The behavior of 3,3-diphenylindan-1,2-dione towards phosphonium ylides

Article abstract of DOI:10.1007/s00706-007-0626-1

The reaction of alkoxycarbonyl- and cyanomethylene(triphenyl)phosphoranes with 3,3-diphenylindan-1,2-dione in dry benzene at room temperature for about 5∈h led to the formation of a mixture of (E)- and (Z)-diastereomers. On the other hand, treatment of the dione with acetylmethylene(triphenyl)phosphorane afforded a mixture of (E)-3,3-diphenyl-1-(2-oxo-2-methylethylidene)indan-2-one and unexpected product (E)-3-(3,3-diphenyl-2-oxoindan-1-ylidene)-4-(triphenyl- λ⁵-phosphanylidene)hexane-2,5-dione, whereas with benzoylmethylene(triphenyl)phosphorane gave a mixture of (E)-3,3-diphenyl-1-(2- oxo-2-phenylethylidene)indan-2-one, [(2R *,3S *)-3-benzoyl-8,8- diphenyl-3,8-dihydro-2H-indeno{2,1-b}furan-2-yl]phenylmethanone and 1,4-diphenyl-2-(3,3-diphenyl-2-hydroxy-3H-inden-1-yl)but-2-ene-1,4-dione. The reaction mechanisms are considered and structural assignments of the new compounds are based on spectroscopic evidence. The molecular structures of the two diastereomers and the unexpected product were elucidated by X-ray crystallography. Springer-Verlag 2007.

Full text of DOI:10.1007/s00706-007-0626-1

Monatshefte fu¨r Chemie 138, 545–552 (2007)
DOI 10.1007/s00706-007-0626-1
Printed in The Netherlands
The Behavior of 3,3-Diphenylindan-1,2-dione Towards Phosphonium Ylides
ꢀ
Fayez H. Osman and Fatma A. El-Samahy
National Research Centre, Dokki, Cairo, Egypt
Received October 10, 2006; accepted (revised) November 19, 2006; published online May 2, 2007
# Springer-Verlag 2007
Summary. The reaction of alkoxycarbonyl- and cyanometh-
ylene(triphenyl)phosphoranes with 3,3-diphenylindan-1,2-
dione in dry benzene at room temperature for about 5 h led
to the formation of a mixture of (E)- and (Z)-diastereomers. On
molecule of the same ylide to form a bis-alkylidene
[24, 27, 29], fused to cyclobutene [27]. The products
of these reactions depend on the nature of the ꢁ-dicar-
bonyls, type of ylides, or reaction conditions [30].
the other hand, treatment of the dione with acetylmethylene
Previously, we have reported the reaction of
4-triphenylmethyl-1,2-benzoquinone and isatin with
phosphonium ylides [2–6]. In the present communi-
cation, we examine the behavior of 3,3-diphenylin-
dan-1,2-dione (1) as an asymmetrical ꢁ-diketone
towards phosphonium ylides 2 and 3.
(triphenyl)phosphorane afforded a mixture of (E)-3,3-diphe-
nyl-1-(2-oxo-2-methylethylidene)indan-2-one and unexpected
product (E)-3-(3,3-diphenyl-2-oxoindan-1-ylidene)-4-(triphe-
nyl-ꢀ5-phosphanylidene)hexane-2,5-dione, whereas with ben-
zoylmethylene(triphenyl)phosphorane gave a mixture of
(E)-3,3-diphenyl-1-(2-oxo-2-phenylethylidene)indan-2-one,
[(2R ,3S )-3-benzoyl-8,8-diphenyl-3,8-dihydro-2H-indeno
{2,1-b}furan-2-yl]phenylmethanone and 1,4-diphenyl-2-(3,3-
diphenyl-2-hydroxy-3H-inden-1-yl)but-2-ene-1,4-dione. The
reaction mechanisms are considered and structural assignments
of the new compounds are based on spectroscopic evidence.
The molecular structures of the two diastereomers and the un-
expected product were elucidated by X-ray crystallography.
ꢀ
ꢀ
Keywords. 3,3-Diphenylindan-1,2-dione; Phosphonium
ylides; X-Ray crystallography.
