Synthesis of a new class of highly functionalized phosphorus ylides containing heterocyclic compounds

Article abstract of DOI:10.1002/cjoc.201200199

The zwitterionic intermediate generated from the reaction of triphenylphosphine with electron deficient acetylenic compounds was trapped by various NH acids. The synthesis resulted in a new class of highly functionalized heterocyclic compounds. Some of the reactions produced E and Z isomers. And the stability and transformation of them were studied by dynamic ¹H NMR and density functional theory (DFT) calculations.

Full text of DOI:10.1002/cjoc.201200199

FULL PAPER
DOI: 10.1002/cjoc.201200199
Synthesis of a New Class of Highly Functionalized Phosphorus
Ylides Containing Heterocyclic Compounds
Shaabani, Ahmad*
Keshipour, Sajjad
Aghaei, Morteza
Khodabandeh, M. Hassan
Zahedi, Mansour
Department of Chemistry, Shahid Beheshti University, G. C., P. O. Box 19396-4716, Tehran, Iran
The zwitterionic intermediate generated from the reaction of triphenylphosphine with electron deficient acety-
lenic compounds was trapped by various NH acids. The synthesis resulted in a new class of highly functionalized
heterocyclic compounds. Some of the reactions produced E and Z isomers. And the stability and transformation of
them were studied by dynamic 1H NMR and density functional theory (DFT) calculations.
Keywords highly functionalized heterocyclic compounds, phosphorus ylides, triphenylphosphine, DFT, dynamic
1H NMR
Introduction
Phosphorus compounds have useful functional group
and can be used as reactive speices, which take part in
many reactions of value in organic synthesis. The most
common applications of this functionality is its utiliza-
tion in Wittig,[6-8] Horner-Wadsword-Emmons olefina-
tion,[9] Staudinger,[10-12] Mitsunobu,[13-15] Rauhut-
Currier,[16-21] Morita-Baylis-Hillman[22-24] reactions and
as ligands in transition metal catalyzed processes.[25-28]
All these applications are summarized in numerous re-
views in the literature.[29-31]
As a part of our current studies on the multicompo-
nent reactions (MCRs),[32-35] herein we wish to investi-
gate the possibility of the synthesis of a new class of
bridgehead nitrogen-containing heterocycles 9a — 9c
containing phosphorus ylides (Scheme 1).[36-38]
Bridgehead nitrogen-containing heterocycles are an
important class of compounds with useful biological
activities.[1] Naturally occurring compounds with two
rings junction nitrogen atoms are rare, nigellicine (1)
(isolated from the seeds of Nigella sativa) and its
derivatives nigellidine (2) are the only natural com-
pounds of this group.[2] Cinnopentazone (3) is a pyra-
zolo[1,2-a]pyridazine that exhibits anti-inflammatory,
analgesic, antihypoxic, antipyretic and antibacterial
activities.[3] One of the most important bridgehead
nitrogen-containing heterocyclic molecules with urazole
moiety is the compound 4, which has HSP (heat
shocking protein) inhibitory activity.[4] In addition,
Boatman and co-workers[5] reported the protease inhib-
itors properties for the triazolopyridazine compounds 5
(Figure 1).
Scheme 1 Synthesis of bridgehead nitrogen-containing hetero-
cyclic phosphorus ylide derivatives 9a—9c
-
-
CO2
O
C5H11
Me
O
+
HO
OH
N
N
O
N
R'
N
N N
O
O
EtOAc
N
O
O
+
PPh3
+
Me
r.t., 6 h
RO
OR
6
Ph
HN NH
Nigellicine (1)
Nigellidine (2)
Cinnopentazone (3)
7
8
R3
O
R = Me or Et
a R' = H
b R' = Ph
O
R2
N
N
N Ph
R4
N
O
N
O
N
O
N
N
H
O
Ph3P
O
R1
O
OH
O
N
O
N
H
R'
4
5
O
OR
Figure 1 Examples of some biologically active compounds
with two ring junction nitrogen atoms.
9a − 9c
*
E-mail: a-shaabani@cc.sbu.ac.ir; Fax: 0098-21-22431661
Received February 27, 2012; accepted May 6, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201200199 or from the author.
Chin. J. Chem. 2012, 30, 1893—1900 © 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Shaabani et al.
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Results and Discussion
Scheme 2 Possible mechanism for the formation of products
9a—9c
As indicated in Scheme 1, triphenylphosphine (6),
dialkyl acetylenedicarboxylates 7 and bicarbamimide
derivatives 8a or 8b underwent a smooth 1∶1∶1 addi-
tion reaction to afford interesting heterocylic com-
pounds 9a—9c in ethyl acetate at room temperature. As
can be seen from Table 1, the reaction is straightforward
and the yields of products 9a—9c are fairly good.
