Synthesis of new phosphorous ylides containing urethane derivatives

Article abstract of DOI:10.1080/10426500801963574

The readily available (DMAD& DEAD) and triphenylphosphine undergo facile reaction with several urethanes such as methyl-N-phenylcarbamate, ethyl-N-phenylcarbamate, phenyl-N-phenylcarbamate, phenyl-N-(2-methylphenyl) carbamate and phenyl -N(3-methylphenyl)carbamate, to give crystalline phosphorus ylides in good yields. The overall sequence from a 1:1:1 reaction provides a simple and efficient rout to functionalized urethanes. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426500801963574

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Synthesis of New Phosphorous
Ylides Containing Urethane
Derivatives
Esmat Tavakolinejad a , Naeim Ghatali a ,
Mohammad Reza Islami a & Hojat Khabazzadeh a
a Department of Chemistry , Shahid Bahonar,
University of Kerman , Kerman, Iran
Published online: 12 Aug 2008.
To cite this article: Esmat Tavakolinejad , Naeim Ghatali , Mohammad Reza Islami &
Hojat Khabazzadeh (2008) Synthesis of New Phosphorous Ylides Containing Urethane
Derivatives, Phosphorus, Sulfur, and Silicon and the Related Elements, 183:9,
2301-2308, DOI: 10.1080/10426500801963574
To link to this article: http://dx.doi.org/10.1080/10426500801963574
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Phosphorus, Sulfur, and Silicon, 183:2301–2308, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500801963574
Synthesis of New Phosphorous Ylides Containing
Urethane Derivatives
Esmat Tavakolinejad, Naeim Ghatali, Mohammad Reza
Islami, and Hojat Khabazzadeh
Department of Chemistry, Shahid Bahonar, University of Kerman,
Kerman, Iran
The readily available (DMAD& DEAD) and triphenylphosphine undergo
facile reaction with several urethanes such as methyl–N-phenylcarbamate,
ethyl-N-phenylcarbamate, phenyl-N-phenylcarbamate, phenyl-N-(2-methylphenyl)
carbamate and phenyl –N(3-methylphenyl)carbamate, to give crystalline phospho-
rus ylides in good yields. The overall sequence from a 1:1:1 reaction provides a
simple and efficient rout to functionalized urethanes.
Keywords Acetylenic esters; phosphorus compounds; urethanes
INTRODUCTION
The urethanes have attracted considerable attention since they have
been extensively used in organic synthesis polyurethanes during the
past 60 years.1–4 Although the properties and synthesis of these com-
pounds have been widely studied, the closely related highly function-
alized urethane derivatives containing phosphorous ylide moiety are
unknown so far. Recently, our interest focused on the synthesis of phos-
phorous ylides that could be transformed into versatile compounds.5–8
Our aim of this study is to prepare new urethanes containing the ylide
moiety from the reaction of carbamate derivatives with acetylenic es-
ters in the presence of triphenylphosphine as a good nucleophile.9–12
Received October 24, 2007; accepted December 18, 2007.
The authors express appreciation to Shahid Bahonar University of Kerman, Faculty
Research Fund for its support of this investigation.
Address correspondence to Esmat Tavakolinejad, Naeim Ghatali, Mohammad Reza
Islami and Hojat Khabazzadeh, Department of Chemistry, Shahid Bahonar, University
of Kerman, Kerman 76169, Iran. E-mail: etavakoly@yahoo.com.
2301

2302
E. Tavakolinejad et al.
SCHEME 1
RESULTS AND DISCUSSION
The synthesis of compounds 4a–i was accomplished in accordance with
the reaction depicted in Scheme 1. The starting compounds, carbamate
derivatives 3a–i were prepared according to the procedure, which was
reported in the literature. The reaction of compounds 3a–i with dialkyl
acetylenedicarboxylate in the presence of Ph3P gave the stable phos-
phorus ylides 4a–i.
