Reaction of 1,1-Bis(Diphenylphosphino)Methane with O-Quinones and Naphtho[2,1-B]Furan-1,2-Dione. Novel Synthesis of Bis(Diphenylphosphoryl) Derivatives and their Antimicrobial Activity

Article abstract of DOI:10.1080/10426507.2014.887077

The reaction of 1,1-bis(diphenylphosphino)methane with substituted o-quinones afforded the novel 6-[bis(diphenylphosphoryl)methyl]-and 6-bis(diphenyl phosphoryl)methylidene derivatives. Moreover, 1,1-bis(diphenylphosphino)methane reacts with 3,4,5,6-tetrabromo-o-benzoquinone to give only the new 6-[bis(diphenylphosphoryl)methyl] derivative. Mechanisms accounting for the formation of the new products are discussed. The antimicrobial activity of some of the newly synthesized compounds was also examined.

Full text of DOI:10.1080/10426507.2014.887077

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Phosphorus, Sulfur, and Silicon and the
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Reaction of 1,1-
Bis(Diphenylphosphino)Methane
with O-Quinones and Naphtho[2,1-
B]Furan-1,2-Dione. Novel Synthesis of
Bis(Diphenylphosphoryl) Derivatives and
their Antimicrobial Activity
Leila S. Boulosa, Ewies F. Ewiesa, Nabila M. Ibrahima & Maysa E.
Mohramb
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a Department of Organometallic and Organometalloid Chemistry,
National Research Centre, Dokki, Giza, Egypt
b Department of Microbial Chemistry, National Research Centre,
Dokki, Giza, Egypt
Accepted author version posted online: 30 Apr 2014.Published
online: 21 Oct 2014.
To cite this article: Leila S. Boulos, Ewies F. Ewies, Nabila M. Ibrahim & Maysa E. Mohram (2014)
Reaction of 1,1-Bis(Diphenylphosphino)Methane with O-Quinones and Naphtho[2,1-B]Furan-1,2-Dione.
Novel Synthesis of Bis(Diphenylphosphoryl) Derivatives and their Antimicrobial Activity, Phosphorus,
Sulfur, and Silicon and the Related Elements, 189:11, 1706-1717, DOI: 10.1080/10426507.2014.887077
To link to this article: http://dx.doi.org/10.1080/10426507.2014.887077
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Phosphorus, Sulfur, and Silicon, 189:1706–1717, 2014
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2014.887077
REACTION OF 1,1-BIS(DIPHENYLPHOSPHINO)
METHANE WITH O-QUINONES AND NAPHTHO
[2,1-B]FURAN-1,2-DIONE. NOVEL SYNTHESIS
OF BIS(DIPHENYLPHOSPHORYL) DERIVATIVES
AND THEIR ANTIMICROBIAL ACTIVITY
Leila S. Boulos,1 Ewies F. Ewies,1 Nabila M. Ibrahim,1
and Maysa E. Mohram2
1Department of Organometallic and Organometalloid Chemistry, National
Research Centre, Dokki, Giza, Egypt
2Department of Microbial Chemistry, National Research Centre, Dokki, Giza,
Egypt
GRAPHICAL ABSTRACT
O
O
Ph2P
O
PPh2
Ph2P
O
O
O
PPh2
OH
O
OH
O
PPh2
t-Bu
t-Bu
PPh2
O
O
t-Bu
t-Bu
Abstract The reaction of 1,1-bis(diphenylphosphino)methane with substituted o-quinones
afforded the novel 6-[bis(diphenylphosphoryl)methyl]- and 6-bis(diphenyl phospho-
ryl)methylidene derivatives. Moreover, 1,1-bis(diphenylphosphino)methane reacts with
3,4,5,6-tetrabromo-o-benzoquinone to give only the new 6-[bis(diphenylphosphoryl)methyl]
derivative. Mechanisms accounting for the formation of the new products are discussed. The
antimicrobial activity of some of the newly synthesized compounds was also examined.
Keywords 1,1-Bis(diphenylphosphino)methane; o-quinones; bis(diphenyl phosphoryl) deriva-
tives; antimicrobial activity
INTRODUCTION
o-Quinones and their derivatives are of great interest due to their significance in nature.
They play an important role in electron transport and possess various kinds of biological
Received 22 September 2013; accepted 21 January 2014.
