Synthesis of new stable phosphorus ylides and 1,4-diionic organophosphorus compound from a reaction between hexamethyl phosphorous triamide and dimethyl acetylenedicarboxylate in the presence of CH-acids

Article abstract of DOI:10.1002/hc.21067

A simple and efficient one-pot three-component reaction between hexamethyl phosphorous triamide and dimethyl acetylenedicarboxylate (DMAD) in the presence of CH-acids, such as acetylacetone, 1,3-indandione, dibenzoylmethane, anthrone, and N,N-dimethylbarbituric acid, has been studied. In all cases, new and stable phosphorus ylides are obtained in excellent yields. These stable ylides exist in solution as a mixture of two geometrical isomers as a result of restricted rotation around the carbon-carbon partial double bond, resulting from conjugation of the ylide moiety with the adjacent carbonyl group. From the reaction of N,N-dimethylbarbituric acid with DMAD in the presence of hexamethyl phosphorous triamide, a 1,4-diionic organophosphorus compound is obtained.

Full text of DOI:10.1002/hc.21067

Heteroatom Chemistry
Volume 24, Number 1, 2013
Synthesis of New Stable Phosphorus Ylides
and 1,4-Diionic Organophosphorus Compound
from a Reaction between Hexamethyl
Phosphorous Triamide and Dimethyl
Acetylenedicarboxylate in the Presence of
CH-Acids
Morteza Ziyaadini,1 Malek Taher Maghsoodlou,2 Nourollah Hazeri,2
and Sayyed Mostafa Habibi-Khorassani2
1Faculty of Marine Science, Chabahar Maritime University, Chabahar, Iran
2Department of Chemistry, The University of Sistan & Baluchestan, P. O. Box 98135-674,
Zahedan, Iran
Received 3 May 2012; revised 10 October 2012
89, 2013; View this article online at wileyonlineli-
ABSTRACT: A simple and efficient one-pot three-
brary.com. DOI 10.1002/hc.21067
component reaction between hexamethyl phospho-
rous triamide and dimethyl acetylenedicarboxylate
(DMAD) in the presence of CH-acids, such as
acetylacetone, 1,3-indandione, dibenzoylmethane, an-
throne, and N,N-dimethylbarbituric acid, has been
studied. In all cases, new and stable phosphorus
ylides are obtained in excellent yields. These stable
ylides exist in solution as a mixture of two geo-
metrical isomers as a result of restricted rotation
around the carbon–carbon partial double bond, re-
sulting from conjugation of the ylide moiety with the
adjacent carbonyl group. From the reaction of N,N-
INTRODUCTION
Organophosphorus compounds are synthetic targets
of interest, because of their applications in vari-
ety of industrial, biological, pharmacological activ-
ities and also in chemical synthetic uses [1]. The
impact of organophosphorus compounds chemistry
on modern synthetic chemistry is difficult to quan-
tify, but one can safely assume that the study of
this element has influenced many areas of chem-
dimethylbarbituric acid with DMAD in the presence
of hexamethyl phosphorous triamide, a 1,4-diionic
ical endeavor [1–4]. Among the phosphorus com-
ꢀC
organophosphorus compound is obtained.
2012
pounds, the chemistry of phosphorus ylides is very
significant in the chemistry of the twentieth century
[5–9]. Phosphorus ylides are reactive intermediates,
which have been used in many reactions and are in-
volved a lot in the synthesis of organic compounds
[10–21]. In continuation of our investigation on
the organophosphorous synthesis by trivalent phos-
phorus nucleophiles [22–41] and following the first
Wiley Periodicals, Inc. Heteroatom Chem. 24:84–
Correspondence to: M. T. Maghsoodlou; e-mail: mt_maghsood
lou@yahoo.com.
Contract grant sponsor: Research Council of the University of
Sistan & Baluchestan.
ꢀC
2012 Wiley Periodicals, Inc.
84

Synthesis of New Stable Phosphorus Ylides and 1,4-Diionic Organophosphorus Compound 85
CO2Me
CO2Me
Z
H
MeO2C
C
C
Et2O
r.t
P[NMe2]3
+
+
Z-H
P[NMe2]3
CO2Me
1
4
3
2
d
a
b
c
3, 4
O
O
O
O
O
Z
Ph
Ph
O
O
Yield (%)
FIGURE 1 Synthesis of stable phosphorus ylides 4a–d.
