Highly efficient green synthesis of α-hydroxyphosphonates using a recyclable choline hydroxide catalyst

Article abstract of DOI:10.1039/c6nj03948k

Choline hydroxide has been found to be an efficient basic ionic liquid catalyst for the synthesis of α-hydroxyphosphonates. Hydrophosphonylation of aldehydes was performed via the nucleophilic addition of diethylphosphite to aldehydic carbonyl compounds, in the presence of choline hydroxide under neat as well as solvent conditions. A wide array of substrates, including aromatic, fused aromatic, and heterocyclic aldehydes, were efficiently converted to their corresponding products in good yields. This protocol provides an alternative method for the straightforward synthesis of α-hydroxyphosphonates in high yields.

Full text of DOI:10.1039/c6nj03948k

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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
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ARTICLE
Highly efficient green synthesis of αꢀ
hydroxyphosphonates using recyclable choline
hydroxide catalyst
Cite this: DOI: 10.1039/x0xx00000x
Reddi Mohan Naidu Kalla, Yu Zhang and Il Kim*
Received 00th January 2012,
Accepted 00th January 2012
Choline hydroxide has been found to be an efficient basic ionic liquid catalyst for the synthesis of α-
hydroxyphosphonates. The hydrophosphonylation of aldehydes is proceeded by a nucleophilic addition
of diethylphosphite to aldehydic carbonyl compounds, in the presence of choline hydroxide under neat
as well as solvent conditions. A wide array of substrates, including aromatic, fused aromatic, and
heterocyclic aldehydes, were efficiently converted to the corresponding products in good yields. This
protocol provides an alternative method for the straightforward synthesis of α-hydroxyphosphonatesin
high yields.
DOI: 10.1039/x0xx00000x
www.rsc.org/
important OPCs but also to develop improved methods for such
syntheses8.
1. Introduction
The richness of organophosphorus compounds (OPCs), their
remarkable structure, and their specific chemical appearance make
them versatile reagents that play an important role in modern
synthetic organic chemistry and medicinal chemistry.1 OPCs have
been developed by distinguished chemists such as Wittig
(phosphorus ylides), Arbuzov (alkylphosphonates), Hornerꢀ
WadsworthꢀEmmons (phosphonate carbanions), Kabachnik and
Fields (αꢀamino phosphonates), Pudovik (αꢀaminoꢀ and αꢀ
hydroxyphosphonates) and Abramov (αꢀhydroxyphosphonates), and
their wide applications demonstrate the enormous potential of
organophosphorus chemistry.2 Among them, the Pudovik
(dialkylphosphites) and Abramov (trialkyl phosphites) reactions lead
to the formation of αꢀhydroxyphosphonates via nucleophilic addition
of diꢀ or trialkyl phosphites to carbonyl compounds under basic or
acidic conditions; these two reactions proceed by a similar
mechanism involving the attack of the nucleophilic phosphorus atom
on the carbonyl carbon.3In addition, OPCs possess a wide spectrum
of biological properties such as antiviral, antibacterial, pesticidal,
and anticancer activities,4 as well as potent renin inhibitory5and HIV
protease inhibitory effects6. For example, fosfomycin (Fig. 1) is a
naturally occurring compound, first isolated from Streptomyces
fradiae,7containing a C–P bond and with promising anti biotic
activity. It has also been demonstrated that phosphonates are able to
perturb metabolic processes normally involving phosphates of
similar structure. Moreover, materials with other metabolic
regulatory capabilities have been found. As a result, efforts have
been made not only to synthesize biologically and catalytically
Fig. 1. Biologically active HPPs.
αꢀHydroxyphosphonates (HPPs) are an important class of
phosphonate derivatives, which are usually synthesized by the
atomꢀeconomic and simple Pudovik reaction. Inorganic and
organic bases such as potassium fluoride (KF)–alumina9,
magnesium oxide (MgO)10,sodium hydroxide (NaOH)11,
sodium carbonate (Na2CO3)12, calcium oxide (CaO)13,
butyllithium (
ꢀBuLi)14, lithium diisopropylamide (LDA)15,
nꢀ
n
ethylmagnesium bromide (C2H5MgBr)16, quinine17, and
tetramethylguanidine (TMG)18are wellꢀknown promoters of the
Pudovik reaction. However, the majority of these reactions
require equivalent or greater amounts of base, high
temperatures (60−70 °C) or microwave (MW) irradiation, and
long reaction times (several hours) to obtain good yields. HPPs
can also be synthesized using acid catalysts such as
trifluoroacetic acid/trifluoromethanesulfonic acid19, HCl20,
21
InCl3
,
Ti(Oi
Pr)22, and phosphosulfonic acid (PSA)23;
however, these methods also require high temperatures and
long reaction times because of the moistureꢀsensitivity of some
This journal is © The Royal Society of Chemistry 2013
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DOI: 10.1039/C6NJ03948K
acids. Thus, the development of a highly e cient and easily between substituted aromatic/heterocyclic aldehydes and
available catalytic system to synthesize HPPs is still desirable.
Recently, the development of environmentally benign and
diethylphosphite at room temperature.
At the outset, the reaction between benzaldehyde and
sustainable methods has received great interest in various fields diethylphosphite under neat conditions was performed without
of organic synthesis.24From the viewpoint of chemical synthesis, catalyst at room temperature for 10 h; however, no new spot
the use of ecoꢀbenign catalysts and their ready recovery are the was observed on TLC. The same reaction was continuing up to
main targets.25,26In this context, ionic liquids (ILs) as ecoꢀ 24 h, we observed in new spot along with reactant spots, and
friendly solvents and/or catalysts in chemical transformations the product was obtained in very low yield (20%). Next, the
provide
both
ecological
and
environmental reaction was carried out in the presence of an inorganic base
benefits.27,28Recently, the development of functionalized ILs catalyst such as CaCO3, Cs2CO3, LiOH•H2O, K2CO3, and KOH
with unique physicochemical properties has received significant under neat conditions, and the obtained results are summarized
attention; the introduction of acidic or basic functional groups in Table 1(entries 2–6). In all cases, acceptable yields were
results in ILs with good catalytic activity and recyclability, obtained; however, these catalytic systems have drawbacks
providing a green reaction medium for various organic including long reaction times and tedious workup procedures.
reactions.29,30 Choline hydroxide (ChOH) is a nonꢀtoxic IL with Thus, we turned our attention towards organic bases, namely 4ꢀ
a number of advantages in terms of biodegradability, low price, ethylmorpholine, pyrrolidine, piperazine, dimethyl ammonium
high water solubility, and ready availability, and exhibits good carbonate
(DMC),
4ꢀdimethylaminopyridine
(DMAP),
catalytic activity in various organic transformations.31 33ChOH tetramethylethylenediamine (TMEDA), dimethylamine (DMA),
–
shows strong basic properties and can be explored as an diꢀ
environmentally benign solvent and recyclable catalyst for the hexylamine (DHA) (Table 1, entries 7–16), with very similar
preparation of HPPs. pKa values, which were equally efficient in providing the
nꢀbutylamine (DBA), diꢀnꢀpentylamine (DPA), and diꢀnꢀ
In continuation of our ongoing research interest in the desired product
1 in good yield and short reaction time.