Address correspondence to Leila S. Boulos, Department of Organometallic and Organometalloid Chemistry,
National Research Centre, El-Bohouth St., P.O. 12622, Dokki, Giza, Egypt. E-mail: leilagoubran@yahoo.com
1706

NOVEL SYNTHESIS OF BIS(DIPHENYLPHOSPHORYL) DERIVATIVES
1707
Ph2P
O
O
O
O
O
CH2
O
Ph2P
1
2
3
4
O
Br
O
Br
O
O
O
Br
O
O
Br
6
5
7
Figure 1 Starting materials (1–7).
activities. They are also used in the synthesis of metal complexes, nitrogen- or oxygen-
containing heterocycles, and in enantioselective synthesis.1–6 Trivalent phosphorus com-
pounds are widely used in o-quinone chemistry, as a rule, for the preparation of pentacoordi-
nated phosphorus derivatives (phosphoranes) or tetracoordinated ones (quasi-phosphonium
salts having a betaine structure with the P+–OC bond), which are used in organic syn-
thesis.7,8 Recently, we have reported that the reaction of 1,2-bis(diphenylphosphino)
ethane with substituted o-benzoquinones afforded the new bis(6-hydroxycyclohexa-2,4-
dienone) derivatives.9 In view of this and in continuation of our work in the reaction of
organophosphorus chemistry,10–13 it was of considerable interest to investigate the behavior
of 1,1-bis(diphenylphosphino) methane (1) toward o-quinones (2–5, 7) and naphtha[2,1-b]
furan-1,2-dione (6) (Figure 1).
RESULTS AND DISCUSSION
Chemistry
1,1-Bis(diphenylphosphino)methane (1) was treated with two mole equivalents
of 3,5-di-tert-butyl-o-benzoquinone (2) in dry toluene at reflux temperature for 7 h.
Column chromatography of the crude product yielded 6-[bis(diphenylphosphoryl)
methyl]-2,4-di-tert-butyl-6-hydroxycyclohexa-2,4-dien-1-one (10, 33%), 6-[bis(diphenyl-
phosphoryl)methylidene]-2,4-di-tert-butylcyclohexa-2,4-dien-1-one (11, 25%), and meth-
ane-1,2-diylbis(diphenylphosphane)dioxide (8, 10%). 3,5-Di-tert-butyl-catechol (9, 5%)
was also isolated and identified by comparing its melting point (mp 97◦C; Lit. 97–100◦C)
and IR spectrum with those of an authentic specimen.14 The most important feature of
structure 10 is the presence of one signal at δP = 24.2 ppm(s) in its 31P NMR spectrum.
Moreover, the 1H NMR spectrum of compound 10 (at 500 MHz) revealed signals at δH =
1.13 (s, 18H, t-Bu), 2.08 (dd, 2JHP = 25.27 Hz, 1H, Ph2P(O)-CH-P(O)Ph2) corresponding
to the methine proton attached to the two phosphorus atoms. The structure of compound
10 has also been assigned on the basis of 13C NMR data, elemental analysis, and mass
spectral data (FAB+, see Experimental section). Compound 8 (minor product, 10%) was
1
identified as methane-1,1-diylbis(diphenylphosphane)dioxide on the basis of the IR, H,
13C, 31P NMR, and mass spectral data,9,15 as well as by comparing its mp with that of

1708
L. S. BOULOS ET AL.
O
PPh2
PPh2
PPh2
t-Bu
O
t-Bu
OH
OH
H2C
[O]
+
H2C
+
O
PPh2
Redox reaction
O
1
8
t-Bu
t-Bu
toluene
5 h
2
9
condensation reaction
- H2O
addition reaction
2
+
2
+
O
O
PPh2
PPh2
OH
O
t-Bu
t-Bu
PPh2
PPh2
Reflux, toluene
48 h, - H2O
O
O
O
t-Bu
t-Bu
11
(25 %)
Scheme 1
(33 %)
10
a reference sample prepared by oxidation of 1 with hydrogen peroxide.15 It is worthy to
mention that refluxing equimolar amounts of 2 and 8 in dry toluene for 7 h also yielded a
mixture of the same phosphorylated products 10 (35%) and 11 (40%).
A possible explanation of the reaction course of bisphosphine 1 with o-quinone 2 is
depicted in Scheme 1. Apparently, this reaction is redox in nature leading to oxidation of
the tertiary phosphine 1 to the respective diphosphoryl species 8, whereby the o-quinone 2
is partially reduced to the respective dihydroxy derivative 9. Compounds 10 and 11 were
probably obtained through the methylene group in the resulting bisphosphoryl compound 8
by addition or condensation reaction with another molecule of quinone 2 (Scheme 1).9 Upon
refluxing 10 alone in dry toluene for a long period (48 h), it yields 11 almost quantitatively
(see Experimental section).
