Synthesis of some new 1,3,2-oxazaphosphinine, 1,3,2-diazaphosphinine, acyclic, and/or cyclic α-aminophosphonate derivatives containing the chromone moiety

Article abstract of DOI:10.1080/10426500802713309

The synthesis of some new 1,3,2-oxazaphosphinine 18, 1,3,2-diazaphosphinine 19, acyclic, and cyclic -aminophosphonate derivatives 3-17 containing the chromone moiety have been achieved via reaction of 3-(phenyliminomethyl)chromone (1), 3-(phenylaminomethy

Full text of DOI:10.1080/10426500802713309

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Phosphorus, Sulfur, and Silicon and the
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Synthesis of Some New 1,3,2-
Oxazaphosphinine, 1,3,2-
Diazaphosphinine, Acyclic, and/or
Cyclic α-Aminophosphonate Derivatives
Containing the Chromone Moiety
Tarik E. Ali a
a Department of Chemistry, Faculty of Education , Ain Shams
University , Roxy, Cairo, Egypt
Published online: 28 Dec 2009.
To cite this article: Tarik E. Ali (2009) Synthesis of Some New 1,3,2-Oxazaphosphinine, 1,3,2-
Diazaphosphinine, Acyclic, and/or Cyclic α-Aminophosphonate Derivatives Containing the Chromone
Moiety, Phosphorus, Sulfur, and Silicon and the Related Elements, 185:1, 88-96
To link to this article: http://dx.doi.org/10.1080/10426500802713309
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Phosphorus, Sulfur, and Silicon, 185:88–96, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802713309
SYNTHESIS OF SOME NEW 1,3,2-OXAZAPHOSPHININE,
1,3,2-DIAZAPHOSPHININE, ACYCLIC, AND/OR CYCLIC
α-AMINOPHOSPHONATE DERIVATIVES CONTAINING
THE CHROMONE MOIETY
Tarik E. Ali
Department of Chemistry, Faculty of Education, Ain Shams University, Roxy,
Cairo, Egypt
The synthesis of some new 1,3,2-oxazaphosphinine 18, 1,3,2-diazaphosphinine 19, acyclic,
and cyclic α-aminophosphonate derivatives 3–17 containing the chromone moiety have been
achieved via reaction of 3-(phenyliminomethyl)chromone (1), 3-(phenylaminomethylene)-2-
hydroxychromanone (4), and/or 3-(phenylamino-methylene)-2-(phenylamino)chromanone
(5) with diethyl phosphite, tris(2-chloroethyl)phosphite, and phenylphosphonic dichloride.
Structures of the products were verified on the basis of their elemental analyses, IR, 1H, and
31P NMR spectral data.
Keywords
α-Aminophosphonate; chromone; 1,3,2-diazaphosphinine; 1,3,2-oxazaph-
osphinine; synthesis
INTRODUCTION
Chromones are well known natural and synthetic products that possess diverse biolog-
ical activities, namely anticancer,1–3 neuroprotective,4 HIV-inhibitory,5 antimicrobial,6–10
and antioxidant activity.11 Due to their abundance in plants and their low mammalian
toxicity, chromone derivatives are present in large amounts in the diets of humans.12 On
the other hand, the addition of compounds with phosphorus–hydrogen bonds to C C or
C N bonds provides an economic method for the synthesis of organophosphorus deriva-
tives. Among phosphorus compounds, α-aminophosphonic acids and their derivatives have
received considerable attention in recent years because they exhibit intriguing biological
activities.13 Being considered as α-amino acid analogues,14 they have found widespread use
as biologically attractive materials particularly in connection with the design of enzyme in-
hibitors15,16 and as catalytic antibodies.17 In addition, they have been used as antibacterial18
and anti-HIV agents.19
Received 27 August 2008; accepted 26 December 2008.
