,
3
,11
or special treatment for the activation of the reagent.
In recent years, we have started studies on the development of new
methods for the preparation of diethyl α-functionalized phosphonates
from diethyl α-hydroxyphosphonates. Along this line, we have reported
mild oxidation, silylation, halogenation, and azidation procedures for
the preparation of diethyl α-keto and α-trimethylsilyloxy, α-halo and
α-azidophosphonates in high yields.12
RESULTS AND DISCUSSION
Our recent report on the oxidative transformation of organic func-
1
3
tional groups by pyridiinum chlorochromate (PCC) in the absence
1
4
of solvent prompted us to apply this reagent to the important oxida-
tion of diethyl α-hydroxyphosphonates under solvent-free conditions.
Under such reaction conditions, various types of diethyl α-hydroxy-
phenyl, 2-naphthyl, 3-pyridyl, and β,γ -unsaturated phosphonates (1a–
h and 1l–o) were oxidized easily at room temperature in 65–88% yields
◦
(
Table I). Higher temperature (40 C) was needed for the oxidation
of o-, m-, and p-substituted nitro derivatives of diethyl α-hydroxy-
phenylmethyl)phosphonates (1i–k) to produce the desired products in
(
60–75% yields (Scheme 1 and Table I).
We have also tried similar oxidations in the presence of (nico-
1
5
16
tinium dichromate) NDC, (nicotinium chlorochromate) NCC, (ison-
icotinium dichromate) INDC,17 and (pyridinium dichromate) PDC as
the analogs of (pyridinium chlorochromate) PCC under solvent-free con-
ditions. Surprisingly, we observed that none of the oxidants were effec-
tive for this purpose and the starting materials were isolated intact
after long reaction times.
18

Ketophosphonates
1485
SCHEME 1
We have also studied oxidation of diethyl α-hydroxyphosphonates
in the presence of PCC in solvent. In order to optimize the reaction
conditions, we studied the oxidation of 1a to 2a in dry CH3CN,
CH2Cl2, CHCl3, and CCl4. We have found that 1a was oxidized
well by PCC to 2a in dry CH2Cl2 at room temperature. Therefore,
we applied similar conditions for the oxidation of other diethyl α-
hydroxyphosphonates (1b–o) by PCC (Table I). As shown in Table I,
various types of diethyl α-hydroxy-(phenylmethyl)phosphonates
(
1a–k) were cleanly converted into their corresponding diethyl
α-keto-(phenylmethyl) phosphonates (2a–k) in excellent yields
65–87% by PCC). Diethyl α-hydroxy-2-naphthyl, 3-pyridyl, and
(
β,γ -unsaturated phosphonates (1l–o) were also oxidized efficiently
TABLE I Oxidation of α-Hydroxyphosphonates to α-Ketophosphonates by
PCC
Product 2
R
Time (h) Yielda,b (%) Time (h) Yielda,c (%)
a
b
c
d
e
f
g
h
i
j
k
l
m
n
o
C6H5
5.4
6
8.4
5.5
8
8.5
7.5
4
10
9.5
12
11
4.5
88
85
71
73
68
72
76
86
70
60
75
67
65
76
79
2
2.4
2
3.5
2.5
3.5
3
3.5
3
3.5
3.75
8.5
1.75
6.5
9.5
87
85
65
70
71
65
67
78
81
79
80
68
71
80
60
4-CH3C6H4
4-CH3OC6H4
2,4,6-(CH3)3C6H2
2-ClC6H4
3-ClC6H4
4-ClC6H4
2,6-Cl2C6H3
2-O2NC6H4
3-O2NC6H4
4-O2NC6H4
2-naphthyl
3-pyridyl
d
d
d
PhCH CH
CH3CH CH
6
12
a
PCC/substrate = 1/1, isolated yields, room temperature. All compounds were
characterized by comparison of their spectral data with authentic samples.
b
c
d
◦
CH2Cl2, solvent-free, and 40 C.

1
486
H. Firouzabadi et al.
to their corresponding diethyl α-ketophosphonates (2l–o) in 60–80%
yields.
