An efficient and green method to prepare bis-α-hydroxy phosphonates using triethylamine as catalyst

Article abstract of DOI:10.1080/10426507.2020.1825435

An efficient, convenient and environmentally friendly method for the synthesis of bis-α-hydroxy phosphonates via a perfectly atom economical Pudovik reaction is described. Using 5 mol% of triethylamine as a catalyst, a series of aromatic/heteroaromatic dialdehydes reacts with dialkyl phosphites to afford the corresponding bis-α-hydroxy phosphonates, particularly the bio-mass based ones, under solvent-free conditions or in a minimum amount of tetrahydrofuran at room temperature with moderate to excellent yields (52–95%).

Full text of DOI:10.1080/10426507.2020.1825435

Phosphorus, Sulfur, and Silicon and the Related Elements
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An efficient and green method to prepare bis-α-
hydroxy phosphonates using triethylamine as
catalyst
Zehuai Mou , Yinjun Wang & Xi Man
To cite this article: Zehuai Mou , Yinjun Wang & Xi Man (2020): An efficient and green method
to prepare bis-α-hydroxy phosphonates using triethylamine as catalyst, Phosphorus, Sulfur, and
Silicon and the Related Elements, DOI: 10.1080/10426507.2020.1825435
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2020.1825435
An efficient and green method to prepare bis-a-hydroxy phosphonates using
triethylamine as catalyst
Zehuai Mou, Yinjun Wang, and Xi Man
School of Material Science and Chemical Engineering, Ningbo University, Ningbo, China
ABSTRACT
ARTICLE HISTORY
An efficient, convenient and environmentally friendly method for the synthesis of bis-a-hydroxy
phosphonates via a perfectly atom economical Pudovik reaction is described. Using 5 mol% of trie-
thylamine as a catalyst, a series of aromatic/heteroaromatic dialdehydes reacts with dialkyl phos-
phites to afford the corresponding bis-a-hydroxy phosphonates, particularly the bio-mass based
ones, under solvent-free conditions or in a minimum amount of tetrahydrofuran at room tempera-
ture with moderate to excellent yields (52–95%).
Received 3 March 2020
Accepted 16 September 2020
KEYWORDS
Bis-a-hydroxy phosphonate;
Pudovik reaction; green
syntheses; aromatic
dialdehyde; biomass
GRAPHICAL ABSTRACT
Introduction
phosphonates by reacting dialdehyde with trialkyl phosphite
under strong acidic conditions (HCl gas) in dry dioxane.
[18]
a-Hydroxy phosphonates have attracted extensive attention
because they were found to be biologically active and valu-
able synthetic precursors for the synthesis of related organo-
phosphonates, such as a-aminophosphonates, alkoxy- and
acyloxy-phosphonates, ketophosphonates and halophospho-
Unfortunately, the current protocols for the synthesis of bis-
a-hydroxy phosphonates suffer from some inconveniences
such as strong acidic conditions (HCl gas), poor activity and
low efficiency. Therefore, there is a need to develop an envir-
onmentally benign and convenient method for the synthesis of
bis-a-hydroxy phosphonates. In this contribution, we report an
efficient method to synthesize a series of phosphonate diols
[
1]
nates. Moreover, bis-a-hydroxy phosphonates can be used
as excellent candidates as diol monomers for the synthesis of
phosphorus-containing polymers with flame retardant proper-
(bis-a-hydroxy phosphonates) from aromatic and hetero-
[2]
ties. As early as 1988, Mikroyannidis used bis-a-hydroxy
phosphonates (1,4-bis[(dialkoxyphosphinyl)hydroxymethyl]ben-
zene) as diols to prepare phosphorus-containing polyurethanes
which exhibited a higher fire resistance than that of common
aromatic dialdehydes under green and mild conditions.
