A facile synthesis of novel and stable phosphorus ylides containing 2-Aryl-1,3-dioxane-4,6-dione

Article abstract of DOI:10.1080/10426507.2011.621001

The reaction between dialkyl acetylene dicarboxylate and 2-aryl-1,3-dioxane-4,6-dione derivatives in the presence of triphenylphosphine in ethyl acetate led to stable phosphorus ylides in good yields. These stabilized phosphorus ylides exist as a mixture

Full text of DOI:10.1080/10426507.2011.621001

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Phosphorus, Sulfur, and Silicon and the
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A Facile Synthesis of Novel and Stable
Phosphorus Ylides Containing 2-Aryl-1,3-
Dioxane-4,6-Dione
Azizollah Habibi a , Hedyeh Hosseinzadeh a & Seyed Majid Aghvami a
a Faculty of Chemistry , Tarbiat Moallem University , Tehran , Iran
Published online: 31 Jan 2012.
To cite this article: Azizollah Habibi , Hedyeh Hosseinzadeh & Seyed Majid Aghvami (2012) A Facile
Synthesis of Novel and Stable Phosphorus Ylides Containing 2-Aryl-1,3-Dioxane-4,6-Dione, Phosphorus,
Sulfur, and Silicon and the Related Elements, 187:3, 409-420, DOI: 10.1080/10426507.2011.621001
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Phosphorus, Sulfur, and Silicon, 187:409–420, 2012
Copyright ꢀC Xinjiang University
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.621001
A FACILE SYNTHESIS OF NOVEL AND STABLE
PHOSPHORUS YLIDES CONTAINING
2-ARYL-1,3-DIOXANE-4,6-DIONE
Azizollah Habibi, Hedyeh Hosseinzadeh,
and Seyed Majid Aghvami
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
GRAPHICAL ABSTRACT
r
A
r
A
R
R
C O 2
C O 2
O
O
c
A
E t
r .
O
O
O
O
P P h 3
C O 2
P h 3
P
+
+
.
,
t
2 h
O
O
O
R
R
C O 2
10 examples
Abstract The reaction between dialkyl acetylene dicarboxylate and 2-aryl-1,3-dioxane-4,6-
dione derivatives in the presence of triphenylphosphine in ethyl acetate led to stable phosphorus
ylides in good yields. These stabilized phosphorus ylides exist as a mixture of two geometrical
isomers as a result of restricted rotation around the carbon–carbon partial double bond. The
1H NMR variable temperature spectra for 3c are studied and the results are reported.
Keywords Triphenylphosphine; rotamers; stable phosphorus ylides; meldrum’s acid
INTRODUCTION
In any organic synthesis plan, the formation of new carbon–carbon bonds poses a ma-
jor challenge. Several methods have been developed for the synthesis of new compounds in
which new carbon–carbon bond(s) is formed.1 Among these, the application of phosphorus
ylides is one of the most important routes for the formation of target organic compounds.2 In
recent years, interesting applications of phosphorus ylides for the preparations of industrial
and pharmaceutical compounds have been reported.3–16 Ylides are reactive intermediates
that are usually prepared by the treatment of a phosphonium salt with a base, in which
the phosphonium salts are obtained from triphenylphosphine and alkyl halide, and also
Michael addition of phosphorus nucleophiles to activated olefins.
Received 3 June 2011; accepted 29 August 2011.
Address correspondence to Azizollah Habibi, Faculty of Chemistry, Tarbiat Moallem University, No. 43,
Mofateh Avenue, Tehran, Iran. E-mail: habibi@tmu.ac.ir
409

410
A. HABIBI ET AL.
Recently, the use of phosphino-substituted iminium derivatives was published by
Bertrand.14 He reported that phosphino salts were prepared by the treatment of Alder’s
dimer or a chloro iminum salt with phosphines. Also, there are many studies on the reaction
between trivalent phosphorus nucleophiles and acetylenic esters in the presence of a proton
source.15–18 In some cases, the ylide products are stable, but in others they cannot be isolated
and act as intermediates on the pathway that produce the final isolated product.12,18
Our current studies are based on the application of Meldrum’s acid (2,2-dimethyl-
1,3-dioxane-4,6-dione) derivatives in multicomponent reactions.19–22 Meldrum’s acid and
it’s derivatives have attracted considerable attention as important intermediates in organic
synthesis.23–31
Herein, we report an efficient synthetic route to congested phosphorus ylides 3 using
triphenylphosphine, dialkyl acetylenedicarboxylates 1, and 2-aryl-1,3-dioxane-4,6-dione 2
(Scheme 1).
Scheme 1
RESULTS AND DISCUSSION
The reaction of dialkyl acetylenedicarboxylates 1 with 2-aryl-1,3-dioxane-4,6-dione
derivatives 2 in the presence of triphenylphosphine proceeded smoothly at room temperature
in ethyl acetate and was completed within a few hours. 1H, 13C NMR, and 31P NMR spectra
of the crude product clearly indicated the formation of ylides 3. Any product other than 3
could not be detected by NMR spectroscopy.

STABLE YLIDES CONTAINING 2-ARYL-1,3-DIOXANE-4,6-DIONE
411
The structures of compounds 3a–j were deduced from their elemental analyses and
IR, 1H, 13C, and 31P NMR spectra. The most important absorption band in IR spectrum is
the carbonyl group stretching, which appeared at 1633, 1695, and 1732 cm−1
.
The 1H NMR spectrum of 3a exhibited two signals at 3.29 and 3.60 ppm arising from
the methoxy groups in the Z-isomer and two signals at 3.23 and 3.28 ppm for the methoxy
group in the E-isomer. Signals for the methine protons between the two C O appeared as
two doublet of doublets at δ = 4.75 ppm (4JPH = 4.0, 3JHH = 10.6) and δ = 4.66 ppm (4JPH
=
3
11.6, JHH = 7.0), for the E- and Z-isomers, respectively. Also, signals for the methine
protons of P C CH appeared as doublet of doublets at δ = 5.67 ppm (3JPH = 11.0, 3JHH
=
11.0) for the E-isomer and δ = 5.76 ppm (3JPH = 13.6, 3JHH = 11.7) for Z-isomer. Signals
for Ph CH appeared at 6.27 and 5.29 for the E- and Z-isomers, respectively. The aromatic
protons (20 protons from four phenyl groups) appeared as a multiplet at δ = 7.25–7.85. The
13C NMR spectrum of 3a showed 17 distinct resonances in agreement with the proposed
structure. The 31P NMR exhibited two signals at 23.2 and 23.4 ppm for the E- and Z-isomers,
respectively.
These ylides are interestingly stable in different boiling solvents (toluene, DMSO,
and methanol) and they did not undergo any intramolecular reaction and the starting ylides
were unchanged. However, they were destroyed under reflux in the presence of water and
no isolable product was determined.