36
development of green methodologies,34
we report the However, these basic catalysts are not reusable and need to be
catalyst for the removed by washing with an acidic solution.
–
successful use of ChOH IL as
a
hydrophosphonylation of substituted aldehydes with
diethylphosphite (Scheme 1). The reactions were complete
within a few minutes and in high yields (90–98%) of HPPs. The
IL could be reused up to four times without an apparent
decrease in catalytic activity, and the reused catalyst did not
affect the product selectivity. To the best of our knowledge, this
is the first report on the ChOHꢀpromoted synthesis of HPPs.
Table 1. Effect of catalysts on the synthesis of compound 1under neat
conditions at room temperaturea
Catalyst amount
Yield
(%)b
20
55
75
59
50
60
89
88
82
84
81
83
85
90
88
86
nrd
nrd
82
92
93
98
98
Entry
Catalyst
Time (h)
(mol%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Catalyst free
CaCO3
Cs2CO3
LiOH·H2O
K2CO3
KOH
ꢀ
10
10
10
10
10
5
5
5
5
5
5
5
5
5
5
5
5
3
24
4
3.5
4
6
3
3
2
2
1
4ꢀEthyl morpholine
Pyrrolidine
Piperazine
DMC
DMAP
TMEDA
DMA
DBA
DPA
DHA
EDDF
EDDA
ChOH
ChOH
ChOH
ChOH
ChOH
2.5
3
30c
15c
20c
15c
4
5
12c
10c
8c
5c
5c
Scheme 1.Synthesis of a series of α-hydroxyphosphonates (1–22).
5
8
10
13
2. Results and discussion
aReactionconditions: benzaldehyde=1mmol,diethylphosphite=1 mmol, and
ChOH= 10mol%.
Reactions conducted under solventꢀfree (neat) conditions
have attracted great interest because they are ecoꢀfriendly and
costꢀeffective, and they have simple workup procedures, high
reaction rates, and high yields. With the objective to implement
the concept of green chemistry, we have been interested in the
development of organic transformations under solventꢀfree
conditions.37–39 In this context, we describe the efficacy of
ChOH in the synthesis of HPPs by a twoꢀcomponent reaction
bIsolated yield measured gravimetrically.
cReaction is complete within minutes.
dNo reaction.
In order to overcome these problems, we turned our
attention toward recyclable ILs, namely ethylenediammonium
2 | New J. Chem., 2015, 00, 1-3
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diformate (EDDF) and ethylenediammonium diacetate benzaldehydes, namelyanthraceneꢀ9ꢀcarbaldehdye and 1ꢀ
(EDDA); however, in the presence of these ILs, the reaction did pyrenecarboxaldehyde, reacted completely within 10 min
not proceed even after 3h at room temperature (entries 17–18) providing high product yields. Heterocyclic aldehydes also
owing to these catalysts are in neutral medium. At this point, in gave good results in terms of reaction rate and product yield.
view of the efficiency of the aboveꢀmentioned organic bases,
In order to evaluate the advantages of ChOH over other
we tested the applicability of the recyclable basic ChOH IL for inorganic and organic base catalysts for this re action, the
the synthesis of HPPs. Gratifyingly, the reaction proceeded developed methodology was compared with previously
smoothly, producing compound
1 in high yield within a short reported methods, and the results are tabulated in Table 3.
time (entries 19–23).To determine the optimum ChOH catalyst Kaboudin et al.10 developed a synthetic route to HPPs using
loading, the model reaction was carried out using 3, 5, 8, 10, MgO catalyst, which requires 2 h for completion. Keglevich et
and 13mol% of ChOH under neat conditions at room al.12 reported a microwaveꢀassisted method for the synthesis of
temperature, which afforded the product in 85, 95, 95, 98, and HPPs in the presence of Na2CO3; however, this catalyst is
98% yield, respectively. A further increase in the amount of active only at high temperatures (110 °C), leading to the
catalyst had no additional effect on product yield or reaction formation of by products and tedious workup procedures.
rate.
Table 3. Effect of catalysts on the synthesis of compound 1
To compare neat and solventꢀcontaining reactions, the
synthesis of
1 was performed in the presence of ChOH in
Time(min)/
Yield(%)
15/95
20/89
5/99
120/90
12/86
5/98
different solvents (Table 2). When protic solvents, i.e.,
methanol (MeOH), ethanol (EtOH), tetrahedrafuran (THF), and
water (H2O), were used, the reaction proceeded rapidly and
provided the product in acceptable yield (Table 2, entries 2–5).
However, the reactions in aprotic solvents, namely chloroform
(CHCl3), dichloromethane (CH2Cl2), 1,2ꢀdichloroethane,
toluene, and benzene, proceeded more slowly and resulted in
lower product yields (Table 2, entries 6–10).
Compd.
Catalyst (g/mol %)
Solvent
Ref
1
1
1
12
1
1
MgO (0.2g)
Neat
Neat (MW)
Neat
10
12
14
40
18
Na2CO3 (0.75 eq)
nꢀBuLi(0.1 mol%)
DEA(100 mol%)
TMG(20 mol%)
ChOH(10 mol%)
Neat
Neat
Neat
This work
Recently, Yao et al.14described the use of
n
ꢀBuLi as a
Table2. Effect of solvents on the synthesis of compound 1a
catalyst for HPPs synthesis, which resulted in good reaction
rate and product yield; however, the handling of an
organolithium reagent requires special safety precautions
because of its flammability. Moreover, when diethyl amine
(DEA) was used as a catalyst for the preparation of HPPs by
Desai et al.40stoichiometric amounts were needed to achieve
98% yield. Pollini et al.18developed a super base (TMG) for the
synthesis of HPPs at 0 °C; however, the reaction requires into
12hfor completion, and the product yield was quite low
compared to that obtained by our method. Thus, the synthesis
of HPPs using ChOH has obvious advantages compared to the
aboveꢀmentioned methods; in particular, it does not require
harsh reaction conditions, solvents, and tedious workup
procedures.
