Synthesis and spectroscopic characterization of mixed diamidophosphoric acid esters: X-Ray crystal structure of [(CH3)2N]-[p- H3C-C6H4-O]P(O)X (X = NHC(CH3) 3 and p-H3

Article abstract of DOI:10.1515/znb-2009-0513

Mixed diamidophosphoric acid esters [(CH₃)₂N][p- H₃C-C₆H₄-O]P(O)X, where X = NH(CH₃) (1), NHCH(CH₃)₂ (2), NHC(CH₃)₃ (3) and p-H₃C-C

Full text of DOI:10.1515/znb-2009-0513

Synthesis and Spectroscopic Characterization of Mixed Diamido-
phosphoric Acid Esters: X-Ray Crystal Structure of [(CH3)2N]-
[p-H3C-C6H4-O]P(O)X (X = NHC(CH3)3 and p-H3C-C6H4-NH)
Saied Ghadimia, Mehrdad Pourayoubib, and Ali Asghar Ebrahimi Valmoozia
a Department of Chemistry, Imam Hossein University, Tehran, Iran
b Department of Chemistry, Ferdowsi University of Mashhad, Mashhad, Iran
Reprint requests to Dr. Saied Ghadimi. E-mail: ghadimi saied@yahoo.com
Z. Naturforsch. 2009, 64b, 565 – 569; received December 10, 2008
Mixed diamidophosphoric acid esters [(CH3)2N][p-H3C-C6H4-O]P(O)X, where X = NH(CH3)
(1), NHCH(CH3)2 (2), NHC(CH3)3 (3) and p-H3C-C6H4-NH (4) were synthesized and characterized
1
by 31P, 31P{ H}, 13C, 1H NMR, and IR spectroscopy and mass spectrometry, and single crystal X-ray
diffraction analysis for the compounds 3 and 4. Compound 3 crystallizes in the monoclinic, space
◦
˚
group P21/c with unit cell parameters a = 9.006(3), b = 16.286(5), c = 10.319(3) A, β = 99.633(6) ,
3
˚
V = 1492.2(8) A , Z = 4. The final R value is 0.0622 for 2074 reflections [I ≥ 2σ(I)]. Compound
4 crystallizes in the orthorhombic, space group Pna21 with unit cell parameters a = 7.0459(14), b =
3
˚
˚
20.934(4), c = 10.436(2) A, V = 1539.3(5) A , Z = 4. The final R value is 0.0530 for 3025 reflections
[I ≥ 2σ(I)].
Key words: Mixed Diamidophosphoric Acid Ester, Spectroscopic Characterization, X-Ray Crystal
Structure
Introduction
Results and Discussion
General preparation of compounds 1 – 4
The extensive studies on the biochemical prop-
erties of phosphoramidate derivatives revealed vari-
ous possibilities for their application in agrochemistry
and medicine as insecticides, pesticides, and drugs
[1 – 3]. Gerhard Schrader discovered the insecticide
properties of amidophosphoric acid esters [4], which
exert their toxicity by the inhibition of the acetyl-
cholinesterase (AChE), the enzyme responsible for the
degradation of the cholinergic neurotransmitter acetyl-
choline [5].
Compounds 1 – 4 were synthesized from the reac-
tion of N,N-dimethylamido(chloro)phosphoric acid 4-
methyl-phenyl ester and the corresponding amine (or
the hydrochloride salt of the amine for compound 1)
in the presence of triethylamine as an HCl scavenger
(for compounds 1 and 4) or an excess of amine (for
compounds 2 and 3, Eq. 1).