The author is grateful to Prof. Kolio D. Troev and Dr. I. Krachieva, from Institute of Polymers, Bulgarian
Academy of Science, Sofia, Bulgaria, for providing laboratory facilities. The financial support of this research
through the grant of The Egyptian Ministry of Higher Education and Scientific Research (ParOwn Grant) is
gratefully acknowledged as well.
Address correspondence to Tarik E. Ali, Department of Chemistry, Faculty of Education, Ain Shams
University, Roxy 11711, Cairo, Egypt. E-mail: tarik elsayed1975@yahoo.com
88

SYNTHESIS OF α-AMINOPHOSPHONATE DERIVATIVES
89
It is known that the reaction of 3-formylchromone with aniline derivatives in
benzene yielded three different types of condensation products, namely 3-(phenyl-
iminomethyl)chromone (1), 3-(phenylaminomethylene)-2-hydroxychromanone (4), and
3-(phenylaminomethylene)-2-(phenylamino)chromanone (5), depending on the ratio of
reactants and conditions.20 Chromone derivatives of α-aminophosphonates have been
rarely reported in the literature,21–24 and these products were obtained by addition reaction
of dialkyl or trialkyl phosphites to 3-(aryliminomethyl)chromone (1) only. Thus, we
focused our attention on reactions of diethyl phosphite, tris(2-choloroethyl)phosphite,
and phenylphosphonic dichloride with different condensation products of 6-methyl-3-
formylchromone with aniline.
RESULTS AND DISCUSSION
6-Methyl-3-[(phenylimino)methyl]-4H-chromen-4-one (1) reacted with diethyl
phosphite at 90−100◦C without solvent to furnish diethyl[(phenylamino)(6-methyl-4-
oxo-4H-chromen-3-yl)methyl]phosphonate (3) as a pale red crystalline material. Due to
the phosphonate ↔ phosphite tautomerism in diethyl phosphite, the addition to imine 1
occurred by either a four- or five-membered transition state 2 (Kabachink–Fields reaction)
(Scheme 1).25 Elemental analysis of compound 3 confirmed the molecular formula
C21H24NO5P, and the IR spectrum revealed the presence of strong absorption bands at
3385, 1642, 1230, and 1046 cm−1, which are due to NH, C O, P O, and P−O−Et,
1
respectively. Moreover, its H NMR spectrum showed signals for OCH2CH3 groups
attached to phosphorus as a triplet at δ 1.07 (J = 6.8 Hz) and a broad signal at δ 3.92
ppm. The NH proton gave a broad signal at δ 3.05 ppm, and the exocyclic methane proton
appeared as a broad signal at δ 5.45 ppm. Furthermore, the 31P NMR spectrum recorded a
singlet at δ 22.45 ppm.
Scheme 1

90
T. E. ALI
Scheme 2
Similarly, the reaction of 3-(phenylaminomethylene)-2-hydroxy/N-phenylamino-6-
methyl-2,3-dihydro-4H-chromen-4-ones (4) and/or (5) with diethyl phosphite at 90−100◦C
afforded 2-ethoxy-6-methyl-2-oxo-3-phenylamino-2,3,3a,9a-tetrahydro-4H-1,2-oxaphos-
pholo[5,4-b]chromen-4-one (7) and 2-ethoxy-6-methyl-2-oxo-1-phenyl-3-phenylamino-
2,3,3a,9a-tetrahydro-4H-1,2-azaphospholo[5,4-b]chromen-4-one (8), respectively, as cyc-
lic α-aminophosphonate derivatives. Formation of compounds 7 and 8 may be interpreted as
resulting from a nucleophilic attack of the phosphorus atom at the α,β-unsaturated ketone
moiety of 4 and/or 5 (Pudovik reaction) to give the nonisolable intermediate 6. The latter in-
termediate underwent cyclization via elimination of one molecule of ethanol to give the final
products 7 and 8, respectively (Scheme 2). IR spectra of compounds 7 and 8 showed three
absorptions bands for NH, C O, and P O functions at regions 3296−3290, 1644−1646,
and 1223−1232 cm−1, respectively. Both compounds showed 31P NMR chemical shifts
around δ 19.05 and 18.23 ppm, respectively. The 1H NMR spectrum of 7 showed a doublet
signal due to the CH−P proton at δ 5.33 ppm (J = 23.4 Hz) while that at δ 5.41 ppm
(J = 23.8 Hz) was noted for 8. The broad signals of NH protons of both compounds ap-
peared at δ 3.03 and δ 3.02 ppm, respectively. The H−3 and H−2 protons of chromanone
moiety of 7 appeared at δ 6.28 and δ 8.51 ppm, respectively, while in compound 8, they
appeared at δ 6.25 and δ 8.11 ppm, respectively. The remaining aromatic protons of 7 and
8 appeared as multiplets in the range δ 6.60−8.04 ppm, beside the presence of ethoxy
protons as triplets at δ 1.10, 1.15 ppm (J = 7.4/6.4 Hz) and quartets at δ 4.01, 4.04 ppm (J
= 8.2/7.2 Hz), respectively.