Introduction
The reaction of o-quinones and ꢁ-diketones with
stabilized phosphonium ylides have been extensively
studied in considerable details by several investiga-
tors [1–25]. Generally, these reactions initially un-
dergo a Wittig mono-olefination to yield the (Z)- and
(E)-diastereomers. In some cases, the reactive con-
jugated systems undergo a Michael addition with
another ylide molecule, although a second Wittig re-
action might also be observed [26–28]. Sometimes,
the mono-olefination adducts react with another
Results and Discussion
The reaction of equimolar amounts of 1 with sta-
bilized phosphonium ylides 2a–2c in dry benzene
at room temperature for 3 h led to the formation of
a mixture containing (E)-6 and (Z)-7 (examined
by TLC) and triphenylphosphine oxide (Scheme 1).
These two diastereomers were separated by silica gel
column chromatography as pale yellow crystalline
products and their structures were established by
IR, 1H NMR, and MS as well as elemental analyses.
The IR spectra of both isomers 6 and 7 show a strong
ꢀ
Corresponding author. E-mail: osman_f@hotmail.com

546
F. H. Osman and F. A. El-Samahy
Scheme 1
absorption band around 1735cmꢁ1 due to the carbon-
1
yl group and their H NMR spectra reveal the pres-
ence of the olefinic proton. Comparing (E)-6 and
1
(Z)-7 with respect to their H NMR spectra (cf. Ex-
perimental), it is obvious that the chemical shift of
both the ‘‘diagnostic’’ protons at C-7 and the olefinic
ones are always less deshielded in the (Z)-isomers 7
than those of the corresponding (E)-isomers 6 [31].
This is due to the anisotropic effect of either the car-
bonyl group of the ester or the nitrile residue [32].
Moreover, single crystal X-ray diffraction analysis of
(E)-6c (Fig. 1) and (Z)-7c (Fig. 2), taken as examples,
confirm the configurations.
The formation of (E)-6 and (Z)-7 may proceed
through a Wittig reaction affording initially the phos-
phorus betaine 4, which is followed by irreversible
decomposition to give the alkenes 6 and 7 along with
triphenylphosphine oxide. The 1,2-oxaphosphetane 5
was considered to be a transition state between the be-
taine 4 and the final products 6 and 7 (Scheme 1) [33].
On the other hand, if the dione 1 reacts with
two equivalents of acetylmethylene(triphenyl)phos-
phorane (3a) in dry benzene at room temperature
for about 30 h, a mixture of products was obtained
Fig. 1. X-Ray structure of isomer 6c in the ORTEP presen-
ꢂ
˚
tation. Selected bond distances (A) and bond angles ( ):
O(1)–C(9) ¼ 1.211(2), C(2)–C(4)¼ 1.458(3), C(2)–C(9)¼
1.489(3), C(2)–C(13) ¼ 1.343(3), C(5)–C(6) ¼ 1.519(3),
C(13)–C(22) ¼ 1.414(3), N(20)–C(22)¼ 1.141(3), C(13)–
H(13) ¼ 0.950(2),
C(4)–C(2)–C(9) ¼ 107.1(2),
C(4)–
C(2)–C(13) ¼ 132.5(2),
C(9)–C(2)–C(13) ¼ 120.3(2),
O(1)–C(9)–C(2) ¼ 125.0(2), C(2)–C(13)–C(22) ¼ 123.8(2),
C(13)–C(22)–N(20) ¼ 179.3(3),
C(2)–C(13)–H(13) ¼
119.3(13), C(22)–C(13)–H(13) ¼ 117.0(12)

The Behavior of 3,3-Diphenylindan-1,2-dione
547
Fig. 3. X-Ray structure of compound 12 in the ORTEP pre-
ꢂ
˚
sentation. Selected bond distances (A) and bond angles ( ):
P(1)–C(10) ¼ 1.736(3), O(2)–C(13) ¼ 1.218(3), O(3)–C(9)
1.263(3), O(4)–C(25)¼ 1.211(4), C(5)–C(17)¼ 1.361(4),
C(9)–C(10) ¼ 1.407(4),
C(9)–C(34)¼ 1.508(4),
C(10)–
C(17) ¼ 1.466(4), C(17)–C(25)¼ 1.525(4), C(25)–C(38)¼
1.505(5), C(13)–C(5)–C(17)¼ 124.0(3), O(3)–C(9)–C(10) ¼
120.1(3), C(10)–C(9)–C(34) ¼ 123.0(3), P(1)–C(10)–
C(17) ¼ 126.6(2), O(2)–C(13)–C(5) ¼ 125.9(3), C(10)–
Fig. 2. X-Ray structure of isomer 7c in the ORTEPꢂpresenta-
˚