(CH3)2N[p−CH3−C6H4−O]P(O)Cl+2RNH2
→ (CH3)2N[p−CH3−C6H4−O]P(O)NHR
(1)
To the best of our knowledge, little attention
has been given to the crystal structure and spectro-
scopic properties of these compounds [6 – 8]. Herein,
mixed diamidophosphoric acid esters of the formula
[(CH3)2N][p-H3C-C6H4-O]P(O)X, where X = NH-
(CH3) (1), NHCH(CH3)2 (2), NHC(CH3)3 (3) and
p-H3C-C6H4-NH (4) were synthesized and charac-
+RNH3Cl, R=CH(CH3)2 (2) or C(CH3)3 (3)
NMR study
The 31P chemical shifts (δ31P) in the NMR spec-
tra of the title compounds varied from 6.94 (for com-
pound 4) to 15.99 ppm (for compound 1). Compari-
son of δ31P values in compounds 1 – 3 demonstrates
the electron donating effect of the amine groups in the
sequence NH-C(CH3)3 > NH-CH(CH3)2 > NHCH3,
which causes a decrease of the phosphorus chemical
1
terized by 31P, 31P{ H}, 13C, 1H NMR, and IR
spectroscopy and mass spectrometry, and the crys-
tal structures of compounds 3 and 4 were deter-
mined by single crystal X-ray diffraction analy-
sis.
c
0932–0776 / 09 / 0500–0565 $ 06.00 ꢀ 2009 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
- 10.1515/znb-2009-0513
Downloaded from De Gruyter Online at 09/12/2016 01:58:54AM
via free access

566
S. Ghadimi et al. · Mixed Diamidophosphoric Acid Esters
Table 1. Fragment relative intensities in the mass spectra of compounds 1 – 4 and reference molecules [(CH3)2N]P(O)X[O-
C6H4-p-CH3]).
X
M+
[C2H6N]+
[C7H7O]+
[C7H7]+
[M–C7H7O]+
[M–C7H7]+
[M–X]+
Ref.
a
Cl35
CN
OCH3
(C2H5)2N
(C4H8)NO
NH(CH3) (1)
NH(iso-C3H7) (2)
NH(tert-C4H9) (3)
p-H3C-C6H4-NH (4)
100
71
64
10
25
14
3
53
100
100
100
100
100
53
91
35
67
89
87
29
78
10
4
15
12
25
–
62
48
69
28
48
5
79
4
33
4
2
71
2
8
88
3
16
3
16
8
10
–
–
b
[6]
[6]
[6]
c
54
b
c
c
100
100
41
1
2
33
100
–
7
42
12
18
a Synthesis and spectroscopic characterization of [(CH3)2N]P(O)Cl[O-C6H4-p-CH3] have been reported in ref. [9] and the modified strategy
for the synthesis and the X-ray crystallography data in ref. [10]; the intensities reported in Table 1 were determined by the authors; b MS data
of [(CH3)2N]P(O)CN[O-C6H4-p-CH3] and [(CH3)2N]P(O)[NH(iso-C3H7)][O-C6H4-p-CH3] have not been published elsewhere; X-ray data
c
were reported in refs. [11] and [12], respectively; this work.
shift. In the 1H NMR spectra of compounds 1 – 4 dou-
Table 2. Crystallography data for compounds 3 and 4.
3
blet peaks with J(P,H) in the range of 10.0 Hz (for
3
4
compound 3) to 10.2 Hz (for compounds 1 and 4) ap-
pear for the N(CH3)2 moieties. Two-bond P–C cou-
pling constants for the carbon atoms of the N(CH3)2
Formula
Mr
Temperature (K)
C13H23N2O2P C16H21N2O2P
270.30
100(2)
304.32
100(2)
˚
Wavelength (A)
0.71073
monoclinic
P21/c
9.006(3)
16.286(5)
10.319(3)
99.633(6)
1492.2(8)
4
0.71073
orthorhombic
Pna21
7.0459(14)
20.934(4)
10.436(2)
90
2
moiety with J(P,C) are in the range of 3.2 Hz (for
Crystal system
Space group
compound 3) to 4.4 Hz (for compound 1). The data
of the NMR spectra show 3J(P,H) (1) > 3J(P,H) (2) >
˚
a, A
˚
2
2
2
3J(P,H) (3) and J(P,C) (1) > J(P,C) (2) > J(P,C)
(3). The CH3 groups in the NH(iso-C3H7) moiety of
compound 2 are diastereotopic and show two doublet
b, A
˚
c, A
β, deg
3
˚
V, A
1539.3(5)
4
1
3
peaks in the H NMR spectrum (with J(H,H) = 6.5
and 6.4 Hz). Moreover, two doublet peaks appear for
the CH3 carbon atoms with 3J(P,C) = 5.9 and 5.3 Hz.
