Studies on organophosphorus compounds XI: The reaction of phosphorus reagents with hydrazonoyl halides, hydrazonoyl azides, and Shift's bases

Article abstract of DOI:10.1080/10426500500269968

N-(chloro-furan-2-yl)methylene-N′-(4-nitrophenyl)hydrazone (I) reacted with triethylphosphite to produce the phosphonate derivative III. The tetrazine derivative VI was produced by the interaction of I with diethyl-phosphite. Hydrazonoyl azide derivatives

Full text of DOI:10.1080/10426500500269968

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Phosphorus, Sulfur, and Silicon
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Studies on Organophosphorus
Compounds XI: The Reaction
of Phosphorus Reagents
With Hydrazonoyl Halides,
Hydrazonoyl Azides, and Shiff's
Bases
Nadia R. Mohamed a
a Photochemistry Department, National Research
Center , Dokki, Egypt
Published online: 01 Feb 2007.
To cite this article: Nadia R. Mohamed (2006) Studies on Organophosphorus
Compounds XI: The Reaction of Phosphorus Reagents With Hydrazonoyl Halides,
Hydrazonoyl Azides, and Shiff's Bases, Phosphorus, Sulfur, and Silicon and the Related
Elements, 181:3, 683-691, DOI: 10.1080/10426500500269968
To link to this article: http://dx.doi.org/10.1080/10426500500269968
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Phosphorus, Sulfur, and Silicon, 181:683–691, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500500269968
Studies on Organophosphorus Compounds XI:∗
The Reaction of Phosphorus Reagents With Hydrazonoyl
Halides, Hydrazonoyl Azides, and Shiff’s Bases
Nadia R. Mohamed
Photochemistry Department, National Research Center, Dokki, Egypt
N-(chloro-furan-2-yl)methylene-Nꢀ-(4-nitrophenyl)hydrazone (I) reacted with tri-
ethylphosphite to produce the phosphonate derivative III. The tetrazine derivative
VI was produced by the interaction of I with diethyl-phosphite. Hydrazonoyl azide
derivatives VIIIa–c reacted with triphenyl phosphine to form the iminophospho-
rane derivatives Xa–c. On the other hand, the azide derivative VIIIc reacted with
the phosphonium ylide XI to form the 1,2,3-triazole adduct XIII. The reaction of tri-
ethyl phosphite with Shiff’s bases XIVa–c yielded the corresponding phosphonates
XVa–c. The structures of the newly prepared compounds were confirmed with the
analytical and spectroscopic evidences.
Keywords Azides; hydrazonoyl halides; phosphines; phosphites; phosphonium ylides;
Shiff’s bases
INTRODUCTION
Hydrazonoyl halides have been extensively studied and have been
known as useful synthones for heterocyclic compounds.1−4 In a previous
work, we have examined the reactions of these halides with different
phosphorus reagents.5−8 This communication describes the behavior
of hydrazonoyl halides towards phosphites, phosphines, and phospho-
nium ylides. The work is extended also to include the reaction of some
of Shiff’s bases with triethyl phosphite.
DISCUSSION
We have found that the reaction of an equalmolar ratio of N-
(chloro-furan-2-yl)methylene-Nꢀ-(4-nitrophenyl)hydrazones (I) and tri-
ethyl phosphite (II) in toluene proceeded under the condition of the
∗C.f. Reference 20.
Received January 31, 2005; accepted April 15, 2005.
Address correspondence to Nadia R. Mohamed, National Research Center, Photo-
chemistry Department, Dokki, Egypt. E-mail: nadia ragab m@hotmail.com
683