Results and discussion
[3]
polyurethanes. The major synthetic route toward a-hydroxy
As previously mentioned, Et N is a common catalyst for the
3
[
4]
phosphonates is the atom economic Pudovik reaction.
wide range of catalysts has been explored for the synthesis of
A
[15a]
synthesis of a-hydroxy phosphonates, and Blackburn
[
15b]
and Rangel,
respectively, used a stoichiometric amount
[
5]
a-hydroxy phosphonates, such as lipase,
triethylamine
to prepare a few bis-a-hydroxy phosphonates from the reac-
tion of dialdehyde and diethyl phosphonate. In our initial
[
6]
[7]
[8]
[9]
(
Et N),
choline hydroxide,
Bi(NO ) ꢀ5H O,
n-BuLi,
3
3 3
2
[
10]
[11]
Ba(OH)2, , bimetallic lanthanide bis(amido) complexes,
MoO Cl ,
study, different amounts of Et N were tested for the model
3
[
12]
[13]
[14]
MgO
and heterogeneous systems,
but only
2
2
reaction between p-phthalaldehyde and dimethyl phosphite
a few catalysts were reported for bis-a-hydroxy phosphonates, under solvent-free conditions at room temperature. To a
[
15]
including a stoichiometric amount of Et N
and catalytic mixture of p-phthalaldehyde (1.0 eq.) and dimethyl phos-
3
[16]
[17]
amount of DABCO,
heterogeneous KF/Al O
and phite (2.1 eq.) was added Et N (2–20 mol%) under stirring.
2
3
3
[14a]
Fe O -immobilized guanidine.
In addition, Failla and cow- The heterogeneous mixture gradually became into a viscous
orkers reported the synthesis of three bis-a-hydroxy liquid, then into a white precipitate. Washing the resulting
3
4
CONTACT Zehuai Mou
mouzehuai@nbu.edu.cn
School of Material Science and Chemical Engineering, Ningbo University, Ningbo 315211, China.
Supplemental data for this article is available online at https://doi.org/10.1080/10426507.2020.1825435.
ß 2020 Taylor & Francis Group, LLC

2
Z. MOU ET AL.
a
3
Table 1. Synthesis of bis-a-hydroxy phosphonates catalyzed with Et N.
b
Entry
Ar
R
Solv.
Et3N (mol %)
t/min
Product
Yield (%)
1
2
3
4
5
6
7
Me
Me
Me
Me
Et
Me
Et
Neat
Neat
Neat
Neat
Neat
20
10
5
2
5
5
5
5
5
30
60
30
600
600
1a
1a
1a
1a
1b
2a
2b
98
96
95
95
94
93
87
c
THF
c
THF
c
8
9
Me
Et
THF
THF
5
5
120
120
3a
3b
82
87
c
c
1
1
0
1
Me
Et
THF
THF
5
5
600
600
4a
4b
94
69
c
1
1
2
3
Me
Et
neat
neat
5
5
30
30
5a
5b
52
69
a
Reaction conditions: dialdehyde (1.0 mmol), dialkyl phosphite (2.1 mmol), room temperature.
Isolated yield of pure product.
b
c
THF (1.0 mL).
Table 2. Significant NMR parameters of the newly obtained bis-a-hydroxy phosphonates (DMSO-d
6
).
1
13
31
b
H NMR
P–CH (ppm)
C NMR
P NMR
2
3
1
Compound
d
J
PH, JHH (Hz)
dP–C (ppm)
J
PC (Hz)
d
P
(ppm)
2
3
3
4
5
5
b
a
a
b
a
a
5.00 (dd)
5.07 (dd)
4.97 (dd)
13.3, 5.2
13.8, 5.5
13.9, 5.8
–
14.4, 6.3
14.6, 6.6
–
–
–
68.3
68.6
70.7
62.9
63.3
161.1
161.4
157.3
168.6
169.1
23.19, 23.10
21.00, 20.98
22.88 (m)
21.67 (m)
19.42, 18.83
5.07 ꢁ 5.03 (m)
4.96 (dd)
b
4.86 (dd)
2
02 MHz.
precipitate with ethyl ether to remove Et N and excessive circumvent this drawback, dialdehyde and dialkyl phosphite
3
dimethyl phosphite afforded the desired bis-a-hydroxy were dissolved in a minimum amount of tetrahydrofuran
phosphonate, 1,4-bis[(dimethoxyphosphoryl)hydroxymethyl]- (THF) (ca. 1.0 mL) prior to the addition of Et N. In this case,
3
benzene (1a) in excellent yields (Table 1, entries 1–4). Given compounds 2a and 4a precipitated from reaction solution
the reaction time and solution reaction (vide infra), 5 mol% within 600 min at the cost of decreasing activity, but excellent
amount of Et N was employed as standard condition in the yields (93% and 94%) and high purity were obtained after sim-
3
following experiments. With the same procedure, 1,4-bis[(die- ple work-up (Table 1, entries 6 and 10). While compounds 2b,
thoxyphosphoryl)hydroxymethyl]benzene (1b) was synthesized 3 and 4b did not precipitate from the reaction solution and
from p-phthalaldehyde and diethylphosphite within 30 min in were isolated as viscous oils in moderate to good yields (Table
94% yield (Table 1, entry 5). This new strategy avoided the use 1, entries 7–9 and 11).
of reaction solvent and strong acidic gas (HCl) in comparison
with the described method.