A plausible mechanism of the reaction and formation of the final
products is depicted in Scheme 1. The structures of compounds 4a–i
were deduced from their high- field 1H, 13C NMR, and IR spectral data.
The 1H and 13C NMR spectroscopic data for compounds 4a–i exhibit a
mixture of two rotational isomers. The ylide moiety of these compounds
is strongly conjugated with the adjacent carbonyl group and rotation
about the partial double bond in 4-(E) and 4-(Z) geometrical isomer is
low on the NMR time scale at ambient temperature. The structure of
rotamers, which were found in ylides, have been previously established
and reported in the literature.13,14
1
The H NMR spectrum of 4a showed six sharp lines (δ = 2.83, 3.0,
3.42, 3.45, 3.7, 3.86 ppm) due to the methoxy protons, along with signals
for methine protons at δ = 4.92 and 4.96 which appear as two doublets
(3JPH = 16.2Hz) and (3JPH = 18Hz), respectively, for major and minor
geometrical isomers. The aromatic region appeared as a multiplet at
7.26–7.59 ppm. The 13C NMR spectrum of 4a is in agreement with
the mixture of two rotamers. Although the presence of the 31P nucleus
1
complicates both the H and 13C NMR spectra of the compounds 4a-i

Synthesis of New Phosphorous Ylides
2303
but it does help us to obtain some valuable information by long-range
spin-spin coupling constants 31P with 1H and 13C nuclei.
The 1H and 13C NMR spectroscopic data for compound 4b are similar
to those of 4a, except for the ester groups, which exhibited characteristic
resonances with appropriate chemical shifts.
The NMR spectral data for compounds (4c–i) are consistent with the
phosphorane structure.
The structural assignments made for the phosphorane 4a–i based
on the 1H, 13C NMR, and their IR spectra.
The carbonyl group region of the spectrum exhibited two absorption
bands for each compound, the conjugation of one ester group with the
negative charge is a plausible factor in reduction of the wave number
of one carbonyl absorption band.
CONCLUSION
In conclusion, we have demonstrated that the readily available
acetylenedicarboxylates in the presence of triphenylphosphine under-
goes facile reaction with urethane, providing a convenient and rapid
synthesis of urethane derivatives containing the ylide moiety.
EXPERIMENTAL
Dimethyl acetylenedicarboxylate, diethyl acetylenedicarboxylate,
phenylisocyanate, o-cresol, and m-cresol were obtained from Merck Co.
and were used without further purification.
Melting points were obtained on a Gallenkamp melting point appa-
ratus and were uncorrected. IR spectra were measured on a Mattson
1000 FT-IR spectrometer. 1H and 13C NMR spectra were reported on a
BRUKER DRX-500 AVANCE spectrometer at 500.13 and 125.77 MHz,
respectively.
Dimethyl-2-[(methoxycarbonyl)anilino]-3-(1,1,1-triphenyl-λ5-
phosphonylidene)succinate 4a
Dimethyl acetylenedicarboxylate or diethyl acetylenedicarboxylate (2
mmol, 0.24 ml) was added dropwise to a magnetically stirred solution
of triphenylphosphine (2 mmol, 0.53 g) and urethane (2 mmol) in a
15 ml mixture of ethyl acetate-petroleum ether (4:1) at an ambient
temperature After the addition was complete the mixture was stirred
for an additional 6 h and then filtered.

2304
E. Tavakolinejad et al.
The filtrate was washed thoroughly with mixture of ethyl acetate-
petroleum ether to give a white powder. (0.92g, m.p. 156–158◦C, yield
83%); IR (KBr) (νmax, cm−1):1756, 1645, and 1617 (C O). m.p.
