Chemistry of phosphorus ylides. Part 25 [1]. Interaction of hexaphenylcarbodiphosphorane with carbonyls, hydrazone, and Mannich bases. A synthesis of phosphoranylidenes, phosphobetaines, and oxaphosphinin

Article abstract of DOI:10.1007/s00706-007-0843-7

The reaction of the allylic hexaphenylcarbodiphosphorane with carbonyls afforded the corresponding phosphoranylidene derivatives. On the other hand, the stable phosphorbetaines were obtained when the bisphosphorane was allowed to react with the α-diketone and triketone. The azaphosphoranylidene was isolated from the reaction of the bisphosphorane with hydrazone. Moreover, the bisphosphorane reacted with niclosamide and quinoline Mannich bases with the formation of the oxaphosphinins. When the Wittig reaction was performed with the new phosphoranes, the corresponding exocyclic olefins were obtained. On the other hand, the oxaphosphinins were produced when the phosphoranes were treated under the condition of a Hoffmann degradation reaction.

Full text of DOI:10.1007/s00706-007-0843-7

Monatsh Chem 139, 1299–1306 (2008)
DOI 10.1007/s00706-007-0843-7
Printed in The Netherlands
Chemistry of phosphorus ylides. Part 25 [1]. Interaction
of hexaphenylcarbodiphosphorane with carbonyls, hydrazone, and Mannich
bases. A synthesis of phosphoranylidenes, phosphobetaines, and oxaphosphinin
Medhat M. Said, Soher S. Maigali, Mansoura A. Abd-El-Maksoud, Fouad M. Soliman
Department of Organometallic and Organometalloide Chemistry, National Research Centre, Dokki, Cairo, Egypt
Received 4 October 2007; Accepted 30 October 2007; Published online 26 August 2008
# Springer-Verlag 2008
Abstract The reaction of the allylic hexaphenylcar-
bodiphosphorane with carbonyls afforded the cor-
responding phosphoranylidene derivatives. On the
other hand, the stable phosphorbetaines were obtained
when the bisphosphorane was allowed to react with
the ꢀ-diketone and triketone. The azaphosphor-
anylidene was isolated from the reaction of the
bisphosphorane with hydrazone. Moreover, the bis-
phosphorane reacted with niclosamide and quinoline
Mannich bases with the formation of the oxaphosphi-
nins. When the Wittig reaction was performed with
the new phosphoranes, the corresponding exocyclic
olefins were obtained. On the other hand, the oxaphos-
phinins were produced when the phosphoranes were
treated under the condition of a Hoffmann degradation
reaction.
miliar Wittig reagents and 1B implies a molecule
with heteroallene chemistry. In the scope of en-
hanced reactivity and versatility of its nucleophilic
reactions, this bisylide can be considered as an im-
portant reagent used by Bestmann [2] in organic
synthesis, in particular products which are often
difficult to prepare by other methods. Moreover, it
has attracted recent interest because of its impor-
tance as a C-donor ligand in organometallic chem-
istry and various transition metal complexes [3]. It
gives coinage metal complexes with organometallic
compounds [4] and has triboluminescent properties
[5]. On the other hand, the ylide and its derivatives
have different biological applications as fungicides
for soil born-organisms and phytopathogenic fungi
[6].
Moreover, they are used as antiparasitics, which
control large number of helminthes in sheeps [7].
Keywords Hexaphenylcarbodiphosphorane; Phosphoranyl-
idenes; Phosphobetaines; Oxaphosphinins.
Results and discussion
Introduction
As an ongoing program devoted to produce new
bioactive heterocyclic phosphorus compounds [8],
the reaction of hexaphenylcarbodiphosphorane (1),
with ꢀ-diketones 2, 5, p-quinone 7, triketone 9,
2-hydroxyisoindole-1,3-dione (11), indandione 13,
hydrazone 15, and Mannich bases 19 and 26 was
studied.
