Three-component reaction between trivalent phosphorus nucleophiles, dialkyl acetylenedicarboxylates and (2,4-dinitrophenyl) acetic acid

Article abstract of DOI:10.3184/174751912X13403013285904

A three-component reaction between dialkyl acetylenedicarboxylates (DAADs) and phosphites in the presence of (2,4-dinitrophenyl)acetic acid leads to dialkyl 2-(dialkoxyphosphoryl)-3-[3-acetyl-2-(2,4-dinitrophenyl)-4-oxosuccinates in excellent yields. A similar reaction with triphenylphosphine, instead of phosphites, produces the stabilised phosphoranes in good yields.

Full text of DOI:10.3184/174751912X13403013285904

JOURNAL OF CHEMICAL RESEARCH 2012
RESEARCH PAPER 497
AUGUST, 497–499
Three-component reaction between trivalent phosphorus nucleophiles,
dialkyl acetylenedicarboxylates and (2,4-dinitrophenyl) acetic acid
Alireza Hassanabadia*, Mohammad H. Mossleminb, Elaheh Abyarb and
Mohammad Taleb-Malamirib
aDepartment of Chemistry, Islamic Azad University, Zahedan Branch, PO Box 98135-978, Zahedan, Iran
bDepartment of Chemistry, Islamic Azad University, Yazd Branch, PO Box 89195-155, Yazd, Iran
A three-component reaction between dialkyl acetylenedicarboxylates (DAADs) and phosphites in the presence of
(2,4-dinitrophenyl)acetic acid leads to dialkyl 2-(dialkoxyphosphoryl)-3-[3-acetyl-2-(2,4-dinitrophenyl)-4-oxosucci-
nates in excellent yields. A similar reaction with triphenylphosphine, instead of phosphites, produces the stabilised
phosphoranes in good yields.
Keywords: (2,4-dinitrophenyl)acetic acid, dialkyl acetylenedicarboxylate, phosphites, stereoselective synthesis, phosphorus
ylides, triphenylphosphine.
Phosphorus ylides take part in many valuable reactions in
organic synthesis.1–6 Phosphorus ylides are usually prepared
by treatment of a phosphonium salt with a base and the salts
are usually prepared from the phosphine and an alkyl halide.2
Phosphonium salts can also prepared by Michael addition
of phosphine to activated olefins.2 Michael addition of
phosphorus(III) compounds such as triphenylphosphine to
acetylenic esters leads to reactive 1,3-dipolar intermediate
betaines which are not detected even at low temperature.6
These unstable species can be trapped by a protic reagent, such
as methanol, amide and imide, to produce various compounds
e.g. ylides.
The reaction of trimethyl phosphite with dimethylacetyl-
enedicarboxylate (DMAD) in the presence of alcohols are
reported to produce phosphite ylide derivatives which are
stable at low temperatures, but convert to phosphonate deriva-
tives by warming or by treatment with water.7 The reaction of
trimethyl phosphite with DMAD in the presence of 2-naphthol
has been reported to afford stable 2,2-dimethoxy-3,4-dihydro-
1-oxa-2-phosphaphenanthrene-3,4-dicarboxylates in good
yield.8 In continuation of our previous work on three-compo-
nent reactions between trivalent phosphorus nucleophiles,
acetylenic esters and organic acidic compounds,9–15 we report
here the results of our study on the reaction between acetyle-
nic esters and phosphites or triphenylphosphine in the
presence of (2,4-dinitrophenyl)acetic acid.
Results and discussion
Reaction of dialkyl acetylenedicarboxylates with phosphites in
the presence of (2,4-dinitrophenyl)acetic acid leads to dialkyl
2-[4-(dialkoxyphosphoryl)-2-(2,4-dinitrophenyl)-3,4-di(meth
oxycarbonyl)butanoic acid in excellent yields (Scheme 1).
The 1H NMR spectrum of compound 4a displayed two dou-
blets (JHP = 12 Hz) at 3.35 and 3.55 ppm for two POCH3 groups
and two singlets at 3.67 and 3.95 ppm for two methoxycar-
bonyl groups. Three signals resonate at 4.33 (dd, 3JHH = 12 Hz,
2JHP = 21 Hz, CH), 4.70 ppm (dd, JHH = 12 Hz, JHP = 5 Hz,
CH) and 5.32 ppm (m, CH) for three vicinal methine protons.