87
93
85
90
report for the synthesis of C-amino phosphorous
ylides by hexamethyl phosphorous triamide [42], we
have recently described the synthesis of new phos-
phorous ylides from a reaction between hexamethyl
phosphorous triamide and dimethyl acetylenedicar-
boxylate (DMAD) in the presence of N H acids [43].
Herein, we wish to report a convenient and facial
one-pot, three-component reaction between hexam-
ethyl phosphorous triamide and DMAD in the pres-
ence of C H acids 3a–d and 5 for the preparation
of new and stable phosphorous ylides 4a–d and 1,4-
diionic organophosphorus 7, respectively, in excel-
lent yields at ambient temperature (Fig. 1).
[(Me)2N]3P
H
OMe
O
[(Me)2N]3P
H
O
OMe
CO2Me
Z
CO2Me
Z
4-(Z): Minor
4-(E): Major
FIGURE 2 Two rotational interchangeable processes of the
two isomers (Z and E).
for minor isomers. The vicinal methine protons ap-
peared at δ = 4.11 and 7.15 ppm as double doublet
(3JPH = 17.8 Hz and 3JHH = 10.6) and doublet (3JHH
= 10.5 Hz), respectively, for the major isomer and at
δ = 4.18 and 6.78 ppm as double doublet (3JPH = 17.5
Hz and 3JHH = 10.4 Hz) and doublet (3JHH = 10.4 Hz),
respectively, for the minor isomer. The aromatic pro-
tons appear as a multiplet at δ = 7.30–8.25 ppm. The
1H decoupled 13C NMR spectrum of 4a showed 15
distinct resonances in agreement with the phospho-
rane structure (see the Experimental section). Partial
assignments of these resonances for the major iso-
mer are δ = 37.89 (NMe2), 44.84 (P C CH), 44.90
(C P), 52.21 and 52.78 (s, 2OMe), 65.73 [CH(CO)2],
117.75, 118.29, 129.61, 129.94, and 139.74 (10Carom),
169.21 (C O ester), 172.85 (P C C), 189.95 (2C O).
RESULTS AND DISCUSSION
The reaction of hexamethyl phosphorous triamide
1 with DMAD 2 in the presence of acetylacetone,
1,3-indandione, dibenzoylmethane, and anthrone
was conducted in diethyl ether at ambient tem-
perature and was completed immediately. In this
three-component reaction, hexamethyl phospho-
rous triamide has been employed as a trivalent
phosphorus nucleophile for a convenient and rapid
synthesis of new phosphorous ylides 4a–d. No prod-
uct other than 4 could be detected by NMR spec-
troscopy. The structures of compounds 4a–d were
deduced from the elemental analyses and the IR, 1H,
13C, 31P NMR, and mass spectra. The mass spectra of
these stable ylides displayed molecular ion peaks at
appropriate m/z value. Any initial fragmentation in-
volves loss from, or complete loss of the side chains.
The 1H NMR spectra of compound 4a gave two sharp
doublet at δ = 2.57 ppm (3JPH = 9.2 Hz) and 2.58 ppm
(3JPH = 9.2 Hz) for the N(Me)2 groups of major and
minor isomer, respectively. The methoxy group ex-
hibited two sharp singlet (δ = 3.51 and 3.60 ppm)
for major and fairly broad singlet (δ = 3.61 and 3.68)
The H, 13C, and 31P NMR spectrum of ylides 4a–e
1
are consistent with the presence of two isomers. Con-
sidering attractive P+/O− electrostatic interactions,
the (E) isomer is expected to be more stable than the
(Z) isomer [44]. This effect confirms that the (E) and
(Z) isomers appear as the major and minor forms,
respectively. The ylide moiety of these compounds
is strongly conjugated with the adjacent carbonyl
group and rotation around the partial double bond
in 4-(E) and 4-(Z) geometrical isomers (Fig. 2) is
slow on the NMR timescale at ambient temperature.