The phosphallene ylide hexaphenylcarbodiphospho-
rane can be illustrated in two major resonance forms.
The first resonance form 1A, is similar to the fa-
Correspondence: Medhat M. Said, Department of Organome-
tallic and Organometalloide Chemistry, National Research
Centre, El-Tahrir Street, Dokki, Cairo, Egypt. E-mail:
solimanfma@hotmail.com
Thus, naphtho[2,1-b]furan-1,2-dione (2), was trea-
ted with one mole equivalent of hexaphenylcarbodi-

1300
M. M. Said et al.
phosphorane (1), in THF at room temperature for
3 h, and 3-[(triphenylphosphoranylidene)methylene]-
naphtho[2,1-b]furan-2-one (4) together with triphen-
ylphosphine oxide was isolated. The elemental
microanalyses, IR, 13C, 31P NMR, and MS data
agree with structure 4. The IR spectrum showed
strong absorption bands at ꢁꢀ¼ 1610 (C¼O), 1560
(C¼P) and 1440cmꢀ1 (P-phenyl) [9]. In the 13C
NMR spectrum of 4, a signal was observed at
ꢂ ¼ 165.00 ppm, which is attributed to the lactone-
carbonyl, no peak for the keto-carbonyl function,
which appear in the starting material 2 at ꢂ ¼
190.16 ppm [10]. A signal at ꢂ ¼ þ20.50 ppm was
observed in the 31P NMR which fits with phosphor-
anes [11], and in the mass spectrum, the Mþ was
found at m=z ¼ 456 (Scheme 1).
Scheme 1

Chemistry of phosphorus ylides
1301
It could be demonstrated that the formation of
the phosphoranylidene 4 from the reaction of bis
phosphorane 1 and benzocoumarandione 2 can
be explained by initial nucleophilic attack of the
carbanion center in the bisylide 1 on the reactive
keto-carbonyl function in 2 rather than the lactone-
carbonyl [12], to give the phosphobetaine 3a, which
is transformed to the four-membered unstable 1,2-
oxaphosphetane intermediate 3b. The original ylide
C–P bond of 3b is then cleaved to give the zwitter-
ionic adduct 3c. Triphenylphosphine oxide is elimi-
nated with the formation of 4.
When the bisphosphorane 1 was allowed to react
with 5-methylbenzo[b]thiophene-2,3-dione (5), the
reaction occurred at ambient temperature to give
the stable phosphobetaine adduct 6. The structure
of the phosphobetaine 6, was proved from analytical
and spectroscopic data. Its IR spectrum showed
bands at ꢁꢀ¼ 1651 (C¼O, thio-lactone), 1608 (C¼P),
and 1481 cmꢀ1 (P-phenyl). In the 1H NMR spectrum
of 6, signals observed at ꢂ ¼ 2.25 (s, 3H, CH3) and
ꢂ ¼ 7.5 (m, 33H, aromatics) ppm. The 31P NMR
shifts recorded for compound 6 were ꢂ ¼ 20.49 and
25.94 ppm. The values are in accord with ylidene
phosphorane and betaine [11, 13]. In the MS of 6 the
Mþ was found at m=z ¼ 714.
phino]hydrazono]indane-1,3-dione (16) was ob-
tained as red crystals. The IR spectrum of 16
revealed the absence of NH group, and showed bands
at ꢁꢀ¼ 1690, 1650 (C¼O), 1590 (C¼P), and 1490 cmꢀ1
1
(P-phenyl). Moreover, the H NMR of 16 showed
2
signals at ꢂ ¼ 6.4 (dd, 1H, JHP ¼ 21 Hz, CH¼P)
and ꢂ ¼ 7.4 (m, 39H, aromatics) ppm. The 31P
NMR shifts recorded for 16 were ꢂ ¼ 17.44 (P-yli-
dene) and ꢂ ¼ 26.06 (P–N) ppm. The MS showed the
molecular ion peak at m=z ¼ 786.