Even though we have not yet verified experimental evidence through kinetic studies
for the mechanism of this reaction, in an earlier similar work, a reasonable mechanism was
proposed.8 On thebasis of these reports, we can assumethat initial additionof triphenylphos-
phine to the dialkyl acetylene dicarboxylate 1 can be formed zwitterions 4, subsequently
the protonation of intermediate 4 occurs by the C H acid 2. Then, Michael addition of
anion 6 to the vinylphosphonium cation 5 generates phosphorane 3 (Scheme 2).
Ar
CO 2R
Ph 3 P
O
O
Ph 3 P + 1
+
RO 2 C
O
O
2
4
Ar
6
P h 3
P
O
O
3
+
CHCO 2 R
R O 2 C
O
O
5
Scheme 2
1
The H and 13C NMR spectra of diastereomeric ylides 3a–j were consistent with
the presence of two geometric isomers. The ylide moiety of this compound is strongly
conjugated to the adjacent carbonyl group and rotation around the partial double bond
in the 3-(E) and 3-(Z) geometrical isomers is slow on the NMR time scale at ambient
1
temperature (Scheme 3). The H NMR spectrum of ylides shows individual signals for

412
A. HABIBI ET AL.
Ph3P
O
Ph3P
OR
4
O
O
O
3
O
O
O
O
5
Ar
O
Ar
OR
2
CO2R
CO2R
1
O
3-(E)
3-(Z)
Scheme 3
two rotamers in the region of three CH substructure and OCH2 (or OCH3) fragment of the
ester.
1
The methyl region of the H NMR spectrum of 3c in CDCl3 at ambient tempera-
ture (25◦C) exhibits two sharp singlets for the Methyl–Aryl groups of E- and Z-isomers.
◦
Increasing the temperature results in coalescence of the Me–Ar resonances. At 97 C, a
relatively broad singlet was observed for the Me–Ar group. Selected 1H, 13C, and 31P NMR
chemical shifts and coupling constants for the Major (M) and Minor (m) rotamer isomers
of compounds 3a–j are given in Table 1.
1
Table 1 Selected H, 13C, and 31P NMR chemical shifts (δ in ppm) and coupling constants (J in Hz) for H-2,
H-5, CO2R, OR, C-2, and C-3 in the major (M) and minor (m) rotamer isomers of compounds 3a–j
1H NMR Data
13C NMR Data
Comp.
3a
Isomer (%)
H-2 (3JPH
5.67 (11)
5.76 (13.6)
5.65 (11)
5.76 (13.6)
5.68 (11)
5.78 (13.6)
5.67 (11)
5.77 (13.6)
5.66 (11)
5.78 (13.6)
5.60 (11)
5.83 (13.6)
5.56 (11)
5.66 (13.6)
5.58 (11)
)
H-5 (4JPH
)
OR
CO2R
C2
C3 (1JPH
)
31P
M (55)
m (45)
M (55)
m (45)
M (55)
m (45)
M (54)
m (46)
M (58)
m (42)
M (64)
m (36)
M (64)
m (36)
M (67)
m (33)
M (64)
m (36)
M (67)
m (33)
4.75 (4)
4.66 (7)
4.72 (4)
4.66 (7)
4.76 (4)
4.67 (7)
4.75 (4)
4.66 (7)
4.75 (4)
4.68 (7)
4.76 (3.4)
4.71 (6.8)
4.65 (3.4)
4.50 (6.8)
4.75 (3.4)
4.67 (6.8)
4.75 (3.4)
4.69 (6.8)
4.75 (3.4)
4.72 (6.8)
3.23
3.29
3.22
3.30
3.24
3.31
3.24
3.30
3.24
3.31
3.60
4.10
3.59
3.85
3.57
4.04
3.59
4.06
3.60
4.06
3.28
3.60
3.27
3.60
3.29
3.61
3.29
3.61
3.29
3.61
3.76
4.16
3.66
3.99
3.73
4.11
3.75
4.12
3.73
4.12
44.1
44.6
44.0
44.6
44.1
44.7
44.1
44.6
44.1
44.7
44.5
44.7
44.5
44.7
44.5
44.7
44.5
44.7
44.5
44.7
43.5 (91.3)
43.1 (52.1)
43.4 (92.8)
43.2 (52.8)
43.5 (92.0)
43.4 (52.1)
43.5 (91.3)
43.4 (52.1)
43.5 (91.3)
43.4 (52.1)
43.6 (135.8)
43.4 (60.4)
43.6 (138.8)
43.4 (60.4)
43.6 (135.8)
43.4 (60.4)
43.6 (135.8)
43.4 (60.4)
43.6 (135.8)
43.4 (60.4)
23.2
23.3
23.3
23.4
23.2
23.3
23.3
23.3
23.3
23.4
23.1
23.3
22.7
23.3
23.1
23.2
23.1
23.2
23.1
23.3
3b
3c
3d
3e
3f
3g
3h
3i
5.80 (13.6)
5.58 (11)
5.80 (13.6)
5.56 (11)
3j
5.81 (13.6)

STABLE YLIDES CONTAINING 2-ARYL-1,3-DIOXANE-4,6-DIONE
413
Table 2 Selected proton chemical shifts and activation parameters for 3c in nitro benzene and 3h in 1,2-
dichlorobenzene
Ar CH3
Comp.
3c
T (◦C)
ppm
ꢀν (Hz)
k (s−1
20
)
Tc (K)
368
ꢀG=
19.5
18.9
22
97
22
85
2.30
2.32
2.29
2.34
2.33
2.32
9
9
3h
20
358
Although no extensive line-shape analysis for 3 was undertaken, the variable tem-
perature spectra allowed to calculate the free barrier for the restricted C C bond rotation
in 3c.
From the coalesence temperature of the methyl proton resonances and using the
√
πꢀϑ
expression k =
/ 2, we can calculate the first-order rate constant (k) for the dynamic
NMR effect in 3c is 20 s−1 at 368 K. Application of the absolute rate theory with a
transmission coefficient of 1 gives a free energy of activation (ꢀG=) of 19.5 2 kJ mol−1
(Table 2), where all known sources of errors are estimated and included.
In conclusion, our procedure describes a smooth formation of new ylides of triph-
enylphosphine, dialkyl acetylenedicarboxylate, and 2-aryl-1,3-dioxane-4,6 dione. These
ylides can be used as intermediate for synthesis of desired compounds.
EXPERIMENTAL
General Procedure for Preparation of 2a–e
A mixture was prepared by suspending a weighed quantity of the malonic acid
(5.2 g, 0.05 mol) in three times its weight of 95% acetic anhydride [15.6 g (14.5 mL),
0.15 mol], adding concentrated sulfuric acid (0.05–0.1 mL), and allowing the mixture to
stand overnight. The formed acetic acid and excess of anhydride were then removed in a
water bath (below 40 ◦C) under reduced pressure. The aldehyde)0.05 mol(was then added
to the residue and the mixture cooled with water. The mixture solidified after the addition
of the aldehyde. The product was filtered.
