Synthesis of chromonyl-containing -aminophosphonates

Article abstract of DOI:10.1080/10426500802529127

A series of novel chromonyl-containing -aminophosphonates were synthesized by a one-pot reaction from 3-formylchromones, substituted aromatic amines, and dialkylphosphites. Synthesized compounds were characterized by elemental analysis, and 1H NMR and IR

Full text of DOI:10.1080/10426500802529127

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Phosphorus, Sulfur, and Silicon
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Synthesis of Chromonyl-
Containing α-
Aminophosphonates
Si-Yao Lang a , Duo-Zhi Wang a & Ling-Hua Cao a
a College of Chemistry and Chemical Engineering ,
Xinjiang University , Urumqi, Xinjiang, P. R. China
Published online: 21 Sep 2009.
To cite this article: Si-Yao Lang , Duo-Zhi Wang & Ling-Hua Cao (2009) Synthesis of
Chromonyl-Containing α-Aminophosphonates, Phosphorus, Sulfur, and Silicon and the
Related Elements, 184:10, 2560-2568, DOI: 10.1080/10426500802529127
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Phosphorus, Sulfur, and Silicon, 184:2560–2568, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802529127
Synthesis of Chromonyl-Containing
α-Aminophosphonates
Si-Yao Lang, Duo-Zhi Wang, and Ling-Hua Cao
College of Chemistry and Chemical Engineering, Xinjiang University,
Urumqi Xinjiang, P. R. China
A series of novel chromonyl-containing α-aminophosphonates were synthesized by
a one-pot reaction from 3-formylchromones, substituted aromatic amines, and di-
alkylphosphites. Synthesized compounds were characterized by elemental analysis,
and 1H NMR and IR spectroscopy. Single crystal x-ray diffraction data of compound
6e was obtained, and analysis indicates that the crystal belongs to triclinic system
with space group P-1, a = 9.4200(4) Å, b = 10.5970(6) Å, c = 12.3506(5) Å, α =
84.178(2)◦, β = 73.5830(10)◦, γ = 68.2720(10)◦. V = 1098.59(9) Å3, Z = 2, µ =
0.163 mm−1, F(000) = 456, R[F2>2σ(F2)] = 0.0835, ωR(F2) = 0.2328.
Keywords α-Aminophosphate; chromone; crystal structure; synthesis
INTRODUCTION
α-Aminophosphoric acids and α-aminophosphates are phosphorus-
substituted analogs of α-amino carboxylic acids. Their utilities as
enzyme inhibitors, antitumor, antibiotics, antihypertensive, phar-
macological agents, and many other applications have attracted
chemists’ interests since 1959.1–4 Among the literature methods, the
Kabachnik–Fields reaction is one of the most convenient approaches to
the synthesis of α-aminophosphonates. It is a one-pot, three-component
reaction of carbonyl compound, amines, and dialkylphosphites. The re-
action usually needs a Lewis acid catalyst such as indium (III) chlo-
ride, rare earth elements triflates, and scandium tris (dodecyl sul-
fate). Recently, SmI2, LiClO4, metal triflates [M(OTf)n, M = Li, Mg,
Al, Cu, Ce], TaCl5-SiO2, montmorillonite clay, Al2O3, CF3CO2H, scan-
dium (tris-dodecyl sulfate), BF3·H2O, and tetra-tertbutyl-substituted
Received 8 July 2008; accepted 1 October 2008.
This work was supported by the National Natural Science Foundation of China (Grant
No. 20462006).
Address correspondence to Ling-Hua Cao, College of Chemistry and Chemical En-
gineering, Xinjiang University, 14 Shengli Road, Urumqi Xinjiang 830046, P. R. China.
E-mail: clhxj@xju.edu.cn
2560