Niclosamide, (5-chloro-N-(2-chloro-4-nitrophe-
nyl)-2-hydroxybenzamide) (18), is the active in-
gredient of bayluscide, which has been used as
molluscicide of great significance in the last decade
[14]. It is widely used in control programmes, and
is still the molluscicide of choice, since it is effect-
tive against most aquatic snails and its activity per-
sists for several months. Also, it does not adversely
affect any economically important crop plants and
shows no cumulative toxicity on animals [15].
Niclosamide has been introduced as an official drug
in many pharmacopoeas [16]. Therefore, the pres-
ent investigation was extended to synthesize the
niclosamide Mannich base derivatives 19a and
19b, and react them with the bisphosphorane 1 to
prepare the new oxaphosphinin niclosamide deriva-
tive 22 of biological interest. The Mannich reaction
was carried out in neutral media using the bifunc-
tional niclosamide 18 as substrate, formaldehyde,
piperidine, or morpholine as the reagents. When
the bisphosphorane 1, was allowed to react with
niclosamide Mannich bases 19a or 19b, in dry
boiling toluene for 4 h, the corresponding 6-chloro-
N-(2-chloro-4-nitrophenyl)-3,4-dihydro-2,2,2-triphe-
nyl-3-(triphenylphosphoranylidene)-2H-benzo[e]-
1,2-oxaphosphin-8-carboxamide (22) was only
obtained. The IR spectrum of 22 showed bands at
ꢁꢀ¼ 3397 (NH), 1670 (CO, amide), 1570 (C¼P), and
1436 (P-aryl) cmꢀ1. In the 1H NMR spectrum of 22,
When 2,5-diphenyl-p-benzoquinone (7), was al-
lowed to react with one mole or two moles of
the bisphosphorane 1 under the same experimental
conditions, only one product, namely, 2,5-diphenyl-
4-[(triphenylphosphoranylidene)methylene]cyclohexa-
2,5-diene-1-one (8) was isolated.
The reaction of vicinal triketone with 1 was inves-
tigated, too. When 1,2,3-indantrione (9), was allowed
to react with the bisphosphorane 1, the corresponding
phosphobetaine adduct 10 was obtained.
In addition, we studied the behavior of the
bifunctional compounds, 2-hydroxyisoindole-1,3-
dione (11) and indane-1,3-dione (13), towards the
bisphosphorane 1. The reaction proceeded like in
the case of the p-quinone 7, with the formation of
2-hydroxy-3-(triphenylphosphoranylidene)methylene]-
2,3-dihydroisoindol-1-one (12) and 3-[(triphenylphos-
phoranylidene)methylene]indan-1-one (14). No
protonation reaction was observed with >N–OH and
>CH2 groups, even when two moles of the bispho-
sphorane 1 were used.
3
signals at ꢂ ¼ 3.45 (d, JPH ¼ 16 Hz, CH2), ꢂ ¼ 7.40
(m, 35H, aromatics), and ꢂ ¼ 10.5 (s, NH, exchange-
able with D2O) ppm were observed. The 31P NMR
shifts recorded for 22 were ꢂ ¼ 20.35 (phosphorany-
lidene) and ꢂ ¼ 50.35 (oxaphosphinin) ppm [2a].
Presence of the carbonyl amide group in 22 was also
attested by a signal at ꢂ ¼ 163.05 ppm in its 13C NMR
and the Mþ of 22 is at m=z ¼ 874. Compound 22
is equally obtained irrespective whether one or two
mole equivalents of the bisphosphorane 1 are used
When 2-(phenylhydrazono)indan-1,3-dione (15)
was treated with the bisphosphorane 1, 2-[phenyl-
[triphenyl[(triphenylphosphoranylidene)methyl]phos- (Scheme 2).