Z
Dcalcd, g cm−3
Absorption
coefficient, mm−1
F(000), e
1.203
0.182
1.313
0.185
584
648
Cryst. size, mm3
0.35×0.20×0.15 0.25×0.15×0.08
Mass spectrometry investigation
θ range for data collection, deg 2.29 – 27.00
Limiting indices
1.95 – 28.00
Mass spectra of the compounds indicate the pres-
ence of the fragments [N(CH3)2]+, [C7H7O]+, and
P(O)[N(CH3)2]X+, where X = NH(CH3) (1), NH(iso-
C3H7) (2), NH(tert-C4H9) (3) and p-H3C-C6H4-NH
(4) (Table 1). Moreover, the fragment P(O)[N(CH3)2]-
−10 ≤ h ≤ 11, −8 ≤ h ≤ 9,
−20 ≤ k ≤ 20, −24 ≤ k ≤ 27,
−13 ≤ l ≤ 13
9737 / 3137
0.0965
−13 ≤ l ≤ 13
9993 / 3654
0.0528
Refl. collected / unique
Rint
Completeness to θ (%)
96.4
98.6
[O-C6H4-p-CH3]+ is observed in the mass spectra of Observed refls [I ≥ 2σ(I)]
2074
none
3025
Absorption correction
semi-empirical
from equivalents
0.9854 / 0.9552
3654 / 1 / 194
1.005
compounds 3 and 4.
Max. / min. transmission
–
X-Ray crystallography
Data / restraints / parameters
3137 / 0 / 169
0.995
GoF (F2)
The crystal structure of compound 2 was reported in
reference [12]. Single crystals of compounds 3 and 4
were obtained from CHCl3/CH3CN at r. t. The crystal-
lographic data and the details of the X-ray analysis are
presented in Table 2, selected bond lengths and angles
for compounds 3 and 4 are given in Table 3. Hydro-
gen bonding data are listed in Table 4. The molecu-
lar structures of 3 and 4 are shown in Figs. 1 and 2,
respectively. The phosphorus atoms have a distorted
Final R1/wR2 [I ≥ 2σ(I)]
Final R1/wR2 (all data)
Largest diff. peak/hole, e A
0.0622 / 0.1043 0.0530 / 0.1032
0.1068 / 0.1192 0.0695 / 0.1099
0.368 / −0.339 0.655 / −0.410
−3
˚
tetrahedral configuration. The bond angles around the
phosphorus atom are in the range of 102.76(14)◦
[∠O(2)–P(1)–N(2)] to 114.77(14)◦ [∠O(1)–P(1)–
N(2)] in compound 2, 102.32(11)◦ [∠O(1)–P(1)–N(2)]
to 115.58(12)◦ [∠O(2)–P(1)–N(2)] in compound 3
- 10.1515/znb-2009-0513
Downloaded from De Gruyter Online at 09/12/2016 01:58:54AM
via free access

S. Ghadimi et al. · Mixed Diamidophosphoric Acid Esters
567
˚
Table 3. Selected bond lengths (A) and bond angles (deg) for
compounds 3 and 4.