O
O
O
-
OR
RO
PPh3
+
+PPh3 O
RO
OR
6
7
10
-
N NH
N
O
O
O
O
PPh3
O
OR
RO
R'
12
Table 1 Yields of products 9a—9c
RO
+PPh3 O
-
N N
OR
O
9a－9c
Compd.
9a
R
R'
H
Isolated yield/%
11
O
N
Me
Me
Et
86
84
80
R'
13
9b
C6H5
C6H5
9c
To explore the scope and limitations of this reaction,
we extended our studies to the use of various cyclic
compounds containing amide functional group such as
phthalazin-1(2H)-one (14a), 2,3-dihydrophthalazine-
1,4-dione (14b), 3-(phenylimino)indolin-2-one (14c),
3-methyl-1H-pyrazol-5(4H)-one (14d), 3,6-dimethyl-
piperazine-2,5-dione (14e) and oxazolidin-2-one (14f),
and various dialkyl acetylenedicarboxylates with
triphenylphosphine. As indicated in Table 2, the
reaction proceeded efficiently and led to the formation
of a new class of nitrogen-containing heterocyclic com-
pounds with phosphorus ylide group 15a—15j in fairly
A possible mechanism for the formation of products
9a—9c is shown in Scheme 2. Zwitterionic intermediate
10 is formed on the basis of the well-established chem-
istry of triphenylphosphine (6) with dialkyl acetylene-
dicarboxylates 7.[35-38] It is reasonable to assume that the
protonation of the zwitterionic intermediate 10 by the
NH acid (1∶1) followed by quenching of the cationic
center through the conjugate base of the NH acids gen-
erates the intermediate 13. Then, product 9 could be
obtained by an intramolecular condensation reaction of
intermediate 13.
Table 2 Structures, yields and E/Z ratios of products 15a—15j
Entry
1
Amide
R
Product
Isolated yield/%
E∶Z
OMe O
O
O
OMe
Me
91
55∶45
N
N
PPh3
O
15a
NH
N
OMe O
O
O
OEt
14a
N
N
PPh3
2
3
4
Et
Me
Et
88
82
87
62∶38
100∶0
15b
OMe O
O
O
OMe
N
NH
PPh3
O
O
NH
NH
15c
OMe O
O
O
O
OEt
14b
N
NH
PPh3
100∶0
O
15d
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Synthesis of a New Class of Highly Functionalized Phosphorus Ylides
Continued
Entry
Amide
R
Product
Isolated yield/%
E∶Z
OMe
H
N
O
PPh3
O
O
O
N
5
Me
85
90∶10
MeO
N
N
Ph
Ph
14c
15e
O
PPh3
OMe
MeO
HO
N
O
N
6
7
Me
84
83
65∶35
57∶43
H
N
15f
HO
N
O
PPh3
14d
OEt
MeO
HO
N
O
N
Et
15g
O
OEt
O
H
O
N
MeO
O
PPh3
O
N
8
Et
90
63∶37
N
H
14e
O
N
H
15h
O
PPh3
OMe
MeO
O
9
Me
Et
96
91
64∶36
72∶28
N
O
O
H
15i
N
O
O
PPh3
O
O
14f
OEt
MeO
O
N
10
O
15j
carbon double bond on the NMR time scale at ambient
high yields at room temperature.
1
temperature (Scheme 3). Therefore, the H and 13C
It is important to note that phthalazin-1-ones 15a—
15d, pyrazoles 15f, 15g and oxazolidinones 15i, 15j
have received considerable attention due to their syn-
thetic and biological importance.[39-44]
Ylides 9 and 15 both have been examined in the
Wittig reaction under the reported conditions in the lit-
erature.[45,46] However, none of them participated in the
reaction, which resulted from the low activity of prod-
ucts 9 and 15 due to conjugation of the ylide moiety
with carboxylate group.
NMR spectra of ylides 15 are consistent with the pres-
ence of two isomers E and Z.