1302
M. M. Said et al.
Scheme 2
When the Wittig reaction [17] was carried
spectrum of 23, showed signals at ꢂ ¼ 3.84 (s, CH2),
ꢂ ¼ 6.01 (s, CH), ꢂ ¼ 7.51 (m, 24H, aromatics) and
ꢂ ¼ 10.5 (s, NH, exchangeable with D2O) ppm. A
signal at ꢂ ¼ 50.34 ppm was observed in the 31P
NMR of 23, and m=z was found at 747 (Mþ) in the
mass spectrum. Under the condition of Hoffmann
degradation reaction [18] in which 22 was heated for
45 min (110ꢁC) under reduced pressure (0.5 mm Hg),
the corresponding N-(2-chloro-4-nitrophenyl)(6-
out with the oxaphosphinin compound 22, using
4-nitrobenzaldehyde, the new excocyclic olefin
6-chloro-N-(2-chloro-4-nitrophenyl)-3,4-dihydro-
2,2,2-triphenyl-3-(4-nitrobenzylidene)-2H-benzo[e]-
1,2-oxaphosphin-8-carboxamide (23), was isolated
together with triphenylphosphine oxide. The IR
spectrum of 23 showed bands at ꢁꢀ¼ 3200 (NH),
1
1650 (C¼O), and 1430 cmꢀ1 (P-aryl). The H NMR

Chemistry of phosphorus ylides
1303
Scheme 3
chloro-2,2,2-triphenylbenzo[e]-1,2-oxaphosphin-8-
yl)carboxamide (24) was obtained. Compound 24
was formed via migration of the ꢀ-proton in 22, with
expulsion of triphenylphosphine. The IR spectrum
of 24, revealed the presence of strong absorption
bands at ꢁꢀ¼ 3293 (NH), 1663 (C¼O, amide), and
biological and industrial interest. When 7[piperi-
din-1-yl)methyl]quinolin-8-ol (26) was treated with
one mole equivalent of the bisphosphorane 1, the
corresponding triphenyl(3,4-dihydro-2,2,2-triphe-
nyl-2H-1,2-oxaphosphino[5,6-h]quinolin-3-ylidene)-
phosphine (27) was obtained. 3,4-Dihydro-2,2,2-
triphenyl-3-(4-nitrobenzylidene)-2H-1,2-oxaphos-
phino[5,6-h]quinoline (28) was obtained when 27
was treated with 4-nitrobenzaldehyde under the con-
dition of a Wittig reaction. When 27 was heated for
45min (160ꢁC) under reduced pressure (0.5 mm Hg),
the new 2,2,2-triphenyl-2H-1,2-oxaphosphino[5,6-h]-
quinoline (29) was isolated.
1
1494 cmꢀ1 (P-phenyl). In the H NMR spectrum of
24, signals appeared at ꢂ ¼ 7.61 (m, 22H, aromatics)
and ꢂ ¼ 10.5 (s, NH, exchangeable with D2O) ppm.
Moreover, one signal at ꢂ ¼ 50.39 ppm was observed
in its 31P NMR spectrum, and the mass spectrum
showed a peak at m=z ¼ 613 (M þ H)þ.
8-Hydroxyquinoline (25) has been found effective
in controlling photodegradation of the Neem based
pesticide azadirachtin-A derivatives [19]. Moreover,
its derivatives are used as antimalarial drugs [20],
and their copper complexes are useful as chemother-
apeutic agents [21]. Furthermore, they have also
been tested for their antiretroviral activity in HIV-1
infected cells [22]. Therefore, it was of interest to
study the reaction of the bisphosphorane 1 with
the 8-hydroxyquinoline Mannich base 26 to prepare
oxaphosphinoquinoline derivatives of anticipated
Conclusions
The results of the present investigation represent an
interesting approach to the synthesis of new bioac-
tive heterocyclic phosphorus compounds by direct
routes. It can be rationalized that the reaction of
hexaphenylcarbodiphosphorane (1), with the ꢀ-dike-
tones 2 and 5, p-quinone 7, and triketone 9 occurs
by a [2 þ 2] cycloaddition of the reactive carbonyl

