Solvent effects on the chemoselectivity of stable phosphorus ylides involving a sulfonamide

Article abstract of DOI:10.1080/10426500903530883

Hydrazine sulfonamide derivatives undergo a smooth reaction with dialkyl acetylenedicarboxylates in the presence of triphenylphosphine in varieties of solvent for generation of phosphorus ylides in a chemoselective manner. Copyright Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon and the
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Solvent Effects on the Chemoselectivity
of Stable Phosphorus Ylides Involving a
Sulfonamide
Reza Heydari a , Nourallah Hazeri a , Malek Taher Maghsoodlou a
,
Sayyed Mostafa Habibi Khorassani a , Ghasem Marandi b , Nariman
Maleki a , Roya Kabiri c & Bahram Gholipour Soleymani a
a Chemistry Department , The University of Sistan and Baluchestan ,
Zahedan, Iran
b Department of Chemistry , Faculty of Science, Payame Noor
University of Khoy , Khoy, Iran
c Faculty of Chemistry , The University of Tabriz , Tabriz, Iran
Published online: 24 Sep 2010.
To cite this article: Reza Heydari , Nourallah Hazeri , Malek Taher Maghsoodlou , Sayyed
Mostafa Habibi Khorassani , Ghasem Marandi , Nariman Maleki , Roya Kabiri & Bahram Gholipour
Soleymani (2010) Solvent Effects on the Chemoselectivity of Stable Phosphorus Ylides Involving a
Sulfonamide, Phosphorus, Sulfur, and Silicon and the Related Elements, 185:10, 2135-2141, DOI:
10.1080/10426500903530883
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Phosphorus, Sulfur, and Silicon, 185:2135–2141, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500903530883
SOLVENT EFFECTS ON THE CHEMOSELECTIVITY
OF STABLE PHOSPHORUS YLIDES INVOLVING
A SULFONAMIDE
Reza Heydari,1 Nourallah Hazeri,1 Malek Taher Maghsoodlou,1
Sayyed Mostafa Habibi Khorassani,1 Ghasem Marandi,2
Nariman Maleki,1 Roya Kabiri,3
and Bahram Gholipour Soleymani1
1Chemistry Department, The University of Sistan and Baluchestan, Zahedan, Iran
2Department of Chemistry, Faculty of Science, Payame Noor University of Khoy,
Khoy, Iran
3Faculty of Chemistry, The University of Tabriz, Tabriz, Iran
Hydrazine sulfonamide derivatives undergo a smooth reaction with dialkyl acetylenedicar-
boxylates in the presence of triphenylphosphine in varieties of solvent for generation of
phosphorus ylides in a chemoselective manner.
Keywords Acetylenic diesters; chemoselective reaction; hydrazine sulfonamide; phosphorus
ylides; sulfonamide; triphenylphosphine
INTRODUCTION
Sulfonamide derivatives have a great potential as pharmacological and agricultural
agents due to their biological properties.1–4 The impact of organophosphorus chemistry on
modern synthetic chemistry is difficult to quantify, but one can safely assume that the study
of this element has influenced all area of chemical endeavor.5–9 Synthesis of phosphonium
salts often occurs by reaction between triphenylphosphine and an alkyl halide in the presence
of a base, but more recently, there are many reports that triphenylphosphine and acetylenic
esters are used for generation of stable phosphonium ylides.5–17 We describe in this article an
efficient synthetic route for synthesis of stable phosphorus ylides containing sulfonamide
in the presence of various solvents. Solvent selection in organic synthesis is one of the
major routes for approaching goals. For this reason, the effects of various solvents on the
chemoselectivity of stable phosphorus were investigated in the current work.
RESULTS AND DISCUSSION
This report contains the results of the reaction between triphenylphosphine and sul-
fonamides 2, which leads to stable phosphorus ylides 3 and 4 in 89–95% yields (see
Received 2 August 2009; accepted 27 November 2009.
We gratefully acknowledge financial support from the Research Council of the University of Sistan &
Baluchestan.
