Phosphorylation of some new acenaphthenequinone derivatives

Article abstract of DOI:10.1007/s10593-009-0363-y

Acenaphthenequinone reacted with diazofluorene, diphenyldiazomethane, phenybenzoyldiazomethane, phenacyl chloride, o-nitrobenzyl chloride, and diazohydroindenedione to give new oxadiazole, ketoepoxide and dioxadiazepine derivatives. They reacted with trip

Full text of DOI:10.1007/s10593-009-0363-y

Chemistry of Heterocyclic Compounds, Vol. 45, No. 8, 2009
PHOSPHORYLATION OF SOME
NEW ACENAPHTHENEQUINONE
DERIVATIVES
E. A. El-Sawi1*, T. B. Mostafa1, and H. A. Radwan1
Acenaphthenequinone reacted with diazofluorene, diphenyldiazomethane, phenybenzoyldiazomethane,
phenacyl chloride, o-nitrobenzyl chloride, and diazohydroindenedione to give new oxadiazole,
ketoepoxide and dioxadiazepine derivatives. They reacted with triphenylphosphine and triethylphosphite
to give new organophosphorus compounds containing a six-membered or four-membered phosphorane
ring. The structures were elucidated using IR, UV, NMR, and mass spectra, and elemental analyses.
Keywords: acenaphthenequinone, dioxadiazepine, epoxides, oxadiazole, phosphorane, phosphory-
lation.
Many earlier studies have been reported on the reactions of phenanthrenequinones with diazomethane.
Arndt [1] found that it gave the monoethylene oxide derivative when the reaction was carried out using ether
and a small amount of methanol. Reinvestigation of the same reaction [2], using dioxirane containing a small
amount of methanol, gave monospiroepoxy ketone, and in tetrahydrofuran with a small amount of lithium
chloride the product was the bis-epoxide, while in the presence of a large amount of methanol ring expansion
took place.
The reaction of some derivatives of diazomethane with phenanthrenequinone [2-4] gave a
methylenedioxy derivative. The reaction of diphenyldiazomethane and di(p-chlorophenyl)diazomethane with
phenanthrenequinone showed that the structures must be corrected to the ketoepoxide [5]. 3,6-Dibromo-9,10-
phenanthrene reacted with diazoalkanes to give the corresponding ketoepoxide derivatives [6]. The o-methyl
ether of isatin reacted with diazomethane to furnish a quinoline derivative as the major product, together with a
spirooxirane derivative [7]. It has been reported [8] that p-chloroacetophenone reacted with diphenyl-
diazomethane and diazofluorene in benzene in the presence of copper bronze to give nitrogen- and halogen-free
new compounds and p-chlorophenol. The reaction of diazomethane derivatives with 1,2-naphthoquinone-
4-sulfonic acid in benzene gave α-ketoepoxides, cyclopropane, and methylenedioxy derivatives, accompanied
_______
* To whom correspondence should be addressed, e-mail: elsawi_e@yahoo.com.
1Chemistry Department, Faculty of Girls for Arts, Science and Education, Ain Shams University, Heliopolis,
Cairo, Egypt.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1233-1243, August, 2009.
Original article submitted December 31, 2008.
0009-3122/09/4508-0981©2009 Springer Science+Business Media, Inc.
981

