New phosphoramidates: Spectroscopic study and ab initio computations

Article abstract of DOI:10.1080/10426507.2010.532840

New phosphoramidates with formula P(O)(X)[NH-N = C(C₆H ₅)₂]₂, X = Cl (1), C₆H ₅C(O)NH (2), CCl₃C(O)NH (3), C₆H ₅C(O)NHP(O)[NHCH(CH₃)₂]

Full text of DOI:10.1080/10426507.2010.532840

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Phosphorus, Sulfur, and Silicon and the
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New Phosphoramidates: Spectroscopic
Study and Ab Initio Computations
Z. Shariatinia a , A. Sheykhpour b & M. Yousefi b
a Department of Chemistry , Amirkabir University of Technology ,
Tehran, Iran
b Department of Chemistry , Islamic Azad University, Shahre-Rey
Branch , Tehran, Iran
Published online: 11 Aug 2011.
To cite this article: Z. Shariatinia , A. Sheykhpour & M. Yousefi (2011) New Phosphoramidates:
Spectroscopic Study and Ab Initio Computations, Phosphorus, Sulfur, and Silicon and the Related
Elements, 186:8, 1768-1781, DOI: 10.1080/10426507.2010.532840
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Phosphorus, Sulfur, and Silicon, 186:1768–1781, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.532840
NEW PHOSPHORAMIDATES: SPECTROSCOPIC STUDY
AND AB INITIO COMPUTATIONS
Z. Shariatinia,1 A. Sheykhpour,2 and M. Yousefi2
1Department of Chemistry, Amirkabir University of Technology, Tehran, Iran
2Department of Chemistry, Islamic Azad University, Shahre-Rey Branch,
Tehran, Iran
GRAPHICAL ABSTRACT
Abstract New phosphoramidates with formula P(O)(X)[NH-N = C(C6H5)2]2, X = Cl (1),
C6H5C(O)NH (2), CCl3C(O)NH (3), C6H5C(O)NHP(O)[NHCH(CH3)2]2 (4), and P(O)(Cl)[2-
NH-C6H4-C(O)OC2H5]2 (5) were synthesized and characterized by 1H, 13C, 31P NMR, IR
1
spectroscopy, and elemental analysis. The H and 13C NMR spectra of 4 display two sets of
signals for the two unequivalent CH3 groups of the isopropyl substituents due to the presence of
prochiral CH units. Interestingly, the 13C NMR spectrum of 5 indicates long-range 4J(P,Cmeta) =
0.9 Hz. Such a coupling was not observed in previous studies for similar phosphoramidates.
The geometries of phosphoramidates 1–5 were optimized by Gaussian 98 software at HF and
B3LYP levels of theory with standard 6-31G∗ and 6-31+G∗∗ basis sets. The stabilization
energies were calculated from the equation ꢀE = E(molecule) – ꢁi E(i), i = atom. For all
compounds, the B3LYP/6-31G∗ basis set provided the highest negative stabilization energies.
2
The nuclear quadrupole coupling constants (χ) for 14N, H, and 35Cl nuclei were computed
to be 4–6 MHz, 180–190 KHz, and 50, 80 MHz, respectively. The χ values for the 17O atoms
of phosphoryl moieties (5.0 MHz) are almost half than those of C O bonds (10.0 MHz).
Moreover, the χ values of amidic N atoms are smaller than those of amino N atoms.
Keywords Ab initio computation; DFT; NMR; NQR; phosphoramidate
Received 4 July 2010; accepted 10 October 2010.
This investigation was supported by the Research Councils of Amirkabir University of Technology and
Islamic Azad University, Shahre-Rey Branch, which is gratefully acknowledged.
Address correspondence to Z. Shariatinia, Department of Chemistry, Amirkabir University of Technology,
P. O. Box: 159163-4311, Tehran, Iran. E-mail: shariati@aut.ac.ir
1768