tion. Selected bond distances (A) and bond angles ( ): O(1)–
C(4) ¼ 1.210(2), C(2)–C(8) ¼ 1.401(2), C(4)–C(7) ¼ 1.495(2),
C(7)–C(8) ¼ 1.453(2), C(7)–C(12) ¼ 1.339(2), C(12)–C(17) ¼
1.423(3), N(14)–C(17) ¼ 1.150(2), C(12)–H(12) ¼ 0.960(2),
O(1)–C(4)–C(7) ¼ 125.2(13), C(4)–C(7)–C(8) ¼ 107.0(12),
C(4)–C(7)–C(12) ¼ 124.6(14), C(8)–C(7)–C(12) ¼ 128.4(13),
C(17)–C(25) ¼ 116.4(3),
O(4)–C(25)–C(17) ¼ 117.2(3),
O(4)–C(25)–C(38) ¼ 120.9(3)
C(7)–C(12)–C(17) ¼ 124.4(14),
C(12)–C(17)–N(14) ¼
175.0(2), C(7)–C(12)–H(12) ¼ 119.7(2), C(17)–C(12)–
H(12) ¼ 115.8(2)
The unexpected product 12 was isolated as deep red
1
crystals. Its IR and H NMR spectra are consistent
with the proposed structure (cf. Experimental). More-
over, a single crystal X-ray diffraction analysis of 12
(crystallized from acetone) (Fig. 3) confirmed the
configuration. The bond lengths 1.361(4), 1.736(3)
consisting of (E)-3,3-diphenyl-1-(2-methyl-2-oxo-
ethylidene)indan-2-one (9a) and the unexpected
(E)-3-(3,3-diphenyl-2-oxoindan-1-ylidene)-4-(triphenyl-
ꢀ5-phosphanylidene)hexane-2,5-dione (12) together
with another compound which easily decomposed
and could not be isolated in pure form. These com-
pounds were separated by column chromatography
on silica gel. Triphenylphosphine and triphenylphos-
phine oxide were also isolated and identified. The
structures were assigned using elemental analyses
and spectral properties, which were consistent with
expectation. The IR spectrum of the yellow crystal-
line product 9a revealed the presence of absorption
bands around 1731, 1681 cmꢁ1 corresponding to the
˚
A of the corresponding exocyclic C¼C and C¼P are
in agreement with the established structure. A pos-
sible explanation for the formation of the adduct 12
as shown in Scheme 2 is suggested to involve initial
Wittig mono-olefination from the reaction of dione 1
with ylide 3a yielding the alkene (E)-9a, which in
turn reacts with another molecule of 3a to form the
intermediate 10. The phosphonium species 10 af-
forded eventually the novel type of phosphonium
ylide 12 through dehydrogenation of 11.
When dione 1 was treated with two mole equiva-
lents of benzoylmethylene(triphenyl)phosphorane
(3b) in boiling benzene for 35 h, (E)-3,3-diphenyl-
1
carbonyl groups. Its H NMR spectrum showed a
signal at ꢂ ¼ 6.95 ppm for the exocyclic vinyl proton.
The phenyl proton at C-7 appeared as a doublet at
ꢂ ¼ 8.84 ppm with a coupling constant J ¼ 7.8 Hz,
whereas the other two phenyl protons at C-5 and C-
6 appeared as two di-ortho=meta triplets of doublets
[34] at ꢂ ¼ 7.42 and 7.50 ppm with J ¼ 7.5, 1.2 Hz.
1-(2-oxo-2-phenylethylidene)indan-2-one
(9b),
ꢀ
ꢀ
[(2R ,3S )-3-benzoyl-8,8-diphenyl-3,8-dihydro-2H-
indeno-[2,1-b]furan-2-yl]phenylmethanone (14), and
1,4-diphenyl-2-(3,3-diphenyl-2-hydroxy-3H-inden-1-
yl)but-2-ene-1,4-dione (15) were obtained. These

548
F. H. Osman and F. A. El-Samahy
Scheme 2
compounds were separated by column chromatogra-
phy on silica gel. Triphenylphosphine and triphenyl-
phosphine oxide were also isolated and identified.
The assigned structures of the products 9b, 14, and
15 were established from the elemental analyses, IR,
1H NMR, and MS.
Compound 9b was isolated as yellow crystals.
Its IR spectrum exhibited strong bands at 1736,

The Behavior of 3,3-Diphenylindan-1,2-dione
549
1658 cmꢁ1 due to the carbonyl groups. The 1H NMR
spectrum showed a singlet signal at ꢂ ¼ 7.62 ppm
corresponding to the exocyclic vinyl proton and a
doublet at ꢂ ¼ 8.57ppm, with a coupling constant
value J ¼ 8.1 Hz, due to the aromatic proton at C-7.