by desulfonation reactions [9]. The reaction of 3,4-dimethoxyacetophenone with 2-diazo-1,3-dihydroindenedione,
diphenyldiazomethane, and 9-diazofluorene in chlorobenzene proceeded with formation of new four-, five-, and six-
membered rings. These compounds reacted with triphenylphosphine to give five- and six-membered heterorings
via ring opening and cyclization [10]. A derivative of the 2,2-dihydro-1,2-oxaphospholane-4 ring system was
obtained from the reaction of 3-benzylidene-2,4-pentanedione with trimethyl phosphate [11].
Triphenylphosphine and trimethylphosphite as nucleophiles reacted with ketoepoxides spiro(oxirane-
2,9-phenanthrenes) to give heterocyclic hexaoxyphosphorane compound [12]. Triphenylphosphine reacted with
3,4-cyclopropane-1,2-ketoepoxide derivatives of naphthalene to give a four-membered heterophosphorus ring via
cyclization (tetraoxyphosphorane) [13].
We investigated the reaction of the new compounds 1-3 with triphenylphosphine, where phosphorus is in a
low oxidation state, in order to study the mechanism of the reaction.
In continuation of our previous work, the present work is directed toward studying the reactions of some
quinones with diazomethane derivatives, phenacyl chloride, and o-nitrobenzyl chloride, and the reactions of the
products with organophosphorus compounds to obtain new compounds of the expected biological activity.
Acenaphthenequinone reacted with 9-diazofluorene in benzene under reflux for 5 h to give an oxadiazole
derivative 1. The reaction mechanism may be as follows:
O
O
C
N
O
C
N
O
+
N
N
–
O
C
–
N
N
+
O
+
1
The IR spectrum of compound 1 shows the presence of the bands νC=O at 1718 and νN=N at 1622 cm–1.
Diphenyldiazomethane, phenylbenzoyl diazomethane, phenacyl chloride, and o-nitrobenzyl chloride
reacted with acenaphthenequinone to give yellow, green-yellow, and pale-brown ketoepoxide products 2a-d.
O
N
N
O
R
O
O
O
O
R1
2a–d
3
2 a R = R1 = Ph, b R = Ph, R1 = COPh; c R = COPh, R1 = H; d R = o-O2NC6H4, R1 = H
The IR spectra for compounds 3a and 3b show νoxirane at 1267 and 829 cm–1 [14]. For compound 2a its
spectrum shows one νC=O at 1720 cm–1, while the spectrum of compound 2b shows two νC=O at 1731 and 1681
cm–1. The mass spectrum for compound 2b confirmed the suggested structure. The spectrum did not show the
molecular ion peak; the base peak was m/e 167 (Scheme 1).
982

Scheme 1
O
O
+
O
CH
.
C
.
C
–COPh
m/e 195(13.76%)
m/e 165 (48.31%)
O
C
O
C
a
–H
O
O
b
c
O
Ph
+
.
.
C
Ph
+
HC
.
C
Ph
Ph
c-cleavage
m/e 195
β-cleavage
+
M. wt. 376
+
m/e 166 (18.53%)
+H
+H α-cleavage
O
+
O
+
.
O
CH
+
O
C
.
O
Ph
C
H
C
H2C
Ph
Ph
m/e 196
m/e 167 (100%)
+H
O
–CH2P
m/e 300 (17.97%)
+
.
+
+H
C
Ph
O
m/e 105
O
O
CHO
C
+
+
m/e 168 (28.93%)
Ph
+H
HO
+
O
+
.
+
.
m/e 301 (34.26%)
Ph
H
C
m/e 106
+H
–C
–
+
m/e 169 (2.24%)
.
HO
O
CHO
Ph
–OH
C
+
+
.
.
CH2
.
C
m/e 77
m/e 51
–
m/e 302 (7.86%)
+
m/e 152 (27.52%)
The IR spectrum for compound 2c shows νC–H at 2950, two νC=O at 1728 and 1690, and νoxirane at 1228, 852,
and 827 cm–1. The IR spectrum for compound 2d shows νC–H at 2955–2852, νC=O at 1728, νC–H at 3378, νNO2 at 1522
and 1340, and νoxirane at 1187, 856, and 820 cm–1.
Acenaphthenequinone reacted with 2-diazo-1,3-dihydroindenedione in benzene under reflux to give
dioxadiazepine 3.
983