2-phenyl-1,3-dioxane-4,6-dione (2a). White powder, mp 145 ◦C. FT-IR (KBr)
(υmax, cm−1): 1805, 1764 (C O). Anal. Calcd for C10H8O4 (192.17); C, 62.5; H, 4.20%;
Found: C, 62.50; H, 4.13%. 1H NMR (300.1 MHz, acetone-d6): δ 3.63 and 4.49 (2H, 2d,
2JHH = 18 Hz, CH2), 7.20 (1H, s, CH), 7.50–7.65 (5H, m, C6H5). 13C NMR (75.5 MHz,
acetone-d6): δ 39.9 (CH2), 98.5 (CH), 127.5 (Cortho of C6H5), 129.6 (Cpara of C6H5), 131.5
(Cmeta of C6H5), 134.2 (Cipso), 165.1 (2C O).
◦
2-(4-Chlorophenyl)-1,3-dioxane-4,6-dione (2b). White powder, mp 139 C.
FT-IR (KBr) (υmax, cm−1): 1807, 1765 (C O). Anal. Calcd for C10H7ClO4)226.61); C,
1
53.0; H, 3.11%; Found: C, 53.20; H, 2.94%. H NMR (300.1 MHz, CDCl3) :δ 3.68 and
3.84 (2H, d, 2JHH = 18 Hz, CH2), 6.76 (1H, s, CH), 7.46 and 7.51 (4H, 2d, 3JHH = 8.7 Hz,
Ar). 13C NMR (75.5 MHz, CDCl3): δ 39.0 (CH2), 97.2 (CH), 127.8 (Cortho of C6H4), 129.3
(Cmeta of C6H4), 131.5 (C Cl), 134.2 (Cipso), 162.7 (2C O).
◦
2-(4-methylphenyl)-1,3-dioxane-4,6-dione (2c). White powder, mp 106 C.
FT-IR)KBr) (υmax, cm−1): 1808, 1765 (C O). Anal. Calcd for C11H10O4)206.19); C,

414
A. HABIBI ET AL.
64.08; H, 4.69%; Found: C, 63.90; H, 4.56%. 1H NMR)300.1 MHz, CDCl3): δ 2.40)3H, s,
CH3(, 3.62 and 3.81)2H, 2d, 2JHH = 18 Hz, CH2(, 6.76)1H, s, CH(, 7.27 and 7.42 (4H, 2d,
3JHH = 8.4 Hz, Ar). 13C NMR (75.5 MHz, CDCl3): δ 21.4)CH3), 39.0)CH2(, 98.1)CH),
126.2) Cortho of C6H4 (129.2) Cmeta of C6H4), 129.7)C CH3(, 141.3)Cipso), 163.3)2
C O).
◦
2-(4-methoxyphenyl)-1,3-dioxane-4,6-dione (2d). Pink powder, mp 134 C.
FT-IR)KBr) (υmax, cm−1): 1806, 1766 (C O). Anal. Calcd for C11H10O5 (222.19); C,
1
59.46; H, 4.54%; Found: C, 59.49; H, 4.35%. H NMR)300.1 MHz, acetone-d6): δ 3.59
and 4.45)2H, 2d, 2JHH = 18 Hz, CH2(, 3.84)3H, s, OCH3(, 7.12 (1H, s, CH), 7.05 and 7.54
(4H, 2d, 3JHH = 9 Hz, Ar). 13C NMR (75.5 MHz, acetone-d6): δ 39.8 (CH2), 55.7 (OCH3),
98.6 (CH), 114.9 (Cmeta of C6H4), 126.2 (Cortho of C6H4), 129.1 (Cipso), 162.4 (C OCH3),
165.3 (2C O).
2-(4-flourophenyl)-1,3-dioxane-4,6-dione (2e). White powder, mp 170 ◦C. FT-
IR)KBr) (υmax, cm−1): 1805, 1768 (C O). Anal. Calcd for C10H7FO4)210.16); C, 57.15; H,
3.36%; Found: C, 57.06; H, 3.33%. 1H NMR)300.1 MHz, acetone-d6): δ 3.63 and 4.59)2H,
2
3
3
2d, JHH = 18 Hz, CH2(, 7.21(1H, s, CH), 7.30 (2H, dd, JHH = 8.7 Hz, JHF = 8.7 Hz,
CHmeta), 7.70 (2H, dd, 3JHH = 8.7 Hz, JHF = 5.3 Hz, CHortho). 13C NMR (75.5 MHz,
4
2
acetone-d6): δ 39.8 (CH2), 97.8 (CH), 116.6 (d, JCF = 22.3 Hz, Cmeta of C6H4), 130.0
3
1
(d, JCF = 8.8 Hz, Cortho of C6H4), 130.5 (Cipso), 164.7 (d, JCF = 249 Hz, C F), 164.9
(2C O).
General Procedure for Preparation of 3a–j(Exemplified by 3a)
Dimethyl 2-[5-(2-phenyl-1,3-dioxane-4,6-dion)]-3(Triphenyl-λ5-phospha
nylidene)-succinate (3a). A mixture of dimethyl acetylenedicarboxylate 1a (0.12 mL,
1 mmol) in ethyl acetate (2 mL) was added dropwise at room temperature over 10 min to
a magnetically stirred solution of 2a (0.212 g, 1 mmol) and triphenyl phosphine (0.26 g,
1 mmol) in ethyl acetate (10 mL). The mixture was allowed to stand at room temperature
◦
(25 C) along with stirring for 1 h. The resulting mixture was filtered to give ylide 3a as
a white powder. mp 150 C, and yield 81%. FT-IR (KBr) (υmax, cm−1): 1633, 1695, and
◦
1732 (C O). Anal. Calcd for C34H29O8P (596.16); C, 68.45; H, 4.90%. Found: C, 68.33;
H, 4.88%.
1
Major isomer (E)-3a (55%), H NMR (300.1 MHz, CDCl3): δ 3.23 and 3.28 (6H,
4
2s, 2OCH3), 4.75 (1H, dd, JPH = 4.0 Hz, 3JHH = 11 Hz, CH(C O)2), 5.67 (1H, dd,
3
3JPH = 11 Hz, JHH = 11 Hz, P C CH), 6.27 (1H, s, Ar CH), 7.25–7.85 (20H, m,
4 Ar). 13C NMR (75.46 MHz, CDCl3): δ 43.5 (d, 1JPC = 91.3 Hz, P C), 44.1 (P C CH),
1
52.6 and 53.0 (2OCH3), 72.2 (CH(C O)2), 96.1 (CH Ar), 121.3 (d, JPC = 83.8 Hz,
3
Cipso), 126.5, 127.9, 128.7, and 135.9 (Ar), 129.4 (d, JPC = 12.9 Hz, Cmeta), 134.2
2
4
(d, JPC = 9.8 Hz, Cortho), 133.8 (d, JPC = 2.9 Hz, Cpara), 167.6 (C O), 168.3 (d,
2JPC = 26.4 Hz, P C C), 174.0 (CO2CH3). 31PNMR (121.5 MHz, CDCl3): δ 23.2
(Ph3P+ C).