Reaction of compounds 1, 4, and/or 5 with tris(2-chloroethyl)phosphite in the pres-
ence of a certain amounts of distillated water, which accelerate the reactions, produced the
corresponding α-aminophosphonate derivatives 11, 14, and 15, respectively.22 A possible
mechanism for these reactions could involve a nucleophilic phosphorus attack on the elec-
trophilic carbons of compounds 1, 4, and/or 5 to give the intermediate dipolar species of
type 9 and/or 12, respectively, which could be solvated by water present in the reaction
media to give transients such as 10 and/or 13, respectively. The latter transients decompose
via removal of a 2-chloroethanol molecule to afford the final products 11, 14, and 15,
respectively (Schemes 3 and 4).

SYNTHESIS OF α-AMINOPHOSPHONATE DERIVATIVES
91
Scheme 3
Scheme 4

92
T. E. ALI
The structure of 11 was established on the basis of elemental analysis and spectral
data. Its IR spectrum showed absorption bands at 3396, 1620, and 1212 cm−1 due to NH,
C O, and P O functions, respectively. In addition, the 31P NMR spectrum displayed a
singlet at δ 24.06 ppm, while the 1H NMR spectrum revealed two broad signals at δ 3.25
and δ 5.40 ppm corresponding to NH and CH P, respectively. In addition, the aromatic
protons were recorded at δ 7.02−7.97 ppm with multiplets at δ 3.42−4.03 ppm, which
were due to 2-chloroethoxy protons.
1
In a similar way, the structures 14 and 15 were deduced. Their H NMR spectra
showed signals for CH P protons at δ 5.42 and δ 5.72 ppm, respectively, coupled with the
phosphorus atom (J = 22.8 Hz), while signals for C3 H protons appeared at δ 6.40 and δ
6.13 ppm, respectively. The eight protons of 2-chloroethoxy moieties in both compounds 14
and 15 gave multiplets signals at δ 3.62−4.22 ppm. However, weak signals for OH and/or
NH at C 2 of the chromanone moieties appeared at δ 4.5 and/or δ 3.29 ppm, respectively.
In addition, protons of C2 H appeared at δ 8.18 and δ 8.20 ppm for 14 and 15, respectively.
The 31P NMR spectra of 14 and 15 recorded positive signals at δ 20.37 and 20.56 ppm,
respectively. Furthermore, their IR spectra showed presence of OH, NH groups, C O, and
P O functions at regions 3387−3260, 1639−1640, and 1209−1205 cm−1, respectively.