3
4
P(1)–O(2)
P(1)–O(1)
P(1)–N(2)
P(1)–N(1)
O(1)–C(1)
N(1)–C(9)
N(1)–C(8)
N(2)–C(10)
C(1)–C(6)
1.462(2)
1.608(2)
1.631(2)
1.641(2)
1.409(3)
1.452(4)
1.458(4)
1.486(3)
1.373(4)
P(1)–O(2)
P(1)–O(1)
P(1)–N(2)
P(1)–N(1)
O(1)–C(8)
N(1)–C(1)
N(2)–C(16)
N(2)–C(15)
C(1)–C(6)
1.474(2)
1.604(2)
1.633(3)
1.648(3)
1.421(3)
1.430(4)
1.441(4)
1.458(4)
1.389(4)
O(2)–P(1)–O(1)
O(2)–P(1)–N(2)
O(1)–P(1)–N(2)
O(2)–P(1)–N(1)
O(1)–P(1)–N(1)
N(2)–P(1)–N(1)
C(1)–O(1)–P(1)
C(9)–N(1)–C(8)
C(6)–C(1)–C(2)
C(6)–C(1)–O(1)
C(2)–C(1)–O(1)
C(1)–C(2)–C(3)
C(4)–C(3)–C(2)
C(10)–N(2)–P(1)
114.19(11)
115.58(12)
102.32(11)
110.06(12)
102.94(12)
110.85(12)
120.41(17)
114.4(2)
121.3(3)
119.7(2)
118.7(2)
119.0(3)
O(2)–P(1)–O(1)
O(2)–P(1)–N(2)
O(1)–P(1)–N(2)
O(2)–P(1)–N(1)
O(1)–P(1)–N(1)
N(2)–P(1)–N(1)
C(8)–O(1)–P(1)
C(1)–N(1)–P(1)
C(6)–C(1)–C(2)
C(6)–C(1)–N(1)
C(2)–C(1)–N(1)
C(3)–C(2)–C(1)
C(4)–C(3)–C(2)
C(15)–N(2)–P(1)
114.82(13)
110.64(12)
105.10(12)
114.64(13)
100.51(12)
110.37(13)
120.81(17)
123.1(2)
119.1(3)
119.6(3)
121.2(3)
119.6(3)
Fig. 2. Molecular structure and atom labeling scheme for
[(CH3)2N]P(O)[p-NHC6H4-CH3][p-OC6H4-CH3] (4) with
displacement ellipsoids at the 50 % probability level.
121.5(3)
126.10(18)
121.7(3)
120.8(2)
Table 4. Hydrogen bond parameters for compounds 3 and 4
˚
(A, deg).
D-H···A
d(D-H) d(H··A) d(D··A) ∠DHA
3: N(2)-H(2N)··O(2) 0.880 2.022 2.869(3) 161
[x, −y+1/2, z + 1/2]
4: N(1)-H(1N)··O(2) 0.90
[−x+1, −y, z + 1/2]
2.07 2.957(4) 170
Fig. 3. Hydrogen bond (P(1)–O(2)···H(1N) in compound 4.
character, P–O–C: 120.30(2)◦ (2), 120.41(17)◦ (3) and
120.81(17)◦ (4). Their P–O bond lengths (1.607(2),
˚
1.608(2) and 1.604(2) A) are shorter than a standard
˚
P–O single bond (1.64 A [13]). The P=O bond lengths
Fig. 1. Molecular structure and atom labeling scheme
for [tert-C4H9NH]P(O)[(CH3)2N][p-O-C6H4-CH3] (3) with
displacement ellipsoids at the 50 % probability level.
in molecules 2, 3 and 4 are 1.473(2), 1.462(2) and
1.474(2) A, respectively, and thus longer than the nor-
˚
˚
mal P=O bond length (1.45 A for P(O)Cl3) [13].
and 100.51(12)◦ [∠O(1)–P(1)–N(1)] to 114.82(13)◦ Also, the P–N bond lengths are shorter than the stan-
˚
[∠O(2)–P(1)–O(1)]in compound 4. The oxygen atoms dard P–N single bond length (1.77 A for NaHPO3-
of the O-C6H4-p-CH3 moieties may be ascribed sp2 NH2 [13]). The nitrogen atoms of the aliphatic amine
- 10.1515/znb-2009-0513
Downloaded from De Gruyter Online at 09/12/2016 01:58:54AM
via free access

568
S. Ghadimi et al. · Mixed Diamidophosphoric Acid Esters
groups in the title compounds indicate sp2 hybridiza- 6H, N(CH3)2), 3.00 – 3.15 (m, 1H, methylamine-NH),
7.04 – 7.12 (m, 4H, Ar-H). – 13C NMR (62.90 MHz,
tion. For example, in compound 4, the angles P(1)–
◦
CDCl3, 25 C, TMS): δ = 20.69 (s, 1C, p-CH3), 27.02 (s,
N(2)–C(16), C(16)–N(2)–C(15) and C(15)–N(2)–P(1)
are 121.4(2)◦, 114.1(3)◦ and 120.8(2)◦, respectively.