684
N. R. Mohamed
Arbusov reaction9 via the loss of ethyl chloride to yield the phospho-
nate derivative III (Scheme 1).
SCHEME 1
Structure III is given to this product according to the analytical and
spectroscopic evidence. The Ms of compound III showed ion peaks at
m/z = 367 [M+], 338 [M+ C2H5], and at 230 [M+-O P(OC2H5)2]. Its IR
spectrum revealed the presence of strong bands at 1260 cm−1 (P O),
1
1030 [P O-alkyl], and 3400 (NH). Moreover, the H NMR spectrum
of this compound disclosed the presence of the characteristic triplet
quintet pattern for the ethoxy group attached to phosphorus: a triplet
at δ = 1.29 ppm (6H) and a quintet at δ = 4.23 ppm (4H). The furanyl
protons appeared as a triplet at δ = 6.7865 ppm (1H), two doublets at
δ = 6.65 ppm (1H), and at δ = 7.11 ppm (1H). The four aromatic protons
appeared as two doublets centered at δ = 7.50 ppm and at δ = 8.25 ppm
(AB system). The NH proton appeared as singlet at δ = 11.16 ppm.
The tetrazine VI was produced when diethyl phosphite IV and was
allowed to react with I under the same experimental conditions quan-
titatively. It was probably formed via a head-to-tail dimerization of the
corresponding nitrilimine V. The nitrilimine was firstly formed by the
action of I with dialkyl hydrogen phosphite in the presence of K2CO3.
Tetrazine derivatives were previously reported to be formed when com-
pound I in toluene was heated in the presence of triethylamine by a
similar head-to-tail dimerization10 (Scheme 2). The formation of these
derivatives could be explained also in terms of the Hard-Soft, Acid Base
principle.11−14 The structure of the tetrazine derivative V was sup-
ported by analytical and spectral evidences (c.f. Experimental section).
1-azido-1-(phenylhydrazone)propane-2-one, ethyl-1-azido-1-(pheny-
lhydrazone)acetate and N-(azido-thiophene-2-yl)methylene-Nꢀ(4-nitro-
phenyl)hydrazine VIIIa–c were prepared by the action of sodium azide
on the respective hydrazonoyl halides VIIa–c (c.f. Scheme 3).

Studies on Organophosphorus Compounds XI
685
SCHEME 2
SCHEME 3
We have found that the reaction of triphenyl phosphine IX with the
azide derivative VIIIa in dry benzene yielded a chromatographically
pure adduct formulated as Xa. The structure elucidation of this com-
pound was verified by the following evidences:
1. Correct analytical values corresponded to C27H24N3OP.
2. The Ms showed ion peaks at m/z = 437 [M+], 394 [M+-COCH3], 276
[N =P (C6H5)3], 303 [M+-C6H5N], and at 288 [M+-C6H5-N-NH].
3. The IR spectrum of compound Xa revealed the absence of the azide
absorption, which appeared as a strong band at ν = 2136 cm−1 in
the spectrum of the starting azide VIIIa. The spectrum showed

686
N. R. Mohamed
absorption bands at 1438 cm−1 (P-Ph), 1365 cm−1 (N = P), and 3250
cm−1 (NH).
1
4. The H NMR spectrum of this compound revealed the presence of
signals at δ = 2.25 ppm (3H, acetyl CH3, s), δ = 7.26–7.78 ppm (20H,
aromatic protons, m), and δ = 9.28 ppm (1H, NH, s).
5. The 31P NMR spectrum of this compound has one signal at δ = 20.10
ppm (iminophosphorane).
In a similar manner, the reaction of triphenylphosphine with azides
VIIIb, c proceeded under the same conditions to yield compounds bear-
ing the iminophosphorane structures Xb, c, respectively. This is based
on analytical and spectroscopic data (c. f. Experimental section).
It has been established15−17 that a nucleophilic attack by phosphorus
on azides gives rise to 3 dipolar ion structures A, B, C. Forms A and B
are resonance forms for D. However, form C decomposes to afford E
(Scheme 4). According to this assumption, a possible explanation for
the reaction of azides VIIIa–c is postulated. This involves an initial
attack of phosphorus on the azide nitrogen attached to the carbon atom
(form C) to give the iminophosphoranes (Xa–c).15
SCHEME 4
On the other hand, when azide VIIIc was allowed to react with
acetylmethylenetriphenylphosphorane XI, the 1,2,3-triazole adduct
XIII was produced in a quantitative yield. A mechanism that accounts
for the formation of this compound is depicted in Scheme 5. This in-
volves a 1,3 dipolar cycloaddition of azide VIIIc to the C C bond of the