NEW PHOSPHORAMIDATES: SPECTROSCOPIC STUDY
1769
INTRODUCTION
Nowadays, the phosphoramidate chemistry is of great interest due to the wide applica-
tion of phosphoramidates in various areas of science such as medicine,1–3 agriculture,4–6 co-
ordination chemistry,7–10 theoretical chemistry,11,12 and structural13–15 investigations. There
have been many efforts for the synthesis, characterization, and structural studies on these
compounds.16–18 Ab initio quantum chemical computations were conducted on phospho-
ramidates to predict their structural parameters and to compare the calculated results with
the experimental ones.19,20 Nuclear quadrupole coupling constants are very helpful to esti-
mate the structural properties.21,22 Previous studies have reported the χ values for the 14N,
2
17O, and H atoms to be 5.0, 10.0 MHz and 300.0 kHz, respectively.21,22 The χ values
for the 35Cl atoms were measured from 35–40 MHz23 to 50–70 MHz.24 In this article, we
report on new phosphoramidates with the formula P(O)(X)[NH-N = C(C6H5)2]2, X =
Cl (1), C6H5C(O)NH (2), CCl3C(O)NH (3), C6H5C(O)NHP(O)[NHCH(CH3)2]2 (4), and
P(O)(Cl)[2-NH-C6H4-C(O)OC2H5]2 (5), which were synthesized and characterized by 1H,
13C, 31P NMR, IR spectroscopy and elemental analysis. To further study the structural
properties of these compounds, their geometries were initially optimized with Hyperchem
7.0 software and then by the Gaussian 98 program25 at the HF and B3LYP levels of theory
using standard 6-31G∗ and 6-31+G∗∗ basis sets. The stabilization energies were computed
from the equation ꢀE = E(molecule) – ꢁi E(i), i = atom. Nuclear quadrupole coupling
constants (χ) were calculated for the quadrupole 14N, 2H, 17O, and 35Cl atoms. Finally, these
results were compared with previously reported data and found to be in good agreement
with them.
RESULTS AND DISCUSSION
Spectroscopic Study
In the present study, novel phosphoramidates 1–5 were synthesized from the reaction
of POCl3 and some phosphoramidic dichlorides with benzophenonehydrazone, isopropy-
lamine, and ethyl 2-aminobenzoate (Scheme 1). A summary of the NMR and IR parameters
1
of these compounds are given in Table 1. The 31P{ H} NMR spectrum of compound 1 shows
the 31P NMR signal at 3.78 ppm, which is shifted upfield in the spectra of compounds 2 and
3. This upfield shift shows stronger electron donation of benzoyl and acetyl substituents
relative to the Cl atom. A comparison of the analogous molecules 2 and 4 reveals that δ31P
is at higher field in compound 2, indicating stronger electron donation of benzophenone
hydrazone moiety as compared to isopropyl groups at the phosphorus atom. Also, com-
paring the analogous compounds 1 and 5, containing one Cl substituent, δ31P of 1 appears
at lower field, which indicates lower electron donation of benzophenone hydrazone group
with respect to the 2-ethylbenzoate moiety.
The 1H and 13C NMR spectra of compound 1 exhibit two sets of signals for the two
phenyl groups of the benzophenonehydrazone substituent, confirming that the two phenyl
1
moieties are not equivalent. Interestingly, the H and 13C NMR spectra of compound
4 display two sets of signals for the two diastereotopic CH3 groups of the isopropyl
3
substituents, due to the presence of prochiral CH units. Two JHH (6.5, 6.5 Hz) and two
3JPC (5.0, 7.0 Hz) coupling constants were observed. When comparing compound 1 with its
analogues 6 and 7 (Table 1), it can be noted that the isopropyl groups in these compounds
show similar effect. That is, there are two distinct signals for the two methyl moieties of an
isopropyl group, confirming that the CH3 groups are diastereotopic.

1770
Z. SHARIATINIA ET AL.
Scheme 1 Syntheses of phosphoramidates 1–5.
4
Long-range coupling constant J(P,Cmeta) = 0.9 Hz was observed in the 13C NMR
spectrum of 5 (Figure 1). Such a coupling has not been observed in our previous studies for
26 6
other similar phosphoramidates.16–20 7JPH
,
J
, and 4JHH27 coupling constants have been
PH
reported earlier, but there is no statement about the presence of 4JPC in phosphoramidates.
Moreover, two different values of 3JPC = 3.7, 8.7 Hz were observed for the coupling of the
ortho carbon atoms with the phosphorus atom in compound 5.
Table 1 Selected spectroscopic NMR and IR data of compounds 1–5
δ
31P 2J(PNH)amine 3J(P,C)aliphatic 3J(P,C)aromatic ν(P O) ν(C O)
No.
Compound∗
(ppm)
(Hz)
(Hz)
(Hz)
(cm−1
)
(cm−1
)
Ref.
∗∗
∗∗
∗∗
∗∗
∗∗
1
2
3
4
5
6
(Cl)P(O)R1
3.8
0.4
–1.1
7.3
–5.6
13.7
—
—
—
12.1
11.1
—
—
—
—
—
—
2.8
8.1
3.7, 8.7
4.8
1176
1197
1176
1207
1166
1227
—
2
(C6H5C(O)NH)P(O)R1
1658
1686
1650
1687
—
2
2
(CCl3C(O)NH)P(O)R1
2
(C6H5C(O)NH)P(O)R2
5.0, 7.0 (CH3)
—
5.9, 5.3 (CH3)
(Cl)P(O)R3
2
[(CH3)2N](p-CH3-C6H4-
O)P(O)R2
35
2
7
R2P(O)(NHC6H4C(O)
NH)P(O)R2
9.2
9.3
—
4.7, 5.4,
3.4, 2.1
7.0, 8.0
1225,
1169
1602
36
∗R1 = NH-N = C(C6H5)2, R2 = NH-CH(CH3)2, R3 = 2-NH-C6H4-C(O)OC2H5.
∗∗This work.

NEW PHOSPHORAMIDATES: SPECTROSCOPIC STUDY
1771
1
Figure 1 Selected region of the 13C{ H} NMR spectrum of 5 showing long-range 4J(P,Cmeta) = 0.9 Hz.
A comparison of the IR spectra of the two analogue compounds 2 and 3 (and also
of compounds 2 and 4) shows that as the δ31P shifts to upfield, the ν(P O) value de-
creases, a behavior which is just the opposite to that of ν(C O). The IR spectra re-
veal that ν(P O) has the greatest value in compound 4 while it has the smallest value
in compound 5. The frequency ν(C O) shows the opposite trend: it has the largest
value in compound 5 and the smallest value in compound 4. This phenomenon can
be attributed to the resonance interaction between P O and C O bonds (Scheme 2)
in compound 4, which causes weakening of the C O bond. This interaction is not present
in compound 5, and the C O bonds are free and strong. The tautomerism effect has
been extensively described in other similar phosphoramidates.28 For example, it was pro-
posed that the acidic cleavage of P-N or P-S bonds takes place via an amide-imidoyl
tautomerism.29
H
H
O
P
O
O
P
O
R
N
R
N
Scheme 2 Tautomerism involving the carbonyl and phosphoryl moiety.