Chromonyl-Containing α-Aminophosphonates
2561
phthalocyanines Pht-1-Pht-3 have also been reported as catalysts. A
broad range of catalysts has been employed for the Kabachnik–Fields
reaction. However, many of these catalysts are expensive. The catalyst-
free synthesis of α-aminophosphonates is rather limited.5
Chromones and their derivatives are a group of naturally occurring
compounds that are ubiquitous in nature, especially in fruits, vegeta-
bles, nuts, seeds, flowers, and tree bark. Due to their abundance in
plants and their low mammalian toxicity, chromone derivatives are
present in large amounts in the diet of humans.6,7 Chromones not only
have been extracted from natural products, but also synthesized by
chemical methods.8 In studies to improve the bioactivity of chromones,
chemists have found that chromone-linked heterocyclic frameworks
have a broad biological activity, especially at the C-3 position, with
strong propensities to act as antitumor, antibacterial, antivirus, an-
timicrobial, and antiphlogistic agents.9 Several flavonoid and chromone
derivatives have also been found with inhibitory activity against the
AR enzyme.10
In this article, the catalyst-free synthesis and physical characteri-
zation of new α-aminophosphonates containing chromonyl group are
described. Base on previous work,11 compounds 5a–5g and 6a–6g were
synthesized, and a single-crystal structure of compound 6e was ob-
tained. All new compounds were analyzed by elemental analysis, and
1H NMR and IR spectroscopy. The route of synthesis is shown in
Scheme 1.
SCHEME 1
RESULTS AND DISCUSSION
In the process of the synthesis of these all new compounds, we found
that the reaction could take more time when there is an electron-
withdrawing group (for instance NO2) on the benzene-ring, but is faster
with electron-contributing groups, for example OCH3. The data of

2562
S.-Y. Lang et al.
TABLE I Physical Data and Elemental Analysis of Compounds
Analysis found (calcd.)%
Compd.
mp (◦C)
Yield (%)
Formula
C
H
N
5a
5b
5c
5d
5e
5f
5g
6a
6b
6c
6d
6e
6f
169–170
152–154
151–153
168–169
148–150
165.5–167
177–180
165–166
164–166
181.5–182.5
199–201
185–186
134–135
176–177.5
59.4
42.4
57.1
65.7
59.4
52.2
16.0
51.7
51.9
57.1
53.4
69.5
18.3
47.5
C19H20NO5P
60.98(61.11) 5.42(5.40) 3.74(3.75)
61.87(62.00) 5.71(5.73) 3.63(3.62)
61.82(62.00) 5.71(5.73) 3.61(3.62)
C
C
C
C
C
C
C
C
C
C
C
C
C
20H22NO5P
20H22NO5P
19H19ClNO5P 55.89(56.01) 4.68(4.70) 3.42(3.44)
20H22NO6P
19H19N2O7P
19H19N2O7P
21H24NO5P
22H26NO5P
22H26NO5P
59.66(59.54) 5.52(5.50) 3.45(3.47)
54.64(54.53) 4.57(4.58) 6.68(6.70)
54.42(54.53) 4.60(4.58) 6.68(6.70)
62.94(62.82) 6.01(6.03) 3.50(3.49)
63.71(63.59) 6.33(6.31) 3.38(3.37)
63.46(63.59) 6.29(6.31) 3.36(3.37)
21H23ClNO5P 58.03(57.92) 5.31(5.33) 3.23(3.22)
22H26NO6P
21H23N2O7P
21H23N2O7P
61.35(61.23) 6.06(6.08) 3.26(3.25)
56.60(56.49) 5.22(5.20) 6.26(6.28)
56.38(56.49) 5.18(5.20) 6.30(6.28)
6g
physical properties and elemental analysis of all new compounds are
listed in Table I.
In the IR spectra, all new compounds exhibited medium-strong
bands at 3400∼3100 cm−1, assigned to their NH stretches. The strong
band that appeared at about 1650 cm−1 was assigned to the carbonyl
group of all new compounds.
1
In the H NMR spectra, the signal of methyl group protons that
connects with chromone appeared at about δ 2.3, and the proton in
chromone at C-2 position appeared at about δ 8.0. The signal of NH
appeared as a broad peak, at about δ 4.5. Because of coupling with the
phosphorus atom, the proton of P(O)CH exhibited a doublet at about δ
5.2 and their coupling constants (2JHP) are around 24.0 Hz. The data of
1
the H NMR and IR spectra of the new compounds are listed in Table
II.
A single crystal of compound 6e was gained by slow evaporation
of solvent in its diluted toluene solution. X-ray single crystal diffrac-
tion analysis indicates that the crystal belongs to triclinic system with
space group P-1, a = 9.4200(4) Å, b = 10.5970(6) Å, c = 12.3506(5) Å,
α = 84.178(2)◦, β = 73.5830(10)◦, γ = 68.2720(10)◦. V = 1098.59(9) Å3,
Z = 2, µ = 0.163 mm−1, F(000) = 456, R[F2>2σ(F2)] = 0.0835, ωR(F2)
= 0.2328. The benzene ring [C(12), C(13), C(14), C(15), C(17), C(18)]
and the conjunction nitrogen N(1) atom are fairly planar, and the de-
viation from the least squares plane through the ring atom is 0.0188
Å. The plane equation is 1.5323 (0.0124) ×−6.2256 (0.0126) y + 8.8682