Address correspondence to Malek Taher Maghsoodlou, Chemistry Department, The University of Sistan
and Baluchestan, P. O. Box 98135-674, Zahedan, Iran. E-mail: mt maghsoodlou@yahoo.com
2135

2136
R. HEYDARI ET AL.
RO2C
RO2C
H
PPh3
R''
CO2R
C
H
PPh3
NH
R''
R'
NH
O
S
N
i: apropriate solvent
N
CO2R
PPh3
+
+
CO2R
X
O
NH
O
S
C
O
S
O
or
O
CO2R
3
1
2
4
X
X
in 2 R' = NH2, PhNH
in 3 and 4 R'' = Ph, H
Solvent
ether
Selectvity (%) of 3 and 4
2
R
R'
X
66
6
34
94
a
Me
NH2
Me
ethyl acetate
b
c
Et
NH2
H
H
H
acetonitrile
----
single product
10
: 1
Me
PhNH
PhNH
ether / acetone
single product
single product
----
----
t-butyl
d
ether
Scheme 1
Scheme 1). In continuation of our research on the development of synthesic routes of
heterocyclic and organophosphorus compounds,18–20 we describe in this article the effects
of solvents on the chemoselectivity of new ylides 3 and 4. Compounds 3 and 4 are stable
solids whose structures are fully characterized and supported by elemental analyses and
spectroscopic data.
1
The H NMR spectrum of 3a exhibited single sharp lines arising from methyl (δ
= 2.41 ppm), methoxycarbonyl groups (δ = 3.10 and 3.55 ppm), a broad singlet from
SO2NNH2 (δ = 4.11 ppm), and a doublet from methine proton (δ = 4.94 ppm, J =
17.0 Hz), respectively. Aromatic protons of 3a resonated at δ = 7.22–7.75 ppm for the
major diasteroisomer. The 13C NMR spectrum of compound 3a showed carbonyl groups
at δ = 170.70 ppm, J = 7.5 Hz and δ = 172.36 ppm, J = 13.8 Hz, respectively. Other
partial spectroscopic information is reported in the Experimental section for the minor
diasteroisomer.
1
The H NMR spectrum of 4a displayed single sharp lines arising from methyl (δ
= 2.46 ppm), methoxycarbonyl groups (δ = 3.07 and 3.74 ppm), a doublet from methine
proton (δ = 4.61 ppm, J = 8.3 Hz), a doublet from SO2HNNH (δ = 3.61 ppm, J = 9.3
Hz), and a doublet from SO2HNNH (δ = 6.62 ppm, J = 2.7 Hz), respectively. Aromatic
protons of 4a resonated in δ = 7.25–7.75 ppm for the major diasteroisomer. The 13C NMR
spectrum of compound 4a showed characteristic carbonyl groups at δ = 169.75 ppm, J
= 11.5 Hz and δ = 173.32 ppm, J = 11.3 Hz, respectively. Other partial spectroscopic
information is available in the Experimental section for the minor diasteroisomer.
The mass spectra of compounds 3a and 4a displayed molecular ion peaks at appro-
priate m/z values.
On the basis of the well-established chemistry of trivalent phosphorus nucle-
ophiles,5–13 it is reasonable to assume that phosphorus ylides 3 and 4 result from the
initial addition of triphenylphosphine to the acetylenic ester and subsequent protonation of
the 1:1 adduct by the NH-compounds to form phosphoranes 3 and 4 (see Scheme 2).
The ylides 3 and 4 exist in solution as two geometrical isomers (Z) and (E) because
the negative charge of the ylide moiety of these compounds is strongly conjugated with
the adjacent carbonyl group. Rotation around the carbon–carbon double bond is slow on

CHEMOSELECTIVITY OF STABLE PHOSPHORUS YLIDES
2137
O
S
H
CO2R
H2N
N
Ar
O
CO2R
C
3
RO2C
H
PPh3
RO2C
Ph3P
2a
PPh3
+
C
H
O
S
CO2R
CO2R
CO2R
PPh3
Ar
HN
N
O
1
4
RO2C
Scheme 2
the NMR time scale for interconversion process between both (Z)- and (E)- geometrical
isomers at ambient temperature (Scheme 3). Due to the sheer difficulty of the separation in
the mixture of both geometrical isomers (Z) and (E) from each other in solution, preparation
of a single crystal is impossible.
PPh3
PPh3
H
N
H
N
RO2C
O
RO2C
OR
O
OR
NH2
O
O
NH2
S
S
O
Ar
O
Ar
(E)-3, Minor
(Z)-3, Major
Scheme 3
In conclusion, the reaction between triphenylphosphine and acetylenic esters in the
presence of NH-compounds such as sulfonamides provides a simple, one-pot, and efficient
entry for the synthesis of stable, sulfonamide-containing ylides with probable pharmacolog-
ical properties. The present method carries the advantages involving generation of different
products in the presence of various solvent media, neutral conditions, and possible mixture
of substances without any prior activation and modification.