1772
Z. SHARIATINIA ET AL.
Computational Details
The structures of compounds 1–5 were optimized with the Hyperchem 7.0 program
suite. Also, log P values were computed with Hyperchem in order to evaluate the lipophilic-
ity of these molecules. Ab initio quantum chemical calculations were performed to fully
optimize the geometry of the structures using the Gaussian 98 program25 at the HF and
B3LYP levels of theory and standard 6-31G∗, 6-31+G∗∗ basis sets. The optimizations
were followed by computations of the harmonic and vibrational frequencies, so that no
imaginary frequencies were obtained in these computations. Nuclear quadrupole coupling
constants (χ) were calculated from the equation χ = e2qzzQ/h,30 assuming that the electric
2
quadrupole moments (Q) of H, 17O, 35Cl, and 14N nuclei are 2.860, –25.58, –81.65, and
20.44 mb, respectively.31 The principal components of the EFG tensor, qii, are computed in
atomic units (1 au = 9.717365 × 1021 V m−2), with |qzz| ≥ |qyy| ≥ |qxx| and qxx + qyy + qzz =
0. These diagonal elements relate to each other by the asymmetry parameter: ηQ = |qyy
–
qxx|/|qzz|, 0 ≤ ηQ ≤ 1, which measures the EFG tensor deviation from axial symmetry.
The computed qzz component of the EFG tensor is used to obtain the nuclear quadrupole
coupling constants (χ).
Ab Initio Calculations
To further study the structural properties of phosphoramidates 1–5, their geometries
were optimized using Gaussian 98 software at the HF and B3LYP levels of theory with
standard 6-31G∗ and 6-31+G∗∗ basis sets (Scheme 3). Stabilization energies were calcu-
lated from the equation ꢀE = E(molecule) - ꢁi E(i), i = atom (Table 2). For all compounds,
the B3LYP/6-31G∗ basis set provides the highest negative stabilization energies. Among
compounds 1–5, molecule 2 has the greatest stabilization energy. The stabilization energy
decreases in the order 2 >> 3 >> 1 >> 4 > 5. Although molecules 4 and 5 do not have
similar structures, their ꢀE values are very close to each other. The results show that the ꢀE
values do not increase by increasing the level of the basis set from 6-31G∗ to 6-31+G∗∗.
Calculated dipole moments (µ, Debye) for compounds 1–5 are given in Table 3. The
data show higher values at the HF as compared to the B3LYP level of theory. Among these
compounds, 5 indicates the largest µ value at the HF/6-31G∗ level of theory. Compounds
2 and 3 with similar structures reveal nearly the same dipole moments. Structure-activity
relationship (SAR) investigations are based on the idea that physicochemical changes af-
fecting the biological activities have electronic, steric, and hydrophobic origins, while
other factors such as hydrogen bonding, polarizability, and dipole moment appear to be
Table 2 Calculated stabilization energies (kcal/mol) for compounds 1–5∗
Compound
E(HF/6-31G∗)
E(HF/6-31+G∗∗
)
E(B3LYP/6-31G∗)
E(B3LYP/6-31+G∗∗
)
1
2
3
4
5
–5759.808
–7306.097
–6489.488
–4579.041
–4269.931
–5754.394
–7299.737
–6482.225
–4584.786
–4265.272
–7620.470
–9658.732
–8616.063
–5797.174
–5774.118
–7588.150
–9619.991
–8580.914
–5795.914
–5759.036
∗ꢀE = E(molecule) – ꢁi E(i), i = atom.

NEW PHOSPHORAMIDATES: SPECTROSCOPIC STUDY
1773
O7
C
O1
P
H9
N2
O1
P
H8
N4
N5
H7
N4
H8
N2
N5
N6
N3
H10
Cl3
N6
2
1
O7
C
O1
P
O5
C
H11
N4
H13
H12
O1
CH3
H9
Cl10
N5
H6
N4
H7
N2
N2
N6
P
N3
CH3
Cl9
Cl8
N3
CH3
H10
H8
H3C
4
3
O1
P
H9
N4
H10
N2
Cl3
O7
O8
O5
O6
C2H5
5
C2H2
Scheme 3 Selected numbering of the atoms for the optimized structures of phosphoramidates 1–5.
less important.32 It has been indicated that lipophilicity is an important parameter for bio-
chemical, pharmacological, and environmental processes in quantitative structure-activity
relationship (QSAR) studies.33 Here, the lipophilicities of compounds 1–5 were computed
using Hyperchem software to predict their toxicities (Table 3). The log P values, which
correspond to log (1/IC50), reveal an order of toxicity 2 ≈ 3 > 1 ≈ 5 > 4. It can be seen
that the size of a molecule is the most important parameter (steric effect) affecting log P,
Table 3 Calculated dipole moments (µ, Debye) and log P for compounds 1–5
Compound
µ(HF/6-31G∗)
µ(HF/6-31+G∗∗
)
µ(B3LYP/6-31G∗)
µ(B3LYP/6-31+G∗∗
)
log P
1
2
3
4
5
7.036
5.714
5.572
3.768
7.577
6.960
5.722
5.392
3.948
7.489
6.503
4.835
4.758
3.582
6.692
6.560
5.372
4.737
3.856
6.639
9.14
11.71
11.67
6.38
9.16