Chromonyl-Containing α-Aminophosphonates
2563
TABLE II 1H NMR and IR Data of Compounds
Compd.
1H NMR (CDCl3) δ
IR ν cm−1
5a
8.10–6.55 (m, 8H, ArH), 8.04 (s, 1H, OCH), 5.40 (d, 2J = 3334 (NH), 1682
23.8 Hz, 1H, NCH), 4.71 (br, 1H, NH), 4.01 (d, 3J =
10.4 Hz, 3H, POCH3), 3.76 (d, 3J = 10.4 Hz, 3H,
POCH3), 2.42 (s, 3H, CH3)
(C=O), 1339
(P=O), 1060
(P−O−C)
5b
5c
5d
5e
5f
8.20–6.77 (m, 7H, ArH), 8.10 (s, 1H, OCH), 5.36 (d, 2J = 3350 (NH), 1680
22.6 Hz, 1H, NCH), 4.40 (br, 1H, NH), 3.98 (d, 3J =
10.8 Hz, 3H, POCH3), 3.86 (d, 3J = 10.8 Hz, 3H,
POCH3), 2.35 (s, 3H, CH3), 2.24 (s, 3H, CH3)
(C=O), 1342
(P=O), 1066
(P−O−C)
7.96–6.70 (m, 7H, ArH), 8.06 (s, 1H, OCH), 5.29 (d, 2J = 3451 (NH), 1684
23.0 Hz, 1H, NCH), 4.73 (br, 1H, NH), 3.91 (d, 3J =
10.8 Hz, 3H, POCH3), 3.61 (d, 3J = 10.8 Hz, 3H,
POCH3), 2.52 (s, 3H, CH3), 2.35 (s, 3H, CH3)
(C=O), 1339
(P=O), 1084
(P−O−C)
8.10–6.70 (m, 7H, ArH), 8.03 (s, 1H, OCH), 5.30 (d, 2J = 3300 (NH), 1643
24.0 Hz, 1H, NCH), 4.70 (br, 1H, NH), 3.92 (d, 3J =
10.8 Hz, 3H, POCH3), 3.68 (d, 3J = 10.8 Hz, 3H,
POCH3), 2.42 (s, 3H, CH3)
(C=O), 1324
(P=O), 1033
(P−O−C)
8.01–6.70 (m, 7H, ArH), 8.03 (s, 1H, OCH), 5.31 (d, 2J = 3100 (NH), 1674
22.6 Hz, 1H, NCH), 4.35 (br, 1H, NH), 3.92 (d, 3H,
OCH3), 3.73 (d, 3J = 10.6 Hz, 3H, POCH3), 3.68 (d, 3J
= 10.6 Hz, 3H, POCH3), 2.43 (s, 3H, CH3)
(C=O), 1277
(P=O), 1014
(P−O−C)
7.83–6.69 (m, 7H, ArH), 8.14 (s, 1H, OCH), 5.34 (d, 2J = 3270 (NH), 1698
23.8 Hz, 1H, NCH), 4.68 (br, 1H, NH), 3.64 (d, 3J =
11.0 Hz, 3H, POCH3), 3.39 (d, 3J = 11.0 Hz, 3H,
POCH3), 2.42 (s, 3H, CH3)
(C=O), 1337
(P=O), 1035
(P−O−C)
5g
6a
7.84–6.80 (m, 7H, ArH), 8.14 (s, 1H, OCH), 5.32 (d, 2J = 3342 (NH), 1652
23.8 Hz, 1H, NCH), 4.68 (br, 1H, NH), 3.91 (d, 3J =
11.0 Hz, 3H, POCH3), 3.58 (d, 3J = 11.0 Hz, 3H,
POCH3), 2.42 (s, 3H, CH3)
(C=O), 1311
(P=O), 1059
(P−O−C)
8.10–6.74 (m, 8H, ArH), 8.04 (d, 4J = 1.2 Hz, 1H, OCH), 3492 (NH), 1686
5.35 (d, 2J = 23.6 Hz, 1H, NCH), 4.70 (br, 1H, NH),
4.26 (m, 2H, POCH2), 4.09 (m, 2H, POCH2), 2.50 (s,
3H, CH3), 1.32 (t, 3J = 7.2 Hz, 3H, CH3), 1.22 (t, 3J =
7.2 Hz, 3H, CH3)
(C=O), 1270
(P=O), 1020
(P−O−C)
6b
6c
6d
8.14–6.76 (m, 7H, ArH), 8.01 (d, 4J = 1.2 Hz, 1H, OCH), 3332 (NH), 1682
5.34 (d, 2J = 23.4 Hz, 1H, NCH), 4.72 (br, 1H, NH),
4.01 (m, 2H, POCH2), 3.97 (m, 2H, POCH2), 2.52 (s,
3H, CH3), 2.35 (s, 3H, CH3), 1.23 (t, 3J = 7.1 Hz, 3H,
CH3), 1.11 (t, 3J = 7.1 Hz, 3H, CH3)
(C=O), 1354
(P=O), 1004
(P−O−C)
7.98–6.67 (m, 7H, ArH), 8.03 (d, 4J = 1.6 Hz, 1H, OCH), 3421 (NH), 1681
5.43 (d, 2J = 24.0 Hz, 1H, NCH), 4.52 (br, 1H, NH),
4.11 (m, 2H, POCH2), 4.05 (m, 2H, POCH2), 2.49 (s,
3H, CH3), 2.34 (s, 3H, CH3), 1.20 (t, 3J = 7.4 Hz, 3H,
CH3), 1.14 (t, 3J = 7.4 Hz, 3H, CH3)
(C=O), 1331
(P=O), 1048
(P−O−C)
7.70–6.37 (m, 7H, ArH), 8.20 (d, 4J = 1.2 Hz, 1H, OCH), 3418 (NH), 1641
5.21 (d, 2J = 23.2 Hz, 1H, NCH), 4.56 (br, 1H, NH),
3.97 (m, 2H, POCH2), 3.67 (m, 2H, POCH2), 2.40 (s,
3H, CH3), 1.28 (t, 3J = 7.1 Hz, 3H, CH3), 1.12 (t, 3J =
7.1 Hz, 3H, CH3)
(C=O), 1339
(P=O), 1011
(P−O−C)
(Continued on next page)

