Reaction of secondary phosphine oxides with acylacetylenes

Article abstract of DOI:10.1134/S1070428010040056

Secondary phosphine oxides reacted with 1-alkanoyl-2-phenylacetylenes in chemoselective fashion under mild conditions (20°C, THF) in the absence of a catalyst (diphenylphosphine oxide) or in the presence of potassium hydroxide [bis(2-phenylethyl)phosphine oxide] to give 1-alkyl-1-diphenyl(or 2-phenylethyl)-phosphoryl-3-phenylprop-2-yn-1-ols in up to 96% yield. The reaction of diphenylphosphine oxide with 1-alkanoyl-2-phenylacetylenes in the system KOH-THF (20°C) afforded not only adducts at the carbonyl group but also products of double α,β-addition at the triple bond, 2,3-bis(diphenylphosphoryl)-3-phenylpropan-1-ones.

Full text of DOI:10.1134/S1070428010040056

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 4, pp. 485–490. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.Yu. Dvorko, T.E. Glotova, I.A. Ushakov, N.K. Gusarova, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46,
No. 4, pp. 495–500.
Reaction of Secondary Phosphine Oxides with Acylacetylenes
M. Yu. Dvorko, T. E. Glotova, I. A. Ushakov, and N. K. Gusarova
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: glotova@irioch.irk.ru
Received May 15, 2009
Abstract—Secondary phosphine oxides reacted with 1-alkanoyl-2-phenylacetylenes in chemoselective fashion
under mild conditions (20°C, THF) in the absence of a catalyst (diphenylphosphine oxide) or in the presence of
potassium hydroxide [bis(2-phenylethyl)phosphine oxide] to give 1-alkyl-1-diphenyl(or 2-phenylethyl)-
phosphoryl-3-phenylprop-2-yn-1-ols in up to 96% yield. The reaction of diphenylphosphine oxide with
1-alkanoyl-2-phenylacetylenes in the system KOH–THF (20°C) afforded not only adducts at the carbonyl
group but also products of double α,β-addition at the triple bond, 2,3-bis(diphenylphosphoryl)-3-phenyl-
propan-1-ones.
DOI: 10.1134/S1070428010040056
Tertiary phosphine oxides are key targets in the
chemistry of organophosphorus compounds. They are
widely used as ligands for metal complex catalysts
[1–3], special solvents for stabilization of nanosystems
in the synthesis of semiconductors [4], extractants for
noble, rare-earth, and transuranium elements [5–7],
fire-retardants [8], and photochromic [9] and lumines-
cent materials [10]. Phosphine oxides are successfully
used as building blocks, e.g., in the Wittig–Horner
reaction [11–14], specifically, for the synthesis of sub-
stituted vitamin D3 analogs [14]. Of particular interest
are polyfunctionalized tertiary phosphine oxides; how-
ever, their synthesis involves some difficulties. A con-
venient synthetic approach to such compounds is based
on the addition of secondary phosphine oxides to
functionally substituted alkenes [15–18], alkynes [15,
17] (including α,β-acetylenic ketones [19]), aldehydes
[20–24], and ketones [20, 21]. In the recent publication
[25] we briefly reported on reactions of secondary
phosphine oxides with 1-acetyl- and 1-butanoyl-2-
phenylacetylenes in the system KOH–THF, which
occurred in chemoselective fashion at the C=O group
and led to the formation of functionalized tertiary
phosphine oxides having a hydroxy group and an acet-
ylenic fragment.
selectivity and efficiency, depending on the reactant
structure and experimental conditions, as well as to
develop a procedure for the synthesis of new polyfunc-
tionalized tertiary phosphine oxides.
We have found that diphenylphosphine oxide (I)
reacts with 1-alkanoyl-2-phenylacetylenes IIa–IIc
under mild conditions in the absence of a catalyst
(20°C, THF); the reaction is chemoselective, and the
products are the corresponding adducts at the carbonyl
group, (diphenylphosphoryl)phenylalkynols IIIa–IIIc
(Scheme 1, Table 1). At an equimolar reactant ratio,
the yield of IIIa–IIIc did not exceed 41% (Table 1;
run nos. 1, 4, 6). The use of 2 equiv of diphenylphos-
phine oxide (I) allowed us to raise the yield of IIIa–
IIIc to 65–96% (Table 1, run nos. 3, 5, 7). Increase in
the yield of IIIa–IIIc in the presence of excess phos-
Scheme 1.
