Reactions of trisdialkylaminophosphines with acrylohydrazide and imidazolinone derivatives for the synthesis of new organophosphorus derivatives

Article abstract of DOI:10.1080/00397910802564733

Trisdimethylaminophosphine reacts with 2-benzamido-N-arylidene-3-aryl- acrylohydrazide to give phosphoryl benzamide and phosphoryl-cyano-benzamide adducts depending on the reaction conditions. Moreover, 1-aryliden-amino-2- phenyl-4-aryliden-2-imidazolin-5

Full text of DOI:10.1080/00397910802564733

Synthetic Communications1, 39: 1626–1639, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802564733
Reactions of Trisdialkylaminophosphines
with Acrylohydrazide and Imidazolinone
Derivatives for the Synthesis of
New Organophosphorus Derivatives
Mona H. N. Arsanious
Department of Organometallic and Organometalloid Chemistry, National
Research Center, Dokki, Cairo, Egypt
Abstract: Trisdimethylaminophosphine reacts with 2-benzamido-N-arylidene-
3-aryl-acrylohydrazide to give phosphoryl benzamide and phosphoryl-
cyano-benzamide adducts depending on the reaction conditions. Moreover,
1-aryliden-amino-2-phenyl-4-aryliden-2-imidazolin-5-ones react with trisdialkyla-
minophosphines to yield tetraalkylphosphonic diamide adducts. Possible reaction
mechanisms are considered, and the structural assignments are based on
analytical and spectroscopic evidence and X-ray analysis.
Keywords: 3-Arylacrylohydrazides, 4-aryliden-2-imidazolin-5-ones, trisdialkyl-
aminophosphines
INTRODUCTION
Hydrazides and heterocyclic ring systems represent important classes
of compounds not only for their theoretical interest but also for their
biological activities.[1–3] Furthermore, it is known that phosphorus sub-
stituents regulate important biological functions[4–6] and that the incor-
poration of phosphorus into organic molecules could increase their
biological and pharmaceutical activity.[7–9] This together with our interest
Received October 5, 2008.
Address correspondence to Mona H. N. Arsanious, Department of Organo-
metallic and Organometalloid Chemistry, National Research Center, Dokki,
Cairo, Egypt. E-mail: mona.arsanious@gmail.com
1626

Trisdialkylaminophosphines
1627
Scheme 1. Reagents and substrates.
in organophosphorus chemistry[10–12] led us to explore the synthesis of new
phosphorus compounds that may possess increased biological activity.
The present study deals with the reaction of trisdialkylaminophosphines
1a and 1b with 2-benzamido-N-arylidene-3-aryl-acrylo-hydrazides 2a
and 2b and its cyclic-dehydration derivatives namely 1-aryliden-amino-
2-phenyl-4-arylidene-2-imidazolin-5-one 3a and 3b (Scheme 1).
RESULTS AND DISCUSSION
When 2-benzamido-N-(4-methoxy-benzylidene)-3-(4-methoxyphenyl)
acrylohydrazide (2a) was allowed to react with two mol. equivalents of
trisdimethylaminophosphine (1a) in boiling toluene for 10 h, two adducts
were formed as compounds 4a (major product) and 5a (Scheme 2).
Structural support for N-[(Z)-2-{bis(dimethylamino)phosphoryl-1-
[(2-methoxyphenyl)methylidene)hydrazine)carbonyl]-2-[(4-methoxyphenyl)
ethenyl]benzamide (4a) is deduced from its spectroscopic data. The infra-
red (IR) spectrum of 4a, in KBr, revealed the presence of an intense band
at 1251 cmꢀ1 (P¼O) absorption[13] and two bands at 1320, 838 cmꢀ1 due
to the absorption of P[N(CH3)2]2,[14] 1692 cmꢀ1 (C¼O), and 3100 (NH).
The 1H NMR spectrum of 4a (CDCl3, d ppm) gives a doublet at
d ¼ 2.73 ppm with 2JHP ¼ 10.8 Hz due to 12 protons of the two equivalent
NMe2 groups attached to the phosphorus atom, one singlet at 7.58
(N¼CH), and two singlets at 8.84 and 9.88 ppm (NH). The 13C NMR
spectrum of 4a adds good support to the proposed structure, which
reveals two signals at 165.9 and 165.6 (2 C¼O) and two doublets of ethe-
nyl C¼C attached to the phosphorus atom at 110.3 (1JCP ¼ 141.7 Hz) and