1304
M. M. Said et al.
11, 13, or hydrazone 15 (0.01 mol) in 50 cm3 THF. The
reaction mixture was stirred from 3 to 6 h until no more
of the starting materials could be detected (TLC). THF was
distilled off under reduced pressure and the remaining resi-
due was crystallized from the appropriate solvent to give
the phosphoranylidenes 4, 8, 12, 14, phosphobetaines 6, 10,
or azaphosphoranylidene 16. When the reaction was repeated
using one mole of carbonyls 2, 5, 7, 9, 11, 13, or hydrazone 15
and two moles of the hexaphenylcarbodiphosphorane (1) the
same products were isolated of phosphoranylidenes 4, 8, 12,
14, betaines 6, 10, or azaphosphoranylidene 16.
group to the ylidic C¼P of the bisphosphorane 1 to
yield the phosphobetaines, which are stable like
compounds 6 and 10.
On the other hand, the intermediate betains of the
starting materials 2 and 7 are unstable and transformed
to the phosphoranylidenes 4 and 8 with the elimination
of triphenylphosphine oxide. In the case of the bifunc-
tional compounds 11 and 13, the reaction proceeded
like in the case with p-quinone 7 with the formation of
the phosphoranylidenes 12 and 14, even when two
moles of the bisphosphorane 1 are used. In the case
of the 1:1 adduct 16 produced from the reaction of
the (phenylhydrazono)indandione (15) and the bispho-
sphorane 1, this adduct was recovered practically un-
changed under the condition of intramolecular Wittig
olefination and no diazaphosphinin 17 and triphenyl-
phosphine oxide were obtained. On the other hand, the
bisphosphorane 1 reacted readily with the phenolic
OH group of the Mannich base 19 to give firstly
the phosphorus ylide 20, which is transformed into
the intermediate 21 by nucleophilic substitution of
the dialkylamine anion. Elimination of the amine
from 21 afforded the oxaphosphinin 22. In addition,
the new heterocyclic phosphorus compounds, oxa-
phosphinins 23, 24, 28, and 29 were obtained by
applying the Wittig and Hoffmann degradation reac-
tions on 22 and 27. These processes can be consid-
ered as new and simple routes for the preparation
of different ring systems, which can not be obtained
by other conventional methods.
3-[(Triphenylphosphoranylidene)methylene]naphtho[2,1-b]-
furan-2-one (4, C31H21O2P)
Mp 182ꢁC (benzene=pet.ether.); yield 85% (yellow crystals).
2,5-Diphenyl-4-[(triphenylphosphoranylidene)methylene]-
cyclohexa-2,5-diene-1-one (8, C37H27OP)
The residue was chromatographed on silica gel using pet.-
ether=acetone as eluent (50=50, v=v) and yielded the phos-
phoranylidene 8. It was recrystallized from cyclohexane. Mp
198ꢁC; yield 60% (buff crystals); IR: ꢁꢀ¼ 1791 (C¼O), 1630
(C¼P), 1471 (P-phenyl) cmꢀ1
;
13C NMR: ꢂ ¼ 178.74 (C¼O)
31
ppm; P NMR: ꢂ ¼ 20.03 ppm; MS: m=z ¼ 518 (Mþ).
2-Hydroxy-3-[(triphenylphosphoranylidene)methylene]-2,3-
dihydroisoindol-1-one (12, C27H20NO2P)
Purification on silica gel column using pet-ether=acetone
(65=35, v=v) as an eluent yielded phosphoranylidene 12. It
was recrystallized from n-hexane. Mp 128ꢁC; yield 60% (or-
ange crystals); IR: ꢁꢀ¼ 3434 (OH), 1699 (C¼O), 1681 (C¼P),
1488 (P-phenyl) cmꢀ1; 1H NMR: ꢂ ¼ 7.5 (m, 19H, aromatics),
9.8 (s, 1H, OH, exchangeable with D2O) ppm; 31P NMR:
ꢂ ¼ 20.47 ppm; MS: m=z ¼ 420 (M–H)þ.