Scheme 3 E and Z isomers with rotation around C＝C bond
OMe
O
-
O
OMe
OMe
O
H
N
N
O
O
H
N
N
OMe
-
O
+PPh3
+PPh3
(Z)-15a isomer
(E)-15a isomer
It is interesting to note that the conjugation in prod-
ucts 15 caused slow rotation around the partial carbon-
Tc = 232 K
ΔG# = (17.14 ±1) kJ/mol
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To evaluate the transformation of the two isomers,
dynamic 1H NMR of product 15a has been studied. The
1H NMR spectrum for the 15a showed two resonances
at δ 3.37 and 3.49 (s) arising from methoxy groups
(MeO—C＝C—P) that were separated appreciably at
20 ℃. The resonance coalescence occurred at 50 ℃
(323 K) which is relevant to restrict a rotational process
around carbon-carbon double bond (Figure 2-I). More-
over, this process has been observed for methine pro-
tons (H—C—C—P) that appeared as two doublets at δ
5.65 and 5.71 (3JHP＝7.28 Hz) (Figure 2-II).
that was exchangeable with temperature made us curi-
ous to identify the stable isomer. In order to determine
the stable isomer, theoretical conformational analysis
has been performed.
After conformational search, geometry optimization
has been shown that the E conformer is more stable than
the Z conformer by about 1.3 kcal/mol. The E moiety,
however, becomes more stable through electrostatic
attraction of opposite charges on phosphorus and oxy-
gen as well as the reduction of repulsion between OCH3
groups with phenyl groups linked to phosphorus. Thus,
the two structures become competitive. Therefore, con-
version of one structure to the other has been considered.
The B3LYP-free energy profile as well as the geometry
of stationary points found for the mechanism is repre-
sented in Figure 3.
Figure 2 Partial 1H NMR spectra of (Z)-15a and (E)-15a in
DMSO at various temperatures in two spectral area. Methoxy
signals at δ 3.49 and 3.37 (I) and CH signals at δ 5.65 and 5.71 (II)
ascribed to the starting of transformation of two isomers.
Figure 3 Conversion mechanism of E to Z. Free energy profile,
in kcal/mol, for the B3LYP optimized structures (bond lengths in
Å). Relative free energies with respect to E.
Investigation of the temperature dependence 1H
NMR spectra of 15a for the methoxy group and methine
hydrogen allowed calculating the rotational energy bar-
rier (ΔG#) for the restricted rotational processes around
the heteroatom carbon-carbon double bond. With ap-
plying expression kc＝πΔν/ 2 , first-order rate constant
was calculated for bond rotational process. With respect
to the experimental data, activation value of free Gibbs
rotational energy barrier was calculated. As it has been
predictable, both of calculations for methoxy and me-
thine moieties showed the same result and one con-
firmed another (Table 3).
Focusing on the activation-free energy (Table 4),
one can observe that the highest energy barrier corre-
sponding to E and Z conversion via TS is about 17
kcal/mol. Bond lengths that are shown in Figure 3, for
both conformers are very similar. Calculated C—C
length in E conformer is slightly shorter than that in Z
(1.438 Å in Z and 1.431 Å in E). Also, natural bond
analysis (nbo) showed hybridization of C(1) of P—C(1)
—C(2) bond for both E and Z structures is sp2, whereas,
along the path of conversion, p character of hybridiza-
tion of this atom increases. Finally, hybridization of this
atom in C—C bond in TS structure changes to sp2.4.
Therefore, C—C bond length is longer than that of the
reactants, so rotation occurs around the C—C bond.
Paying attention to the C(1)—P bond in TS species, a
slight change in its hybridization has been noted,
namely its p character has been reduced. Decreasing
bond length of C(1)—P in TS structure in comparison
of the reactant has been attributed to this reduction of p
character in C(1) (Figure 3).
1
Table 3 Selected H chemical shifts (at 300 MHz) and activa-
tion value of free Gibbs rotational energy barrier of phosphorus
ylide 15a, in DMSO at Tc＝323 K, for rotation around the car-
bon-carbon double bond
1
δ
Δν/Hz
kc/s−
ΔG#/(kcal/mol)
17.14±1
3.50, 3.52
7.38
16.38
Existence of both isomers and their respective ratio
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Chin. J. Chem. 2012, 30, 1893—1900

Synthesis of a New Class of Highly Functionalized Phosphorus Ylides
Table 4 Activation energy (Ee, E0, E298), enthalpy (ΔH298) and
free energy (ΔG298) (in kcal/mol).
analyses were performed with an Elementar Analysen-
systeme GmbH VarioEL. The chemicals used in this
work were purchased from Merck and Fluka Chemical
Companies.