The colorless crystals 14 showed characteristic bands
in the IR spectrum at 1745, 1685, and 1674 cmꢁ1 for
photometer Model FT=IR-3000E. The NMR spectra were
recorded on a Varian MERCURY 300 spectrometer for H
operating at 300 MHz. Chemical shifts are given in positive
values downfield from internal TMS. The mass spectra (MS)
were determined at 70 eV on a Finnigan MAT SSQ 7000
spectrometer.
1
X-Ray Structure Determination
1
The crystal data were measured at T ¼ 298 K on a Kappa CCD
Enraf Nonius FR 590 diffractometer. The crystal structure
was solved and refined using maXus (Nonius, Delft and
the carbonyl groups and its H NMR disclosed the
presence of two doublets at ꢂ ¼ 4.10, 4.18 ppm with
coupling constant J ¼ 7.8 Hz, ascribed to the two
vicinal protons Ha and Hb, which are in a cis-config-
uration. This value is supported by the recorded
coupling constants bearing a considerable likeness
to those values reported for other similar cis-deriva-
tives of dihydrofuran [15, 16]. The red product 15
revealed the presence of the hydroxyl group from
an absorption band at 3421 cmꢁ1 in the IR spec-
˚
MacScience, Japan). Mo-Kꢁ radiation (ꢀ ¼ 0.71073 A) and a
graphite monochromator were used for data collection.
Further details of the structure determination (complete bond
lengths and angles, H atom coordinates, structure factors,
temperature factors) were deposited at the Cambridge Crystal-
lographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
United Kingdom. Any request should be accompanied by
the full literature citation and the CCDC reference numbers
626563 (6c), 626564 (7c), and 626565 (12).
1
trum and in the H NMR spectrum a singlet at ꢂ ¼
Reaction of Dione 1 with Methoxycarbonylmethylene(tri-
phenyl)phosphorane (2a)
4.85 ppm exchangeable with D2O. The proposed
mechanism for the formation of 14 and 15 is shown
in Scheme 2. Compounds 1 and 3b initially undergo
a Wittig mono-olefination to form 8b and 9b, which
by further Michael addition of a second ylide 3b
afford the indenoxy anion intermediate 13. Intramo-
lecular hydrogen abstraction of the ꢃ-hydrogen, or
nucleophilic attack at the ꢁ-carbon of the phospho-
nium group by the indenoxy anion in 13 accompa-
nied by triphenylphosphine elimination results in the
formation of 14 and 15.
A mixture of 0.6g 1 [35] (2mmol) and 0.73 g 2a [36]
(2.2mmol) in 20 cm3 dry benzene was stirred at room tem-
perature for about 5 h. Then, the solvent was evaporated under
reduced pressure and the residue was chromatographed on
silica gel using n-hexane and acetone as eluent to afford 6a,
7a, and triphenylphosphine oxide.
(E)-(3,3-Diphenyl-2-oxoindan-1-ylidene)acetic acid methyl
ester (6a, C24H18O3)
Yield 70%; pale yellow crystals; mp 159–160ꢂC (benzene=n-
hexane); IR: ꢄꢀ¼ 1736, 1714 (C¼O) cmꢁ1; 1H NMR (CDCl3):
ꢂ ¼ 3.85 (s, OMe), 6.69 (s, ¼CH), 7.09–7.32 (m, 11 ArH),
7.45, 7.50 (2dt, J ¼ 7.5, 1.5Hz, 2 ArH at C-5, C-6), 8.92 (d,
J ¼ 7.2 Hz, ArH at C-7) ppm; MS: m=z (%) ¼ 354 (Mþ, 3).
Conclusion
From the results of the present investigation it was
derived that the reaction of 1 with alkoxycarbonyl-
methylene(triphenyl)phosphoranes (2a, 2b) and cya-
nomethylene(triphenyl)phosphorane (2c) proceeds in
a mono-olefination at only one carbonyl group to yield
the corresponding diastereomeric (E)-6 and (Z)-7. If
1 reacts with acetylmethylene(triphenyl)phosphorane
(3a) it affords 9a and 12, and with benzoylmethylene-
(triphenyl)phosphorane (9b), 14 and 15. This means
that the reactivity of the stabilized phosphoranes to-
wards ꢁ-diketones is influenced to a great extent by the
substituents at the ylide carbon atom and also depends
on the type of the ꢁ-dicarbonyl compounds.