EXPERIMENTAL
Melting points and IR spectra of all compounds were measured on an Electrothermal
1
9100 apparatus and a Shimadzu IR-460 spectrometer, respectively. The H, 13C, and 31P
NMR spectra were obtained with a Bruker DRX-500 Avance instrument using CDCl3 as
applied solvent TMS as internal standard at 500.1, 125.8, and 202.4 MHz, respectively. El-
emental analyses for C, H, and N were performed using a Heraeus CHN-O-Rapid analyzer.
In addition, the mass spectra were recorded on a Shimadzu GC/MS QP 5050 mass spec-
trometer operating at an ionization potential of 70 eV. Dialkyl acetylenedicarboxylates and
triphenylphosphine were purchased from Fluka and were used without further purification.
All sulfonamides have been prepared by known procedures.21

2138
R. HEYDARI ET AL.
General Procedures for Preparation of Stable Phosphorus Ylides 3 or 4
To a magnetically stirred solution of triphenylphosphine (0.26 g, 1 mmol) and NH
compound 2 (1 mmol) in diethyl ether (10 mL), a mixture of dimethyl acetylenedicar-
boxylates (0.14 g,1 mmol) in diethyl ether (3 mL) was added dropwise over 10 min at
ambient temperature. After the appropriate time (4–12 h) stirring at ambient temperature,
the product was filtered off and recrystallized from ethyl acetate.
Dimethyl 2-(Para-toluenesulfonamido-N-amino-N-yl)-3-
(triphenylphosphoranylidene)butandioate (3a)
Yellow powder, yield: 0.54 g (92%), mp 136–139 ◦C. IR (KBr) (λmax, cm−1): 3422
and 3315 (NH2), 1733 and 1630 (2 C Oester), 1319 and 1144 (SO2). MS (m/z,%): 590 (M+,
1), 573 (2), 456 (2), 417 (1), 392 (4), 333 (17), 262 (56), 183 (100), 157 (26), 108 (48),
91 (53). Anal Calcd for C31H31N2O6PS (590.63): C, 63.04; H, 5.29; N, 4.74%; Found: C,
63.22; H, 5.17; N, 4.61%.
1
Major isomer (Z)-3a (65%): H NMR: 2.41 (3H, s, Me), 3.10 and 3.55 (6H, 2s, 2
OCH3), 4.11 (2H, br s, NH2), 4.94 (1H, d, 3JHP = 17.0 Hz, P C CH), 7.22 (2H, d, 3JHH
= 8.1 Hz, CHaryl), 7.28 (2H, d, 3JHH = 8.1 Hz, CHaryl), 7.54–7.75 (15H, m, 3 C6H5). 13
C
NMR: 21.48 (s, Me), 41.13 (d, 1JPC = 125.8 Hz, P C CH), 48.90 and 49.15 (2s, 2 OCH3),
62.25 (d, 2JPC = 15.5 Hz, P C CH), 126.46 (d, 1JPC = 92.3 Hz, Cipso of 3 C6H5), 128.13
3
and 128.70 (2s, 4 CHaryl), 128.9 (d, JPC = 15.5 Hz, Cmeta of 3 C6H5), 129.30 (s, Caryl),
2
132.24 (Cpara of 3 C6H5), 133.74 (d, JPC = 9.8 Hz, Cortho of 3 C6H5), 143.30 (s, Caryl),
170.70 (d, 2JPC = 7.5 Hz, C Oester), 172.36 (d, 3JPC = 13.8 Hz, C Oester). 31P NMR: 23.18
(Ph3P+-C).
Minor isomer (E)-3a (35%): 1H NMR: 2.47 (3H, s, Me), 3.43 and 3.71 (6H, 2s, 2
OCH3), 3.93 (2H, br s, NH2), 5.00 (1H, d, 3JHP = 16.4 Hz, P C CH), 7.21–7.23 (4H, m,
4 CHaryl), 7.54–7.82 (15H, m, 3 C6H5). 13C NMR: 21.54 (s, Me), 41.83 (d, 1JPC = 123.7
2
Hz, P C CH), 49.17 and 50.02 (2s, 2 OCH3), 62.17 (d, JPC = 14.7 Hz, P C CH),
126.79 (d, 1JPC = 91.5 Hz, Cipso of 3 C6H5), 128.42 and 128.80 (2s, 4 CHaryl), 129.01 (d,
3JPC = 12.3 Hz, Cmeta of 3 C6H5), 129.30 (s, Caryl), 132.22 (Cpara of 3 C6H5), 133.74 (d,
2JPC = 9.8 Hz, Cortho of 3 C6H5), 142.38 (s, Caryl), 169.13 (d, 2JPC = 7.3 Hz, C Oester),
172.14 (d, 3JPC = 12.9 Hz, C Oester). 31P NMR: 24.71 (Ph3P+-C).