Heteroatom Chemistry DOI 10.1002/hc

86 Ziyaadini et al.
MeO2C
MeO2C
3
+
1
2
4
C C CO Me
C C CO2Me
+
Z
2
H
[(Me)2N]3P
[(Me)2N]3P
FIGURE 3 Proposed reaction mechanism for synthesis of stable phosphorus ylide 4.
O
CO2Me
CO2Me
H
P[NMe2]3
H
H3C
O
CH3
O
C
+
Et2O
r.t
N
N
P[NMe2]3
[Me2N]3P
H
+
MeO2C
H
C
CO2Me
CO2Me
CO2Me
5
O
O
O
O
O
O
N
N
N
N
N
H3C
N
CH3
H3C
CH3
Me
Me
Me
Me
N
N
Proton shift
O
O
O
H
O
O
O
CO2Me
CO2Me
(2S, 3S)-7 or (2R, 3R)-7
(2R, 3S)-7 or (2S, 3R)-7
MeO2C
MeO2C
P[NMe2]3
P[NMe2]3
Major
minor
6
7
FIGURE 5 Two diasteroisomers of 1,4-diionic compound 7
with anti H–C–C–H arrangements.
FIGURE 4 Synthesis of stable 1,4-diionic compound 7.
5 Hz and Janti between 10 and 14 Hz. Observation of
3JHH = 11.2 Hz for the vicinal protons in compound
7 indicates an antiarrangement for these centers.
Since compound 7 possesses two chirality centers,
two diasteroisomers with anti H C C H arrange-
ments are possible (Fig. 5).
The three-bond carbon-phosphorus coupling,
3JPC, depends on configuration, as expected, tran-
soid couplings being larger than cisoid ones. The
Karplus relation can be derived from the data
for organophosphorus compounds with tetra- and
penta-coordinate phosphorus [47]. The observation
for 3JPC of 32.1 Hz for the P C C C moiety (see the
Experimental section) is in agreement with the anti
arrangement. The 3JPC for the P C C C(O) moiety
is 16.4 and 8.4 Hz, which corresponds to (2S,3S)-7
and its mirror image (2R,3R)-7, as well as (2R,3S)-7
and its mirror image (2S,3R)-7 geometries for major
and minor isomers, respectively.
1
Selected H, 13C, and 31P NMR chemical shifts
and coupling constants in the major and minor ge-
ometrical isomers of compound 4 are presented
in the Experimental section. On the basis of well-
established chemistry of trivalent phosphorus nucle-
ophiles, it is reasonable to assume that compounds
4a–d result from the initial addition of hexamethyl
phosphorous triamide 1 to the DMAD 2 and sub-
sequent protonation of the 1:1 adduct by the CH-
acid 3. Then the positively charged ion is attacked by
the anion of CH-acid to generate phosphorus ylide 4
(Fig. 3).
The reaction of dimethyl acetylendicarboxylate
with N,N-dimethylbarbituric acid in the presence
of hexamethyl phosphorous triamide leads to sta-
ble 1,4-diionic compound 7. This compound results
from the proton transfer reaction in the initial ylide
6 (Fig. 4).
The transformation of the ylidic form 6 to 1,4-
diionic 7, first of all, is related to Pka 1,3-dicarbonyl
compound and delocalization of negative charge be-
tween two carbonyl functional group in CH-acid and
then to the hydrogen bonding formed between the
ylide region and carbonyl functional group of 1,3-
dicarbonyl compound in products. Thus, here the
proton shift occurs. The presence of the 31P nucleus
in compound 7 helps in the assignment of the sig-
nals by long-range couplings with 1H and 13C nuclei
(see the Experimental section). The vicinal proton–
proton coupling constant (3JHH) as a function of the
torsion angle can be obtained from the Karplus equa-
tion [45,46]. Typically, Jgauche varies between 1.5 and
In conclusion, we have prepared novel phos-
phorous ylides via the one-pot reaction between
hexamethyl phosphorous triamide and dimethyl
acetylenedicarboxilate in the presence of CH-acids.
The present method carries the advantage that not
only in the reaction performed under neutral condi-
tion but also that the substances can be mixed with-
out any activation or modification.