Finally, the recyclability of ChOH was examined. After
completion of the reaction (TLC), water (3 mL) was added; the
resulting product was separated using a separating funnel after
adding 10 mL of CH2Cl2, and washed with water. The aqueous
phase containing the IL was evaporated using a rotavapour to
remove water, and the obtained IL was reused without further
purification. The same procedure was repeated after each
reaction. The catalyst could be reused up to four consecutive
runs without significant loss of activity (Fig. 2).
Entry
1
2
3
4
5
6
7
8
Solvent
Solventꢀfree
MeOH
EtOH
THF
H2O
CHCl3
Time (min)
Yield (%)
5
98
85
83
79
85
65
68
71
55
50
20
22
30
25
50
52
56
50
52
CH2Cl2
1,2ꢀdichloroethane
Toluene
Benzene
9
10
aReaction conditions: Benzaldehyde = 1 mmol, diethylphosphite = 1 mmol,
and ChOH=10 mol%.
With the optimum conditions in hand (Table 1, entry 22),
we explored the scope of the reaction of various aromatic and
hetero aromatic aldehydes employing a catalytic amount of
ChOH for the synthesis of HPPs (Scheme 1). Substitution on
the aromatic ring of the aldehyde had little effect on the product
yield and reaction time. The reactions of aldehydes bearing
electronꢀdonating groups (OMe or OEt) were faster and gave
better yields than those of aldehydes with alkyl groups (Me or
iPr). Halogen substitution of aldehydes was well tolerated,
giving good yields in short reaction times; nevertheless, the
reactions of 2–Cl, 2–Br, 2–Me, and 2–OMe benzaldehydes
required a longer time for completion compared with those of
other aldehydes, because of the steric hindrance of the
substituents at the 2ꢀposition. The reactions of aldehydes
bearing an electronꢀwithdrawing nitro or fluoro substituent
were relatively slow, and the product was obtained in low yield
due to the electron deficiency. On the other hand, fused
On the basis of these results, a reaction mechanism for the
formation of HPPs in the presence of ChOH was proposed
(Scheme 2). As the initial catalyst screening showed the
importance of the hydroxyl group, we believe that the carbonyl
compounds are activated via hydrogen bonding with ChOH.41
Thus, the basic ChOH IL may influence the phosphiteꢀ
phosphonate equilibrium35 because, after hydrogen bonding
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formation, the phosphite can attack the electrophilic carbonyl
carbon to give the corresponding HPP.
The substituted benzaldehydes and diethylphosphite
(SigmaꢀAldrich Co.) were used as received. All experiments
were carried out under neat conditions; preꢀcoated silica gel
plates (Merck Chem., Germany) developed with iodine were
used for analytical TLC. Melting points determined on a digital
Stuart SMP3 apparatus (Bibby Scientific Limited,
1
Staffordshire, UK) and were uncorrected. The HNMR (400
MHz), 13C NMR (100 MHz), and 31P NMR (161.9 MHz)
spectra were recorded on a Varian INOVA 400 NMR
spectrometer at room temperature. Chemical shift values were
relative to tetramethylsilane (Me4Si). The data are presented as
follows: chemical shift (ppm), multiplicity (s = singlet, d =
doublet, t = triplet, m = multiplet, brs = broad singlet), and
coupling constant J(Hz). The FTIR spectra were recorded as
KBr discs in the range 3500–500 cm−1using a Shimadzu IR
Prestige 21 spectrometer at room temperature.
Fig. 2.Effect of ChOH recycling on the yield of HPPs.
4.2.General procedure for the preparation of ChOH.
ChOH IL was synthesized according to a literature
procedure.45Choline chloride (7 mmol) was dissolved in
methanol (15 mL), KOH (7 mmol) was added slowly at room
temperature, and the mixture was heated at reflux for 12h. After
cooling to room temperature, the reaction mixture was filtered
to remove solid KCl, concentrated to remove methanol until the
weight of the residue remained constant, and used without
further purification. Furthermore the ChOH was characterized
by using IR and NMR spectra (Fig. S1 in the Supporting
Information), and mass spectrum (Fig. S2). The NMR45and IR46
spectra show good agreement with reported results. The mass
Scheme 2. Plausible mechanism for α-hydroxyphosphonate formation in the
presence of ChOH.
The chemical structures of all HPPs were confirmed by IR,
1H NMR, 13C NMR, and 31P NMR spectroscopy. The IR
spectra of compounds 1–22 showed the expected absorption
bands at 3412–3246, 1204–1034, and 876–780 cm−1, which are
attributed to –OH, P=O, and P–C stretching vibrations,
respectively.42 In the1H NMR spectra, the P–CH proton signal
appeared as a doublet in the region of 6.60–4.79 ppm due to
coupling with the phosphorus and ethylene oxy protons43,44; the
remaining proton signals were observed in the expected
regions. In the 13C NMR spectra, a doublet in the region of
70.7–64.4 ppm (1JPC=167.1–157.8 Hz) confirmed the presence
spectrum clearly shows that the exact molecular weight of
1
ChOH. ChOH: H NMR (400 MHz, D2O):
δ
(ppm) 3.90–3.86
(m, 2H), 3.31 (t, 2H,
MHz, D2O):
J
= 5.2 Hz), 3.03 (s, 9H); 13C NMR (100
δ
(ppm)68.0, 55.6, 53.7, 53.6, 48.7.MS (FAB,
m/z): [M + H]+ calcd for C5H15NO2, 122.11; found 122.09.
4.3. General procedure for the preparation of HPPs 1–22.
of a carbon directly attached to the phosphorus atom. In the 31
P
ChOH (10 mol%) was added to a mixture of benzaldehyde
(1 mmol) and diethylphosphite (1 mmol) in a 25ꢀmL flask
equipped with a magnetic stirrer. The resulting mixture was
stirred for the appropriate time at room temperature. After
completion of the reaction (monitored by TLC), water (3 mL)
was added, and the mixture was extracted with 10 mL of ethyl
acetate. The solvent was evaporated under reduced pressure,
and the obtained residue was recrystallized from ethanol (10
mL) to yield the pure product. The same method was adopted
for the synthesis of all the targeted HPPs.
NMR spectra, a signal in the region of 21.7–18.6 ppm was
observed for all synthesized compounds. A detailed description
of the spectral data for all products (1–22) is given in the
experimental section.
3. Conclusions
We have described the use of choline hydroxide as a highly
efficient ionic liquid catalyst for the synthesis of αꢀ
hydroxyphosphonates under neat conditions at room
temperature. The ready availability of this nonꢀtoxic and
inexpensive reagent as well as the operational simplicity, good
yields, mild reaction conditions, and easy workup procedure
make this methodology an ecoꢀfriendly alternative to existing
protocols.