The aromatic protons resonated at δ 7.27–7.97 ppm. One signal
observed at 8.16 ppm disappeared after addition of a few drops
of D2O to CDCl3 solution of compound 4a. This signal is
related to the OH proton. The 13C NMR spectrum of compound
4a showed 16 distinct resonances in agreement with the
proposed structure. The structural assignments made on the
basis of the NMR spectra of compound 4a were supported by
its IR spectrum, Strong absorption bands were observed at
3095–3505 cm−1 for the OH and at 1735 cm−1 for the carbonyl
group. The 31P NMR spectrum of compound 4a displays a
signal at 21.65 ppm.
It is reasonable to assume that compound 4 results from the
initial addition of phosphites 3 to dialkyl acetylenedicarboxyl-
ates 2 and subsequent protonation of the 1:1 adduct by (2,4-
dinitrophenyl)acetic acid 1 (Scheme 2). Then, the positively
charged ion 5 is attacked by the anion 6 to form ylide 7 that is
then tautomerised and hydrolysed to phosphonate 4.
3
3
The reaction of acetylenic ester 2 with triphenylphosphine
8 in the presence of (2,4-dinitrophenyl)acetic acid 1 leads to
phosphorus ylides 9 in excellent yields (Scheme 3).
The IR spectrum of 9a showed absorption bands at 1725 cm–1
for the carbonyl group and OH group at 3510 cm–1. The nitro
stretching vibrations observed absorption bonds at 1342 and
1
1530 cm−1. The H NMR spectrum of 9a exhibited two sharp
signals at δ 3.45 and 3.58 ppm arising from two OCH3 groups.
The doublet at δ 2.62 (3JHH = 10.8 Hz and 3JPH = 16.4 Hz) and
the doublet at δ 3.61 (3JHH = 10.8 Hz) were attributed to
CHCHC=P and CHCH=P protons respectively. The aromatic
protons show multiplets at δ 7.32–8.39 ppm. One signal is
Scheme 1 Three-component reaction between dialkyl
acetylenedicarboxylates and phosphites in the presence
of (2,4-dinitrophenyl)acetic acid.
Scheme 2 Suggested mechanism for formation of
compound 4.
* Correspondent. E-mail: ar_hasanabadi@yahoo.com

498 JOURNAL OF CHEMICAL RESEARCH 2012
Experimental
Melting points were determined with an Electrothermal 9100 appara-
tus. Elemental analyses were performed at the analytical laboratory
of Science and Researches Unit of Islamic Azad University. Mass
spectra were recorded on a Finnigan-MAT 8430 mass spectrometer
operating at an ionisation potential of 70 eV. IR spectra were recorded
1
on a Shimadzu IR-470 spectrometer. H, 13C and 31P NMR spectra
were recorded on Bruker DRX-500 Avance spectrometer in d6-DMSO
or CDCl3 using TMS as internal standard or 85% H3PO4 as external
standard. The chemicals used in this work were purchased from Fluka
(Buchs, Switzerland) and were used without further purification.
Preparation of compounds 4a–e; general procedure
A mixture of phosphite (2 mmol) in 2 mL acetone was added to a
magnetically stirred solution of (2,4-dinitrophenyl)acetic acid (2 mmol)
and DAAD (2 mmol) in 10 mL acetone at room temperature. The
reaction mixture was then stirred for 24 h. The solvent was removed
under reduced pressure and the residue was purified by column
chromatography on silica gel (60, 230–400 mesh) using hexane–ethyl
acetate (3:1) mixture as eluent.
Scheme 3 Three-component reaction between
triphenylphosphine, dialkyl acetylenedicarboxylates
and (2,4-dinitrophenyl)acetic acid.
Dimethyl 2-[2-(3,4-di(methoxycarbonyl)-4-(dimethoxyphosphoryl)
2,4-dinitrophenyl)]butanoic acid (4a): Yield: 90%;Yellow oil. IR (KBr)
(νmax, cm−1): 3095–3505 (OH), 1735 (C=O). Calcd for C16H19N2O13P:
C, 40.18; H, 4.00; N, 5.86. Found: C, 40.07; H, 3.86; N, 5.96%. MS
(m/z, %): 478 (M+, 7). 1H NMR (500 MHz, CDCl3): δ 3.35 and 3.55
(6 H, d 3JPH = 12 Hz, 2POCH3), 3.67 and 3.95 (6 H, 2 s, 2 OCH3), 4.33
observed at 8.64 ppm that disappeared after addition of a few
drops of D2O to d6-DMSO solution of compound 9a. This
signal is related to the OH proton. 13C NMR spectra of com-
pound 9a shows 18 distinct signals, which is consistent with
the proposed structure. The 31P NMR spectrum of compound
9a displays a signal at 24.49 ppm.