Recently, the scientific community has sought biomass-
[18]
When m-phthalaldehyde, 5-bro- derived molecules as alternatives for replacing building blocks
[
19]
moisophthalaldehyde and 2,6-pyridinedicarboxaldehyde were arising from petrochemicals.
5-Hydroxymethylfurfural
used as substrates, the reactions proceeded rapidly and exother- (HMF), derived from the dehydration of renewable carbohy-
mally, accordingly, partial substrates (aldehydes) were covered drates, is considered as one of the most promising platform
[
20]
by newly produced precipitate and did not convert completely, chemicals.
As one important derivative of HMF, 2,5-fur-
and resulted in difficulty in separation and low yields. To andicarbaldehyde was used as dialdehyde to react with

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
1
6
Figure 1. H NMR (500 MHz, DMSO-d ) spectrum of P–CH–OH system in 5a.
dialkyl phosphite. Unlike p-phthalaldehyde, the 2,5-furandi- approach for biomass-based bis-a-hydroxy phosphonates
carbaldehyde reacted with dialkyl phosphite in the presence and application of these bis-a-hydroxy phosphonates to pre-
of Et N under solvent-free condition afforded an orange oil, pare phosphorus-containing polymers are underway in
3
and precipitate was not observed. Recrystallization from our laboratory.
THF/Et O solution produced desired biomass-based bis-
2
a-hydroxy phosphonates as pale-yellow solid in moderate
yields (Table 1, entries 12 and 13).
Experimental section
The addition of dialkyl phosphites to dialdehydes gener-
ated two chiral carbon atoms in the corresponding bis-
All reactions were conducted in an argon atmosphere. HMF,
m-phthalaldehyde, p-phthalaldehyde, 2,6-pyridinedicarboxal-
a-hydroxy phosphonates, which accordingly existed in two dehyde, 5-bromoisophthalaldehyde, dimethyl phosphite,
diastereoisomers (meso- and racemic forms). The newly diethyl phosphite and triethylamine were purchased from
1
13
obtained compounds have been characterized with H,
C
Energy Chemical (Shanghai) and used as received. 2,5-
3
1
and P NMR spectroscopy (DMSO-d ), and significant Furandicarbaldehyde was prepared from HMF according to
6
NMR parameters are collected in Table 2. For the known the reported literature.[22] NMR ( H, C, P) spectra were
1
13
31
compounds such as 1a, 1b, 2b and 4b, the NMR data (Table recorded on a Bruker Ascend 500 or 400 spectrometer at
ꢂ
S1, see Supplemental Materials) were consistent with those 25 C and referenced internally to residual solvent resonan-
[
16,18]
1
1
13
13
reported in the literatures.
5
In the H NMR spectrum of ces (DMSO-d : 2.50 ppm for H NMR, 39.52 ppm for
a, the P–CH–OH system exhibited two doublets of dou- NMR). The Supplemental Materials contain sample H,
C
C
6
1
31
blets (–CH: 4.96 ppm, dd, J ¼ 14.4, 6.3 Hz; –OH: 6.36 ppm, and P NMR for products 1–5 (Supplemental Materials
dd, J ¼ 12.8, 6.3 Hz) which resulted from the coupling of Figures S1–S24).