1628
M. H. N. Arsanious
Scheme 2. Mechanism for the formation of adducts 4 and 5.
128.7 (2JCP ¼ 38.4 Hz) ppm.[15] Moreover, the structure assigned to 4a was
unambiguously supported by X-ray analysis (Fig. 1, Table 1).
Carrying out the reaction of 2a with two mol equivalents of 1a in
boiling xylene for 3 h led to formation of 4a and 5a (major product)
(Scheme 2). Structure elucidation of compound 5a is based on its spectro-
1
scopic data (cf. Experimental). The H NMR of 5a reveals signals at
3
2
d ¼ 2.85 [d, 12H, JHP ¼ 9.6 Hz, 2 N-(CH3)2], 5.31 (dd, 1H, JHP ¼ 24.6,
JHH ¼ 10.5 Hz), 3.74 (dd, 1H, 3JHP ¼ 11.2 Hz, JHH ¼ 10.5 Hz) for methane
attached to phosphorus. The 31P NMR shows signal d ¼ 33.2 ppm. The
mass spectrum of 5a yielded a prominent ion peak for Mþ at m=z 414.

Trisdialkylaminophosphines
1629
ꢁ
˚
Figure 1. Compound 4a: Selected bond lengths (A) and angles ( ): P1–O2 1.486
(2), P1–N7 1.640 (2), P1–N8 1.632 (2), P1–C15 1.804 (2), N7–C31 1.454 (4),
N7–C38 1.465 (4), N8–C34 1.457 (4), N8–C39 1.466 (4), C15–C12 1.353 (3),
O2–P1–N7 110.47 (11), O2–P1–N8 116.92 (11), O2–P1–C15 109.36 (10), N7–
P1–C15 111.48 (11), N8–P1–C15 104.59 (11), N8–P1–N7–C31 ꢀ48.2 (4), N7–
P1–N8–C34 169.0 (4), N8–P1–N7–C38 154.3 (4), N7–P1–N8–C39 ꢀ34.2 (4).
The structure of compound 5a is confirmed by X-ray analysis instead of
the expected imidazolone adduct 6 (cf. Fig. 2, Table 1, Scheme 3).
Similarly, 2b reacts with two mol. equivalents of trisdimethylamino-
phosphine (1a) in boiling toluene to give colorless crystalline compounds
formulated as 4b (major product) and 5b, whereas the reaction of 2b with
two mol. equivalents of 1a in boiling xylene gives 4b and 5b (major pro-
duct) (Scheme 2).
The structure of new compounds 4b and 5b are assigned on the basis
of their full set of spectral data (cf. Experimental).
It is worth mentioning that when 2a and 2b were allowed to react with
trisdimethylaminophosphine 1a using 1:1 mol. equivalents, a mixture of the
substrates and products 4a,b and 5a,b were obtained, whereas when using
two mol. equivalents of 1a, adducts were obtained as sole products.
A possible explanation for the reaction of trisdiameylamino-
phosphines 1a with 2a,b is shown in Scheme 2. Initial attack of