Compounds 11, 14, and/or 15 were heated in absolute ethanol containing a catalytic
amount of triethylamine. This reaction afforded 3-[2-(2-chloroethoxy)-2-oxo-4-phenyl-
1,4,2-oxazaphosphinan-3-yl]-6-methyl-4-oxo-4H-chromen-4-one (17) (IR, mp, and mixed
mp gave no depression). Formation of compound 17 is assumed to take place via loss of one
HCl molecule from 11, 14, and 15, followed by elimination of both water and/or aniline in
the case of 14 and 15, respectively. Hydrogen bonding between XH and NH groups gives
stability to systems 14 and 15, but destruction of this hydrogen bond, after removing the
HCl molecule, may facilitate elimination of water and/or aniline (Scheme 5).
Structure 17 was confirmed on the basis of its correct elemental analysis and spectral
data. Its IR spectrum was void of OH, NH groups but showed the presence of C O and
C C at 1639 and 1614 cm−1, respectively. The 1H NMR spectrum had a signal at δ 5.04
ppm, which is assigned to the CH P proton, in addition to multiplets at δ 3.24−3.28 and δ
3.62−3.75 ppm, corresponding to 2-chloroethoxy and OCH2CH2N moieties, respectively.
Moreover, the 31P NMR spectrum was characterized by a signal at δ 13.72 ppm.
1,3,2-Oxazaphosphinane and 1,3,2-diazaphosphinane derivatives have attracted great
interest due to their valuable pharmacological effects and potential for synthetic applica-
tions.26 Thus, cyclization of compounds 4 and/or 5 with phenylphosphonic dichloride was
performed in dry benzene containing few drops of triethylamine to produce 2,3-diphenyl-7-
methyl-2-oxo-3,10a-dihydro-2H,5H-chromeno[3,2-e][1,3,2]oxazaphosphinin-5-one (18)
and
7-methyl-2-oxo-1,2,3,-triphenyl-10a-tetrahydro-5H-chromeno[2,3-d][1,3,2]dia-
zaphosphinin-5-one (19), respectively, in good yields (Scheme 6). The IR spectra showed
the absence of OH and NH groups and the presence of strong bands at 1641−1650 and
1
1620−1605 cm−1 corresponding to C O and C C, respectively. Also, the H NMR
spectra of 18 and 19 revealed multiplets signals at δ 7.01−7.95 and δ 7.28−7.60 ppm,
respectively, which are due to aromatic protons. The 31P NMR spectra recorded signals at
δ 20.75 and δ 20.05 ppm for both compounds, respectively.27
EXPERIMENTAL
Melting points of the products were determined on a Kofler microscope and were
uncorrected. The IR spectra were recorded on a Bruker IFS 1113 spectrophotometer or

SYNTHESIS OF α-AMINOPHOSPHONATE DERIVATIVES
93
Scheme 5
1
Elmer 293 spectrophotometer (cm−1) using KBr disks. H NMR spectra were recorded
on Gemini-200 spectrometer (200 MHz), using DMSO-d6 as a solvent and TMS (δ,
0.0 ppm) as the internal standard. 31P NMR spectra were registered on a Varian Inova
500 MHz spectrometer at room temperature using DMSO-d6 as a solvent and TMS as in-
ternal standard and 85% H3PO4 as external reference, respectively. The purity of the synthe-
sized compounds was checked by thin layer chromatography (TLC), which was performed
on Kieselgel 60 F254 plastics sheets (Merck Sigma Chemical Co., Germany). Elemental
microanalyses were performed at the microanalysis center at the Bulgarian Academy of Sci-
ence, Sofia, Bulgaria. 3-(Phenyliminomethyl)chromone (1), 3-(phenylaminomethylene)-2-
hydroxychromanone (4), and 3-(phenylaminomethylene)-2-(N-phenylamino)chromanone
(5) were prepared according to the reported methods.20
Scheme 6

94
T. E. ALI
Reaction of Compounds 1, 4, and/or 5 with Diethyl Phosphite:
Formation of 3, 7, and 8: General Procedure
A mixture of compounds 1, 4, and/or 5 (0.005 mol) and diethyl phosphite
(0.008 mol, 1.03 mL), was heated on water bath at 90−100◦C for 10 h. Excess diethyl
phosphite was removed under vacuum. The residues were treated with petroleum ether. The
solids obtained were filtered off and crystallized from benzene to give the corresponding
products 3, 7, and 8, respectively.
