Catalyst- and solvent-free rapid addition of secondary phosphine chalcogenides to aldehydes: Another click chemistry

Article abstract of DOI:10.1055/s-0034-1380408

Abstract An efficient catalyst- and solvent-free method for the synthesis of tertiary α-hydroxyphosphine chalcogenides, via the almost quantitative addition of secondary phosphine chalcogenides to diverse aldehydes under mild conditions (20-52 °C, from 10 min to 5 h), is reported.

Full text of DOI:10.1055/s-0034-1380408

SYNTHESIS
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
© Georg Thieme Verlag Stuttgart · New York
2015, 47, 1611–1622
paper
1611
N. K. Gusarova et al.
Paper
Synthesis
Catalyst- and Solvent-Free Rapid Addition of Secondary Phos-
phine Chalcogenides to Aldehydes: Another Click Chemistry
R1
Ch
Nina K. Gusarova
Nina I. Ivanova
R1
R1
Ch
20–52 °C
R2
P
+
R2
P
25 examples
O
R1
H
0.1–5 h
Pavel A. Volkov
OH
Kseniya O. Khrapova
Luydmila I. Larina
Vladimir I. Smirnov
Tatyana N. Borodina
Boris A. Trofimov*
96–98%
Ch = O, S, Se; R1 = Ph, Ph(CH2)2, 2-Py(CH2)2;
Ph
N
N
N
,
2 = Ph, 2-Py, 3-Py, 4-Py, 2-furyl,
,
,
R
N
N
N
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk,
Russian Federation
boris_trofimov@irioch.irk.ru
Received: 24.12.2014
Accepted after revision: 30.01.2015
Published online: 09.03.2015
aryl or hetaryl ethenes, elemental phosphorus, sulfur, or se-
lenium8) to diverse aldehydes under catalyst- and solvent-
free conditions.
DOI: 10.1055/s-0034-1380408; Art ID: ss-2014-t0773-op
Based on the examples of bis(2-phenylethyl)phoshine
oxide (1), diphenylphosphine oxide (2) and bis(2-phenyl-
ethyl)phoshine sulfide (3), we have shown that secondary
phosphine oxides and sulfides react with aldehydes 4–11
under mild conditions (r.t. or 50–52 °C, from 10 min to 3 h,
no catalyst and solvent) to give the corresponding tertiary
α-hydroxyphosphine oxides 12a–k and sulfide 12l in al-
most quantitative yields (Table 1).
Abstract An efficient catalyst- and solvent-free method for the syn-
thesis of tertiary α-hydroxyphosphine chalcogenides, via the almost
quantitative addition of secondary phosphine chalcogenides to diverse
aldehydes under mild conditions (20–52 °C, from 10 min to 5 h), is re-
ported.
Key words addition, aldehydes, green method, phosphine chalco-
genides
Previously, it has been shown that implementation of
the above reactions in the presence of organic solvents
(THF, benzene, СH2Cl2, 1,4-dioxane), with other conditions
being the same, requires a longer reaction time (up to 84
times) (Table 1). The other benefit of the solvent-free reac-
tions includes higher (in some cases) yield of the end prod-
ucts 12a–l (Table 1, entries 1, 2, 7, 8, 12).
This green solvent-free protocol is successfully expand-
ed by us over secondary phosphine sulfides 3, 13, 14 and
selenides 15, 16 as well as over other aldehyde 17. Thus, a
series of previously unknown tertiary α-hydroxyphosphine
chalcogenides 18a–m have been prepared in 96–98% yields
(Table 2).
Addition reactions remain among the most important
approaches to atom-economic syntheses of diverse organic
and elementoorganic compounds. Particular emphasis is
placed on green click methods, which are implemented un-
der mild conditions using available starting materials and
reagents without catalyst and solvent with a minimum
number of reaction steps, and efficient strategies for prod-
uct isolation and purification to ensure high yields of ad-
ducts.
Over the last decade, important examples of hydrophos-
phorylation of aldehydes with secondary phosphine ox-
ides,1 sulfides,1k,2 and selenides1k,2c,3 have been reported.
Addition of these P–H compounds across the C=O bonds
proceeds in the harmful organic solvents such as tetrahy-
drofuran,1d,e,g,m,2a 1,4-dioxane,1b,c methanol,1a benzene,1k
and dichloromethane1f,l at 20–52 °C or in the presence of
sodium carbonate under microwave activation (110 °C, 20
min)1j to afford tertiary α-hydroxyphosphine chalco-
genides. The latter can be used as ligands for the design of
metal complex catalysts,4 flame retardants for polymeric
materials,5 reagents for pulp bleach,6 as well as drug precur-
sors7 with, for example, antiviral properties.7b
In the 1Н NMR spectra of the compounds 12 and 18, the
most typical signals are those of the HОСНР=X (O, S, Se)
group. These signals are observed as a doublet at 4.4–6.3
ppm, with the coupling constants 31Р–С–1Н of 1.8–11.9 Hz.
Noteworthy, the geminal constants 31Р–С–1Н in spectra of
some α-hydroxyphosphine chalcogenides are small thus
making the splitting of proton resonance signal not always
observable.3,9 As a result, the signals of tertiary phosphine
chalcogenides may show up as a singlet. In the 13С NMR
spectra of the compounds 12 and 18, the signals of
HОСНР=X fragments appear as a typical doublet at ~63.1–
73.5 ppm with the 31Р–13С constant being equal to 42.7–
87.5 Hz.
Here we report an improved green route toward α-hy-
droxyphosphine chalcogenides via addition of available
secondary phosphine chalcogenides (easily prepared from
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Table 1 Solvent-Free Synthesis of Tertiary α-Hydroxyphosphine Chalcogenides 12a–l and Known Data for Similar Synthesis in a Solventa,b
R1
R1
X
R1
R1
X
H
20–52 °C
P
R2
R2
4–11
P
+
O
OH
12a–l
1–3
Aldehyde
Entry
Phosphine chalcogenide
Temp (°C)
20–22
Reaction timeb
Product 12
Isolated yield (%)b
O
O
P
1
3 h (84 h)1d
96 (87)1d
H
O
P
OH
H
4
1
12a
O
O
P
2 h (10 h)1c
97 (82)1c
O
P
2
50–52
H
OH
5
H
1
12b
O
H
1 h (26 h)1e
98 (98)1e
98 (99)1k
97 (92)1k
O
O
O
3
4
5
50–52
20–22
20–22
O
P
P
O
O
6
H
HO
1
12c
O
H
15 min (1.5 h)1k
O
P
P
N
7
H
HO
N
1
12d
O
H
N
30 min (2 h)1k
O
P
P
8
H
N
HO
1
12e
O
O
O
P
6
7
20–22
20–22
30 min (24 h)1l
97 (99)1l
P
H
H
OH
4
5
2
12f
O
H
O
O
15 min (50
min)1m
98 (85)1m
P
H
P
HO
2
12g
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Synthesis
Table 1 (continued)
Entry
Phosphine chalcogenide
Aldehyde
Temp (°C)
Reaction timeb
30 min (24 h)1f
Product 12
Isolated yield (%)b
O
H
O
O
O
8
20–22
20–22
20–22
20–22
98 (77)1f
P
P
P
P
P
H
O
HO
6
2
12h
O
N
N
O
H
O
9
10 min (1 h)1b
30 min (1 h)1b
45 min (1 h)1b
97 (99)1b
96 (96)1b
97 (97)1b
P
N
H
N
HO
9
2
12i
O
N
N
O
H
O
P
10
N
N
H
HO
10
2
12j
O
H
N
O
O
N
11
P
N
N
H
HO
11
2
12k
S
O
P
3 h (40 h)2a
96 (75)2a
H
S
12
50–52
P
OH
H
4
3
12l
a Standard reaction conditions: molar ratio phosphine chalcogenides 1–3/aldehydes 4–11 = 1:1, argon.
b In parentheses, literature data (reaction time and adducts yield) for the process in organic solvents (THF,1d,e,m,2a benzene,1k CH2Cl2,1f,l 1,4-dioxane1b,c) are given.
Nonequivalence of signals of two phenyl or phenylethyl
groups in the 1Н and 13С NMR spectra of phosphine chalco-
genides is caused by the presence of a chiral carbon atom in
the HОСНР=X fragment.
The structures of α-hydroxyphosphine chalcogenides
12a–l and 18a–m have been elucidated by multinuclear 1H,
13C, 15N, 31P, 77Se NMR spectroscopy and X-ray diffraction
analysis. Three crystal structures are presented here: 12l
(Figure 1), 18d (Figure 2), and 18m (Figure 3).
The α-hydroxyphosphine chalcogenides 12, 18 pre-
pared are prospective building blocks for organic synthesis.
Thus, the secondary alcohol 12d is easily (r.t., 5 h, THF) vi-
nylated by methyl propiolate in the presence of triethyl-
amine to afford the highly functionalized acrylate 19 in 88%
Figure 1 ORTEP diagram of the molecular structure of α-hydroxyphos-
phine sulfide 12l
yield (Scheme 1).