In accord with the mechanistic proposal, one equivalent of the corresponding catechol
should be formed during the oxidative conversion of 1 to diphosphoryl species 8 due to the
presence of unavoidable moisture that acts as the source of hydrogen and oxygen during
the reaction course.
The reaction of 1,1-bis(diphenylphosphino)methane (1) with phenanthrene-9,10-
dione (3) was also investigated. When two mole equivalents of 3 were treated with one
mole of 1,1-bis(diphenylphosphino)methane (1) in boiling toluene for 7 h, products 13
(34%), 14 (50%), and 8 (10%) were isolated together with phenanthrene-9,10-diol 12 (5%)
(Scheme 2). Structural assignments for compounds 13 and 14 are based upon elemental
1
analysis and spectroscopic (IR, H, 13C, 31P NMR, and mass spectrum (MS)) data (see
Experimental section).

NOVEL SYNTHESIS OF BIS(DIPHENYLPHOSPHORYL) DERIVATIVES
1709
O
PPh2
PPh2
PPh2
O
OH
OH
H2C
[O]
+
H2C
+
O
PPh2
Redox reaction
O
1
8
toluene
3
12
7 h
condensation reaction
addition reaction
3
+
3
- H2O
+
O
PPh2
O
PPh2
OH
PPh2
O
PPh2
O
O
O
14
13
Scheme 2
Similarly, when two moles of acenaphthenequinone (4) are allowed to react with
one mole equivalent of 1 in refluxing toluene for 7 h, 2-[bis(diphenylphosphoryl)methyl]-
2-hydroxyacenaphthylen-1(2H)-one (16), 2-[bis(diphenylphosphoryl)methylidene] acena-
phthylen-1(2H)-one (17), compound 8, and acenaphthylene-1,2-diol (15) are obtained14
(Scheme 3). The structures assigned for compounds 16, 17 are gained from their spectro-
scopic data (see Experimental section).
O
PPh2
OH
O
PPh2
+ 4
O
addition reaction
16
HO
OH
toluene
7h,
O
PPh2
[O]
+
4
1
8
+
Redox reaction
O
PPh2
O
+ 4
- H2O
15
condensation reaction
17
Scheme 3

1710
L. S. BOULOS ET AL.
O
PPh2
PPh2
PPh2
O
O
OH
OH
H2C
[O]
+
H2C
+
PPh2
Redox reaction
5
O
1
8
18
toluene
7 h
condensation reaction
addition reaction
5
- H2O
+
5
+
O
PPh2
O
PPh2
OH
PPh2
PPh2
O
O
O
O
20
19
Scheme 4
Similarly, o-naphthoquinone (5) reacts with 1 to give both the addition product 19
in a 32% yield and the condensation product 20 in a 28% yield as the major products.
Methane-1,1-diylbis(diphenylphosphane)dioxide (8) (10%) and benzocatechol 18 (5%)
were also isolated (Scheme 4). Structural assignments for compounds 19 and 20 are based
1
upon elemental analysis and spectroscopic (IR, H, 13C, 31P NMR, and MS) data (see
Experimental section).
Also, the study was extended to include the behavior of naphtho[2,1-b]furan-
1,2-dione (6) towards 1,1-bis(diphenylphosphino)methane (1) in order to determine the
preferential site of attack. We have found that when 6 was allowed to react with
1,1-bis(diphenylphosphino)methane (1) in refluxing toluene for 7 h, the corresponding
1-[bis(diphenylphosphoryl)methyl]-1-hydroxynaphtho[2,1-b]furan-2(1H)-one (22) and 1-
[bis(diphenylphosphoryl)methylidene]naphtho[2,1-b]furan-2(1H)-one (23) were isolated
as major products. Compound 8 and naphtho[2,1-b]furan-1,2-diol (21) were also isolated
and identified by comparing their mps and IR spectra with those of authentic specimens.14
Structural assignments for compounds 22 and 23 are based upon elemental analysis and
spectroscopic (IR, 1H, 13C, 31P NMR, and MS) data (see Experimental section).