3-[(Triphenylphosphoranylidene)methylene]indan-1-one
(14, C28H21OP)
Experimental
Mp 175ꢁC (benzene); yield 40% (violet crystal); IR: ꢁꢀ¼ 1610
(C¼O) cmꢀ1
;
1H NMR: ꢂ ¼ 3.70, 7.5 (m, 19H, aromatic)
All melting points were measured on a Gallenkamp electrother-
mal melting point apparatus. The infrared spectra were re-
corded using KBr pellets on a Pye unicam SP 3300 and FTIR
8101PC Shimadzu Infrared Spectrometers. NMR spectra were
obtained in CDCl3 or DMSO-d6 on a Varian Mercury (1H:
300 MHz, 13C: 75 MHz) spectrometer using TMS as an internal
reference.31P NMR spectra were run on the same spectrometer
using H3PO4 (85%) as external reference. Mass spectra were
recorded on a Shimadzu GC-MS QP 1000 Ex Spectrometer (EI,
70eV). Elemental analyses were carried out at Microanalytical
center of National Research Center, El-Tahrir Street, Dokki,
Cairo. The results were in agreement with the calculated values.
31
ppm; P NMR ꢂ ¼ 20.51 ppm; MS: m=z ¼ 403 (M–H)þ.
2,3-Dihydro-5-methyl-2-oxo-3-[(triphenylphosphinio)-
(triphenylphosphoranyliden)methyl]benzo[b]thiophene-3-
olat (6, C46H36O2P2S)
Mp 150ꢁC (chloroform=pet.ether.); yield 70% ( pink crystals).
1,3-Dioxo-2-[(triphenylphosphinio)(triphenylphos-
phoranyliden)methyl]indan-2-olat (10, C16H34O3P2)
Mp 142ꢁC (benzene=pet.ether.); yield 40% (brown crystals);
IR: ꢁꢀ¼ 1777, 1718 (C¼O), 1588 (C¼P), 1479 (P-phenyl)
1
cmꢀ1; H NMR (CDCl3): ꢂ ¼ 7.8 (m, 19H, aromatics) ppm;
31P NMR: ꢂ ¼ 20.51 (P-ylidene), 26.00 (P-betaine) ppm; MS:
Reaction of hexaphenylcarbodiphosphorane (1) with
carbonyls 2, 5, 7, 9, 11, 13, and hydrazone 15.
Synthesis of phosphoranylidenes 4, 8, 12, 14,
m=z ¼ 695 (M–H)þ.
2-[Phenyl-[1,1,1-triphenyl]phosphino]hydrazono-
[(triphenylphosphoranylidene)-methyl]indane-1,3-dione
(16, C52H40N2O2P2)
phosphobetaines 6, 10, and azaphosphoranylidene 16
A solution of hexaphenylcarbodiphosphorane (1) [23]
(0.01 mol) in 50 cm3 THF was added with stirring at
room temperature to the solution of carbonyls 2, 5, 7, 9,
Mp 223ꢁC, yield 75% (red crystals).

Chemistry of phosphorus ylides
1305
Attempted cyclization of azaphosphoranylidene (16)
When 16 was boiled in toluene for 12 h or heated
alone at 180ꢁC for 1 h under reduced pressure (0.5 mm
Hg), neither diazaphosphinin 17 nor triphenylphosphine
oxide were obtained, and 16 was recovered practically
unchanged.