R
Ph2PHO
+
Ph
O
I
IIa–IIc
Ph
O
R
Ph
P
THF, 20°C
*
Ph
In the present work we performed a detailed study
on nucleophilic addition of secondary phosphine
oxides to bielectrophilic 1-alkanoyl-2-phenylacety-
lenes with a view to elucidate its chemo- and regio-
OH
IIIa–IIIc
R = Me (a), Pr (b), i-Pr (c).
485

DVORKO et al.
486
Table 1. Reaction of diphenylphosphine oxide (I) with
acetylenic ketones IIa–IIca
more than twofold) when the reaction of diphenyl-
phosphine oxide (I) with 1-acetyl-2-phenylacetylene
(IIa) was carried out with equimolar amounts of the
reactants in the presence of 10 mol % of KOH
(Table 1; cf. run nos. 1 and 2). However, further in-
crease in the amount of KOH resulted in reduced
chemoselectivity of the process. The reactions of di-
phenylphosphine oxide (I) with equimolar amounts of
acetylenes IIa–IIc in the presence of 20 mol % of
KOH (20°C, THF) gave mixtures of adducts IIIa–IIIc
and products of double α,β-addition at the triple bond,
2,3-bis(diphenylphosphoryl)-3-phenylpropan-1-ones
IVa–IVc (Scheme 2; Table 2, run nos. 1–3) whose
fraction increased in going from 1-acetyl-2-phenyl-
acetylene IIa to acylacetylenes IIb and IIc having
bulkier substituents (propyl and isopropyl groups,
respectively) at the carbonyl carbon atom (Table 2, run
nos. 1–3). We succeeded in obtaining compounds IVa–
IVc as the major products using 2 equiv of phosphine
oxide I with respect to acetylenic ketone IIa–IIc
(Table 2, run nos. 4–6).
Run
no.
Reactant
ratio I:II
Reaction
time, h
Yield of III,b
R
%
1
c2c
3
Me
Me
Me
Pr
1:1
1:1
2:1
1:1
2:1
1:1
2:1
09
04
09
35
35
35
35
40 (a)
71 (a)
96 (a)
41 (b)
77 (b)
13 (c)
65 (c)
4
5
Pr
6
i-Pr
i-Pr
7
a
All reactions were carried out in THF at room temperature under
argon.
b
c
Calculated on the initial amount of II.
The reaction was carried out with 10 mol % of KOH (with
respect to I).
phine oxide I may be related to equilibrium character
of the process [26] (see below).
As follows from the data in Table 1, the rate and
efficiency of this reaction depend on the structure of
the alkyl radical R in acetylenes IIa–IIc; their reac-
tivity decreases in the series IIa > IIb > IIc, i.e., in
parallel with increase in the degree of branching of the
R radical. The yield of adduct IIIa increased almost
twofold (simultaneously, the reaction time shortened
Scheme 2.
KOH, THF, 20°C
I
+
IIa–IIc
IIIa–IIIc
O
*
Ph
Ph
P
Ph
+
*
Ph
O
P
Ph
R
O
Table 2. Reaction of diphenylphosphine oxide (I) with
acetylenic ketones IIa–IIc in the presence of 20 mol % of
KOH (with respect to phosphine oxide I)a
IVa–IVc
R = Me (a), Pr (b), i-Pr (c).
Yield, b %
Unlike diphenylphosphine oxide (I), bis(2-phenyl-
ethyl)phosphine oxide (V) failed to react with 4-phen-
ylbut-3-yn-2-one (IIa) in the absence of KOH (equi-
molar reactant ratio, 20°C, 9 h, THF; Table 3, run
no. 1). The use of 2 equiv of phosphine oxide V with
respect to acetylenic ketone IIa and prolonged contact
of the reactants (20°C, 240 h, THF) led to formation of
an insignificant amount of the adduct at the carbonyl
group (compound VIa; Scheme 3; Table 3, run no. 2).