Minor isomer (Z)-3a (45%), 1H NMR (300.1 MHz, CDCl3): δ 3.29 and 3.60 (6H, 2s,
2OCH3), 4.66 (1H, dd, 4JPH = 7.0 Hz, 3JHH = 11.7 Hz, CH(C O)2), 5.76 (1H, dd, 3JPH
=
13.6 Hz, 3JHH = 11.7 Hz, P C CH), 5.29 (1H, s, Ar CH), 7.25–7.85 (20H,m, 4 Ar). 13
C
NMR (75.46 MHz, CDCl3): δ 43.1 (d, 1JPC = 52.1 Hz, P C), 44.6 (P C CH), 52.8 and
53.4 (2OCH3), 72.7 (CH(C O)2), 94.9 (CH Ar), 118.1 (d, 1JPC = 80.5 Hz, Cipso), 126.4,
3
2
127.8, 128.8, and 136.5 (Ar), 129.8 (d, JPC = 12.8 Hz, Cmeta), 134.1 (d, JPC = 9.9 Hz,

STABLE YLIDES CONTAINING 2-ARYL-1,3-DIOXANE-4,6-DIONE
415
Cortho), 134.6 (d, 4JPC = 3 Hz, Cpara), 167.1 (C O), 167.7 (d, 2JPC = 22.6 Hz, P C C),
173.9 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.3 (Ph3P+ C).
Dimethyl 2-[5-(2-(4-chlorophenyl)-1,3-dioxane-4,6-dion)]-3(Triphenyl-λ5-
phosphanylidene)-succinate (3b). White powder, mp 146 ◦C, and yield 65%. FT-IR
(KBr) (υmax, cm−1): 1750, 1726, 1690, and 1623 (C O). Anal. Calcd for C34H29ClO8P
(630.12); C, 64.72; H, 4.47%; Found: C, 64.72; H, 4.59%.
Major isomer (E)-3b (55%), 1H NMR (300.1 MHz, CDCl3): δ 3.22 and 3.27 (6H, 2s,
2OCH3), 4.72 (1H, dd, 3JHH = 11 Hz, 4JPH = 4.0 Hz, CH(C O)2), 5.65 (1H, dd, 3JHH
=
3
11 Hz, JPH = 11 Hz, P C CH), 6.24 (1H, s, Ar CH), 7.25–7.84 (19H, m, 4Ar). 13C
NMR (75.46 MHz, CDCl3): δ 43.4 (d, 1JPC = 92.8 Hz, P C), 44.0 (P C CH), 52.7 and
53.0 (2OCH3), 72.2 (CH(C O)2), 95.4 (CH Ar), 121.3 (d, 1JPC = 88.3 Hz, Cipso), 128.0,
3
2
128.2, 134.6, and 135.2 (Ar), 129.4 (d, JPC = 12.2 Hz, Cmeta), 134.2 (d, JPC = 9.8 Hz,
Cortho), 133.8 (d, 4JPC = 2.3 Hz, Cpara), 168.1 (d, 2JPC = 20.1 Hz, P C C), 167.6 (C O),
173.9 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.3 (Ph3P+ C).
Minor isomer (Z)-3b (45%), 1H NMR (300.1 MHz, CDCL3: δ 3.30 and 3.60 (6H, 2s,
2OCH3), 4.66 (1H, dd, 3JHH = 11.6 Hz, 4JPH = 7.0 Hz, CH(C O)2), 5.76 (1H, dd, 3JHH
=
11.6 Hz, 3JPH = 13.6 Hz, P C CH), 5.28 (1H, s, Ar CH), 7.25–7.84 (19H, m, 4Ar). 13
C
NMR (75.46 MHz, CDCl3): δ 43.2 (d, 1JPC = 52.8 Hz, P C), 44.6 (P C CH), 52.8 and
53.4 (2OCH3), 72.8 (CH(C O)2), 94.2 (CH Ar), 118.0 (d, 1JPC = 86.8 Hz, Cipso), 127.8,
3
2
128.1, 134.4, and 135.0 (Ar), 129.8 (d, JPC = 15.1 Hz, Cmeta), 134.1 (d, JPC = 9.8 Hz,
Cortho), 134.6 (d, 4JPC = 2.3 Hz, Cpara), 167.4 (d, 2JPC = 17.5 Hz, P C C), 166.8 (C O),
173.7 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.4 (Ph3P+ C).
Dimethyl 2-[5-(2-(4-methylphenyl)-1,3-dioxane-4,6-dion)]-3(Triphenyl-λ5-
phosphanylidene)-succinate (3c). White powder, mp 140 ◦C, and yield 63%. FT-IR
(KBr) (υmax, cm−1): 1729, 1612, and 1685 (C O). Anal. Calcd for C35H31O8P (610.18);
C, 68.85; H, 5.12%; Found: C, 68.82; H, 4.90%.
Major isomer (E)-3c (55%), 1H NMR (300.1 MHz, CDCl3): δ 2.33 (3H, s, CH3), 3.24
and 3.29 (6H, 2s, 2OCH3), 4.76 (1H, dd, 3JHH = 11 Hz, 4JPH = 4.0 Hz, CH(C O)2), 5.68
(1H, dd, 3JHH = 11 Hz, 3JPH = 11 Hz, P C CH), 6.25 (1H, s, Ar CH), 7.07–7.88 (19H,
1
m, 4Ar). 13C NMR (75.46 MHz, CDCl3): δ 21.2 (CH3), 43.5 (d, JPC = 92.0 Hz, P C),
44.1 (P C CH), 52.7 and 53.0 (2OCH3), 72.3 (CH(C O)2), 95.0 (CH Ar), 121.4 (d,
3
1JPC = 90.5 Hz, Cipso), 126.3, 128.5, 133.7, and 138.6 (Ar), 129.4 (d, JPC = 14.3 Hz,
Cmeta), 134.3 (d, 2JPC = 6.0 Hz, Cortho), 134.3 (d, 4JPC = 2.3 Hz, Cpara), 168.4 (d, 2JPC
=
39.3 Hz, P C C), 167.7 (C O), 174.0 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.2
(Ph3P+ C).