CONCLUSION
In general, conversion of α-hydroxyphosphonates to their α-
ketophosphonates using PCC as an oxidant proceeded well in solution
or under solvent-free conditions. Our results show that reactions in so-
lution proceeded with higher yields and required longer reaction times
in comparison with those under solvent–free conditions. Workup of the
reaction mixtures is easy, and by a simple vacuum distillation pure
products are isolated in good-to-excellent yields. Lack of cleavage of
C(O) P bond in both solvent–free conditions and in solution is a strong
practical advantage of the method.
EXPERIMENTAL
General
Chemicals were either prepared in our laboratories or were purchased
from Fluka and Merck Companies. Products were identified by com-
parison of their IR, NMR, and mass spectra with those reported for the
authentic samples. Progress of the reactions was followed by TLC using
silica-gel polygrams SIL G/UV 254 plates or by GC using a Shimadzu
gas chromatograph GC-14A, equipped with a flame ionization detector
and a glass column packed with DC-200 stationary phase and nitro-
gen as the carrier gas. IR spectra were record on a Perkin-Elmer 781
spectrophotometer. NMR spectra were run on a Bruker Avance DPX
2
50 MHz instrument. Mass spectra were recorded by GCMS-QP 1000
23
EX at 20 eV (Shimadzu).
General Procedure for the Preparation of Diethyl
α-Ketophosphonates by the Oxidation of Diethyl
α-Hydroxyphosphonates with PCC under
Solvent-Free Conditions
Pyridinium chlorochromate (1.077 g, 5 mmol) and substrate (5 mmol)
were ground in a mortar and left at room temperature or in an oven
◦
(
40 C) without further grinding for the appropriate reaction times
(
Table I). The reaction mixture was washed with CCl4 (4 × 25 ml) and
dried over Na2SO4. After evaporation of the solvent, the pure product
was obtained by bulb-to-bulb vacuum distillation in 60–88% yields.

Ketophosphonates
1487
General Procedure for the Preparation of Diethyl
α-Ketophosphonates by Oxidation of Diethyl
α-Hydroxyphosphonates with PCC
To a solution of the α-hydroxyphosphonate (5 mmol) in dry CH2Cl2
50 ml), the PCC (5 mmol) was added. The resulting mixture was
(
stirred at room temperature for the appropriate time (Table I). After
completion of the reaction (monitoring by TLC or GC), the mixture
was filtered and the solid material was washed with the same reaction
solvent (2 × 25 ml). Evaporation of the solvent under reduced pres-
sure and then bulb-to-bulb vacuum distillation afforded the desired
α-ketophosphonates in 80–92% yields (Table I).
Spectral Data of α-Ketophosphonates
Diethyl benzoyl phosphonate (2a). Yield = 97–99%; b.p. = 125–
◦
◦
2a 1
1
(
4
3
5
1
26 C, 0.05 mmHg (reported b.p. = 106–109 C, 0.01 mmHg); H NMR
2
CDCl3, TMS): δ 1.37–1.68 (t, 6H, JHH = 7.1 Hz, 2-OCH2CH3), 4.08–
2
2
.28 (dq, 4H, JPH = 7.1 Hz, JHH = 7.1 Hz, 2-OCH2CH3), 7.28–7.6 (m,
H), 8.03–8.25 (m, 2H) ppm; 1 C NMR (CDCl3, TMS): 16.64 (d, JCP =
3
3
.7 Hz, 2-OCH2CH3), 64.31 (d, 2 JCP = 7.5 Hz, 2-OCH2CH3), 129.15,
1
30.06, 135.03, 136.29 ( C6H5), 199.12 (d, JCP = 177.5 Hz, C O) ppm;
−
1
+
IR (neat): ν 1650 (C O), 1267 (P O) cm ; MS: M (242), M P(O)(OEt)2
(
105); C H O P requires: C, 54.5; H, 6.2. Found: C, 54.2; H, 6.0.
