N-2,4-Dichlorobenzoyl phosphoric triamides: Synthesis, spectroscopic and X-ray crystallography studies

Article abstract of DOI:10.1007/s12039-010-0089-5

New phosphoric triamides 1-9 were synthesized by the reaction of N-2,4-dichlorobenzoyl phosphoramidic dichloride with various cyclic aliphatic amines and the products were characterized by ¹H, ¹³C, ³¹P NMR, IR spectroscopy

Full text of DOI:10.1007/s12039-010-0089-5

J. Chem. Sci., Vol. 122, No. 4, July 2010, pp. 549–559. © Indian Academy of Sciences.
N-2,4-Dichlorobenzoyl phosphoric triamides: Synthesis, spectroscopic
and X-ray crystallography studies
a,
KHODAYAR GHOLIVAND *, NASRIN OROUJZADEH and ZAHRA SHARIATINIA
a
b
a
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
b
Department of Chemistry, Amirkabir University of Technology, P. O. Box: 159163-4311, Tehran, Iran
e-mail: gholi_kh@modares.ac.ir
MS received 29 November 2009; revised 28 January 2010; accepted 16 February 2010
Abstract. New phosphoric triamides 1–9 were synthesized by the reaction of N-2,4-dichlorobenzoyl
phosphoramidic dichloride with various cyclic aliphatic amines and the products were characterized by
1
13
H, C, P NMR, IR spectroscopy and elemental analysis. Surprisingly, the H NMR spectrum of 2 indi-
31
1
6
cated long range J (P, H) coupling constant = 1⋅3, 1⋅4 Hz and those of molecules 3, 4, 6–8 display long-
4
range J (H, H) coupling constants (1⋅8–1⋅9 Hz) for the coupling of aromatic protons in 2,4-
1 3
dichlorophenyl rings. H NMR spectra indicated J (PNCH) for enantiotopic and diastereotopic benzylic
CH protons in compounds 7 and 8. The spectroscopic data of newly synthesized compounds were com-
2
pared with those related N-benzoyl derivatives. The structures of compounds 5, 8 and 10 (2,4-Cl -
2
C H C(O)NHP(O)[NCH CH(CH ) ] ) have been determined by X-ray crystallography. The structures
6 3 2 3 2 2
form centrosymmetric dimers through intermolecular strong –P=O…H–N-hydrogen bonds. The dimers
connect to each other via rather strong and weak C–H…O plus weak C–H…Cl H-bonds to produce a 1-D
network for 5 while 3-D polymeric chains for 8 and 10.
Keywords. Phosphoric triamides; NMR; long range coupling; X-ray crystallography; hydrogen bonds.
1. Introduction
Hydrogen bonding is an important topic of intense
36,37
research in both chemistry and biology.
Swamy
Nowadays, there is a growing interest to research on
phosphoramidates chemistry that is because of the
valuable applications of these derivatives. Specially,
pharmacologists try to find novel and efficient drugs
from this class of compounds similar to cyclo-
et al investigated very strong C–H…O, N–H…O
and O–H…O hydrogen bonds in a cyclic phos-
38,39
phate.
The formation of centrosymmetric dimers
via strong and weak N–H…O hydrogen bonds were
40,41
studied.
previous studies, new N-2,4-dichorobenzoyl phos-
phoric triamides have been prepared and character-
In the present paper, following on our
1–5
phosphamide. Moreover, they have important ap-
6–9
plications as insecticides and pesticides
and
10–13
1
13
31
ized by H, C, P NMR, IR spectroscopy. Also,
efficient ligands in coordination chemistry.
14–17
The
20–
18,19
synthesis,
24
theoretical
and structural studies
the structures of compounds 5, 8 and 10 (2,4-Cl2-
42
have been performed on these compounds. The
structures of several phosphoramidates have already
20–27,28–31
C6H3C(O)NHP(O)[NCH2CH(CH3)2]2)
have been
determined by X-ray crystallography and their hy-
drogen bonded networks have been analysed. The
spectroscopic data of newly synthesized compounds
have been compared with those related N-benzoyl
analogues.
been determined by X-ray crystallography.
N-benzoylphosphoric triamides are one such signi-
ficant category of phosphoramidates derivatives. In
fact, the existence of –C(O)NHP(O)– skeleton as
peptide group in these molecules cause them bio-
32–34
logically active urease inhibitors.
Recently, it
2. Experimental
has been reported that phosphorus triester deriva-
tives of 3-azido-3-deoxythymidine (AZT) bearing
amino acid moieties revealed enhanced anti-HIV ac-
2.1 X-ray measurements
35
tivity.
X-ray data of compound 5 were collected on a
43a
X-area 1.31 and those of compounds 8 and 10 on
*For correspondence
549

550
Khodayar Gholivand et al
43b
a Bruker SMART 1000 CCD single crystal dif- 2.3b N-2,4-dichlorobenzoyl-dihydroxy phosphor-
fractometer with graphite monochromated MoKα amide (2): A solution of 1 mmol N-2,4-
radiation (λ = 0⋅71073 Å). The structures were re- dichlorobenzoyl phosphoramidic dichloride (1) in
44
fined with SHELXL-97 by full matrix least distilled water was stirred for 6 h. The precipitate
2
squares on F . The positions of hydrogen atoms was filtered and dried. Yield: 96%; m.p. = 139⋅6°C.
were obtained from the difference Fourier map. Anal. Calcd. for C7H6Cl2NO4P (%): C, 31⋅11; H,
While the shape of crystal determined optically in 5, 2⋅22; N, 5⋅18. Found: C, 31⋅10; H, 2⋅23; N, 5⋅18. IR
routine Lorentz and polarization corrections were (KBr, cm ): 3170 (m, CH), 2835 (m), 1697 (s,
–1
applied and an absorption correction was performed C=O), 1574 (m), 1425 (s), 1278 (m), 1251 (m), 1222
using the SADABS program for structures 8 and (s, P=O), 1098 (s), 1040 (m), 958 (m), 892 (m), 778
45
1
(m), 676 (m), 583 (m), 512 (m). H NMR
10.