On the other hand, when one mole equivalent of tetrabromo-o-benzoquinone (7)
was treated with one mole of 1,1-bis(diphenylphosphino)methane (1) in dry toluene at
room temperature for 3 h, the corresponding 6-[bis(diphenylphosphoryl)methyl]-2,3,4,5-
tetrabromo-6-hydroxycyclohexa-2,4-dien-1-one (25) was isolated as the major product
(61% yield). Methane-1,1-diylbis(diphenylphosphane) dioxide (8) was also isolated as a
minor product (10%). Tetrabromocatechol (24) was also isolated (5%) from the reaction

NOVEL SYNTHESIS OF BIS(DIPHENYLPHOSPHORYL) DERIVATIVES
1711
O
PPh2
PPh2
PPh2
O
OH
[O]
H2C
H2C
+
+
PPh2
Redox reaction
O
O
O
OH
O
8
21
6
1
toluene
condensation reaction
- H2O
addition reaction
6
+
6
+
O
PPh2
O
PPh2
OH
PPh2
O
PPh2
O
O
O
O
O
23
Scheme 5
22
mixture and identified by comparing its mp and IR spectra with those of an authentic
sample14 (Scheme 6).
ANTIMICROBIAL ACTIVITY
The antibacterial and antifungal activities16–20 were carried out in the Microbial
Chemistry Department, National Research Centre, using the diffusion plate method. A
filter paper sterilized disk saturated with the measured quantity (25 μL) of the sample
(1 mg/mL) was placed on a plate (9 cm diameter) containing a solid bacterial medium
(nutrient agar) or a fungal medium (potato dextrose agar) that was seeded with the spore
suspension of the test organism. After incubation at 37◦C for 24 h for bacteria (in case of
fungi, at 25◦C for 72 h), the diameter of the clear zone of inhibition surrounding the sample is
taken as a measure of the inhibitory power of the sample against the particular test organism
(% inhibition = sample inhibition zone (cm)/plate diameter × 100). All measurements were
done in methanol as a solvent that has zero inhibition activity. The antimicrobial activity
Br
Br
O
PPh2
O
PPh2
OH
O
+7
Br
Br
Br
OH
OH
[O]
Redox reaction
toluene
3 h
r.t.
H2C
1
7
+
+
PPh2
PPh2
O
stirring
O
Br
8
Br
Br
24
25
Scheme 6

1712
L. S. BOULOS ET AL.
of the new compounds was examined against Gram positive bacteria Bacillus subtilis,
Bacillus cereus, and Staphylococcus aureus, as well as Gram negative bacteria Escherichia
coli, Pseudomonas aeruginose and fungus Candida albicans. The obtained results are
compared with the reference antibiotics that were purchased from Egyptian markets.16–20
Tables S1 and S2 (supplemental materials) contain data of the antibacterial and antifungal
testing.
CONCLUSION
From the results of the present investigation, it can be concluded that although
1,1-bis(diphenylphosphino)methane (1) shows marked stability toward auto-oxidation even
upon prolonged heating solely in the presence of a solvent,9 it undergoes redox reaction
with o-quinones 2–5, 7, and naphtho[2,1-b]furan-1,2-dione (6) leading to bisphosphine
dioxide 8 together with the corresponding hydroquinones (9, 12, 15, 18, 21, 24). This
process is accompanied by addition or condensation reaction of 8 with another molecule
of the starting quinone.9 This mechanism represents a new model for phosphorylated aryl
compounds. Moreover, we noted that fast oxidation of the tertiary phosphine 1 in the redox
reaction with o-quinone prevents the lone pair on phosphorus in 1 to attack the carbonyl
carbon in o-quinones 2–5, 7, and in 6 according to the convention reaction.8b,21–23
EXPERIMENTAL
General Procedures for the Reaction of 1,1-Bis(diphenylphosphino)
methane (1) With o-Quinone 2–6
o-Quinones (2–6, 2 mmol) and 1,1-bis(diphenylphosphino)methane (1, 1 mmol)
were refluxed in dry toluene (30 mL) for 7 h and the reaction was followed by TLC (thin
layer chromatography). The volatile materials were evaporated under reduced pressure.
The residue was chromatographed on silica gel column to give two products: addition
hydroxyl derivatives (10, 13, 16, 19, or 22) and condensation derivatives (11, 14, 17, 20, or
23) together with methane-1,1-diylbis(diphenylphosphane)dioxide (8, data in supplemental
materials). Catechol (9, 12, 15, 18, or 21) was also isolated and identified by comparing its
melting point and IR spectrum with those of an authentic specimen.14 The supplemental
1
materials file contains sample H, 13C, and 31P NMR spectra for compounds 17 and 23
(Figures S1–S6).
Worthy of mention is that when 1,1-bis(diphenylphosphino)methane (1) was boiled
in dry tetrahydrofuran (THF) or dry toluene for more than 10 h, the same reagent 1 was
isolated unchanged (mp, mix mp).