11 15 4
Diethyl 4-methyl-benzoyl phosphonate (2b). Yield = 90–96%; b.p. =
◦
◦
2a
1
30–131 C, 0.05 mmHg (reported b.p. = 116–117 C, 0.03 mmHg);
1
2
H NMR (CDCl3, TMS): δ 1.29–1.42 (t, 6H, JHH = 7.1 Hz, 2-OCH2CH3),
2
2
2
2
(
6
(
1
.35 (s, 3H, CH3), 4.11–4.16 (dq, 4H, JPH = 7.1 Hz, JHH = 7.1 Hz,
1
3
-OCH2CH3), 7.12–7.21 (m, 2H), 8.04–8.07 (m, 2H) ppm; C NMR
3
CDCl3, TMS): 16.67 (d, JCP = 5.7 Hz, 2-OCH2CH3), 22.18 ( CH3),
2
4.24 (d, JCP = 7.5 Hz, 2-OCH2CH3), 127.35, 129.89, 130.31, 146.41
1
C6H4), 198.46 (d, JCP = 176.6 Hz, C O) ppm; IR (neat): ν 1650 (C O),
−1
+
261 (P O) cm ; MS: M (256), M P(O)(OEt)2 (119); C H O P re-
12 17 4
quires: C, 56.2; H, 6.6. Found: C, 56.0; H, 6.1.
Diethyl 4-methoxy-benzoyl phosphonate (2c). Yield = 90–94%; b.p.
◦
◦
2a
=
166–167 C, 0.05 mmHg (reported b.p. = 175–179 C, 1.5 mmHg);
1
2
H NMR (CDCl3, TMS): δ 1.11–1.29 (t, 6H, JHH = 7.1 Hz, 2-OCH2CH3),
2
2
3
2
(
6
(
1
.80 (s, 3H, CH3), 3.90–4.10 (dq, 4H, JPH = 7.1 Hz, JHH = 7.1 Hz,
1
3
-OCH2CH3), 6.84–6.90 (m, 2H), 7.42–7.50 (m, 2H) ppm; C NMR
3
CDCl3, TMS): 16.75 (d, JCP = 5.7 Hz, 2-OCH2CH3), 55.59 ( CH3),
2
3.46 (d, JCP = 7.5 Hz, 2-0CH2CH3), 114.03, 128.82, 129.21, 159.78
1
C6H4), 198.01 (d, JCP = 176.2 Hz, C O) ppm; IR (neat): ν 1655 (C O),
−1
+
265 (P O) cm ; MS: M (272), M P(O)(OEt)2 (135); C H O P re-
12 17 5
quires: C, 52.9; H, 6.2. Found: C, 52.2; H, 5.9.

1
488
H. Firouzabadi et al.
Diethyl 2,4,6-trimethyl-benzoyl phosphonate (2d). Yield = 88–95%;
◦
◦
2a
b.p. = 108–109 C, 0.07 mmHg (reported b.p. = 131–132 C, 0.3 mmHg);
1
2
H NMR (CDCl3, TMS): δ 1.25–1.32 (t, 6H, JHH = 7.1 Hz, 2-OCH2CH3),
2
2
7
.23 (s, 6H, 2,6-diCH3), 2.27 (s, 3H, 4-CH3), 4.06–4.17 (dq, 4H, JPH =
2
13
.1 Hz, JHH = 7.1 Hz, 2-OCH2CH3), 6.83 (s, 2H) ppm; C NMR (CDCl3,
3
TMS): 16.81 (d, JCP = 5.7 Hz, 2-OCH2CH3), 21.17 (2,6-diCH3), 21.38
2
(
4-CH3), 63.12 (d, JCP = 7.5 Hz, 2-OCH2CH3), 129.74, 130.3, 137.69,
1
1
37.75 ( C6H2), 199.01 (d, JCP = 177.0 Hz, C O) ppm; IR (neat): ν
−
1
+
1
665 (C O), 1250 (P O) cm ; MS: M (284), M P(O)(OEt)2 (142);
C H O P requires: C, 59.1; H, 7.4. Found: C, 59.3; H, 7.6.
1
4
21
4
Diethyl 2-chloro-benzoyl phosphonate (2e). Yield = 87–97%; b.p. =
◦
◦
19 1
1
05–106 C, 0.05 mmHg (reported b.p. = 158–160 C, 2.3 mmHg);
H
2
NMR (CDCl3, TMS): δ 1.58 (t, 6H, JHH = 7.1 Hz, 2-OCH2CH3), 4.17–
4
.30 (m, 4H, 2-OCH2CH3), 7.24–7.44 (m, 3H), 8.14–8.20 (m, 1H) ppm;
1
3
3
C NMR (CDCl3, TMS): 16.65 (d, JCP = 5.7 Hz, 2-OCH2CH3), 64.82
2
(
1
d, JCP = 7.4 Hz, 2-0CH2CH3), 126.84, 127.10, 130.64–132.07, 132.68–
1
33.85, 134.16–135.98 ( C6H4), 200.53 (d, JCP = 182.0 Hz, C O) ppm;