EXPERIMENTAL
Melting point and IR spectra of all com-
pounds were measured on an Electrothermal 9100
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of New Stable Phosphorus Ylides and 1,4-Diionic Organophosphorus Compound 87
2
apparatus (UK) and a JASCO FT-IR spectrometer
(d, JCP = 17.1 Hz, P C CH), 52.46 and 53.20 (s,
2OMe), 65.73 [CH(CO)2], 117.48, 117.75, 129.25,
133.32, and 140.06 (10Carom), 167.62 (s, C O es-
ter), 173.10 (d, 2JCP = 20.0 Hz, P C C), 189.61 and
189.95 (2C O). 31P NMR (CDCl3, 162.0 MHz): δP
63.54 [(Me2N)3P+ C].
(Japan), respectively. Moreover, 1H, 13C, and 31P
NMR spectra were obtained with a Bruker DRX-
400 Avance instruments (Germany) using CDCl3 as
a solvent and TMS as an internal standard at 400.2,
100.6, and 162.0 MHz, respectively. Elemental anal-
yses for C, H, and N were performed using a Heraeus
CHN-O-Rapid analyzer (Germany). In addition, the
mass spectra were recorded on a Shimadzu GCMS-
QP5050A mass spectrometer (Japan) operating at an
ionization potential of 70 eV. Hexamethyl phospho-
rous triamide, DMAD, and CH-acid derivatives were
purchased from Fluka (Buchs, Switzerland), Merck
(Darmstadt, Germany), and Acros (Geel, Belgium)
and used without further purification.
Dimethyl 2-(1-acetyl-2-oxopropyl)-(tris(dimethyl-
amino)phosphorany1idene)-succinate (4b)
White powder, yield 90% (0.36 g); mp 149–151◦C,
IR (KBr) (υmax, cm−1): 1719 and 1609 (C O). MS
(m/z, %): 405 (M+, 10), 362 (M+ – CH3CO, 12), 306
(M+ – C5H7O2, 100), 163 [P(NMe2)3, 17], 119
[P(NMe2)2, 70], 76 (PNMe2, 41), 43 (CH3CO, 86).
Anal. Calcd for C17H32NO6P: C, 50.36; H, 7.96; N,
10.36. found: C, 50.47; H, 7.90; N, 10.28.
General Procedure (Exemplified by 4a)
1
Major isomer (E)-4b: (60%), H NMR (CDCl3,
To
zoylmethane 3a (0.22 g, 1 mmol) and dimethyl
acetylenedicarboxilate (0.14 g, mmol) in
a magnetically stirred solution of diben-
400.2 MHz): δH 2.27 and 2.32 (6H, 2s, 2CH3), 2.65
3
(18H, d, JPH = 9.2 Hz, 3NMe2), 3.57 and 3.63 (6H,
s, 2OMe), 3.62 (1H, br, P C CH), 5.54 [1H, d, 3JHH
= 10.0 Hz, CH(CO)2]. 13C NMR (CDCl3, 100.6 MHz):
2
1
Et2O (5 mL), hexamethyl phosphorous triamide
1 (0.16g, 1 mmol) was added dropwise over 10
min at ambient temperature. After 2 h of stirring
at ambient temperature, the product was filtered
and washed with 10 mL of cold Et2O to yield
4a dimethyl 2-(1,3-diphenylpropane-l,3-dione-2-
y1) - 3 -(tris (dimethylamino)phosphorany1idene) -
butanedioat (4a)
2
δC 30.76 and 33.78 (2CH3), 37.55 (d, JCP = 5.0 Hz,
2
3NMe2), 43.80 (d, JCP = 15.1 Hz, P C CH), 46.28
(d, 1JCP = 196.1 Hz, C P), 49.77 and 51.59 (2OMe),
65.54 [CH(CO)2], 170.29 (d, 2JCP = 17.1 Hz, P C C),
3
175.45 (d, JCP = 4.0 Hz, C O ester), 202.23 and
204.37 (2C O). 31P NMR (CDCl3, 162.0 MHz): δP
62.15 [(Me2N)3P+ C].