Diethyl[(phenylamino)(6-methyl-4-oxo-4H-chromen-3-yl)methyl]phos-
phonate (3). Pale red crystals, yield 66%; mp 100−102◦C. IR (KBr), ν (cm−1):
3385 (NH), 3029 (C Harom), 2977, 2921, 2862 (C Haliph), 1642 (C Opyrone), 1615
(C C), 1230 (P O), 1046 (P O C). 1H NMR (DMSO-d6), δ: 1.07 (t, 6H, J = 6.8 Hz,
CH3CH2O), 2.36 (s, 3H, CH3), 3.05 (br, 1H, NH), 3.92 (br, 4H, CH3CH2O), 5.45 (br, 1H,
CH P), 6.90−7.80 (m, 8H, Ph−H, H−8, H−7 and H−5), 8.15 (br, 1H, H−2). 31P NMR
(DMSO-d6) δ: 22.45 ppm. Anal. Calcd for C21H24NO5P (401.39): C, 62.84; H, 6.03; N,
3.49; Found: C, 62.59; H, 5.81; N, 3.22.
2-Ethoxy-6-methyl-2-oxo-3-phenylamino-2,3,3a,9a-tetrahydro-4H-1,2-o-
xaphospholo[5,4-b]chromen-4-one (7). Yellow crystals, yield 44%; mp 142−142◦C.
IR (KBr), ν (cm−1): 3296 (NH), 3034 (C Harom), 2981, 2924, 2854 (C Haliph), 1644
(C Opyrone), 1601 (C C), 1223 (P O), 1023 (P−O−C). 1H NMR (DMSO-d6), δ: 1.10 (t,
3H, J = 7.4 Hz, CH3CH2O), 2.38 (s, 3H, CH3), 3.03 (br, 1H, NH), 4.01 (q, 2H, J = 8.2 Hz,
CH3CH2O), 5.33 (d, 1H, J = 23.4 Hz, CH P), 6.28 (t, 1H, J = 4.6 Hz, H−3chromanone),
6.60−7.77 (m, 7H, Ph H, H 8 and H 7), 7.91 (s, 1H, H−5), 8.51 (d, 1H, J = 3.4
Hz, H−2chromanone). 31P NMR (DMSO-d6) δ: 19.05 ppm. Anal. Calcd for C19H20NO5P
(373.33): C, 61.12; H, 5.40; N, 3.75; Found: C, 60.83; H, 5.21; N, 3.58.
2-Ethoxy-6-methyl-2-oxo-1-phenyl-3-phenylamino-2,3,3a,9a-tetrahydro-
4H-1,2-azaphospholo[5,4-b]chromen-4-one (8). Yellow crystals, yield 51%; mp
128−130◦C. IR (KBr), ν (cm−1): 3290 (NH), 3051 (C Harom), 2982, 2907 (C Haliph),
1646 (C Opyrone), 1600 (C C), 1232 (P O), 1028 (P O C). 1H NMR (DMSO-d6), δ:
1.15 (t, 3H, J = 6.4 Hz, CH3CH2O), 2.32 (s, 3H, CH3), 3.02 (br, 1H, NH), 4.04 (q, 2H,
J = 7.2 Hz, CH3CH2O), 5.41 (d, 1H, J = 23.8 Hz, CH P), 6.25 (br, 1H, H 3chromanone),
6.63−7.74 (m, 12H, Ph H, H 8 and H 7), 8.04 (s, 1H, H 5), 8.11 (d, 1H, J = 3.4
Hz, H 2chromanone). 31P NMR (DMSO-d6) δ: 18.23 ppm. Anal. Calcd for C25H25N2O4P
(448.45): C, 66.96; H, 5.62; N, 6.25; Found: C, 66.59; H, 5.48; N, 5.97.