Minor isomer (Z)-3c (45%), 1H NMR (300.1 MHz, CDCl3): δ 2.30 (3H, s, CH3), 3.31
and 3.61 (6H, 2s, 2OCH3), 4.67 (1H, dd, 3JHH = 11.6 Hz, 4JPH = 7.0 Hz, CH(C O)2), 5.78
3
3
(1H, dd, JHH = 11.6 Hz, JPH = 13.6 Hz, P C CH), 5.27 (1H, s, Ar CH), 7.07–7.88
1
(19H, m, 4Ar). 13C NMR (75.46 MHz, CDCl3): δ 21.2 (CH3), 43.4 (d, JPC = 52.1 Hz,
P C), 44.7 (P C CH), 52.9 and 53.4 (2OCH3), 72.8 (CH(C O)2), 96.2 (CH Ar), 118.2
(d, 1JPC = 90.5 Hz, Cipso), 126.5, 128.6, 133.1, and 138.5 (Ar), 129.8 (d, 3JPC = 13.6 Hz,
Cmeta), 134.2 (d, 2JPC = 6.0 Hz, Cortho), 133.8 (d, 4JPC = 2.3 Hz, Cpara), 167.4 (d, 2JPC
=
24.1 Hz, P C C), 167.2 (C O), 173.6 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.3
(Ph3P+ C).
Dimethyl 2-[5-(2-(4-methoxyphenyl)-1,3-dioxane-4,6-dion)]-3(Triphenyl-
◦
λ5-phosphanylidene)-succinate (3d). White powder, mp 158 C, and yield 71%.
FT-IR (KBr) (υmax, cm−1): 1752, 1726, 1686, and 1620 (C O). Anal. Calcd for C35H31O9P
(626.17); C, 67.09; H, 4.99%; Found: C, 66.92; H, 5.18%.

416
A. HABIBI ET AL.
Major isomer (E)-3d (54%), 1H NMR (300.1 MHz, CDCl3): δ 3.24, 3.29, and 3.78
(9H, 3s, 3OCH3), 4.75 (1H, dd, 3JHH = 11 Hz, 4JPH = 4.0 Hz, CH(C O)2), 5.67 (1H, dd,
3JHH = 11 Hz, 3JPH = 11 Hz, P C CH), 6.23 (1H, s, Ar CH), 7.25–7.88 (19H, m, Ar).
1
13C NMR (75.46 MHz, CDCl3): δ 43.5 (d, JPC = 91.3 Hz, P C), 44.1 (P C CH),
1
52.7, 53.0, and 55.2 (3OCH3), 72.2 (CH(C O)2), 96.2 (CH Ar), 121.4 (d, JPC
=
3
90.5 Hz, Cipso), 113.3, 127.8, 129.0, and 159.9 (Ar), 129.4 (d, JPC = 15.0 Hz, Cmeta),
2
4
2
134.2 (d, JPC = 9.8 Hz, Cortho), 133.8 (d, JPC = 2.3 Hz, Cpara), 168.4 (d, JPC = 39.3
Hz, P C C), 167.6 (C O), 174.0 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.3
(Ph3P+ C).
Minor isomer (Z)-3d (46%), 1H NMR (300.1 MHz, CDCl3): δ 3.30, 3.61, and 3.77
3
4
(9H, 3s, 3OCH3), 4.66 (1H, dd, JHH = 11.6 Hz, JPH = 7.0 Hz, CH(C O)2), 5.77
3
3
(1H, dd, JHH = 11.6 Hz, JPH = 13.6 Hz, P C CH), 5.24 (1H, s, Ar CH), 7.25–7.88
(19H, m, Ar). 13C NMR (75.46 MHz, CDCl3): δ 43.4 (d, JPC = 52.1 Hz, P C), 44.6
1
(P C CH), 52.6, 54.8, and 55.1 (3OCH3), 72.7 (CH(C O)2), 94.9 (CH Ar), 118.1 (d,
1JPC = 90.5 Hz, Cipso), 113.1, 127.9, 128.4, and 160.0 (Ar), 129.7 (d, JPC = 15.0 Hz,
3
Cmeta), 134.1 (d, 2JPC = 9.9 Hz, Cortho), 134.6 (d, 4JPC = 2.3 Hz, Cpara), 167.8 (d, 2JPC
=
22.8 Hz, P C C), 167.2 (C O), 174.0 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.3
(Ph3P+ C).
Dimethyl 2-[5-(2-(4-flourophenyl)-1,3-dioxane-4,6-dion)]-3(Triphenyl-λ5-
phosphanylidene)-succinate (3e). White powder, mp 162 ◦C, and yield 50%. FT-IR
(KBr) (υmax, cm−1): 1734, 1719, and 1627 (C O). Anal. Calcd for C34H28FO8P (614.15);
C, 66.45; H, 4.59%; Found: C, 66.41; H, 4.48%.
Major isomer (E)-3e (58%), 1H NMR (300.1 MHz, CDCl3): δ 3.24 and 3.29 (6H, 2s,
2OCH3), 4.75 (1H, dd, 3JHH = 11 Hz, 4JPH = 4.0 Hz, CH(C O)2), 5.66 (1H, dd, 3JHH
=
3
3
11 Hz, JPH = 11 Hz, P C CH), 6.26 (1H, s, Ar CH), 7.00 (2H, dd, JHH = 9 Hz,
3JHF = 8.7 Hz, CHmeta of C6H4F), 7.25 (2H, dd, 3JHH = 9 Hz, 4JHF = 5.3 Hz, CHortho of
C6H4F), 7.58–7.86 (15H, m, 3Ar). 13C NMR (75.46 MHz, CDCl3): δ 43.5 (d, 1JPC = 91.3
Hz, P C), 44.1 (P C CH), 52.6 and 53.0 (2OCH3), 72.2 (CH(C O)2), 95.6 (CH Ar),
1
2
121.3 (d, JPC = 88.3 Hz, Cipso), 114.9 (d, JCF = 21.7 Hz, Cmeta of C6H4F), 128.5 (d,
3JCF = 8.3 Hz, Cortho of C6H4F), 129.5 (d, 3JPC = 12.8 Hz, Cmeta), 132.6 (Cipso of C6H4F),
4
2
1
133.9 (d, JPC = 2.3 Hz, Cpara), 134.2 (d, JPC = 9.8 Hz, Cortho), 163.0 (d, JCF = 241.5
Hz, C F), 168.2 (d, 2JPC = 22.6 Hz, P C C), 167.6 (C O), 174.0 (CO2CH3). 31P NMR
(121.5 MHz, CDCl3): δ 23.3 (Ph3P+ C).