It is reasonable to assume that compound 9 results from
the initial addition of triphenylphosphine 8 to acetylenic ester
2 and subsequent protonation of the 1:1 adduct by (2,4-
dinitrophenyl)acetic acid 1. Then, the positively charged ion
10 is attacked by the anion 11 to form ylide 9 (Scheme 4).
Because of the existence of two stereogenic centres in the
products, mixtures of two diastereomers were expected but
the 1H NMR spectra of product 9 showed the existence of only
one isomer. Comparing the coupling constant of two methine
hydrogens with those for similar compounds reported previ-
ously,16 we concluded that the obtained isomer is (2R,3R)-9
and its enantiomer (Scheme 5).
In summary, we report that the three-component reaction
between phosphites, dialkyl acetylenedicarboxylates and
(2,4-dinitrophenyl)acetic acid provides a simple and efficient
one-pot route for the synthesis of dialkyl 2-[2-(2,4-dinitrophe-
nyl)-4-(dialkoxyphosphoryl)-3,4-di(methoxycarbonyl)
butanoic acid in good yields and the reaction between dialkyl
acetylenedicarboxylates and triphenylphosphine by (2,4-
dinitrophenyl)acetic acid produces highly functionalised,
salt-free phosphorus ylides in excellent yields. The present
method has the advantage that the reaction is performed in
neutral conditions and the starting materials can be mixed
without any activation or modification.
2
3
3
(1 H, dd, JHP = 21 Hz, JHH = 12 Hz, P–CH), 4.70 (1 H, dd, JHP
=
3
5 Hz, JHH = 12 Hz, P–C–CH), 5.32 (1 H, m, P–C–CH), 7.27–7.97
(3 H, m, 3 CH aromatic), 8.16 (1H, s, OH) ppm. 13C NMR
1
(125.8 MHz, CDCl3): δ 41.13 (CH), 48.64 (d, Jcp = 145 Hz, P–C),
2
53.05 and 53.46 (2 OCH3), 54.67 (d, JCP = 3 Hz, CH), 53.54–54.67
(m, 2 POCH3), 120.15, 126.75, 33.85, 140.56, 143.72, and 150.09
(C, aromatic), 168.27 (d, 2JCP = 5 HZ, C=O), 170.18 (d, 3JCP = 21 Hz,
C=O), 175.32 (C=O) ppm. 31P NMR (202.5 MHz, CDCl3): δ 21. 65 ppm.
Diethyl 2-[2-(3,4-di(methoxycarbonyl)-4-(dimethoxyphosphoryl)
2,4-dinitrophenyl)]butanoic acid (4b): Yield: 86%;Yellow oil. IR (KBr)
(νmax, cm−1): 3143-3580 (OH), 1739 (C=O). Calcd for C18H23N2O13P:
C, 42.70; H, 4.58; N, 5.53. Found: C, 42.89; H, 4.40; N, 5.60%.
1
MS (m/z, %): 506 (M+, 5). H NMR (500 MHz, CDCl3): δ 1.01 and
3
1.18 (6 H, 2 t, JHH = 7 Hz, 2 CH3), 3.66–3.81 (6 H, m, 2 POCH3),
3.91–4.68 (6 H, m, 2 OCH2 and 2H), 5.04 (1 H, m, P–C–CH), 7.27–
7.38 (3 H, m, 3 CH aromatic), 8.42 (1H, s, OH) ppm. 13C NMR
(125.8 MHz, CDCl3): δ 13.84 and 14.38 (2 CH3), 41.60 (CH), 48.42
(d, 1Jcp = 145 Hz, P–C), 54.02 (d, 2JCP = 3 Hz, CH), 53.75 and 53.87
(2 d, 2JCP 7 Hz, 2 POCH3), 62.48 and 63.39 (2 OCH2), 120.48, 126.23,
2
133.84, 140.27, 143.84, and 152.14 (C, aromatic), 166.95 (d, JCP
=
5 Hz, C=O), 170.31 (d, JCP = 21 Hz, C=O), 175.57 (C=O) ppm. 31P
3
NMR (202.5 MHz, CDCl3): δ 21.78 ppm.