(500⋅13 MHz, d6-DMSO, 25°C, TMS): δ 7⋅42 (d,
3
3
J (H, H) = 8⋅2 Hz, 1H), 7⋅47 (dd, J (H, H) =
2.2 Spectroscopic measurements
6
8⋅3 Hz, J (P, H) = 1⋅3 Hz, 1H, Ar-H), 7⋅64 (d,
6
2
1
13 31
H, C and P spectra were recorded on a Bruker
J (P, H) = 1⋅4 Hz, 1H, Ar-H), 9⋅64 (d, J (PNH) =
1
31
1
Avance DRS 500 spectrometer. H and C chemical
13
9⋅5 Hz, 1H, NH), 11⋅93 (s, 2H, OH). H{ P} NMR
3
31
shifts were determined relative to internal Me4Si, P
(500⋅13 MHz, d6-DMSO, 25°C, TMS): δ 7⋅42 (d, J
3
(H, H) = 8⋅2 Hz, 1H), 7⋅47 (d, J (H, H) = 8⋅3 Hz,
1H, Ar-H), 7⋅64 (s, 1H, Ar-H), 9⋅64 (s, 1H, NH),
11⋅93 (s, 2H, OH). C NMR (125⋅76 MHz, d6-
chemical shifts relative to 85% H3PO4 as external
standards, respectively. The field strengths to
13
13
1
31
acquisition of H, C and P NMR spectra were
500.13, 125.77, and 202.46 MHz, respectively. In-
frared (IR) spectra were recorded on a Shimadzu
model IR-60 spectrometer. Elemental analysis
was performed using a Heraeus CHN-O-RAPID
apparatus.
DMSO, 25°C, TMS): δ 127⋅09 (s), 129⋅04 (s),
130⋅08 (s), 130⋅97 (s), 134⋅65 (s), 135⋅17 (d,
3
31
1
J(P,C) = 10⋅3 Hz, C ), 166⋅75 (s, C=O). P{ H}
ipso
NMR (202⋅46 MHz, d6-DMSO, 25°C, H3PO4 exter-
nal): δ –6⋅10 (s).
2.4 General procedure for the synthesis of
compounds 3–9
2.3 Synthesis
2.3a N-2,4-dichlorobenzoyl phosphoramidic dichlo-
ride (1): Phosphorus pentachloride and 2,4-dichlo-
robenzamide in 1 : 1 molar ratio were refluxed in
CCl4 for 8 h, and then the resulting solution allowed
to cool to the room temperature. Formic acid was
syringed drop-wise into the stirring solution in
20 min and was stirred for 6h to yield the white
precipitate that was filtered and dried in vacuum.
Yield: 71%. M.p. = 120⋅4°C. Anal. Calcd. for
C7H4Cl4NO2P (%): C, 27⋅40; H, 1⋅31; N, 4⋅56.
To a solution of 10 mmol N-2,4-dichlorobenzoyl
phosphoramidic dichloride (1) in dry acetonitrile at
–5°C, 40 mmol of corresponding amine was added
drop-wise and the mixture was stirred for 6 h. After
evaporating the solvent, the residue was washed
with distilled water and acetonitrile and then recrys-
tallized in a methanol/chloroform solution.
2.4a N-2,4-Dichlorobenzoyl-N′,N″-diallyl
phos-
–1
phoric triamide (3): Yield: 73%; m.p. = 159⋅1°C.
Anal. Calcd. for C13H16Cl2N3O2P (%): C, 44⋅83; H,
5⋅00; N, 12⋅07. Found: C, 44⋅81; H, 5⋅01; N, 12⋅06.
Found: C, 27⋅39; H, 1⋅31; N, 4⋅55. IR (KBr, cm ):
νmax = 3100 (s), 2850 (w), 1707 (s, C=O), 1582 (s),
1428 (s), 1276 (m), 1249 (m), 1227 (s, P=O), 1102
(m), 1043 (m), 896 (s), 832 (m), 781 (m), 756 (m),
–1
IR (KBr, cm ): 3235 (s, NH), 2885 (w), 1648 (s,
1
678 (m), 586 (m), 516 (m). H NMR (500⋅13 MHz;
C=O), 1577 (m), 1434 (s), 1276 (m), 1236 (m), 1196
(s, P=O), 1130 (m), 1096 (m), 1038 (m), 985 (m),
918 (m), 887 (m), 860 (m), 767 (m), 567 (w), 495
1
(m), 430 (m). H NMR (500⋅13 MHz, d6-DMSO,
3
CDCl3; Me4Si): δ 7⋅40 (dd, J (H,H) = 8⋅3 Hz,
4
4
J (H,H) = 1⋅9 Hz, 1H, Ar-H), 7⋅51 (d, J (H,
3
H) = 1⋅9 Hz, 1H, Ar-H), 7⋅75 (d, J (H,H) = 8⋅3 Hz,
13
25°C, TMS): δ 3⋅48 (m, 4H, CH2), 4⋅58 (m, 2H,
1H, Ar-H), 9⋅23 (s, 1H, NH).