The suggested structure is based on the following data from elemental analysis, IR, and UV/Vis spectra.
Fluorenylidene derivative
oxadiazaphosphorane 4.
1
reacted with triphenylphosphine to give
a
six-membered ring
The reaction mechanism may be as follows:
C
C
N
O
N
O
C
O
O
C
N
N
N
O
O
+
N
–
+
PPh3
N
O
N
PPh3
P
Ph3
O
+
–
..
PPh3
4
1
Its IR spectrum shows a new absorption band due to νP–Ph at 1440 and νC=O at 1717 cm–1, indicating the
presence of one C=O group. The mass spectrum shows the molecular ion peak [M−2]+ at m/e 634 (1.49%) and the
base peak at m/e 356 (100%) (Table 1).
The reactions of triphenylphosphine with α-ketoepoxide derivatives 2a–d in tetrahydrofuran gave new
products via nucleophilic attack of the trivalent phosphorus on the electron-deficient carbon followed by bond
cleavage and cyclization with the formation of a four-membered heterophosphorus ring (tetraoxyphosphorane
compounds) 5a–d.
TABLE 1. The Fragments of Product 4 with their % Relative Abundances
Relative
m/e
Fragment
1
abundance, %
3
2
N
N
C
O
O
634
1.49
P
Ph3
+
[M–2]
O
Ph
Ph
Ph
Ph
Ph
Ph
P
P
552
499
1.25
1.99
C
Ph
Ph
O
N
+
C H
O
4
6
N
984

TABLE 1 (continued)
1
2
3
+
.
356
100
N
N
+
327
77.71
277
254
191
4.36
6.23
1.74
+
P
O
+
C4H5
P
O
+
N
N
C
178
166
29.51%
3.11%
C
+
N
O
+
:
C
.
+
163
74
74.89%
4.61%
C
..
+
.
C6H5
C
+
.
C
C
CH
HC
C
985

The mechanism of the reaction may be as follows:
Ph
P
Ph
P
Ph
Ph
Ph
Ph
–
–
:PPh3
O
C
O
C
O
C
+
O
O
O
R
R1
O
R
R1
R
R1
O
R
R1
+
:PPh3
+
5a–d
5a R = R1 = Ph, b R = Ph, R1 = COPh; c R = COPh, R1 = H; d R = o-O2NC6H4, R1 = H
The IR spectrum for compounds 5a shows νC=O at 1726, νP–Ph at 1437, and νP–O–C at 1022 cm–1, while the IR
spectrum for compound 5b shows two bands νC=O at 1727 and 1690, νP–Ph at 1448, and νP–O–C at 1034 cm–1. The
UV/Vis spectrum for compound 5b shows λmax at 348 nm (ε 2.0×104) and a shoulder at 350 nm (ε 1.3×103). The IR
spectrum for compound 5c shows νC–H at 2926, two νC=O at 1727, 1690, νPPh at 1449, and νP–O–C at 1188 cm–1. For
compound 5d the IR spectrum shows νC–H at 2968–2852, only one νC=O at 1728, νP–Ph at 1460, and νP–O–C at 1187
cm–1. The UV/Vis spectrum for compound 5c shows λmax at 348 nm (ε 2.0×104). The signal δ 5.32 ppm (1H) in the
1H NMR spectrum of compound 5d can be attributed to CH (methine) protons.
Triphenylphosphine reacted with dioxadiazepine derivative 3 to give 6-membered oxadiazaphosphorane 6.
O
O
N
O
N
P
Ph3
O
6
The IR spectrum shows 3 bands νC=O at 1774, 1722, 1673, νP–Ph at 1437.6 and νP–O–C at 1032 cm–1. The
UV/Vis spectrum shows λmax at 397 nm (ε 7.52×102). The mass spectrum of compound 6 shows the molecular ion
peak [M+1]+ at m/e 617 (10.06%). The different fragments in each case are tabulated in Table 2 with their relative
abundances.
Triethylphosphite reacted with compound 2b to afford four-membered ring oxyphosphorane 7 via the
same reaction mechanism. The IR spectrum of compound 7 shows new absorption bands at 2958 and
1030 cm–1 due to νC–H and νP–O–alkyl
.
OEt
P
EtO
OEt
O
O
Ph
O
O
C
N
O
COPh
N
P
O
(OEt)3
7
8
986