Dimethyl 2-[3,4-di(methoxycarbonyl)-2-(2,4-dinitrophenyl)-4-(dip
henoxyphosphoryl)]butanoic acid (4c): Yield: 80%; Yellow oil.
IR (KBr) (νmax, cm−1): 3100–3630 (OH), 1735 (C=O). Calcd for
C26H23N2O13P: C, 51.84; H, 3.85; N, 4.65. Found: C, 51.90; H, 3.70;
N, 4.50%. MS (m/z, %): 602 (M+, 10). 1H NMR (500 MHz, CDCl3):
δ 3.69 and 3.75 (6 H, 2 s, 2 OCH3), 4.35 (1 H, dd, 2JHP = 22 Hz, 3JHH
=
12 Hz, P–CH), 4.70 (1 H, d, 3JHH = 1.5 Hz, CH), 4.76 (1 H, m, P–C–
CH), 7.16–7.39 (13 H, m, 13 CH aromatic), 8.18 (1H, s, OH) ppm. 13
C
1
NMR (125.8 MHz, CDCl3): δ 43.06 (CH), 44.05 (d, Jcp = 145 Hz,
P–C), 53.45 (d, 2JCP = 3 Hz, CH), 53.67 and 53.75 (2 OCH3), 120.12,
126.42, 133.62, 140.14, 143.55, and 150.38 (C, aromatic), 120.64
(d, 3JCP = 5 Hz, 4 CHortho), 126.70 (s, 2 CHpara), 130.18 (d, 4Jcp = 8 Hz,
4 CHmeta), 150.35 (d, 2Jcp = 10 Hz, Cipso), 150.72 (d, 2Jcp = 10 Hz, Cipso),
168.25 (d, 2JCP = 5 Hz, C=O), 171.88 (d, 3JCP = 21 Hz, C=O), 175.12
(C=O) ppm. 31P NMR (202.5 MHz, CDCl3): δ 21.51 ppm.
Scheme 4 Suggested mechanism for formation of
compound 9.
Dimethyl 2-[4-(diethoxyphosphoryl)-3,4-di(methoxycarbonyl)-2-
(2,4-dinitrophenyl)butanoic acid (4d): Yield: 83%; Yellow oil. IR
(KBr) (νmax, cm−1): 3141-3583 (OH), 1735 (C=O). Anal. Calcd for
C18H23N2O13P: C, 42.70; H, 4.58; N, 5.53. Found: C, 42.89; H, 4.40;
1
N, 5.60%. MS (m/z, %): 506 (M+, 3). H NMR (500 MHz, CDCl3):
δ 1.21 and 1.32 (6 H, 2 t 3JHH = 7 Hz, 2 CH3), 3.74 and 3.97 (6 H, 2 s,
2 OCH3), 4.02–4.16 (4H, m, 2 OCH2), 4.35 (1 H, dd, 2JHP = 21 Hz, 3JHH
= 12 Hz, P–CH), 4.77 (1 H, dd, 3JHP = 5 Hz, 3JHH = 12 Hz, P–C–CH),
5.38 (1 H, m, P–C–CH), 7.31 -7.84 (3 H, m, 3 CH aromatic), 8.23
(1H, s, OH) ppm. 13C NMR (125.8 MHz, CDCl3): δ 16.51 and 16.63
(2 CH3), 41.15 (CH), 48.58 (d, 1Jcp = 145 Hz, P–C), 53.12 and 53.49
2
Scheme 5 Two diastereomers.
(2 OCH3), 54.65 (d, JCP = 3 Hz, CH), 63.54–63.97 (m, 2 POCH2),

JOURNAL OF CHEMICAL RESEARCH 2012 499
1
120.12, 126.70, 33.87, 140.62, 143.75, and 150.18 (C, aromatic),
168.33 (d, 2JCP = 5 HZ, C=O), 170.24 (d, 3JCP = 21 Hz, C=O), 175.36
(C=O) ppm. 31P NMR (202.5 MHz, CDCl3): δ 21. 48 ppm.
CHCHC=P), 57.48, 60.97 (2OCH2), 126.82 (d, JPC = 85 Hz, C ipso),
129.35 (d, JPC = 12.0 Hz, C meta), 132.84 (d, JPC = 3.0 Hz, C para),
134.15 (d, 2JPC = 9 Hz, C ortho), 120.52, 127.56, 136.48, 144.35, 146.66
and 149.73 (6C, aromatic), 168.41 (d, 2JPC = 12.95 Hz, C=O), 170.10
(d, 3JPC = 17.98 Hz, C=O), 175.08 (C=O) ppm. 31P NMR (202.5 MHz,
d6-DMSO): δ 24.57 ppm.