Energy
Eea
Theoretical
17.3
Experimental
—
—
a
Preparation of bridgehead nitrogen-containing
heterocycles
E0
17.0
a
E298
16.5
—
a
Taking synthesis of 15a as the example, to a mag-
netically stirred solution of triphenylphosphine (0.26 g,
1.0 mmol) and phthalazin-1(2H)-one (0.15 g, 1.0 mmol)
in EtOAc (10 mL) was added dropwise a solution of
dimethyl acetylenedicarboxylate (0.14 g, 1.0 mmol) in
EtOAc (2 mL) at 0 ℃ over 10 min and then the reac-
tion mixture brought to ambient temperature and was
stirred for 6 h. The precipitate was filtered off, washed
with EtOAc (5 mL×2) and dried in a vacuum oven to
obtain the corresponding product 15a as a white powder
(0.50 g, yield 91%).
ΔH298
16.5
—
a
ΔG298
17.4
17.1
a Activation energy.
Conclusions
We have developed a very simple and highly effi-
cient approach to the synthesis of a library of phospho-
rus ylides containing heterocyclic compounds from
various cyclic amides and dialkyl acetylenedicarboxy-
lates in the presence of triphenylphosphine in high
yields. The work-up procedure is very simple and the
products do not require further purification. The coales-
cence temperature for linear phosphorus ylides E and Z
isomers is determined and ΔG# transformation of these
Methyl 1,3,7-trioxo-6-(triphenylphosphoranylidene)-
hexahydropyrazolo[1,2-a][1,2,4]triazole-5-carboxylate
1
(9a): White powder, yield 86%; m.p. 156—160 ℃; H
NMR (DMSO-d6) δ: 3.70 (s, 3H), 6.75 (s, 1H), 7.51—
7.81 (m, 15H), 14.66 (br s, 1H); 13C NMR (DMSO-d6) δ:
1
two isomers is obtained with dynamic H NMR study
2
40.6, 52.4, 61.9 (d, JPC＝15 Hz), 121.1, 129.0, 129.2,
and DFT calculations. There is a very good accordance
at ΔG# transformation between the experimental and
calculated values. The E conformer as the stable isomer
was identified in the gas phase.
130.4, 130.5, 131.8, 131.9, 132.0, 132.3, 132.4, 133.3,
133.4, 156.4, 159.1, 159.6, 165.1; MS (70 eV) m/z (%):
473 (M＋, 25), 442 (15), 414 (30), 344 (100), 217 (60),
173 (10), 135 (30), 108 (60), 83 (90), 55 (70). Anal.
calcd for C25H20N3O5P: C 63.43, H 4.26, N 8.88; found
C 63.41, H 4.27, N 8.83.
Experimental
Computational details
Methyl 1,3,7-trioxo-2-phenyl-6-(triphenylphospho-
ranylidene)hexahydropyrazolo[1,2-a][1,2,4]triazole-5-
carboxylate (9b): White powder; m.p. 140—145 ℃; 1H
The adequacy of density functional methods in study
of the conformational behaviours of organic structures
has been the subject of several papers.[47,48] It is shown
that hybrid functionals, in particular the B3LYP,[49-51]
provide very similar structural parameters, vibrational
frequencies and intensities compared with the experi-
mental data. Thus, the geometry optimization and vibra-
tional frequency calculations have been performed at
the B3LYP level. Furthermore, geometry calculations
have been performed using the 6-31＋G(d,p)[52,53] basis
set for all atoms without constraints by applying an un-
restricted formalism. All calculations have been carried
out assuming the gas phase. Net atomic charges and
spin densities were obtained using the natural popula-
tion analysis of Weinhold et al.[54] All calculations were
performed by the Gaussian 98 programs.[55]
3
NMR (CDCl3) δ: 3.20 (s, 3H), 4.81 (d, JPH＝16.0 Hz,
1H), 7.31—7.74 (m, 20H); 13C NMR (CDCl3) δ: 53.2,
57.9, 60.4, 125.6, 125.8, 127.7, 128.4, 128.5, 128.7,
129.0, 129.1, 129.2, 132.0, 132.1, 132.7, 133.4, 133.5,
133.7, 133.8, 151.0, 171.2; 31P NMR (CDCl3) δ: 23.40;
IR (KBr) ν: 3446, 3061, 2948, 1768, 1734, 1698, 1645,
－
＋
1
1436 cm ; MS (70 eV) m/z (%): 549 (M , 5), 518 (10),
490 (5), 445 (65), 405 (80), 365 (40), 345 (55), 262
(100), 183 (80), 148 (70), 116 (30), 77 (40), 55 (70);
Anal. calcd for C31H24N3O5P: C 67.76, H 4.40, N 7.65;
found C 67.71, H 4.41, N 7.63.