On the other hand, in the presence of KOH (20°C,
35 h, THF) phosphine oxide V chemoselectively added
to acetylenic ketones IIa–IIc to give acetylenic alco-
hols VIa–VIc in 67, 63, and 19% yield, respectively
(Scheme 3; Table 3, run nos. 3–5). As in the reaction
with diphenylphosphine oxide (I), acylacetylene IIc
having an isopropyl group at the carbonyl carbon atom
turned out to be least reactive toward bis(2-phenyl-
ethyl)phosphine oxide (V). Our results indicated
Run
no.
Reactant Reaction
R
ratio I:II
time, h
III
IV
1
2
3
4
5
6
Me
Pr
1:1
1:1
1:1
2:1
2:1
2:1
4
4
9
4
4
9
69 (a)
16 (b)
08 (c)
36 (a)
Tracesd
04 (a)
75 (b)
33 (c)
37 (a)
82 (b)
52 (c)
i-Pr
Me
Pr
i-Pr
Not
detectedd
c7c
Me
1:1
4
71 (a)
Not
detectedd
a
All reactions were carried out in THF at room temperature under
argon.
b
c
Calculated on the initial amount of II.
The reaction was carried out with 10 mol % of KOH (with
respect to I).
d
31P NMR monitoring.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010

REACTION OF SECONDARY PHOSPHINE OXIDES WITH ACYLACETYLENES
487
Scheme 3.
Table 3. Reaction of bis(2-phenylethyl)phosphine oxide (V)
with acetylenic ketones IIa–IIca
(PhCH2CH2)2PHO
+
IIa–IIc
V
Run
no.
Amount of Reaction Reactant Yield of
R
KOH, mol % time, h ratio V:II VI,b %
Ph
c
Ph
1
2
3
4
5
Me
Me
Me
Pr
00
00
20
20
20
009
240
035
035
035
1:1
2:1
1:1
1:1
1:1
–
O
R
06c (a)
67 (a)
63 (b)
19 (c)
P
KOH, THF, 20°C
*
Ph
HO
VIa–VIc
i-Pr
R = Me (a), Pr (b), i-Pr (c).
a
All reactions were carried out in THF at room temperature under
argon.
higher reactivity of diphenylphosphine oxide (I)
compared to bis(2-phenylethyl)phosphine oxide (V);
a probable reason is higher acidity of phosphine oxide
I and hence higher concentration of diphenylphos-
phinite ions.
b
c
Calculated on the initial amount of II.
31P NMR monitoring.
building blocks for organic and organometallic syn-
thesis and intermediate products for the design of
specialty substances and materials.
Tertiary phosphine oxides IIIa–IIIc, IVa–IVc, and
VIa–VIc are crystalline substances that are stable at
room temperature. However, adducts IIIa and VIa at
the carbonyl group were shown (1H, 13C, and 31P NMR
monitoring) to undergo decomposition into initial
acetylacetylene IIa and the corresponding phosphine
oxide I or V on heating in CDCl3 (50–55°C, 7–33 h;
Scheme 4). The conversion of phosphine oxide IIIa
was ~90% in 13 h, while the conversion of VIa was
only ~15% over the same period of time. The observed
decomposition of adducts IIIa–IIIc on heating in
CDCl3 and increase in their yield upon raising the
concentration of one of the reactants (Table 1, run
nos. 3, 5, 7) suggest equilibrium character of the
process.
EXPERIMENTAL
The IR spectra were recorded in KBr on a Bruker
1
IFS-25 spectrometer. The H, 13C, and 31P NMR
spectra were measured from solutions in CDCl3 on
a Bruker DPX-400 instrument (400.13, 101.61, and
161.98 MHz, respectively); the chemical shifts were
determined relative to hexamethyldisiloxane (1H, 13C)
or 85% phosphoric acid (31P). Signals in the NMR
spectra were assigned using two-dimensional homo-
and heteronuclear correlation techniques (HSQC,
HMBC, NOESY).
Diphenylphosphine oxide (I) and bis(2-phenyl-
ethyl)phosphine oxide (V) were synthesized as
reported in [27] and [28], respectively. Initial α,β-acet-
ylenic ketones IIa–IIc were prepared from phenyl-
acetylene and the corresponding aldehyde according to
the procedure described in [29].
Scheme 4.
CDCl3, 50–55°C
IIIa or VIa
IIa
+
R2PHO
I, V
I, IIIa, R = Ph; V, VIa, R = PhCH2CH2.