(125⋅75 MHz; CDCl3; Me4Si): δ 127⋅95 (s), 129⋅85
(d, J (P,C) = 10⋅7 Hz), 130⋅83 (s), 131⋅91 (s),
C
NMR
2
3
NHamine), 5⋅01 (dd, J(H,H) = 1⋅7 Hz, J(H,H) =
10⋅3 Hz, 2H), 5⋅21 (m, 2H), 5⋅84 (m, 2H), 7⋅48 (m,
3
4
31
132⋅53 (s), 139⋅44 (s), 164⋅30 (s, C=O). P NMR
2H), 7⋅66 (d, J(H,H) = 1⋅9 Hz, 1H, Ar-H), 9⋅50 (d,
J(PNH) = 7⋅2 Hz, 1H, NHamide). C NMR (125⋅76
2
13
(202⋅46 MHz; CDCl3; 85% H3PO4): δ 5⋅99 (m).

N-2,4-Dichlorobenzoyl phosphoric triamides: synthesis, spectroscopic and X-ray crystallography studies 551
MHz, d6-DMSO, 25°C, TMS): δ 43⋅37 (s, CH2), Anal. Calcd. for C17H16Cl2N3O4P (%): C, 47⋅66; H,
115⋅35 (s, CH2), 128⋅04 (s), 129⋅98 (s), 131⋅13 (s), 3⋅74; N, 9⋅81. Found: C, 47⋅64; H, 3⋅73; N, 9⋅82. IR
3
–1
131⋅76 (s), 135⋅60 (s), 136⋅21 (d, J (P, C) = 8⋅7 Hz, (KBr, cm ): 3245 (s, NH), 3140 (m), 2895 (m),
3
C
), 138⋅43 (d, J (P, C) = 6⋅2 Hz, CH), 168⋅03 (s, 1662 (s, C=O), 1575 (m), 1466 (m), 1421 (s), 1273
31 1
ipso
C=O).
P{ H} NMR (202⋅46 MHz, d6-DMSO, (m), 1202 (s, P=O), 1139 (m), 1094 (m), 1065 (m),
25°C, H3PO4 external): δ 8⋅34 (s).
1006 (m), 919 (m), 880 (m), 768 (m), 734 (m), 687
1
(w), 593 (w), 460 (m). H NMR (500.13 MHz, d6-
2.4b N-2,4-Dichlorobenzoyl-N′,N″-diisopropyl
DMSO, 25°C, TMS): δ 4⋅02 (m, 4H, CH2), 4⋅98 (m,
phosphoric triamide (4): Yield: 74%; m.p. = 2H, NHamine), 6⋅26–6⋅36 (m, 4H), 7⋅41 (d,
3
3
4
J(H,H) = 8⋅3 Hz, 1H), 7⋅47 (dd, J (H,H) = 1⋅9 Hz,
144⋅9°C. Anal. Calcd. for C13H20Cl2N3O2P (%): C,
44⋅32; H, 5⋅68; N, 11⋅93. Found: C, 44⋅30; H, 5⋅67;
3
J (H, H) = 8⋅2 Hz, 1H), 7⋅52 (d, J (H, H) = 0⋅8 Hz,
–1
4
N, 11⋅91. IR (KBr, cm ): 3360 (m, NH), 3090 (m), 2H), 7⋅64 (d, J (H, H) = 1⋅9 Hz, 1H), 9⋅57
2
13
2975 (m), 1656 (s, C=O), 1581 (m), 1475 (m), 1436 (d, J (PNH) = 7⋅9 Hz, 1H, NHamide). C NMR
(s), 1286 (m), 1214 (s, P=O), 1132 (m), 1106 (m), (125⋅76 MHz, d6-DMSO, 25°C, TMS): δ 37⋅01
1039 (m), 1016 (m), 898 (m), 847 (w), 769 (m), 691 (s,CH2), 106⋅25 (s), 110⋅26 (s), 127⋅00 (s), 129⋅01
1
3
(w), 572 (m), 538 (m), 464 (w). H NMR (s), 130⋅29 (s), 130⋅86 (s), 134⋅72 (s), 135⋅02 (d, J
3
(500⋅13 MHz, d6-DMSO, 25°C, TMS): δ 1⋅08 (m, (P, C) = 8⋅8 Hz, C ), 141⋅69 (s), 154⋅02 (d, J (P,
ipso
3
31
1
P{ H} NMR
12H, CH3), 3⋅29–3⋅35 (m, 2H, CH), 4⋅14 (dd, J (H, C) = 6⋅9 Hz), 167⋅04 (s, C=O).
2
H) = 9⋅1, J(PNH) = 9⋅6 Hz, 2H, NHamine), 7⋅42 (d, (202⋅46 MHz, d6-DMSO, 25°C, H3PO4 external): δ
3
3
J(H, H) = 8.2 Hz, 1H, Ar-H), 7⋅47 (dd,
J
7⋅42 (s).
4
(H, H) = 8⋅2, J (H, H) = 1⋅9 Hz, 1H, Ar-H), 7⋅64 (d,
4
J (H, H) = 1⋅9 Hz, 1H, Ar-H), 9⋅41 (s, 1H, NHamide). 2.4e N-2,4-Dichlorobenzoyl-N′,N″-dibenzyl phos-
13
C NMR (125⋅76 MHz, d6-DMSO, 25°C, TMS): δ phoric triamide (7): Yield: 87%; m.p. = 175⋅5°C.
3
3
24⋅93 (d, J (P, C)Aliphatic = 5⋅0 Hz, CH3), 25⋅31 (d, J Anal. Calcd. for C21H20Cl2N3O2P (%): C, 56⋅25; H,
(P, C)Aliphatic = 6⋅0 Hz, CH3), 42⋅22 (s, CH), 127⋅15 4⋅46; N, 9⋅37. Found: C, 56⋅24; H, 4⋅45; N, 9⋅36. IR
–1
(s), 128⋅79 (s), 129⋅10 (s), 130⋅12 (s), 130⋅85 (s), (KBr, cm ): 3280 (s, NH), 3135 (m), 1669 (s, C=O),
3
134⋅61 (s), 135⋅42 (d, J (P, C) = 8⋅6 Hz, C ), 1586 (m), 1474 (m), 1432 (s), 1183 (s, P=O), 1125
ipso
31
1
166⋅97 (s, C=O). P{ H} NMR (202⋅46 MHz, (m), 1100 (m), 1026 (m), 995 (w), 881 (m), 832 (w),
1
766 (m), 737 (m), 690 (m), 603 (w). H NMR
d6-DMSO, 25°C, H3PO4 external): δ 4⋅28 (s).