1774
Z. SHARIATINIA ET AL.
i.e., with decreasing size of a molecule, log P decreases. Thus the analogous compounds
2 and 3 and also compounds 1 and 5 with nearly the same size indicate similar toxicities.
It is interesting that the lipophilicity of compound 2 is the greatest, while that of 4 is the
smallest, although they have similar structures (both of them have a benzoyl substituent).
Selected computed bond lengths, angles, and torsion angles are presented in Ta-
ble 4. These data are compared with those of previously reported similar compounds,
10–12,16–20,26,27,35,36 and are in good agreement with the published data. It becomes evident
that the B3LYP method yields a better agreement with the experimental values as compared
to the HF method. In compounds 2–4, the P-N(amide) bonds are longer than the P-N(amine)
bonds, because of the resonance interaction of the N(amide) with the C O π system. All
P-N bonds are shorter than the typical P-N single bond (1.77 Å),34 and the P O bond
lengths are larger than the normal P O bond length (1.45 Å).34
In molecules 1–5, the nitrogen environment is practically planar. In compound 1,
the angles P(1)-N(2)-N(5), P(1)-N(2)-H(8), and N(5)-N(2)-H(8) are 118.73◦, 118.48◦, and
119.13◦, respectively, with an average value of 118.78◦. The sum of angles around the
N(4) atom is 348.43◦, with an average of 116.14◦, indicating deviation from planarity. The
N(5) and N(6) atoms have a planar surroundings, with N-N-C angles equal to 119.97◦ and
120.17◦, respectively. Similar results were obtained for the nitrogen atoms of structures
2–5. This observation suggests the existence of partial multiple bond character between
phosphorus and nitrogen atoms, which has been confirmed by the crystallographic data of
similar compounds previously studied by us.10–12,16–20,26,27,35,36
The P O and C O bonds in compounds 2–4 have anti configuration relative to each
other with P O···C O pseudo-torsion angle of 54.63◦ (in 2), 98.55◦ (in 3) and 75.50◦ (in
4) at the B3LYP/6-31G∗ level of theory. In these molecules, the phosphorus atoms display
distorted tetrahedral configuration; for example, the angles around it vary from 97.75◦ to
121.39◦ in 1 at the HF/6-31G∗ level of theory. Similar results were observed for other
compounds and at other levels of theory.
Selected calculated nuclear quadrupole coupling constants (χ) for the quadrupole
2
14N, H, 17O, and 35Cl nuclei of compounds 1–5 are presented in Table 5. The B3LYP
method yields higher χ values than HF method. In molecules 1–3, the nitrogen atoms
connected to the phosphorus atom have smaller χ values than the N atoms of the N=C
groups. Also, in compounds 2–4, the smaller χ values for the amidic N atoms as compared
with those of the amino N nuclei are perhaps due to the electron withdrawing amidic moiety,
which leads to a shielding of the amidic N atom. In compounds 2–5, the oxygen atoms of
P O and C O units have χ values about 5.0 and 10.0 MHz, respectively. The reason for
the fact that the χ values of the oxygen atoms in phosphoryl moieties are almost half of
the corresponding values of the oxygen atoms in the carbonyl groups might be the more
positive carbonyl oxygen atoms, as well as resonance interactions. The χ values for 14N
and 2H were obtained to be 4–6 MHz and 180–190 KHz, respectively. The 35Cl nuclei in
compounds 1 and 5 show χ values of about 50 MHz, while the 35Cl atoms of compound 3
display χ ≈ 80 MHz.
To find which resonance structures of compounds 2 and 3 are in agreement with
above results, the two tautomeric structures A and B for each molecule were optimized at
the HF and B3LYP levels of theory using the 6-31G∗ basis set (Scheme 4). Results indicate
that the RC(OH) = N-P(O) form (2B, 3B) is the preferred form, as compared to RC(O)N =
P(OH) (2A, 3A). Although the stabilization energies of the two resonance forms A and B
are close to each other (Table 6), the χ values of 2A and 3A are very consistent with those
of compounds 2 and 3 (Table 7). The dipole moments of 2B and 3B are smaller than those

NEW PHOSPHORAMIDATES: SPECTROSCOPIC STUDY
1775
H8
H8
O1
O7
C
O7
C
O1
P
H9
N2
H9
N2
N5
P
N5
N4
N4
N3
N3
H10
H10
N6
N6
2B
2A
H11
O7
C
O1
P
H11
H12
N2
O7
O1
P
Cl10
N5
H12
N2
N4
Cl10
C
N5
N3
N4
H13
Cl9
H13
Cl8
N3
N6
Cl9
Cl8
N6
3B
3A
Scheme 4 Tautomeric structures 2A, 2B and 3A, 3B for compounds 2 and 3.
of 2A and 3A, respectively. The log P values show the order of 2A < 2B < 2 and also 3A
< 3B < 3, indicating that the lipophilicity of form B is closer to the main structure than
that of form A.
EXPERIMENTAL
1H, 13C, and 31P spectra were recorded with a Bruker Avance DRS 500 spectrometer.
1H and 13C chemical shifts are given relative to internal TMS, 31P chemical shifts relative
to 85% H3PO4 as external standard. Infrared (IR) spectra were recorded with a Shimadzu
model IR-60 spectrometer. Elemental analysis was performed using a Heraeus CHN-O-
RAPID apparatus. Melting points were obtained with an Electrothermal instrument.
N,Nꢁ-Bis(benzophenone hydrazinyl) Phosphoramidic Chloride (1)
To a solution of phosphorylchloride (1.54 g, 10 mmol) in dry acetonitrile, benzophe-
nonehydrazone (3.92 g, 20 mmol) and triethylamine (2.02 g, 20 mmol) were added dropwise
at 0◦C, and the mixture was stirred for 12 h. Then the white precipitate was filtered, washed
with distilled water, and dried. Yield: 59%; Anal. Calcd. For C26H22ClN4OP: C, 66.03; H,
1
4.96; N, 11.85%. Found: C, 66.00; H, 4.95; N, 11.86%. 31P{ H} NMR (CDCl3): δ = 3.8
(s). 1H NMR (CDCl3): δ = 7.26–7.51 (m, 11H, arom-H). 13C NMR (CDCl3): δ = 127.9,