1630
M. H. N. Arsanious
Table 1. Crystal structure and data refinement parameters
Compound
4a
5a
Empirical formula
Formula weight
C29H34N5PO5
563.595
Monoclinic
11.3248 (4)
16.7066 (6)
18.2159 (8)
90.00
C21H27N4O3P
414.446
Prismatic
9.1887 (7)
10.6982 (8)
13.2843 (14)
98.851
104.953
114.654
1094.6 (2)
2
Crystal system=space group
˚
a (A)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
12. (18) ꢂ 1010
90.00
3
˚
V (A )
2960.7 (2)
4
1.264
0.14
Colorless=cube
298
Z
Dx (Mg=cmꢀ3
)
1.257
0.15
Colorless=prismatic
298
m (mmꢀ1
Color=shape
Temperature (K)
)
Theta range for collection
Reflections collected
Independent reflections
Data=restraints=parameters
R (gt)
2.910–21.967
6648
3948
262
0.060
Rint 0.035
2.910–22.986
4888
3387
356
0.053
Rint 0.049
Final R indices [I > 2r(I)]
aminophosphine 1a on the most reactive center of the a,b-unsaturated
carbonyl system leads to the formation of the dipolar adduct [A]. Addi-
tion of elements of water (unavoidable moisture) to intermediate [A] pro-
duces a transient intermediate [B] with pentacovalent phosphorus.[8]
Adducts 4a,b are then formed by loss of HNMe2 molecule followed by
auto-oxidation[16] of an intermediate such as [C] (Scheme 2).
Formation of products 5a and 5b can be explained in terms of fission of
the hydrazide bond of intermediate [C] followed by formation of the corre-
sponding cyanide by the action of excess of trisdialkylaminophoshine 1.[17,18]
The isolation of diarylideneazine confirms this postulation (Scheme 3).
We have also investigated the reaction of trisdialkylaminophosphine
1a,b with 1-arylidenamino-2-phenyl-4-aryliden-2-imidazolin-5-ones 3a,b to
establish whether they would behave in a similar manner. Thus, we have
found that the reaction of 1a and=or 1b with 3a and=or 3b in tetrahydro-
furan (THF) and=or toluene proceeds at room temperature to give chroma-
tographically pure adducts formulated as tetraalkylphosphonic diamides
7a–d (Scheme 4). The structural assignments for 7a–d were deduced from
1
their elemental analyses; infrared (IR); H, 13C, and 31P NMR, and mass
spectral data (cf. Experimental).

Trisdialkylaminophosphines
1631
ꢁ
˚
Figure 2. Compound 5a: Selected bond lengths (A) and angles ( ): P1–O2 1.483
(2), P1–N5 1.642 (3), P1–N7 1.641 (3), P1–C13 1.826 (4), N5–C25 1.434 (5),
N5–C28 1.469 (5), N7–C17 1.458 (5), N7–C23 1.442 (5), C13–C11 1.519 (5),
C16–N19 1.132 (5), O2–P1–N7 113.9(2), O2–P1–N5 110.1 (2), O2–P1–C13
108.76 (15), N7–P1–C13 107.9 (2), N5–P1–N7 106.7 (2), N5–P1–C13 109.4 (2),
N5–P1–N7–C23 ꢀ71.3 (6), N5–P1–N7–C17 87.1 (6), N7–P1–N5–C25 ꢀ40.1
(6), N7–P1–N5–C28 154.1 (7).
Scheme 3. Formation of adduct 5 not 6.

1632
M. H. N. Arsanious
Scheme 4.
From the results of the present investigation, it could be concluded that
the reaction of trisdimethylaminophosphines 1a with arylacrylohydrazides
2 leads to different products depending on the reactions conditions. Aryli-
deneimid-azolinones 3 react with trisdialkylaminophosphines 1a,b at room
temperature to give tetraalkylphosphonic diamides. Besides, the addition of
the phosphorus reagents occurs at the unsaturated carbon atom b- to the
carbonyl group of substrates 2 and 3 respectively to give the new substituted
dialkylamino-phosphoryl derivatives.
EXPERIMENTAL
Melting points were determined in open glass capillaries using an Electro-
themal IA 9000 series digital melting-point apparatus (Electrothermal,
Essex, U.K.) and are uncorrected. 2-Benzamido-N-arylidene-3-aryl-acryl-
hydrazides 2a,b and 1-arylidenamino-2-phenyl-4-aryliden-2-imidazolin-
5-ones 3a,b were prepared according to reported procedures.[19] The IR
spectra were measured in KBr pellets with a Perkin-Elmer Infracord spec-
1
trophotometer model 157 (Grating). The H and 13CNMR spectra were
recorded in CDCl3 and dimethyl sulfoxide (DMSO) as solvent on a Joel
300 MHz spectrometer, and the chemical shifts were recorded in d values
relative to tetramethylsilane (TMS). The 31P NMR spectra were taken
with a Varian CFT-20 (vs. external 85% H3PO4 standard). The mass
spectra were performed at 70 eV on a Shimadzu GCS-OP 1000 Ex