Ethyl 1,3,7-trioxo-2-phenyl-6-(triphenylphospho-
ranylidene)hexahydropyrazolo[1,2-a][1,2,4]triazole-5-
carboxylate (9c): White powder; m.p. 230—232 ℃; 1H
NMR (DMSO-d6) δ: 1.22 (t, 3JHH＝6.8 Hz, 3H), 4.18 (q,
3JHH＝6.8 Hz, 2H), 6.75 (s, 1H), 7.38—7.64 (m, 20H);
General information
2
13C NMR (DMSO-d6) δ: 14.4, 50.3 (d, JPC＝14.7 Hz,
Melting points were measured on an Electrothermal
9100 apparatus and uncorrected. Mass spectra were re-
corded on a FINNIGAN-MAT 8430 mass spectrometer
operating at an ionization potential of 70 eV. IR spectra
P—C—CH), 61.5, 129.1, 129.2, 129.3, 129.4, 131.9,
132.0, 132.5, 133.6, 133.7, 133.8, 137.0, 137.1, 164.8;
IR (KBr) ν: 3425, 3049, 2975, 2918, 2881, 1706, 1664,
1592, 1570, 1476; MS (70 eV) m/z (%): 563 (M＋, 5),
529 (35), 475 (30), 405 (35), 262 (70), 183 (100), 149
(80), 130 (30), 104 (60), 76 (65), 50 (30). Anal. calcd
for C32H26N3O5P: C 68.20, H 4.65, N 7.46; found C
68.20, H 4.64, N 7.46.
1
were recorded on a Shimadzu IR-470 spectrometer. H
NMR spectra were recorded on a Bruker DRX-300
Avance spectrometer at 300.13 MHz. The 13C NMR
spectra were recorded at 75.47 MHz and 31P NMR
spectra were recorded at 121.49 MHz. The elemental
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3
Dimethyl 2-(1-oxophthalazin-2(1H)-yl)-3-(triphenyl-
phosphoranylidene)succinate (15a): White powder; m.p.
1H), 7.34—7.73 (m, 17H), 8.13 (d, JHH＝6.6 Hz, 1H),
8.35 (d, JHH＝6.7 Hz, 1H), 11.82 (br s, 1H); 13C NMR
3
1
1
230—235 ℃; H NMR (CDCl3) E and Z isomers δ:
(CDCl3) E isomer δ: 15.1, 15.9, 42.1 (d, JPC＝124.1
2
3.16 and 3.67 (2s, 6H, E), 3.58 and 3.60 (2s, 6H, Z),
5.83 (d, 3JPH＝17.3 Hz, 1H, E), 5.98 (d, 3JPH＝19.71 Hz,
1H, Z), 7.28—7.71 (m, 38H, E and Z), 8.21 (s, 1H, E),
8.26 (s, 1H, Z); 13C NMR (CDCl3) E and Z isomers δ:
37.9 (d, 1JPC＝125.0 Hz), 39.7 (d, 1JPC＝125.0 Hz), 49.1,
50.5, 52.3, 52.5, 61.1, 61.3, 61.8, 61.8, 125.6, 126.3,
126.6, 127.0, 127.6, 128.6, 128.7, 129.8, 130.8, 131.0,
132.0, 132.7, 132.8, 133.6, 133.7, 133.8, 136.6, 158.7,
158.9, 171.5, 171.6; 31P NMR (CDCl3) E and Z isomers
δ: 23.20 (Z), 23.48 (E); IR (KBr) ν: 3049, 2975, 1728,
1655, 1589; MS (70 eV) m/z (%): 550 (M＋, 5), 532 (10),
515 (30), 491 (35), 405 (40), 345 (10), 262 (100), 183
(95), 146 (20), 108 (20), 89 (20), 59 (10). Anal. calcd
for C32H27N2O5P: C 69.81, H 4.94, N 5.09; found C
69.81, H 4.93, N 5.13.
Hz), 51.1, 52.6, 63.2 (d, JPC＝16.9 Hz), 124.7, 125.8,
127.2, 127.4, 128.4, 128.5, 129.1, 129.3, 129.9, 132.0,
132.1, 132.6, 133.1, 133.4, 133.6, 133.7, 155.2, 155.5,
164.7, 171.0, 173.3; 31P NMR (CDCl3) E isomer δ:
23.92; MS (70 eV) m/z (%): 593 (M＋, 20), 573 (20),
560 (15), 549 (10), 522 (10), 475 (70), 262 (50), 183
(100), 149 (70), 130 (20), 76 (45), 50 (50). Anal. calcd
for C34H31N2O6P: C 68.68, H 5.26, N 4.71; found C
68.69, H 5.21, N 4.72.