1776
Z. SHARIATINIA ET AL.
Table 4 Selected calculated bond lengths (Å), angles (◦), and torsion angles (◦) for compounds 1–5
Compound
HF/6-31G∗
HF/6-31+G∗∗
B3LYP/6-31G∗
B3LYP/6-31+G∗∗
1
P
O
1.446
1.647
2.042
1.447
1.646
2.045
1.476
1.672
2.089
1.477
1.673
2.089
P-N
P-Cl
N-N
1.364
1.363
1.367
1.368
C
O
O
P-N-N
O
N
P-N
P-Cl
1.260
1.261
1.292
1.292
121.39
111.03
118.72
–40.948
–171.41
116.19
110.93
118.62
–40.046
–170.80
116.31
111.67
119.04
–37.684
–170.48
116.11
111.62
119.16
–37.869
–170.72
P-N-N
P-N-N
C
2
P
O
1.457
1.672
1.665
1.460
1.671
1.662
1.484
1.693
1.692
1.488
1.691
1.686
P-Namide
P-Namine
N-N
1.358
1.359
1.361
1.364
C
C
O
O
P-N-N
O
N
O
1.261
1.195
1.262
1.197
1.293
1.221
1.294
1.224
P-Namide
P-Namine
120.52
108.45
121.46
–178.65
–175.99
120.19
108.27
121.35
–178.59
–174.52
121.51
108.45
120.77
–178.89
179.18
121.63
107.70
121.30
–179.90
–176.12
P-N-N
P-N-N
C
3
4
5
P
O
1.453
1.707
1.669
1.369
1.261
1.455
1.705
1.664
1.367
1.261
1.481
1.734
1.681
1.376
1.293
1.484
1.734
1.681
1.373
1.293
P-Namide
P-Namine
N-N
C
O
O
P-N-N
O
P-N-N
N
P-Namide
P-Namine
115.80
110.40
119.94
166.64
–152.86
115.53
110.05
120.00
175.29
–157.60
115.86
110.54
119.86
179.07
–154.52
115.61
109.72
120.74
177.67
–162.07
P-N-N
C
P
O
1.462
1.703
1.657
1.198
1.382
114.69
118.38
135.83
73.98
1.463
1.701
1.653
1.200
1.382
114.66
117.80
135.98
70.360
41.416
1.492
1.731
1.681
1.225
1.397
114.52
120.02
135.88
77.650
44.524
1.493
1.730
1.677
1.228
1.397
114.69
119.26
136.21
70.684
40.982
P-Namide
P-Namine
C
C-Namide
O
O
P-Namide-C
O
O
O
P-Namide
P-Namine
P-Namide-C
P-Namine-C
43.76
P
P-N
O
1.451
1.653
1.452
1.651
1.480
1.675
1.482
1.674
P-Cl
2.027
2.030
2.073
2.072
C
C
O
O
P-N-C
O
O
O
P-N
P-Cl
1.201
1.318
1.202
1.317
1.230
1.345
1.232
1.345
117.94
113.29
133.47
179.85
–49.710
117.81
113.02
133.45
–178.61
–48.198
117.89
114.41
132.85
178.38
–51.199
118.00
114.06
132.99
179.09
–50.593
P-N-C
N-P-N-C

NEW PHOSPHORAMIDATES: SPECTROSCOPIC STUDY
1777
Table 5 Calculated nuclear quadrupole coupling constants (χ) for 2H (KHz) and 17O, 14N, 35Cl (MHz) atoms of
compounds 1–5
Compound
HF/6-31G∗
HF/6-31+G∗∗
B3LYP/6-31G∗
B3LYP/6-31+G∗∗
1
O1
N2
Cl3
N4
N5
N6
H7
H8
4.9178
5.5122
49.092
5.4919
5.9770
5.8462
278.9
4.9169
5.5033
49.740
5.4757
5.9705
5.8298
282.7
5.2541
4.9086
50.5535
4.9465
5.1154
5.0117
236.2
5.3367
4.8960
51.511
4.9411
5.1043
5.0099
239.9
274.8
278.9
234.3
238.2
2
O1
N2
N3
N4
N5
N6
O7
H8
H9
H10
5.0526
5.6141
5.6226
4.2568
5.9437
5.9031
10.530
280.0
5.0990
5.5969
5.6680
4.2447
5.9102
5.8751
10.420
282.8
5.3759
5.0498
5.1206
3.8157
5.0614
4.9424
9.7292
235.6
5.4908
5.0027
5.1083
3.8055
5.0346
4.9244
9.6459
236.1
281.3
279.7
285.1
284.4
240.0
239.2
243.1
242.6
3
O1
N2
N3
N4
N5
N6
O7
Cl8
Cl9
Cl10
H11
H12
H13
4.7398
5.4930
5.5159
4.4101
5.8154
5.7730
10.024
83.951
80.576
79.530
284.1
4.7745
5.4751
5.4994
4.3721
5.8192
5.7907
10.045
84.004
80.761
79.576
288.0
5.0127
4.9407
4.9183
3.8846
4.9678
4.9535
8.9863
81.780
79.176
77.065
246.7
5.1280
4.9493
4.8989
3.8031
4.9887
4.9928
9.0141
81.898
79.573
77.080
249.0
277.1
268.8
281.4
271.9
235.8
224.8
240.6
227.1
4
O1
N2
N3
N4
O5
H6
H7
H8
H9
H10
4.8597
5.0674
5.2362
4.2818
10.408
285.5
289.9
294.9
201.3
202.8
4.9202
5.0511
5.2072
4.2122
10.336
288.3
297.3
300.2
200.5
202.2
5.1356
4.7272
5.0690
3.9783
9.5765
249.3
249.0
257.8
181.1
183.2
5.2366
4.7410
5.0210
3.8751
9.4903
251.5
257.8
263.1
181.4
183.9
5
O1
N2
Cl3
N4
O5
O6
O7
O8
H9
H10
5.0775
4.2856
51.1882
4.6857
9.4310
10.119
9.4300
10.133
251.8
5.1108
4.2604
52.090
4.6280
9.4262
10.022
9.475
10.028
254.0
263.4
5.3788
3.8184
51.9943
4.1799
8.5390
9.2551
8.50381
9.2655
204.1
5.4407
3.7737
53.086
4.1005
8.5350
9.1844
8.5710
9.1800
205.8
261.4
212.5
212.1