Trisdialkylaminophosphines
1633
spectrometer provided with a data system. Elemental analyses were per-
formed using the Elmeuter Varu EL (Germany) instrument.
Reaction of 2-Benzamido-N-(4-methoxybenzylidene)-3-(4-methoxyphenyl)
acrylohydrazide (2a) with Trisdimethylaminophosphine 1a
Trisdiamethylaminophosphine 1a (2 mmol) was added dropwise to a
solution of compound 2a (0.42 g, 1 mmol) in toluene (30 cm3), and the
reaction mixture was refluxed for 10–12 h. After evaporation of the vola-
tile materials under reduced pressure, the residue was applied to silica-gel
column chromatography. The eluent, yield, and mp are given for adducts
4a and 5a.
N-2-[Bis(dimethylamino) phosphoryl]-1-[(2-(4-methoxyphenyl) methylidene)
hydrazino)carbonyl]-2-[(4-methoxyphenyl)ethenyl]benzamide (4a)
Eluent: ethyl acetate=petroleum ether (65:35, v=v). Product 4a was
separated as colorless crystals, Yield 60%, mp 247–248ꢁC; 1H NMR
3
(300 MHz, CDCl3) d (ppm): 2.73{d, 12H, JHP ¼ 10.8 Hz, P-[N(CH3)2]2},
3.74, 3.81 [2s, 6H, 2 (OCH3)], 6.82–6.86 (d, 2H, J ¼ 8.1 Hz, Ar), 6.98–
7.01 (d, 2H, J ¼ 8.1 Hz, Ar), 7.45–7.48 (m, 5H, Ar), 7.82–7.85 (d, 2H,
J ¼ 8.1 Hz, Ar), 7.58 (s, 1H, ¼CH), 8.02–8.05 (d, 2H, J ¼ 8.1 Hz, Ar),
8.84, 9.88 (2s, 2H, 2NH); 13C NMR (75 MHz, CDCl3) d (ppm): 110.3 (d,
2
1JCP ¼ 141.7 Hz, C¼C-P), 128.7 (d, JCP ¼ 38.4 Hz, C¼C-P), 36.1{d,
2JCP ¼ 27 Hz, P[N-(CH3)2]}, 54.8, 54.5 (p-OCH3), 160.4, 113.0, 130.2,
126.4 (C6H4), 128.2, 126.2, 113.4, 158.5 (C6H4), 165.9, 165.6 (2C¼O),
144.6 (C¼N-N), 131.6, 128.1, 127.4, 126.0 (C6H5); IR (KBr): vmax=cmꢀ1
1692 (CONH), 3100 (NHCOPh), 1251 (P¼O), 1320, 860 [N(CH3)2]. MS
m=z (%) 563 (Mþ, 45). For C29H34N5O5P (563.58) calcd.: C, 61.80; H,
6.08; N, 12.43; P, 5.50%. Found: C, 61.86; H, 6.20; N, 12.36; P, 5.60%.
X-Ray Crystallographic Study[20–24]
A single crystal of 4a was grown by crystallization from cyclohexane. The
crystal structure was solved and refined, using maXus (Nonius, Delft,
˚
and Mac Science, Japan). Moka (k ¼ 0.71073 A) and a graphite mono-
chromator were used for data collection. A summary of the crystal ana-
lysis parameters is given in Table 1. CCDC 698572 contains the
supplementary crystallographic data for this article. These data can be
obtained free of charge from the Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.