Minor isomer (Z)-3e (42%), 1H NMR (300.1 MHz, CDCl3): 3.31 and 3.61 (6H, 2s,
2OCH3), 4.68 (1H, dd, 3JHH = 11.6 Hz, 4JPH = 7.0 Hz, CH(C O)2), 5.78 (1H, dd, 3JHH
=
11.6 Hz, 3JPH = 13.6 Hz, P C CH), 5.29 (1H, s, Ar CH), 6.98 (2H, dd, 3JHH = 9 Hz,
3JHF = 8.7 Hz, CHmeta of C6H4F), 7.32 (2H, dd, 3JHH = 9 Hz, 4JHF = 5.3 Hz, CHortho of
C6H4F), 7.58–7.91 (15H, m, 3Ar). 13C NMR (75.46 MHz, CDCl3): δ 43.4 (d, 1JPC = 52.1
Hz, P C), 44.7 (P C CH), 52.8 and 53.4 (2OCH3), 72.6 (CH(C O)2), 94.4 (CH Ar),
118.1 (d, 1JPC = 86.0 Hz, Cipso), 114.8 (d, 2JCF = 21.7 Hz, Cmeta of C6H4F), 128.4 (d, 3JCF
=
8.3 Hz, Cortho of C6H4F), 132.5 (Cipso of C6H4F), 162.9 (d, 1JCF = 241.5 Hz, C F), 129.8
3
2
4
(d, JPC = 12.8 Hz, Cmeta), 134.1 (d, JPC = 10.6 Hz, Cortho), 134.1 (d, JPC = 2.3 Hz,
Cpara), 167.5 (d, JPC = 16.5 Hz, P C C), 166.9 (C O), 173.7 (CO2CH3). 31P NMR
2
(121.5 MHz, CDCl3): δ 23.4 (Ph3P+ C).
Diethyl 2-[5-(2-phenyl-1,3-dioxane-4,6-dion)]-3(Triphenyl-λ5-phosphanyli
◦
dene)-succinate (3f). White powder, mp 156 C., and yield 72%. FT-IR (KBr) (υmax
,
cm−1): 1744, 1717, 1685, 1616 (C O). Anal. Calcd for C36H33O8P (624.19); C, 69.22; H,
5.33%; Found: C, 69.02; H, 5.27%.

STABLE YLIDES CONTAINING 2-ARYL-1,3-DIOXANE-4,6-DIONE
417
1
Major isomer (E)-3f (64%), H NMR (300.1 MHz, CDCl3): δ 0.84 and 0.98 (6H,
2t, 3JHH = 7.1 Hz, 2CH3), 3.60 and 3.76 (4H, 2q, 3JHH = 7.1 Hz, 2OCH2CH3), 4.76 (1H,
3
4
3
3
dd, JHH = 11 Hz, JPH = 3.4 Hz, CH(C O)2), 5.60 (1H, dd, JHH = 11 Hz, JPH = 11
Hz, P C CH), 5.38 (1H, s, Ar CH), 7.25–7.92 (20H, m, 4Ar). 13C NMR (75.46 MHz,
CDCl3): δ 13.6 and 13.7 (OCH2CH3), 43.6 (d, 1JPC = 138.8 Hz, P C), 44.5 (P C CH),
61.7 and 62.8 (2OCH2CH3), 72.2 (CH(C O)2), 96.1 (CH Ar), 122.3 (d, 1JPC = 89.0 Hz,
Cipso), 126.6, 127.9, 128.8, and 136.6 (Ar), 129.4 (d, 3JPC = 12.8 Hz, Cmeta), 134.3 (d, 2JPC
=
9.7 Hz Cortho), 133.7 (d, 4JPC = 3.1 Hz, Cpara), 168.5 (d, 2JPC = 37.7 Hz, P C C), 167.3
(C O), 173.6 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.1 (Ph3P+ C).
Minor isomer (Z)-3f (36%), 1H NMR (300.1 MHz, CDCl3): δ 0.93 and 1.16 (6H, 2t,
3JHH = 7.1 Hz, 2CH3), 4.10 and 4.16 (4H, q, 3JHH = 7.1 Hz, 2OCH2CH3), 4.71 (1H, dd,
3JHH = 11.7 Hz, 4JPH = 6.8 Hz, CH(C O)2), 5.83 (1H, dd, 3JHH = 11.7 Hz, 3JPH = 14.2
Hz, P C CH), 5.28 (1H, s, Ar CH), 7.25–7.92 (20H, m, 4Ar). 13C NMR (75.46 MHz,
CDCl3): δ 13.4 and 14.1 (OCH2CH3), 43.4 (d, 1JPC = 60.4 Hz, P C), 44.7 (P C CH),
61.4 and 62.2 (2OCH2CH3), 72.6 (CH(C O)2), 94.9 (CH Ar), 118.8 (d, 1JPC = 90.5 Hz,
Cipso), 126.4, 127.8, 128.8, and 136.4 (Ar), 129.7 (d, 3JPC = 15.1 Hz, Cmeta), 134.2 (d, 2JPC
=
9.7 Hz Cortho), 134.5 (d, 4JPC = 3.1 Hz Cpara), 167.5 (d, 2JPC = 24.1 Hz, P C C), 167.2
(C O), 173.6 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.3 (Ph3P+ C).
Diethyl 2-[5-(2-(4-chlorophenyl)-1,3-dioxane-4,6-dion)]-3(Triphenyl-λ5-
phosphanylidene)-succinate (3g). White powder, mp 154 ◦C, and yield 66%. FT-IR
(KBr) (υmax, cm−1): 1744, 1718, 1689, and 1621 (C O). Anal. Calcd for C36H32ClO8P
(658.15); C, 65.61; H, 4.89%; Found: C, 65.49; H, 4.89%.
1
Major isomer (E)-3g (64%), H NMR (300.1 MHz, CDCl3): δ 0.83 and 0.97 (6H,
2t, 3JHH = 7.1 Hz, 2CH3), 3.60 and 3.73 (4H, q, 3JHH = 7.1 Hz, 2OCH2CH3), 4.74 (1H,
3
4
3
3
dd, JHH = 11 Hz, JPH = 3.4 Hz, CH(C O)2), 5.56 (1H, dd, JHH = 11 Hz, JPH = 11
Hz, P C CH), 6.27 (1H, s, Ar CH), 7.25–7.86 (19H, m, 4Ar). 13C NMR (75.46 MHz,
CDCl3): δ 13.6 and 13.7 (OCH2CH3), 43.6 (d, 1JPC = 138.8 Hz, P C), 44.5 (P C CH),
1
61.8 and 62.8 (2OCH2CH3), 72.2 (CH(C O)2), 95.4 (CH Ar), 121.2 (d, JPC = 89.0,
Cipso), 128.0, 128.2,134.5, and 135.0 (Ar), 129.4 (d, 3JPC = 12.8 Hz, Cmeta), 134.2 (d, 2JPC
=
9.9 Hz Cortho), 133.8 (d, 4JPC = 3.0 Hz Cpara), 168.1 (d, 2JPC = 37.0 Hz, P C C), 167.2
(C O), 173.4 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 22.7 (Ph3P+ C).