1778
Z. SHARIATINIA ET AL.
Table 6 Calculated stabilization energies, dipole moments, and log P values for compounds 2A, 2B, 3A, and 3B
E
µ
Compound
HF/6-31G∗
B3LYP/6-31G∗
HF/6-31G∗
B3LYP/6-31G∗
log P
2A
2B
3A
3B
–7293.777
–7291.702
–6479.449
–6468.789
–9650.645
–9645.995
–8604.162
–8597.365
5.8360
2.4895
7.620
5.8473
2.7128
6.709
9.99
10.34
9.94
4.534
4.036
10.29
128.0, 128.6, 128.7, 129.3, 129.6, 135.6, 138.2, 158.9. IR (KBr, cm−1): 3421 (NH), 3098
(CH), 3023 (CH), 1176 (P O).
N-Benzoyl-Nꢁ,Nꢁꢁ-bis(benzophenone hydrazinyl) Phosphoric
Triamide (2)
To a solution of N-benzoyl phosphoramidic dichloride37 (2.38 g, 10 mmol) in
dry acetonitrile, benzophenonehydrazone (3.92 g, 20 mmol) and triethylamine (2.02 g,
20 mmol) were added dropwise at 0◦C, and the mixture was stirred for 10 h. Then the white
precipitate was filtered, washed with distilled water, and dried. Yield: 66%; Mp 158◦C.
Table 7 Calculated nuclear quadrupole coupling constants (χ) for 2H (KHz) and 17O, 14N, 35Cl (MHz) atoms of
compounds 2A, 2B, 3A, and 3B
Compound
HF/6-31G∗
B3LYP/6-31G∗
Compound
HF/6-31G∗
B3LYP/6-31G∗
2A
2B
O1
N2
N3
N4
N5
N6
O7
H8
7.6854
5.5484
5.5083
3.4494
5.8710
6.0502
8.8216
270.4
6.4642
5.0602
4.9340
3.0889
5.0952
5.0116
7.1600
276.0
O1
N2
N3
N4
N5
N6
O7
H8
5.1208
5.5791
5.6864
3.5012
6.1970
6.0981
9.7340
328.9
5.4109
4.9702
4.9220
3.2139
5.2405
5.1347
8.8892
270.3
H9
274.7
236.3
H9
280.2
237.0
H10
3A
275.5
238.4
H10
3B
279.3
238.7
O1
N2
N3
N4
N5
N6
O7
Cl8
Cl9
Cl10
H11
H12
H13
9.0279
5.7301
5.3410
3.6621
5.7756
5.7764
9.7405
80.444
78.688
79.519
337.6
8.4819
5.2347
4.6924
3.3551
4.9479
4.9684
8.8214
79.356
77.235
78.108
284.2
O1
N2
N3
N4
N5
N6
O7
Cl8
Cl9
Cl10
H11
H12
H13
4.8785
5.7086
5.5176
4.2957
5.9941
5.8896
10.082
79.515
79.096
85.609
333.6
5.1193
5.1280
4.8626
3.7473
5.0896
5.0425
9.1661
77.968
77.127
83.561
274.7
280.0
261.8
239.8
212.3
280.9
275.6
239.2
233.6