−
1
+
IR (neat): ν 1650 (C O), 1245 (P O) cm ; MS: M (276), M+2 (279),
M P(O)(OEt)2 (139); C11H ClO P requires: C, 47.8; H, 5.1. Found: C,
14
4
47.5 H, 4.9.
Diethyl 3-chloro-benzoyl phosphonate (2f). Yield = 89–98%; b.p. =
◦
◦
20 1
1
(
01–102 C, 0.06 mmHg (reported b.p. = 127 C, 0.4 mmHg);
H NMR
CDCl3, TMS): δ 1.28–1.34 (m, 6H, 2-OCH2CH3), 4.16–4.27 (m, 4H, 2-
1
3
OCH2CH3), 7.22–7.53 (m, 3H), 7.96 (s, 1H) ppm; C NMR (CDCl3,
TMS): 18.44 (d, 3 JCP = 5.7 Hz, 2-OCH2CH3), 66.45 (d, JCP = 7.4
2
1
Hz, 2-0CH2CH3), 130.15–139.50 ( C6H4), 201.46 (d, JCP = 182.0 Hz,
−
1
+
C O) ppm; IR (neat): ν 1650 (C O), 1267 (P O) cm ; MS: M (276),
M+2 (279), M P(O)(OEt)2 (139); C H ClO P requires: C, 47.8; H,
1
1
14
4
5
.1. Found: C, 47.4; H, 4.7.
Diethyl 4-chloro-benzoyl phosphonate (2g). Yield = 93–95%; b.p. =
◦
◦
2a
1
42–143 C, 0.06 mmHg (reported b.p. = 112–113 C, 0.01 mmHg);
1
2
H NMR (CDCl3, TMS): δ 1.13–1.42 (t, 6H, JHH = 7.1 Hz, 2-OCH2CH3),
2
2
4
7
(
1
.15–4.33 (dq, 4H, JPH = 7.1 Hz, JHH = 7.1 Hz, 2-OCH2CH3), 7.47–
.50 (m, 2H), 8.21–8.24 (m, 2H) ppm; C NMR (CDCl3, TMS): 16.75
13
3
2
d, JCP = 5.7 Hz, 2-OCH2CH3), 64.49 (d, JCP = 7.5 Hz, 2-OCH2CH3),
1
29.62, 131.58, 133.72, 141.85 ( C6H4), 198.09 (d, JCP = 180.0 Hz,
−
1
+
C O) ppm; IR (neat): ν 1650 (C O), 1260 (P O) cm ; MS: M (277),
M+2 (279), M P(O)(OEt)2 (139); C H ClO P requires: C, 47.8; H,
1
1
14
4
5
.1. Found: C, 47.9; H, 5.3.
Diethyl 2,6-dichloro-benzoyl phosphonate (2h). Yield = 92–99%;
◦
1
b.p. = 150–151 C, 0.05 mmHg; H NMR (CDCl3, TMS): δ 1.04–1.24 (t,

Ketophosphonates
1489
2
2
6
H, JHH = 7.1 Hz, 2-OCH2CH3), 3.95–4.23 (dq, 4H, JPH = 7.1 Hz,
2
13
JHH = 7.1 Hz, 2-OCH2CH3), 6.90–7.09 (m, 3H) ppm; C NMR (CDCl3,
3
2
TMS): 16.61 (d, JCP = 5.7 Hz, 2-OCH2CH3), 64.85 (d, JCP = 7.5 Hz,
1
2
1
-OCH2CH3), 128.06, 128.56, 131.51, 132.07 ( C6H3), 204.36 (d, JCP =
−
1
95.5 Hz, C O) ppm; IR (neat): ν 1691 (C O), 1264 (P O) cm ; MS:
+
M (311), M+2 (313), M+4 (315), M P(O)(OEt)2 (174); C H Cl O P
11
13
2
4
requires: C, 42.4; H, 4.2. Found: C, 42.0; H, 4.0.
