Chemistry of phosphorus ylides. part 36 reactions of 2-hydroxyisoindole-, isoindoline-, and indane-1,3-dione with stable and active phosphonium ylides

Article abstract of DOI:10.1080/10426507.2012.700350

The stabilized alkylidenephosphoranes namely, acetyl-, benzoyl-, methoxycarbonyl-, and ethoxycarbonyl-methylenetriphenylphosphorane react with 2-hydroxyisoindole-1,3-(2H)dione to give the corresponding isoindoline-ylidenes, along with triphenylphosphane o

Full text of DOI:10.1080/10426507.2012.700350

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Chemistry of Phosphorus Ylides. Part
36 Reactions of 2-Hydroxyisoindole-,
Isoindoline-, and Indane-1,3-Dione With
Stable and Active Phosphonium Ylides
Soher S. Maigali a , Fouad M. Soliman a & Mysa E. Moharam b
a Department of Organometallic and Organometalloid Chemistry ,
National Research Centre , Dokki , Cairo , Egypt
b Department of Microbial Chemistry , National Research Centre ,
Dokki , Cairo , Egypt
Accepted author version posted online: 22 Jun 2012.Published
online: 31 May 2013.
To cite this article: Soher S. Maigali , Fouad M. Soliman & Mysa E. Moharam (2013): Chemistry of
Phosphorus Ylides. Part 36 Reactions of 2-Hydroxyisoindole-, Isoindoline-, and Indane-1,3-Dione With
Stable and Active Phosphonium Ylides, Phosphorus, Sulfur, and Silicon and the Related Elements,
188:5, 633-641
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Phosphorus, Sulfur, and Silicon, 188:633–641, 2013
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.700350
CHEMISTRY OF PHOSPHORUS YLIDES. PART 36
REACTIONS OF 2-HYDROXYISOINDOLE-, ISOINDOLINE-,
AND INDANE-1,3-DIONE WITH STABLE AND ACTIVE
PHOSPHONIUM YLIDES
Soher S. Maigali,1 Fouad M. Soliman,1 and Mysa E. Moharam2
1Department of Organometallic and Organometalloid Chemistry,
National Research Centre, Dokki, Cairo, Egypt
2Department of Microbial Chemistry, National Research Centre, Dokki,
Cairo, Egypt
GRAPHICAL ABSTRACT
Abstract The stabilized alkylidenephosphoranes namely, acetyl-, benzoyl-, methoxycarbonyl-,
and ethoxycarbonyl-methylenetriphenylphosphorane react with 2-hydroxyisoindole-1,3-
(2H)dione to give the corresponding isoindoline-ylidenes, along with triphenylphosphane ox-
ide. On the other hand, the reaction of active phosphacumulenes, (N-phenyliminovinylidene)-,
and (2-oxovinylidene)-triphenylphosphorane with hydroxyisoindole-, isoindoline-, and
indane-1,3-dione afforded phosphanylidenecyclobutylidenes derivatives, together with
triphenylphosphane oxide. Mechanisms accounting for the formation of the new products are
discussed. The antimicrobial activities for the new compounds are also reported.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
Keywords Isoindolinones; stable phosphonium ylides; phosphacumulenes; phosphanyli-
denecyclobutylidene derivatives; antimicrobial activities
Received 25 January 2012; accepted 19 May 2012.
Address correspondence to Fouad M. Soliman, Department of Organometallic and Organometalloid Chem-
istry, National Research Centre, El-Behoos St., P.O. 12622, Dokki, Cairo, Egypt. E-mail: solimanfma2@
yahoo.com
633

634
S. S. MAIGALI ET AL.
INTRODUCTION
1,3-Indanedione derivatives have attracted considerable interest due to their antico-
agulant, parasiticidal, herbicidal,1 analgesic, and antimicrobial activities.2 Moreover, they
have found broad applications as adrenergic receptor antagonists.3 On the other hand, N-
substituted indane-1,3-diones have proven to be potent cytotoxic agents effective against
the growth of single cell leukemia tumors and cell lines derived from solid tumors.4,5
Our interest in the reactions of phosphonium ylides,6,7 led us to investigate the behavior
of these stabilized carbanions toward 2-hydroxyisoindole-1,3(2H)dione (1). The reaction
of the active phosphacumulenes 5a,b with the hydroxyisoindole-(1), isoindoline-(8), and
indane-1,3-dione (10) was investigated, to prepare new phosphanylidenecyclobutylidene
derivatives of anticipated antitumor activity.