(Z)-(3,3-Diphenyl-2-oxoindan-1-ylidene)acetic acid methyl
ester (7a, C24H18O3)
Yield 11%; pale yellow crystals; mp 164–165ꢂC (CHCl3=n-
hexane); IR: ꢄꢀ¼ 1732, 1707 (C¼O) cmꢁ1; 1H NMR (CDCl3):
ꢂ ¼ 3.87 (s, OMe), 6.11 (s, ¼CH), 7.18–7.33 (m, 10 ArH),
7.40–7.48 (m, 2 ArH at C-4, C-5), 7.63 (dt, J ¼ 7.5, 1.5 Hz,
ArH at C-6), 7.85 (d, J ¼ 7.2 Hz, ArH at C-7) ppm; MS: m=z
(%) ¼ 354 (Mþ, 32).
Triphenylphosphine Oxide
Yield quantitative; colorless crystals; identified by mp and
mixed mp with an authentic sample.
Reaction of Dione 1 with Ethoxycarbonylmethylene(tri-
phenyl)phosphorane (2b)
Carrying out the same experimental procedure as described
above using 0.6 g 1 (2mmol), 0.77g 2b [36] (2.2mmol), and
20cm3 dry benzene. The chromatographic separation by n-
hexane and acetone as eluent gave the two isomers 6b, 7b, and
triphenylphosphine oxide.
Experimental
Melting points were determined on an electrical digital-
melting-point apparatus. The IR spectra were recorded in
KBr disks, on a Jasco Fourier Transform Infra-red spectro-

550
F. H. Osman and F. A. El-Samahy
(CDCl3): ꢂ ¼ 5.98 (s, ¼CH), 7.08–7.32 (m, 10 ArH), 7.32 (d
overlapped, J ¼ 7.2 Hz, ArH at C-4), 7.50, 7.55 (2 dt, J ¼ 7.5,
1.2 Hz, 2 ArH at C-5 and C-6), 7.69 (d, J ¼ 7.2Hz, ArH at
C-7) ppm; MS: m=z (%) ¼ 321 (Mþ, 69).
(E)-3,3-Diphenyl-2-oxoindan-1-ylidene)acetic acid ethyl
ester (6b, C25H20O3)
Yield 65%; pale yellow crystals; mp 111–112ꢂC [benzene=
petroleum ether (bp 60–80ꢂC)]; IR: ꢄꢀ¼ 1738, 1709 (C¼O)
cmꢁ1; 1H NMR (CDCl3): ꢂ ¼ 1.35 (t, J ¼ 7.2 Hz, OCH2CH3),
4.32 (q, J ¼ 7.2 Hz, OCH2), 6.68 (s, ¼CH), 7.08–7.32 (m, 11
ArH), 7.44, 7.49 (2dt, J ¼ 7.5, 1.5 Hz, 2 ArH at C-5, C-6), 8.91
(d, J ¼ 7.2 Hz, ArH at C-7) ppm; MS: m=z (%) ¼ 368 (Mþ, 5).
Crystallographic Data of 7c
C23H15NO, Mr ¼ 321.379, monoclinic, crystallizes in space
˚
group P21=c, a ¼ 8.8281(2), b ¼ 16.8513(4), c ¼ 13.7453(3) A,
3
V ¼ 1707.86(7) A , Z ¼ 4, Dc ¼ 1.25g cmꢁ1, ꢅ values 2.91–
˚
25.35ꢂ, absorption coefficient
ꢆ
(Mo-Kꢁ) ¼ 0.08 mmꢁ1
,
(Z)-(3,3-Diphenyl-2-oxoindan-1-ylidene)acetic acid ethyl
ester (7b, C25H20O3)
F(000) ¼ 672. The unique reflections measured were 3446,
of which 2092 reflections with threshold expression I>3ꢇ(I)
were used in the structural analysis. Convergence for 226
variable parameters by least-squares refinement on F2 with
Yield 14%; pale yellow crystals; mp 143–144ꢂC (CHCl3=n-
hexane); IR: ꢄꢀ¼ 1728, 1709 (C¼O) cmꢁ1; 1H NMR (CDCl3):
ꢂ ¼ 1.37 (t, J ¼ 7.2 Hz, OCH2CH3), 4.36 (q, J ¼ 7.2 Hz, OCH2),
6.11 (s, ¼CH), 7.18–7.33 (m, 10 ArH), 7.40–7.47 (m, 2 ArH
at C-4 and C-5), 7.62 (dt, J ¼ 7.5, 1.5 Hz, ArH at C-6), 7.35 (d,
J ¼ 7.2 Hz, ArH at C-7) ppm; MS: m=z (%) ¼ 368 (Mþ, 16).