1
Major isomer, 4a-(E) (57.2%), H NMR: δ 3.09, 3.45, and 3.77 (9H,
3s, 3OCH3), 4.92(1H, d, 3JPH = 16.2 Hz, P C CH)*, 7.26–7.59 (40H, m,
1
arm)*. 13C NMR: δ 40.87 (d, JPC = 135.8 Hz, P C), 49.35, 52.03, and
2
52.34(3OCH3), 61.12(d, JPC = 17.0Hz, P C CH), 126.65, and 127.35
(2CH)*,126.27 (d, 1JPC = 91.9Hz, Cipso), 128.53 (d, 3JPC = 12.4Hz, Cmeta ),
4
2
131.24 (1C)*, 132.04 (d, JPC = 4.0Hz, Cpara), 133.79 (d, JPC = 9.8Hz,
Cortho), 139.14 and 155.78 (2C), 168.4 (C O), 169.99 (d, 2JPC = 17.8Hz,
C O) *, 173.50 (d, 3JPC = 3.7Hz, C O).*
Minor isomer, 4a-(Z) (42.8%), 1H NMR: δ 2.87, 3.42, and 3.86 (9H,
3s, 3OCH3), 13C NMR: 38.65 (d, JPC = 136.6Hz, P C), 48.70, 52.28
1
2
and 52.43(3OCH3), 61.96 (d, JPC = 16.6Hz, P C CH), 126.13 (d,
1JPC = 96.8Hz, Cipso), 128.63 (d, 3JPC = 12.4Hz, Cmeta ), 131.94 (d, 4JPC
=
3.60Hz, Cpara), 133.56 (d, 2JPC = 9 .7Hz, Cortho), 139.41, and 155.44 (2C),
168.51 (C O).
Diethyl-2-[(methoxycarbonyl)anilino]-3-(1,1,1-triphenyl-λ5-
phosphonylidene)succinate 4b
(0.87g, m.p. 170–173◦C, yield 75%); IR (KBr) (νmax, cm−1):1750, 1651,
and 1621 (C O).
Major isomer, 4b-(E) (51.1%), 1H NMR: δ 0.30 and 1.33 (6H,2t, CH3),
3.34 (3H, s, OCH3), 3.39, and 4.21 (4H,2q, OCH2-), 4.90 (1H, d, JPH
=
16.4 Hz, P C CH)*, 7.23–7.62 (40H, m, arm)*. 13C NMR: δ 13.9 and
1
14.3 (2CH3), 40.72 (d, JPC = 134.7Hz, P C), 52.40(OCH3), 57.37 and
2
1
60.81 (2OCH2-), 61.12(d, JPC = 17.0Hz, P C CH), 126.15 (d, JPC
=
91.3Hz, Cipso), 127.39, and 127.56 (2C)*, 128.44 (d, JPC = 12.2Hz,
3
Cmeta ), 131.43 (1C)*, 132.04 (d, JPC = 2.6Hz, Cpara), 133.67 (d, JPC
9.7Hz, Cortho), 139.51, and 155.81(2C), 167.97 (C O), 168.82 (d, 2JPC
18.0Hz, C O)*, 172.68 (d, 3JPC = 13.6Hz, C O)*.
=
=
4
2
Minor isomer, 4b-(Z) (49.9%), 1H NMR: δ 0.94, and 1.36 (6H, 2t, CH3),
3.37 (3H, s, OCH3), 3.43 and 4.26 (4H, 2q, OCH2-),13C NMR: 14.28 and
14.45 (2CH3), 38.42 (d, 1JPC = 127.8Hz, P C), 52.40 (OCH3), 57.91 and
2
1
60.12 (2OCH2-), 61.96 (d, JPC = 16.6Hz, P C CH), 126.13 (d, JPC
=
91.9Hz, Cipso), 128.56 (d, 3JPC = 12.3Hz, Cmeta ), 131.97 (d, 4JPC = 2.7Hz,
C
para), 133.80 (d, 2JPC = 9.8Hz, Cortho), 139.22, and 155.49 (2C), 167.86
(C O).