Dimethyl 2-(Para-toluenehydrazidsulfonamido-N-yl)-
3-(triphenylphosphoranylidene)butandioate (4a)
Yellow powder, yield: 0.56 g (95%), mp 153–156 ◦C. IR (KBr) (λmax, cm−1): 3370
and 3262 (2 NH), 1732 and 1680 (2 C Oester), 1330 and 1127 (SO2). MS (m/z,%): 590
(M+, 2), 575 (3), 406 (2), 390 (3), 347 (17), 262 (91), 183 (100), 108 (44), 91 (62). Anal
Calcd for C31H31N2O6PS (590.63): C, 63.04; H, 5.29; N, 4.74%; Found: C, 62.98; H, 5.21;
N, 4.83%.
1
Major isomer (Z)-4a (68%): H NMR: 2.46 (3H, s, Me), 3.07 and 3.74 (6H, 2s, 2
OCH3), 3.61 (1H, m, P C CH), 4.61 (1H, br d, 3JHH = 8.3 Hz, SO2HNNH), 6.62 (1H,
d, J = 2.7 Hz, SO2HNNH), 7.25–7.75 (20H, m, 3 C6H5 and 4 CHaryl). 13C NMR: 21.53 (s,
Me), 41.33 (d, 1JPC = 124.7 Hz, P C CH), 48.89 and 52.04 (2s, 2 OCH3), 63.71 (d, 2JPC
= 15.6 Hz, P C CH), 126.71 (d, 1JPC = 92.7 Hz, Cipso of 3 C6H5), 128.13 and 128.70
(2s, 4 CHaryl), 128.7 (d, 3JPC = 12.1 Hz, Cmeta of 3 C6H5), 132.08 (Cpara of 3 C6H5), 133.75

CHEMOSELECTIVITY OF STABLE PHOSPHORUS YLIDES
2139
(d, 2JPC = 9.4 Hz, Cortho of 3 C6H5), 133.79 and 143.29 (2s, 2 Caryl), 169.75 (d, 3JPC = 11.5
Hz, C Oester), 173.32 (d, 2JPC = 11.3 Hz, C Oester). 31P NMR: 23.25 (Ph3P+-C).
Minor isomer (E)-4a (32%):1H NMR: 2.40 (3H, s, Me), 3.44 and 3.70 (6H, 2s, 2
OCH3), 3.55 (1H, m, P C CH), 4.39 (1H, br d, 3JHH = 9.7 Hz, SO2HNNH), 6.62 (1H,
d, J = 2.7 Hz, SO2HNNH), 7.25–7.83 (20H, m, 3 C6H5 and 4 CHaryl). 13C NMR: 21.53 (s,
Me), 41.73 (d, 1JPC = 125.1 Hz, P C CH), 49.86 and 51.92 (2s, 2 OCH3), 63.11 (d, 2JPC
= 15.3 Hz, P C CH), 126.94 (d, 1JPC = 91.8 Hz, Cipso of 3 C6H5), 128.17 (s, 2 CHaryl),
128.91 (d, 3JPC = 12.3 Hz, Cmeta of 3 C6H5), 129.30 (s, 2 CHaryl), 132.23 (Cpara of 3 C6H5),
133.75 (d, 2JPC = 9.4 Hz, Cortho of 3 C6H5), 135.67 and 142.80 (2s, 2 Caryl), 169.13 (d, 3JPC
= 12.1 Hz, C Oester), 173.51 (d, 2JPC = 11.8 Hz, C Oester). 31P NMR: 23.74 (Ph3P+-C).
Diethyl 2-(Benzenehydrazidsulfonamido-N-yl)-3-
(triphenylphosphoranylidene)butandioate (4b)
Yellow powder, yield: 0.55 g (91%), mp 152–154 ◦C. IR (KBr) (λmax, cm−1): 3323
and 3270 (2 NH), 1732 and 1657 (2 C Oester), 1330 and 1127 (SO2). MS (m/z,%): 604
(M+, 2), 573 (8), 531 (23), 502 (7), 374 (48), 262 (73), 183 (100), 108 (53), 156 (25). Anal
Calcd for C32H33N2O6PS (604.65): C, 63.56; H, 5.50; N, 4.63%; Found: C, 63.48; H, 5.63;
N, 4.52%.