The sum of the angles around the N2 and N1 atoms
are 354.9◦ and 355.8◦ for compound 3. The deviation
from the ideal value of 360◦ may be caused by steric
effects. Molecules of compounds 2 – 4 are linked via
N–H···O=P hydrogen bonds into chains. Fig. 3 shows
the N–H···O=P hydrogen bond in crystals of com-
pound 4. H-bonded chains spreading along the crys-
tallographic c axis in the crystal of compound 4 are
connected into ribbons through π stacking between p-
H3C-C6H4-NH moieties. The angle and the distance
between◦mean planes of neighboring moieties is equal
1C, methylamine-CH3), 36.80 (d, 2J(P,C) = 4.4 Hz, 2C,
3
N(CH3)2), 120.05 (d, J(P,C) = 4.8 Hz, 2C, Cortho), 130.00
(s, 2C, Cmeta), 133.70 (s, 1C, Cpara), 149.05 (d, 2J(P,C) =
1
6.3 Hz, 1C, Cipso). – 31P{ H} NMR (101.25 MHz, CDCl3,
◦
25 C, H3PO4 external): δ = 15.99 (s). – 31P NMR: δ =
15.99 (m). – IR (KBr): ν = 3220 (NH), 3010, 2920, 2800,
1600, 1580, 1505, 1300, 1225 (P=O), 1170, 1118, 1070,
988 (P–O), 920, 810, 715 (P–N), 645 cm−1. – MS (20 eV,
EI): m/z (%) = 228 (14) [M]+, 137 (88) [M–C7H7]+, 121
(5) [M–C7H7O]+, 107 (54) [C7H7O]+, 91 (12) [C7H7]+,
44 (100) [C2H6N]+.
N,N-Dimethyl-Nꢀ-iso-propyl-diamidophosphoric acid
4-methyl-phenyl ester, (CH3)2NP(O)[NH(iso-C3H7)]
[O-C6H4-p-CH3] (2)
˚
to 8.7(1) and 3.26(1) A, respectively, The shortest dis-
tances between the center of the phenylene ring and
the H atom of a neighboring methyl group is equal to
To
a solution of (CH3)2NP(O)Cl[O-C6H4-p-CH3]
˚
2.682(3) A.
(0.82 g, 3.5 mmol) in 30 mL of dry chloroform, iso-
propylamine (0.42 g, 7.1 mmol) was slowly added and
the mixture stirred at 0 ◦C for 12 h. The solvent was
evaporated in vacuo. Single crystals of the product were
obtained from a solution in chloroform-acetonitrile (4 : 1)
after slow evaporation at r. t. Yield: 73 %. M. p. 61 – 64 ◦C. –
1H NMR (500.13 MHz, CDCl3, 25 ◦C, TMS): δ = 1.12
(d, 3J(H,H) = 6.5 Hz, 3H, iso-propylamine-CH3), 1.15 (d,
3J(H,H) = 6.4 Hz, 3H, iso-propylamine-CH3), 2.25 (s, 3H,
p-CH3), 2.33 (b, 1H, NH), 2.68 (d, 3J(P,H) = 10.1 Hz,
6H, N(CH3)2), 3.38 – 3.39 (m, 1H, iso-propylamine-CH),
7.03 (m, 4H, Ar-H). – 13C NMR (125.75 MHz, CDCl3,
25 ◦C, TMS): δ = 20.64 (s, 1C, p-CH3), 25.27 (d, 3J(P,C) =
5.9 Hz, 1C, iso-propylamine-CH3), 25.52 (d, 3J(P,C) =
5.3 Hz, 1C, iso-propylamine-CH3), 36.96 (d, 2J(P,C) =
3.8 Hz, 2C, N(CH3)2), 43.38 (s, 1C, iso-propylamine-CH),
119.92 (d, 3J(P,C) = 4.8 Hz, 2C, Cortho), 129.96 (s, 2C,
Experimental Section
Materials
Acetonitrile (99 %), iso-propylamine (99 %), tert-butyl-
amine (99 %), methylamine (46 % aqueous solution), trieth-
ylamine (98 %), and chloroform (99 %) (Merck) were used
as supplied. [(CH3)2N]P(O)Cl[O-C6H4-p-CH3] was synthe-
sized according to the literature [10].