3
4
Dimethyl 2-[4-(dibutoxyphosphoryl)-3,4-di(methoxycarbonyl)-2-
(2,4-dinitrophenyl)] butanoic acid (4e): Yield: 81%; Yellow oil.
IR (KBr) (νmax cm−1): 3148–3593 (OH), 1745 (C=O). Anal. Calcd for
C22H31N2O13P: C, 46.98; H, 5.56; N, 4.98. Found: C, 46.90; H, 5.45;
N, 5.14%. MS (m/z, %): 562 (M+, 11). 1H NMR (500 MHz, CDCl3):
δ 0.84, and 0.89 (6 H, 2 t, 2 CH3), 1.37 (4 H, m, 2 CH2), 1.54 (4 H, m,
2 CH2), 3.72 and 3.90 (6 H, 2 s, 2 OCH3), 3.96- 4.07 (4 H, m, 2 OCH2),
4.40 (1 H, dd, 2JHP = 21 Hz, 3JHH = 12 Hz, P–CH), 4.76 (1 H, dd, 3JHP
= 5 Hz, 3JHH = 12 Hz, P–C–CH), 5.39 (1 H, m, P–C–CH), 7.31–7.95
(3 H, m, 3 CH aromatic), 8.23 (1H, s, OH) ppm. 13C NMR (125.8
MHz, CDCl3): δ 13.86 and 13.94 (2 CH3), 18.90 and 18.97 (2 CH2),
32.61 and 32.76 (2d, 3JCP = 7Hz, 2 CH2), 48.66 (d, 1Jcp = 145 Hz, P–C),
Di-tert-butyl-3,4-di(methoxycarbonyl)-2-[2-(2,4-dinitrophenyl)]-
3-(triphenyl-λ5-phosphanylidene)]butanoic acid (9c): Yield: 82%;
Yellow powder; m.p. 197–199 °C. IR (KBr) (νmax, cm−1): 3505 (OH),
1712 (C=O), 1339 and 1530 (NO2). Calcd for C38H39N2O10P: C, 63.86;
H, 5.50; N, 3.92. Found: C, 64.02; H, 5.35; N, 3.74%. MS (m/z, %):
714 (M+, 3). H NMR (500 MHz, d6-DMSO): δ 0.88 (9H, s, 3CH3),
1
3
3
1.39 (9H, s, 3CH3), 2.43 (dd, 1H, JPH = 16.4 Hz, JHH = 10.8 HZ,
CHCHC=P), 3.66 (d, 1H, 3JHH = 10.8 Hz, CHCHC=P), 7.34–8.35 (m,
18H, aromatic), 8.62 (1H, broad s, OH) ppm. 13C NMR (125.8 MHz,
2
53.12 and 53.42 (2 OCH3), 54.68 (d, JCP = 3 Hz, CH), 66.82–67.57
3
d6-DMSO): δ 28.76 and 28.87 (6CH3), 33.61 (d, JPC = 10.8 Hz,
(m, 2 POCH2), 120.19, 126.81, 33.77, 140.62, 143.70, and 150.19
(C, aromatic), 168.17 (d, 2JCP = 5 HZ, C=O), 170.23 (d, 3JCP = 21 Hz,
C=O), 175.36 (C=O) ppm. 31P NMR (202.5 MHz, CDCl3): δ 21.61
ppm.
1
2
CHCHC=P), 39.19 (d, JPC = 125 Hz, C=P), 46.14 (d, JPC = 14 Hz,
1
CHCHC=P), 76.69 and 80.19 (2C), 126.92 (d, JPC = 85 Hz, C ipso),
129.19 (d, JPC = 12.0 Hz, C meta), 132.76 (d, JPC = 3.0 Hz, C para),
134.22 (d, 2JPC = 9 Hz, C ortho), 120.51, 127.42, 136.25, 144.83, 146.56
and 149.78 (6C, aromatic), 168.28 (d, 2JPC = 12.95 Hz, C=O), 170.16
(d, 3JPC = 17.98 Hz, C=O), 174.38 (C=O) ppm.31P NMR (202.5 MHz,
d6-DMSO): δ 23.94 ppm.