Dimethyl 2-(2-oxo-3-(phenylimino)indolin-1-yl)-3-
(triphenylphosphoranylidene)succinate (15e): White
powder; m.p. 208—210 ℃; H NMR (CDCl3) E and Z
1
isomers δ: 3.01 and 3.69 (2s, 6H, Z), 3.35 and 3.73 (2s,
3
3
6H, E), 5.13 (d, JPH＝15.9 Hz, 1H, Z), 5.15 (d, JPH＝
15.9 Hz, 1H, E), 6.38—7.61 (m, 48H, E and Z); 13C
NMR (CDCl3) E and Z isomers δ: 37.9, 38.1, 40.3 (d,
Diethyl 2-(1-oxophthalazin-2(1H)-yl)-3-(triphenyl-
phosphoranylidene)succinate (15b): White powder; m.p.
1JPC＝127.1 Hz), 40.6 (d, JPC＝127.1 Hz), 55.7, 56.5,
1
1
150—155 ℃; H NMR (CDCl3) E and Z isomers δ:
60.3, 61.0, 61.4, 62.4, 125.6, 126.2, 126.7, 127.4, 129.1,
129.4, 129.5, 129.6, 131.9, 132.8, 133.1, 133.7, 158.2,
158.9, 168.5, 169.9, 170.3, 172.6; IR (KBr) ν: 3449,
3057, 2950, 1733, 1639, 1465 cm ; MS (70 eV) m/z
(%): 626 (M＋, 20), 547 (20), 472 (15), 445 (35), 405
(75), 364 (75), 345 (70), 291 (20), 262 (100), 218 (20),
183 (70), 108 (30), 77 (45), 51 (50). Anal. calcd for
C38H31N2O5P: C 72.83, H 4.99, N 4.47; found C 72.81,
H 4.93, N 4.46.
Dimethyl 2-(5-hydroxy-3-methyl-1H-pyrazol-1-yl)-
3-(triphenylphosphoranylidene)succinate (15f): White
powder; m.p. 157—160 ℃; H NMR (CDCl3) E and Z
isomers δ: 2.07 (s, 3H, E and Z), 2.14 (s, 3H, E and Z),
3.24—3.68 (m, 12H, E and Z), 3.88 (br, 2H, E and Z),
7.34—7.67 (m, 32H, E and Z), 10.85 (br, 2H, E and Z);
13C NMR (CDCl3) E and Z isomers δ: 30.2, 30.3, 39.9
3
1.14—1.34 (m, 12H, E and Z), 3.75 (q, JHH＝7.1 Hz,
2H, E), 4.06—4.15 (m, 4H, E and Z), 4.26 (q, 3JHH＝7.1
－
3
1
Hz, 2H, Z), 5.81 (d, JPH＝17.8 Hz, 1H, E), 5.87 (d,
3JPH＝17.8 Hz, 1H, Z), 7.28—7.75 (m, 38H, E and Z),
8.24 (s, 1H, Z), 8.26 (s, 1H, E); 13C NMR (CDCl3) E
1
and Z isomers δ: 13.9, 14.1, 14.9, 38.8 (d, JPC＝129.9
1
Hz), 41.1 (d, JPC＝129.8 Hz), 57.6, 58.4, 60.4, 61.0,
61.8, 125.5, 126.7, 127.8, 128.4, 128.5, 128.6, 128.7,
130.7, 131.9, 132, 132.1, 133.5, 133.6, 133.7, 133.8,
133.9, 136.5, 158.7, 158.8, 165.0, 169.5, 169.7, 170.8,
171.2; IR (KBr) ν: 3049, 2976, 1721, 1655, 1588, 1437
1
－
＋
1
cm ; MS (70 eV) m/z (%): 578 (M , 5), 489 (10), 428
(100), 374 (30), 341 (30), 301 (25), 262 (60), 208 (25),
175 (30), 109 (20), 77 (30). Anal. calcd for C34H31N2-
O5P: C 70.58, H 5.40, N 4.84; found C 70.51, H 5.44, N
4.80.