2564
S.-Y. Lang et al.
TABLE II 1H NMR and IR Data of Compounds (Continued)
Compd.
1H NMR (CDCl3) δ
IR ν cm−1
6e
7.92–6.40 (m, 7H, ArH), 8.14 (d, 4J = 1.6 Hz, 1H, OCH), 3491 (NH), 1689
5.18 (d, 2J = 22.8 Hz, 1H, NCH), 4.65 (br, 1H, NH),
3.97 (m, 2H, POCH2), 3.73 (m, 2H, OCH3), 3.67 (m,
3H, POCH2), 2.53 (s, 3H, CH3), 1.26 (t, 3J = 7.5 Hz,
3H, CH3), 1.14 (t, 3J = 7.5 Hz, 3H, CH3)
(C=O), 1390
(P=O), 1005
(P−O−C)
6f
8.08–6.47 (m, 7H, ArH), 8.11 (d, 4J = 1.4 Hz, 1H, OCH), 3497 (NH), 1698
5.30 (d, 2J = 23.0 Hz, 1H, NCH), 4.65 (br, 1H, NH),
4.11 (m, 2H, POCH2), 3.78 (m, 2H, POCH2), 2.36 (s,
3H, CH3), 1.20 (t, 3J = 7.3 Hz, 3H, CH3), 1.12 (t, 3J =
7.3 Hz, 3H, CH3)
(C=O), 1396
(P=O), 1034
(P−O−C)
6g
8.12–6.60 (m, 7H, ArH), 8.12 (d, 4J = 1.4 Hz, 1H, OCH), 3481 (NH), 1686
5.36 (d, 2J = 23.0 Hz, 1H, NCH), 4.58 (s, 1H, NH), 4.10
(m, 2H, POCH2), 3.88 (m, 2H, POCH2), 2.34 (s, 3H,
CH3), 1.36 (t, 3J = 7.2 Hz, 3H, CH3), 1.18 (t, 3J = 7.2
Hz, 3H, CH3)
(C=O), 1297
(P=O), 1020
(P−O−C)
(0.0112) z = 3.8664 (0.0097). Atoms in chromone ring [C(1), C(2), C(3),
C(4), C(5), C(7), C(8), C(9), C(10), O(2)] are also quite planar, and the
deviation from the least squares plane through the ring atom is 0.0136
Å. The plane equation is –7.2607 (0.0042) ×−0.5413 (0.0100) y + 4.2302
(0.0070) z = 2.4239 (0.0068).The dihedral angle between the plane of
chromone group and the plane of the benzene is 83.84(0.08)◦, and the
torsion angle of C(10)-C(11)-N(1)-C(12) is 74.5(4)◦. The structure of the
phosphorus atom in compound 6e is distorted tetrahedron. Two kinds
of hydrogen bond exist in the crystal lattice. Intramolecular H-bond
exists in this structure and the structure is stabilized by the hydrogen
bond between the hydrogen attached to the amine nitrogen (N1) and the
phosphite oxygen (O5). The N1−H1. . .O5 distance is 3.158(4)Å and the
N1−H1. . .O5 angle is 104.2◦. The data of the crystal of the compound
are listed in Table III, Table IV, and Table V. The molecular structure
of the title compound 6e is shown in Figure 1. The packing diagram of
the unit cell of compound 6e is shown in Figure 2. Complete crystal-
lographic data for the structural analysis of compound 6e have been
deposited with the Cambridge Crystallographic Data Centre, CCDC
numbers 684911.
EXPERIMENTAL
General Method
Melting points were taken on a Yanaco MP-S3 micromelting point ap-
paratus. The IR spectra were recorded in KBr pellets on a Bruker