6-Chloro-N-(2-chloro-4-nitrophenyl)-3,4-dihydro-2,2,2-
triphenyl-3-(4-nitrobenzylidene)-2H-benzo[e]-1,2-
oxaphosphin-8-carboxamide (23, C40H28Cl2N3O6P)
A mixture of oxaphosphinin 22 (0.01 mol) and 4-nitrobenzal-
dehyde (0.01 mol) in dry toluene was refluxed for 10h. Tolu-
ene was distilled off and the residue was crystallized from
benzene=pet.ether to give the exocyclic olefin. Mp 197ꢁC
(benzene=pet.ether); yield 65% (orange crystals). The benzene
filtrate afforded upon concentration and addition of pet.ether,
colorless crystals of triphenylphosphine oxide (mp and mixed
mp 151ꢁC) [25].
Mannich reaction on niclosamide [5-chloro-N-(2-chloro-4-
nitrophenyl)]-2-hydroxybenzamide (18)
An aqueous solution of formaldehyde (40%, 0.01 mol) was
added dropwise with stirring to a solution of niclosamide
(18) [24] and the amine (piperidine or morpholine)
(0.011 mol) in about 40 cm3 of ethanol, while maintaining
the temperature below 10ꢁC. The reaction mixture was
then boiled under reflux for 2 h, and left overnight at room
temperature. After removing the volatile materials under
reduced pressure, the product was isolated and recrystal-
lized from ethanol. When the above described procedure
was performed using two mole equivalents of both of the
base and aqueous formaldehyde no change in the nature of
the products was observed and the corresponding niclosa-
mide Mannich bases 19a and 19b were obtained.
N-(2-Chloro-4-nitrophenyl)-6-chloro-2,2,2-triphenyl-2H-
benzo[e]-1,2-oxaphosphin-8-carboxamide
(24, C33H23Cl2N2O4P)
When 0.6 g oxaphosphinin 22 were heated in an oil bath for
45 min at 110ꢁC under reduced pressure (1 mm Hg) the
residue was triturated with ether, filtered off, and recrystal-
lized from chloroform=pet.ether to give 0.3 g of the oxapho-
sphinin derivative 24. Mp 202ꢁC (chloroform=pet.ether);
yield 50% (buff crystals). Triphenylphosphine was isolated
from the filtrate upon concentration. (mp and mixed mp
78ꢁC).
5-Chloro-N-(2-chloro-4-nitrophenyl)-2-hydroxy-3-
(piperidinomethyl)benzamide (19a, C19H19Cl2N3O4)
Mp 232ꢁC (acetone=n-hexane); yield 87% (yellow powder);
IR (KBr): ꢁꢀ¼ 3422 (OH), 3222 (NH), 2633(CH2), 1655
Triphenyl(3,4-dihydro-2,2,2-triphenyl-2H-1,2-oxaphosphino-
[5,6-h]quinolin-3-ylidene)phosphine (27, C47H37NOP2)
To
a solution of 5.36g hexaphenylcarbodiphosphorane
(C¼O, amide) cmꢀ1
;
1H NMR (CDCl3): ꢂ ¼ 2.5 (t, 4H, 2
(1) (0.01 mol) in 20cm3 dry toluene, was added a solution of
2.42g 8-hydroxyquinoline Mannich base (26) [26] (0.01 mol)
in 30cm3 of dry toluene. The reaction mixture was refluxed
for 6 h. After the solvent was distilled off under reduced pres-
sure, the residue was recrystallized from ether=pet.ether to
provide 3.46g of oxaphosphinoquinoline (27). Mp 142ꢁC;
CH2 morpholin), 3.0 (t, 4H, 2 CH2 morpholin), 3.5 (s, 2H,
CH2), 4.4 (s, H, NH), 8.6 (OH), 7.8 (m, 5H, aromatics) ppm;
MS: m=z ¼ 424.