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Table 2 Solvent-Free Synthesis of New Tertiary α-Hydroxyphosphine Chalcogenides 18a–ma
R1
R1
X
R1
R1
20–52 °C
X
H
P
R2
R2
+
P
O
OH
18a–m
1, 3, 13–16
4–6, 10, 11, 17
Entry
Phosphine chalcogenide
Aldehyde
Temp (°C)
Reaction time
Product 18a–m
Isolated yield (%)
O
O
P
O
S
S
1
20–22
50–52
50–52
1.5 h
98
P
N
H
17
H
N
HO
18a
18b
18c
1
O
H
S
P
2
3 h
97
P
5
H
HO
3
O
S
P
3
3 h
97
P
O
O
H
6
H
HO
3
O
H
S
P
S
P
4
5
6
7
20–22
20–22
25 min
98
96
97
96
H
5
6
HO
13
18d
O
S
P
S
P
2 h
O
O
H
H
HO
18e
13
O
N
H
S
P
S
S
20–22
45 min
P
N
N
N
H
HO
10
11
18f
13
O
N
S
P
N
H
50–52
4 h
P
N
N
H
HO
18g
13
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Synthesis
Table 2 (continued)
Entry
Phosphine chalcogenide
Aldehyde
Temp (°C)
Reaction time
Product 18a–m
Isolated yield (%)
N
N
O
H
S
S
8
50–52
1 h
97
P
P
5
H
N
N
HO
18h
14
N
N
O
S
S
9
50–52
1 h
4 h
4 h
97
96
97
P
P
O
O
H
6
H
N
N
HO
18i
14
O
Se
H
Se
10
50–52
P
P
H
4
HO
15
18j
18k
18l
O
Se
Se
11
50–52
P
P
H
5
H
HO
15
O
Se
Se
12
50–52
5 h
97
P
P
O
O
H
6
H
HO
15
O
Se
Se
13
20–22
35 min
98
P
P
H
H
5
HO
16
18m
a Standard reaction condition: molar ratio phosphine chalcogenides 1–3, 13–16/aldehydes 4–6, 10, 11, 17 = 1:1, argon.
In summary, catalyst- and solvent-free click method for
the synthesis of α-hydroxyphosphine chalcogenides via the
atom-economic quantitative addition of secondary phos-
phine chalcogenides to diverse aldehydes under room tem-
perature or mild heating has been developed. The α-hy-
droxyphosphine chalcogenides prepared are reactive build-
ing blocks for organic synthesis, promising ligands in
transition-metal catalysis, flame retardants for polymeric
materials, and prospective precursors for design of antiviral
drugs.
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Synthesis
O
O
Et3N
+
HC
C
CO2Me
P
P
N
N
r.t., 5 h
O
OH
CO2Me
12d
19
Scheme 1 Reaction of α-hydroxyphosphine oxide 12d with methyl propiolate
Figure 2 ORTEP diagram of the molecular structure of α-hydroxyphos-
phine sulfide 18d
Figure 3 ORTEP diagram of the molecular structure of α-hydroxyphos-
phine selenide 18m
2D NMR spectra were recorded by using a standard gradient Bruker
pulse programs. HSQC spectra via double INEPT transfer in the phase-
sensitive TPPI mode with GARP decoupling during acquisition were
recorded.12 HMBC spectra were obtained with the inverse technique
and processed in the magnitude mode.13 IR spectra were recorded on
a Bruker Vertex 70 instrument. Melting points were recorded on a
Stuart melting point apparatus and are uncorrected. The microanaly-
ses were performed on a Flash EA 1112 Series elemental analyzer.
All reactions were carried out under an argon atmosphere. Commer-
cially available (Aldrich) diphenylphosphine oxide (2) and aldehydes
4–8 were used as received. Aldehydes 9–11 were prepared according
to the literature protocol.10 Diphenylphosphine sulfide (13) and di-
phenylphosphine selenide (16) were prepared by oxidation of com-
mercially available diphenylphosphine (Aldrich) with elemental sul-
fur or selenium.11 Secondary phosphine chalcogenides 1, 3, 14, and 15
were prepared from styrene or 2-vinylpyridine and elemental phos-
phorus as previously reported.8 The reaction was monitored using 31
P
X-ray Crystallographic Data14
NMR spectroscopy by the disappearance of peaks of the initial sec-
ondary phosphine chalcogenides 1–3, 13–16 (δP = 2.2–32.4) and ap-
pearance of new peaks corresponding to α-hydroxyphosphine chal-
cogenides 12a–l and 18a–m (δP = ~28–61). The 1H, 13C, 15N, 31P, and
77Se NMR spectra were recorded on Bruker DPX 400 and Bruker AV-
400 spectrometers (400.13, 100.61, 40.56, 161.98, and 76.31 MHz, re-
spectively) in CDCl3 and DMSO-d6 solutions and referenced to TMS
Data were collected on a Bruker D8 Venture Photon 100 CMOS dif-
fractometer with MoKα radiation (λ = 0.71073 Å) using the ϕ and ω
scan techniques. The structures were solved and refined by direct
methods using the SHELX.15 Data were corrected for absorption ef-
fects using the multi-scan method (SADABS). All non-hydrogen atoms
were refined anisotropically using SHELX.15 The coordinates of the
hydrogen atoms were calculated from geometrical positions (for com-
pound 18m); in all other cases a mixed method was used.
(1H NMR, 13C NMR), MeNO2
77Se NMR). The values of the δ 15N were measured through the 2D
1H-15N HMBC experiment. Coupling constants are given in hertz. All
( (
15N NMR), H3PO4 31P NMR), and Me2Se
(
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Synthesis
α-Hydroxyphosphine Chalcogenides 12a–l and 18a–m; General
Procedure
13C NMR (100.61 Hz, CDCl3): δ = 27.0 (d, 1JCP = 59.9 Hz, CH2P), 27.4 (2
d, 1JCP = 3.4 Hz, PhCH2), 67.2 (d, 1JCP = 77.6 Hz, PCH), 109.7 (d, 3JCP = 6.0
Hz, C-3, furyl), 111.1 (C-4, furyl), 126.4, 126.5 (Cp, C6H5), 128.2 (Co,
A mixture of respective secondary phosphine chalcogenide 1–3, 13–
16 (1 mmol) and the appropriate aldehyde 4–11 (1 mmol) was stirred
at 20–52 °C for 10 min to 5 h (Tables 1, 2). The residue was recrystal-
lized from hexane and dried under vacuum to afford the proper α-hy-
droxyphosphine chalcogenides 12a–l and 18a–m.
3
C6H5), 128.68, 128.7 (Cm, C6H5), 141.0 (d, JCP = 13.4 Hz, Cipso, C6H5),
3
141.3 (d, JCP = 13.4 Hz, Cipso, C6H5), 142.8 (C-5, furyl), 150.5 (C-2, fu-
ryl).
31P NMR (161.98 MHz, CDCl3): δ = 49.4.
Anal. Calcd for C21H23O3P: C, 71.17; H, 6.54; P, 8.74. Found: C, 71.08;
H, 6.51; P, 8.70.
(2E)-1-[Bis(2-phenylethyl)phosphoryl]-3-phenylprop-2-en-1-ol
(12a)
Prepared from 1 (258 mg, 1 mmol) and 4 (132 mg, 1 mmol); yield:
374 mg (96%); white powder; mp 161–162 °C (hexane).
IR (KBr): 3106 (OH), 1143 cm–1 (P=O).
[Bis(2-phenylethyl)phosphoryl](pyridin-2-yl)methanol (12d)
Prepared from 1 (258 mg, 1 mmol) and 7 (107 mg, 1 mmol); yield:
358 mg (98%); white powder; mp 106–107 °C (hexane).
1H NMR (400.13 MHz, CDCl3): δ = 1.97–2.13, 2.19–2.29 (m, 4 H, CH2P),
IR (KBr): 3140 (OH), 1146 cm–1 (P=O).
1H NMR (400.13 MHz, CDCl3): δ = 1.71–1.88 (m, 2 H, CH2P), 2.13–2.31
(m, 1 H, PhCH2), 2.35–2.42 (m, 1 H, CH2P, 1 H, PhCH2), 2.59–2.69 (m, 1
2.89–2.98, 3.00–3.05 (m, 4 H, PhCH2), 4.75 (dd, 3JНН = 6.4 Hz, 2JНP = 9.1
3
3
3
Hz, 1 Н, PCH), 6.31, 6.36 (2 dd, JНН = 15.9 Hz, JНН = 6.4 Hz, JНP = 4.0
Hz, 1 H, =CH), 6.74, 6.78 (2 d, 3JНН = 15.9 Hz, 4JНP = 3.4 Hz, 1 H, =CHPh),
2
H, CH2P), 3.05–3.12 (m, 2 H, PhCH2), 5.19 (d, JНP = 7.7 Hz, 1 Н, PCH),
3
7.15 (d, JНН = 7.3 Hz, 4 H, Ho, C6H5CH2), 7.27–7.29 (m, 9 H, Hm, Hp,
5.31 (br s, 1 H, OH), 6.99 (d, 3JНН = 7.7 Hz, 2 Ho, C6H5), 7.13–7.30 (m, 9
H, 2 Ho, 4 Hm, 2 Hp, C6H5 + 1 H, H-5, Py), 7.18–7.79 (m, 2 H, H-3,4, Py),
8.57 (d, 3JНН = 4.9 Hz, H-4, Py).
C6H5CH2, C6H5C=), 7.34 (d, 3JНН = 7.2 Hz, 2 H, Ho, C6H5C=).
13C NMR (100.61 Hz, CDCl3): δ = 26.9 (d, 1JCP = 38.5 Hz, СН2Р), 27.5 (d,
2
1JCP = 37.4 Hz, СН2Р), 27.55, 27.6 (2 d, JPC = 4.0 Hz, PhСН2), 71.3 (d,
13C NMR (100.61 Hz, CDCl3): δ = 26.4 (d, JPC = 60.0 Hz, СН2Р), 27.2,
1
2
1JCP = 76.7 Hz, PCH), 124.0 (d, JCP = 1.5 Hz, PCC=), 126.5, 126.6 (Cm,
2
1
27.4 (2 d, JPC = 3.5 Hz, PhСН2), 28.4 (d, JPC = 61.2 Hz, СН2Р), 70.4 (d,
1JPC = 74.7 Hz, PCH), 122.6 (d, 1JPC = 2.6 Hz, C-3, Py), 123.3 (d, 5JCP = 1.9
Hz, C-5, Py), 126.3, 126.4 (Cp, C6H5), 128.0, 128.1 (Co, C6H5), 128.6,
C6H5C=), 126.69, 126.7 (Co, C6H5C=), 128.1 (Cp, C6H5C=), 128.2 (Co,
3
C6H5CH2), 128.7 (Cm, C6H5CH2), 128.8 (Cp, C6H5CH2), 132.6 (d, JCP
=
10.4 Hz, PhC=), 136.2 (d, 4JCP = 2.7 Hz, Cipso, C6H5C=), 141.1, 141.7 (2 d,
3JPC = 12.5 Hz, Cipso, C6H5CH2).