1634
M. H. N. Arsanious
N-[2-[Bis(dimethylamino)phosphoryl]-1-cyano-2-(4-
methoxyphenyl)ethyl]benzamide (5a)
Eluent: acetone=petroleum ether (30:70, v=v). Product 5a was separated as
colorless crystals. Yield 20%; mp 226–227ꢁC; 1H NMR (300 MHz, CDCl3)
3
d (ppm): 2.85 [d, 12H, JHP ¼ 9.6 Hz, P(N-(CH3)2)2], 3.74 (dd, 1H,
3JHP ¼ 11.2 Hz, JHH ¼ 10.5Hz, CH-CH-P), 3.77 (s, 3H, p-OCH3), 5.31
(dd, 1H, 2JHP ¼ 24.6 Hz, JHH ¼ 10.5Hz, CH-CH-P), 6.85 (d, 1H, J ¼ 7.8 Hz,
Hz, Ar), 7.44–7.55 (m, 7H, Ar),7.95 (d, 1H, J ¼ 7.8 Hz, Ar), 9.49 (s, 1H,
NH). IR (KBr): vmax=cmꢀ1 1240 (P¼O), 1713 (C¼O), 3100 (NH); MS
m=z (%) 414 (Mþ, 100). For C21H27N4O3P (414.45) calcd.: C, 60.86; H,
6.57; N, 13.2; P, 7.47%. Found: C, 60.94; H, 6.76; N, 13.05; P, 7.54%.
X-Ray Crystallographic Study[20–24]
A single crystal of 5a was grown by crystallization from n-hexane. The
crystal structure was solved and refined using maXus (Nonius, Delft,
˚
and Mac Science, Japan). Moka (k ¼ 0.71073 A) and a graphite
monochromator were used for data collection. A summary of the crystal
analysis parameters is given in Table 1. CCDC 698573 contains the
supplementary crystallographic data for this article. These data can be
obtained free of charge from the Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Reaction of 2-(Benzamido)-N-benzylidene-3-phenylacrylohydrazide (2b)
with Trisdmethylaminophosphine 1a
To a solution of 2b (0.36 g, 1 mmol) in 30 cm3 toluene, trisdimethylamino-
phosphine 1a (2 mmol) was added dropwise at room temperature with
stirring, and the reaction mixture was refluxed for 6–8 h. The reaction
mixture was evaporated under reduced pressure, and the residue was
applied to silica-gel column chromatography. The eluent, yield, and mp
are given for adducts 4b and 5b.
N-2-[Bis(dimethylamino)phosphoryl]-1-[(2-(phenylmethyliden)hydrazino)
carbonyl]-2-[(4-methoxyphenyl)ethenyl]benzamide (4b)
Eluent: ethyl acetate=petroleum ether (60:40, v=v). Product 4b was sepa-
rated as colorless crystals. Yield 55%; mp 271–272ꢁC. 1H NMR
3
(300 MHz, CDCl3) d (ppm): 2.83 [d, 12H, JHP ¼ 8.1 Hz, P(N(CH3)2)2],