Chromonyl-Containing α-Aminophosphonates
2565
TABLE III Crystal Data and Structure Refinement for 6e
Empirical formula
C22H26NO6P
Limiting indices
-12< = h< = 12, -13< =
k< = 13, -13< = l< =
16
Formula weight
Temperature
Wavelength
431.41
Reflections
10899/4995 [R(int) =
collected/unique
Completeness to
theta = 27.48
Max. and min.
transmission
Refinement
0.0186]
153(2) K
0.71073 Å
99.1%
0.9483 and 0.9058
Crystal system, space triclinic, P-1
group
Unit cell dimensions a = 9.4200(4) Å, Data/restraints/
Full-matrix
method
least-squares on F2
4995/0/272
parameters
b = 10.5970(6) Å,
c = 12.3506(5) Å
α = 84.178(2)◦,
β = 73.5830(10)◦,
γ = 68.2720(10)◦
Volume
1098.59(9) Å3
Goodness-of-fit on 1.117
F2
Z, Calculated density 2, 1.304 Mg/m3
Absorption coefficient 0.163 mm−1
Final R indices
[I>2sigma(I)]
R indices (all data) R1 = 0.1061, ωR2 =
R1 = 0.0835, ωR2 =
0.2328
0.2635
F(000)
456
Absolute structure 0(10)
parameter
Crystal size
0.62 × 0.58 ×
Extinction
coefficient
0.014(5)
0.33 mm
Theta range for data 3.31 to 27.48 deg. Largest diff. peak 1.710 and -1.601 e. Å−3
collection
and hole
TABLE IV Selected Bond Lengths (Å) for the Compound 6e
P(1)-O(5)
P(1)-O(6)
P(1)-O(4)
P(1)-C(11)
N(1)-C(12)
N(1)-C(11)
O(1)-C(9)
C(1)-C(10)
O(2)-C(1)
O(2)-C(2)
O(3)-C(15)
1.429(4) O(3)-C(16)
1.530(4) O(4)-C(19)
1.541(3) O(6)-C(21)
1.812(3) C(1)-C(10)
1.407(4) C(2)-C(3)
1.454(4) C(2)-C(8)
1.233(4) C(3)-C(4)
1.345(4) C(4)-C(5)
1.342(4) C(5)-C(6)
1.377(4) C(5)-C(7)
1.388(4) C(7)-C(8)
1.335(5) C(8)-C(9)
1.463(4)
1.457(4)
1.517(4)
1.392(4)
1.386(5)
1.391(5)
1.381(5)
1.381(5)
1.394(4)
1.442(7)
1.418(9)
1.464(4) C(9)-C(10)
1.160(8) C(10)-C(11)
1.345(4) C(12)-C(18)
1.382(5) C(12)-C(13)
1.388(4) C(13)-C(14)
1.378(5) C(14)-C(15)
1.399(5) C(15)-C(17)
1.513(5) C(17)-C(18)
1.385(5) C(19)-C(20)
1.405(4) C(21)-C(22)