Spectroscopic measurements
1H, 13C and 31P NMR spectra were recorded on Bruker
(Avance DRS) 250 and 500 MHz spectrometers. 1H, 13C and
31P chemical shifts were obtained in CDCl3 relative to TMS
and 85 % H3PO4 as external standards, respectively. IR spec-
tra were obtained using KBr pellets on a Perkin Elmer 783
model spectrometer. A Varian Star 3400 CX mass spectrom-
eter was used for mass spectrometry investigation. Melting
points were obtained with an Electrothermal instrument.
2
Cmeta), 133.50 (s, 1C, Cpara), 149.12 (d, J(P,C) = 6.1 Hz,
1
◦
1C, Cipso). – 31P{ H} NMR (202.45 MHz, CDCl3, 25 C,
H3PO4 external): δ = 13.70 (s). – 31P NMR: δ = 13.70
(m). – IR (KBr): ν = 3210 (NH), 2949, 2940, 1599, 1499,
1455, 1297, 1227 (P=O), 1198, 1162, 1040, 985 (P–O), 906,
816, 794, 705 cm−1 (P–N). – MS (20 eV, EI): m/z (%) = 257
(30) [M+1]+, 256 (3) [M]+, 165 (3) [M–C7H7]+, 149 (79)
[M–C7H7O]+, 107 (100) [C7H7O]+, 91 (25) [C7H7]+, 44
(53) [C2H6N]+.
N,N-Dimethyl-Nꢀ-methyl-diamidophosphoric acid 4-methyl-
phenyl ester, (CH3)2NP(O)[(CH3)NH][O-C6H4-p-CH3] (1)
To
a solution of (CH3)2NP(O)Cl[O-C6H4-p-CH3]
(0.82 g, 3.5 mmol) in 30 mL of dry acetonitrile, methyl-
amine hydrochloride (0.24 g, 3.5 mmol) and triethylamine
(0.71 g, 7 mmol) were added at 0 ◦C. After 12 h stirring, the
solvent was evaporated in vacuo. Then, the flash gradient
chromatography method was used for the purification of the
product (silicagel, hexane-ethyl acetate 9 : 1). The solvent
was evaporated in vacuo to afford the product as a colorless
N,N-Dimethyl-Nꢀ-tert-butyl-diamidophosphoric acid
4-methyl-phenyl ester, [(CH3)2N]P(O)[NH(tert-C4H9)]-
[O-C6H4-p-CH3] (3)
Compound 3 was prepared following the procedure de-
liquid. Yield: 68 %. – 1H NMR (250.13 MHz, CDCl3, scribed for compound 2 by using tert-butylamine instead of
◦
◦
1
25 C, TMS): δ = 2.30 (s, 3H, p-CH3), 2.60 (d, 3J(P,H) = iso-propylamine. Yield: 82 %. M. p. 83 – 86 C. – H NMR
12.2 Hz, 3H, methylamine-CH3), 2.73 (d, 3J(P,H) = 10.2 Hz, (250.13 MHz, CDCl3, 25 C, TMS): δ = 1.32 (s, 9H, tert-
◦
- 10.1515/znb-2009-0513
Downloaded from De Gruyter Online at 09/12/2016 01:58:54AM
via free access

S. Ghadimi et al. · Mixed Diamidophosphoric Acid Esters