4.4. Spectral characterization
4.4.1. Diethyl (hydroxy(phenyl)methyl)phosphonate (1).
1
98% yield after 5 min reaction; H NMR (400 MHz, CDCl3):
δ
(ppm) 8.15 (s, 1H, −OH), 7.47–7.26 (m, 5H, Ar–H), 5.02 (d,
J
=10.8 Hz, 1H, −P–CH), 4.06–3.94 [m, 4H, −(OCH2)2], 1.24 (t,
=7.0 Hz, 3H, −CH3), 1.18 (t,
=7.0 Hz, 3H, −CH3); 13C NMR
(ppm) 136.5 (d, =1.9 Hz), 132.9, 130.0,
=3.5 Hz), 128.0 (d, =3.2 Hz), 127.0 (d, =5.9 Hz),
70.7 (d, JCP =157.8 Hz), 63.4 (d, =7.0 Hz), 63.1 (d, =7.20
J
J
4. Experimental
(100 MHz, CDCl3):
128.2 (d,
δ
J
J
J
J
4.1. General
1
J
J
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Hz), 16.3 (d,
MHz, CDCl3):
2966, 2105, 1656, 1424, 1204, 1060, 764.
4.4.2. Diethyl
chlorophenyl)(hydroxy)methyl)phosphonate (2). 92% yield
J
=4.0 Hz), 16.2 (d,
δ
J
=3.8 Hz); 31P NMR (161.9 −(OCH2)2], 1.27 (t,
J
=7.2 Hz, 3H, −CH3), 1.17 (t,
J=7.2 Hz,
(ppm) 21.7; FTIR (KBr): νmax/cmꢀ1= 3341, 3H, −CH3); 13C NMR (100 MHz, CDCl3):
δ (ppm) 163.2 (d,
1
J
=2.7 Hz), 134.4, 130.0, 125.6, 122.9, 115.1, 66.7 (d, JCP
((2- =162.1 Hz), 63.6 (d,
=1.8 Hz), 16.3 (d,
(ppm) (161.9 MHz, CDCl3):
7.74–7.32 (m, 1H, Ar–H), 7.30–7.22 (m, 2H, Ar–H), 7.21–7.18 3358, 2874, 2198, 1646, 1390, 1034, 782.
(m, 1H, Ar–H), 5.98 (s, 1H, −OH), 5.56 (d, =11.2 Hz, 1H, −P– 4.4.7. Diethyl
CH), 4.14–3.97 [m, 4H, −(OCH2)2], 1.26 (t,
−CH3), 1.18 (t,
=7.0 Hz, 3H, −CH3); 13C NMR (100 MHz, after 7 min reaction; 1H NMR(400 MHz, CDCl3):
CDCl3): (ppm) 135.0 (d, =11.7 Hz), 132.9 (d, =8.0 Hz), 7.45 (m, 1H, Ar–H), 7.21 (t, 1H, =8.4 Hz, Ar–H), 7.12–7.09
130.5, 129.4 (d, =3.0 Hz), 129.2 (d, =10.4 Hz), 126.9 (d, (m, 1H, Ar–H), 5.68 (s, 1H, –OH),5.24 (d, 1H, =17.2 Hz, –P–
=2.8 Hz), 66.8 (d, 1JCP =160.8 Hz), 63.7 (d,
=7.2 Hz), 63.2 (d, CH), 4.04–3.94 (m, 4H, –OCH2), 1.19–1.12[m, 6H,–(CH3)2];
=7.3 Hz), 16.3 (d,
J
=7.2 Hz), 63.4 (d,
J=7.1 Hz), 60.6 (d,
J
J
=5.8 Hz), 16.2 (d,
δ
(ppm) 18.9; FTIR (KBr): νmax/cmꢀ1=
J
=5.7 Hz); 31P NMR
1
after 7 min reaction; H NMR (400 MHz, CDCl3):
δ
J
((4-bromo-2-
J
=7.0 Hz, 3H, fluorophenyl)(hydroxy)methyl)phosphonate(7). 91% yield
(ppm) 7.50–
J
δ
δ
J
J
J
J
J
J
J
J
J
J
=7.3 Hz), 16.2; 31P NMR (161.9 MHz, 13CNMR (100 MHz, CDCl3):
δ(ppm)160.4, 157.9 (d,
J=6.5
CDCl3):
δ
(ppm) 18.8; FTIR (KBr): νmax/cmꢀ1= 3412, 2975, Hz), 130.2, 127.4, 124.1, 121.8, 118.2, 63.6 (d,
J
=7.2 Hz), 63.2
1
1
2246, 1632, 1516, 1062, 940, 756.
4.4.3. Diethyl
(d,
J
=7.2 Hz), 63.1 (d, JCP=165.3 Hz), 16.2 (d, JCP=5.1 Hz);
((2- 31PNMR (161.9 MHz, CDCl3):
δ(ppm)19.6;FTIR (KBr):
bromophenyl)(hydroxy)methyl)phosphonate (3). 93% yield νmax/cmꢀ1 =3356, 3135, 2975, 1465, 1296, 1046, 876.
1
after 5 min reaction; H NMR (400 MHz, CDCl3):
δ (ppm) 4.4.8. Diethyl (hydroxy(o-tolyl)methyl)phosphonate (8). 90%
1
7.71–7.34 (m, 1H, Ar–H), 7.32–7.16 (m, 1H, Ar–H), 7.15–7.12 yield after 10 min reaction; H NMR (400 MHz, CDCl3):
(m, 1H, Ar–H), 7.12–7.11 (m, 1H, Ar–H), 5.50 (d, =11.2 Hz, (ppm) 7.62–7.24 (m, 1H, Ar–H), 7.23–7.19 (m, 2H, Ar–H),
1H, −P–CH), 4.52 (s, 1H, −OH), 4.15–3.91 [m, 4H, −(OCH2)2], 7.18–7.12 (m, 1H, Ar–H), 5.25 (d, =10.8 Hz, 1H, −P–CH),
1.27 (t, =7.0 Hz, 3H, −CH3), 1.17 (t, 4.07–3.88 [m, 4H, −(OCH2)2], 3.41 (s, 1H, −OH), 2.36 (s, 3H,
=7.0 Hz, 3H, −CH3); 13
NMR (100 MHz, CDCl3): (ppm) 155.0, 136.5, 132.4, 129.4, −CH3), 1.26 (t, =7.2 Hz, 3H, −CH3), 1.18 (t, =7.0 Hz, 3H,
127.5 (d, =11.6 Hz), 123.2 (d, (ppm) 135.8 (d,
=8.8 Hz), 69.3 (d, JCP =160.6 −CH3); 13C NMR (100 MHz, CDCl3):
Hz), 63.8 (d, =7.20 Hz), 63.3 (d, =1.9 Hz), 130.2 (d, =2.3 Hz), 128.0 (d,
=7.40 Hz), 19.3, 16.2; 31P Hz), 134.8 (d,
NMR (161.9 MHz, CDCl3): (ppm) 18.7; FTIR (KBr): Hz), 127.0 (d, =4.3 Hz), 126.1 (d,
νmax/cmꢀ1= 3246, 2890, 2194, 1592, 1486, 1072, 980, 726.