4
3
128.7 (Cm, C6H5), 137.2 (d, JPC = 1.9 Hz, C-4, Py), 141.2 (d, JCP = 13.6
Hz, Cipso, C6H5), 147.9 (d, 4JCP = 1.8 Hz, C-6, Py), 154.2 (C-2, Py).
31P NMR (161.98 MHz, CDCl3): δ = 50.4.
15N NMR (40.56 MHz, CDCl3): δ = –86.9.
31P NMR (161.98 MHz, CDCl3): δ = 50.9.
Anal. Calcd for C25H27O2P: C, 76.90; H, 6.97; P, 7.93. Found: C, 76.85;
H, 6.92; P, 7.89.
Anal. Calcd for C22H24NO2P: C, 72.31; H, 6.62; N, 3.83; P, 8.48. Found:
C, 72.27; H, 6.59; N, 3.79; P, 8.44.
[Bis(2-phenylethyl)phosphoryl](phenyl)methanol (12b)
Prepared from 1 (258 mg, 1 mmol) and 5 (106 mg, 1 mmol); yield:
353 mg (97%); white powder; mp 144–145 °C (hexane).
IR (KBr): 3168 (OH), 1139 cm–1 (P=O).
[Bis(2-phenylethyl)phosphoryl](pyridin-4-yl)methanol (12e)
Prepared from 1 (258 mg, 1 mmol) and 8 (107 mg, 1 mmol); yield:
354 mg (97%); white powder; mp 153–154 °C (hexane).
IR (KBr): 3139 (OH), 1141 cm–1 (P=O).
1Н HMR (CDCl3): δ = 1.80–1.91, 1.90–2.10, 2.20–2.30 (m, 4 H, CH2P),
2.45–2.56 (m, 4 H, PhCH2), 5.05 (d, 2JНP = 11.9 Hz, 1 H, РСН), 6.00 (br s,
1 H, OH), 7.00 (d, 3JНН = 7.0 Hz, 2 Ho, C6H5), 7.12 (d, 3JНН = 7.1 Hz, 2 Ho,
C6H5), 7.13–7.39 (m, 6 H, 4 Hm, 2 Hp, C6H5), 7.40 (d, 3JНН = 3.4 Hz, 2 H,
H-3,5, Py), 8.40 (d, 3JНН = 3.4 Hz, 2 H, H-2,6 Py).
1H NMR (400.13 MHz, CDCl3): δ = 1.84–2.10 (m, 4 Н, CH2P), 2.82–2.84
2
(m, 4 Н, PhCH2), 4.14 (br s, 1 H, OH), 5.06 (d, JНP = 6.5 Hz, 1 H, PCH),
7.10 (br s, 4 H, Ho, C6H5CH2), 7.14–7.20 (m, 2 H, Hp, C6H5CH2), 7.23–
7.32 (m, 5 H, Hp, C6H5CHOH, Hm, C6H5CH2), 7.36 (dd, 3JНH = 7.4 Hz, 2 H,
Hm, C6H5CHOH), 7.44 (d, 3JНH = 7.0 Hz, 2 H, Ho, C6H5CHOH).
13C NMR (100.61 Hz, CDCl3): δ = 26.4 (d, 1JPC = 59.5 Hz, СН2Р), 26.5 (d,
1JCP = 60.4 Hz, СН2Р), 27.0 (PhСН2), 71.9 (d, 1JCP = 75.0 Hz, PCH), 125.9
(Co, C6H5CHOH), 126.0, 126.1 (Cp, C6H5CH2), 127.6, 127.7 (Co, C6H5CH2),
1
13C NMR (100.61 Hz, CDCl3): δ = 25.9 (d, JCP = 59.0 Hz, СН2Р), 27.2,
2
1
27.3 (2 d, JCP = 3.0 Hz, PhСН2), 27.4 (d, JPC = 61.2 Hz, СН2Р), 70.0 (d,
128.17–128.21 (m, Cm, Cp, C6H5CHOH, Cm, C6H5CH2), 136.7 (Cipso
,
1JCP = 76.2 Hz, PCH), 121.6 (C-3,5, Py), 126.57, 126.6 (Cp, C6H5), 128.0,
C6H5CHOH), 140.7 (d, 3JCP = 13.8 Hz, Cipso, C6H5CH2).
128.1 (Co, C6H5), 128.7, 128.8 (Cm, C6H5), 140.7 (2 d, 3JPC = 12.2 Hz, Cipso
,
31P NMR (161.98 MHz, CDCl3): δ = 50.0.
C6H5), 148.1 (C-4, Py), 149.0 (C-2,6, Py).
Anal. Calcd for C23H25O2P: C, 75.80; H, 6.91; P, 8.50. Found: C, 75.68;
H, 6.89; P, 8.44.
15N NMR (40.56 MHz, CDCl3): δ = –77.4.
31P NMR (161.98 MHz, CDCl3): δ = 51.2.
Anal. Calcd for C22H24NO2P: C, 72.31; H, 6.62; N, 3.83; P, 8.48. Found:
C, 72.29; H, 6.59; N, 3.81; P, 8.43.
[Bis(2-phenylethyl)phosphoryl](2-furyl)methanol (12c)
Prepared from 1 (258 mg, 1 mmol) and 6 (96 mg, 1 mmol); yield: 347
mg (98%); white powder; mp 83–84 °C (hexane).
IR (KBr): 3149 (OH), 1148 cm–1 (P=O).
(2E)-1-(Diphenylphosphoryl)-3-phenylprop-2-en-1-ol (12f)
Prepared from 2 (202 mg, 1 mmol) and 4 (132 mg, 1 mmol); yield:
324 mg (97%); white powder; mp 147–148 °C (hexane).
IR (KBr): 3147 (OH), 1151 cm–1 (P=O).
1H NMR (400.13 MHz, CDCl3): δ = 1.87–1.97, 2.01–2.09 (m, 4 Н, CH2P),
2.79–2.95 (m, 4 Н, PhCH2), 5.04 (br s, 1 H, OH), 5.12 (d, 2JНP = 6.6 Hz, 1
H, PCH), 6.40 (dd, 3JНН = 3.4 Hz, 3JНН = 1.8 Hz, 1 H, H-4, furyl), 6.48 (dd,
3
3JНP = 2.8 Hz, JНН = 3.4 Hz, 1 H, H-3, furyl), 7.10–7.30 (m, 10 H, 2 ×
C6H5), 7.42 (dd, 3JНН = 1.8 Hz, 5JPН = 3.9 Hz, 1 H, H-5, furyl).
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1H NMR (400.13 MHz, CDCl3): δ = 5.22 (dd, 3JНН = 6.2 Hz, 2JНP = 9.0 Hz,
1 Н, PCH), 6.29, 6.33 (2 dd, 3JНН = 15.8 Hz, 3JНН = 6.2 Hz, 3JНP = 5.1 Hz, 1
H, =CH), 6.39 (br s, 1 H, OH), 6.52, 6.57 (2 d, JНН = 15.8 Hz, JНP = 4.2
Hz, 1 H, =CHPh), 7.18–7.19 (m, 15 H, 3 × C6H5).
1H NMR (400.13 MHz, CDCl3): δ = 1.34 (t, JНН = 7.3 Hz, 3 H, CH3),
2
4.08–4.20 (m, 2 H, NCH2), 5.67 (d, JНP = 5.4 Hz, 1 Н, PCH), 6.82 (d,
3JНН = 1.1 Hz, 1 H, H-4, imidazolyl), 6.86 (d, 3JНН = 1.1 Hz, 5JНP = 1.5 Hz,
3
4
3
5
1 H, H-5, imidazolyl), 7.35 (dt, JНН = 7.6 Hz, JНP = 2.6 Hz, 2 H, Hp,
C6H5), 7.42–7.55 (m, 4 H, Hm, C6H5), 7.62 (dd, 3JНН = 7.7 Hz, 3JНP = 11.1
Hz, 2 H, Ho, C6H5), 7.93 (dd, 3JНН = 7.7 Hz, 3JНP = 11.1 Hz, 2 H, Ho, C6H5).
13C NMR (100.61 Hz, CDCl3): δ = 15.8 (CH3), 41.5 (NCH2), 67.7 (d, 1JCP
84.5 Hz, PCH), 120.3 (C-5, imidazolyl), 127.2 (C-4, imidazolyl), 128.0,
1
13C NMR (100.61 Hz, CDCl3): δ = 71.4 (d, JPC = 87.5 Hz, PCH), 125.9
3
(PCHC=), 126.2 (Cm, C6H5C=), 127.7 (Cp, C6H5C=), 128.3 (d, JCP = 11.2
Hz, Cm, C6H5P), 128.5 (d, 3JPC = 10.8 Hz, Cm, C6H5P), 131.3 (Co, C6H5C=),
=
131.7 (d, 2JCP = 8.2 Hz, Co, C6H5P), 132.0 (d, 3JCP = 10.3 Hz, PhC=), 132.1
1
3
1
(m, Co, Cp, C6H5P), 132.7 (d, JCP = 92.7 Hz, Cipso, C6H5P), 136.3 (Cipso
,
128.4 (2 d, JCP = 11.6 Hz, Cm, C6H5), 129.5, 131.0 (2 d, JCP = 96.1 Hz,
C6H5C=).
C
ipso, C6H5), 131.7, 132.2 (2 d, 2JCP = 9.1 Hz, Co, C6H5), 132.0 (d, 1JCP = 1.7
Hz, Cp, C6H5), 142.8 (C-2, imidazolyl).
31P NMR (161.98 MHz, CDCl3): δ = 29.1.
15N NMR (40.56 MHz, CDCl3): δ = –204.1 (N-1), –128.8 (N-3).
31P NMR (161.98 MHz, CDCl3): δ = 31.6.
Anal. Calcd for C21H19O2P: C, 75.44; H, 5.73; P, 9.26. Found: C, 75.29;
H, 5.69; P, 9.19.