Diethyl 2-nitro-benzoyl phosphonate (2i). Yield = 89–91%; b.p. =
◦
1
2
1
7
2
1
5
1
46–147 C, 0.05 mmHg; H NMR (CDCl3, TMS): δ 1.34 (t, 6H, JHH =
2 2
.0 Hz, 2-OCH2CH3), 4.20–4.32 (dq, 4H, JPH = 7.2 Hz, JHH = 7.3 Hz,
2
-OCH2CH3), 7.4 (d, 1H, JHH = 7.4 Hz), 7.70–7.85 (m, 2H), 8.44 (d,
2
13
3
H, JHH = 7.7 Hz,) ppm; C NMR (CDCl3, TMS): 16.64 (d, JCP =
.7 Hz, 2-OCH2CH3), 64.92 (d, 2 JCP = 7.2 Hz, 2-OCH2CH3), 123.92,
24.48, 128.56–130.44, 131.93–132.88, 136.24, 147.08 ( C6H4), 203.86
1
(
d, JCP = 180.0 Hz, C O) ppm; IR (neat): ν 1655 (C O), 1260 (P O)
−
1
+
cm ; MS: M (287), M P(O)(OEt)2 (150); C H NO P requires: C,
1
1
14
6
46.0; H, 4.9. Found: C, 46.3; H, 5.3.
Diethyl 3-nitro-benzoyl phosphonate (2j). Yield = 88–91%; b.p. =
◦
1
1
2
4
(
5
1
=
49–150 C, 0.05 mmHg; H NMR (CDCl3, TMS): δ 1.15–1.43 (m, 6H,
2
-OCH2CH3), 4.10–4.20 (q, 2H, JHH = 7.1 Hz, 2-OCH2CH3), 4.30–
2
.39(q, 2H, JHH = 7.1 Hz, 2-OCH2CH3), 8.44–8.48 (m, 2H), 8.59–8.62
m, 1H), 8.84 (s, 1H) ppm; 1 C NMR (CDCl3, TMS): 16.63 (d, JCP =
3
3
.5 Hz, 2-OCH2CH3), 65.12 (d, 2 JCP = 7.5 Hz, 2-OCH2CH3), 129.04,
1
29.94, 130.64, 132.74, 135.71–137.33, 167.0 ( C6H4), 197.75 (d, JCP
−
1
183.4 Hz, C O) ppm; IR (neat): ν 1650 (C O), 1260 (P O) cm ; MS:
M (287), M P(O)(OEt)2 (150); C H NO6P requires: C, 46.0; H, 4.9.
+
11
14
Found: C, 45.8 H, 4.6.
Diethyl 4-nitro-benzoyl phosphonate (2k). Yield = 87–90%; m.p. =
◦
◦
21
1
1
1
(
140.141 C (reported m.p. = 142–143 C);
H NMR (CDCl3, TMS): δ
.23–1.321 (m, 6H, 2-OCH2CH3), 4.00–4.18 (m, 2H, 2-OCH2CH3), 7.66
2
2
d, 2H, JHH = 7.5 Hz), 8.7 (d, 2H, JHH = 8.7 Hz) ppm; IR (KBr):
−
1
+
ν 1650 (C O), 1260 (P O) cm ; MS: M (287), M P(O)(OEt)2 (150);
C H NO P requires: C, 46.0; H, 4.9. Found: C, 46.4; H, 5.2.
1
1
14
6
Diethyl 2-naphthoyl phosphonate (2l). Yield = 87–91%; b.p. =
◦
◦
19
1
52–153 C, 0.07 mmHg (reported b.p. = 188–191 C, 1.2 mmHg);
1
H NMR (CDCl3, TMS): δ 11.33–1.44 (m, 6H, 2-OCH2CH3), 4.28–
4
8
.39 (m, 4H, 2-OCH2CH3), 7.57–7.64 (m, 2H), 7.85–7.93 (m, 2H),
.04–8.14 (m, 2H), 9.08 (s, 1H) ppm; 13C NMR (CDCl3, TMS): 16.79 (d,
3
2
JCP = 5.7 Hz, 2-OCH2CH3), 64.52 (d, JCP = 7.3 Hz, 2-OCH2CH3),
1
1
23.75–136.67, 169.90 (C10H7), 199.07 (d, JCP = 174.9 Hz, C O)
−
1
+
ppm; IR (neat): ν 1655 (C O), 1260 (P O) cm ; MS: M (292),

1
490
H. Firouzabadi et al.
M P(O)(OEt)2 (155); C H O P requires: C, 61.6; H, 5.8. Found: C,
15
17
4
61.2; H, 5.3.