Triethylphosphite reacted with dioxadiazepine derivative 3 to give the product cyclophosphorane 8. The IR
spectrum of compound 8 shows three νC=O at 1775, 1731, 1672 and νP–O-alkyl at 1030 and 1227 cm–1.
TABLE 2. The Fragments of Compound 7 with their Relative Abundances
Relative abundance,
Fragment
m/e
%
+
.
O
C
C
O
C
N
O
617
10.06
N
O
P
Ph
Ph
Ph
6
O
C
OH
O
H
H
N
N
C
C
+
369
337
7.55
C
O
O
C
O
C
N
N
C
+
10.69
C
O
+
Ph
Ph
Ph
.
278
277
15.72
P
O
+
55.97%
P
P
O
Ph
Ph
Ph
Ph
199
149
23.27
41.51
H2C
+
+
H
OH
CH
C
C
HO
H
+
.
H P
C
C
H
57
51
52.20
100
+
C4H3
987

TABLE 3. Physical Properties and Analyses of Products
Found, %
Calculated, %
——————
Com-
pound
Empirical
formula
mp, °C*
Yield, %
C
H
N
P
1
C25H14N2O2
C25H16O2
80.88
80.21
86.39
86.20
82.65
82.97
79.53
80.00
71.64
71.92
70.92
71.18
80.88
81.15
84.62
84.59
82.71
82.75
81.00
81.13
75.99
76.68
75.65
75.97
70.82
70.84
61.69
62.30
3.64
3.74
4.21
4.59
4.28
4.25
3.69
4.00
3.17
3.47
2.67
2.82
3.10
2.98
5.26
5.08
4.88
4.85
4.80
4.77
4.74
4.49
3.96
4.05
5.67
5.71
4.63
4.80
7.52
7.48
188-189
167-168
140-141
138-139
~340
35.41
49.42
30.92
63
2a
2b
2c
2d
3
C26H16O3
C20H12O3
C19H11NO4
C21H10N2O4
C43H29N2O2P
C43H31O2P
C44H31O3P
C38H27O3P
C37H26NO4P
C39H25N2O4P
C32H31O6P
C27H25N2O7P
4.10
4.41
7.74
7.90
4.64
4.55
47
112-113
208-209
120-121
130-131
207-208
172-173
254-256
123-124
90-91
57
4
4.66
4.87
5.32
5.08
4.95
4.85
5.24
5.51
5.30
5.35
5.40
5.03
5.70
5.71
5.90
5.96
73
5a
5b
5c
5d
6
69
53
53
2.32
2.41
4.31
4.45
44
86
7
60
8
4.83
5.38
75
_______
* Solvent of crystallization: petroleum ether 40-60o (compounds 1, 7, 8), ether
(compounds 2a,b, 3, 4, 5a,b), EtOH (compound 2c), MeOH (compound 2d),
THF (compound 5c,d, 6).
EXPERIMENTAL
Melting points were determined with Gallenkamp melting point apparatus and are uncorrected. Elemental
analyses were performed by the Microanalytical Lab., Cairo University, Giza. FTIR spectra were recorded on a
Bruker vector apparatus, Germany, and on Mattson 1000 spectrophotometer at the Microanalytical Lab., Cairo
University, Giza. UV/Vis spectra were recorded using a vis Shimadzu UV-1601 spectrometer. Mass spectra were
measured on a GCQ Finnigan MAT apparatus at Ain Shams University. 1H NMR spectra were recorded on a Gemini
200 spectrometer in DMSO solution with TMS as an internal standard at Cairo University, Giza.
Compound 1. A mixture of acenaphthenequinone (0.47 g, 2.5 mmol), 9-diazofluorene (1.44 g,
7.5 mmol), and copper bronze (0.50 g, 7.8 mmol) in benzene (100 ml) was boiled under reflux for 10 h. Copper
bronze was removed by filtration and copper oxide (1.98 g, 25 mmol) was added to the filtrate, which was then
refluxed for 10 h. Copper oxide was removed by filtration, whereby an orange product 1 was obtained after
crystallization from petroleum ether (40-60oC). The UV-Vis spectrum shows λ
at 350 (ε = 2.0×103), 415.2
max
(ε = 1.6×103), and 462.5 nm (ε = 1.88×103).
Compound 2a. A mixture of acenaphthenequinone (0.91 g, 5 mmol) and diphenyldiazomethane (1.94 g,
10 mmol) was boiled under reflux in benzene (100 ml) for 10 h. A yellowish brown crystalline product 3a was
formed, filtered off, and recrystallized from ether. The UV/Vis spectrum showed λmax at 350 (ε 1.3×104) and 379
nm (ε 8.43×103) for compound 2a.
988