569
butylamine-CH3), 2.29 (s, 3H, p-CH3), 2.32 (b, 1H, NH), 3J(P,C) = 4.7 Hz, 2C, tolyl, Cortho), 129.91 (s, 2C, toluidine,
2.67 (d, 3J(P,H) = 10.0 Hz, 6H, N(CH3)2),◦ 7.07 (m, 4H, Cmeta), 130.05 (s, 1C, toluidine, Cpara), 130.23 (s, 2C, tolyl,
Ar-H). – 13C NMR (62.90 MHz, CDCl3, 25 C, TMS): δ = Cmeta), 134.20 (s, 1C, tolyl, Cpara), 138.64 (d, 2J(P,C) =
3
20.70 (s, 1C, p-CH3), 31.36 (d, J(P,C) = 5.0 Hz, 3C, tert- 1.2 Hz, 1C, toluidine, Cipso), 148.56 (d, 2J(P,C) = 6.0 Hz, 1C,
1
butylamine-CH3), 36.91 (d, 2J(P,C) = 3.2 Hz, 2C, N(CH3)2), tolyl, Cipso). – 31P{ H} NMR (101.25 MHz, CDCl3, 25 ◦C,
50.80 (s, 1C, tert-butylamine-C), 119.90 (d, 3J(P,C) = 4.8 Hz, H3PO4 external): δ = 6.94 (s). – 31P NMR: δ = 6.98 (m). – IR
2C, Cortho), 130.00 (s, 2C, Cmeta), 133.40 (s, 1C, Cpara), (KBr): ν = 3215 (NH), 2955, 2930, 1600, 1500, 1445, 1305,
1
149.2 (d, 2J(P,C) = 6.1 Hz, 1C, Cipso). – 31P{ H} NMR 1235 (P=O), 1190, 1155, 1025, 970 (P–O), 915, 710 cm−1
◦
(101.25 MHz, CDCl3, 25 C, H3PO4 external): δ = 10.71 (P–N). – MS (20 eV, EI): m/z (%) = 305 (29) [M+1]+, 304 (2)
3
(s). – 31P NMR: δ = 10.71 (hept, J(P,H) = 10.0 Hz). – IR [M]+, 213 (7) [M–C7H7]+, 198 (12) [M–C7H7NH]+, 197
(KBr): ν = 3180 (NH), 2923, 2880, 1580, 1565, 1485, 1450, (33) [M–C7H7O]+, 107 (41) [C7H7O]+, 91 (18) [C7H7]+,
1290, 1230 (P=O), 1190, 1158, 1015, 978 (P–O), 910, 813, 44 (100) [C2H6N]+.
750 (P–N), 708 cm−1. – MS (20 eV, EI): m/z (%) = 271
(35) [M+1]+, 270 (1) [M]+, 198 (42) [M–C4H10N]+, 163
X-Ray structure determinations
(4) [M–C7H7O]+, 107 (100) [C7H7O]+, 44 (33) [C2H6N]+.
X-Ray data of compounds 3 and 4 were collected on
a Bruker SMART 1000 CCD single crystal diffractome-
N,N-Dimethyl-Nꢀ-paratoluidyl-diamidophosphoric acid
4-methyl-phenyl ester, [(CH3)2N]P(O)[NH-C6H4-p-CH3]
[O-C6H4-p-CH3] (4)
ter with graphite-monochromatized MoKα radiation (λ =
˚
0.71073 A) [14]. Routine Lorentz and polarization correc-
tions were applied, and an absorption correction was per-
formed using the program SADABS [15]. The structures were
refined with SHELXL-97 by full-matrix least-squares proce-
dures on F2 [16]. The positions of hydrogen atoms were ob-
tained from a difference Fourier map.