Anal. Calcd for C18H19N2O2P: C, 66.25; H, 5.87; N, 8.58; P, 9.49. Found:
C, 66.21; H, 5.86; N, 8.57; P, 9.45.
(Diphenylphosphoryl)(phenyl)methanol (12g)
Prepared from 2 (202 mg, 1 mmol) and 5 (106 mg, 1 mmol); yield:
302 mg (98%); white powder; mp 152–153 °C (hexane).
(Diphenylphosphoryl)(1-vinyl-1H-imidazol-2-yl)methanol (12j)
IR (KBr): 3182 (OH), 1163 cm–1 (P=O).
Prepared from 2 (202 mg, 1 mmol) and 10 (122 mg, 1 mmol); yield:
311 mg (96%); yellow powder; mp 145–146 °C (hexane).
IR (KBr): 2690 (OH), 1204 cm–1 (P=O).
1H NMR (400.13 MHz, CDCl3): δ = 5.42 (d, 2JPН = 8.9 Hz, 1 H, PCH), 6.24
(br s, 1 H, OH), 7.12–7.17 (m, 5 H, C6H5CHOH), 7.32–7.38, 7.43–7.45
(m, 6 H, 4 Hm, 2 Hp, C6H5P), 7.73, 7.80 (2 dd, JНН = 7.9 Hz, JPН = 11.0
3
3
3
1H NMR (400.13 MHz, CDCl3): δ = 4.86 (d, JНH = 8.4 Hz, 1 Н, =CH2),
Hz, 4 H, Ho, C6H5P).
5.16 (d, 3JНH = 15.4 Hz, 1 Н, =CH2), 5.69 (d, 2JНP = 5.3 Hz, 1 H, PCH), 6.83
(s, 1 H, H-4, imidazolyl), 7.18 (s, 1 H, H-5, imidazolyl), 7.37–7.54 (m, 7
H, 4 Hm, 2 Hp, C6H5 + 1 H, =CH), 7.65 (dd, 3JНН = 8.6 Hz, 3JНP = 11.9 Hz, 2
H, Ho, C6H5), 7.91 (dd, 3JНН = 8.6 Hz, 3JНP = 12.0 Hz, 2 H, Ho, C6H5).
1
13C NMR (100.61 Hz, CDCl3): δ = 72.5 (d, JCP = 86.2 Hz, PCH), 127.1
(Cm, C6H5CHOH), 127.1 (Cp, C6H5CHOH), 127.2 (Co, C6H5CHOH), 127.5
(d, 3JCP = 11.6 Hz, Cm, C6H5P), 127.8 (d, 3JPC = 11.2 Hz, Cm, C6H5P), 129.4
1
(d, JCP = 95.7 Hz, Cipso, C6H5P), 131.2 (Cp, C6H5P), 131.3 (Cp, C6H5P),
1
13C NMR (100.61 Hz, CDCl3): δ = 63.2 (d, JCP = 83.6 Hz, PCH), 98.2
2
2
131.3 (d, JCP = 8.6 Hz, Co, C6H5P), 131.9 (d, JCP = 8.6 Hz, Co, C6H5P),
(=CH2), 112.64 (C-5, imidazolyl), 123.3 (C-4, imidazolyl), 123.4 (d,
1JCP= 12.1 Hz, Cm, C6H5), 123.7 (d, 1JCP = 11.6 Hz, Cm, C6H5), 124.0 (d, 1JCP
= 97.8 Hz, Cipso, C6H5), 125.1 (CH=), 125.7 (d, 1JCP = 97.0 Hz, Cipso, C6H5),
132.0 (d, 1JCP = 95.7 Hz, Cipso, C6H5P), 137.2 (Cipso, C6H5CHOH).
31P NMR (161.98 MHz, CDCl3): δ = 28.6.
1
126.9 (d, JCP = 9.0 Hz, Co, C6H5), 127.4–127.5 (m, Co, Cp, C6H5), 138.3
Anal. Calcd for C19H17O2P: C, 74.02; H, 5.56; P, 10.05. Found: C, 73.97;
H, 5.53; P, 9.98.
(C-2, imidazolyl).
15N NMR (40.56 MHz, CDCl3): δ = –197.1 (N-1), –124.1 (N-3).
31P NMR (161.98 MHz, CDCl3): δ = 31.6.
(Diphenylphosphoryl)(2-furyl)methanol (12h)
Prepared from 2 (202 mg, 1 mmol) and 6 (96 mg, 1 mmol); yield: 292
mg (98%); yellow powder; mp 156–157 °C (hexane).
IR (KBr): 3149 (OH), 1150 cm–1 (P=O).
Anal. Calcd for C18H17N2O2P: C, 66.66; H, 5.28; N, 8.64; P, 9.55. Found:
C, 66.62; H, 5.27; N, 8.64; P, 9.52.
2
1H NMR (400.13 MHz, CDCl3): δ = 4.98 (br s, 1 H, OH), 5.50 (d, JHP
=
(Diphenylphosphoryl)(1-vinyl-1H-benzimidazol-2-yl)methanol
(12k)
5.6 Hz, 1 H, PCH), 6.21 (dd, 3JHH = 3.6 Hz, 3JHH = 1.7 Hz, 1 H, H-4, furyl),
6.28 (dd, 3JHH = 3.6 Hz, 4JHP = 2.7 Hz, 1 H, H-3, furyl), 7.23 (dd, 5JНP = 3.2
Prepared from 2 (202 mg, 1 mmol) and 11 (172 mg, 1 mmol); yield:
363 mg (97%); yellow powder; mp 184–185 °C (hexane).
IR (KBr): 3130 (OH), 1190 cm–1 (P=O).
Hz, 3JНH = 1.7 Hz, 1 H, H-5, furyl), 7.38, 7.45 (2 ddd, 3JHH = 7.8 Hz, 3JHH
=
7.6 Hz, 3JHH = 2.8 Hz, 4 H, Hm, C6H5), 7.48, 7.55 (2 t, 3JHH = 7.6 Hz, 2 H,
Hp, C6H5), 7.66, 7.80 (2 dd, 3JHH = 7.8 Hz, 3JHP = 10.4 Hz, 4 H, Ho, C6H5).
1H NMR (400.13 MHz, DMSO-d6): δ = 5.14 (d, 3JНH = 9.1 Hz, 1 Н, =CH2),
13C NMR (100.61 Hz, DMSO-d6): δ = 67.5 (d, 1JCP = 83.6 Hz, PCH), 109.0
5.57 (d, 3JНH = 16.1 Hz, 1 Н, =CH2), 6.12 (dd, 3JНН = 5.3 Hz, 2JНP = 8.2 Hz,
(d, 3JCP = 4.7 Hz, C-3, furyl), 110.2 (C-4, furyl), 127.6, 127.8 (2 d, 1JPC
=
=
3
3
1 H, PCH), 6.98 (dd, JНН = 5.3 Hz, JНP = 15.8 Hz, 1 H, OH), 7.22 (dd,
3JНН = 7.5 Hz, 3JНН = 8.8 Hz, 1 Harom, H-5), 7.29 (dd, 3JНН = 7.8 Hz, 3JНН
1
2
11.0 Hz, Cm, C6H5), 129.9 (d, JCP = 96.1 Hz, Cipso, C6H5), 131.2 (d, JCP
=
4
8.6 Hz, Co, C6H5), 131.3, 131.4 (2 d, JPC = 2.6 Hz, Cp, C6H5), 131.6 (d,
8.8 Hz, 1 Harom, H-6), 7.47–7.60 (m, 8 H, 4 Hm, 2 Hp, C6H5, + 1 Harom, H-
1JCP = 96.1 Hz, Cipso, C6H5), 131.8 (d, 2JCP = 8.6 Hz, Co, C6H5).
3
4, + 1 H, =CH), 7.71 (d, JНH = 7.8 Hz, 1 Harom, H-7), 7.82, 7.90 (2 ddd,
31P NMR (161.98 MHz, DMSO-d6 + CDCl3): δ = 31.1.
3JНН = 8.6 Hz, 3JНP = 11.6 Hz, 4 H, Ho, C6H5).
1
Anal. Calcd for C17H15O3P: C, 68.45; H, 5.07; P, 10.38. Found: C, 68.41;
H, 5.05; P, 10.34.
13C NMR (100.61 Hz, CDCl3): δ = 68.0 (d, JPC = 81.0 Hz, PCH), 109.9
(=CH2), 111.8 (C-7, Ar), 119.6 (C-4, Ar), 123.2 (C-5, Ar), 123.9 (C-6, Ar),
128.3, 128.8 (2 d, 3JCP = 12.1 Hz, Cm, C6H5), 128.6 (d, 1JCP = 91.4 Hz, Cipso
,
C6H5), 129.7 (CH=), 130.8 (d, 1JCP = 96.9 Hz, Cipso, C6H5), 131.9 (d, 2JCP
=
(Diphenylphosphoryl)(1-ethyl-1H-imidazol-2-yl)methanol (12i)
4
9.1 Hz, Co, C6H5), 132.3 (d, JCP = 2.6 Hz, Co, C6H5), 132.6 (Cp, C6H5),
132.7 (d, 2JCP = 9.1 Hz, Co, C6H5), 134.8 (C-9, Ar), 141.9 (C-8, Ar), 150.0
(C=N).
15N NMR (40.56 MHz, CDCl3): δ = –216.8 (N-1), –138.4 (N-3).
31P NMR (161.98 MHz, DMSO-d6): δ = 32.4.
Prepared from 2 (202 mg, 1 mmol) and 9 (124 mg, 1 mmol); yield:
316 mg (97%); white powder; mp 138–139 °C (hexane).
IR (KBr): 2634 (OH), 1194 cm–1 (P=O).
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Anal. Calcd for C22H19N2O2P: C, 70.58; H, 5.12; N, 7.48; P, 8.27. Found:
C, 70.55; H, 5.10; N, 7.49; P, 8.24.