RESULTS AND DISCUSSION
When 2-hydroxyisoindole-1,3(2H)dione (1) was treated with equimolar
amounts of acetyl-(2a), benzoyl-(2b), methoxycarbonyl-(2c), or ethoxycarbonyl-
methylenetriphenylphosphorane (2d) in refluxing dry toluene for 3 h, the corresponding
isoindoline ylidenes 4a–d together with triphenylphosphane oxide were isolated. A
[2+2]-cycloaddition of the C O bond of compound 1 to the ylidic C–P bond of 2a–d is
proposed to generate the unstable oxaphosphetane 3.8–10 In the case of weakly nucleophilic
stabilized ylides 2a–d, the first stage of the reaction is the threobetaine, which is more
stable than the erythrobetaine.11,12 By this means, subsequent formation of the intermediate
four-membered ring13 and its decomposition into the trans olefin14 and triphenylphosphane
oxide are mainly formed.
The structure of the new compounds 4a–d is assignable from their analyses, IR, 1H,
13C NMR and mass spectral (MS) data. The IR spectrum of 4a, (KBr, ν, cm−1) taken as
an example, showed the OH group at 3245, the CO–CH3 at 1791, and isoindolone CO at
1668. The most important feature of structure 4a is the presence of signals at δ 2.62 (s) for
the methyl protons, 5.95 (s) for the methine proton, 7.45–7.65 (m) for the aromatic protons,
and the OH group gave rise to a signal at 7.91 ppm, which disappeared upon addition of
1
D2O in its H NMR spectrum. The 13C NMR spectrum of 4a (CDCl3) displayed distinct
resonances of the methyl group at δ 30.0, the CH methine at 109.6, the isoindolone CO at
157.5, and the acetyl CO at 197.5 ppm. The MS indicated the presence of an ion peak at
m/z (%): 204 [(M++H), 100]. The structure of 4a is also assigned on the basis of elemental
analysis (Scheme 1).
The phosphacumulene ylides 5a,b, are potentially useful building blocks used for the
synthesis of phosphorus substituted carbocycles.15 As part of our interest in these active
phosphorus reagents,15–22 we described here the behavior of (N-phenyliminovinylidene)-
(5a), (2-oxovinylidene)-triphenylphosphorane (5b), toward the bifunctional compound 2-
hydroxyisoindole-1,3-(2H)dione (1). When 1 mol equivalent of compound 1 was treated
with 2 mol equivalents of the phosphorus reagent 5a in tetrahydrofuran (THF) at room tem-
perature for 3 h, phosphanylidenecyclobutylidenisoindoline 7a, along with triphenylphos-
phane oxide was obtained. Formation of the phosphanylidene 7a is proposed to occur by
initial nucleophilic attack of the carbanion center in the ylide 5a on the carbonyl function
rather than the OH group in 1, to give the unstable oxaphosphetane,19,21–24 which decom-
posed to triphenylphosphane oxide and the unstable ketene 6.24 A second molecule of the
ylide 5a was added to the ketene 6, to give the stable phosphanylidenecyclobutylidene 7a.