=158.3 Hz), 63.4 (d, =7.1 Hz), 63.0 (d,
4.4.4. Diethyl ((3- (d,
=5.9 Hz), 16.2; 31P NMR (161.9 MHz, CDCl3):
bromophenyl)(hydroxy)methyl)phosphonate (4). 95% yield 19.3; FTIR (KBr): νmax/cmꢀ1= 3351, 2940, 2206, 1609, 1492,
after 6 min reaction; 1H NMR (400 MHz, CDCl3):
(ppm) 7.59 1105, 1040, 786.
(s, 1H, Ar–H), 7.39–7.34 (m, 2H, Ar–H), 7.16 (t, =7.8 Hz, 1H, 4.4.9.
Ar–H), 6.38 (s, 1H, −OH), 4.98 (d, =11.2 Hz, 1H, −P–CH), dimethylphenyl)(hydroxy)methyl)phosphonate (9). 92%
4.07–3.98 [m, 4H, −(OCH2)2], 1.22 (t,
=7.0 Hz, 3H, −CH3), yield after 8 min reaction; 1H NMR (400 MHz, CDCl3):
1.19 (t, (ppm) 6.98 (s, 2H, Ar–H), 6.80 (s, 1H, Ar–H), 4.83 (d, =11.6
=7.0 Hz, 3H, −CH3); 13C NMR (100 MHz, CDCl3):
(ppm) 139.1, 130.9 (d, =3.1 Hz), 129.9, 129.6 (d, =2.6 Hz), Hz, 1H, −P–CH), 3.93–3.87 [m, 4H, −(OCH2)2], 2.19 [s, 6H,
125.7 (d, =5.5 Hz), 122.2 (d,
Hz), 63.9 (d, =7.1 Hz), 63.4 (d,
NMR (161.9 MHz, CDCl3):
δ
J
J
J
J
C
δ
J
J
1
J
J
δ
J
J
=7.2
=3.2
1
J
J
J
J
J
δ
J
=3.0 Hz), 67.2 (d, JCP
J
J
=7.3 Hz), 19.5, 16.3
(ppm)
J
δ
δ
J
Diethyl
((3,5-
J
J
δ
J
δ
J
J
J
1
J
J
=2.9 Hz), 69.7 (d, JCP =159.8 −(CH3)2], 1.13 (t,
J
=6.4 Hz, 3H, −CH3), 1.10 (t,
=7.4 Hz), 16.3, 16.2; 31P −CH3); 13C NMR (100 MHz, CDCl3):
(ppm) 137.3 (d,
=3.0 Hz), 124.9 (d,
=7.0 Hz), 62.9 (d,
=3.2 Hz), 16.2 (d,
=3.1 Hz); 31P
(ppm) 19.5; FTIR (KBr):
(ppm) 7.33 νmax/cmꢀ1= 3362, 2945, 2186, 1595, 1490, 1095, 1023, 779.
=6.0 Hz, 2H, Ar–H),5.95 (s, 4.4.10. Diethyl (hydroxy(p-tolyl)methyl)phosphonate (10).
J
=6.4 Hz, 3H,
J
J
δ
J
=2.5
δ
(ppm) 18.9; FTIR (KBr): Hz), 136.8 (d, J=1.0 Hz), 129.4 (d, J
νmax/cmꢀ1= 3351, 2940, 2206, 1609, 1492, 1105, 1040, 786.
J
J
=5.8Hz), 70.4 (d, 1JCP =159.4 Hz), 63.1 (d,
J
=7.1 Hz), 21.1, 16.2 (d,
4.4.5.
Diethyl
((4-
J
J
bromophenyl)(hydroxy)methyl)phosphonate (5). 96% yield NMR (161.9 MHz, CDCl3):
after 6 min reaction; 1H NMR (400 MHz, CDCl3):
(d, =7.6 Hz, 2H, Ar–H), 7.22 (d,
1H, −OH), 4.87 (d, =12.4 Hz, 1H, −P–CH), 4.02–3.85 [m, 4H, 96% yield after 6 min reaction; H NMR (400 MHz, CDCl3):
−(OCH2)2], 1.23–1.10 [m, 6H, −(CH3)2]; 13C NMR (100 MHz, (ppm) 7.31 (s, 2H, Ar–H), 7.12 (s, 2H, Ar–H), 5.27 (s, 1H,
CDCl3): (ppm) 136.2, 131.0 (d, =2.6 Hz), 128.8 (d, =5.6 −OH), 4.95 (d, =10.0 Hz, 1H, −P–CH), 4.02–3.95 [m, 4H,
Hz), 121.6 (d, =4.2 Hz), 69.7 (d, JCP =161.4 Hz), 63.4 (d, −(OCH2)2], 2.30 (s, 3H, −CH3), 1.23–1.17 (m, 6H, −(CH3)2];
=7.1 Hz), 63.1 (d, =7.4 Hz), 16.2 (d, (ppm) 137.7 (d, =3.2 Hz),
=5.6 Hz), 16.1; 31P 13C NMR (100 MHz, CDCl3):
NMR (161.9 MHz, CDCl3): (ppm) 18.7; FTIR (KBr): 133.3, 128.9 (d, =2.1 Hz), 127.0 (d, =5.9 Hz), 70.5 (d, JCP
νmax/cmꢀ1= 3325, 2916, 2210, 1613, 1472, 1105, 1040, 756.
=158.8 Hz), 63.4 (d, =7.0 Hz), 63.1 (d, =7.3 Hz), 21.1, 16.3
4.4.6. Diethyl ((2-chloro-6- (d, =2.7 Hz), 16.2 (d,
=2.3 Hz); 31P NMR (161.9 MHz,
fluorophenyl)(hydroxy)methyl)phosphonate (6). 92% yield CDCl3):
(ppm) 19.5; FTIR (KBr): νmax/cmꢀ1= 3294, 2809,
after 8 min reaction; 1H NMR (400 MHz, CDCl3):
(ppm) 8.17 2156, 1628, 1450, 1056, 765.