Studies on Organophosphorus Compounds XI
687
ylide XI followed by the loss of triphenylphosphine oxide from the cyclic
intermediate XII to yield XIII (Scheme 5).
SCHEME 5
Structure elucidation of compound XIII was accomplished with
the following evidences: (a) correct analytical values correspond to
C14H11N6O2S; (b) the Ms of XIII showed ion peaks at m/z = 327 [M+],
39.15%, and m/z = 300 [M+-N2] and 27.09%, m/z = 109 [furyl-C=N];
and 41.31; and (c) the IR spectrum of XIII revealed the presence of the
triazole absorption band at 1180 cm−1 and NH absorption at 3180 cm−1
and (d) the 1H NMR spectrum showed signals at δ = 2.20 (d, 3H, CH3),
6.43 (d, 1H), 7.06 (t, 1H), 7.69 (d, 1H), for the thiophene protons. This is
beside two singlet signals at 7.98 and 10.72 for the triazole proton and
the NH, respectively.
A similar behavior of azide VIIIc towards ylide XI was previously
noticed when 3-azidotriazines reacted with the same ylide to produce
1-triazino-1,2,3-triazoles.18
SCHEME 6

688
N. R. Mohamed
Next, the reaction of triethylphosphite II with the Shiff’s bases
benzothiazo(2,l)-arylidine amine derivatives XIVa–c was investi-
gated.19 The reaction proceeded in toluene with stirring at r.t. overnight,
whereby the reactants disappeared (TLC) and the corresponding phos-
phonates XVa–c were produced and identified (Scheme 6). This is based
on analytical and spectroscopic evidences. (c.f. Experimental section).
EXPERIMENTAL
All melting points were uncorrected. Solvents used were distilled and
dried over sodium sulfate. Microanalysis experiments were carried out
in the analytical lab unit at the National Research Centre, Dokki,
Egypt. IR spectra were taken in KBr on a OK 9712 IR spectrometer
with DMSO-D6 as a solvent and TMS as an internal reference. Chemical
shifts are expressed as δ units (ppm). The mass spectra were recorded
on Kratos (75 ev) Ms equipment.
N-(DIETHYLPHOSPHONATE-FURAN-2-YL)METHYLENE-Nꢀ-
(4-NITROPHENYL)HYDRAZONE III
To a solution of hydrazonoyl halide I (2.66 g, 0.01 mol) in benzene, 30 mL
containing 0.5 gm of K2CO3, and triethylphosphite II (0.01 mol) was
added. The reaction mixture was stirred at r.t. for 3 h. The inorganic salt
filtered and the filterate was evaporated under vacuum. The remaining
residue triturated with n-hexane.
Compound III: yellow crystals, m.p. 88–89◦C cryst., solvent: ben-
zene, yield = 2.38 g, (65%) IR ν: 3400 (NH), 1260 (P O), 1030 (P-O-
alkyl) cm−1; 1H NMR (DMSO-D6) = δ 1.29 (t, 6H, 2CH3), 4.23 (quintet,
4H, 2CH2), 6.78 (t, 1H, furan protons), 6.65, 7.11 (2d, 2H, furan protons),
7.50, 8.25 (2d, 4H, aromatic protons), 11.16 (s, 1H, NH); MS: m/z = 376
(M+); 338 (M+-C2H5); 230 (M+-O=PO(C2H5)2). Anal. found C: 48.89; H:
4.71; N: 11.11; P: 8.14. Calcd. for C15H18N3O6P (367.30): C: 49.05; H: 4.
93; N: 11.44; P: 8.43.
REACTION OF HYDRAZONOYL HALIDE I WITH
DIETHYLPHOSPHITE
To a solution hydrazonoyl halide I (2.66 g, 0.01 mol) in benzene, 25 mL
containing 0.5 gm of K2CO3 and diethyl phosphite (0.01 mol) was added.
The reaction mixture was stirred for 3 h and then heated under reflux
for 3 h. The formed inorganic salt was isolated by filtration; the residual
material formed after evaporation of the solvent under vacuum was
treated with cyclohexane.