(500⋅13 MHz, d6-DMSO, 25°C, TMS): δ 4⋅08 (dd,
3
3
2.4c N-2,4-Dichlorobenzoyl-N′,N″-di-tert-butyl phos-
J (H, H) = 7⋅3, J (PNCH) = 11⋅7 Hz, 4H, CH2),
3 2
phoric triamide (5): Yield: 95%; m.p. = 5⋅05 (td, J (H, H) = 7⋅1 Hz, J (PNH) = 7⋅2 Hz, 2H,
3
175⋅3°C. Anal. Calcd. for C15H24Cl2N3O2P (%): C, NHamine), 7⋅17–7⋅38 (m, 11H, Ar-H), 7⋅45 (dd, J (H,
4
4
47⋅37; H, 6⋅32; N, 11⋅05. Found: C, 47⋅35; H, 6⋅33; H) = 8⋅3 Hz, J (H, H) = 1⋅9 Hz, 1H), 7⋅64 (d, J (H,
–1
13
N, 11⋅04. IR (KBr, cm ): 3365 (m), 3105 (m), 2970 H) = 1⋅9 Hz, 1H), 9⋅59. (s, 1H, NHamide). C NMR
(m), 1655 (s, C=O), 1583 (m), 1479 (m), 1430 (s), (125⋅76 MHz, d6-DMSO, 25°C, TMS): δ 43⋅72 (s,
1385 (m), 1286 (m), 1251 (m), 1219 (s, P=O), 1105 CH2), 126⋅49 (s), 127⋅02 (s), 127⋅22 (s), 127⋅98 (s),
(m), 1041 (m), 1009 (m), 890 (m), 861 (m), 772 (m), 129⋅04 (s), 130⋅25 (s), 130⋅88 (s), 134⋅69 (s), 135⋅25
1
3
3
749(m), 684 (w), 588 (w), 539 (w). H NMR (d, J (P, C) = 8⋅9 Hz, C ), 141⋅00 (d, J (P,
ipso
31
1
P{ H} NMR
(500.13 MHz, d6-DMSO, 25°C, TMS): δ 1⋅24 (s, C) = 5⋅8 Hz), 167⋅14 (s, C=O).
2
18H, CH3), 4⋅01 (d, J(PNH) = 7⋅6 Hz, 2H, NHamine), (202⋅46 MHz, d6-DMSO, 25°C, H3PO4 external): δ
7⋅47 (m, 2H, Ar-H), 7⋅63 (s, 1H, Ar-H), 9⋅58 (s, 1H, 7⋅36 (s).
NHamide). C NMR (125⋅76 MHz, d6-DMSO, 25°C,
13
3
TMS): δ 31⋅26 (d, J(P,C)Aliphatic = 4⋅8 Hz, CH3), 2.4f N-2,4-Dichlorobenzoyl-N′,N″-bis (N-methyl-
50⋅41 (s), 126⋅99 (s), 129⋅11 (s), 130⋅36 (s), 131⋅04 benzyl) phosphoric triamide (8): Yield: 91%;
3
(s), 134⋅58 (s), 135⋅27 (d, J (P, C) = 6⋅9 Hz, C ), m.p. = 169⋅3˚C. Anal. Calcd. for C23H24Cl2N3O2P
ipso
31
1
166⋅93 (s, C=O). P{ H} NMR (202⋅46 MHz, (%): C, 52⋅94; H, 5⋅04; N, 8⋅82. Found: C, 52⋅95; H,
–1
d6-DMSO, 25°C, H3PO4 external): δ 0⋅85 (s).
5⋅02; N, 8⋅84. IR (KBr, cm ): 3015 (s), 2835 (s),
1676 (s, C=O), 1573 (m, νring), 1440 (s), 1340 (m),
2.4d N-2,4-Dichlorobenzoyl-N′,N″-difurfuryl phos- 1282 (m), 1212 (s), 1180 (s, P=O), 1127 (s), 1100
phoric triamide (6): Yield: 89%; m.p. = 133⋅7°C. (m), 1045 (m), 1011 (s), 947 (s), 867 (m), 814

552
Khodayar Gholivand et al
31
(m),776 (m), 728 (m), 532 (m), 502 (m), 441 (m). in table 1. It is interesting that P NMR chemical
1
31
H NMR (500⋅13 MHz, d6-DMSO, 25°C, TMS): δ shift, δ ( P), in compound 2 with two OH groups is
3
2
2⋅55 (d, J (P, H) = 10⋅1 Hz, 6H, CH3), 4⋅16 (dd, J the most upfield while in other compounds contain-
3
2
(H, H) = 15⋅1, J (P, H) = 8⋅7 Hz, 2H), 4⋅24 (dd, J ing two chlorine atoms or amino moieties, the δ
3
31
(H, H) = 15⋅1, J (P, H) = 9⋅3 Hz, 2H), 7⋅27 (m, 2H), ( P) greatly shifts to down field. In compounds 3–5
31
7⋅35 (m, 4H), 7⋅42 (m, 4H), 7⋅46 (m, 1H), 7⋅51 (dd, with aliphatic amino groups, δ ( P) decreases from
J (H, H) = 8⋅2, J (H, H) = 1⋅8 Hz, 1H), 7⋅71 (d, J 3 to 5 and it is nearly 8 and 4 times greater in 3 and
3
4
4
13
31
4 than in 5, respectively. The P NMR chemical
(H, H) = 1⋅8 Hz, 1H), 9⋅80 (s, 1H, NHamide).