C6H5CH2), 128.81 (d, JCP = 2.6 Hz, Cm, C6H5CHOH), 128.82 (Co,
C6H5CH2), 128.9 (d, 5JCP = 3.0 Hz, Cp, C6H5CHOH), 136.2 (d, 2JCP = 2.2 Hz,
C
3
3
ipso, C6H5CHOH), 140.6, 140.7 (2 d, JCP = 13.8 Hz, JPC = 14.7 Hz, Cipso,
C6H5CH2).
(2E)-1-[Bis(2-phenylethyl)phosphorothioyl]-3-phenylprop-2-en-
31P NMR (161.98 MHz, CDCl3): δ = 59.3.
1-ol (12l)
Prepared from 3 (274 mg, 1 mmol) and 4 (132 mg, 1 mmol); yield:
390 mg (96%); yellow powder; mp 126–127 °C (hexane).
IR (KBr): 3271 (OH), 599 cm–1 (P=S).
Anal. Calcd for C23H25OPS: C, 72.60; H, 6.62; P, 8.14; S, 8.43. Found: C,
72.57; H, 6.61; P, 8.09; S, 8.42.
1H NMR (400.13 MHz, CDCl3): δ = 1.97–2.07, 2.09–2.27 (m, 4 H, CH2P),
[Bis(2-phenylethyl)phosphorothioyl](2-furyl)methanol (18c)
2.91–3.02 (m, 4 H, PhCH2), 4.46 (ddd, 3JНН = 6.8 Hz, 3JНН = 1.3 Hz, 2JНP
=
Prepared from 3 (274 mg, 1 mmol) and 6 (96 mg, 1 mmol); yield: 359
3.1 Hz, 1 Н, PCH), 6.24 (ddd, 3JНН = 15.8 Hz, 3JНН = 6.8 Hz, 3JНP = 4.2 Hz,
1 H, =CH), 6.69 (dd, 3JНН = 15.8 Hz, 4JНP = 4.2 Hz, 1 H, =CHPh), 7.13 (d,
3JНН = 7.1 Hz, 2 H, Ho, C6H5CH2), 7.27–7.29 (m, 13 H, 4 H, Ho, 6 H, Hm, 3
H, Hp, C6H5CH2, C6H5C=).
mg (97%); white powder; mp 87–88 °C (hexane).
IR (KBr): 3213 (OH), 604 cm–1 (P=S).
1H NMR (400.13 MHz, CDCl3): δ = 1.82–1.92, 1.96–2.07, 2.11–2.28 (m,
4 Н, CH2P), 2.68–2.81, 2.91–2.91 (m, 4 Н, PhCH2), 3.66 (br s, 1 H, OH),
4.89 (s, 1 H, PCH), 6.41 (dd, 3JНН = 3.4 Hz, 3JНН = 1.8 Hz, 1 H, H-4, furyl),
6.46 (dd, 3JНP = 4.2 Hz, 3JНН = 3.4 Hz, 1 H, H-3, furyl), 7.07 (d, 3JНН = 7.5
Hz, 2 H, Ho, C6H5), 7.12–7.30 (m, 8 H, 2 H, Ho, 4 H, Hm, 2 H, Hp, C6H5),
7.42 (dd, 3JНН = 1.8 Hz, 5JPН = 2.9 Hz, 1 H, H-5, furyl).
13C NMR (100.61 Hz, CDCl3): δ = 28.5, 28.6 (2 d, 2JCP = 3.0 Hz, PhСН2),
29.6, 30.0 (2 d, 1JCP = 44.8 Hz, СН2Р), 72.3 (d, 1JCP = 54.3 Hz, PCH), 123.1
2
(d, JCP = 3.5 Hz, PCHC=), 126.6 (Cp, PhC=), 126.81–126.83 (m, Co, Cm,
C6H5C=), 128.35, 128.4 (Cm, C6H5CH2), 128.5 (Cp, C6H5CH2), 128.78,
3
4
128.8 (Co, C6H5CH2), 133.7 (d, JCP = 11.2 Hz, C6H5C=), 135.8 (d, JCP
=
13C NMR (100.61 Hz, CDCl3): δ = 28.3, 28.4 (2 d, 2JCP = 3.0 Hz, PhCH2),
2.6 Hz, Cipso, C6H5C=), 140.7 (dd, 3JCP = 13.4 Hz, Cipso, C6H5CH2).
29.8, 30.8 (2 d, 2JCP = 44.4 Hz, CH2P), 67.3 (d, 1JCP = 53.5 Hz, PCH), 109.2
31P NMR (161.98 MHz, CDCl3): δ = 57.9.
3
4
(d, JCP = 6.0 Hz, C-3, furyl), 111.2 (d, JCP = 2.2 Hz, C-4, furyl), 126.3,
126.5 (Cp, C6H5), 128.2, 128.4 (Co, C6H5), 128.6, 128.8 (Cm, C6H5), 140.5
(d, 3JCP = 13.8 Hz, Cipso, C6H5), 140.7 (d, 3JCP = 14.7 Hz, Cipso, C6H5), 143.0
(d, 1JCP = 2.6 Hz, C-5, furyl), 149.5 (d, 1JCP = 3.0 Hz, C-2, furyl).
Anal. Calcd for C25H27OPS: C, 73.86; H, 6.69; P, 7.62; S, 7.89. Found: C,
73.42; H, 6.61; P, 6.99; S, 7.79.
31P NMR (161.98 MHz, CDCl3): δ = 59.6.
[Bis(2-phenylethyl)phosphoryl](pyridin-3-yl)methanol (18a)
Prepared from 1 (258 mg, 1 mmol) and 17 (107 mg, 1 mmol); yield:
358 mg (98%); white powder; mp 101–102 °C (hexane).
IR (KBr): 3139 (OH), 1140 cm–1 (P=O).
Anal. Calcd for C21H23O2PS: C, 68.09; H, 6.26; P, 8.36; S, 8.66. Found: C,
68.08; H, 6.25; P, 8.33; S, 8.65.
(Diphenylphosphorothioyl)(phenyl)methanol (18d)16
1H NMR (400.13 MHz, CDCl3): δ = 1.89–1.99 (m, 4 Н, CH2P), 2.09–2.19
2
(m, 4 Н, PhCH2), 5.06 (d, JНP = 8.2 Hz, 1 Н, PCH), 7.05, 7.10 (2 d,
Prepared from 13 (218 mg, 1 mmol) and 5 (106 mg, 1 mmol); yield:
318 mg (98%); white powder; mp 120–121 °C (hexane).
IR (KBr): 3289 (OH), 596 cm–1 (P=S).
3JНН =7.8 Hz, 4 H, Ho, C6H5), 7.17–7.26 (m, 6 H, Hm, Hp, C6H5), 7.84 (d,
3JНН = 7.6 Hz, 1 H, H-4, Py), 8.48 (d, 3JНН = 3.4 Hz, 1 H, H-6, Py), 8.63 (H-
2, Py).
1H NMR (400.13 MHz, CDCl3): δ = 3.67 (br s, 1 H, OH), 5.53 (s, 1 H,
PCH), 7.04 (d, 3JНН = 7.6 Hz, 2 H, Hо, C6H5CHOH), 7.08 (dd, 3JНН = 7.8 Hz,
13C NMR (100.61 Hz, CDCl3): δ = 25.8 (d, 1JCP = 59.6 Hz, СН2Р), 27.4 (d,
1JCP = 60.9 Hz, СН2Р), 27.5 (PhСН2), 69.1 (d, 1JCP = 78.1 Hz, PCH), 123.4
(С-5, Py), 126.5, 126.6 (Сp, C6H5), 128.0, 128.1 (Сo, C6H5), 128.7 (Сm,
C6H5), 133.9 (С-6, Py), 134.8 (С-1, Py), 140.7, 140.8 (2 d, 3JCP = 9.4 Hz,
3
3JНН = 7.6 Hz, 2 H, Hm, C6H5CHOH), 7.16 (t, JНН = 7.6 Hz, 1 H, Hp,
3
C6H5CHOH), 7.23–7.27 (m, 2 H, Hm, C6H5P), 7.39 (t, JНН = 7.7 Hz, 1 H,
Hp, C6H5P), 7.43–7.50 (m, 4H, 2 H, Ho, 2 H, Hm, C6H5P), 7.54 (t, 3JНН = 7.7
С
ipso, C6H5), 147.4 (С-2, Py), 148.7 (C-4, Py).
3
3
Hz, 1 H, Hp, C6H5P), 7.90 (dd, JНН = 7.5 Hz, JНP = 12.3 Hz, 2 H, Ho,
15N NMR (40.56 MHz, CDCl3): δ = –73.4.
31P NMR (161.98 MHz, CDCl3): δ = 51.4.
C6H5P).
13C NMR (100.61 Hz, CDCl3): δ = 73.5 (d, 1JCP = 54.3 Hz, PCH), 127.5 (d,
4
3JCP = 4.7 Hz, Co, C6H5CHOH), 127.7 (d, JCP = 2.6 Hz, Cm, C6H5CHOH),
Anal. Calcd for C22H24NO2P: C, 72.31; H, 6.62; N, 3.83; P, 8.48. Found:
C, 72.27; H, 6.60; N, 3.82; P, 8.45.
3
5
128.2 (d, JCP = 12.1 Hz, Cm, C6H5P), 128.3 (d, JCP = 3.4 Hz, Cp,
C6H5CHOH), 128.8 (d, 3JCP = 12.1 Hz, Cm, C6H5P), 129.4 (d, 1JCP = 76.3 Hz,
C
ipso, C6H5P), 130.6 (d, 1JCP = 76.7 Hz, Cipso, C6H5P), 131.2, 132.3 (d, 2JCP
=
[Bis(2-phenylethyl)phosphorothioyl](phenyl)methanol (18b)
2
9.5 Hz, Co, C6H5P), 132.7 (d, JCP = 9.9 Hz, Co, C6H5P), 135.8 (Cipso
,
Prepared from 3 (274 mg, 1 mmol) and 5 (106 mg, 1 mmol); yield:
369 mg (97%); white powder; mp 111–112 °C (hexane).
IR (KBr): 3305 (OH), 592 cm–1 (P=S).
C6H5CHOH).