CHEMISTRY OF PHOSPHORUS YLIDES
635
R(O)C
PPh3
CHC(O)R
NOH
H
Ph3P=CHCOR
O
+ Ph3P=O
2a, R = CH3
b, R = C6H5
c, R = OCH3
d, R = OC2H5
N OH
O
O
4a, R = CH3
b, R = C6H5
c, R = OCH3
3
O
d, R = OC2H5
NOH
O
1
PPh3
X
C C
X
X
NOH
Ph3P=C=C=X
+ 5
5a, X = N- C6H5
b, X = O
NOH
O
6
O
7a, X = N -C H5
b, X = O
6
+
Ph3P=O
Scheme 1
The assignment of the proposed structure 7a was based on the following observations. The
IR spectrum of 7a (KBr, ν cm−1) showed the OH stretching vibration at 3400, the CO at
1670, the C N at 1630, C P at 1610,25 and 1443 (P-phenyl).26 The 1H NMR spectrum of
7a (CDCl3) showed the OH signal at δ 10.22, which disappeared upon addition of D2O,
and at 7.45–7.65 ppm (m, 29H, arom-H). The 13C NMR spectrum of 7a (CDCl3) showed
the presence of signals at δ 160.3 (C O), 167.6 (C N), and 145.6 ppm (d, 1JCP = 95.7 Hz,
C P). Moreover, a signal at δ 19.7 ppm was observed in its 31P NMR spectrum, which fits
for a phosphanyl group at a four-membered ring (Scheme 1).27,28
The reaction of compound 1 with the phosphorane reagent 5b was performed in dry
boiling toluene. The phosphanylidenecyclobutylidene derivative 7b together with triph-
enylphosphane oxide was produced. Compound 7b was identified on the basis of its IR,
1H, 13C, 31P NMR, and MS data. The 1H NMR and 31P NMR of 7b are shown in Figures
S1 and S2 (available online in Supplemental Materials).
The reaction of isoindoline-1,3-dione (8), with the active phosphacumulenes 5a,b
was also studied. The reaction proceeded in THF at room temperature for 4 h in case of 5a,
and in boiling toluene for 6 h in case of 5b to give the corresponding phosphanylidenecy-
clobutylidenisoindole derivatives 9a and 9b, respectively. Triphenylphosphane oxide was
also isolated and identified (mp and mixed mp) (Scheme 2).
Finally, the reaction of indane-1,3-dione (10) with the active ylides 5a and 5b was per-
formed to give triphenylphosphane oxide and the indene phosphanylidenecyclobutylidene
derivatives 11a and 11b, respectively (Scheme 2).

636
S. S. MAIGALI ET AL.
PPh3
X
O
X
+ 5a, b
NH
+ Ph3P=O
NH
O
O
8
9a, X = N-C6H5
b, X = O
PPh3
O
O
X
X
+ 5a, b
+ Ph3P=O
10
O
11a, X = N-C6H5
b, X = O
Scheme 2
Structural assignment for compounds 9a, 9b, 11a, and 11b was based upon elemental
analyses and spectroscopic data (IR, 1H, 13C, 31P NMR, and MS).
CONCLUSION
The reaction of the bifunctional 2-hydroxyisoindole-dione 1 with the stabilized phos-
phonium ylides 2a–d differs markedly from that of the respective active phosphacumulenes
5a,b. Although, the initial step in these reactions is nucleophilic attack by the carbanion
center of the phosphorane at the carbonyl group rather than the hydroxyl group, the con-
sequences of reaction varied markedly according to the structure of these phosphoranes.
While the stabilized phosphonium ylides afforded the isoindoline-ylidenes 4a–d, the active
phosphacumulenes gave the phosphanylidenecyclobutylideneisoindoles 7a and 7b. More-
over, the difference in the nucleophilic character of (N-phenyliminovinylidene)-(5a), and
(2-oxovinylidene)-triphenylphosphorane (5b) can be observed too, (5a > 5b).29 While 5a
reacts smoothly with 1, 8, and 10, the oxo analogue reacts less rapidly.
BIOLOGICAL EVALUATION OF THE TESTED COMPOUNDS
Biological Screening
The antibacterial and antifungal activities were carried out in the Microbial Depart-
ment, National Research Centre, using the diffusion plate method.30–33

CHEMISTRY OF PHOSPHORUS YLIDES
637
Antibacterial and Antifungal Activities
The antimicrobial activity of the tested compounds was examined against Gram-
positive bacteria Bacillus subtilis, Bacillus cereus, and Staphylococcus aureus, Gram-
negative bacteria Escherichia coli, Pseudomonas aeruginose, and Salmonella, and fungus
Candida albicans. The obtained results are compared with the reference antibiotics30–33
that were purchased from Egyptian markets.