NEW PHOSPHORAMIDATES: SPECTROSCOPIC STUDY
1779
Anal. Calcd. For C33H28N5O2P: C, 71.08; H, 5.06; N, 12.56%. Found: C, 71.06; H, 5.05;
1
1
N, 12.55%. 31P{ H} NMR (CDCl3): δ = 0.4 (s). H NMR (CDCl3): δ = 7.25–7.57 (m,
28H, arom-H). 13C NMR (CDCl3): δ = 127.3, 127.9, 128.0, 128.1, 128.6, 128.7, 128.8,
129.3, 129.6, 158.9 (C O). IR (KBr, cm−1): 3368 (NH), 3169 (CH), 3056 (CH), 1658
(C O), 1197 (P O).
N-Trichloroacetyl-Nꢁ,Nꢁꢁ-bis(benzophenone hydrazinyl) Phosphoric
Triamide (3)
To a solution of N-trichloroacetyl phosphoramidic dichloride38 (2.80 g, 10 mmol)
in dry acetonitrile, benzophenonehydrazone (3.92 g, 20 mmol) and triethylamine (2.02 g,
20 mmol) were added dropwise at 0◦C, and the mixture was stirred for 13 h. Then the white
precipitate was filtered, washed with distilled water, and dried. Yield: 56%; Anal. Calcd.
For C28H23Cl3N5O2P: C, 56.16; H, 3.87; N, 11.69%. Found: C, 56.15; H, 3.86; N, 11.68%.
1
31P{ H} NMR (d6-DMSO): δ = –1.1 (s). 1H NMR (d6-DMSO): δ = 7.27 (d, 3JHH = 7.0
Hz, 4H, arom-H), 7.33–7.46 (m, 19H, arom-H). 13C NMR (d6-DMSO): δ = 91.3 (CCl3),
128.0 (d, 3JPC = 2.8 Hz), 128.2, 128.7, 135.1, 137.4, 168.8 (C O). IR (KBr, cm−1): 3241
(CH), 3022 (CH), 1686 (C O), 1176 (P O).
N-Benzoyl-Nꢁ,Nꢁꢁ-diisopropyl Phosphoric Triamide (4)
To a solution of N-benzoyl phosphoramidic dichloride37 (2.38 g, 10 mmol) in dry
acetonitrile, isopropylamine (1.18 g, 20 mmol) and triethylamine (2.02 g, 20 mmol) were
added dropwise at 0◦C, and the mixture was stirred for 15 h. Then the white precipitate
was filtered, washed with distilled water, and dried. Yield: 73%; Mp 164◦C. Anal. Calcd.
For C13H20N3O2P: C, 55.51; H, 7.17; N, 14.94%. Found: C, 55.50; H, 7.18; N, 14.93%.
1
31P{ H} NMR (CDCl3): δ = 7.3 (s). 1H NMR (CDCl3): δ = 1.12 (d, 3JHH = 6.5 Hz, 6H,
3
3
CH3), 1.19 (d, JHH = 6.5 Hz, 6H, CH3), 3.07 (dd, JHH = 8.9 Hz, 2JPH = 12.1 Hz, 2H,
3
3
NHamine), 3.54 (m, 2H, CH), 7.44 (t, JHH = 7.7 Hz, 2H, arom-H), 7.64 (t, JHH = 7.7
Hz, 1H, arom-H), 8.04 (d, 3JHH = 7.7 Hz, 2H, arom-H), 9.04 (br, 1H, NHamide). 13C NMR
3
3
(CDCl3): δ = 25.3 (d, JPC = 5.0 Hz, CH3), 25.7 (d, JPC = 7.0 Hz, CH3), 43.4 (CH),
128.0, 128.6, 132.4, 133.4 (d, 3JPC = 8.1 Hz, Cipso), 169.1 (s, C O). IR (KBr, cm−1): 3261
(CH), 2957 (CH), 1650 (C O), 1207 (P O).
N,Nꢁ-Bis(ethyl 2-benzoate) Phosphoramidic Chloride (5)
To a solution of phosphorylchloride (1.54 g, 10 mmol) in dry acetonitrile, ethyl 2-
aminobenzoate (3.30 g, 20 mmol) and triethylamine (2.02 g, 20 mmol) were added dropwise
at 0◦C, and the mixture was stirred for 15 h. Then the white precipitate was filtered, washed
with distilled water, and dried. Yield: 51%; Mp 128◦C. Anal. Calcd. For C18H20ClN2O5P:
1
C, 52.63; H, 4.91; N, 6.82%. Found: C, 52.61; H, 4.90; N, 6.81%. 31P{ H} NMR (CDCl3):
δ = –5.6 (s). 1H NMR (CDCl3): δ = 1.36 (t, 3JHH = 7.2 Hz, 6H, CH3), 4.31 (q, 3JHH = 7.2
Hz, 4H, CH2), 6.93 (t, 3JHH = 8.3 Hz, 2H, arom-H), 7.42 (t, 3JHH = 8.3 Hz, 2H, arom-H),
7.80 (t, 3JHH = 8.3 Hz, 2H, arom-H), 7.99 (d, 3JHH = 8.3 Hz, 2H, arom-H), 9.63 (d, 2JPH
=
11.1 Hz, 1H, NH). 13C NMR (CDCl3): δ = 14.2 (CH3), 61.1 (CH2), 114.7 (d, 3JPC = 8.7
Hz), 118.6 (d, 3JPC = 3.7 Hz), 120.4, 131.2, 134.5, 144.2 (d, 4JPC = 0.9 Hz), 168.3 (C O).
IR (KBr, cm−1): 3224 (CH), 2980 (CH), 1687 (C O), 1166 (P O).