Minor isomer (Z)-3g (36%), 1H NMR (300.1 MHz, CDCl3): δ 0.92 and 1.18 (6H, 2t,
3JHH = 7.1 Hz, 2CH3), 3.85 and 3.99 (4H, q, 3JHH = 7.1 Hz, 2OCH2CH3), 4.60 (1H, dd,
3JHH = 11.7 Hz, 4JPH = 6.8 Hz, CH(C O)2), 5.66 (1H, dd, 3JHH = 11.7 Hz, 3JPH = 14.2
Hz, P C CH), 5.13 (1H, s, Ar CH), 7.25–7.86 (19H, m, 4Ar). 13C NMR (75.46 MHz,
CDCl3): δ 13.3 and 14.1 (OCH2CH3), 43.4 (d, 1JPC = 60.4 Hz, P C), 44.7 (P C CH),
61.4 and 62.3 (2OCH2CH3), 72.6 (CH(C O)2), 94.6 (CH Ar), 118.1 (d, 1JPC = 86.5 Hz,
Cipso), 127.8, 128.1, 134.7, and 135.3 (Ar), 129.7 (d, 3JPC = 12.8 Hz, Cmeta), 134.3 (d, 2JPC
=
9.9 Hz Cortho), 134.5 (d, 4JPC = 3.1 Hz Cpara), 167.5 (d, 2JPC = 24.5 Hz, P C C), 167.2
(C O), 173.4 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.3 (Ph3P+ C).
Diethyl 2-[5-(2-(4-methylphenyl)-1,3-dioxane-4,6-dion)]-3(Triphenyl-λ5-
phosphanylidene)-succinate (3h). White powder, mp 175 ◦C, and yield 78%. FT-IR
(KBr) (υmax, cm−1): 1740, 1718, 1684, and 1616 (C O). Anal. Calcd for C37H35O8P
(638.64); C, 69.58; H, 5.52%; Found: C, 69.44; H, 5.36.
1
Major isomer (E)-3h (67%), H NMR (300.1 MHz, CDCl3): δ 0.83 and 0.97 (6H,
3
3
2t, JHH = 7.1 Hz, 2CH3), 2.32 (3H, s, CH3), 3.57 and 3.73 (4H, q, JHH = 7.1 Hz,
2OCH2CH3), 4.75 (1H, dd, 3JHH = 11 Hz, 4JPH = 3.4 Hz, CH(C O)2), 5.58 (1H, dd, 3JHH
=
3
11 Hz, JPH = 11 Hz, P C CH), 6.27 (1H, s, Ar CH), 7.06–7.90 (19H, m, 4Ar). 13C

418
A. HABIBI ET AL.
1
NMR (75.46 MHz, CDCl3): δ 13.6 and 13.7 (2OCH2CH3), 21.2 (CH3), 43.6 (d, JPC
=
138.8 Hz, P C), 44.5 (P C CH), 61.7 and 62.8 (2OCH2CH3), 72.2 (CH(C O)2), 96.2
1
(CH Ar), 121.8 (d, JPC = 89.0, Cipso), 126.4, 128.6, 133.1, and 138.5 (Ar), 129.4 (d,
2
4
3JPC = 12.8 Hz, Cmeta), 134.2 (d, JPC = 9.8 Hz Cortho), 133.7 (d, JPC = 2.9 Hz Cpara),
168.3 (d, 2JPC = 42.9, P C C), 167.3 (C O), 173.5 (CO2CH3). 31P NMR (121.5 MHz,
CDCl3): δ 23.1 (Ph3P+ C).
1
Minor isomer (Z)-3h (33%), H NMR (300.1 MHz, CDCl3): δ 0.92 and 1.15 (6H,
3
3
2t, JHH = 7.1 Hz, 2CH3), 2.29 (3H, s, CH3), 4.04 and 4.11 (4H, q, JHH = 7.1 Hz,
3
4
2OCH2CH3), 4.67 (1H, dd, JHH = 11.7 Hz, JPH = 6.8 Hz, CH(C O)2), 5.80 (1H, dd,
3JHH = 11.7 Hz, 3JPH = 14.2 Hz, P C CH), 5.31 (1H, s, Ar CH), 7.06–7.90 (19H, m,
4Ar). 13C NMR (75.46 MHz, CDCl3): δ 13.3 and 14.0 (OCH2CH3), 21.2 (CH3), 43.4 (d,
1JPC = 60.4 Hz, P C), 44.7 (P C CH), 61.4 and 62.2 (2OCH2CH3), 72.6 (CH(C O)2),
95.0 (CH Ar), 118.2 (d, 1JPC = 86.8 Hz, Cipso), 126.3, 128.5, 133.2, and 138.5 (Ar), 129.7
(d, 3JPC = 12.8 Hz, Cmeta), 134.3 (d, 2JPC = 9.8 Hz Cortho), 134.5 (d, 4JPC = 2.9 Hz, Cpara),
167.6 (d, 2JPC = 23.8 Hz, P C C), 167.2 (C O), 173.3 (CO2CH3). 31P NMR (121.5
MHz, CDCl3): δ 23.2 (Ph3P+ C).
Diethyl 2-[5-(2-(4-methoxyphenyl)-1,3-dioxane-4,6-dion)]-3(Triphenyl-λ5-
◦
phosphanylidene)-succinate (3i). White powder, mp 155 C, and yield 77%. FT-IR
(KBr) (υmax, cm−1): 1744, 1715, 1686, and 1616 (C O). Anal. Calcd for C37H35O9P
(654.64); C, 67.88; H, 5.39%; Found: C, 67.83; H, 5.24%.
1
Major isomer (E)-3i (64%), H NMR (300.1 MHz, CDCl3): δ 0.83 and 0.98 (6H,
3
3
2t, JHH = 7.1 Hz, 2CH3), 3.78 (3H, s, OCH3), 3.59 and 3.75 (4H, q, JHH = 7.1 Hz,
3
4
2OCH2CH3), 4.75 (1H, dd, JHH = 11 Hz, JPH = 3.4 Hz, CH(C O)2), 5.58 (1H, dd,
3JHH = 11 Hz, 3JPH = 11 Hz, P C CH), 6.26 (1H, s, Ar CH), 6.85–7.86 (19H, m, 4Ar).