31P NMR (161.98 MHz, CDCl3): δ = 53.0.
Anal. Calcd for C19H17OPS: C, 70.35; H, 5.28; P, 9.55; S, 9.89. Found: C,
70.31; H, 5.27; P, 9.52; S, 9.87.
1H NMR (400.13 MHz, CDCl3): δ = 1.69–1.79, 1.88–1.96, 2.04–2.23 (m,
4 H, CH2P), 2.59–2.62, 2.71–2.73, 2.91–2.98 (m, 4 H, PhCH2), 3.76 (br s,
1 H, OH), 4.87 (s, 1 Н, PCH), 7.00 (d, 3JНН = 7.5 Hz, 2 H, Ho, C6H5CHOH),
(Diphenylphosphorothioyl)(2-furyl)methanol (18e)
7.15–7.22 (m, 4 H, Hm, 2 H, Hp, C6H5CH2), 7.28 (dd, 3JНН = 8.9 Hz, 3JНН
=
Prepared from 13 (218 mg, 1 mmol) and 6 (96 mg, 1 mmol); yield:
301 mg (96%); yellow powder; mp 100–101 °C (hexane).
IR (KBr): 3272 (OH), 595 cm–1 (P=S).
7.5 Hz, 2 H, Hm, C6H5CHOH), 7.33–7.39 (m, 4 H, Ho, C6H5CH2, 1 H, Hp,
C6H5CHOH).
13C NMR (100.61 Hz, CDCl3): δ = 28.4, 28.6 (2 d, 2JPC = 3.0 Hz, PhСН2),
29.2, 30.4 (d, 1JCP = 44.4 Hz, СН2Р), 72.7 (d, 1JCP = 49.6 Hz, PCH), 126.5
1H NMR (400.13 MHz, CDCl3): δ = 4.01 (br s, 1 H, OH), 5.56 (s, 1 H,
3
3
3
(Cp, C6H5CH2), 126.69 (d, JCP = 4.7 Hz, Co, C6H5CHOH), 126.7 (Cp,
PCH), 6.19 (dd, JНН = 3.4 Hz, JНН = 1.8 Hz, 1 H, H-4, furyl), 6.24 (dd,
C6H5CH2), 128.2 (Cm, C6H5CH2), 128.4 (Cm, C6H5CH2), 128.7 (Co,
3JНН = 3.4 Hz, 3JНН = 2.7 Hz, 1 H, H-3, furyl), 7.14 (d, 3JНН = 1.8 Hz, 1 H,
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H-5, furyl), 7.34 (ddd, 3JНН = 7.6 Hz, 5JНP = 3.9 Hz, 2 H, Hp, C6H5), 7.42–
7.55 (m, 4 H, Hm, C6H5), 7.61 (dt, 3JНН = 7.2 Hz, 2JНP = 11.9 Hz, 2 H, Ho,
C6H5), 7.90 (dt, 3JНН = 7.2 Hz, 2JНP = 11.9 Hz, 2 H, Ho, C6H5).
[Bis(2-pyridin-2-ylethyl)phosphorothioyl](phenyl)methanol (18h)
Prepared from 14 (276 mg, 1 mmol) and 5 (106 mg, 1 mmol); yield:
371 mg (97%); white powder; mp 110–111 °C (hexane).
13C NMR (100.61 Hz, CDCl3): δ = 68.1 (d, 1JCP = 59.9 Hz, PCH), 109.8 (d,
3JCP = 5.2 Hz, C-3, furyl), 110.8 (d, 4JCP = 1.7 Hz, C-4, furyl), 126.9, 128.4
(2 d, 1JCP = 12.1 Hz, Cо, C6H5), 129.4 (d, 1JCP = 79.7 Hz, Cipso, C6H5), 130.6
IR (KBr): 3200 (OH), 614 cm–1 (P=S).
1H NMR (400.13 MHz, CDCl3): δ = 2.09–2.27, 2.60–2.68, 2.69–2.77 (m,
4 Н, PyCH2), 2.89–2.99, 3.13–3.24, 3.26–3.37 (m, 4 Н, CH2P), 4.03 (br s,
(d, 1JCP = 78.4 Hz, Cipso, C6H5), 132.0–132.4 (Cm, Cp, C6H5), 142.5 (d, 4JCP
=
3
1 H, OH), 5.05 (s, 1 Н, PCH), 7.05 (d, JНН = 7.9 Hz, 1 H, H-3, Py), 7.10
2.6 Hz, C-5, furyl), 149.6 (C-2, furyl).
31P NMR (161.98 MHz, CDCl3): δ = 51.2.
3
3
3
(dd, JНН = 7.6 Hz, JНН = 5.3 Hz, 1 H, H-4, Py), 7.18 (dd, JНН = 7.6 Hz,
3JНН = 5.3 Hz, 1 H, H-4, Py), 7.24 (d, 3JНН = 7.9 Hz, 1 H, H-3, Py), 7.28–
7.35 (m, 3 H, Hm, Hp, C6H5CHOH), 7.56 (m, 3 H, 1 H, H-5, Py, 2 H, Ho,
Anal. Calcd for C17H15O2PS: C, 64.96; H, 4.81; P, 9.85; S, 10.20. Found:
C, 64.93; H, 4.79; P, 9.81; S, 10.18.
3
3
C6H5CHOH), 7.66 (dd, JНН = 7.9 Hz, JНН = 7.6 Hz, 1 H, H-5, Py), 8.47
(m, 2 H, H-6, Py).
(Diphenylphosphorothioyl)(1-vinyl-1H-imidazol-2-yl)methanol
(18f)
13C NMR (100.61 Hz, CDCl3): δ = 24.8 (d, 1JCP = 47.0 Hz, CH2P), 25.9 (d,
1JCP = 47.0 Hz, CH2P), 29.0 (PyCH2), 29.8 (d, 1JCP = 2.6 Hz, PyCH2), 73.3
1
(d, JCP = 56.5 Hz, PCH), 121.0, 121.3 (C-5, Py), 122.1, 122.4 (C-3, Py),
Prepared from 13 (218 mg, 1 mmol) and 10 (122 mg, 1 mmol); yield:
330 mg (97%); yellow powder; mp 128–129 °C (hexane).
IR (KBr): 2685 (OH), 613 cm–1 (P=S).
3
4
126.6 (d, JCP = 3.4 Hz, Co, C6H5CHOH), 127.3 (d, JCP = 2.6 Hz, Cm,
3
C6H5CHOH), 127.4 (d, JCP = 3.0 Hz, Cp, C6H5CHOH), 135.6 (Cipso
,
C6H5CHOH), 136.1, 136.6 (C-4, Py), 148.0, 148.6 (C-6, Py), 159.6 (d,
1H NMR (400.13 MHz, DMSO-d6): δ = 4.71 (d, 3JНH = 8.8 Hz, 1 Н, =CH2),
3JCP = 10.8 Hz, C-2, Py), 159.8 (d, 3JCP = 14.2 Hz, C-2, Py).
5.30 (d, 3JНH = 15.7 Hz, 1 Н, =CH2), 6.16 (dd, 3JНН = 5.3 Hz, 2JНP = 6.7 Hz,
15N NMR (40.56 MHz, CDCl3): δ = –65.9.
31P NMR (161.98 MHz, CDCl3): δ = 61.0.
1 H, PCH), 6.85 (s, 1 H, H-4, imidazolyl), 6.92 (dd, 3JНН = 5.3 Hz, 3JНP
=
15.2 Hz, 1 H, OH), 6.92 (m, 7 H, 4 Hm, 2 Hp, C6H5 + 1 H, =CH), 7.62 (s, 1
3
3
H, H-5, imidazolyl), 7.86, 7.99 (2 dd, JНН = 7.8 Hz, JНP = 12.1 Hz, Ho,
Anal. Calcd for C21H23N2OPS: C, 65.95; H, 6.06; N, 7.32; P, 8.10; S, 8.38.
Found: C, 65.91; H, 6.05; N, 7.31; P, 8.07; S, 8.37.
C6H5).
13C NMR (100.61 Hz, DMSO-d6): δ = 69.9 (d, 1JCP = 71.1 Hz, PCH), 101.2
(=CH2), 117.3 (C-5, imidazolyl), 127.9 (C-4, imidazolyl), 128.3 (2 d,
3JCP = 12.6 Hz, 3JCP = 12.5 Hz, Cm, C6H5), 130.4 (CH=), 130.7 (d, 1JCP = 78.9
Hz, Cipso, C6H5), 131.7 (d, 4JCP = 8.2 Hz, Cp, C6H5), 131.8 (d, 2JCP = 9.9 Hz,
Co, C6H5), 131.9 (d, 1JCP = 78.9 Hz, Cipso, C6H5), 132.7 (d, 2JCP = 9.9 Hz, Co,
C6H5), 142.9 (C-2, imidazolyl).
15N NMR (40.56 MHz, CDCl3): δ = –194.1 (N-1), –118.0 (N-3).
31P NMR (161.98 MHz, CDCl3): δ = 47.0.
[Bis(2-pyridin-2-ylethyl)phosphorothioyl](2-furyl)methanol (18i)
Prepared from 14 (276 mg, 1 mmol) and 6 (96 mg, 1 mmol); yield:
361 mg (97%); yellow powder; mp 94–95 °C (hexane).
IR (KBr): 3143 (OH), 613 cm–1 (P=S).
1H NMR (400.13 MHz, CDCl3): δ = 2.17–2.23, 2.45–2.47, 2.60–2.66 (m,
4 Н, PyCH2), 3.02–3.15, 3.26–3.30 (m, 4 Н, CH2P), 5.03 (d, 2JНP = 1.8 Hz,
3
3
1 H, PCH), 6.36 (dd, JНН = 3.1 Hz, JНН = 2.0 Hz, 1 H, H-4, furyl), 6.47
3
3
(dd, JНН = 3.9 Hz, JНН = 3.1 Hz, 1 H, H-3, furyl), 6.80 (br s, 1 H, OH),
Anal. Calcd for C18H17N2OPS: C, 63.52; H, 5.03; N, 8.23; P, 9.10; S, 9.42.