Reaction of 3,5-Di-tert-butyl-o-benzoquinone (2) With Methane-1,
1-diylbis(diphenylphosphane)dioxide (8)
3,5-Di-tert-butyl-o-benzoquinone (2, 1 mmol) and methane-1,1-diylbis(diphenylpho
sphane)dioxide (8, 1 mmol) were refluxed in dry toluene (30 mL) for 7 h and the reaction
was followed by TLC. The volatile materials were evaporated under reduced pressure.
The residue was chromatographed on silica gel column to give the same phosphorylated
products 10 (35%) and 11 (40%).

NOVEL SYNTHESIS OF BIS(DIPHENYLPHOSPHORYL) DERIVATIVES
1713
Conversion of Addition Hydroxyl Derivative (10) and Condensation
Derivatives (11)
1 mmol of 6-[bis(diphenylphosphoryl)methyl]-2,4-di-tert-butyl-6-hydroxycyclohe-
xa-2,4-dien-1-one (10) was refluxed alone in dry toluene (30 mL) for 48 h and the reaction
was followed by TLC. The volatile materials were evaporated under reduced pressure. The
residue was washed by ethyl acetate (3∗20 mL) and recrystalized by ethyl acetate to give
6-[bis(diphenylphosphoryl)methylidene]-2,4-di-tert-butylcyclohexa-2,4-dien-1-one (11).
6-[Bis(diphenylphosphoryl)methyl]-2,4-di-tert-butyl-6-hydroxycy-
clohexa-2,4-dien-1-one (10)
Eluent: petroleum ether/acetone (90/10, v/v). Product 10 was separated as colorless
crystals, yield 0.27 g (33%). mp 182–184◦C. IR (KBr): ν˜ = 1182 (P O), 1435 (P-Ph),
1677 (C O), 3262 (OH) cm−1. 1H NMR (500 MHz, CDCl3): δ = 1.13 (s, 18H, tert-butyl),
2
2.08 (dd, JHP = 25.27 Hz, 1H, Ph2P(O)-CH-P(O)Ph2), 2.55 (s, 1H, OH, exchangeable
with D2O), 5.54, 7.28 (s, 2H, cyclohexadienone), 7.35–8.50 (m, 20H, Harom.) ppm. 13C
NMR (125 MHz, CDCl3): δ = 25.1 (d, JCP = 130 Hz, C P O), 30.2, 30.7, 31.3, 34.9 (4 s,
tert-butyl), 64.8 (cyclic C-OH, 2JCP = 40.1 Hz), 113.6, 129.3, 131.32, 132.4, 135.0, 140.4,
141.8, 144.8 (aromatic, C H), 162.50 (C O) ppm. 31P NMR (CDCl3): δ = 24.2 ppm.
MS (EI 70 eV): m/z (%) = 636 (10) [M]+, 435 (25) [M-201]+, 415(55) [Ph2P(O)-CH-
P(O)Ph2]+. Anal. Calcd. for C39H42O4P2 (636.7): C, 73.57; H, 6.65; P, 9.73. Found: C,
73.42; H, 6.60; P, 9.64.
6-[Bis(diphenylphosphoryl)methylidene]-2,4-di-tert-butylcyclohexa-
2,4-dien-1-one (11)
Eluent: petroleum ether/acetone (10/90, v/v). Product 11 was separated as yellow
crystals, yield 0.20 g (24%). mp > 320◦C. IR (KBr): ν˜ = 1190 (P O), 1644 (C C), 1698
1
(C O) cm−1. H NMR (500 MHz, CDCl3): δ = 1.02 (s, 18H, tert-butyl), 6.59, 7.28 (s,
2H, cyclohexadienone), 7.35–7.73 (m, 20H, Harom.) ppm. 13C NMR (125 MHz, CDCl3):
δ = 25.5, 27.4, 29.5, 30.9 (4 s, tert-butyl), 130.1 (d, JCP = 130 Hz, C P O), 150.1
(cyclic C = C P, 2JCP = 40.1 Hz), 113.6, 129.3, 131.32, 132.4, 135.0, 140.4, 141.8, 144.8
(aromatic, C H), 166.23 (C O) ppm. 31P NMR (CDCl3): δ = 30.9 ppm. MS (EI 70 eV):
m/z (%) = 618 (10) [M]+, 415 (65) [Ph2P(O)-CH-P(O)Ph2]+, 417 (20) [M-201]+. Anal.
Calcd. for C39H40O3P2 (618.25): C, 75.71; H, 6.52; P, 10.01. Found: C, 75.69; H, 6.60; P,
10.11.