Reaction of Compounds 1, 4, and/or 5 with Tris(2-chloroethyl) Phosph-
ite: Formation of 11, 14, and 15: General Procedure
A mixture of 1, 4, and/or 5 (0.005 mol) and tris(2-chloroethyl) phosphite
(0.008 mol, 1.62 mL) in the presence of distillated water (0.005 mol, 0.09 mL) was
heated on a water bath at 90−100◦C for 10 h. Excess tris(2-chloroethyl) phosphite was
removed under vacuum. The solids obtained were crystallized from methanol to give the
corresponding products 11, 14, and 15, respectively.
Bis(2-chloroethyl)[(phenylamino)(6-methyl-4-oxo-4H-chromen-3-yl)me-
thyl]phosphonate (11). Pale brown crystals, yield 71%; mp 113−115◦C. IR (KBr), ν
(cm−1): 3396 (NH), 3059 (C Harom), 2923, (C Haliph), 1620 (C Opyrone), 1212 (P O),
1036 (P−O−C). 1H NMR (DMSO-d6), δ: 2.37 (s, 3H, CH3), 3.25 (br, 1H, NH), 3.42–4.03
(m, 8H, CH2CH2), 5.40 (br, 1H, CH P), 7.02−7.81 (m, 7H, Ph−H, H−8 and H 7), 7.97

SYNTHESIS OF α-AMINOPHOSPHONATE DERIVATIVES
95
(s, 1H, H 5), 8.76 (br, 1H, H 2). 31P NMR (DMSO-d6) δ: 24.06 ppm. Anal. Calcd for
C21H22Cl2NO5P (470.28): C, 53.63; H, 4.72; N, 2.98; Found: C, 53.28; H, 4.53; N, 2.68.
Bis(2-chloroethyl)[(2-hydroxy-6-methyl-4-oxo-3,4-dihydro-2H-chromen-
3-yl)(phenyl-amino)methyl]phosphonate (14). Brown crystals, yield 69%; mp
142−144◦C. IR (KBr), ν (cm−1): 3375 (OH), 3260 (NH), 3050 (C Harom), 2923,
1
(C Haliph), 1639 (C Opyrone), 1621 (C C), 1209 (P O), 1078 (P O C). H NMR
(DMSO-d6), δ: 2.38 (s, 3H, CH3), 3.09 (br, 1H, NH), 3.62–4.00 (m, 8H, CH2CH2), 4.5 (br,
1H, OH), 5.42 (br, 1H, CH P), 6.40 (br, 1H, H 3), 7.04−7.80 (m, 7H, Ph H, H 8 and
H−7), 7.96 (s, 1H, H 5), 8.18 (br, 1H, H 2). 31P NMR (DMSO-d6) δ: 20.37 ppm. Anal.
Calcd for C21H24Cl2NO6P (488.29): C, 51.65; H, 4.95; N, 2.87; Found: C, 51.31; H, 4.69;
N, 2.59.
Bis(2-chloroethyl)[(2-phenylamino-6-methyl-4-oxo-3,4-dihydro-2H-chro
men-3-yl)(phenylamino)methyl]phosphonate (15). Brown crystals, yield 56%;
mp 132−135◦C. IR (KBr), ν (cm−1): 3387 (NH), 3050 (C Harom), 2925, (C Haliph), 1640
1
(C Opyrone), 1619 (C C), 1205 (P O), 1071 (P O C). H NMR (DMSO-d6), δ: 2.29
(s, 3H, CH3), 3.07 (br, 1H, NH), 3.29 (br, 1H, NH), 3.62−4.22 (m, 8H, CH2CH2), 5.72
(d, 1H, J = 22.8 Hz, CH P), 6.13 (t, 1H, H-3), 6.84−8.20 (m, 14H, Ph H, H 8, H−7,
H−5 and H−2). 31P NMR (DMSO-d6) δ: 20.56 ppm. Anal. Calcd for C27H29Cl2N2O5P
(563.40): C, 57.56; H, 5.19; N, 4.97; Found: C, 57.23; H, 4.88; N, 4.69.