Trisdialkylaminophosphines
1635
7.91 (s, 1H, N¼CH), 7.28–7.24 (m, 10H, Ar), 7.51–7.46 (m, 5H, Ar), 9.55
(b, 2H, 2 NH). 13C NMR (75 MHz, CDCl3) d (ppm): 113.2 (d,
2
1JCP ¼ 141.2 Hz, C¼C-P), 128.2 (d, JCP ¼ 38.1 Hz, C¼C-P), 35.71{d,
2JCP ¼ 28.3 Hz, P[N (CH3)2]2}, 143.0 (N¼CH), 168.0, 163.6 (2C¼O).
IR (KBr): vmax=cmꢀ1 1230 (P ¼ O), 1692 (C¼O); MS m=z (%) 503
(Mþ, 20). For C27H30N5O3P (503.40) calcd. C, 64.40; H, 6.01; N,
13.91; P, 6.15. Found: C, 64.0; H, 6.12; N, 13.79; P, 6.10%.
N-[2-[Bis(dimethylamino)phosphoryl]-1-cyano-2-(phenyl)ethyl]benzamide
(5b)
Eluent: ethyl acetate=petroleum ether (60:40, v=v). Product 5b was sepa-
rated as colorless crystals. Yield 20%; mp 243–245ꢁC; 1H NMR
3
(300 MHz, CDCl3) d (ppm): 2.37 [d, 12H, JHP ¼ 9.2 Hz, P(N-(CH3)2)2],
3.79 (dd, 1H,3JHP ¼ 14.5 Hz, JHH ¼ 9.9 Hz, CH-CH-P), 5.32 (dd, 1H,
2JHP ¼ 22.1 Hz, JHH ¼ 9.9 Hz, CH-CH-P), 7.48–7.30 (m, 3H, Ar),7.55–
7.53 (m, 5H, Ar), 7.95–7.93 (d, 2H, Ar), 9.59 (s, 1H, NH). 13C NMR
(75 MHz, CDCl3) d (ppm): 43.1 (d,1JCP ¼ 136.25 Hz, HC-P), 44.1 (d,
2
2JCP ¼ 24.0 Hz, CH-CH-P), 36.4 {d, JCP ¼ 22.6 Hz, P[N-(CH3)2]},
116.4 (CN), 166.4 (C¼O), 132.1, 128.7, 127.3, 130 (C6H5); 31P NMR
(300 MHz, d (ppm): 33.5. IR (KBr): vmax=cmꢀ1 1240 (P¼O), 1715
(C¼O), 3200 (NH); MS m=z (%) 384 (Mþ, 100). For C20H25N4O2P
(384.41) calcd.: C, 62.49; H, 6.56; N, 14.57; P, 8.06%. Found: C, 62.56;
H, 6.49; N, 14.50; P, 8.16%.
Reaction of Trisdimethylaminophosphine 1a with 2a and=or 2b
To a solution of 2a and=or 2b (1 mmol) in 30 cm3 xylene, trisdialkylami-
nophosphine 1a (2 mmol) was added dropwise, and the reaction mixture
was refluxed for 3 h. After evaporation of the volatile materials under
reduced pressure, the residue was applied to silica-gel column chromato-
graphy to give 4a,b and 5a,b. Compounds 4 and 5 were obtained in
refluxing toluene in yields of 20% and 60%, respectively.
Reaction of 4-(4-Methoxybenzylidene)-1-(4-methoxybenzylideneamino)-2-
phenyl-1H-imidazol-5(4H)-one 3a with Ttrisdialkylaminophosphines 1a,b
To a solution of 3a (0.41 g, 1 mmol) in THF (20 cm3), 1a and=or 1b
(2 mmol) was added dropwise, and the reaction mixture was stirred for