1
1
(d, JPC＝126.8 Hz), 40.3 (d, JPC＝126.9 Hz), 49.1,
50.9, 52.3, 52.9, 122.6, 122.8, 123.1, 124.0, 125.7,
126.0, 126.4, 127.1, 128.8, 128.9, 129.1, 129.7, 132.3,
132.4, 133.5, 133.8, 148.1, 148.6, 159.9, 164.3, 169.7,
172.0, 172.5; IR (KBr) ν: 3429, 3209, 2948, 1725, 1621,
Dimethyl 2-(1,4-dioxo-3,4-dihydrophthalazin-2(1H)-
yl)-3-(triphenylphosphoranylidene)succinate
(15c):
White powder; m.p. 170—173 ℃; 1H NMR (CDCl3) E
isomer δ: 3.75 (s, 3H), 3.79 (s, 3H), 5.70 (d, 3JPH＝17.4
－
＋
3
1
Hz, 1H), 7.31—7.70 (m, 17H), 8.10 (d, JHH＝6.1 Hz,
1525 cm ; MS (70 eV) m/z (%): 502 (M , 20), 470
(40), 389 (15), 315 (100), 262 (50), 214 (10), 198 (20),
115 (10), 78 (20). Anal. calcd for C28H27N2O5P: C 66.93,
H 5.42, N 5.57; found C 66.99, H 5.41, N 5.53.
Diethyl 2-(5-hydroxy-3-methyl-1H-pyrazol-1-yl)-3-
(triphenylphosphoranylidene)succinate (15g): White
3
1H), 8.33 (d, JHH＝6.1 Hz, 1H), 11.73 (br s, 1H); 13C
1
NMR (CDCl3) E isomer δ: 43.7 (d, JPC＝127.5 Hz),
50.4, 53.1, 57.4 (d, 2JPC＝17.1 Hz), 124.6, 125.8, 127.1,
127.5, 128.4, 128.6, 129.0, 129.2, 129.6, 132.0, 132.1,
132.6, 132.7, 133.4, 133.5, 133.7, 154.0, 156.6, 171.0,
173.6; 31P NMR (CDCl3) E isomer δ: 25.47; IR (KBr) ν:
1
powder; m.p. 123—126 ℃; H NMR (DMSO-d6) E
－
1
3441, 2929, 1745, 1636, 1602, 1436 cm ; MS (70 eV)
m/z (%): 566 (M＋, 5), 521 (5), 435 (5), 404 (15), 365
(40), 331 (100), 262 (70), 173 (25), 119 (40), 77 (30).
Anal. calcd for C32H27N2O6P: C 67.84, H 4.80, N 4.94;
found C 67.84, H 4.81, N 4.91.
and Z isomers δ: 1.05—1.20 (br, 12H, E and Z), 2.02 (s,
3H, E), 2.07 (s, 3H, Z), 3.46 (br, 2H, E), 3.53 (br, 2H, E),
4.02—4.18 (br, 2H, E and Z), 7.23—7.59 (m, 32H, E
and Z), 10.79 (br, 2H, E and Z); 13C NMR (DMSO-d6) E
and Z isomers δ: 14.1, 14.5, 14.7, 15.0, 30.3, 32.5, 57.2,
57.4, 62.2, 62.5, 121.9, 122.6, 123.3, 124.3, 126.1,
126.8, 127.2, 129.0, 129.3, 131.9, 132.9, 133.7, 133.8,
143.2, 143.6, 165.8, 166.1, 171.9, 172.4; IR (KBr) ν:
Diethyl 2-(1,4-dioxo-3,4-dihydrophthalazin-2(1H)-
yl)-3-(triphenylphosphoranylidene)succinate
(15d):
White powder; m.p. 174—178 ℃; 1H NMR (CDCl3) E
－
1
3
isomer δ: 1.3 (t, JHH＝6.6 Hz, 3H), 2.11 (br, 3H), 3.82
3430, 3226, 3054, 2965, 2918, 2845, 1736, 1595 cm ;
(br, 2H), 4.19—4.26 (m, 2H), 5.71 (d, JPH＝17.4 Hz,
MS (70 eV) m/z (%): 530 (M＋, 15), 484 (10), 449 (60),
3
1898
www.cjc.wiley-vch.de
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 1893—1900

Synthesis of a New Class of Highly Functionalized Phosphorus Ylides
418 (40), 328 (30), 262 (100), 183 (85), 152 (30), 108
(45), 77 (35), 51 (30). Anal. calcd for C30H31N2O5P: C
67.91, H 5.89, N 5.28; found C 67.84, H 5.93, N 5.21.
Diethyl 2-(2,5-dimethyl-3,6-dioxopiperazin-1-yl)-3-
(triphenylphosphoranylidene)succinate (15h): White
us the software (G98W suite of programs) and hardware
(machine time) facilities and also giving us the opportu-
nity to access some new features of Gaussian products.