∗For two rotamers

Synthesis of New Phosphorous Ylides
2305
Dimethyl-2-[(ethoxycarbonyl)anilino]-3-(1,1,1-triphenyl-λ5-
phosphonylidene)succinate 4c
(0.99g, m.p. 150–151◦C, yield 86%); IR (KBr) (νmax, cm−1): 1754, 1650,
and 1619 (C O).
1
Major isomer, 4c-(E) (53.1%), H NMR: δ 1.1 (CH3)*, 2.88 and 3.77
(3H, 2s, OCH3), 3.97 (4H,m, OCH2-)*, 4.90 (1H, d, JPH = 1 6.3 Hz,
P C CH)*, 7.26–7.58 (40H, m, arm)*. 13C NMR: δ 14.53 (CH3)*, 40.77
1
(d, JPC = 135.1Hz, P C), 49.40 (OCH2-) 52.03(OCH3), 61.03(OCH3),
2
61.95(d, JPC = 16.5Hz, P C CH)*, 125.93, 126.75 and 126.64 (C)*,
126.61 (d, 1JPC = 90.6 Hz, Cipso), 128.64 (d, 3JPC = 12.3Hz, Cmeta ), 131.20
4
2
(1C)*, 132.03(d, JPC = 2.6Hz, Cpara), 133.78 (d, JPC = 9.9Hz, Cortho),
139.25 and 155.36(2C), 168.56 (C O), 169.98 (d, 2JPC = 18.8Hz, C O)*,
173.54 (d, 3JPC = 6.8Hz, C O)*. Minor isomer, 4c-(Z) (46.9%), 1H NMR:
δ 3.1 and 3.90 (3H, 2s, OCH3), 3.43 and 4.26 (4H, 2q, OCH2-),13C NMR:
1
38.61 (d, JPC = 129.5Hz, P C), 48.75 (OCH2-), 52.32 (OCH3), 60.94
(OCH3), 126.26 (d, JPC = 92.1Hz, Cipso), 128.54 (d, JPC = 12.3Hz,
Cmeta ), 131.93 (d, 4JPC = 2.5Hz, Cpara), 133.55 (d, 2JPC = 9.7Hz, Cortho),
139.49 and 154.99 (2C), 168.45(C O).
1
3
Diethyl-2-[(ethoxycarbonyl)anilino]-3-(1,1,1-triphenyl-λ5-
phosphonylidene)succinate 4d
(0.96 g, m.p. 155–156◦C, yield 78%); IR (KBr) (νmax, cm−1):1754, 1660,
and 1625 (C O).
1
Major isomer, 4d-(E) (50.3%), H NMR: δ 0.29, 0.95, and 1.33 (9H,
3t, CH3), 3.33, 3.92, and 4.20 (6H,3q, OCH2-), 4.91 (1H, d, JPH
=
16.4 Hz, P C CH)*, 7.23–7.61 (40H, m, arm)*. 13C NMR: δ 13.89, 14.30,
1
and 14.57 (3CH3), 40.62 (d, JPC = 134.8Hz, P C), 57.38, 60.92, and
2
61.14 (3OCH2-), 61.89(d, JPC = 16.6Hz, P C CH)*, 125.96,126.71,
1
3
and 127.34 (3C)*, 126.51 (d, JPC = 91.9Hz, Cipso), 128.55 (d, JPC
=
12.3Hz, Cmeta ), 131.43 (1C)*, 131.86 (d, 4JPC = 2.7Hz, Cpara), 133.67 (d,
2JPC = 9.7Hz, Cortho), 139.33 and 155.40(2C), 168.00 (C O), 169.28 (d,
2JPC = 18.8Hz, C O)*, 172.82 (d, 3JPC = 4.9Hz, C O)*.