(s, 1H, −OH), 7.21–7.13 (m, 2H, Ar–H), 6.99–6.94 (m, 1H, Ar– 4.4.11. Diethyl
H), 5.58 (d, =15.2 Hz, 1H, −P–CH), 4.20–3.98 [m, 4H, methoxyphenyl)methyl)phosphonate (11). 92% yield after 5
δ
δ
J
J
1
J
δ
δ
J
J
J
1
J
J
J
J
δ
J
1
δ
J
J
J
J
J
J
δ
δ
(hydroxy(2-
J
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ARTICLE
New Journal of Chemistry
DOI: 10.1039/C6NJ03948K
min reaction; 1H NMR (400 MHz, CDCl3):
δ
(ppm) 8.16 (s, 1H, 63.2 (d,
J
=7.4 Hz), 16.3 (d,
J
=2.0 Hz), 16.2 (d,
(ppm) 19.3; FTIR (KBr):
=8.0 Hz, 1H, Ar–H), νmax/cmꢀ1= 3361, 2950, 2215, 1592, 1406, 1052, 779.
=12.0 Hz, 1H, −P–CH), 4.12–3.87 [m, 4H, 4.4.16. Diethyl (hydroxy(4-
−(OCH2)2], 3.80 (s, 3H, −OCH3), 1.24 (t, =7.0 Hz, 3H, −CH3), isopropylphenyl)methyl)phosphonate (16). 97% yield after 6
1.14 (t,
=7.2 Hz, 3H, −CH3); 13C NMR (100 MHz, CDCl3):
(ppm) 156.6, 129.2, 128.6, 124.9, 127.7, 110.4 (d, =2.3 Hz),
65.2 (d, 1JCP =160.2 Hz), 63.3 (d,
=7.1 Hz), 63.0 (d, =7.0 Hz), 2H, Ar–H), 4.95 (d,
55.4, 16.3 (d, =5.9 Hz), 16.2 (d,
=5.9 Hz); 31P NMR (161.9 4H, −(OCH2)2], 2.85–2.78 [m, 1H, −(CH)], 1.19–1.11 [m, 12H,
MHz, CDCl3): (ppm) 148.5 (d,
(ppm) 19.5; FTIR (KBr): νmax/cmꢀ1= 3351, −(CH3)4]; 13C NMR (100 MHz, CDCl3):
2940, 2206, 1609, 1492, 1105, 1040, 786. =3.4 Hz), 133.9 (d, =1.5 Hz), 130.1, 127.1 (d, =6.0 Hz),
4.4.12. Diethyl =7.1 Hz), 63.2 (d, =7.4 Hz),
(ppm)
J=1.8 Hz), 14.7;
−OH), 7.51 (d,
6.94 (t, =7.6 Hz, 1H, Ar–H), 6.83 (d,
5.42 (d,
J δ
=7.6 Hz, 1H, Ar–H), 7.26–7.21 (m, 1H, Ar–H), 31P NMR (161.9 MHz, CDCl3):
J
J
J
J
1
J
δ
min reaction; H NMR (400 MHz, CDCl3):
=8.4 Hz, 2H, Ar–H), 7.28 (s, 1H, −OH), 7.11 (d,
=11.2 Hz, 1H, −P–CH), 4.10–3.95 [m,
δ
(ppm) 7.32 (d,
J
J
J
J=8.4 Hz,
J
J
J
J
δ
δ
J
J
J
J
(hydroxy(4- 70.2 (d, 1JCP =160.0 Hz), 63.5 (d,
J
methoxyphenyl)methyl)phosphonate (12). 98% yield after 6 33.7, 23.8, 16.2, 16.1; 31P NMR (161.9 MHz, CDCl3):
δ
1
min reaction; H NMR (400 MHz, CDCl3):
δ
(ppm) 7.36 (d, 19.6; FTIR (KBr): νmax/cmꢀ1= 3349, 2914, 2211, 1703, 1402,
J
=6.4 Hz, 2H, Ar–H), 6.84 (d,
J
=8.4 Hz, 2H, Ar–H), 5.73 (s, 1028, 784.
1H, −OH), 4.90 (d,
J=10.0 Hz, 1H, −P–CH), 4.03–3.91 [m, 4H, 4.4.17. Diethyl (hydroxy(2-nitrophenyl)methyl)phosphonate
1
−(OCH2)2], 3.76 (s, 3H, −OCH3), 1.23 (t,
J
=7.0 Hz, 3H, −CH3), (17). 90% yield after 10 min reaction; H NMR (400 MHz,
CDCl3): (ppm) 7.96 (d, =8.0 Hz, 2H, Ar–H), 7.65 (t, =7.8
=6.0 Hz, 1H, Ar–H), 7.45–7.40 (m, 1H, Ar–H), 6.25 (d, =14.0 Hz,
=2.3 Hz), 70.3 (d, JCP =160.3 Hz), 63.2 (d, 1H, −P–CH), 4.35 (s, 1H, −OH), 4.11–4.05 [m, 4H, −(OCH2)2],
=7.2 Hz), 55.2, 16.4 (d, =3.8 Hz), 16.2 (d, 1.23 (t, =7.0 Hz, 3H, −CH3), 1.18 (t,
=7.0 Hz, 3H, −CH3); 13
=3.8 Hz); 31P NMR (161.9 MHz, CDCl3):
(ppm) 18.7; FTIR NMR (100 MHz, CDCl3): (ppm) 147.5 (d,
(d, =3.1 Hz), 132.8 (d, =1.8 Hz), 128.9 (d,
((3,5- (d, =3.2 Hz), 124.6 (d,
dimethoxyphenyl)(hydroxy)methyl)phosphonate (13). 95% 64.2 (d, =7.2 Hz), 63.3 (d,
yield after 5 min reaction; 1H NMR (400 MHz, CDCl3): =5.7 Hz); 31P NMR (161.9 MHz, CDCl3):
(d,
(ppm) 6.55 (t, =2.2 Hz, 2H, Ar–H), 6.27 (q,
=2.0 Hz, 1H, Ar– FTIR (KBr): νmax/cmꢀ1= 3356, 2921, 2206, 1639, 1394, 1043,
H), 5.35 (s, 1H, −OH), 4.85 (d, =11.6 Hz, 1H, −P–CH), 3.96– 769.