Tertiary phosphine oxides IIIa–IIIc (general
procedure) (Table 1, run nos. 3, 5, 7). A solution of
1 mmol of diphenylphosphine oxide (I) and 0.5 mmol
of acetylenic ketone IIa–IIc in 4 ml of THF was
stirred under argon at room temperature. When the
reaction was complete, the solvent was removed under
reduced pressure, the residue was ground with 8 ml of
diethyl ether, and the precipitate was filtered off and
dried under reduced pressure. The mother liquor con-
tained only unreacted acetylene IIa–IIc (identified by
Thus, we have developed a convenient, effective,
chemoselective, and atom-economic synthesis of phos-
phorus-containing acetylenic alcohols via addition of
secondary phosphine oxides at the carbonyl group of
1-acyl-2-phenylacetylenes. Under certain conditions
the reaction with diphenylphosphine oxide may be
directed toward predominant (or even exclusive)
formation of 2,3-bis(diphenylphosphoryl)-3-phenyl-
propan-1-ones as a result of double α,β-addition at the
triple bond. The newly synthesized polyfunctionalized
tertiary phosphine oxides are promising as reactive
1
TLC) and phosphine oxide I (identified by H and 31P
NMR spectroscopy).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010

DVORKO et al.
488
2-(Diphenylphosphoryl)-4-phenylbut-3-yn-2-ol
sure over CaCl2. In run no. 4 (Table 2), the solvent was
removed from the mother liquor to isolate 0.062 g
(36%) of phosphine oxide IIIa.
(IIIa) (Table 1, run no. 3). Yield 0.166 g (96%), white
powder, mp 140–142°C (decomp.). IR spectrum, ν,
cm–1: 3141 (OH), 2234 w (C≡C), 1175 (P=O).
3,4-Bis(diphenylphosphoryl)-4-phenylbutan-2-
one (IVa) (Table 2, run no. 4). Yield 0.101 g (37%),
white powder, mp 240–242°C. IR spectrum, ν, cm–1:
1709 (C=O); 1193, 1179 (P=O). 1H NMR spectrum, δ,
ppm: 1.66 s (3H, Me), 4.74–4.89 m (2H, 3-H, 4-H),
6.40–6.87 m (3H, o-H, p-H in PhC), 7.11–7.91 m
(22H, Harom). 13C NMR spectrum, δC, ppm: 32.16
3
1H NMR spectrum, δ, ppm: 1.80 d (3H, Me, JPH
=
13.2 Hz), 4.00 br.s (1H, OH), 7.21–7.40 m (5H, PhC),
7.45–7.65 m (6H, p-H, m-H in PhP), 8.00–8.20 m (4H,
o-H in PhP). 13C NMR spectrum, δC, ppm: 25.85 d
2
1
(Me, JPC = 3.7 Hz), 69.86 d (C2, JPC = 87.0 Hz),
3
89.09 d (PhC≡C, JPC = 7.7 Hz), 88.90 d (PhC≡C,
2JPC = 2.2 Hz), 122.83 (Ci in PhC≡), 129.1–129.6,
130.7–132.2 (Ph). 31P NMR spectrum: δP 34.32 ppm.
Found, %: C 76.56; H 5.87; P 9.09. C22H19O2P. Cal-
culated, %: C 76.29; H 5.53; P 8.94.
1
2
(Me), 46.25 d.d (C4, JPC = 63.1, JPC = 2.8 Hz),
56.60 d (C3, JPC = 53.9 Hz), 126.64–127.94, 130.31–
1
2
3
132.68 (Ph), 203.93 d.d (C=O, JPC = 1.4, JPC
=
2.5 Hz). 31P NMR spectrum (CDCl3), δP, ppm: 23.42 d
(3JPP = 40.2 Hz), 32.93 d (3JPP = 40.2 Hz). Found, %:
C 74.16; H 5.51; P 11.51. C34H30O3P2. Calculated, %:
C 74.44; H 5.51; P 11.29.
3-(Diphenylphosphoryl)-1-phenylhex-1-yn-3-ol
(IIIb) (Table 1, run no. 5). Yield 0.144 g (77%), white
powder, mp 112–114°C (decomp.). IR spectrum, ν,
cm–1: 3050 (OH), 2218 w (C≡C), 1170 (P=O).