Conclusion
From Tables S1 and S2 (available online in Supplemental Materials), compound
4b was the only compound that exhibited antibiological activity against all the tested
microorganisms (both Gram-positive and Gram-negative bacteria in addition to Candida
albicans fungus) with nearly 50% efficiency compared to the reference antibiotic with the
same concentration (mg/mL). It is worth noting that the starting material 1 and 2b have
no antimicrobial activity, but the product 4b showed remarkably positive antimicrobial
activities. Excellent inhibition (clear zone) to Salmonella pathogen was achieved by both
11b and 4d compounds knowing that their starting compounds (10, 5b) and (1, 2d) have no
antibiological activity against this pathogen. The clear inhibition zone reached 20 mm in
case of 11b, that is, equivalent to the strength of the reference antibiotic, while it exceeds
twice the activity of it in case of compound 4d. Other tested compounds resulted in moderate
different antibiological activities.
EXPERIMENTAL
Melting points (mp) were measured in open glass capillaries using Electrothermal
IA 9100 series digital melting point apparatus (Electrothermal, Essex, UK). The IR spectra
were recorded in KBr pellets on a Pye Unicam SP 3300 and Shimadzu FT IR 8101 PC
infrared spectrophotometers (Pye Unicam Ltd. Cambridge, England and Shimadzu, Tokyo,
Japan, respectively). The 1H, 13C NMR spectra were obtained from a JEOL ECA 500 MHz
NMR spectrometer (Tokyo, Japan) using CDCl3 as a solvent and tetramethylsilane (TMS)
as an internal reference at 500.14, 125.76 MHz, respectively, and the 31P NMR spectra
were obtained from a JEOL ECA 500 MHz spectrometer at 200.4 MHz NMR spectrometer
using H3PO4 (85%) as an external reference. Mass spectra (EI-MS) were recorded at 70 eV
on a Finnigan MAT SSQ 7000 spectrometer (England). Elemental analyses (C, H, and
N) were performed using Elementar Vario EL-Germany Instrument, P was measured by
spectrophotometric methods at the analytical laboratory of the National Research Center.
The experimental values agreed well with the calculated ones. The reported yields are
used upon pure materials isolated by column chromatography on silica gel 60 (Merck,
Darmstadt, Germany).
Reaction of 2-Hydroxyisoindole-1,3(2H)dione (1) with Stabilized
Phosphonium Ylides 2a–d
General Procedure. To a solution of 2-hydroxyisoindole 1 (0.326 g, 2 mmol) in dry
toluene (20 mL), was added a solution of the methylenetriphenylphosphoranes 2a–d,34,35
(2 mmol) in dry toluene (30 mL) and the reaction mixture was refluxed for 3 h monitored
by thin layer chromatography (TLC). The solvent was distilled off and the residue was

638
S. S. MAIGALI ET AL.
chromatographed on silica gel using petroleum ether 60–80 ◦C/acetone as eluent affording
compounds 4a–d, together with triphenylphosphane oxide (mp and mixed mp 151 ◦C).
2-Hydroxy-3-(2-oxopropylidene) isoindolin-1-one (4a)
Eluent: petroleum ether 60–80 ◦C/acetone (35:65, v/v). Yellow crystals; yield 70%;
mp 103–105 ◦C. IR (KBr, ν cm−1): 3245 (OH), 1791 (CO–CH3), 1668 (C O, isoindolone).
1H NMR (500.14 MHz, CDCl3, δ ppm): 2.62 (s, 3H, CH3), 5.95 (s, 1H, CH), 7.45–7.65 (m,
4H, arom-H), 7.91 (OH, exchangeable with D2O). 13C NMR (125.76 MHz, CDCl3, δ ppm):
30.0 (CH3), 109.6 (CH), 157.5 (C O, isoindolone), 197.5 (CO–CH3). MS m/z (%) = 204
[(M+H), 100]. Anal. calcd. for C11H9NO3 (203.06): C, 65.02; H, 4.46; N, 6.89%. Found:
C, 65.10; H, 4.30; N, 6.56%.