3.92 [m, 4H, −(OCH2)2], 3.65 [s, 6H, −(OCH3)2], 1.25–1.10 [m, 4.4.18. Diethyl (hydroxy(4-nitrophenyl)methyl)phosphonate
6H, −(CH3)2]; 13C NMR (100 MHz, CDCl3): (ppm) 160.4 (d, (18). 92% yield after 8 min reaction; 1H NMR (400 MHz,
=2.4 Hz), 139.2, 105.0 (d, =5.6 Hz), 100.1 (d, =3.0 Hz), CDCl3): (ppm) 8.10 (d, =8.4 Hz, 2H, Ar–H), 7.59 (t, =9.2
70.5 (d, 1JCP =159.7 Hz), 63.3 (d,
=7.0 Hz), 63.1 (d, =7.3 Hz), Hz, 2H, Ar–H), 5.10 (d, =13.6 Hz, 1H, −P–CH), 4.70 (s, 1H,
55.1, 16.3 (d, =1.9 Hz), 16.2 (d,
=1.8 Hz);31P NMR (161.9 −OH), 4.06–3.98 [m, 4H, −(OCH2)2], 1.28–1.15 [m, 6H,
MHz, CDCl3): (ppm) 147.3 (d,
(ppm) 19.3; FTIR (KBr): νmax/cmꢀ1= 3343, −(CH3)2]; 13C NMR (100 MHz, CDCl3):
2891, 2192, 1636, 1394, 1034, 780. =5.2 Hz), 123.1 (d,
4.4.14. Diethyl =7.2 Hz), 63.3 (d,
=2.7 Hz), 69.8 (d, 1JCP =159.5 Hz), 63.8 (d,
trimethoxyphenyl)methyl)phosphonate (14). 94% yield after =7.4 Hz), 16.3 (d, =4.0 Hz), 16.2 (d,
=6.5 Hz); 31P NMR
(ppm) 19.5; FTIR (KBr): νmax/cmꢀ1=
1.17 (t,
J
=7.0 Hz, 3H, −CH3); 13C NMR (100 MHz, CDCl3):
δ
δ
J
J
(ppm) 159.4 (d,
Hz), 113.6 (d,
J
J
=2.8 Hz), 128.6 (d,
J
1
=2.0 Hz), 128.4 (d,
J
J
J
J
=7.0 Hz), 63.0 (d,
J
J
J
J
C
δ
δ
J
J
1
=6.0 Hz), 133.2
=4.5 Hz), 128.3
(KBr): νmax/cmꢀ1= 3348, 2954, 2189, 1664, 1405, 1031, 788.
J
J
J
J
4.4.13.
Diethyl
=2.5 Hz), 65.4 (d, JCP =159.5 Hz),
J
J
=7.4 Hz), 16.2 (d,
J
=5.5 Hz), 16.1
(ppm) 19.3;
δ
J
δ
J
J
J
δ
J
J
J
δ
J
J
J
J
J
J
J
δ
δ
J
J
J
=3.8 Hz), 144.7 (d, J=1.9 Hz), 127.7 (d, J
((hydroxy)(3,4,5-
J
J
J
1
5 min reaction; H NMR (400 MHz, CDCl3):
δ
(ppm) 6.59 (d, (161.9 MHz, CDCl3):
δ
J
=2.0 Hz, 2H, Ar–H), 4.80 (s, 1H, −OH), 4.79 (d,
J
=11.6 Hz, 3353, 2882, 2215, 1651, 1386, 1048, 786.
1H, −P–CH), 3.92–3.67 [m, 4H, −(OCH2)2], 3.66 [s, 9H, 4.4.19.
Diethyl
(anthracen-9-
−(OCH3)3], 1.20–1.05 [m, 6H, −(CH3)2]; 13C NMR (100 MHz, yl(hydroxy)methyl)phosphonate (19). 94% yield after 6 min
1
CDCl3):
δ
(ppm) 152.7 (d,
J
=2.7 Hz), 137.3 (d,
J
=3.7 Hz), reaction; H NMR (400 MHz, CDCl3):
δ
(ppm) 8.42 (d,
=8.4 Hz, 2H, Ar–H), 7.78 (s, 2H, Ar–
=1.8 Hz), 55.8, 16.3 (d, H), 7.50–7.41 (m, 4H, Ar–H),6.60 (d, =15.6 Hz, 1H, −P–CH),
=3.2 Hz); 31P NMR (161.9 MHz, CDCl3): 3.99–3.64 [m, 4H, −(OCH2)2], 3.39 (s, 1H, −OH), 1.14 (t,
=7.0
(ppm) 18.6; FTIR (KBr): νmax/cmꢀ1= 3349, 2861, 2168, 1667, Hz, 3H, −CH3), 0.91 (t, =7.0 Hz, 3H, −CH3); 13C NMR (100
(ppm) 134.0, 131.5 (d, =1.5 Hz), 130.3, 129.2
=4.7 Hz), 128.9, 127.1 (d, =2.7 Hz), 125.8 (d, =2.9 Hz),
=7.1 Hz), 62.9 (d,
=5.6 Hz); 31P NMR
(ppm) 21.1; FTIR (KBr): νmax/cmꢀ1=
=10.4 Hz, 1H, −P–CH), 3.98–3.91 [m, 6H, 3364, 2869, 2183, 1598, 1409, 1044, 780.
=7.0 Hz, 3H, −CH3), 1.18 (t, =7.2 Hz, 4.4.20. Diethyl (hydroxy(pyren-1-yl)methyl)phosphonate
=7.0 Hz, 3H, −CH3); 13C NMR (100 MHz, (20). 93% yield after 7 min reaction; 1H NMR (400 MHz,
=2.9 Hz), 128.5, 128.4, 114.1 (d, CDCl3): (ppm) 8.36 (dd, =8.0 Hz, 1H, Ar–H), 8.26 (d, =9.2
J=2.8
1
132.4, 104.1 (d,
J
=5.8 Hz), 70.4 (d, JCP =161.0 Hz), 63.1 (d, Hz, 2H, Ar–H), 7.96 (d,
=7.1 Hz), 63.0 (d, =7.3 Hz), 60.6 (d,
=3.2 Hz), 16.2 (d,
J
J
J
δ
J
J
J
J
J
J
1389, 1042, 790.
4.4.15.