1
Yellow powder, yield 87% (0.46 g); mp 132–
138◦C, IR (KBr) (υmax, cm−1): 1727, 1691, and 1661
(C O). MS (m/z, %): 529 (M+, 8), 470 (M+ – CO2Me,
40), 306 (M+ – C15H11O2, 100), 163 [P(NMe2)3, 24],
119 [P(NMe2)2, 74], 76 (PNMe2, 28). Anal. Calcd for
C27H36N3O6P: C, 61.24; H, 6.85; N, 7.93. found: C,
61.32; H, 6.81; N, 8.00.
Minor isomer (Z)-4b: (40%), H NMR (CDCl3,
400.2 MHz): δH 2.24 and 2.27 (6H, 2s, 2CH3), 2.67
3
(18H, d, JPH = 9.2 Hz, 3NMe2), 3.57 and 3.61 (6H,
s, 2OMe), 3.62 (1H, br, P C CH), 5.12 [1H, d, 3JHH
= 10.3 Hz, CH(CO)2]. 13C NMR (CDCl3, 100.6 MHz):
2
δC 30.33 and 33.78 (2CH3), 37.46 (d, JCP = 5.0 Hz,
2
3NMe2), 42.68 (d, JCP = 15.1 Hz, P C CH), 47.19
Major isomer (E)-4a: (70%), 1H NMR (CDCl3,
400.2 MHz): δH 2.57 (18H, br, 3NMe2), 3.51 and
(d, 1JCP = 199.2 Hz, C P), 49.22 and 51.59 (2OMe),
66.96 [CH(CO)2], 169.90 (d, 2JCP = 24.1 Hz, P C C),
3
3
3.60 (6H, s, 2OMe), 4.11 (1H, dd, JHP = 17.8 Hz,
175.78 (d, JCP = 8.0 Hz, C O ester), 202.00 and
3
3JHH = 10.6 Hz, P C CH), 7.15 [1H, d, JHH
=
204.19 (2C O). 31P NMR (CDCl3, 162.0 MHz): δP
10.5 Hz, CH(CO)2], 7.30–8.25 (10H, m, CHarom). 13
C
63.34 [(Me2N)3P+ C].
NMR (CDCl3, 100.6 MHz): δC 37.89 (d, 2JCP = 4.0 Hz,
2
3NMe2), 44.84 (d, JCP = 17.1 Hz, P C CH), 44.90
2-(Indane-1,3-dione-2-yl-2-yild)-(tris(dimethyla-
mino)phosphorany1idene)-butanedioat (4c)
1
(d, JCP 196.2 Hz, C P), 52.21 and 52.78 (s, 2OMe),
65.73 [CH(CO)2], 117.75, 118.29, 129.61, 129.94, and
139.74 (10Carom), 169.21 (s, C O ester), 172.85 (d,
2JCP = 20.1 Hz, P C C), 189.95 (2C O). 31P NMR
(CDCl3, 162.0 MHz): δP 61.71 [(Me2N)3P+ C].
Brown powder, yield 93% (0.41 g); mp 130–132◦C,
IR (KBr) (υmax, cm−1): 1740, 1726, 1616 (C O). MS
(m/z, %): 451 (M+, 2), 436 (M+ – CH3, 14), 419 (M+ –
CH3O, 53), 374 (M+ – C6H5, 16) 163 [P(NMe2)3, 4],,
119 [P(NMe2)2, 52], 44 (NMe2, 100). Anal. Calcd for
C21H30N3O6P: C, 55.87; H, 6.70; N, 9.31. found: C,
56.01; H, 6.77; N, 9.40.