2
2
2
! ¼ 1=[ꢇ (Fo ) þ 0.10000 Fo ]. The final agreement factors
were R ¼ 0.039 and wR ¼ 0.074 with a goodness-of-fit of
1.254.
Triphenylphosphine Oxide
Yield quantitative; colorless crystals; identified by mp and
mixed mp with an authentic sample.
Triphenylphosphine Oxide
Yield quantitative; colorless crystals; identified by mp and
mixed mp with an authentic sample.
Reaction of Dione 1 with Acetylmethylene(triphenyl)-
phosphorane (3a)
Reaction of Dione 1 with Cyanomethylene(triphenyl)-
phosphorane (2c)
A solution of 0.6 g 1 (2mmol) and 1.27 g 3a [38] (4.2mmol)
in 20cm3 dry benzene was stirred at room temperature for
about 30h. Then, the volatile material was evaporated under
reduced pressure and the residue was chromatographed on
silica gel, using acetone and petroleum ether (bp 60–80ꢂC)
as eluent to produce isomer 9a, 12, triphenylphosphine, and
triphenylphosphine oxide besides a compound which easily
decomposed and could not be isolated in pure form.
The reaction of 0.6 g 1 (2 mmol) with 0.66 g 2c [37]
(2.2 mmol) in 20 cm3 dry benzene was carried out for 7 h
and the reaction mixture was worked up according to the
above described procedure for ylide 2a. The chromatographic
separation gave two isomers 6c, 7c, and triphenylphosphine
oxide.
(E)-(3,3-Diphenyl-2-oxoindan-1-ylidene)acetonitrile (6c,
C23H15NO)
Yield 63%; pale yellow crystals; mp 149–150ꢂC (ethyl
(E)-3,3-Diphenyl-1-(2-methyl-2-oxoethylindene)indan-2-one
(9a, C24H18O2)
acetate=n-hexane); IR: ꢄꢀ¼ 2216 (CꢃN), 1734 (C¼O) cmꢁ1
;
Yield 20%; yellow crystals; mp 143–144ꢂC (CHCl3=n-hexane);
IR: ꢄꢀ¼ 1731, 1682 (C¼O) cmꢁ1; 1H NMR (CDCl3): ꢂ ¼ 2.44
(s, Me), 6.95 (s, ¼CH), 7.06–7.36 (m, 11 ArH), 7.42, 7.50
(2dt, J ¼ 7.5, 1.2 Hz, 2 ArH at C-5 and C-6), 8.84 (d,
J ¼ 7.8Hz, ArH at C-7) ppm; MS: m=z (%) ¼ 338 (Mþ, 100).
1H NMR (CDCl3): ꢂ ¼ 6.11 (s, ¼CH), 7.04–7.36 (m, 11 ArH),
7.52, 7.57 (2dt, J ¼ 7.5, 1.5 Hz, 2 ArH at C-5, C-6), 8.45
(dd, J ¼ 7.0, 1.2Hz, ArH at C-7) ppm; MS: m=z (%) ¼ 321
(Mþ, 61).
Crystallographic Data of 6c
C23H15NO, Mr ¼ 321.379, triclinic, crystallizes in space
(E)-3-(3,3-Diphenyl-2-oxoindan-1-ylidene)-4-(triphenyl-ꢀ5-
phosphanylidene)hexane-2,5-dione (12, C45H35O3P)
Yield 18%; deep red crystals; mp 147–148ꢂC (benzene=n-
hexane); IR: ꢄꢀ¼ 1712, 1681 (C¼O) cmꢁ1; 1H NMR (CDCl3):
ꢂ ¼ 1.10, 2.00 (2s, 2 Me), 7.00–7.78 (m, 28 ArH), 8.23 (d,
J ¼ 7.2 Hz, ArH at C-7) ppm; MS: m=z (%) ¼ 654 (Mþ, 3).
˚
group P-1, a ¼ 8.4354(2), b ¼ 10.0223(3), c ¼ 10.7948(5) A,
3
V ¼ 863.70(5) A , Z ¼ 2, Dc ¼ 1.236 g cmꢁ1, ꢅ values 2.91–
˚
27.48ꢂ, absorption coefficient
ꢆ
(Mo-Kꢁ) ¼ 0.08mmꢁ1
,
F(000)¼ 336. The unique reflections measured were 4419,
of which 2091 reflections with threshold expression I>3ꢇ(I)
were used in the structural analysis. Convergence for 256
variable parameters by least-squares refinement on F2 with
Triphenylphosphine and Triphenylphosphine Oxide
Yields quantitative; colorless crystals; identified by mp and
mixed mp with an authentic samples.