C
NMR (125⋅76 MHz, d6-DMSO, 25°C, TMS): δ shifts in 6 and 7 are close to each other. Comparison
2
2
33⋅33 (d, J (P, C) = 4⋅2 Hz, CH3), 52⋅02 (d, J (P, of compounds 7–9 containing benzylic substituents
C) = 4⋅4 Hz, CH2), 127⋅06 (s), 127⋅32 (s), 127⋅99 indicate that replacement of CH2C6H5 groups in 7 by
(s), 128⋅31 (s), 129⋅16 (s), 130⋅09 (s), 130⋅85 (s), N(CH3)(C6H5) and N-CH(CH3)(C6H5) moieties in 8
3
134⋅92 (s), 135⋅39 (s), 138⋅21 (d,
C) = 4⋅4 Hz), 168⋅61 (s, C=O).
J
(P, and 9 cause a highly deshielded and shielded phos-
P{ H} NMR phorus atom, respectively. This means the effects of
(202⋅46 MHz, d6-DMSO, 25°C, H3PO4 external): δ these two substituents are opposite to each other.
31
1
31
12⋅90 (s).
Comparison of δ ( P) values for compounds 4–10
(containing 2,4-dichlorobenzoyl moiety) and their
2.4g N-2,4-Dichlorobenzoyl-N′,N″-bis (α-methyl- analogues 13–19 (containing benzoyl moiety) reveal
31
benzyl) phosphoric triamide (9): Yield: 95%; that the δ ( P) values are at down fields for 13–19.
m.p. = 208.9°C. Anal. Calcd. for C23H24Cl2N3O2P It seems that the presence of two Cl atoms on the
(%): C, 57⋅98; H, 5⋅04; N, 8⋅82. Found: C, 57⋅96; H, phenyl ring in molecules 4–10 cause more shielded
–1
5⋅05; N, 8⋅83. IR (KBr, cm ): 3255 (s, NH), 2955 phosphorus atoms by electron donation via reso-
(m), 1664 (s, C=O), 1586 (m), 1473 (m), 1424 (s), nance effect.
1
Interestingly, the H NMR spectra of compounds
6
(m), 891 (m), 768 (m), 694 (m). H NMR 2 and 10 indicated long range J (P, H) coupling
1280 (m), 1202 (s, P=O), 1103 (m), 1041 (m), 973
1
3
(500⋅13 MHz, d6-DMSO, 25°C, TMS): δ 1⋅37 (d, J constants = 1⋅3, 1⋅4 Hz and 1⋅7, 1⋅7 Hz, respectively,
3
(H, H) = 6⋅8 Hz, 3H, CH3), 1⋅39 (d, J (H, for the splitting of meta protons (a, b protons shown
2
H) = 6⋅8 Hz, 3H, CH3), 4⋅38 (m, 2H), 4⋅80 (dd, J in scheme 1) with phosphorus atom. Figure 1 indi-
3
1
1
31
(PNH) = J (H, H) = 10⋅2 Hz, 1H, NHamine), 4⋅92 cates the H- and H{ P} NMR spectra of com-
(dd, J (PNH) = J(H,H) = 10.2 Hz, 1H, NHamine), pound 2. Also, the spectra of molecules 1, 3, 4, 6–8
2
3
2
4
7⋅10–7⋅61 (m, 13H, Ar-H), 9⋅44 (d, J(PNH) = display long-range J (H, H) coupling constants
13
7⋅9 Hz, 1H, NHamide). C NMR (125⋅76 MHz, d6- (1⋅8–1⋅9 Hz) for the coupling of aromatic protons in
3
DMSO, 25°C, TMS): δ 25⋅14 (d, J (P, C) = 5⋅0 Hz, 2,4-dichlorophenyl rings. This coupling was ob-
CH3), 25⋅51 (d, J (P, C) = 6⋅3 Hz, CH3), 46⋅68 (s), served neither for compounds 11–19 nor for our
49⋅88 (s), 125⋅91 (s), 126⋅00 (s), 126⋅24 (s), 126⋅29 previously reported phosphoric triamides.
3
24,25,28–31,43–45
4
(s), 126⋅90 (s), 127⋅92 (s), 127⋅94 (s), 129⋅00 (s), Typically, J (H, H) coupling constants for the
3
130⋅25 (s), 130⋅88 (s), 134⋅65 (s), 135⋅08 (d, J (P, phenyl ring are in the range of 1–3 Hz and particular
3
C) = 8⋅8 Hz), 146⋅01 (d, J (P, C) = 3.7 Hz), 146⋅22 values seem to depend as much on the pattern of
(d, J (P, C) = 5.4 Hz), 166⋅95 (s, C=O). P{ H} substitution as the nature of the substituent.
3
31
1
46
1
The H NMR spectrum of compound 3 exhibited
NMR (202⋅46 MHz, d6-DMSO, 25°C, H3PO4 exter-
nal): δ 3⋅99 (s).