Studies on Organophosphorus Compounds XI
689
Compound VI: Pale yellow crystals, m.p. 164◦C cryst., solvent: cy-
1
clohexane; yield = 2.57 g, (68%) IR ν: 1560 aromatic C C; H NMR
(DMSO-D6) = δ 6.56 (m, 2H, furanyl protons), 7.01–7.13 (2d, 2H, fu-
ranyl protons), 7.47, 7.58 (2d, 2H, furanyl protons) 7.73 and 8.39 (m,
8H, aromatic protons). Ms: m/z = 458 [M+]; 221 [nitrile imine]. Anal.
found: C: 57.55; H: 3.68; N: 18.01. Calcd. for C22H14N6O6 (458.39): C:
57.64; H: 3.78; N: 18.33.
REACTION OF 1-AZIDOHYDRAZONOYL DERIVATIVES VIIIa–c
WITH TRIPHENYL PHOSPHINE
To a solution of azidohydrazonoyl derivatives VIIIa–c (0.01 mol) in
toluene, 25 mL of triphenyl phosphine (2.62 g, 0.01 mol) was added.
The reaction mixture was heated under reflux for 3 h. The residual
material remained after evaporation, and the solvent under vacuum
was treated with pet-ether at 80–100◦C.
Iminophosphorane Xa: Yellow crystals, m.p. 166◦C cryst., solvent:
benzene/n-hexane; yield = 1.45 g, (72%); IR ν: 3250 (NH), 1438 (P-Ph),
1
1365 (N P)cm−1; H NMR = δ 2.25 (s, 3H, CH3), 7.26–7.78 (m, 20H,
aromatic protons), 9.28 (s, 1H, NH) ppm. 31P NMR δ = 20.10 ppm (imino
phosphorane); MS: m/z = 437 (M+); 394 (M+-COCH3); 276 [N P(Ph)3]
303 (M+-NPh)] and 288 [M+-Ph-N-NH]. Anal. found: C: 74.10; H: 5.40;
N: 9.48; P: 6.97. Calcd. for C27H24N3OP (437.48): C: 74.12; H: 5.52; N:
9.60; P: 7.08.
Iminophosphorane Xb: Pale yellow crystals, m.p. 149–150◦C cryst.,
solvent: benzene, yield = 3.27 g, (70%); IR ν: 3300 (NH), 1440 (P-Ph),
1360 (N P)cm−1; 1H NMR (DMSO-d6) = δ 1.01 (t, 3H, CH3), 3.88 (q, 2H,
CH2), 6.74–7.52 (m, 10H, aromatic protons), 7.57–7.80 (m, 10, aromatic
protons), 9.01 (s, 1H, NH); MS: m/z = 467 [M+]. Anal. found: C: 71.63;
H: 5.49; N: 8.87; P: 6.50. Calcd. for C28H26N3O2P (467.51): C: 71.93; H:
5.60; N: 8.98; P: 6.62.
Iminophosphorane Xc: Orange crystals, m.p. 184◦C cryst., solvent:
cyclohexane; yield = 3.81 g, (71%); IR ν: 3305 (NH), 1435 (P-Ph), 1355
1
(N P)cm−1; H NMR (DMSO-d6) = δ 6.62 (m, 3H, thiophene protons),
7.61 (m, 4H-aromatic protons), 7.71–8.01 (m, 15H, aromatic protons),
9.30 (s, 1H, NH); MS: m/z = 522 [M+]. Anal. found: C: 66.60; H: 4.30;
N: 10.48; S: 6.00. Calcd. for C29H23N4O2SP (522.57): C: 66.65; H: 4.43;
N: 10.72; S: 6.13, P: 5.92.
N-(1,2,3-TRIAZOLO-THIOPHENE-2-YL)METHYLENE-Nꢀ-
(4-NITROPHENYL) HYDRAZINE XIII
A solution of toluene (30 mL) containing azido hydrazonoyl VIIIc
(2.88 g, 0.01 mol) and acetylmethylenetriphenylphosphorane XI