2-Hydroxy-3-(2-oxo-2-phenylethylidene)isoindolin-1-one (4b)
Eluent: petroleum ether 60–80 ◦C/acetone (30:70, v/v). Yellow crystals; yield 73%;
mp 146–148 ◦C. IR (KBr, ν cm−1): 3201 (OH), 1658 (CO–Ph), 1612 (C O, isoindoline).
1H NMR (500.14 MHz, CDCl3, δ ppm): 5.62 (s, 1H, CH), 7.40–8.00 (m, 9H, arom-H),
9.54 (OH, exchangeable with D2O). MS, m/z (%) = 265 (M+, 37.39), 160 [M+−(CO–Ph),
30.41], 105 [(CO–Ph), 100]. Anal. calcd. for C16H11NO3 (265.07): C, 72.45; H, 4.18; N,
5.28%. Found: C, 72.22; H, 4.02; N, 5.11%.
Methyl-2-(2-hydroxy-3-oxoisoindolin-1-ylidene)acetate (4c)
Eluent: petroleum ether 60–80 ◦C/acetone (40: 60, v/v). Yellow crystals; yield
◦
69%; mp 174–176 C. IR (KBr, ν cm−1): 3210 (OH), 1790 (CO–OCH3), 1665 (C O,
1
isoindoline). H NMR (500.14 MHz, CDCl3, δ ppm): 3.75 (s, 3H, OCH3), 5.55 (s, 1H,
CH), 7.65–7.86 (m, 4H, arom-H), 9.10 (s, 1H, OH, exchangeable with D2O). 13C NMR
(125.76 MHz, CDCl3, δ ppm): δ 51.8 (OCH3), 102.5 (CH), 156.5 (C O, isoindoline), 168.5
(CO–OCH3). MS, m/z (%) = 219 (M+, 5.40), 218 [M+−(H), 4.97], 204 [M+−(CH3), 4.86],
202 [M+−(OH), 8.52], 188 [M+−(OCH3), 5.11]. Anal. calcd. for C11H9NO4 (219.19): C,
60.27; H, 4.14; N, 6.39%. Found: C, 60.10; H, 4.00; N, 6.26%.
Ethyl-2-(2-hydroxy-3-oxoisoindolin-1-ylidene)acetate (4d)
Eluent: petrol◦eum ether 60–80 ◦C/acetone (60:40, v/v). Yellow crystals; yield
72%; mp 149–151 C. IR (KBr, ν cm−1): 3391 (OH), 2922 (CH3), 2854 (CH2), 1771
(CO–OC2H5), 1668 (C O, isoindoline). 1H NMR (500.14 MHz, CDCl3, δ ppm): 1.25 (t,
3H, CH2–CH3), 4.20 (q, 2H, CH2–CH3), 5.55 (s, 1H, CH), 7.60–7.81 (m, 4H, arom-H), and
9.00 (s, 1H, OH, exchangeable with D2O). 13C NMR (125.76 MHz, CDCl3, δ ppm): 14.1
(CH3), 62.5 (CH2), 106.5 (CH), 158.5 (C O, isoindoline), 168.7 (CO–OC2H5). MS, m/z
(%) = 232 [M+−(H), 1.02], 205 [M+−(CO), 1.27]. Anal. calcd. for C12H11NO4 (233.07):
C, 61.80; H, 4.75; N, 6.01%. Found: C, 61.55; H, 4.50; N, 6.00%.

CHEMISTRY OF PHOSPHORUS YLIDES
639
Reaction of 2-Hydroxyisoindole-1,3(2H)dione (1), Isoindoline-1,3-dione
(8) and Indane-1,3-dione (10) with Phosphacumulene 5a
General Procedure. To a solution of 1, 8, or 10 (1 mmol) in dry THF (20 mL), was
added dropwise with stirring a solution of (N-phenyliminovinyldene)triphenylphosphorane
(5a)36 (0.754 g, 2 mmol). The reaction mixture was stirred at room temperature for 3 h in
case of compound 1, and for 4 h when compounds 8 or 10 was used (TLC), during which the
color changed from yellow to deep orange. The solvent was removed under reduced pressure
and the residue was chromatographed on silica gel using petroleum ether 60–80 ◦C/ethyl
acetate or acetone as eluent affording compounds 7a, 9a, and 11a. Triphenylphosphane
oxide was also isolated from the reaction medium and identified (mp and mixed mp).