2566
S.-Y. Lang et al.
TABLE V Selected Bond Angles (◦) for the Compound 6e
O(5)-P(1)-O(6)
O(5)-P(1)-O(4)
O(6)-P(1)-O(4)
O(5)-P(1)-C(11)
O(6)-P(1)-C(11)
O(4)-P(1)-C(11)
111.8(4)
117.4(2)
102.6(3)
115.39(17) C(3)-C(4)-C(5)
106.7(2) C(7)-C(5)-C(4)
101.62(14) C(7)-C(5)-C(6)
O(2)-C(2)-C(3)
C(3)-C(2)-C(8)
C(4)-C(3)-C(2)
116.5(3) C(9)-C(10)-C(11)
122.2(3) N(1)-C(11)-C(10) 115.4(2)
118.4(3) C(10)-C(11)-P(1) 113.6(2)
122.1(3) C(18)-C(12)-N(1) 118.8(3)
118.0(3) C(13)-C(12)-N(1) 122.9(3)
119.5(3)
121.0(3) C(17)-C(15)-O(3)
121.5(3) C(14)-C(15)-O(3)
124.6(3)
115.2(3)
C(12)-N(1)-C(11) 119.1(3)
C(16)-O(3)-C(15) 120.5(3)
C(5)-C(7)-C(8)
C(1)-C(10)-C(9) 119.7(3) C(15)-C(17)-C(18) 119.1(3)
C(19)-O(4)-P(1)
C(21)-O(6)-P(1)
O(2)-C(1)-C(10)
122.2(3)
156.2(7)
125.5(3)
C(2)-C(8)-C(7)
C(2)-C(8)-C(9)
N(1)-C(11)-P(1) 107.3(2) O(6)-C(21)-C(22)
117.8(3) C(12)-C(18)-C(17) 121.6(3)
120.6(3) C(20)-C(19)-O(4)
110.1(4)
133.6(8)
1
FT-IR Equinox apparatus. The H NMR spectra were recorded on a
Varian INOVA-400 (using TMS as internal standard, CDCl3 as sol-
vent). Elemental analyses were performed on a Thermo Flash EA-1112
elemental analyzer. X-ray single-crystal diffraction data for compound
FIGURE 1 Molecular structure of compound 6e. (Displacement ellipsoid view
with 30% ellipsoids.)

Chromonyl-Containing α-Aminophosphonates
2567
FIGURE 2 Packing diagram of the unit cell of compound 6e. (Displacement
ellipsoid view with 50% ellipsoids.)
6e were collected on a Bruker Smart 1000 CCD diffractometer at 293(2)
K with Mo-Kα radiation (λ = 0.71073Å) by ω-φ scan mode. The struc-
tures was solved by direct methods using the SHELXS program of
the SHELXTL package and refined by full-matrix least-squares meth-
ods with SHELXL.12 Analytical thin-layer chromatography (TLC) was
performed by GF254 and 0.5% CMC. Detection made use of UV light;
the mobile phase was petroleum ether (fraction boiling in the range of
60–90◦C) and ethyl acetate (1:2). All reagents were commercial prod-
ucts of analytical grade and were used directly without processing ex-
cept when mentioned.
Compounds 1–3
Compounds 1–3 were prepared according to reported methods.13,14
Preparation of N-Aryl-α-amino-α-(chromon-3-yl)-O,O’-
dialkylphosphites (5a–5g, 6a–6g)
To a stirred solution of 6-methyl-3-formylchromone (1 mmol) and sub-
stituted aniline (1 mmol) in anhydrous toluene (40 mL), an equimolar

2568
S.-Y. Lang et al.
amount of dialkylphosphite was added. The mixture was refluxed for
2–5 h. The end of the reaction was detected by TLC. The reaction
mixture was concentrated. The precipitate was filtered off and recrys-
tallized from ethanol–water.
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