3
4
Synthesis of compounds 9a–c; general procedure
A mixture of triphenylphosphine (2 mmol) in 2 mL acetone was added
to a magnetically stirred solution of (2,4-dinitrophenyl) acetic acid
(2 mmol) and DAAD (2 mmol) in 10 mL acetone at room tempera-
ture. The reaction mixture was then stirred for 2 h. The solvent
was evaporated at reduced pressure. The residue was precipitated in a
solution of diethyl ether–hexane. The solid was filtered and washed
with diethyl ether to give the pure product.
We gratefully acknowledge financial support from the Research
Council of Islamic Azad University of Yazd and The Islamic
Azad University of Zahedan of Iran.
Dimethyl
2-[3,4-di(methoxycarbonyl)-2-(2,4-dinitrophenyl)]-3-
Received 19 April 2012; accepted 13 June 2012
Paper 1201275 doi: 10.3184/174751912X13403013285904
Published online: 8 August 2012
(triphenyl-λ5-phosphanylidene)]butanoic acid (9a): Yield: 90%;
Yellow powder; m.p. 195–197 °C. IR (KBr) (νmax, cm−1): 3510 (OH),
1725 (C=O), 1342 and 1530 (NO2). Calcd for C32H27N2O10P: C, 60.96;
H, 4.32; N, 4.44. Found: C, 60.81; H, 4.50; N, 4.36%. MS (m/z, %):
630 (M+, 4). H NMR (500 MHz, d6-DMSO): δ 2.62 (dd, 1H, JPH
=
1
3
References
16.4 HZ, 3JHH = 10.8 HZ, CHCHC=P), 3.45 (s, 3H, OCH3), 3.58 (s, 3H,
OCH3), 3.61 (d, 1H, 3JHH = 10.8 Hz, CHCHC=P), 7.32–8.39 (m, 18H,
aromatic), 8.64(1 H, broad s, OH) ppm.13C NMR (125.8 MHz, d6-
1
2
3
4
5
6
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3
1
DMSO): δ 33.49 (d, JPC = 10.8 Hz, CHCHC=P), 39.21 (d, JPC
=
2
125 Hz C=P), 45.42 (d, JPC = 14 HZ, CHCHC=P), 49.34, 52.38
(2OCH3), 126.69 (d, 1JPC = 85 Hz, C ipso), 129.46 (d, 3JPC = 12.0 Hz,C
meta), 132.91 (d, JPC = 3.0 Hz, C para), 134.08 (d, JPC = 9 Hz, C ortho),
120.53, 127.61, 136.48, 144.08, 146.69 and 149.71 (6C, aromatic),
168.55 (d, 2JPC = 12.95 HZ, C=O), 170.08 (d, 3JPC = 17.98 Hz, C=O),
175.64 (C=O) ppm.31P NMR (202.5 MHz, d6-DMSO): δ 24.49 ppm.
Diethyl 2-[3,4-di(methoxycarbonyl)-2-(2,4-dinitrophenyl)]-3-(tri-
phenyl-λ5-phosphanylidene)]butanoic acid (9b): Yield: 92%; Yellow
powder; m.p. 145–147 °C. IR (KBr) (νmax, cm−1): 3505 (OH), 1723
(C=O), 1344 and 1529 (NO2). Calcd for C34H31N2O10P: C, 62.01; H,
4.74; N, 4.25. Found: C, 61.90; H, 4.65; N, 4.17%. MS (m/z, %): 658
(M+, 8). 1H NMR (500 MHz, d6-DMSO): δ 0.37 (t, 3 H, 3JHH = 7.1 Hz,
4
2
8
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3
3
CH3), 1.21(t, 3H, JHH = 7.1 Hz, CH3), 2.60 (dd, 1H, JPH = 16.4 Hz,
3JHH = 10.8 Hz, CHCHC=P), 3.50 (m, 2H, OCH2), 3.68 (d, 1H,
3JHH = 10.8 Hz, CHCHC=P), 4.04 (m, 2H, OCH2), 7.35–8.37 (m,
18H, aromatic), 8.65(1H, broad s, OH) ppm. 13C NMR (125.8 MHz,
d6-DMSO): δ 14.66 and 14.97 (2CH3), 33.54 (d, JPC = 10.8 HZ,
CHCHC=P), 39.10 (d, JPC = 125 Hz, C=P), 45.30 (d, JPC = 14 Hz,
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