1
Minor isomer (Z)-4a: (30%), H NMR (CDCl3,
400.2 MHz): δH 2.57 (18H, br, 3NMe2), 3.61 and
3
3.68 (6H, s, 2OMe), 4.18 (1H, dd, JHP = 17.5 Hz,
3
3JHH = 10.4 Hz, P C CH), 6.78 [1H, d, JHH
=
10.4 Hz, CH(CO)2], 7.30–8.25 (10H, m, CHarom). 13
C
Major isomer (E)-4c: (74%), 1H NMR (CDCl3,
400.2 MHz): δH 2.74 (18H, d, 3JPH = 10.0 Hz, 3NMe2),
2
NMR (CDCl3, 100.6 MHz): δC 37.60 (d, JCP = 4.0
1
3
Hz, 3NMe2), 43.96 (d, JCP = 160.0 Hz, C P), 44.84
3.59 and 3.78 (6H, s, 2OMe), 4.46 (1H, dd, JHH
Heteroatom Chemistry DOI 10.1002/hc

88 Ziyaadini et al.
3
P C CH), 126.50, 126.60, 126.69, 127.15, 129.09,
130.57, 131.92, 132.71, 133.34, 145.01, and 146.41
(12Carom), 170.53 (d, 2JCP = 22.1 Hz, P C C), 173.82
(d, 3JCP = 3.0 Hz, C O ester), 186.75 (C O). 31P NMR
(CDCl3, 162.0 MHz): δP 64.23 [(Me2N)3P+ C].
= 10.6 Hz, JHP = 10.6 Hz, P C CH), 7.24 [1H,
br, CH(CO)2], 7.25–7.29 (4H, m, CHarom). 13C NMR
2
(CDCl3, 100.6 MHz): δC 37.56 (d, JCP = 5.0 Hz,
2
3NMe2), 45.97 (d, JCP = 15.1 Hz, P C CH), 47.40
(d, 1JCP = 192.1 Hz, C P), 49.87 and 51.58 (2OMe),
3
55.45 [d, JCP = 4.0 Hz, CH(CO)2], 128.36, 128.77,
129.31, 132.58, 133.18, and 137.94 (6Carom), 170.69
Dimethyl-2-(1,3-dimethylbarbituric acid-5-yl-5-
yid)-3-(tris(dimethylamino)phosphoniobuta-1,
4-dioat (7)
2
3
(d, JCP = 17.1 Hz, P C C), 175.87 (d, JCP = 5.0
Hz, C O ester), 195.28 and 196.08 (2C O). 31P NMR
(CDCl3, 162.0 MHz): δP 56.56 [(Me2N)3P+ C].
Minor isomer (Z)-4c: (26%), 1H NMR (CDCl3,
400.2 MHz): δH 2.79 (18H, d, 3JPH = 10.0 Hz, 3NMe2),
3.64 and 3.66 (6H, s, 2OMe), 5.30 (1H, br, P C CH),
Yellow powder, yield 80% (0.36 g); mp 124–126◦C,
IR (KBr) (νmax, cm−1): 1727 and 1676 (C O), 1591
(2NC O), 1433 (N2C O). MS (m/z, %): 461 (M+, 7),
393 (M+ – CO2Me, 2), 306 (M+ – C8H4NO2, 9), 163
[P(NMe2)3, 55], 147 (C8H5NO2, 37), 119 [P(NMe2)2,
79], 76 (PNMe2, 53). Anal. Calcd for C18H32N5O7P:
C, 46.85; H, 6.99; N, 15.18. found: C, 46.71; H, 7.03;
N, 15.28.
7.23 [1H, br, CH(CO)2], 7.25–7.29 (4H, m, CHarom).
13C NMR (CDCl3, 100.6 MHz): δC 37.50 (d, JCP
=
2
6.0 Hz, 3NMe2), 44.90 (d, 2JCP = 15.1 Hz, P C CH),
1
47.90 (d, JCP = 188.1 Hz, C P), 49.24 and 49.27
3
(2OMe), 56.47 [d, JCP = 5.0 Hz, CH(CO)2], 128.50,
Major isomer: (60%), 1H NMR (CDCl3, 500.1
MHz): δH 2.73 (18H, d, 3JPH = 9.8 Hz, 3NMe2), 3.26
(6H, s, 2NMe), 3.58 and 3.79 (6H, s, 2OMe), 4.85 (1H,
dd, 3JHH = 10.7 Hz, 3JPH = 5.7 Hz, P CH CH), 4.97
128.63, 129.09, 132.69, 133.34, and 137.32 (6Carom),
2
3
169.70 (d, JCP = 21.2 Hz, P C C), 176.12 (d, JCP
= 6.0 Hz, C O ester), 195.05 and 195.36 (2C O). 31
P
NMR (CDCl3, 162.0 MHz): δP 55.95 [(Me2N)3P+ C].