Minor isomer, 4d-(Z) (49.7%), 1H NMR: δ 0.97, 0.98, and 1.34 (9H, 3t,
CH3), 3.68, 4.1, and 4.38 (6H, q, OCH2-), 3.43 and 4.26 (4H, 2q, OCH2-),
13C NMR: 14.28, 14.39 and 14.45 (3CH3), 38.61 (d, JPC = 133.6Hz,
1
P C),52.40 (OCH3), 57.92, 60.87, and 60.97 (3OCH2-), 126.84 (d, 1JPC
=
91.3Hz, Cipso), 128.43 (d, 3JPC = 12.3Hz, Cmeta ), 131.94 (d, 4JPC = 2.7Hz,
Cpara), 133.79 (d, 2JPC = 9.8Hz, Cortho), 139.61 and 155.06 (2C), 167.90
(C O).
∗For two rotamers

2306
E. Tavakolinejad et al.
Dimethyl-2-[(phenoxycarbonyl)anilino]-3-(1,1,1-triphenyl-λ5-
phosphonylidene)succinate 4e
(0.98g, m.p. 140–142◦C, yield 77%); IR (KBr) (νmax, cm−1): 1755, 1660,
and 1616 (C O).
Major isomer, 4e-(E) (53.5%), 1H NMR: δ 2.91 and 3.8 (6H,
2s, OCH3), 5.02(1H, d, JPH = 19.9 Hz, P C CH), 6.92–7.63 (50H,
1
m, arm)*. 13C NMR: δ 40.66(d, JPC = 135.4Hz, P C)*, 49.46 and
2
52.20(2OCH3), 61.69(1H, d, JPC = 17.4Hz, P C CH), 121.42 and
121.46 (2Cortho,OPh)*, 124.72, 127.50, 127.79, and 131.14 (4CH)*,
1
126.15 (d, JPC = 92.0Hz, Cipso), 127.39 and 127.56 (4CH)* 128.75 (d,
4
3JPC = 12.2Hz, Cmeta), 131.43 (1C)*, 132.18 (d, JPC = 2.6Hz, Cpara),
2
133.78 (d, JPC = 9.9Hz, Cortho), 139.51, 151.67, 153.65 and 155.81
(4C), 168.51(C O), 169.99 (d, 2JPC = 16.7Hz, C O)*, 173.17 (d, 3JPC
=
16.4Hz, C O)*.
Minor isomer, 4e-(Z) (46.5%), 1H NMR: δ 3.1 and 3.9 (6H,2s, OCH3),
5.04 (1H, d, JPH = 17.7), 13C NMR: 14.28 and 14.45 (2CH3), 48.84 and
2
1
52.50 (2OCH3), 62.63 (d, JPC = 16.9Hz, P C CH), 126.47 (d, JPC
=
87.7Hz, Cipso), 128.65(d, 3JPC = 11.8Hz, Cmeta), 129.80, 139.15, 151.68,
and 153.66(4C), 132.08 (d, 4JPC = 2.7Hz, Cpara), 133.58 (d, 2JPC = 9.8Hz,
Cortho), 139.22 and 155.49 (2C), 168.62 (C O).
Diethyl-2-[(phenoxycarbonyl)anilino]-3-(1,1,1-triphenyl-λ5-
phosphonylidene)succinate 4f
(0.96g, m.p. 160–161◦C, yield 72%); IR (KBr) (νmax, cm−1): 1748, 1650,
and 1617 (C O).
Major isomer, 4f-(E) (69.0%), 1H NMR: δ 0.32 and 1.36 (6H,2t, CH3),
3.34 and 4.10 (4H,2q, OCH2-), 5.02 (1H, d, JPH = 12.4 Hz, P C CH)*,
6.91–7.65 (50H, m, arm)*. 13C NMR: δ 13.9 and 14.3 (2CH3), 40.50
1
2
(d, JPC = 135.0Hz, P C)*, 57.48 and 60.33 (2OCH2-), 60.99(d, JPC
=
16.6Hz, P C CH)*, 121.41 and 121.47 (Cortho, OPh)*, 124.66, 126.44,
127.70, and 131.31 (4CH)*, 126.40 (d, 1JPC = 89.8Hz, Cipso), 128.65 (d,
3JPC = 12.7Hz, Cmeta), 131.43 (4CH)*, 132.00 (d, JPC = 2.7Hz, Cpara),
4
133.77 (d, JPC = 9.8Hz, Cortho), 139.24 and 151.75(2C), 167.95 (C O),
2
168.82 (d, 2JPC = 17.4Hz, C O)*, 172.68 (d, 3JPC = 6.6Hz, C O)*.
