Synthesis of highly electron-poor alkenes from in situ generated stabilized phosphorus ylides and ninhydrin via intermolecular Wittig reaction

Article abstract of DOI:10.1080/10426500490466166

Protonation of the highly reactive 1:1 intermediates, produced in the reaction between triphenylphosphine and dialkyl acetylenedicarboxylates, by alcohols leads to vinyltriphenylphosphonium salts, which undergo Michael addition reaction with conjugate base to produce the corresponding stabilized phosphorus ylides. Intermolecular Wittig reaction of the stabilized phosphorus ylides with ninhydrin leads to the corresponding, highly electron-poor alkenes.

Full text of DOI:10.1080/10426500490466166

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SYNTHESIS OF HIGHLY ELECTRON-POOR ALKENES
FROM IN SITU GENERATED STABILIZED PHOSPHORUS
YLIDES AND NINHYDRIN VIA INTERMOLECULAR WITTIG
REACTION
Ali Ramazani a & Ali Bodaghi a
a Chemistry Department, Zanjan University , Zanjan, Iran
Published online: 16 Aug 2010.
To cite this article: Ali Ramazani & Ali Bodaghi (2004) SYNTHESIS OF HIGHLY ELECTRON-POOR ALKENES FROM IN SITU
GENERATED STABILIZED PHOSPHORUS YLIDES AND NINHYDRIN VIA INTERMOLECULAR WITTIG REACTION, Phosphorus, Sulfur, and
Silicon and the Related Elements, 179:8, 1615-1620, DOI: 10.1080/10426500490466166
To link to this article: http://dx.doi.org/10.1080/10426500490466166
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Phosphorus, Sulfur, and Silicon, 179:1615–1620, 2004
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490466166
SYNTHESIS OF HIGHLY ELECTRON-POOR
ALKENES FROM IN SITU GENERATED
STABILIZED PHOSPHORUS YLIDES
AND NINHYDRIN VIA INTERMOLECULAR
WITTIG REACTION
Ali Ramazani and Ali Bodaghi
Chemistry Department, Zanjan University, Zanjan, Iran
(Received December 9, 2003)
Protonation of the highly reactive 1:1 intermediates, produced in the
reaction between triphenylphosphine and dialkyl acetylenedicarboxy-
lates, by alcohols leads to vinyltriphenylphosphonium salts, which un-
dergo Michael addition reaction with conjugate base to produce the
corresponding stabilized phosphorus ylides. Intermolecular Wittig re-
action of the stabilized phosphorus ylides with ninhydrin leads to the
corresponding, highly electron-poor alkenes.
Keywords: Acetylenic ester; alcohol; intermolecular Wittig reaction;
ninhydrin; triphenylphosphine
INTRODUCTION
Organophosphorus compounds have been extensively used in organic
synthesis.1−16 β-additions of nucleophiles to the vinyl group of vinylic
phosphonium salts, which leads to the formation of new alkylidenephos-
phoranes has attracted much attention as a very convenient and syn-
thetically useful method in organic synthesis.1−16 In the past we have
established a convenient, one-pot method for preparing stabilized phos-
phorus ylides utilizing in situ generation of the phosphonium salts.1−16
In this article, we report on the one-pot synthesis of dialkyl [indane-1,3-
dione-2-ylidene]alkoxysuccinates (9) from the reaction of alcohols (3),
dialkyl acetylenedicarboxylates (2), triphenylphosphine (1), and ninhy-
drin (6) in low-to-good yields5 (Scheme 1).
The Zanjan University Research Council supported this work.
Address correspondence to Ali Ramazani, Chemistry Department, Zanjan University,
P.O. Box 45195-313, Zanjan, Iran. E-mail: a-ramazani@mail.znu.ac.ir
1615

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A. Ramazani and A. Bodaghi
RESULTS AND DISCUSSION
Reactions are known in which an α,β-unsaturated carbonyl compound
is produced from a phosphorane and a carbonyl compound such as an
aldehyde or ketone.17−23 Thus, compounds 8 may be regarded as the
product of an intermolecular Wittig reaction. Such addition-olefination
products may result from an initial addition of triphenylphosphine 1 to
the acetylenic ester 2 and concomitant protonation of the 1:1 adduct,
followed by attack of the alkoxide on the vinylphosphonium cation to
form phosphorane 5. Attack of the stabilized ylide 5 on the highly
electron-deficient carbonyl group of indane-1,2,3-trione 7 in a normal
intermolecular Wittig reaction would lead to the dialkyl [indane-1,3-
dione-2-ylidene]alkoxysuccinates 9(Scheme 1). TLC indicated that the
reaction was completed after 24 h in CH2Cl2 at room temperature. The
reaction proceeds smoothly and cleanly under mild conditions, and no
SCHEME 1