Compound 4 was prepared following the procedure
described for compound 1 by using para-toluidine in-
stead of methylamine hydrochloride. (para-toluidine : trietyl-
amine, 1 : 1). Yield: 75 %. M. p. 75 – 79 ◦C. – 1H NMR
CCDC 693076 (3) and CCDC 393077 (4) contain the
supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data
request/cif.
◦
(250.13 MHz, CDCl3, 25 C, TMS): δ = 2.28 (s, 3H, tolui-
3
dine, p-CH3), 2.30 (s, 3H, tolyl, p-CH3), 2.74 (d, J(P,H) =
10.2 Hz, 6H, N(CH3)2), 5.09 (d, 2J(P,H) = 8.2 Hz, 1H,
NH), 6.89 – 7.03 (m, 4H, toluidine, Ar-H), 7.08 (m, 4H, tolyl,
Ar-H). – 13C NMR (62.90 MHz, CDCl3, 25 ◦C, TMS):
δ = 2.67 (s, 1C, toluidine, p-CH3), 2.80 (s, 1C, tolyl, p-
CH3), 36.73 (d, 2J(P,C) = 4.3 Hz, 2C, N(CH3)2), 117.90
Acknowledgement
Support of this work by Imam Hossein University is grate-
(d, 3J(P,C) = 6.7 Hz, 2C, toluidine, Cortho), 120.22 (d, fully acknowledged.
[1] W. Mallender, T. Szegletes, T. Rosenberry, Biochem-
istry 2000, 39, 7753.
[2] A. Baldwin, Z. Huang, Y. Jounaidi, D. Waxman, Arch.
Biochem. Biophys. 2003, 409, 197.
[10] S. Ghadimi, A. A. Ebrahimi Valmoozi, M. Pourayoubi,
Z. Kristallogr. NCS 2007, 222, 339.
[11] S. Ghadimi, A. A. Ebrahimi Valmoozi, M. Pourayoubi,
Acta. Crystallogr. 2007, E63, o3260.
[3] Y. Pang, T. Kollmeyer, F. Hong, J. Lee, P. Hammond,
S. Haugabouk, S. Brimijoin, Biochem. Biol. 2003, 10,
491.
[12] M. Pourayoubi, S. Ghadimi, A. A. Ebrahimi Valmoozi,
Acta. Crystallogr. 2007, E63, o4093.
[13] D. E. C. Corbridge, Phosphorus, an Outline of its
Chemistry, Biochemistry and Technology, Elsevier,
Amsterdam 1995.
[4] L. Costa, Clinic. Chim. Acta 2006, 366, 1, and refs.
therein.
[5] K. Kamil, B. Jirl, C. Jirl, K. Jirl, Bioorg. Medic. Chem.
Lett. 2003, 13, 3545.
[6] S. Ghadimi, A. A. Ebrahimi Valmoozi, M. Pourayoubi,
K. A. Samani, J. Enzy. Inhibit. Medic. Chem. 2008, 23,
556.
[7] K. Gubina, J. Shatrava, V. Ovchynnikov, V. Amir-
khanov, Polyhedron 2000, 19, 2203.
[8] K. Gholivand, Z. Shariatinia, M. Pourayoubi, Z. Natur-
forsch. 2005, 60b, 67.
[14] Bruker, SMART (version 5.059), Bruker Molecular
Analysis Research Tool, Bruker AXS, Madison, WI
(USA) 1998.
[15] G. M. Sheldrick, SADABS (version 2.01), Bruker/
Siemens Area Detector Absorption Correction Pro-
gram, Bruker AXS, Madison, WI (USA) 1998.
[16] G. M. Sheldrick, SHELXTL (version 5.10), Structure
Determination Software Suit, Bruker AXS, Madison,
WI (USA) 1998.
[9] K. Gholivand, A. Mahmoudkhani, M. Khosravi, Phos-
phorus Sulfur and Silicon 1995, 106, 173.
- 10.1515/znb-2009-0513
Downloaded from De Gruyter Online at 09/12/2016 01:58:54AM
via free access