1780
Z. SHARIATINIA ET AL.
REFERENCES
1. Li, Z.; Han, J.; Jiang, Y.; Browne, P.; Knox, R. J.; Hu, L. Bioorg. Med. Chem. 2003, 11,
4171–4178.
2. Borch, R. F.; Liu, J.; Joswig, C.; Baggs, R. B.; Dexter, D. L.; Mangold, G. L. J. Med. Chem.
2001, 44, 74–77.
3. Baldwin, A.; Huang, Z.; Jounaidi, Y.; Waxman, D. J. Arch. Biochem. Biophys. 2003, 409,
197–206.
4. Zou, X. J.; Jin, G. Y.; Zhang, Z. X. J. Agricult. Food Chem. 2002, 50, 1451–1454.
5. Berlicki L.; Kafarski, P. Pestic. Biochem. Phys. 2002, 73, 94–103.
6. Pardio, V. T.; Ibarra, N.; Rodriguez, M. A. J. Agricult. Food Chem. 2001, 49, 6057–6062.
7. Denmark, S. E.; Fu, J. J. Am. Chem. Soc. 2003, 125, 2208–2216.
8. Gubina, K. E.; Shatrava, J. A.; Amirkhanov, V. A.; Ovchynnikov, V. A.; Amirkhanov, V. M.
Polyhedron 2000, 19, 2203–2209.
9. Silvestru, C.; Ro¨sler, R.; Silvestru, A.; Drake, J. E. J. Organomet. Chem. 2002, 642, 71–79.
10. Gholivand, K.; Shariatinia, Z. J. Organomet. Chem. 2006, 691, 4215–4224.
11. Gholivand, K.; Vedova, C. O. D.; Anaraki Firooz, A.; Madani Alizadegan, A.; Michelini, M. C.;
Pis Diez, R. J. Mol. Struct. 2005, 750, 64–71.
12. Gholivand, K.; Farshadian, S.; Erben, M. F.; Ve´dova, C. O. D. J. Mol. Struct. 2010, 978, 67–73.
13. Necas, M.; Foreman, M. R. St. J.; Dastych, D.; Novosad, J. Inorg. Chem. Commun. 2001, 4,
36–40.
14. Gubina, K. E.; Amirkhanov, V. M. Z. Naturforsch. 2000, 55b, 1015–1019.
15. Gubina, K. E.; Ovchynnikov, V. A.; Amirkhanov, V. M.; Silva, T. Y.; Skopenko, V. V.; Glowiak,
T.; Kozlowski, H. Z. Naturforsch. 1999, 54b, 1357–1359.
16. Gholivand, K.; Pourayoubi, M.; Shariatinia, Z. Polyhedron 2007, 26, 837–844.
17. Gholivand, K.; Shariatinia, Z.; Pourayoubi, M. Z. Anorg. Allg. Chem. 2006, 632, 160–166.
18. Gholivand, K.; Shariatinia, Z.; Pourayoubi, M. Polyhedron 2006, 25, 711–721.
19. Gholivand, K.; Vedova, C. O. D.; Mahzouni, H. R.; Shariatinia, Z.; Amiri, S. J. Mol. Struct.
2008, 874, 178–186.
20. Gholivand, K.; Shariatinia, Z.; Pourayoubi, M. Z. Naturforsch. 2005, 60b, 67–74.
21. Esrafili, M. D.; Behzadi, H.; Hadipour, N. L. Chem. Phys. 2008, 348, 175–180.
22. Esrafili, M. D.; Behzadi, H.; Hadipour, N. L. Biophys. Chem. 2008, 133, 11–18.
23. Palmer M. H.; Nelson, A. D. J. Mol. Struct. 2007, 828, 91–101.
24. Wulfsberg, G.; Kravchenko, E.; Morgunov, V. G.; Miller, S.; Anderson, O.; Barnes, T.; Briggs,
R.; MacDougall, P. Inorg. Chim. Acta 2008, 361, 2471–2482.
25. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.;
Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E. J. Jr; Burant, C.; Dapprich, S.; Millam,
J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.;
Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.;
Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman,
J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz,
P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng,
C. Y.; Nanayakkara, A.; Challacombe, M. P.; Gill, M. W.; Johnson, B.; Chen, W.; Wong, M.
W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98,
Revision A9; Gaussian, Inc: Pittsburgh, PA, 1998.
26. Gholivand, K.; Ghadimi, S.; Naderimanesh, H.; Forouzanfar, A. Magn. Reson. Chem. 2001, 39,
684–688.
27. Gholivand, K.; Oroujzadeh, N. Main Group Chem. 2008, 7, 251–269.
28. Amirkhanov, V. M.; Ovchinnikov, V. A.; Trush, V. A.; Skopenko, V. V. Zh. Org. Khim. 1996, 32,
356–360.
29. Zabirov, N. G.; Shamsevaleev, F. M.; Cherkasov, R. A. Russ. Chem. Rev. 1991, 60, 1128–1144.
30. Bersohn, R. J. Chem. Phys. 1952, 20, 1505–1509.

NEW PHOSPHORAMIDATES: SPECTROSCOPIC STUDY
31. Pyyko¨, P. Mol. Phys. 2001, 99, 1617–1629.
1781
32. Hansch C.; Leo, A. Exploring QSAR; ACS Professional References Book: Washington, DC,
1995, pp. 1–161.
33. Renxiao, W.; Ying, F.; Luhua, L. J. Chem. Inf. Comput. Sci. 1997, 37, 615–621.
34. Corbridge, D. E. C. Phosphorus, an Outline of Its Chemistry, Biochemistry and Technology, 5th
ed.; Elsevier: Amsterdam, 1995, pp. 55, 57.
35. Ghadimi, S.; Pourayoubi, M.; Ebrahimi Valmoozi, A. A. Z. Naturforsch. 2009, 64b, 565–569.
36. Gholivand, K.; Shariatinia, Z.; Mashhadi, S. M.; Daeepour, F.; Farshidnasab, N.; Mahzouni, H.
R.; Taheri, N.; Amiri, S.; Ansar, S. Polyhedron 2009, 28, 307–321.
37. Gubina, K. E.; Ovchynnikov, V. A.; Swiatek-Kozlowska, J.; Amirkhanov, V. M.; Sliva, T. Y.;
Domasevitch, K. V. Polyhedron. 2002, 21, 963–967.
38. Cates, L. A.; Lemke, T. L. J. Pharm. Sci. 1974, 63, 1736–1739.