Wittig Reaction
1617
side reactions were observed. We have also used less-reactive aldehydes
(benzaldehyde and 4-nitrobenzaldehyde) and ketones (acetone and ace-
tophenone) in this reaction, but no products were observed even at re-
flux temperature (toluene as solvent) after 24 h. TLC indicated that the
solution contained ylide 5 and the starting aldehyde or ketone. In this
reaction, in the cases of EtOH, i-PrOH, and n-BuOH, the yields of the
corresponding products 9 were very low (Scheme 1). The weak acidity
of these alcohols may be the factor in the reduction of yields (Scheme 1).
In summary, we have developed a convenient, one-pot method for
preparing dialkyl [indane-1,3-dione-2-ylidene]alkoxysuccinates 9 uti-
lizing in situ generation of the phosphorane 5 (Scheme 1). Other aspects
of this process are under investigation.
EXPERIMENTAL
Melting points were measured on an Electrothermal 9100 apparatus
and are uncorrected. Elemental analyses were performed using a Her-
aeus CHN-O-Rapid analyzer. Ultraviolet (UV) spectra were recorded
on a Shimadzu UV-2100 spectrophotometer. Infrared (IR) spectra were
1
recorded on a Shimadzu IR-460 spectrometer. H and 13C NMR spec-
tra were measured with a BRUKER DRX-500 AVANCE spectrometer
at 500 and 125 MHz, respectively. Mass spectra were recorded on a
Finnigan-Matt 8430 mass spectrometer operating at an ionization po-
tential of 70 eV.
General Procedure for the Preparation of Dialkyl
[Indane- 1,3-dione-2-ylidene]alkoxysuccinates (9a–h)
To a magnetically stirred solution of triphenylphosphine 1 (0.262 g,
1 mmol) and 3 (1 mmol) in CH2Cl2 (5 ml) was added dropwise a mixture
of 2 (1 mmol) in CH2Cl2 (5 ml) at −10◦C over 15 min. The mixture was
allowed to warm up to room temperature, and then powdered ninhydrin
6 (0.18 g, 1 mmol) was added and stirred for 24 h. The solvent was
removed under reduced pressure, and the viscous residue was purified
by flash column chromatography (silica gel; hexane-ethyl acetate). The
solvent was removed under reduced pressure and the products were
obtained as white crystals (9a, m.p. 115.5–117.5◦C; 9c, m.p. 130.9–
132.9◦C) and viscous colorless oils (9b, 9d–h).
Spectral Data for Dimethyl [Indane-1,3-dione-2-ylidene]-
methoxysuccinate (9a)
UV (ethanol, 95%), λmax/nm (logε): 206 (4.02), 247 (4.26), and 281 (4.12).
1
IR (KBr) (νmax, cm−1): 2960, 1749, and 1718. H NMR (CDCl3) δH: 0.9

1618
A. Ramazani and A. Bodaghi
and 1.3 (2H, 2 br. s, 2 OH), 3.15, 3.76 and 3.86 (9H, 3 s, 3 OCH3), 5.97
(1H, s, OCH), 7.67 (1H, t, 3 J = 7.5 Hz, CH (arom.)), 7.79 (1H, t, 3 J
HH
HH
3
= 7.5 Hz, CH (arom.)), 7.86 (1H, d, J = 7.6 Hz , CH (arom.)), 8.28
HH
(1H, d, 3 J = 7.7 Hz, CH (arom.)). 13C NMR (CDCl3) δC: 52.64, 52.80,
HH
53.27, 90.10, 114.26, 122.88, 125.73, 128.52, 132.80, 136.36, 138.55,
140.63, 149.41, 162.43, 168.60 and 190.03. MS, m/z(%): 318 (M+, 30),
290 (32), 274 (60), 259 (54), 243 (100), 231 (90), 187 (20), 157 (38), 129
(30), 75 (17), and 59 (73). Analysis: Calc. for C16H14O7(318.28): C, 60.38;
H, 4.43. Found: C, 60.32; H, 4.68.
Spectral Data for Diethyl [Indane-1,3-dione-2-ylidene]-
methoxysuccinate (9b)
UV (ethanol, 95%), λmax/nm (logε): 206 (4.09), 246 (4.25), and 279 (4.13).
IR (KBr) (νmax, cm−1): 2991, 1749, and 1720. 1H NMR (CDCl3) δH : 1.05,
and 1.14 (2 H, 2 br. s, 2 OH), 1.20, and 1.29 (6H, 2 t, 3 J = 7.1 Hz,
HH
2 CH3 of 2 Et); 3.44 (3H, s, OCH3), 4.1–4.3 (4H, 2 m, 2 OCH2 of 2 Et),
5.90 (1H, s, OCH), 7.57 (1H, t, 3 J = 7.5 Hz, CH (arom.)), 7.72 (1H, t,
HH
3
3 J = 7.5 Hz, CH (arom.)), 7.78 (1H, d, J = 7.6 Hz , CH (arom.)),
HH
HH
8.23 (1H, d, 3 J = 7.7 Hz, CH (arom.)). 13C NMR (CDCl3) δC: 14.30,
HH
14.48, 52.65, 61.92, 62.31, 90.27, 114.30, 123.37, 125.71, 128.67, 132.68,
136.27, 138.57, 140.48, 149.02, 161.93, 168.20, and 190.12.
Spectral Data for di-tert-butyl [Indane-1,3-dione-2-
ylidene]methoxysuccinate (9c)
UV (ethanol, 95%), λmax/nm (logε): 204.8 (3.69), 247.2 (3.79) and 280.0
(3.99). IR (KBr) (νmax, cm−1): 2978, 2930, 1738, and 1700. 1H NMR
(CDCl3) δH : 1.43, and 1.55 (18H, 2 s, 2 OC (CH3)3), 3.49 (3H, s, OCH3),
5.77 (1H, s, OCH), 7.59 (1H, t, 3 J = 7.6 Hz, CH (arom.)), 7.75 (1H, t,
HH
3 JHH = 7.6 Hz, CH (arom.)), 7.83 (1H, d, 3 JHH = 7.6 Hz, CH (arom.)), 8.29
(1H, d, 3 J
= 7.6 Hz, CH (arom.)). 13C NMR (CDCl3) δC: 28.18,
HH
28.50, 52.52, 82.87, 83.39, 91.95, 114.59, 125.20, 125.51, 128.71, 132.20,
136.05, 139.04, 140.32, 147.36, 161.48, 167.26, and 190.71. MS, m/z (%):
402 (M+, 6), 371 (28), 347 (42), 315 (45), 291 (55), 271 (16), 258 (14), 245
(30), 228 (42), 57 (100%), 41 (32). Analysis: Calc. for C22H26O7 (402.45):
C, 65.66; H, 6.51. Found: C, 65.23; H, 6.55.
Spectral Data for Dimethyl [Indane-1,3-dione-2-
ylidene]benzoxysuccinate (9d)
UV (ethanol, 95%), λmax/nm (logε): 207 (4.02), 247 (3.98), and 282 (3.85).
1
IR (KBr) (νmax, cm−1): 2980, 1757, and 1720. H NMR (CDCl3) δH: 1.1