13
P–H and H–H (Figure 1), and in the C NMR spectrum
(
Figure S20, see Supplemental Materials), the resonance of
Synthesis of bis-a-hydroxy phosphonates
,3-Bis[(dimethoxyphosphoryl)hydroxymethyl]benzene (2a): m-
P–CH–OH appeared at 62.9 ppm (d, J ¼ 168.6 Hz). The
CP
3
1
P NMR spectra, which were utilized to determine the dia-
stereomeric purity of bis-a-hydroxy/amino phospho-
1
phthalaldehyde (0.134 g, 1.0 mmol) and dimethyl phosphite
0.231 g, 2.1 mmol) were dissolved in THF (ca. 1.0ml), and
[
17,18,21]
nates,
displayed two singlets or multiplets suggesting
(
that the obtained bis-a-hydroxy phosphonates synthesized
with Et N were mixtures of diastereoisomers, for example,
the major isomer in 5b is about 72% (Figure S24, see
Supplemental Materials).
Et N (5 mg, 50lmol) was added under stirring, 10 h later, pre-
3
3
cipitate formed. Removal of solution, washing with ethyl ether,
ꢂ
dryness under vacuo at 60 C for 12 h gave the title compound
1
2
a. Yield: 0.329 g, 93%. H NMR (500 MHz, DMSO-d ), d 7.50
6
(
–
m, Ph–H, 1H), 7.34 (m, Ph–H, 3H), 6.31 (dd, J¼ 15.1, 5.4 Hz,
OH, 2H), 5.00 (dd, J¼ 13.3, 5.2 Hz, PCH, 2H), 3.62 (dd,
J¼ 10.3, 1.6 Hz, –OCH , 12H), 3.57 ppm (dd, J¼ 10.3, 2.9 Hz,
Conclusion
3
In summary, a simple procedure has been developed for the –OCH , 3H). HRMS (ESI): m/z calcd for C H O P Na
synthesis of bis-a-hydroxy phosphonates via Pudovik reac- [M þ Na] 377.0531, found 377.0540.
3
12 20 8 2
þ
tion between dialdehyde and 2.1 equivalents of dimethyl
1,3-Bis[(dimethoxyphosphoryl)hydroxymethyl]-5-bromo-
phosphite or diethyl phosphite in the presence of a catalytic benzene (3a): 5-bromoisophthalaldehyde (0.213 g, 1.0 mmol)
amount of Et N at room temperature, especially the bio- and dimethyl phosphite (0.231 g, 2.1 mmol) were dissolved
3
mass-based bis-a-hydroxy phosphonates. The advantages of in THF (ca. 1.0 ml), and Et N (5 mg, 50 lmol) was added
3
this method are mild conditions, high activity and oper- under stirring for 2 h. Removal of solution, washing with
ꢂ
ational simplicity. In the cases of m-phthalaldehyde, p- ethyl ether, dryness under vacuo at 60 C for 12 h gave the
1
phthalaldehyde and 2,6-pyridinedicarboxaldehyde, the title compound 3a as viscous oil. Yield: 0.355 g, 82%. H
desired products precipitated directly from the reaction mix- NMR (400 MHz, DMSO-d ), d 7.51 (s, Ph–H, 2H), 7.48 (s,
6
ture with excellent yields. Exploring a more efficient Ph–H, 1H), 6.50 (dd, J ¼ 16.9, 5.6 Hz, –OH, 2H), 5.07 (dd,

4
Z. MOU ET AL.
J ¼ 13.8, 5.5 Hz, PCH, 2H), 3.65–3.58 ppm (m, –OCH , 2H), 4.09–3.93 (m, –OCH CH , 8H), 1.20 ppm (dt, J ¼ 26.5,
3
2
3
1
3
13
1
2H). C NMR (125 MHz, DMSO-d ), d 140.9, 129.1, 125.2 7.1 Hz, –OCH CH , 12H). C NMR (125 MHz, DMSO-d ),
6
2 3 6
(
m), 120.9, 68.3 (d, J ¼ 161.1 Hz), 53.7 (m), 53.2 (m) d 151.3, 109.7, 63.3 (d, JCP ¼ 169.1 Hz), 62.4 (m), 62.2 (m),
CP
3
1
31
ppm. P NMR (202 MHz, DMSO-d ), d 23.19, 23.10, 22.82. 16.4 (m) ppm. P NMR (202 MHz, DMSO-d
), d 19.42,
Na
6
6
þ
HRMS (ESI): m/z calcd for C H BrO P Na [M þ Na]
18.83 ppm. HRMS (ESI): m/z calcd for C14
[M þ Na] 423.0950, found 423.0940.
H
26
O
9
P
2
12
19
8 2
þ
4
54.9636, found 454.9621.