MHz, CDCl3):
((4- (d,
δ
J
Diethyl
J
J
J
1
ethoxyphenyl)(hydroxy)methyl)phosphonate (15). 96% yield 124.8, 68.2 (d, JCP =162.5 Hz), 63.2 (d,
after 6 min reaction; 1H NMR (400 MHz, CDCl3):
(ppm) 7.30 =7.1 Hz), 16.3 (d, =5.7 Hz), 16.0 (d,
(d, =6.8 Hz, 2H, Ar–H), 6.78 (d, =8.4 Hz, 2H, Ar–H), 6.56 (s, (161.9 MHz, CDCl3):
1H, −OH), 4.90 (d,
J
δ
J
J
J
J
J
δ
J
J
J
−(OCH2)3], 1.33 (t,
3H, −CH3), 1.13 (t,
CDCl3):
J
δ
(ppm) 158.7 (d,
J
δ
J
J
1
J
=2.2 Hz), 70.0 (d, JCP =161.3 Hz), 63.5 (d,
J=7.1 Hz), 63.3, Hz, 1H, Ar–H), 8.21–8.14 (m, 3H, Ar–H),8.06–7.97 (m, 4H,
6 | New J. Chem., 2015, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 7 of 9
New Journal of Chemistry
New Journal of Chemistry
View ArticAle ROnTliInCeLE
DOI: 10.1039/C6NJ03948K
Ar–H),6.14 (d,
−(OCH2)2], 3.19 (s, 1H, −OH), 1.17 (t,
1.04 (t,
=7.0 Hz, 3H, −CH3); 13C NMR (100 MHz, CDCl3):
(ppm) 131.2, 131.1, 129.7 (d, =2.7 Hz), 128.3, 128.2, 127.6,
=2.0 Hz), 125.9,125.3, 125.2, 125.1, 125.0, 124.9 (d, 3.R. Engel, "Phosphorus Addition at sp² Carbon" Organic Reactions.
J
=11.2 Hz, 1H, −P–CH), 4.09–3.77 [m, 4H,
689–692; (h) M.I. Kabachnik and T.Y. Medved, Dokl. Akad. Nauk
SSSR 1952, 84, 717–720; (i) E.K. Fields, J. Am. Chem. Soc., 1952,74
1528–1531; (j) A.N. Pudovik and I.V. Konovalova, Synthesis,1979,
, 81–96.
J
=7.0 Hz, 3H, −CH3),
,
J
δ
J
2
127.4 (d,
J
1
J
=3.2 Hz), 124.5, 122.9, 122.8, 67.6 (d, JCP =159.9 Hz), 63.6
John wiley, New York, 2004.
(d,
J
=7.2 Hz), 63.2 (d,
J
=7.6 Hz), 16.3, 16.2; 31P NMR (161.9 4.(a) D.L. Pompliano, E. Rands, M.D. Schaber, S.D. Mosser, N.J.
(ppm) 19.8; FTIR (KBr): νmax/cmꢀ1= 3354,
MHz, CDCl3):
2876, 2216, 1628, 1393, 1029, 774.
4.4.21. Diethyl (furan-2-yl(hydroxy)methyl)phosphonate
(21). 92% yield after 4 min reaction; 1H NMR (400 MHz,
CDCl3):
δ
Anthony and J.B. Gibbs, Biochemistry, 1992, 31, 3800–3807; (b) M.
Tao, R. Bihovsky, G.J. Wells and J.P. Mallamo, J. Med. Chem.,
1998, 41, 3912–3916; (c) M.L. Peters, M. Leonard and A.A. Licata,
Cleve. Clin. J. Med., 2001, 68, 945–951; (d) R. Snoeck, A. Holý, C.
DewolfꢀPeeters, J. Van Den Oord, E. De Clercq and G. Andrei,
Antimicrob. Agents Chemother., 2002, 46, 3356–3361.
δ
(ppm) 7.32–7.31 (m, 1H, Ar–H), 6.42 (t,
J
=3.0 Hz,
1H, Ar–H), 6.27 (q,
J
=11.2 Hz, 1H, Ar–H), 4.95 (d,
J=13.6 Hz,
1H, −P–CH), 4.63 (s, 1H, −OH), 4.09–3.93 [m, 4H, −(OCH2)2], 5.(a) J.F. Dellaria Jr., R.G. Maki, H.H. Stein, J. Cohen, D. Whittern, K.
1.21 (t,
NMR (100 MHz, CDCl3):
110.5 (d, =7.6 Hz), 109.1 (d,
Hz), 63.4 (d, =6.8 Hz), 63.2 (d,
16.2; 31P NMR (161.9 MHz, CDCl3):
(KBr): νmax/cmꢀ1= 3365, 2894, 2189, 1656, 1386, 1051, 783.
4.4.22. Diethyl (hydroxy(1-phenyl-1H-pyrazol-4-
yl)methyl)phosphonate (22). 94% yield after 5 min reaction;
1H NMR (400 MHz, CDCl3):
H), 4.94 (d, =10.4 Hz, 1H, −P–CH), 4.56 (s, 1H, −OH), 4.14–
4.01 [m, 4H, −(OCH2)2], 1.34–1.20 [m, 6H, −(CH3)2]; 13C 9. F. TextierꢀBoullet and A. Foucaud, Tetrahedron Lett., 1986, 27, 3515–
NMR (100 MHz, CDCl3): (ppm) 147.5, 130.0 (d, =2.1 3516.
Hz),129.2, 128.1 (d, =6.1 Hz), 124.3, 123.2 (d, =2.3 Hz), 10. A.R. Sardarian and B. Kaboudin, Synth. Commun., 1997, 27, 543–
122.9 (d, =13.2 Hz), 70.5 (d, JCP =159.1 Hz), 63.4 (d, 551.
Hz), 63.2 (d, =7.2 Hz), 16.4 (d, =4.8 Hz), 16.2 (d, =4.9 Hz); 11. G. Keglevich, M. Sipos, D. Takacs and I. Greiner, Heteroatom Chem.,
(ppm) 19.6; FTIR (KBr):
J
=7.2 Hz, 3H, −CH3), 1.15 (t,
J
=7.2 Hz, 3H, −CH3); 13
=10.4 Hz),
C
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(ppm) 150.2, 142.5 (d,
J
1
J
J
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=7.0 Hz), 16.3 (d,
(ppm) 19.6; FTIR
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J
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δ
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J
δ
J
J
J
1
J
J=7.2
J
J
J
31P NMR (161.9 MHz, CDCl3):
δ
2007, 18, 226–229.
νmax/cmꢀ1= 3356, 2910, 2206, 1656, 1396, 1046, 788.
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This work was supported by the Basic Science Research
Program through the National Research Foundation of Korea
(2015R1D1A1A09057372). The authors also thank the BK21
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Highly efficient green synthesis of αꢀhydroxyphosphonates using recyclable
choline hydroxide catalyst
Reddi Mohan Naidu Kalla, Yu Zhang and Il Kim
Aldehydic carbonyl groups are eco-friendly and efficiently hydrophosphonylated by diethylphosphite using basic ionic liquid, choline
hydroxide.