3
= 17⋅2 Hz for
the coupling of terminal CH2 protons of –CH=CH2
3
J (H, H) = 10⋅3 Hz and J (H, H)
cis
trans
3
with CH proton. J (PNCH) was observed in com-
3. Results and discussion
pounds 7 and 8 for the splitting of benzylic CH2 and
CH3 protons with phosphorus atom. The unequal
diastereotopic CH2 protons in 8 caused two different
3.1 Spectroscopic study
3
J (PNCH) values while they are identical in 7. This
2
constant similar to J (P, C)aliphatic is greater for CH3
In this work, several new phosphoric triamides 1–9
were prepared from the reaction of N-2,4-
Cl2C6H3C(O)NHP(O)Cl2 (1) with H2O or various
amines (scheme 1). Some spectroscopic data of the
new compounds and their analogues are summarized
group than for CH2 in molecule 8 and its analogue
1
13
17. The H- and C NMR spectra of compound 9
and its analogue 18 indicated two series of signals

N-2,4-Dichlorobenzoyl phosphoric triamides: synthesis, spectroscopic and X-ray crystallography studies 553

554
Khodayar Gholivand et al
Scheme 1. The preparation pathway for the synthesis of compounds 1–9.
for the two unequal α-methylbenzyl moieties that is lengths and angles are presented in table 3 and
due to the effect of chiral carbon atoms. Similarly, molecular structures (ORTEP view) are shown in
1 13
the H- and C NMR spectra of analogous com- figures 1–3.
pounds 10 and 19 demonstrated two series of signals
In these structures, the phosphoryl and the car-
for two different CH3 groups of diisobutyl substitu- bonyl groups indicate anti configurations and the
ents which is a result of prochiral CH carbon atoms. phosphorus atoms have distorted tetrahedral con-
13
The C NMR spectrum of compound 4, containing figuration. The bond angles around P(1) atoms in the
two isopropyl groups, revealed two different values compounds are in the range of 104⋅88(7)° to
3
for the J (P, C)aliphatic that could be attributed to the 118⋅21(7)°. The P–Namide bond lengths (about
presence of prochiral CH carbon atom.
1⋅69 Å) are longer than the P–Namine bonds (about
The ν (P=O) and ν (C=O) in 1 have the greatest 1⋅63 Å), because of the resonance interaction of the
values among these molecules. For the molecules Namide with the C=O π system that cause a partial
3–5, ν (P=O) value becomes larger from 3 to 5 but multiple bond character in C–Namide (the C–Namide
ν (C=O) does not change significantly. The ν (P=O) bond lengths are shorter than the C–Namine bond
values in compounds 8, 9 are smaller than in 7 while lengths). All the P–N bonds are shorter than the
47
ν (C=O) exhibits a reverse influence. This could be typical P–N single bond (1⋅77 Å ). This is probably
described by the resonance interaction of P=O and owing to the electrostatic effects of polar bonds that
48
C=O groups as follows in which the superior form in overlap with P–N sigma bond. The P=O bond
8 is I while in 9 it is form II.
lengths in these compounds are larger than the
47
normal P=O bond length (1⋅45 Å).
The environment of the nitrogen atoms is practi-
cally planar. For example, in compound 5 the angles
C(7)–N(1)–P(1), C(7)–N(1)–H(1A) and P(1)–N(1)–
H(1A) are 124⋅4(3)°, 117⋅8° and 117⋅8°, respec-
tively with an average 120⋅0°. The sum of surround-
ing angles around N(2) and N(3) atoms are 352⋅1°
and 358⋅4°, respectively. Similar results were obtai-
ned for the nitrogen atoms of other structure that
A comparison of similar compounds 1, 11 and 12
with formula RC(O)NHP(O)Cl2, R = 2,4-Cl2 C6H3,
4-ClC6H4 and C6H5 reveals that with increasing the
chlorine atoms on the phenyl ring, both ν (P=O) and
ν (C=O) amounts decrease.
2
confirm the sp hybridization for the N atoms,
although due to the repulsion and steric interactions,
some angles are greater, and others are smaller than
120°. This observation suggests the existence of par-
tial multiple bond character between phosphorus and
nitrogen atoms that has always been confirmed by
the crystallographic data of our previously reported
3.2 X-Ray crystallography
Single crystals of compounds 5, 8 and 10 (N-2,4-
C6H3C(O)NHP(O)[NCH2CH(CH3)2]2) were obtained
from a mixture of methanol/chloroform at room
temperature. The crystal data and the details of the
X-ray analysis are given in table 2. Selected bond
24,25,28–31,42,49–51
similar compounds.
These structures contain one amidic hydrogen
atom and form centrosymmetric dimers through
strong intermolecular –P=O…H–N– hydrogen bonds

N-2,4-Dichlorobenzoyl phosphoric triamides: synthesis, spectroscopic and X-ray crystallography studies 555
Table 2. Crystallographic data for compounds 5, 8 and 10.