Wittig Reaction
1619
and 1.4 (2H, 2 br. s, 2 OH), 3.75 and 3.82 (6H, 2 s, 2 OCH3), 4.72
(1H, d,2 J = 9.0 Hz, OCH2), 4.98 (1H, d,2 J = 9.0 Hz, OCH2), 5.98
HH
HH
(1H, s, OCH), and 7.0–8.4 (9H, m, 9 CH (arom.)). 13C NMR (CDCl3)
δC: 52.33, 52.90, 67.35, 89.67, 113.73, 122.57, 125.38, 126.97, 127.54,
128.03, 128.47, 132.42, 136.01, 136.94, 138.25, 140.24, 149.32, 162.07,
168.22, and 189.88.
Spectral Data for Dimethyl [Indane-1,3-dione-2-
ylidene]alloxysuccinate (9e)
UV (ethanol, 95%), λmax/nm (logε): 206 (4.16), 247 (4.31), and 282 (4.16).
IR (KBr) (νmax, cm−1): 2929, 2860, 1757, and 1721. 1H NMR (CDCl3) δH:
1.1 and 1.3 (2H, 2 br. s, 2 OH), 3.78 and 3.91 (6 H, 2 s, 2 OCH3), 4.2–
4.4 (2H, m,OCH2), 5.0–5.4 (2H, m, CH2), 5.6–5.8 (1H, m, CH), 6.01
(1H, s, OCH) and 7.2–8.4 (4H, m, 4 CH (arom.)). 13C NMR (CDCl3)
δC: 52.33, 52.86, 66.17, 89.59, 113.53, 117.68, 133.56, 152.34, 128.31,
132.38, 135.97, 122.53, 138.17, 140.24, 149.24, 162.07, 168.18, and
189.76.
Spectral Data for Dimethyl [Indane-1,3-dione-2-
ylidene]ethoxysuccinate (9f)
3
1H NMR (CDCl3) δH: 1.24 (3H, t, J = 6.8 Hz, CH3 of Et); 3.79 and
HH
3
3.95 (6H, 2 s, 2 OCH3), 3.85 (2H, q, J = 6.8 Hz, OCH2 of Et); 6.01
HH
(1H, s, OCH), and 7.5–8.4 (4H, m, 4 CH (arom.)).
Spectral Data for Dimethyl [Indane-1,3-dione-2-
ylidene]iso-propoxysuccinate (9g)
1H NMR (CDCl3) δH: 1.11 (3H, d, 3 J = 6.8 Hz, CH3 of iso-propyl);
HH
3
1.33 (3H, d, J = 6.8 Hz, CH3 of iso-propyl), 3.80 and 3.91 (6H, 2 s,
HH
2 OCH3), 4.2–4.5 (1H, m, OCH of iso-propyl ), 6.00 (1H, s, OCH), and
7.5–8.3 (4H, m, 4 CH (arom.)).
Spectral Data for Dimethyl [Indane-1,3-dione-2-
ylidene]butoxysuccinate (9h)
1H NMR (CDCl3) δH: 0.8–1.0 (7H, m, n-butyl), 1.0–1.3 (2H, 2 br. s, 2 OH),
3.7–4.0 (8H, m, 2 OCH3 and 1 OCH2), 5.98 (1H, s, OCH) and 7.5–8.4
(4H, m, 4 CH (arom.)).
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