Found: C, 63.51; H, 5.02; N, 8.23; P, 9.07; S, 9.39.
7.09, 7.14 (2 dd, 3JНН = 7.6 Hz, 3JНН = 4.6 Hz, 1 H, H-5, Py), 7.20, 7.18 (2
3
3
d, JНН = 8.0 Hz, 2 H, H-3, Py), 7.39 (d, JНН = 2.0 Hz, 1 H, H-5, furyl),
7.57, 7.51 (2 dd, 3JНН = 7.6 Hz, 3JНН = 8.0 Hz, 2 H, 4-H, Py), 8.43, 8.47 (2
dd, 3JНН = 2 H, H-6, Py).
(Diphenylphosphorothioyl)(1-vinyl-1H-benzimidazol-2-yl)metha-
nol (18g)
13C NMR (100.61 Hz, CDCl3): δ = 26.4, 27.1 (2 d, 1JPC = 47.0 Hz, CH2P),
29.3, 30.3 (PyCH2), 69.0 (d, 1JPC = 58.2 Hz, PCH), 109.5 (d, 3JCP = 6.0 Hz,
C-3, furyl), 110.8 (C-4, furyl), 121.6, 121.8 (C-5, Py), 123.1, 123.6 (C-3,
Prepared from 13 (218 mg, 1 mmol) and 11 (172 mg, 1 mmol); yield:
374 mg (96%); yellow powder; mp 167–168 °C (hexane).
IR (KBr): 3167 (OH), 614 cm–1 (P=S).
1
Py), 136.7, 137.2 (C-4, Py), 142.8 (d, JCP = 2.2 Hz, C-5, furyl), 148.6,
1H NMR (400.13 MHz, DMSO-d6): δ = 5.16 (d, 3JНH = 9.2 Hz, 1 Н, =CH2),
149.1 (C-6, Py), 149.4 (C-2, furyl), 159.9 (3JCP = 9.5 Hz, C-2, Py), 160.2
(3JCP =13.8 Hz, C-2, Py).
5.52 (d, 3JНH = 16.0 Hz, 1 Н, =CH2), 6.29 (dd, 3JНН = 6.1 Hz, 2JНP = 7.6 Hz,
3
3
1 H, PCH), 7.16 (dd, JНН = 6.1 Hz, JНP = 14.0 Hz, 1 H, OH), 7.24 (dd,
3JНН = 7.9 Hz, 3JНН = 8.8 Hz, 1 Harom, H-5), 7.30 (dd, 3JНН = 7.8 Hz, 3JНН
15N NMR (40.56 MHz, CDCl3): δ = –72.6, –81.2.
31P NMR (161.98 MHz, CDCl3): δ = 60.5.
=
8.8 Hz, 1 Harom, H-6), 7.51–7.62 (m, 8 H, 4 Hm, 2 Hp, C6H5, 1 Harom, H-4,
+ 1 H, =CH), 7.72 (d, 3JНH = 7.9 Hz, 1 Harom, H-7), 7.95, 8.02 (2 ddd, 3JНН
7.5 Hz, 3JНP = 11.9 Hz, 4 H, Ho, C6H5).
=
Anal. Calcd for C19H21N2O2PS: C, 61.28; H, 5.68; N, 7.52; P, 8.32; S,
8.61. Found: C, 61.26; H, 5.68; N, 7.51; P, 8.28; S, 8.60.
13C NMR (100.61 Hz, DMSO-d6): δ = 70.7 (d, 1JCP = 69.8 Hz, PCH), 107.2
(=CH2), 112.4 (C-7, Ar), 119.9 (C-4, Ar), 123.2 (C-5, Ar), 124.1 (C-6, Ar),
(2E)-1-[Bis(2-phenylethyl)phosphoroselenoyl]-3-phenylprop-2-
en-1-ol (18j)
3
3
128.5 (d, JCP = 12.1 Hz, Cm, C6H5), 128.9 (d, JCP = 11.6 Hz, Cm, C6H5),
129.9 (d, 1JCP = 78.0 Hz, Cipso, C6H5), 130.4 (CH=), 132.0 (d, 2JCP = 9.9 Hz,
Prepared from 15 (321 mg, 1 mmol) and 4 (132 mg, 1 mmol); yield:
435 mg (96%); yellow powder; mp 116–117 °C (hexane).
IR (KBr): 3343 (OH), 440 cm–1 (P=Se).
4
4
Co, C6H5), 132.2 (d, JCP = 2.2 Hz, Cp, C6H5), 132.25 (d, JCP = 2.6 Hz, Cp,
1
2
C6H5), 132.3 (d, JCP = 78.4 Hz, Cipso, C6H5), 133.3 (d, JCP = 9.9 Hz, Co,
C6H5), 133.7 (C-9, Ar), 142.6 (C-8, Ar), 150.2 (C-2, Ar).
1H NMR (400.13 MHz, CDCl3): δ = 2.10–2.18, 2.22–2.38 (m, 4 H, CH2P),
2.90–3.05 (m, 4 H, PhCH2), 3.14 (br s, 1 H, OH), 4.49 (dd, 3JНН = 6.8 Hz,
15N NMR (40.56 MHz, DMSO-d6): δ = –214.4 (N-1), –129.2 (N-3).
31P NMR (161.98 MHz, DMSO-d6): δ = 46.4.
3
3
2JНP = 1.5 Hz, 1 Н, PCH), 6.25, 6.28 (2 dd, JНН = 15.9 Hz, JНН = 6.8 Hz,
3JНP = 4.5 Hz, 1 H, =CH), 6.70, 6.74 (2 d, 3JНН = 15.9 Hz, 4JНP = 3.8 Hz, 1 H,
=CHPh), 7.14–7.38 (m, 15 H, 3 × C6H5).
Anal. Calcd for C22H19N2OPS: C, 67.68; H, 4.90; N, 7.17; P, 7.93; S, 8.21.
Found: C, 67.65; H, 4.90; N, 7.15; P, 7.89; S, 8.19.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 1611–1622

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13C NMR (100.61 Hz, CDCl3): δ = 28.9 (d, 1JPC = 37.6 Hz, СН2Р), 29.3 (d,
77Se NMR (161.98 MHz, CDCl3): δ = –459.8 ( 1JSeP = 697.9 Hz).
2
1JPC = 37.9 Hz, СН2Р), 29.28, 29.4 (2 d, JCP = 2.5 Hz, PhСН2), 71.5 (d,
Anal. Calcd for C21H23O2PSe: C, 60.44; H, 5.55; P, 7.42; Se, 18.92.
Found: C, 60.41; H, 5.52; P, 7.39; Se, 18.90.
1JCP = 47.6 Hz, PCH), 122.7 (d, 2JCP = 3.0 Hz, PCHC=), 126.6 (Cm, C6H5C=),
126.7 (Co, C6H5C=), 128.3, 128.4 (Co, C6H5СН2), 128.5 (Cp, C6H5C=),
4
128.7 (Cp, C6H5CH2), 128.8 (Cm, C6H5CH2), 133.6 (d, JCP = 2.9 Hz, Cipso
,
(Diphenylphosphoroselenoyl)(phenyl)methanol (18m)
3
3
C6H5C=), 133.8 (d, JCP = 11.2 Hz, PhC=), 140.3 (d, JCP = 11.0 Hz, Cipso
,
Prepared from 16 (266 mg, 1 mmol) and 5 (106 mg, 1 mmol); yield:
365 mg (98%); white powder; mp 129–130 °C (hexane).
IR (KBr): 3256 (OH), 492 cm–1 (P=Se).
C6H5CH2), 140.5 (d, 3JCP = 11.8 Hz, Cipso, C6H5CH2).
1
31P NMR (161.98 MHz, CDCl3): δ = 51.6 (s), (+d satellite, JPSe = 697.1
Hz).
1H NMR (400.13 MHz, CDCl3): δ = 3.91 (br s, 1 H, OH), 5.53 (s, 1 H,
PCH), 6.98 (d, 3JНН = 7.6 Hz, 2 H, Hо, C6H5CHOH), 7.08 (dd, 3JНН = 7.9 Hz,
77Se NMR (161.98 MHz, CDCl3): δ = –450.3 ( 1JSeP = 697.1 Hz).
Anal. Calcd for C25H27OPSe: C, 66.22; H, 6.00; P, 6.83; Se, 17.41. Found:
C, 66.19; H, 6.01; P, 6.79; Se, 17.39.
3
3JНН = 7.6 Hz, 2 H, Hm, C6H5CHOH), 7.15 (t, JНН = 7.6 Hz, 1 H, Hp,
C6H5CHOH), 7.20–7.25 (m, 2 H, Hm, C6H5P), 7.35–7.39 (m, 1 H, Hp,
C6H5P), 7.41–7.47 (m, 2 H, Ho, C6H5P, 2 H, Hm, C6H5P), 7.49–7.52 (m, 2
H, Hp, C6H5P), 7.87 (dd, 3JНН = 7.6 Hz, 3JНН = 12.2 Hz, 2 H, Ho, C6H5P).
[Bis(2-phenylethyl)phosphoroselenoyl](phenyl)methanol (18k)
Prepared from 15 (321 mg, 1 mmol) and 5 (106 mg, 1 mmol); yield:
414 mg (97%); white powder; mp 88–89 °C (hexane).
IR (KBr): 3297 (OH), 458 cm–1 (P=Se).
13C NMR (100.61 Hz, CDCl3): δ = 72.5 (d, 1JCP = 46.5 Hz, PCH), 127.5 (d,
4
3JCP = 4.7 Hz, Co, C6H5CHOH), 127.6 (d, JCP = 2.6 Hz, Cm, C6H5CHOH),
3
5
128.2 (d, JCP = 12.1 Hz, Cm, C6H5P), 128.4 (d, JCP = 3.0 Hz, Cp,
C6H5CHOH), 128.8 (d, 3JCP = 11.6 Hz, Cm, C6H5P), 129.8 (d, 1JCP = 68.5 Hz,
1H NMR (400.13 MHz, CDCl3): δ = 1.75–1.86, 1.93–2.03, 2.11–2.31 (m,
4 H, CH2P), 2.55–2.75, 2.91–2.98 (m, 4 H, PhCH2), 3.82 (br s, 1 H, OH),
4.88 (s, 1 Н, PCH), 6.99 (d, 3JНН = 7.6 Hz, 2 H, Ho, C6H5CHOH), 7.14–7.23
C
ipso, C6H5P), 132.0 (d, 2JCP = 3.5 Hz, Cp, C6H5P), 132.1 (d, 2JCP = 3.5 Hz, Cp,
C6H5P), 135.5 (Cipso, C6H5CHOH).