(1H, dd, 3JHH = 11.2 Hz, 2JPH = 14.4 Hz, P CH). 13
C
NMR (CDCl3, 125.7 MHz): δC 27.31 (2NMe), 37.73
(d, 2JCP = 3.7 Hz, 3NMe2), 42.41 (P CH CH), 44.10
(d, 1JCP = 104.0 Hz, CH P), 52.28 and 52.78 (2OMe),
77.06 [d, 3JPC = 32.1 Hz, C(CO)2], 153.58 (C O urea),
Anthracen-10(9H)-one-2-yl-(tris(dimethyla-
mino)phosphorany1idene)-butanedioat (4d)
Brown powder, yield 85% (0.42 g); mp 113–115◦C,
IR (KBr) (υmax, cm−1): 1736, 1665, 1650 (C O). MS
(m/z, %): 500 (M+ + 1, 3), 306 (M+ – C14H9O, 100),
193 (C14H9O, 36), 119 [P(NMe2)2, 45], 76 (PNMe2,
16), 44 (NMe2, 27). Anal. Calcd for C26H34N3O6P: C,
62.51; H, 6.86; N, 8.41. found: C, 62.64; H, 6.80; N,
8.33.
2
163.39 (O C C C O), 168.76 (d, JCP = 1.4 Hz,
C O ester), 173.66 (d, 3JCP = 16.4 Hz, C O ester). 31
P
NMR (CDCl3, 202.4 MHz): δP 56.10 [(Me2N)3P+ C].
Minor isomer: (40%), 1H NMR (CDCl3, 500.1
MHz): δH 2.79 (18H, d, 3JPH = 9.6 Hz, 3NMe2), 3.26
(6H, s, 2NMe), 3.60 and 3.63 (6H, s, 2OMe), 4.84
(1H, dd, 3JHH = 9.3 Hz, 3JPH = 6.3 Hz, P CH CH),
1
Major isomer (E)-4d: (59%), H NMR (CDCl3,
3
2
400.2 MHz): δH 2.26 (18H, d, 3JPH = 9.2 Hz, 3NMe2),
5.16 (1H, dd, JHH = 9.3 Hz, JPH = 11.7 Hz,
P CH). 13C NMR (CDCl3, 125.7 MHz): δC 27.31
3.49 and 3.62 (6H, s, 2OMe), 3.63 (1H, br, CH), 5.74
2
3
(2NMe), 37.70 (d, JCP = 3.7 Hz, 3NMe2), 42.41
(1H, d, JHP = 10.0 Hz, P C CH), 7.31–8.12 (8H,
(P CH CH), 44.71 (d, 1JCP = 98.3 Hz, CH P), 52.50
and 52.95 (2OMe), 77.44 [s, C(CO)2], 153.68 (C O
urea), 162.99 (O C C C O), 167.51 (s, C O es-
m, CHarom). 13C NMR (CDCl3, 100.6 MHz): δC 37.45
2
3
(d, JCP = 5.0 Hz, 3NMe2), 42.93 (d, JCP = 6.0 Hz,
1
P C CH CH), 47.16 (d, JCP = 189.1 Hz, C P),
3
ter), 173.59 (d, JCP = 8.4 Hz, C O ester). 31P NMR
2
49.70 and 50.81 (2OMe), 57.75 (d, JCP = 14.1 Hz,
(CDCl3, 202.4 MHz): δP 56.49 [(Me2N)3P+ C].
P C CH), 126.49, 126.60, 126.69, 127.18, 129.16,
130.98, 131.52, 131.93, 132.86, 132.91, 145.35, and
146.54 (12Carom), 169.66 (d, 2JCP = 17.1 Hz, P C C),
REFERENCES
3
173.59 (d, JCP = 3.0 Hz, C O ester), 186.96
(C O). 31P NMR (CDCl3, 162.0 MHz): δP 63.16
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1
Minor isomer (Z)-4d: (41%), H NMR (CDCl3,
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3.47 and 3.74 (6H, s, 2OMe), 3.63 (1H, br, CH), 5.33
3
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