Diethyl 3-pridoyl phosphonate (2m). Yield = 96–97%; b.p. = 125–
◦
◦
22
1
1
(
2
2
(
1
26 C, 2 mmHg (reported b.p. = 128 C, 2 mmHg);
H NMR
CDCl3, TMS): δ 1.23–1.36 (m, 6H, 2-OCH2CH3), 4.14–4.30 (m, 4H,
2
-OCH2CH3), 7.38–7.43 (m, 1H), 7.90 (d, 2H, JHH = 7.9 Hz), 8.78 (d,
2
1
3
H, JHH = 3.8 Hz), 9.34 (s, 1H) ppm; C NMR (CDCl3, TMS): 16.72
3
2
d, JCP = 5.5 Hz, 2-OCH2CH3), 64.72 (d, JCP = 7.5 Hz, 2-OCH2CH3),
1
24.11, 131.96, 151.27, 154.90 (C5H4N), 199.18 (d, JCP = 183.5 Hz,
−
1
+
C O) ppm; IR (neat): ν 1654 (C O), 1245 (P O) cm ; MS: M (243),
M P(O)(OEt)2 (106); C H NO P requires: C, 49.4; H, 5.8. Found: C,
10
14
4
49.0; H, 5.4.
Diethyl 1-oxo-3-phenyl-2-propenylphosphonate (2n). Yield 90–95%;
◦
1
b.p. 108–109 C, 0.05 mmHg; H NMR (CDCl3, TMS): δ 1.30 (t, 6H,
2
2
2
JHH = 7.1 Hz, 2-OCH2CH3), 4.14 (dq, 4H, JPH = 7.1 Hz, JHH =
7
(
.1 Hz, 2-OCH2CH3), 7.38–7.43 (m, 1H), 8.45–8.48 (m, 1H), 8.77–8.78
m, 1H), 9.34 (s, 1H) ppm; 1 C NMR (CDCl3, TMS): 16.72 (d, JCP = 5.7
3
3
2
Hz, 2-OCH2CH3), 64.72 (d, JCP = 7.5 Hz, 2-OCH2CH3), 124.11, 137.34,
1
1
(
51.27, 154.90 ( C5H5N), 199.18 (d, JCP = 195.5 Hz, C O) ppm; IR
−
1
+
neat): ν 1655 (C O), 1260 (P O) cm ; MS: M (268), M P(O)(OEt)2
131); C13H17O4P requires: C, 58.2; H, 6.3. Found: C, 58.0; H, 6.1.
(
Diethyl 1-oxo-2-butenylphosphonate (2o). Yield = 85–88%; b.p. =
◦
◦
2d 1
1
(
05–105 C, 10 mmHg; (reported b.p. = 109 C, 10 mmHg);
H NMR
CDCl3, TMS): δ 1.18–1.33 (m, 6H, 2-OCH2CH3), 1.90–1.96 (m, 3H,
CH3), 4.02–4.20 (m, 4H, 2-OCH2CH3), 6.27–6.42 (m, 1H), 7.38–7.53
3
(
2
1
(
m, 1H) ppm; 13C NMR (CDCl3, TMS): 16.71 (d, JCP = 5.5 Hz,
2
-OCH2CH3), 18.18 (CH3), 63.14 (d, JCP = 7.3 Hz, 2-OCH2CH3),
1
26.10, 129.78 (CH CH), 198.08 (d, JCP 189.5 Hz, C O) ppm; IR
−
1
+
neat): ν 1665 (C O), 1265 (P O) cm ; MS: M (206), M P(O)(OEt)2
69); C H O P requires: C, 46.46; H, 7.3. Found: C, 46.41; H, 7.1.
(
8
15
4
REFERENCES
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1] a) R. Engel, Chem. Rev., 77, 349 (1977); b) R. Engel, Synthesis of Carbon-Phosphorus
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Ketophosphonates
1491
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3
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[
[
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[
[
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4
4
2, 4369 (2001); b) H. Firouzabadi, N. Iranpoor, and S. Sobhani, Tetrahedron Lett.,
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[
[
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[
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[
[
[
[
[
[
[
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[
23] Compounds 2i, 2j, and 2n are known compounds, and they are reported in the
1
1b
Literature.
Physical and analytical data are not reported for any of them.