We gratefully acknowledge the financial support from
the Research Council of Shahid Beheshti University.
1
powder; m.p. 205—208 ℃; H NMR (DMSO-d6) E
and Z isomers δ: 1.16—1.25 (br, 12H, E and Z), 3.90 (br,
4H, E and Z), 4.19 (q, 3JHH＝7.1 Hz, 4H, E and Z), 6.75
(s, 1H, Z), 7.23 (s, 1H, E), 7.38—7.62 (m, 30H, E and
Z), 8.11 (br, 2H, E and Z); 13C NMR (DMSO-d6) E and
Z isomers δ: 14.2, 14.4, 18.9, 19.4, 50.2, 50.3, 61.6,
129.1, 129.3, 129.4, 131.9, 132.0, 132.5, 133.6, 133.7,
133.8, 136.9, 137.1, 137.2, 164.7, 164.9, 169.1, 169.5;
IR (KBr) ν: 3414, 3195, 3054, 2970, 2923, 2887, 1689,
1668, 1592, 1569, 1481 cm ; MS (70 eV) m/z (%): 573
(M＋－1, 10), 532 (10), 546 (5), 529 (15), 501 (5), 399
(15), 327 (10), 262 (65), 183 (45), 142 (30), 99 (90), 44
(100). Anal. calcd for C32H35N2O6P: C 66.89, H 6.14, N
4.88; found C 66.88, H 6.14, N 4.86.
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Dimethyl 2-(2-oxooxazolidin-3-yl)-3-(triphenyl-
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1
3.12 (s, 3H, E), 3.53 (s, 3H, Z), 3.72 (s, 3H, Z), 3.76 (s,
3H, E), 3.81—3.84 (m, 2H, E), 3.98 (dd, 2JHH＝16.1 Hz,
3
3JHH＝7.4 Hz, 1H, Z), 4.01 (d, JHH＝8.4 Hz, 1H, E),
2
3
4.13 (dd, JHH＝17.2 Hz, JHH＝7.4 Hz, 2H, E and Z),
3
4.31—4.33 (m, 2H, Z), 4.35 (d, JPH＝13.7 Hz, 1H, Z),
3
4.45 (d, JPH＝17.4 Hz, 1H, E), 7.52—7.68 (m, 30H, E
and Z); 13C NMR (CDCl3) E and Z isomers δ: 39.6, 41.3,
42.2, 42.6, 49.1, 49.9, 52.3, 52.5, 56.3, 56.6, 62.5, 125.3,
126.0, 126.5, 127.2, 128.8, 128.9, 129.0, 129.1, 132.3,
132.4, 133.4, 133.5, 157.7, 169.7, 169.8, 172.3, 172.4;
31P NMR (CDCl3) E and Z isomers δ: 24.52 (Z), 25.23
(E); IR (KBr) ν: 3451, 3060, 2946, 1738, 1633, 1436
－
＋
1
cm ; MS (70 eV) m/z (%): 491 (M , 15), 460 (10), 432
(100), 405 (20), 303 (30), 262 (75), 183 (30), 130 (30),
108 (20), 86 (20), 59 (15). Anal. calcd for C27H26NO6P:
C 65.98, H 5.33, N 2.85; found C 65.97, H 5.33, N 2.27.
Diethyl 2-(2-oxooxazolidin-3-yl)-3-(triphenylphos-
phoranylidene)succinate (15j): White powder; m.p.
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1
138—140 ℃; H NMR (300.13 MHz, DMSO-d6) E
3
and Z isomers δ: 0.35 (t, JHH＝7.1 Hz, 3H, E), 1.07 (t,
3JHH＝7.1 Hz, 3H, Z), 1.24—1.28 (m, 6H, E and Z),
3.52 (m, 2H, E), 3.70—4.33 (m, 16H, E and Z), 7.38—
7.67 (m, 30H, E and Z); 13C NMR (DMSO-d6) E and Z
isomers δ: 14.3, 14.5, 14.6, 15.1, 38.2, 42.5, 56.3, 56.5,
57.4, 61.0, 61.2, 62.6, 125.6, 126.1, 126.8, 127.4, 129.1,
129.3, 129.4, 129.6, 131.9, 132.9, 133.6, 133.7, 157.4,
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1
2986, 2923, 2897, 1736, 1630, 1437 cm ; MS (70 eV)
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We are grateful to Prof. Seik Weng Ng for providing
Chin. J. Chem. 2012, 30, 1893—1900
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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www.cjc.wiley-vch.de
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 1893—1900