10-[Bis(diphenylphosphoryl)methyl]-10-hydroxyphenanthren-9(10H)-
one (13)
Eluent: petroleum ether/ethyl acetate (93/7, v/v). Product 13 was separated as yellow
crystals, yield 0.26 g (34%). mp 178–180◦C. IR (KBr): ν˜ = 1185 (P O), 1693 (C O),
3260 (OH) cm−1. 1H NMR (500 MHz, CDCl3): δ = 2.04 (s, 1H, OH, exchangeable with
D2O), 4.03 (dd, 2JHP = 27.27 Hz, 1H, Ph2P(O)-CH-P(O)Ph2), 7.20–7.74 (m, 28H, Harom.
)
ppm. 13C NMR (125 MHz, CDCl3): δ = 21.7 (dd, JCP = 135.57 Hz, C P), 76.7 (d, 2JCP
= 55.38 Hz, cyclic C OH), 128.8, 128.9, 130.8, 131.3, 131.4, 131.8, 132.1, 132.2, 132.7
(aromatic C H), 175.75 (C O) ppm. 31P NMR (CDCl3): δ = 24.4 ppm. MS (EI 70 eV):

1714
L. S. BOULOS ET AL.
m/z (%) = 624 (15) [M]+, 423 (25) [M-(201)]+, 201 (50) [O=PPh2]. Anal. Calcd. for
C39H30O4P2 (624.16): C, 74.99; H, 4.84; P, 9.92. Found: C, 74.95; H, 3.99; P, 9.89.
10-[Bis(diphenylphosphoryl)methylidene]phenanthren-9(10H)-one (14)
Eluent: petroleum ether/ethyl acetate (80/20, v/v). Product 14 was separated as yellow
crystals, yield 0.39 g (50%). mp 128–130◦C. IR (KBr): ν˜ = 1180, 1185 (P O), 1445
(P-Ph), 1628 (C C) cm−1. 1H NMR (500 MHz, CDCl3): δ = 7.52–8.72 (m, 28H, Harom.
)
ppm. 13C NMR (125 MHz, CDCl3): δ = 122.8, 127.0, 129.4, 131.5, 132.1, 132.2, 132.7,
133.4 (aromatic C H), 131.5 (dd, JCP = 135.57 Hz, C P), 164.6 (dd, 2JCP = 55.38 Hz,
C C P), 178.7 (C O) ppm. 31P NMR (CDCl3): δ = 38.3 ppm. MS (EI 70 eV): m/z
(%) = 606 (15) [M]+, 405 (25) [M+-(201)]. Anal. Calcd. for C39H28O3P2 (606.59): C,
77.22; H, 4.65; P, 10.21. Found: C, 77.24; H, 4.61; P, 10.23.
2-[Bis(diphenylphosphoryl)methyl]-2-hydroxyacenaphthylen-1(2H)-one
(16)
Eluent: petroleum ether/ethyl acetate (85/15, v/v). Product 16 was separated as yellow
crystals, yield 0.28 g (36%). mp 148–150◦C. IR (KBr): ν˜ = 1180 (P O), 1447 (P-Ph), 1695
(C O), 3250 (OH) cm−1. 1H NMR (500 MHz, CDCl3): δ = 2.02 (s, 1H, OH, exchange-
able with D2O), 7.32–8.54 (m, JHH = 8.37 Hz, 26H, Harom) ppm. 13C NMR (125 MHz,
CDCl3): δ = 32.5 (dd, JCP = 135.57 Hz, C P), 128.1, 128.5, 130.4, 131.8, 132.6, 134.6,
135.1, 140.3 (aromatic C H), 189.7 (C O) ppm. 31P NMR (CDCl3): δ = 24.3 ppm. MS
(EI 70 eV): m/z (%) = 598 (15) [M]+, (80) 201 [O = PPh2]+. Anal. Calcd. for C37H28O4P2
(598.56): C, 74.24; H, 4.72; P, 10.35. Found: C, 74.22; H, 4.75; P, 10.31.
2-[Bis(diphenylphosphoryl)methylidene]acenaphthylen-1(2H)-one (17)
Eluent: petroleum ether/ethyl acetate (10/90, v/v). Product 17 was separated as brown
crystals, yield 0.34 g (44%). mp 243–245◦C. IR (KBr): ν˜ = 1185 (P O), 1445 (P-Ph),
1628 (C C), 1678 (C C) cm−1. 1H NMR (500 MHz, CDCl3): δ = 7.88–8.41 (m, JHH
=
8.37 Hz, 26H, Harom.) ppm. 13C NMR (125 MHz, CDCl3): δ = 121.7, 128.1, 129.1, 129.3,
131.0, 132.8 (aromatic C H), 144.8 (d, JCP = 135.57 Hz, C = P), 188.1 (C O) ppm. 31
P
NMR = 33.3 ppm. MS (EI 70 eV): m/z (%) = 580 (15) [M]+, 201(80) [O = PPh2]+. Anal.