1636
M. H. N. Arsanious
15–20 h at room temperature. The reaction mixture was evaporated
under reduced pressure, and the residue was applied to silica-gel column
chromatography. The eluent, yield, and mp are given for adducts 7a
and 7b.
N,N,N,N-Tetramethyl-P-{1-[(4-methoxyphenyl)methylidene]amino-
[(5-oxo-2-phenyl-4,5-dihydro-1H-imidazol-4-ylidene)(4-methoxyphenyl)
methyl]phosphonic diamide (7a)
Eluent: acetone=petroleum ether (25:75, v=v). Product 7a was separated
1
as colorless crystals. Yield 60%; mp 223–225ꢁC; H NMR (300 MHz,
3
CDCl3) d (ppm): 2.75 (d, 12H, JHP ¼ 9.9 Hz, P(N-CH3)2), 3.76, 3.83
(2s, 6H, 2OCH3), 6.88–6.85 (m, 4 H, Ar), 7.49–7.37 (m, 5H, Ar),
8.08–8.05 (m, 4H, Ar), 7.58 (s, 1H, ¼CH). 13C NMR (75 MHz, CDCl3)
1
2
d (ppm): 132.0 (C¼C-P, d, JCP ¼ 124.6 Hz), 135.8 [d, JCP ¼ 28.7 Hz,
2
P-C¼C], 42.5 {d, JCP ¼ 26.7 Hz, P[N(CH3)2]2}, 169.6 (C¼O), 164.1 (N
¼C-imidazolone), 154.8, 113.0, 126.1, 132.2 (C6H4), 158.6, 114.2, 127.6,
128.5 (C6H4), 132.1, 128.7, 127.3,130.4 (C6H5); 31P NMR (300 MHz) d
(ppm): 34.5; IR (KBr) vmax=cmꢀ11240 (P¼O),1312, 865 {P[N(Me)2]2};
MS m=z (%) 545 (Mþ, 35). For C29H32N5O4P (545.57) calcd.: C, 63.84;
H, 5.91; N, 12.84; P, 5.68%. Found: C, 63.95; H, 5.81; N, 12.70; P, 5.7%.
N,N,N,N-Tetraethyl-P-{1-[(4-methoxy-phenyl)methylidene]amino-
[(5-oxo-2-phenyl-4,5-dihydro-1H-imidazol-4-ylidene)
(4-methoxyphenyl)methyl]phosphonic diamide}(7b)
Eluent: ethyl acetate=petroleum ether (40:60, v=v). Product 7b was
separated as colorless crystals. Yield 70%, mp 233–235ꢁC; 1H NMR
(300 MHz, CDCl3) d (ppm): 1.06 [t, 12H, N-(CH2CH3)2], 3.87, 3.85
(2s, 6H, 2OCH3), 3.35 [q, 8H, N(CH2CH3)2], 6.82–6.91(m, 2H, Ar),
6.94 (d, 1H, J ¼ 8.7 Hz, Ar), 7.45–7.47 (m, 5H, Ar), 7.59–7.67 (m, 4H,
Ar), 8.40 (d, 1H, J ¼ 8.7 Hz, Ar), 7.56 (s, 1H, ¼CH). 13C NMR
1
(75 MHz, CDCl3) d (ppm): 132.7 (d, JCP ¼ 130.2 Hz, C¼C-P), 136.1
2
(d, JCP ¼ 32.2 Hz, C¼C-P), 168.2 (C¼O), 165.6 (N¼C), 40.6
2
[N(CH2CH3)2], 14.8 {d, JCP ¼ 22.4 Hz, P[N(CH2-CH3)2]}, 56.8, 54.8
(p-OCH3), 162.8, 113.0, 132.2, 126.0 (C6H4), 158.6, 114.2, 127.4, 128.1
(C6H4), 129.3, 127.5, 126.8, 131.3 (C6H5). IR (KBr): vmax=cmꢀ1 1240
(P¼O) cmꢀ1, 1310, 854 {P[N(Et)2]2}. MS m=z (%) 601 (Mþ, 12). For
C33H40N5O4P (601.68) calcd. C, 65.87; H, 6.70; N, 11.64; P, 5.15%.
Found: C, 65.90; H, 6.86; N, 11.58; P, 5.20%.