2,4-Bis(phenylimino)-3-[(triphenylphosphanylidene)cyclobutylidene)]-
2-hydroxyisoindolin-1-one (7a)
◦
Eluent: petroleum ether 60–80 C/ethyl acetate (80:20, v/v). Yellow crystals; yield
65%; mp 211–213 ◦C. MS, m/z (%) = 361 [M+−(Ph3P O), 100]. Anal. calcd. for
C42H30N3O2P (639.21): C, 78.86; H, 4.73; N, 6.57; P, 4.84%. Found: C, 78.56; H, 4.48; N,
6.50; P, 4.53%.
3-[2,4-Bis(phenylimino)-3-(triphenyl-λ5-phosphanylidene)
cyclobutylidene]isoindolin-1-one (9a)
Eluent: petroleum ether 60–80 ◦C/acetone (70:30, v/v). Orange crystals; yield 69%;
mp 227–229 ◦C. IR (KBr, ν cm−1): 3197 (NH), 1674 (C O), 1624 (C N), 1565 (C P),
1
1467 (P-phenyl). H NMR (500.14 MHz, CDCl3, δ ppm): 8.30 (s, 1H, NH, exchange-
able with D2O), 6.45–7.69 (m, 29H, arom-H). 13C NMR (125.76 MHz, CDCl3, δ ppm):
1
146.6 (d, JCP = 92.4 Hz, C P), 149.6 (C C–NH), 162.6 (C N), 165.5 (C O). 31P
NMR (202.4 MHz, CDCl3, δ ppm): 15.2. MS, m/z (%) = 278 (Ph3P O, 100), 345
[M+−(Ph3P O), 100]. Anal. calcd. for C42H30N3OP (623.21): C, 80.88; H, 4.85; N,
6.74; P, 4.97%. Found: C, 80.77; H, 4.53; N, 6.53; P, 4.76%.
3-[2,4-Bis(phenylimino)-3-(triphenyl-λ5phosphanylidene)
cyclobutylidene]-2,3-dihydro-1H-iden-1-one (11a)
Eluent: ◦petroleum ether 60–80 ◦C/acetone (60:40, v/v). Yellow crystals; yield 66%;
mp 263–265 C. IR (KBr, ν cm−1): 1720 (C O), 1622 (C N), 1566(C P), 1446 (P-
1
phenyl). H NMR (500 MHz, CDCl3, δ ppm): 2.50 (s, 2H, CH2), 6.62–7.62 (m, 29H,
arom-H). 13C NMR (125.76 MHz, CDCl3, δ ppm): 42.5 (CH2), 148.2 (d, 1JCP = 93.5 Hz,
C P), 169.5 (C N), 189.0 (C O). 31P NMR (202.4 MHz, CDCl3, δ ppm): −4.22 Anal.
calcd for C43H31N2OP (622.22): C, 82.94; H, 5.02; N, 4.50; P, 4.97%. Found C, 82.73; H,
4.85; N, 4.30; P, 4.53%.
Reaction of 2-Hydroxyisoindole-1,3(2H)dione (1), Isoindoline-1,3-dione
(8) and Indane-1,3-dione (10) with Phosphacumulene 5b
General Procedure. To a solution of 1, 8, or 10 (1 mmol) in dry toluene (20 mL)
was added a solution of (2-oxovinylidene)triphenylphosphorane (5b)37 (0.604 g, 2 mmol) in

640
S. S. MAIGALI ET AL.
dry toluene (30 mL). The reaction mixture was refluxed for 5 h when compound 1 was used
and for 6 h in case of 8 or 10 (TLC). Toluene had been distilled off under reduce◦d pressure.