Calcd. for C37H26O3P2 (580.55): C, 76.55; H, 4.51; P, 10.67. Found: C, 76.51; H, 4.53; P,
10.69.
2-[Bis(diphenylphosphoryl)methyl]-2-hydroxynaphthalen-1(2H)-
one (19)
Eluent: petroleum ether/ethyl acetate (80/20, v/v). Product 19 was separated as color-
less crystals, yield 0.22 g (32%). mp 138–140◦C. IR (KBr): ν˜ = 1187, 1190 (P O), 1698
(C O), 3265 (OH) cm−1. 1H NMR (500 MHz, CDCl3): δ = 2.03 (dd, 2JHP = 35.27 Hz,
1H, CH), 2.4 (s, 1H, OH, exchangeable with D2O), 7.32–7.87 (m, 26H, Harom.) ppm. 13
C
NMR (125 MHz, CDCl3): δ = 31.7 (dd, JCP = 135.57 Hz, 2JCP = 55.38 Hz, CH-P), 52.3
2
(dd, JCP = 55.38 Hz, cyclic C OH), 128.8, 128.9, 130.8, 131.3, 131.4, 131.8, 132.1,
132.2, 132.4, 134.3, 135.1, 136.9 (aromatic C H), 172.6 (C O) ppm. 31P NMR (CDCl3):
δ = 24.1 ppm. MS (EI 70 eV): m/z (%) = 574(15) [M]+, 373 (25) [M+-201]+, 201 (75)

NOVEL SYNTHESIS OF BIS(DIPHENYLPHOSPHORYL) DERIVATIVES
1715
[O PPh2]+. Anal. Calcd. for C37H28O4P2 (574.54): C, 73.17; H, 4.91; P, 10.78; found: C,
73.20; H, 4.90; P, 10.75.
2-[Bis(diphenylphosphoryl)methylidene]naphthalen-1(2H)-one (20)
Eluent: petroleum ether/ethyl acetate (20/80, v/v). Product 20 was separated as black
crystals, yield 0.19 g (28%). mp 238–240◦C. IR (KBr): ν˜ = IR (KBr): ν˜ = 1180, 1185
1
(P O), 1444 (P-Ph), 1626 (C C) cm−1. H NMR (500 MHz, CDCl3): δ = 7.52–8.72
(m, 26H, Harom.) ppm. 13C NMR (125 MHz, CDCl3): δ = 130.5 (dd, JCP = 135.57 Hz,
C P), 122.6, 125.1, 127.7, 128.9, 130.8, 131.3, 131.4, 131.8, 132.1, 132.2, 132.4, 133.2,
134.3, 135.1 (aromatic C H), 163.2 (dd, 2JCP = 55.38 Hz, C C P), 175.6 (C O) ppm.
31P NMR (CDCl3): δ = 21.3 ppm. MS (EI 70 eV): m/z (%) = 556 (15) [M]+, 201 (75)
[O PPh2]+. Anal. Calcd. for C37H26O3P2 (556.53): C, 75.54; H, 4.71; P, 11.13. Found: C,
75.55; H, 4.61; P, 11.15.
1-[Bis(diphenylphosphoryl)methyl]-1-hydroxynaphtho
[2,1-b]furan-2(1H)-one (22)
Eluent: petroleum ether/ethyl acetate (80/20, v/v). Product 22 was separated as yellow
crystals, yield 0.19 g (25%). mp < 300◦C. IR (KBr): ν˜ = 1185, 1195 (P O), 1672 (C O),
1
2
3250 (OH) cm−1. H NMR (500 MHz, CDCl3): δ = 3.98–4.06 (dd, JHP = 35.27 Hz,
1H, CH), 7.04–7.87 (m, 26H, Harom.) 8.02 (s, 1H, OH, exchangeable with D2O) ppm. 13
C
NMR (125 MHz, CDCl3): δ = 30.1 (dd, JCP = 135.57 Hz, 2JCP = 55.38 Hz, CH-P), 45.6
2
(dd, JCP = 55.38 Hz, cyclic C OH), 128.7, 128.9, 130.8, 131.3, 131.4, 131.8, 132.1,
132.2, 132.4, 133.2, 134.3, 135.1 (aromatic C H), 172.6 (C O) ppm. 31P NMR (CDCl3):
δ = 26.3 ppm. MS (EI 70 eV): m/z (%) = 614 (15) [M]+, 413 (25) [M-201]+. Anal. Calcd.
for C37H28O5P2 (614.56): C, 72.31; H, 4.59; P, 10.08. Found: C, 72.21; H, 4.60; P, 10.10.