,3-Bis[(diethoxyphosphoryl)hydroxymethyl]-5-bromo-
1
benzene (3b): 5-bromoisophthalaldehyde (0.213 g, 1.0 mmol)
and diethyl phosphite (0.290 g, 2.1 mmol) were dissolved in
Disclosure statement
THF (ca. 1.0 ml), and Et N (5 mg, 50 lmol) was added No potential conflict of interest was reported by the authors.
3
under stirring for 2 h. Removal of solution, washing with
ꢂ
ethyl ether, dryness under vacuo at 60 C for 12 h gave the
Funding
title compound 3 b as viscous white solid. Yield: 0.425 g,
7%. H NMR (400 MHz, DMSO-d ), d 7.50 (s, Ph–H, 2H), The authors acknowledge financial support from the National Natural
1
8
6
Science Foundation of China [Grant 21805143], the Natural Science
Foundation of Ningbo [Grant 2018A610118], K. C. Wong Magna Fund
in Ningbo University, and Open Research Fund of State Key
Laboratory of Polymer Physics and Chemistry, Changchun Institute of
7
.48 (s, Ph–H, 1H), 6.38 (dd, J ¼ 15.1, 5.8 Hz, –OH, 2H),
4
.97 (dd, J ¼ 13.9, 5.8 Hz, PCH, 2H), 4.02–3.89 (m, –OCH ,
2
13
8
H), 1.20–1.15 (m, –OCH CH , 12H). C NMR (125 MHz,
2 3
DMSO-d6),
d
140.8, 129.0, 125.2, 120.4, 68.6 (d, Applied Chemistry (CIAC), Chinese Academy of Sciences [2018-28].
31
JCP ¼ 161.4 Hz), 62.4, 62.1, 16.3.
P NMR (202 MHz,
DMSO-d ), d 21.00, 20.98 ppm. HRMS (ESI): m/z calcd for
6
þ
C H BrO P Na [M þ Na] 511.0262, found 511.0248.
1
6
27
8 2
References
2
,6-Bis[(dimethoxyphosphoryl)hydroxymethyl]pyridine
(
4a): 2,6-pyridinedicarboxaldehyde (0.135 g, 1.0 mmol) and
[1] (a) Radai, Z.; Keglevich, G. Synthesis and Reactions of Alpha-
Hydroxyphosphonates. Molecules 2018, 23, 1493. DOI: 10.1080/
dimethyl phosphite (0.231 g, 2.1 mmol) were dissolved in
THF (ca. 1.0 ml), and Et N (5 mg, 50 lmol) was added
under stirring, 10 h later, precipitate formed. Removal of
solution, washing with ethyl ether, dryness under vacuo at
6
9
Py–H, 1H), 7.46 (m, Py–H, 2H), 6.45–6.38 (m, –OH, 2H),
5
3
10426507.2018.1544132. (b) Radai, Z. Alpha-Hydroxyphosphonates
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[
2] (a) El Khatib, W.; Youssef, B.; Bunel, C.; Mortaigne, B.
Fireproofing of Polyurethane Elastomers by Reactive
Organophosphonates. Polym. Int. 2003, 52, 146–152. DOI: 10.
ꢂ
0 C for 12 h gave the title compound 4a. Yield: 0.334 g,
1
4%. H NMR (500 MHz, DMSO-d ), d 7.87 (t, J ¼ 7.8 Hz,
6
1002/pi.1009. (b) Wendels, S.; Chavez, T.; Bonnet, M.; Salmeia,
K. A.; Gaan, S. Recent Developments in Organophosphorus
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Preparation and Application of Phosphorous-Containing Bio-
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.07–5.03 (m, PCH, 2H), 3.67 (dd, J ¼ 10.4, 2.0 Hz, –OCH ,
3
13
H), 3.63–3.58 ppm (m, –OCH , 3H). C NMR (125 MHz,
3
DMSO-d ), d 156.5, 156.4, 137.2, 121.3, 121.1, 70.7 (d,
6
31
JCP ¼ 157.3 Hz), 53.3 (m), 53.1 (m) ppm.
P NMR
(202 MHz, DMSO-d ), d 22.88 ppm. HRMS (ESI): m/z calcd
6
þ
for C H NO P Na [M þ Na] 378.0484, found 378.0471.