(m, 4 H, Hm, C6H5CH2, 2 H, Hp, C6H5CH2), 7.28 (dd, 3JНН = 8.0 Hz, 3JНН
=
31P NMR (161.98 MHz, CDCl3): δ = 51.1 (s) (+d satellite, JPSe = 713.2
1
7.6 Hz, 2 H, Hm, C6H5CHOH), 7.33–7.40 (m, 4 H, C6H5CH2, 1 H, Hp,
C6H5CHOH).
Hz).
77Se NMR (161.98 MHz, CDCl3): δ = –380.0 ( 1JSeP = 713.2 Hz).
13C NMR (100.61 Hz, CDCl3): δ = 28.6 (d, 1JCP = 37.1 Hz, СН2Р), 29.4 (d,
Anal. Calcd for C19H17OPSe: C, 61.47; H, 4.62; P, 8.34; Se, 21.27. Found:
C, 61.45; H, 4.62; P, 8.31; Se, 21.28.
1
2JCP = 2.6 Hz, PhСН2), 29.6 (d, 2JCP = 2.6 Hz, PhСН2), 30.0 (d, JCP = 37.5
1
Hz, СН2Р), 71.9 (d, JCP = 42.7 Hz, PCH), 126.6 (Cp, C6H5CH2), 126.7 (d,
3JCP = 4.7 Hz, Co, C6H5CHOH), 126.8 (Cp, C6H5CH2), 128.3, 128.4 (Cm,
Reaction of α-Hydroxyphosphine Oxide 12d with Methyl Propio-
late
4
C6H5CH2), 128.7 (Co, C6H5CH2), 128.8 (d, JCP = 2.6 Hz, Cm, C6H5CHOH),
128.83 (Co, C6H5CH2), 129.0 (d, 5JCP = 3.0 Hz, Cp, C6H5CHOH), 135.8 (d,
A solution of α-hydroxyphosphine oxide 12d (365 mg, 1.0 mmol),
methyl propiolate (92 mg, 1.1 mmol), and Et3N (101 mg, 1 mmol) in
THF (4 mL) was stirred at 20–22 °C for 5 h. The solvent was removed
under reduced pressure. The residue was washed with hexane (2 × 0.5
mL) and dried under vacuum to afford methyl (E)-3-[(diphenethyl-
phosphoryl)(2-pyridinyl)methoxy]prop-2-enoate (19); yield: 395 mg
(88%); white powder; mp 96–97 °C (hexane).
2JCP = 2.2 Hz, Cipso, C6H5CHOH), 140.3 (d, 3JCP = 13.8 Hz), 140.5 (d, 3JCP
=
14.7 Hz, Cipso, C6H5CH2).
1
31P NMR (161.98 MHz, CDCl3): δ = 54.5 (s) (+d satellite, JPSe = 696.0
Hz).
77Se NMR (161.98 MHz, CDCl3): δ = –461.3 ( 1JSeP = 696.0 Hz).
Anal. Calcd for C23H25OPSe: C, 64.64; H, 5.90; P, 7.25; Se, 18.48. Found:
C, 64.60; H, 5.89; P, 7.22; Se, 18.46.
IR (KBr): 1716 (C=O), 1641, 1627 (C=C of vinyl), 1157 cm–1 (P=O).
1H NMR (400.13 MHz, CDCl3): δ = 1.95–2.79 (m, 4 Н, CH2P), 2.74–2.98
(m, 4 Н, PhCH2), 3.64 (3 H, CH3), 5.27 (d, 3JНН = 12.6 Hz, 1 H, =CH), 5.29
(d, 3JНН = 7.8 Hz, 1 H, PCH), 7.14–7.21 (m, 6 H, Hp, Hm, C6H5), 7.24–7.29
(m, 5 H, 4 Ho, C6H5 + H-4, Py), 7.45 (d, 3JНН = 7.6 Hz, 1 H, H-6, Py), 7.50
(d, 3JНН = 12.6 Hz, 1 H, OCH=), 7.74 (dd, 3JНН = 7.6 Hz, 3JНН = 8.4 Hz, 1 H,
H-5, Py), 8.62 (3JНН = 4.6 Hz, H-3, Py).
[Bis(2-phenylethyl)phosphoroselenoyl](2-furyl)methanol (18l)
Prepared from 15 (321 mg, 1 mmol) and 6 (96 mg, 1 mmol); yield:
404 mg (97%); white powder; mp 76–77 °C (hexane).
IR (KBr): 3203 (OH), 484 cm–1 (P=Se).
1H NMR (400.13 MHz, CDCl3): δ = 1.89–1.99, 2.05–2.15, 2.19–2.39 (m,
4 Н, CH2P), 2.71–2.80, 2.92–2.99 (m, 4 Н, PhCH2), 3.65 (br s, 1 H, OH),
4.91 (s, 1 H, PCH), 6.41 (dd, 3JНН = 3.3 Hz, 3JНН = 1.8 Hz, 1 H, H-4, furyl),
6.48 (dd, 3JНP = 3.9 Hz, 3JНН = 3.3 Hz, 1 H, H-3, furyl), 7.07 (d, 3JНН = 7.7
Hz, 2 H, Ho, C6H5), 7.15–7.30 (m, 2 H, Ho, 4 H, Hm, 2 H, Hp, C6H5), 7.43
(dd, 3JНН = 1.8 Hz, 5JPН = 2.9 Hz, 1 H, H-5, furyl).
13C NMR (100.61 Hz, CDCl3): δ = 26.9, 27.0 (2 d, 2JCP = 3.6 Hz, PhCH2),
27.5 (d, 1JCP = 62.0 Hz, CH2P), 27.6 (d, 1JCP = 61.2 Hz, CH2P), 50.9 (CH3),
81.1 (d, 1JCP = 72.0 Hz, PCH), 99.8 (=CH), 122.3 (d, 3JCP = 2.6 Hz, C-6, Py),
123.4 (C-4, Py), 126.15, 126.2 (Cp, C6H5), 127.7, 127.8 (Co, C6H5), 128.3,
128.4 (Cm, C6H5), 136.9 (C-5, Py), 140.2, 140.3 (2 d, 3JCP = 10.8 Hz, Cipso
C6H5), 149.4 (C-3, Py), 152.5 (C-1, Py), 160.4 (d, JCP = 9.9 Hz, OCH=),
,
1
13C NMR (100.61 Hz, CDCl3): δ = 29.26, 29.3 (2 d, 2JPC = 2.6 Hz, PhCH2),
166.7 (C=O).
1
1
29.4 (d, JPC = 37.1 Hz, CH2P), 30.3 (d, JPC = 37.9 Hz, CH2P), 66.5 (d,
15N NMR (40.56 MHz, CDCl3): δ = –68.8 (d, 2JNН = 14.6 Hz).
31P NMR (161.98 MHz, CDCl3): δ = 43.5.
1JPC = 46.1 Hz, PCH), 109.4 (d, JCP = 6.0 Hz, C-3, furyl), 111.2 (d, JCP
=
3
4
2.2 Hz, C-4, furyl), 126.7, 126.8 (Cp, C6H5) 128.4, 128.5 (Co, C6H5) 128.8,
3
3
128.9 (Cm, C6H5), 140.4 (d, JCP = 14.2 Hz, Cipso, C6H5), 140.6 (d, JCP
=
=
Anal. Calcd for C26H28NO4P: C, 69.48; H, 6.28; N, 3.12; P, 6.89. Found:
C, 69.44; H, 6.23; N, 3.09; P, 6.85.
1
1
15.5 Hz, Cipso, C6H5), 143.0 (d, JCP = 3.0 Hz, C-5, furyl), 143.1 (d, JCP
3.0 Hz, C-2, furyl).
1
31P NMR (161.98 MHz, CDCl3): δ = 53.6 (s) (+d satellite, JPSe = 697.9
Hz).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 1611–1622

1622
N. K. Gusarova et al.
Paper
Synthesis
Acknowledgment
(2) (a) Trofimov, B. A.; Gusarova, N. K.; Ivanova, N. I.; Konovalova, N.
A.; Bogdanova, M. V.; Albanov, A. I.; Avseenko, N. D.; Sukhov, B.
G. Russ. J. Gen. Chem. 2004, 74, 1625. (b) Ivanova, N. I.;
Baikalova, L. V.; Konovalova, N. A.; Zyryanova, I. A.; Albanov, A.
I.; Sinegovskaya, L. M.; Kukhareva, V. A.; Tatarinova, A. A.;
Avseenko, N. D.; Sukhov, B. G.; Gusarova, N. K.; Trofimov, B. A.
Chem. Heterocycl. Compd. 2005, 41, 317. (c) Ivanova, N. I.;
Volkov, P. A.; Baikalova, L. V.; Gusarova, N. K.; Trofimov, B. A.
Chem. Heterocycl. Compd. 2008, 44, 1359.
This work was supported by the Council on Grants of the President of
the Russian Federation for State Support of Leading Scientific Schools
(Grant NSh-156.2014.3).
Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0034-1380408.
(3) Gusarova, N. K.; Ivanova, N. I.; Konovalova, N. A.; Sukhov, B. G.;
Baikalova, L. V.; Sinegovskaya, L. M.; Pavlov, D. V.; Trofimov, B. A.
Synthesis 2006, 4159.
S
u
p
p
ortioInfgrmoaitn
S
u
p
p
ortiInfogrmoaitn
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2015, 47, 1611–1622