3-[2-(2-Chloroethoxy)-2-oxo-4-phenyl-1,4,2-oxazaphosphinan-3-yl]-6-m
ethyl-4H-chromen-4-one (17). A solution of 11, 14, and/or 15 (0.5 g) in absolute
ethanol (10 mL) containing a few drops of triethylamine was heated under reflux for 6 h.
The solids obtained after cooling were filtered off and crystallized from ethanol to give
brown crystals, in yields 62–64%; mp 282−285◦C. IR (KBr), ν (cm−1): 3030 (C Harom),
1
2925, (C Haliph), 1639 (C Opyrone), 1614 (C C), 1228 (P O), 1061 (P−O−C). H
NMR (DMSO-d6), δ: 2.41 (s, 3H, CH3), 3.24−3.28 (m, 4H, CH2CH2), 3.62−3.75 (m,
4H, CH2CH2), 5.04 (br, 1H, CH P), 7.03−7.81 (m, 8H, Ph H, H 8, H 7 and H 5),
8.76 (br, 1H, H−2). 31P NMR (DMSO-d6) δ: 13.72 ppm. Anal. Calcd for C21H21ClNO5P
(433.82): C, 58.14; H, 4.88; N, 3.23; Found: C, 57.82; H, 4.51; N, 2.89.
Reaction of Compounds 4 and/or 5 with Phenylphosphonic Dichloride:
Formation of 18 and 19: General Procedure
A mixture of 4 and/or 5 (0.005 mol) and phenylphosphonic dichloride (0.005 mol,
0.72 mL) in dry benzene (20 mL) containing a few drops of triethylamine was heated under
reflux for 4 h. The solids obtained were filtered off and crystallized from ethanol to give
the corresponding products 18 and 19, respectively.
2,3-Diphenyl-7-methyl-2-oxo-3,10a-dihydro-2H,5H-chromeno[3,2-e][1,3,
2]oxazaphosphinin-5-one (18). Yellow crystals, yield 57%; mp 166−167◦C. IR
(KBr), ν (cm−1): 3045 (C Harom), 2936, (C Haliph), 1641 (C Opyrone), 1620 (C C),
1
1204 (P O), 1033 (P O C). H NMR (DMSO-d6), δ: 2.50 (s, 3H, CH3), 7.01−7.95
(m, 13H, aromatic protons), 8.13−8.17 (m, 2H, C4 Hoxazaphosphinine and C2−Hchromone).
31P NMR (DMSO-d6) δ: 20.75 ppm. Anal. Calcd for C23H18NO4P (403.36): C, 68.49; H,
4.50; N, 3.47; Found: C, 68.09; H, 4.18; N, 3.12.
7-Methyl-2-oxo-1,2,3,-triphenyl-10a-tetrahydro-5H-chromeno[2,3-
d][1,3,2]diazaphosphinin-5-one (19). Yellow crystals, yield 67%; mp 169−170◦C.
IR (KBr), ν (cm−1): 3036 (C Harom), 2935, (C Haliph), 1650 (C Opyrone), 1605 (C C),

96
T. E. ALI
1207 (P O), 1032 (P O C). 1H NMR (DMSO-d6), δ: 2.51 (s, 3H, CH3), 7.28−7.60 (m,
18H, aromatic protons), 7.96 (br, 2H, C4−Hdiazaphosphinine and C2−Hchromone). 31P NMR
(DMSO-d6) δ: 20.05 ppm. Anal. Calcd for C29H23N2O3P (478.47): C, 72.80; H, 4.85; N,
5.85; Found: C, 72.41; H, 4.52; N, 5.55.
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