1-[Bis(diphenylphosphoryl)methylidene]naphtho[2,1-b]furan-2(1H)-one
(23)
Eluent: petroleum ether/ethyl acetate (20/80, v/v). Product 23 was separated as color-
less crystals, yield 0.16 g (21%). mp 238–240◦C. IR (KBr): ν˜ = IR (KBr): ν˜ = 1180, 1190
(P O), 1634 (C C), 1726 (C O lactone) cm−1. 1H NMR (500 MHz, CDCl3): 6.22–8.01
(m, 26H, Harom.) ppm. 13C NMR (125 MHz, CDCl3): δ = 138.5 (dd, JCP = 135.57 Hz,
2JCP = 55.38 Hz, C P), 122.6, 125.1, 127.7, 128.9, 130.8, 131.3, 131.4, 131.8, 132.1,
2
132.2, 132.4, 133.2 (aromatic C H), 162.2 (dd, JCP = 55.38 Hz, cyclic C C), 169.5
(C O) ppm. 31P NMR (CDCl3): δ = 25.1 ppm. MS (EI 70 eV): m/z (%) = 596 (15) [M]+,
201 (75) [O PPh2]+. Anal. Calcd. for C37H26O4P2 (596.13): C, 74.49; H, 4.39; P, 10.38.
Found: C, 74.45; H, 4.41; P, 10.35.
Reaction of 1,1-Bis(diphenylphosphino)methane (1) with
3,4,5,6-Tetrabromo-o-benzoquinone (7)
0.42 g (1 mmol) 3,4,5,6-tetrabromo-o-benzoquinone (7) and 0.38 g (1 mmol) 1,1-
bis(diphenylphosphino)methane (1) were stirred in dry toluene (30 mL) at room temperature
for 3 h and the reaction was followed by TLC. The volatile materials were evaporated un-
der reduced pressure. The residue was chromatographed on silica gel column to give two

1716
L. S. BOULOS ET AL.
products 6-[bis(diphenylphosphoryl)methyl]-2,3,4,5-tetrabromo-6-hydroxycyclohexa-2,4-
dien-1-one (25) and methane-1,1-diylbis(diphenylphosphane)dioxide (8). Tetrabromocate-
chol (24) was also isolated and identified by comparing its mp 188–190◦C (Lit. 189–193◦C)
and IR spectra with those of an authentic specimen.
6-[Bis(diphenylphosphoryl)methyl]-2,3,4,5-tetrabromo-6-hydro-
xycyclohexa-2,4-dien-1-one (25)
Eluent: petroleum ether/ethyl acetate (75/25, v/v). Product 25 was separated as green
crystals, yield 0.49 g (61%). mp 223–225◦C. IR (KBr): ν˜ = 1185 (P O), 1435 (P-Ph), 1677
(C O), 3252 (OH) cm−1. 1H NMR (500 MHz, CDCl3): δ = 1.80 (s, 1H, OH, exchangeable
with D2O), 4.02 (dd, JHH = 5.6 Hz, 2JHP = 30 Hz, 1H, Ph2P(O)-CH-P(O)Ph2), 7.37–7.84
(m, 20H, Harom.) ppm. 13C NMR (125 MHz, CDCl3): δ = 30.7 (d, JCP = 130 Hz, C P O),
76.5 (cyclic C-OH, 2JCP = 40.1 Hz), 118.1, 125.3, 128.3, 129.3, 129.6, 131.2, 133.5, 142.9
(aromatic C H), 185.6 (C O) ppm. 31P NMR (CDCl3): δ = 24.3 ppm. MS (EI 70 eV): m/z
(%) = 840 (5) [M+], 638 (25) [M-201]+, 415 (85) [Ph2P(O)CH-P(O)Ph2]+. Anal. Calcd.
for C31H22Br4O4P2 (840.07): C, 44.32; H, 2.64; Br, 38.05; P, 7.37; found: C, 44.30; H,
2.65; Br, 38.15; P, 7.35.
SUPPLEMENTAL MATERIAL
Supplementary data for this article can be accessed on the publisher’s website,
www.tandfonline.com/gpss
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