2
2
2
! ¼ 1=[ꢇ (Fo ) + 0.10000 Fo ]. The final agreement factors
were R ¼ 0.041 and wR ¼ 0.074 with a goodness-of-fit of
0.906.
Preparation of a Single Crystal of 12
(Z)-(3,3-Diphenyl-2-oxoindan-1-ylidene)acetonitrile (7c,
C23H15NO)
A single crystal X-ray diffraction of 12 was prepared from
acetone solution with molecular formula C45H35O3P ꢄ C3H6O
and molecular weight 712 (i.e. the crystal contains one mole
of acetone).
Yield 17%; pale yellow crystals; mp 177–178ꢂC (CHCl3=n-
1
hexane); IR: ꢄꢀ¼ 2214 (CꢃN), 1743 (C¼O) cmꢁ1; H NMR

The Behavior of 3,3-Diphenylindan-1,2-dione
551
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[5] Osman FH, El-Samahy FA (2000) Heterocycl Commun
6: 175
[6] Osman FH, El-Samahy FA (2000) Tetrahedron 56:
1863
[7] Baldoumi V, Gautam DR, Litinas KE, Nicolaides DN
(2006) Tetrahedron 62: 8016
Crystallographic Data of 12
C45H35O3P ꢄ C3H6O, Mr ¼ 712.834, triclinic, crystallizes in
space group P1, a ¼ 9.4780(5), b ¼ 9.8221(6), c ¼ 22.4452(12)
3
A, V ¼ 1967.9(2) A , Z ¼ 2, Dc ¼ 1.205 g cmꢁ1, ꢅ values
˚
˚
2.910–22.213ꢂ, absorption coefficient
ꢆ
(Mo-Kꢁ) ¼
0.11mmꢁ1, F(000)¼ 754. The unique reflections measured
were 5689, of which 2119 reflections with threshold ex-
pression I>3ꢇ(I) were used in the structural analysis.
Convergence for 478 variable parameters by least-squares
[8] Nicolaides DN, Gautam DR, Litinas KE, Hadjipavlou-
Litina DJ, Fylaktakidou KC (2004) Eur J Med Chem
39: 323
2
refinement on F2 with ! ¼ 1=[ꢇ (Fo ) þ 0.10000 Fo ]. The
final agreement factors were R ¼ 0.054 and wR ¼ 0.098 with
a goodness-of-fit of 2.351.
2
2
¨
¨
¨
[9] Ungoren SH, Sacmaci M, Akcamur Y, Arici C, Ulkii D
(2004) J Heterocyclic Chem 41: 151
[10] Saalfrank RW, Hafner W, Markmann J, Bestmann HJ
(1988) Tetrahedron 44: 5095
Reaction of Dione 1 with Benzoylmethylene(triphenyl)-
phosphorane (3b)
[11] Nicolaides DN, Adamopoulos SG, Lefkaditis DA,
Litinas KE (1990) J Chem Soc Perkin Trans I 2127
[12] Nicolaides DN, Adamopoulos SG, Lefkaditis DA,
Litinas KE, Tarantili PV (1992) J Chem Soc Perkin
Trans I 283
[13] Nicolaides DN, Litinas KE, Lefkaditis DA, Adamopoulos
SG, Raptopoulou CP, Terzis A (1994) J Chem Soc
Perkin Trans I 2107
A mixture of 0.6 g 1 (2mmol) and 1.6g 3b [38] (4.2mmol) in
20cm3 dry benzene was heated under reflux for about 35h.
After removal of the volatile materials under reduced pressure,
the residue was chromatographed on silica gel, using n-hexane
and ethyl acetate as eluent. The isomer 9b, 14, 15, triphenyl-
phosphine, and triphenylphosphine oxide were obtained.