Minor isomer, 4f-(Z) (31.0%), 1H NMR: δ 1.25 and 2.04 (6H, 2t, CH3),
3.71 and 4.43 (4H, 2q, OCH2-),13C NMR: 14.28 and 14.45 (2CH3), 38.42
1
2
(d, JPC = 127.8Hz, P C), 57.48 and 60.12 (2OCH2-), 61.96 (d, JPC
=
16.6Hz, P C CH), 126.78 (d, JPC = 91.5Hz, Cipso), 128.75 (d, JPC
=
1
3
10.8Hz, Cmeta), 132.08 (d, JPC = 2.6Hz, Cpara), 133.79 (d, JPC = 9.9,
4
2
Cortho), 138.95 and 152.62 (2C), 168.05 (C O).
∗For two rotamers

Synthesis of New Phosphorous Ylides
2307
Dimethyl-2-{[(2-methylphenoxy)carbonyl]anilino}-3-(1,
1,1-triphenyl-λ5-phosphonylidene) Succinate 4g
(0.95g, m.p. 130–132◦C, yield 70%); IR (KBr) (νmax, cm−1):1754, 1662,
and 1618 (C O).
1
Major isomer, 4g-(E) (56.7%), H NMR: δ 2.06 (CH3), 3.13 and 3.79
(6H, 2s, OCH3), 4.99 (1H, d, JPH = 19.4 Hz, P C CH)*, 6.91–7.63 (48H,
1
m, arm)*. 13C NMR: δ 16.17 (CH3), 40.49 (d, JPC = 135.4Hz, P C)*,
2
49.41 and 52.14 (OCH3), 61.50(d, JPC = 16.1Hz, P C CH)*, 121.89,
125.01, 126.37, 127.21, 127.45, 127.74, and 131.30 (9CH)*, 126.18 (d,
3
1JPC = 92.0Hz, Cipso), 128.72 (d, JPC = 12.2Hz, Cmeta), 139.00, and
4
2
150.11 (3C)*, 132.07 (d, JPC = 2.5Hz, Cpara), 133.77 (d, JPC = 9.8Hz,
Cortho), 68.84 (C O), 170.02 (d, 2JPC = 17.1Hz, C O)*, 172.97 (d, 3JPC
=
13.7Hz, C O)*.
Minor isomer, 4g-(Z) (43.3%), 1H NMR: δ 2.03 (CH3), 2.89 and 3.88
(6H, 2s, OCH3), 13C NMR: 16.25 (CH3), 48.79 and 52.40 (OCH3), 126.66
1
3
(d, JPC = 91.8Hz, Cipso), 128.63 (d, JPC = 11.7Hz, Cmeta), 132.05 (d,
4JPC = 2.5Hz, Cpara), 133.59 (d, 2JPC = 9.7Hz, Cortho), 139.22 and 155.49
(2C), 168.58(C O).
Diethyl-2-{[(2-methylphenoxy)carbonyl] anilino}-3-(1,
1,1-triphenyl-λ5-phosphonylidene)succinate 4h
(0.93g, m.p. 163–165◦C, yield 66%); IR (KBr) (νmax, cm−1): 1745, 1653,
and 1622 (C O).