Major isomer (Z)-4b (70%): 1H NMR: 0.42 (3H, t, J = 6.7 Hz, OCH2CH3), 1.28 (3H,
t, J = 6.4 Hz, OCH2CH3), 3.54–3.59 (2H, m, OCH2CH3), 3.60–3.64 (2H, m, OCH2CH3),
3
3.84 (1H, br s, P C CH), 4.70 (1H, br d, JHH = 9.8 Hz, SO2HNNH), 6.72 (1H, br s,
SO2HNNH), 7.46–7.83 (20H, m, 3 C6H5 and 4 CHaryl). 13C NMR: 13.89 and 14.28 (2s, 2
1
OCH2CH3), 41.77 (d, JPC = 125.8 Hz, P C CH), 57.54 and 60.78 (2s, 2 OCH2CH3),
63.60 (d, 2JPC = 14.6 Hz, P C CH), 126.93 (d, 1JPC = 92.0 Hz, Cipso of 3 C6H5), 128.11
3
and 128.64 (2s, 4 CHaryl), 128.70 (d, JPC = 12.6 Hz, Cmeta of 3 C6H5), 131.93 (Cpara of
2
3 C6H5), 132.54 (s, Caryl), 133.79 (d, JPC = 9.8 Hz, Cortho of 3 C6H5), 138.79 (s, Caryl),
169.35 (d, 3JPC = 11.7 Hz, C Oester), 174.80 (d, 2JPC = 11.1 Hz, C Oester). 31P NMR:
23.11 (Ph3P+-C).
1
Minor isomer (E)-4b (30%): H NMR: 1.06 (3H, t, J = 6.8 Hz, OCH2CH3), 1.28
(3H, t, J = 6.4 Hz, OCH2CH3), 4.00 (1H, br s, P C CH), 4.07–4.19 (2H, m, OCH2CH3),
4.23–4.29 (2H, m, OCH2CH3), 4.57 (1H, br d, 3JHH = 10.0 Hz, SO2HNNH), 6.72 (1H, br
s, SO2HNNH), 7.46–7.91 (20H, m, 3 C6H5 and 4 CHaryl). 13C NMR: 14.28 and 14.87 (2s,
2 OCH2CH3), 41.98 (d, 1JPC = 124.97 Hz, P C CH), 57.99 and 60.78 (2s, 2 OCH2CH3),
62.82 (d, 2JPC = 14.8 Hz, P C CH), 128.15 (d, 1JPC = 91.7 Hz, Cipso of 3 C6H5), 128.24
3
and 128.46 (2s, 4 CHaryl), 128.49 (d, JPC = 12.5 Hz, Cmeta of 3 C6H5), 129.11(s, Caryl),
132.00 (Cpara of 3 C6H5), 133.15 (s, Caryl), 134.01 (d, 2JPC = 10.5 Hz, Cortho of 3 C6H5),
169.27 (d, 3JPC = 11.5 Hz, C Oester), 174.92 (d, 2JPC = 11.7 Hz, C Oester). 31P NMR:
23.67 (Ph3P+-C).
Dimethyl 2-(Benzenesulfonamido-N-aniline-N-yl)-3-
(triphenylphosphoranylidene)butandioate (3c)
◦
Pale white powder, yield: 0.52 g (92%), mp 142–145 C. IR (KBr) (λmax, cm−1):
3414 (NH), 1746 and 1619 (2 C Oester), 1345 and 1151 (SO2). MS (m/z,%): 562 (M+, 1),
545 (32), 277 (63), 183 (22), 173 (34), 108 (15), 77 (100), 57 (14), 51 (44). Anal Calcd
for C36H33N2O6PS (652.70): C, 66.25; H, 5.10; N, 4.29%; Found: C, 66.15; H, 5.19; N,
4.13%.