13C NMR (75.46 MHz, CDCl3): δ 13.6 and 13.7 (2OCH2CH3), 43.6 (d, 1JPC = 138.8 Hz,
P C), 44.5 (P C CH), 55.2 (OCH3), 61.7 and 62.8 (2OCH2CH3), 72.2 (CH(C O)2),
96.1 (CH Ar), 121.9 (d, 1JPC = 89.0 Hz, Cipso), 113.3, 127.9, 129.0, and 159.9 (Ar), 129.4
(d, 3JPC = 12.8 Hz, Cmeta), 134.2 (d, 2JPC = 9.8 Hz Cortho), 133.7 (d, 4JPC = 2.8 Hz Cpara),
168.3 (d, 2JPC = 42.9, P C C), 167.3 (C O), 173.5 (CO2CH3). 31P NMR (121.5 MHz,
CDCl3): δ 23.1 (Ph3P+ C).
1
Minor isomer (Z)-3i (36%), H NMR (300.1 MHz, CDCl3): δ 0.92 and 1.15 (6H,
3
3
2t, JHH = 7.1 Hz, 2CH3), 3.76 (3H, s, OCH3), 4.06 and 4.12 (4H, q, JHH = 7.1 Hz,
3
4
2OCH2CH3), 4.69 (1H, dd, JHH = 11.7 Hz, JPH = 6.8 Hz, CH(C O)2), 5.80 (1H, dd,
3JHH = 11.7 Hz, 3JPH = 14.2 Hz, P C CH), 5.30 (1H, s, Ar CH), 6.85–7.86 (19H, m,
4Ar). 13C NMR (75.46 MHz, CDCl3): δ 13.3 and 14.1 (OCH2CH3), 43.4 (d, 1JPC = 60.4 Hz,
P C), 44.7 (P C CH), 55.2 (OCH3), 61.4 and 62.2 (2OCH2CH3), 72.6 (CH(C O)2),
94.9 (CH Ar), 118.3 (d, 1JPC = 86.0 Hz, Cipso), 113.1, 127.8, 128.4, and 160.1 (Ar), 129.7
(d, 3JPC = 12.8 Hz, Cmeta), 134.3 (d, 2JPC = 9.8 Hz, Cortho), 134.5 (d, 4JPC = 2.8 Hz, Cpara),
167.5 (d, 2JPC = 23.8, P C C), 167.2 (C O), 173.5 (CO2CH3). 31P NMR (121.5 MHz,
CDCl3): δ 23.2 (Ph3P+ C).
Diethyl
2-[5-(2-(4-flourophenyl)-1,3-dioxane-4,6-dion)]-3(Triphenyl-λ5-
◦
phosphanylidene)-succinate (3j). White powder, mp 146 C, and yield 53%. FT-IR
(KBr) (υmax, cm−1): 1743, 1717, 1688, and 1620 (C O). Anal. Calcd for C36H32FO8P
(642.61); C, 67.29; H, 5.02%; Found: C, 67.29; H, 5.0%.
Major isomer (E)-3j (67%), 1H NMR (300.1 MHz, CDCl3): δ 0.83 and 0.97 (6H, 2t,
3JHH = 7.1 Hz, 2CH3), 3.60 and 3.73 (4H, q, 3JHH = 7.1 Hz, 2OCH2CH3), 4.75 (1H, dd,
3JHH = 11 Hz, 4JPH = 3.4 Hz, CH(C O)2), 5.56 (1H, dd, 3JHH = 11 Hz, 3JPH = 11 Hz,
P C CH), 6.27 (1H, s, Ar CH), 7.01 (2H, dd, 3JHH = 8.7 Hz, 3JHF = 9 Hz, CHmeta of

STABLE YLIDES CONTAINING 2-ARYL-1,3-DIOXANE-4,6-DIONE
419
C6H4F), 7.25 (2H, dd, 3JHH = 9 Hz, 4JHF = 5.3 Hz, CHortho of C6H4F), 7.58–7.91 (15H,
m, 3Ar). 13C NMR (75.46 MHz, CDCl3): δ 13.6 and 13.7 (2OCH2CH3), 43.6 (d, 1JPC
138.8 Hz, P C), 44.5 (P C CH), 61.8 and 62.8 (2OCH2CH3), 72.2 (CH(C O)2), 95.6
=
1
2
(CH Ar), 121.8 (d, JPC = 89.0 Hz, Cipso), 114.9 (d, JCF = 21.7 Hz, Cmeta of C6H4F),
128.5 (d, 3JCF = 8.3 Hz, Cortho of C6H4F), 129.4 (d, 3JPC = 12.8 Hz, Cmeta), 132.6 (Cipso of
C6H4F), 134.2 (d, 2JPC = 9.8 Hz, Cortho), 133.7 (d, 4JPC = 2.8 Hz, Cpara), 163.0 (d, 1JCF
=
241.5 Hz, C F), 168.6 (d, 2JPC = 37.7 Hz, P C C), 167.4 (C O), 173.4 (CO2CH3). 31
P
NMR (121.5 MHz, CDCl3): δ 23.1 (Ph3P+ C).
Minor isomer (Z)-3j (33%), 1H NMR (300.1 MHz, CDCl3): δ 0.92 and 1.15 (6H, 2t,
3JHH = 7.1 Hz, 2CH3), 4.06 and 4.12 (4H, q, 3JHH = 7.1 Hz, 2 OCH2CH3), 4.72 (1H, dd,
3JHH = 11.7 Hz, 4JPH = 6.8 Hz, CH(C O)2), 5.81 (1H, dd, 3JHH = 11.7 Hz, 3JPH = 14.2
Hz, P C CH), 5.34 (1H, s, Ar CH), 6.95 (2H, dd, 3JHH = 9 Hz, 3JHF = 8.7 Hz, CHmeta
of C6H4F), 7.32 (2H, dd, 3JHH = 9 Hz, 4JHF = 5.3 Hz, CHortho of C6H4F), 7.58–7.91 (15H,
1
m, 3Ar). 13C NMR (75.46 MHz, CDCl3): δ 13.3 and 13.6 (OCH2CH3), 43.4 (d, JPC
=
60.4 Hz, P C), 44.7 (P C CH), 61.4 and 62.3 (2OCH2CH3), 72.6 (CH(C O)2), 94.4
1
2
(CH Ar), 118.3 (d, JPC = 86.0 Hz, Cipso), 114.8 (d, JCF = 21.7 Hz, Cmeta of C6H4F),
128.3 (d, 3JCF = 8.3Hz, Cortho of C6H4F), 129.7 (d, 3JPC = 12.8 Hz, Cmeta), 132.5 (Cipso of
C6H4F), 134.3 (d, 2JPC = 9.8 Hz, Cortho), 134.5 (d, 4JPC = 2.9 Hz, Cpara), 161.5 (d, 2JPC
=
24.1 HZ, P C C), 162.9 (d, 1JCF = 241.5 Hz, C F), 167.5 (d, 2JPC = 24.1 Hz, P C C),
167.2 (C O), 173.4 (CO2CH3). 31P NMR (121.5 MHz, CDCl3): δ 23.3 (Ph3P+ C).
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