(E)-3,3-Diphenyl-1-(2-oxo-2-phenylethylidene)indan-2-one
(9b, C29H20O2)
[14] Nicolaides DN, Bezergiannidou-Balouctsi C, Litinas
KE, Malamidou-Xenikaki E, Mentzafos D, Terzis A
(1993) J Chem Res Synop 108
[15] Nicolaides DN, Adamopoulos SG, Hatzigrigoriou EJ,
Litinas KE (1991) J Chem Soc Perkin Trans I 3159
[16] Nicoloides DN, Litinas KE, Argyropoulos NG (1986)
J Chem Soc Perkin Trans I 415
Yield 44%; yellow crystals; mp 183–184ꢂC [benzene=petro-
1
leum ether (40–60ꢂC)]; IR: ꢄꢀ¼ 1736, 1658 (C¼O) cmꢁ1; H
NMR (CDCl3): ꢂ ¼ 7.14–8.08 (m, 18 ArH), 7.62 (s, ¼CH),
8.57 (d, J ¼ 8.1 Hz, ArH at C-7) ppm; MS: m=z (%) ¼ 400
(Mþ, 92).
[17] Kozminkh VO, Shavkunova GA, Berezina ES, Igidov
NM, Kozminykh EN, Syropyatov BYa, Zorin AN,
Semenova ZN (1994) Khim-Farm Zh 28: 31; (1996)
Chem Abstr 125: 33744y
[18] Tacconi G, Gamba IA, Righetti PP, Desimoni G (1980)
J Prakt Chem 322: 711
[19] Takeuchi Y, Choshi T, Tomozane H, Yoshida H, Yamato
M (1990) Chem Pharm Bull 38: 2265; (1991) Chem
Abstr 114: 6184g
[20] Mahran MR, Abdou WM, Khidre MD (1990) Monatsh
Chem 121: 51
[21] Ried W, Schinzel H (1982) Chem-Ztg 106: 183; (1982)
Chem Abstr 97: 72045u
[22] Falsone G, Spur B, Erdmann M, Peters W (1983) Arch
Pharm (Weinheim) 316: 530
[23] Hackler RE, Dreikorn BA, Johnson GW, Varie DL (1988)
J Org Chem 53: 5704
[24] Abdou WM, Ganoub NA, Abd El-Rahman NM (1991)
Phosphorus Sulfur 61: 91
ꢀ
ꢀ
[(2R ,3S )-3-Benzoyl-8,8-diphenyl-3,8-dihydro-2H-
indeno[2,1-b]furan-2-yl]phenylmethanone (14, C37H26O3)
Yield 12%; colorless crystals; mp 253–254ꢂC (benzene=n-
hexane); IR: ꢄꢀ¼ 1745, 1674 (C¼O) cmꢁ1; 1H NMR (CDCl3):
ꢂ ¼ 4.10, 4.18 (2d, J ¼ 7.8 Hz, Ha and Hb), 6.70–7.93 (m, 24
ArH) ppm; MS: m=z (%) ¼ 518 (Mþ, 8).
1,4-Diphenyl-2-(3,3-diphenyl-2-hydroxy-3H-inden-1-yl)but-
2-ene-1,4-dione (15, C37H26O3)
Yield 30%; red crystals; mp 108–109ꢂC (CHCl3=n-hexane);
IR: ꢄꢀ¼ 3421 (OH), 1728, 1685 (C¼O) cmꢁ1
;
1H NMR
(CDCl3): ꢂ ¼ 4.85 (s, OH exchangeable with D2O), 7.13–7.40
(m, 24 ArH and ¼CH) ppm; MS: m=z (%) ¼ 518 (Mþ, 19).
Triphenylphosphine and Triphenylphosphine Oxide
Yields quantitative; colorless crystals; identified by mp and
mixed mp with an authentic samples.
[25] Tanaka K, Watanabe T, Ohta Y, Fuji K (1997) Tetra-
hedron Lett 38: 8943
[26] Bestmann HJ, Lang HJ (1969) Tetrahedron Lett 2101
[27] Sullivan WW, Ullman D, Shechter G (1969) Tetrahedron
Lett 45: 457
[28] Parrick J (1964) Can J Chem 42: 190
[29] Cava MP, Pohl RJ (1960) J Am Chem Soc 82: 5242
[30] Maryanoff BE, Reitz AB (1989) Chem Rev 89: 863
[31] Faita G, Mella M, Righetti PP, Tacconi G (1994) Tetra-
hedron 50: 10955
References
[1] For a review sec: Osman FH, El-Samahy FA (2002)
Chem Reviews 102: 629
[2] Osman FH, Abd El-Rahman NM, El-Samahy FA (1993)
Tetrahedron 49: 8691
[3] Osman FH, El-Samahy FA (1996) Phosphorus Sulfur
108: 21

552
F. H. Osman and F. A. El-Samahy: The Behavior of 3,3-Diphenylindan-1,2-dione
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