The residue was chromatographed on silica gel using petroleum ether 60–80 C/acetone
as eluent, affording 7b, 9b, and 11b, and triphenylphosphane oxide was also isolated and
identified (mp and mixed mp).
2-(2-Hydroxy-3-oxo-2,3-dihydro-1H-isoindol-1-ylidene)-4-(triphenyl-λ5-
phosphanylidene)cyclobutane-1,3-dione (7b)
Eluent: petroleum ether 60–80 ◦C/acetone (80:20, v/v). Yellow crystals; yield 62% mp
163–165 ◦C. IR: (KBr, ν cm−1): 3345 (OH), 1724 (C O, cyclic), 1682 (C O, isoindoline),
1
1438 (P-phenyl). H NMR (500.14 MHz, CDCl3, δ ppm): 6.86–7.52 (m, 19H, arom-H),
10.21 (s, 1H, OH, exchangeable with D2O). 31P NMR (202.4 MHz, CDCl3, δ ppm) =
19.7. MS, m/z (%) = 278 (Ph3P O, 100), 199 [M+−(Ph3P + CO) 24.59]. Anal. calcd. for
C30H20NO4P (489.11): C, 73.62;H, 4.12; N, 2.86; P, 6.34%. Found: C, 73.50; H, 4.00; N,
2.74; P, 6.22%.
2-(3-Oxo-2,3-dihydro-1H-isoindol-1-ylidene)-4-(triphenyl-λ5-
phosphanyli-dene)cyclobutane-1,3-dione (9b)
Eluent: petroleum ether 60–80 ◦C/acetone (70:30, v/v). Yellow crystals; yield 65%;
mp 178–180 ◦C. IR (KBr, ν cm−1): 3048 (NH), 1720 (C O, cyclic), 1659 (C O, isoindole),
1576 (C P), 1436 (P-phenyl). 1H NMR (500.14 MHz, CDCl3, δ ppm): 7.33–7.80 (m, 19H,
arom-H), 8.13 (s, 1H, NH, changed with D2O). 13C NMR (125.76 MHz, CDCl3, δ ppm):
142.6 (d, 1JCP = 95.3 Hz, C P), 168.6 (C C–NH), 165.5 (C O, isoindole), 188.4 (C O,
cyclic). 31P NMR (202.4 MHz, CDCl3, δ ppm): 15.7. MS, m/z (%) = 278 (Ph3P O, 100),
183 [M+−(Ph3P + CO), 12.81]. Anal. calcd for C30H20NO3P (473.12): C, 76.10; H, 4.26;
N, 2.96; P, 6.54%. Found: C, 76.01; H, 4.15; N, 2.40; P, 6.35%.
2-(3-Oxo-2,3-dihydro-1H-inden-1-ylidene)-4-(triphenyl-λ5-
phosphanylidene)cyclobutane-1,3-dione (11b)
Eluent: petroleum ether 60–80 ◦C/acetone (70:30, v/v); orange crystals; mp 220 ◦C;
yield 72%. IR (KBr, ν cm−1): 2848 (CH2), 1723 (C O, cyclic), 1687 (C O, indene), and
1436 (P-phenyl). 1H NMR (CDCl3, δ ppm): 2.40 (s, 2H, CH2), 6.61–7.61 (m, 19H, arom-
H). 13C NMR (125.76 MHz, CDCl3, δ ppm): 48.3 (CH2), 136.6 (C–C O, indene), 137.5
(C–C O, cyclic), 145.5 (C C–C O), 148.3 (d, 1JCP = 96.8, Hz, C P), 172.2 (C–CH2),
189.3 (C O, cyclic), 194.5 (C O, indene). 31P NMR (202.4 MHz, CDCl3, δ ppm): 14.8.
MS, m/z (%) = 278 (Ph3P O, 100), 182 [M+−(Ph3P + CO), 14.62]. Anal. calcd. for
C31H21O3P (472.12): C, 78.81; H, 4.48; P, 6.56%. Found: C, 78.61; H, 4. 21; P, 6.3%.
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