5-Chloro-N-(2-chloro-4-nitrophenyl)-2-hydroxy-3-
(morpholinomethyl)benzamide (19b, C18H17Cl2N3O5)
Mp >300ꢁC (ethanol); yield 95% (yellow powder); IR
(KBr): 3422 (OH), 3222 (NH), 2633(CH2), 1671 (C¼O,
amide) cmꢀ1; 1H NMR (CDCl3): ꢂ ¼ 2.5 (t, 4H, 2CH2 mor-
pholin), 3.0 (t, 4H, 2CH2 morpholin), 3.5 (s, 2H, CH2), 4.4
(s, H, NH), 8.6 (OH), 7.8 (m, 5H, aromatics) ppm; MS:
m=z ¼ 426.
1
3
yield 65% (brown crystal); H NMR: ꢂ ¼ 3.36 (d, JHP
¼
16.5 Hz, CH2), 7.69 (m, 35 H, aromatics) ppm; 31P NMR:
ꢂ ¼ 20.33 (phosphoranylidene) ꢂ ¼ 50.34 (oxaphosphinin)
ppm; MS: m=z ¼ 692 (M–H)þ.
3,4-Dihydro-2,2,2-triphenyl-3-(4-nitrobenzylidene)-2H-1,2-
oxaphosphino[5,6-h]quinoline (28, C36H27N2O3P)
A mixture of 0.64 g oxaphosphinoquinoline 27 (0.01 mol)
and 1.7 g 4-nitrobenzaldehyde in 50 cm3 toluene was re-
fluxed for 10 h. Toluene was distilled off and the residue
was crystallized from benzene to give 0.56 g of the exocylic
olefin. Mp 202ꢁC (benzene=pet.ether); yield 65% (yellow
The reaction of niclosamide Mannich base 19a with
hexaphenylcarbodiphosphorane (1). 6-Chloro-N-(2-chloro-4-
nitrophenyl)-3,4-dihydro-2,2,2-triphenyl-3-
(triphenylphosphoranylidene)-2H-benzo[e]-1,2-
1
crystal). The distinguishing features of the H NMR spec-
oxaphosphin-8-carboxamide (22, C51H38Cl2N2O4P2)
A mixture of niclosamide Mannich base 19a (0.01 mol),
5.3 g hexaphenylcarbodiphosphorane (1) (0.01 mol), and
40 cm3 toluene was boiled for 6 h until no more of the
starting materials could be detected. Toluene was removed
under vacuum and the residue that remained was crystal-
lized from ether=pet.ether to give oxaphosphinin 22. Mp
>300ꢁC (ether=pet.ether); yield 70% (brown crystals).
When the reaction was repeated using one mole of the
second niclosamide Mannich base 19b and hexaphenyl-
carbodiphosphorane (1), the same oxaphosphinin 22 was
obtained.
trum of 28, were the presence of signals at ꢂ ¼ 3.38 (s,
CH2), 6.51 (s, ¼CH), 7.65 (m, 24H, aromatics) ppm; 31P
NMR: ꢂ ¼ 50.34 ppm; MS: m=z ¼ 565 (M–H)þ. The ben-
zene filtrate afforded upon concentration and addition of
n-hexane, colorless crystals of triphenylphosphine oxide,
mp 151ꢁC [25].
2,2,2-Triphenyl-2H-1,2-oxaphosphino[5,6-h]quinoline
(29, C29H22NOP)
Oxaphosphinoquinoline 27 (0.69 g, 1 mmol) was heated for
45min at 160oC under reduced pressure (0.5mm Hg) until

1306
M. M. Said et al.
no more of the starting material could be detected (TLC). The
residue that remained was recrystallized from CH2Cl2=
pet.ether to give 0.43g 29. Mp 216ꢁC (CH2Cl2=pet.ether);
yield 30% (buff powder); 31P NMR: ꢂ ¼ 55.40 ppm; MS:
m=z ¼ 431 (Mþ). The dichloromethane filtrate afforded color-
less crystals of triphenylphosphine upon concentration and
addition of pet.ether mp 78ꢁC.
11. a) Wm Johnson A (1993) Ylides and Imine of Phosphorus,
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12. a) Mustafa A, Sidky MM, Soliman FM (1966) Tetrahe-
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19:245
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