Compound 2b. A mixture of acenaphthenequinone (0.47 g, 2.5 mmol), phenylbenzoyl diazomethane
(1.56 g, 7.5 mol), and copper bronze (0.50 g, 7.8 mmol) was refluxed in benzene for 20 h. Copper bronze was
removed by filtration, whereby a yellowish-green product 3b was formed and recrystallized from ether.
Compounds 2c,d. A mixture of acenaphthenequinone (6 mmol), phenacyl chloride (or o-nitrobenzyl
chloride) (12 mmol), and K2CO3 (7 mmol) in ethyl alcohol (30 ml) was refluxed for 3 h, whereby a yellow (or
pale-brown) product was formed and recrystallized from THF. The UV/Vis spectrum for compound 2c shows
λ
max at 341 nm (ε 2.5×103).
Compound 3. A mixture of acenaphthenequinone (0.47 g, 2.5 mmol) and 2-diazo-1,3-dihydrino-
indenedione (0.86 g, 5 mmol) was refluxed in benzene (100 ml) for 20 h. A deep brown precipitate 4 was
obtained and recrystallized from ether. The IR spectrum, being in accordance with the proposed structure, shows
two νC=O at 1720 and 1681 cm–1. UV/Vis spectrum shows λmax at 407 (ε 5.06×103) and a shoulder at 475 nm (ε
2.3×103).
Compound 4. A mixture of triphenylphosphine (0.13 g, 0.5 mmol) and compound 1 (0.18 g, 5 mmol) in
THF (10 ml) was stirred for 3 h at room temperature, then left to stand overnight, whereby an orange precipitate
5 was separated, filtered off, and recrystallized from ether. The UV/Vis spectrum shows λmax at 350 (ε 1.3×104),
407.5 (ε 10.5×103) and a shoulder at 472.8 nm (ε 2.4×103).
Compounds 5a-d (General Method). A mixture of α-ketoepoxide derivative 2a-d (1 mmol) and
triphenylphosphine (1 mmol) in THF (10 ml) was stirred for 3 h at room temperature, whereby brown,
pale-brown, yellowish-white, and pale-brown products 5a-d were formed and recrystallized from THF.
Compound 6. A mixture of compound 3 (0.17 g, 0.5 mmol) and triphenylphosphine (0.13 g, 0.5 mmol) in
THF (10 ml) was stirred at room temperature for 3 h, whereby a brown product 6 was formed and recrystallized from
THF.
Compounds 7 and 8 (General Method). A mixture of triethylphosphite (0.5 mmol) and compounds 2b
and 3 (0.5 mmol) in THF (10 ml) was stirred for 3 h at room temperature, then left to stand overnight, whereby
yellowish-white and brown crystalline products 7 and 8 were separated, filtered off, dried, and recrystallized
from petroleum ether (40-60oC).
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