Trisdialkylaminophosphines
1637
Reaction of 4-(Benzylidene)-1-(benzylideneamino)-2-phenyl-1H-imidazol-
5(4H)-one (3b) with Trisdialkylaminophosphines 1a,b
To a solution of 3b (0.35 g, 1 mmol) in toluene (20 cm3), 1a and=or 1b
(2 mmol) were added dropwise, and the reaction mixture was stirred for
15–20 h at room temperature. The reaction mixture was evaporated under
reduced pressure, and the residue was applied to silica-gel column chro-
matography. The eluent, yield, and mp are given for adducts 7c and 7d.
N,N,N,N-Tetramethyl-P-{1-[(5-oxo-2-phenyl-1-[(phenymethylidene)-
amino]-4,5-dihydro-1 H-imidazol-4-ylidene)(phenyl)methyl]phosphonic
diamide (7c)
Eluent: acetone=petroleum ether (30:70, v=v). Product 7c was separated
as colorless crystals, (0.34 g, 72%). mp: 223ꢁC. 1H NMR (300 MHz,
3
CDCl3) d (ppm): 2.73 [d, 12 H, JHP ¼ 10.8 Hz, P(N(CH3)2)2], 7.91 (s,
1H, N¼CH), 7.32–7.24 (m, 10H, Ar), 7.52–7.4 (m, 5H, Ar) ppm; 13C
1
NMR (75 MHz, CDCl3) d (ppm): 134.2 (d, JCP ¼ 135.2 Hz, C¼C-P),
2
2
129.8 (d, JCP ¼ 28.1 Hz, C¼C-P), 35.7 {d, JCP ¼ 22.3 Hz, P[N(CH3)2]2},
143.0 (N¼CH), 168.0 (C¼O), 126.2, 129.5, 129.2, 126.0 (C6H5), 128.6,
124.2, 127.4, 128.1 (C6H5), 129.3, 127.5, 126.8, 127.3 (C6H5). 31P NMR
(300 MHz, CDCl3) d (ppm): 33.2. IR (KBr): vmax=cmꢀ1 1240 (P¼O),
1320, 860 {P[N-(Me)2]2}; MS m=z (%) 485 (Mþ, 14). For C27H28N5O2P
(485.52) calcd.: C, 66.79; H, 5.81; N, 14.42; P, 6.3. Found: C, 66.88; H,
5.72; N, 14.32; P, 6.28%.
N,N,N,N-Tetraethyl-P-{1-[(5-oxo-2-phenyl-1-[(phenymethylidene)
amino]-4,5-dihydro-1H-imidazol-4-ylidene)(phenyl)methyl]phosphonic}
diamide 7d
Eluent: acetone=petroleum ether (20:80, v=v). Product 7d was separated as
colorless crystals. Yield 70%, mp 214–215ꢁC; 1H NMR (300MHz, CDCl3)
d (ppm): 0.93 [t, 12H, N(CH2CH3)2], 3.87, 3.85 (2s 6H, 2OCH3), 4.24 [q, 8H,
N(CH2CH3)2], 7.45–7.47 (m, 5H, Ar), 7.59–7.67 (m, 10H, Ar),7.56 (s, 1H,
1
¼CH). 13C NMR (75MHz, CDCl3) d (ppm): 132.7 (d, JCP ¼ 140.4 Hz,
2
C¼C-P), 131.1 (d, JCP ¼ 36.8 Hz, C¼C-P), 40.8 [N(CH2-CH3)2], 14.6 {d,
2JCP ¼ 20.6 Hz, P[N(CH2CH3)2], 126.8, 131.0, 132.2, 126.0 (C6H5), 128.6,
124.2, 127.4, 128.1 (C6H5), 129.3, 127.5, 126.8, 131.3 (C6H5). IR (KBr)
v
max=cmꢀ1 1240 (P¼ O), 1315, 850 {P[N(Et)2]2. MS m=z (%) 541 (Mþ,
20). For C31H36N5O2P (541.62) calcd.: C, 68.74; H, 6.70; N, 12.93; P,
5.72. Found: C, 68.92; H, 6.82; N, 12.80; P, 5.60%.

1638
M. H. N. Arsanious
ACKNOWLEDGMENT
We thank Prof. Dr. Ibrahim S. A. Farag, Departement of Solid State
Physics, National Research Center, Dokki, Cairo, Egypt, and his cowor-
ker for doing X-ray diffraction analysis.
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