5
8
10
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system, space group
Unit cell dimensions
a (Å)
C H Cl N O P
15 24 2 3 2
C H Cl N O P
23 24 2 3 2
C H Cl N O P
23 40 2 3 2
380⋅24
476⋅32
492⋅45
293(2)
120(2)
120(2)
0⋅71073
0⋅71073
0⋅71073
Triclinic, P-1
Tricliniic, P-1
Monocliniic, P2 /n
1
10⋅184(4)
10⋅726(5)
10⋅674(5)
100⋅05(3)
101⋅11(3)
116⋅15(3)
10⋅5670(11)
11⋅0083(11)
11⋅5928(12)
68⋅249(2)
13⋅6999(8)
13⋅3978(8)
14⋅3314(9)
90
b (Å)
c (Å)
α (°)
β (°)
71⋅293(2)
93⋅340(5)
90
γ (°)
68⋅071(2)
3
V (Å )
981⋅4(7)
1135⋅6(2)
2, 1⋅393
0⋅382
2626⋅0(3)
–3
Z, Calculated density (Mg m ) 2, 1⋅287
–1
Absorption coefficient (mm )
F (000)
4, 1⋅246
0⋅423
400
0⋅332
496
1056
Crystal size (mm)
0⋅50 × 0⋅10 × 0⋅05
2⋅03 to 29⋅21
–13 ≤ h ≤ 13;
–14 ≤ k ≤ 14;
–14 ≤ l ≤ 14
0⋅13 × 0⋅12 × 0⋅11
1⋅94 to 27⋅00
–13 ≤ h ≤ 13;
–14 ≤ k ≤ 14;
–14 ≤ l ≤ 14
0⋅25 × 0⋅25 × 0⋅15
2⋅00 to 29⋅00
–18 ≤ h ≤ 18;
–18 ≤ k ≤ 18;
–19 ≤ l ≤ 14
θ range for data collection (°)
Limiting indices
Reflections collected/unique
9512/4853
10886/4953
23120/6964
[R(int) = 0⋅0426]
[R(int) = 0⋅0181]
[R(int) = 0⋅0339]
Completeness to theta (%)
Absorption correction
91⋅4
99⋅9
99⋅7
Numerical
Semi-empirical from
equivalents
Multi-tran
Max. and min. transmission
Refinement method
0⋅980 and 0⋅950
0⋅962 and 0⋅953
0⋅959 and 0⋅926
Full-matrix least-
2
squares on F
Full-matrix least-
2
squares on F
Full-matrix least-
2
squares on F
Data/restraints/parameters
2
Goodness-of-fit on F
4853/0/216
4953/0/280
6964/0/288
1⋅099
1⋅022
1⋅005
Final R indices
R1 = 0⋅0832, wR = 0⋅1991
2
R = 0⋅0379, wR = 0⋅0765
1 2
R = 0⋅0469,
1
wR = 0⋅1074
2
R indices (all data)
R1 = 0⋅1270, wR = 0⋅2244
2
R = 0⋅0458, wR = 0⋅0818
1 2
R = 0⋅0677,
1
wR = 0⋅1159
2
Largest diff. peak
–3
and hole (e.Å )
0⋅673 and –0⋅554
0⋅450 and –0⋅324
0⋅575 and –0⋅300
(table 4). For example, the P1–O2…H1A–N1 hydro- 3⋅180 Å, respectively, while C15–H15H…Cl2
gen bonds produce a centrosymmetric dimer in 5 hydrogen bond is a weak bond (C15…Cl2 distance
and this dimer is connected to neighbouring dimers is 3⋅611 Å). Moreover, in structure 5, there are intra-
via intermolecular N3–H3…O1, C15–H15H…Cl2, molecular electrostatic interaction between N(2),
C1–H1…O2 and intramolecular C9–H9A…O2, O(1) and O(1), Cl(2) atoms with distances of
C11–H11B…O2 and C14–H14B…O2 hydrogen 3⋅012 Å and 2⋅980 Å, respectively.
bonds to yield a one-dimensional polymeric chain
In the structure of 8, strong intermolecular
(figure 4). It is noteworthy that C1–H1…O2, C9– N1–H1…O1 hydrogen bonds yield a centrosymmet-
H9A…O2, C11–H11B…O2 and C14–H14B…O2 ric dimmer that connects to other dimers by rather
hydrogen bonds are rather strong with D…O dis- strong C19–H19A…O2 and C23–H23A…Cl2
tances equal to 3⋅175 Å, 3⋅328 Å, 3⋅262 Å and hydrogen bonds (D…O distances equal to 3⋅230 Å

556
Khodayar Gholivand et al
Table 3. Selected bond lengths (Å) and angles (°) for compounds 5, 8 and 10.
5
8
10
P(1)–O(2)
P(1)–N(1)
P(1)–N(2)
P(1)–N(3)
O(1)–C(7)
N(1)–C(7)
C(3)–Cl(1)
C(5)–Cl(2)
1⋅473(3)
1⋅708(3)
1⋅632(4)
1⋅623(4)
1⋅226(4)
1⋅353(5)
1⋅746(4)
1⋅736(5)
P(1)–O(1)
P(1)–N(1)
P(1)–N(2)
P(1)–N(3)
O(2)–C(1)
N(1)–C(1)
C(3)–Cl(1)
C(5)–Cl(2)
1⋅484(1)
1⋅686(1)
1⋅6378(2)
1⋅630(2)
1⋅215(2)
1⋅374(2)
1⋅738(2)
1⋅735(2)
P(1)–O(1)
P(1)–N(1)
P(1)–N(2)
P(1)–N(3)
O(2)–C(1)
N(1)–C(1)
C(3)–Cl(1)
C(5)–Cl(2)
1⋅481(1)
1⋅698(1)
1⋅638(2)
1⋅645(1)
1⋅221(2)
1⋅360(2)
1⋅738(2)
1⋅738(2)
O(2)–P(1)–N(1)
O(2)–P(1)–N(2)
O(2)–P(1)–N(3)
N(2)–P(1)–N(1)
N(1)–P(1)–N(3)
N(2)–P(1)–N(3)
C(7)–N(1)–P(1)
C(7)–N(1)–H(1A)
P(1)–N(1)–H(1A)
106⋅1(2)
114⋅6(2)
115⋅4(2)
106⋅1(2)
108⋅1(2)
106⋅1(2)
124⋅4(3)
117⋅8
O(1)–P(1)–N(1)
O(1)–P(1)–N(2)
O(1)–P(1)–N(3)
N(2)–P(1)–N(1)
N(1)–P(1)–N(3)
N(2)–P(1)–N(3)
C(1)–N(1)–P(1)
C(1)–N(1)–H(1)
P(1)–N(1)–H(1)
107⋅31(7)
111⋅21(8)
113⋅11(8)
108⋅91(8)
107⋅55(7)
108⋅62(8)
124⋅8(1)
118⋅2
O(1)–P(1)–N(1)
O(1)–P(1)–N(2)
O(1)–P(1)–N(3)
N(2)–P(1)–N(1)
N(1)–P(1)–N(3)
N(2)–P(1)–N(3)
C(1)–N(1)–P(1)
104⋅88(7)
118⋅21(7)
109⋅12(7)
105⋅28(7)
111⋅74(7)
107⋅59(7)
129⋅05(12)
C(1)–N(1)–H(1N) 113⋅8
P(1)–N(1)–H(1N) 117⋅0
117⋅8
117⋅0
Table 4. Hydrogen bond parameters for compounds 5, 8 and 10 (Å, °).