2140
R. HEYDARI ET AL.
1
Major isomer (Z)-3c (77%): H NMR: 2.95 and 3.31 (6H, 2s, 2 OCH3), 4.84 (1H,
d, 3JHP = 18.0 Hz, P C CH), 6.58 (1H, s, SO2NNH), 7.09–7.75 (25H, m, 5 C6H5). 13
C
1
NMR: 49.08 and 51.68 (2s, 2 OCH3), 42.13 (d, JPC = 127.3 Hz, P C CH), 64.20 (d,
2JPC = 16.5 Hz, P C CH), 114.53 (s, 2 Caryl), 120.28 (s, 1 Caryl), 128.31 (d, 1JPC = 97.2
Hz, Cipso of 3 C6H5), 128.73 (d, 3JPC = 12.2 Hz, Cmeta of 3 C6H5),128.91 (s, 2 Caryl), 131.96
(Cpara of 3 C6H5), 149.58 (s, 1 Caryl), 125.41 (s, 2 Caryl), 132.38 (s, 1 Caryl), 133.70 (d, 2JPC
= 9.9 Hz, Cortho of 3 C6H5), 133.87 (s, 2 Caryl), 138.76 (s, 1 Caryl), 170.26 (d, 3JPC = 12.3
Hz, C Oester), 172.28 (d, 2JPC = 12.6 Hz, C Oester). 31P NMR: 25.26 (Ph3P+-C).
Minor isomer (E)-3c (23%):1H NMR: 3.43 and 3.51 (6H, 2s, 2 OCH3), 4.99 (1H,
d, 3JHP = 19.6 Hz, P C CH), 6.30 (1H, s, SO2NNH), 6.90–7.75 (25H, m, 5 C6H5). 13
C
NMR: 50.13 and 51.96 (2s, 2 OCH3), 41.65 (d, 1JPC = 128.11 Hz, P C CH), 63.17 (d,
2JPC = 16.3 Hz, P C CH), 111.83 (s, 2 Caryl), 120.09 (s, 1 Caryl), 126.17 (s, 2 Caryl),
126.24 (d, 1JPC = 91.8 Hz, Cipso of 3 C6H5), 128.82 (d, 3JPC = 11.9 Hz, Cmeta of 3 C6H5),
132.06 (Cpara of 3 C6H5), 133.61 (s, 2 Caryl), 133.80 (d, 2JPC = 9.7 Hz, Cortho of 3 C6H5),
138.12 (s, 1 Caryl), 148.83 (s, 1 Caryl), 169.13 (d, 3JPC = 131.1 Hz, C Oester), 172.13 (d, 2JPC
= 12.6 Hz, C Oester). 31P NMR: 26.11 (Ph3P+-C).
Di-tert-butyl 2-(Benzenesulfonamido-N-aniline-N-yl)-3-
(triphenylphosphoranylidene)butandioate (3d)
◦
White powder, yield: 0.66 g (89%), mp 137–140 C. IR (KBr) (λmax, cm−1): 3342
(NH), 1732 and 1639 (2 C Oester), 1343 and 1164 (SO2). MS (m/z,%): 738 (M+, 2), 601 (9),
573 (24), 371 (11), 262 (49), 183 (56), 108 (27), 91 (100). Anal Calcd for C42H45N2O6PS
(736.86): C, 68.46; H, 6.16; N, 3.80%; Found: C, 68.57; H, 6.21; N, 3.86%.
Major isomer (Z)-3d: 1H NMR: 079 and 1.44 (18H, 2s, 2 OCMe3), 4.69 (1H, d, 3JHP
= 18.8 Hz, P C CH), 6.81 (1H, s, SO2NNH), 6.96–7.75 (25H, m, 5 C6H5). 13C NMR:
1
2
28.15 and 28.25 (2s, 2 OCMe3), 40.50 (d, JPC = 125.7 Hz, P C CH), 64.66 (d, JPC
= 18.0 Hz, P C CH), 77.42 and 80.85 (2s, 2 OCMe3), 114.68 (s, 2 Caryl), 119.90 (s, 1
Caryl), 126.60 (s, 2 Caryl), 128.02 (d, 1JPC = 90.4 Hz, Cipso of 3 C6H5), 128.53 (d, 3JPC
=
12.3 Hz, Cmeta of 3 C6H5), 128.92 (s, 2 Caryl), 129.26 (s, Caryl), 131.70 (Cpara of 3 C6H5),
131.88 (s, 2 Caryl), 133.87 (d, 2JPC = 9.8 Hz, Cortho of 3 C6H5), 138.59 (s, 1 Caryl), 149.83
(s, 1 Caryl), 168.95 (d, 3JPC = 12.5 Hz, C Oester), 170.23 (d, 2JPC = 12.4 Hz, C Oester).
31P NMR: 23.91 (Ph3P+-C).
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