1
1
19
8 2
[
3] Mikroyannidis, J. A. Flame Retardation of Polyurethanes by
Means of 1,4-Bis[(Dialkoxyphosphinyl)Hydroxymethyl]Benzene.
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pola.1988.080260317.
2
,5-Bis[(dimethoxyphosphoryl)hydroxymethyl]furan (5a):
To a mixture of 2,5-furandicarbaldehyde (0.124 g, 1.0 mmol)
and dimethyl phosphite (0.231 g, 2.1 mmol) was added Et N
3
[
[
[
4] Pudovik, A. N.; Arbuzov, B. A. Addition of Dialkyl Phosphites
to Unsaturated Ketones, Nitriles, and Esters. Dokl. Akad. Nauk
S.S.S.R. 1950, 73, 327–329.
5] Koszelewski, D.; Ostaszewski, R. Biocatalytic Promiscuity of
Lipases in Carbon-Phosphorus Bond Formation. ChemCatChem
(5 mg, 50 lmol), and the mixture was stirred for 0.5 h. The
resulting orange oil was recrystallized from THF/Et O, and
gave the title compound 5a as pale yellow solid. Yield:
0
2
1
.179 g, 52%. H NMR (500 MHz, DMSO-d ), d 6.44 (s,
6
2
019, 11, 2554–2558. DOI: 10.1002/cctc.201900397.
6] (a) R ꢀa dai, Z.; Kiss, N. Z.; Mucsi, Z.; Keglevich, G. Synthesis of
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furan-H, 2H), 6.36 (dd, J ¼ 12.8, 6.3 Hz, –OH, 2H), 4.96 (dd,
J ¼ 14.4, 6.3 Hz, PCH, 2H), 3.70 (d, J ¼ 10.4 Hz, –OCH ,
3
13
3
H), 3.62 ppm (d, J ¼ 10.3 Hz, –OCH , 3H). C NMR
3
Phosphorus, Sulfur, Silicon Relat. Elem. 2016, 191, 1564–1565.
DOI: 10.1080/10426507.2016.1213261. (b) Keglevich, G.; R ꢀa dai, Z.;
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a-Hydroxyphosphonates from Substituted Benzaldehydes and
Dialkyl Phosphites. Green Process. Synth. 2017, 6, 197–201. (c)
Grun, A.; Radai, Z.; Soregi-Nagy, D. I.; Greiner, I.; Keglevich, G.
Rational Synthesis of -Hydroxyphosphonic Derivatives Including
Dronic Acids. Phosphorus, Sulfur, Silicon Relat. Elem. 2019, 194,
386–387. DOI: 10.1080/10426507.2018.1555537. (d) Kiss, N. Z.;
Radai, Z.; Keglevich, G. Green Syntheses of Potentially Bioactive
Alpha-Hydroxyphosphonates and Related Derivatives. Phosphorus,
Sulfur, Silicon Relat. Elem. 2019, 194, 1003–1006. DOI: 10.1080/
(125 MHz, DMSO-d ),
d
151.1, 109.9, 62.9 (d,
6
31
JCP ¼ 168.6 Hz), 53.4 (m), 53.0 ppm (m).
P
NMR
(202 MHz, DMSO-d ), d 21.67 ppm. HRMS (ESI): m/z calcd
6
þ
for C H O P Na [M þ Na] 367.0324, found 367.0316.
1
0
18 9 2
2
,5-Bis[(diethoxyphosphoryl)hydroxymethyl]furan (5b):
To a mixture of 2,5-furandicarbaldehyde (0.124 g, 1.0 mmol)
and diethyl phosphite (0.290 g, 2.1 mmol) was added Et N
3
(5 mg, 50 lmol), and the mixture was stirred for 0.5 h. The
resulting orange oil was recrystallized from THF/Et O, and
gave the title compound 5b. Yield: 0.276 g, 69%. H NMR
2
1
1
0426507.2019.1630407.
[7] Kalla, R. M. N.; Zhang, Y.; Kim, I. Highly Efficient Green
Synthesis of a-Hydroxyphosphonates Using Recyclable
(500 MHz, DMSO-d ), d 6.43 (s, furan-H, 2H, 2H), 6.28 (dd,
6
J ¼ 12.7, 6.6 Hz, –OH, 2H), 4.86 (dd, J ¼ 14.6, 6.6 Hz, PCH,
a

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
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[
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