Compound
(D–H…A)
d (D–H)
d (H…A)
d (D…A)
∠DHA
5
N(1)–H(1A)...O(2) #1
N(3)–H(3)...O(1) #2
C1–H(1)...O(2) #1
0⋅86
0⋅77
0⋅93
0⋅96
0⋅96
2⋅03
2⋅48
2⋅48
2⋅58
2⋅83
2⋅833
3⋅219
3⋅175
3⋅262
3⋅611
155
162
132
129
139
Cl1–H(11B)...O(2)
Cl5–H(15B)...Cl2(2) #2
8
N(1)–H(1)...O(1) #3
N(1)–H(1N)...O(1) #4
0⋅83
0⋅90
1⋅96
1⋅82
2⋅790(2)
2⋅721(2)
172
178
10
Symmetry transformations used to generate equivalent atoms: #1 1 – x, 2 – y, 1 – z; #2 – x,
2 – y, 1 – z; #3 –x, –y + 1, –z; #4 –x + 1 ,–y + 1, –z
1
1
Figure 1. The H- and H{ P} NMR spectra of compound 2.
31

N-2,4-Dichlorobenzoyl phosphoric triamides: synthesis, spectroscopic and X-ray crystallography studies 557
and 3⋅355 Å) plus weak intermolecular C4– dimers through weak intermolecular C15–
H4A…O1, C16–H16B…Cl1 and C21–H21A…Cl2 H15A…O2 hydrogen bonds (D…O distance is
hydrogen bonds (D…O distances equal to 3⋅463 Å, 3⋅424 Å) and produce a three-dimensional polymeric
3⋅639 Å and 3⋅734 Å) to give a three dimensional chain. There are also rather strong intramolecular
polymeric chain. There is also π–π stacking of two C8–H8B…O2, C16–H16A…O2 and C18–H18B…O2
phenyl rings with C–C distances of 3⋅312 Å and an hydrogen bonds (D…O distances equal to 3⋅185 Å,
intramolecular electrostatic interaction between O(2) 3⋅249 Å and 3⋅252 Å) in this network.
of C=O group and ortho Cl(1) atom with a distance
equal to 2⋅933 Å.
Similar to 5 and 8, in structure 10, the strong
intermolecular N1–H1N…O1 hydrogen bonds yield
a centrosymmetric dimmer that attaches to other
Figure 2. Molecular structure and atom labelling scheme
for compound 5 (50% probability ellipsoids).
Figure 4. Molecular structure and atom labelling scheme
for compound 10 (50% probability ellipsoids).
Figure 5. A one-dimensional polymeric chain produced
by strong –P=O…H–N–, rather strong and weak C–H…O
plus weak C–H…Cl hydrogen bonds in the crystalline
lattice of compound 5.
Figure 3. Molecular structure and atom labelling scheme
for compound 8 (50% probability ellipsoids).

558
Khodayar Gholivand et al
8. Berlicki L and Kafarski P 2002 Pestic. Biochem.
4. Summary
Phys. 73 94
9. Pardio V T, Ibarra N and Rodriguez M A 2001
J. Agricult. Food Chem. 49 6057
The synthesis, characterization and spectroscopic
1
studies of some new phosphoric triamides by H,
13
10. Denmark S E and Fu J 2003 J. Am. Chem. Soc. 125
2208
31
C, P NMR, IR spectroscopy were performed.
6
4
Long range J (P, H) and J (H, H) coupling con-
stants in the range of 1⋅3–1⋅7 Hz and 1⋅8–1⋅9 Hz
were observed for the coupling of aromatic protons
in 2,4-dichlorophenyl rings with phosphorus atom.
The spectroscopic data of newly synthesized com-
pounds were compared with those related N-benzoyl
derivatives. The crystal structures of three com-
pounds were determined by X-ray crystallography
that indicated intermolecular strong –P=O…H–N–
as well as rather strong and weak C–H…O plus
weak C–H…Cl hydrogen bonds.
11. Gubina K E, Shatrava J A, Amirkhanov V A,
Ovchynnikov V A and Amirkhanov V M 2000 Poly-
hedron 19 2203
12. Silvestru C, Rösler R, Silvestru A and Drake J E
2002 J. Organomet. Chem. 642 71
13. Gholivand K and Shariatinia Z 2006 J. Organomet.
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Supplementary information
18. Anagnostis J and Turnbull M M 2004 Polyhedron 23
125
Supplementary data for the crystallographic data of
the structures 5, 8 and 10 have been deposited
with Cambridge Crystallographic Data Center as
supplementary publication nos. CCDC 709717
(C15H24Cl2N3O2P), CCDC 709122 (C23H24Cl2N3O2P)
and CCDC 727879 (C23H40Cl2N3O2P). Copies of the
data may be obtained, free of charge, on application
to CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK, (fax: +44 1223 336033; e-mail: deposit@
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.
uk).
19. Domínguez Z J, Cortez M T and Gordillo B 2001
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24. Gholivand K, Mostaanzadeh H, Shariatinia Z and
Oroujzadeh N 2006 Main Group Chem. 5 95
25. Gholivand K, Pourayoubi M, Shariatinia Z and
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26. Narula P M, Day C S, Powers B A, Odian M A,
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Acknowledgement
Authors would like to thank the Research Council of
Tarbiat Modares University for the financial support 27. Chivers T, Krahn M, Schatte G and Parvez M 2003
Inorg. Chem. 42 3994
to carryout this work.
28. Gholivand K, Shariatinia Z, Mashhadi S M, Daeepour
F, Farshidnasab N, Mahzouni H R, Taheri N, Amiri S
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