690
N. R. Mohamed
(3.18 g, 0.01 mol) was heated under reflux for 5 h. The solvent was
evaporated under vacuum. The remaining residue was treated with
MeOH.
Compound XIII: yellow crystals, m.p. 233◦C, cryst., solvent: MeOH;
1
yield = 1.79 gm (55%); IR ν: 3180 (NH), 1180 (triazole ab); H NMR
(DMSO-d6) = δ 2.20 (s, 3H, CH3), 6.43 (d, 1H, thiophene proton), 7.6
(t, 1H, thiophene proton), 7.69 (d, 1H, thiophene proton), 7.98 (s, 1H,
triazole protons), 10.72 (s, 1H, NH); Ms: m/z = 327 [M+]. Anal. found:
C: 51.25; H: 3.30; N: 25.55; S: 9.70. Calcd. for C14H11N6O2S (327.35): C:
51.36; H: 3.38; N: 25.67; S: 9.79.
REACTION OF SHIFF’S BASES WITH TRIETHYLPHOSPHITE
General Procedure
To a solution of benzene containing one of the Shiff’s bases XIV (0.01
mol), triethylphosphite (0.01 mol) was added. The reaction mixture was
heated under reflux for 6 h. The solvent was evaporated under vacuum
and the remaining residue was treated with the proper solvent.
Compound XVa: white crystals, m.p. 112◦C, cryst., solvent: benzene/
n-hexane; yield = 3.00 g (80%); IR ν: 3340 (NH), 1258 (P O), 1030 (P-
O-alkyl) cm−1; 1H NMR (DMSO-d6) = δ 1.08, 1.14 (2t, 6H, 2CH3), 3.79,
4.04 (2q, 4H, 2CH2), 5.65 (dd, 1H, CH; JHP = 22.4 Hz, JHH = 9.3 Hz),
7.02–7.38 (m, 5H, aromatic protons), 7.40–7.68 (m, 4H, aromatic pro-
tons), 9.07 (dd, 1H, NH, JHH = 9.3 Hz); MS: m/z = 376 [M+]. Anal. found:
C: 57.22; H: 5.51; N: 7.30; S: 8.38; P: 8.20. Calcd for C18H21N2O3SP
(376.42): C: 57.43; H: 5.62; N: 7.44; S: 8.51; P: 8.22.
Compound XVb: yellow crystals, m.p. 172◦C, cryst., solvent: benzene;
yield = 3.28 g (78%); IR ν: 3350 (NH), 1255 (P O), 1025 (P-O-alkyl)
cm−1; 1H NMR (DMSO-d6) = δ 1.05, 1.15 (2t, 6H, 2CH3), 3.80, 4.15 (2q,
4H, 2CH2), 5.75 (dd, 1H, CH; JHP = 22.4 Hz, JHH = 9.3 Hz), 6.95–7.32
(m, 4H, aromatic protons), 7.40–7.85 (m, 4H, aromatic protons), 9.25
(dd, 1H, NH, JHH = 9.3 Hz); MS: m/z = 421 [M+] Anal. found: C: 51.20;
H: 4.53; N: 9.90; S: 7.46; P: 7.24. Calcd. for C18H20N3O5SP (421.41): C:
51.30; H: 4.78; N: 9.97; S: 7.60; P: 7.35.
Compound XVc: pale yellow crystals, m.p. 195◦C, cryst., solvent: ben-
zene; yield = 3.07 g (75%); IR ν: 3400 (NH), 1258 (P O), 1025 (P-O-alkyl)
cm−1; 1H NMR (DMSO-d6) = δ 1.10, 1.25 (2t, 6H, 2CH3), 3.85, 4.20 (2q,
4H, 2CH2), 5.55 (dd, 1H, CH; JHP = 22.4 Hz, JHH = 9.3 Hz), 7.05-7.85
(m, 8H, aromatic protons), 9.28 (dd, 1H, NH, JHH = 9.3 Hz); MS: m/z =
410 [M+] Anal. found: C: 52.59; H: 4.85; N: 6.51; S: 7.66; Cl: 8.43; P:
7.51. Calcd. for C18H20N2O3SClP (410.86): C: 52.62; H: 4.90; N: 6.81; S:
7.80; Cl: 8.62; P: 7.53.

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691
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