Major isomer, 4h-(E) (63.7%), 1H NMR: δ 0.30 and 1.25 (6H, 2t, CH3),
2.06 (3H, m, CH3)*, 3.34 and 4.11 (4H, 2q, OCH2-), 5.08 (1H, d, JPH
=
17.8Hz, P C CH)*, 6.90–7.66 (48H, m, arm)*. 13C NMR: δ 14.20, 14.32,
1
and 16.32 (3CH3), 40.42 (d, JPC = 132.7Hz, P C), 57.45 and 60.35
2
(2OCH2-), 61.48(d, JPC = 17.9Hz, P C CH), 121.89, 126.36, 126.60,
127.20, 129.86, 130.45, 130.57, and 131.51 (9CH)*, 124.96, 139.04 and
152.87 (3C)*, 126.41 (d, 1JPC = 92.0Hz, Cipso), 128.65 (d, 3JPC = 12.3Hz,
4
2
Cmeta), 131.43 (1C)*, 132.01 (d, JPC = 2.5Hz, Cpara), 133.77 (d, JPC
=
10.1Hz, Cortho), 167.94(C O), 169.87 (d, 2JPC = 17.7Hz, C O)*, 172.37
(d, 3JPC = 5.2Hz, C O)*.
Minor isomer, 4h-(Z) (36.3%), 1H NMR: δ 1.37 and 1.39 (6H, 2t, CH3),
3.72 and 4.38 (4H, 2q, OCH2-),13C NMR: 14,40, 14.49, and 16.23 (3CH3),
1
37.42 (d, JPC = 133.7Hz, P C), 57.99 and 60.94 (2OCH2-), 62.45 (d,
2JPC = 16.7Hz, P C CH), 126.86 (d, JPC = 91.8Hz, Cipso), 128.54 (d,
1
3JPC = 12.3Hz, Cmeta), 132.09 (d, 4JPC = 2.3Hz, Cpara), 133.69(d, 2JPC
=
10.0Hz, Cortho), 139.22 and 155.49 (2C), 168.04(C O).
∗For two rotamers

2308
E. Tavakolinejad et al.
Dimethyl-2-{[(3-methylphenoxy)carbonyl]anilin}-3-(1,
1,1-triphenyl-λ5-phosphonylidene)succinate 4i
(1.07g, m.p. 125–127◦C, yield 79%); IR (KBr) (νmax, cm−1):1749, 1651,
and 1619 (C O).
Major isomer, 4i-(E) (53.7%), 1H NMR: δ 2.27 (3H,s, CH3)*, 3.13 and
3.80 (6H, 2s, OCH3), 5.00 (1H, d, JPH = 19.9 Hz, P C CH), 6.73–7.62
1
(48H, m, arm)*. 13C NMR: δ 21.21 (CH3), 40.67 (d, JPC = 133.2Hz,
2
P C), 48.83 and 52.19(2OCH3), 61.59(d, JPC = 17.1Hz, P C CH),
118.36, 125.52, 126.41, 127.11, 127.47, 127.78, 131.13 and 151.33
(9CH)*, 122.07,138.91 and 153.75 (3C)*, 126.41(d, 1JPC = 92.0Hz, Cipso),
128.73 (d, 3JPC = 12.2Hz, Cmeta), 131.43 (1C)*, 132.16 (d, 4JPC = 2.5Hz,
Cpara), 133.78 (d, 2JPC = 9.8Hz, Cortho), 168.50(C O), 170.00 (d, 2JPC
19.2Hz, C O)*, 173.14 (d, 3JPC = 4.2Hz, C O)*.
=
Minor isomer, 4i-(Z) (46.3%), 1H NMR: δ 2.90 and 3.90 (6H, 2s,
OCH3), 5.03 (1H, d, JPH = 18.1 Hz, P C CH), 13C NMR: 37.39 (d,
2
1JPC = 136.0Hz, P C), 49.47 and 52.50 (2OCH3), 62.56 (d, JPC
=
=
1
3
16.5Hz, P C CH), 126.57(d, JPC = 91.5Hz, Cipso), 128.64 (d, JPC
11.9Hz, Cmeta), 132.05 (d, 4JPC = 2.7Hz, Cpara), 133.58 (d, 2JPC = 9.6Hz,
Cortho), 139.22 and 155.49 (2C), 168.60 (C O).
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∗For two rotamers