1H NMR spectrum (CDCl3), δ, ppm: 0.94 t (3H, Me,
3JHH = 7.1 Hz), 1.7–1.9 m (4H, CH2CH2), 3.18 br.s
1,2-Bis(diphenylphosphoryl)-1-phenylhexan-3-
one (IVb) (Table 2, run no. 5). Yield 0.236 g (82%),
white powder, mp 252–254°C. IR spectrum, ν, cm–1:
1707 (C=O); 1190, 1174 (P=O). 1H NMR spectrum, δ,
ppm: 0.34 t (3H, Me), 0.51 m and 0.63 m (1H each,
MeCH2), 1.71 m and 2.57 m (1H each, EtCH2), 4.73–
4.84 m (2H, 1-H, 2-H), 6.45–6.96 m (3H, o-H, p-H in
PhCH), 7.0–8.0 m (22H, Harom). 13C NMR spectrum,
δC, ppm: 12.95 (Me), 15.51 (MeCH2), 48.64
(1H, OH), 7.3–8.1 m (15H, Harom). 13C NMR spectrum,
3
δC, ppm: 13.57 s (Me), 16.34 d (MeCH2, JPC
=
8.4 Hz), 37.89 d (EtCH2, 2JPC = 3.6 Hz), 72.02 d (COH,
1JPC = 86.3 Hz), 87.04 d (C2, JPC = 2.0 Hz), 89.65 d
2
(C1, JPC = 8.0 Hz), 121.62 (Ci in PhC≡), 127.68–
3
128.28, 131.15–132.37 (Ph). 31P NMR spectrum:
δP 33.39 ppm. Found, %: C 77.29; H 5.99; P 8.26.
C24H23O2P. Calculated, %: C 76.99; H 6.19; P 8.27.
1
2
(CH2C=O), 46.15 d.d (C1, JPC = 62.5, JPC = 2.4 Hz),
56.15 d (C2, JPC = 54.5 Hz), 127.16–128.45, 130.77–
1
3-(Diphenylphosphoryl)-4-methyl-1-phenylpent-
1-yn-3-ol (IIIc) (Table 1, run no. 7). Yield 0.122 g
(65%), white powder, mp 112–113°C (decomp.). IR
spectrum, ν, cm–1: 3081 (OH), 2215 w (C≡C), 1167
2
3
133.24 (Ph), 209.35 d.d (C=O, JPC = 1.0, JPC
1.5 Hz). 31P NMR spectrum, δP, ppm: 23.46 d (3JPP
=
=
41.50 Hz), 32.42 d (3JPP = 41.50 Hz). Found, %:
C 74.67; H 6.14; P 11.01. C36H34O3P2. Calculated, %:
C 74.99; H 5.94; P 10.74.
1
(P=O). H NMR spectrum, δ, ppm: 1.08 d (3H, Me,
2JHH = 6.9 Hz), 1.18 d (3H, Me, 2JHH = 6.6 Hz), 2.19 m
(1H, Me2CH), 3.02 br.s (1H, OH), 7.26–8.12 m (15H,
Harom). 13C NMR spectrum, δC, ppm: 17.48 d (Me,
1,2-Bis(diphenylphosphoryl)-4-methyl-1-phenyl-
pentan-3-one (IVc) (Table 2, run no. 6). Yield 0.150 g
(52%), white powder, mp 226–228°C. IR spectrum, ν,
3
3JPC = 5.8 Hz), 18.67 d (Me, JPC = 3.0 Hz), 35.33 d
2
1
1
cm–1: 1706 (C=O); 1192, 1185 (P=O). H NMR spec-
(Me2CH, JPC = 5.0 Hz), 75.89 d (COH, JPC
=
82.8 Hz), 86.89 d (C2, JPC = 2.0 Hz), 91.16 d (C1,
3JPC = 8.0 Hz), 122.10 (Ci in PhC≡), 128.39–132.87
(Ph). 31P NMR spectrum: δP 32.74 ppm. Found, %:
C 77.26; H 5.97; P 8.11. C24H23O2P. Calculated, %:
C 76.99; H 6.19; P 8.27.
2
3
trum, δ, ppm: 0.28 d and 0.52 d (3H each, Me, JHH
=
=
6.9 Hz), 2.35 m (Me2CH), 4.83 d.d.d (1H, 1-H, 3JHH
2
3
11.3, JPH = 5.1, JPH = 6.0 Hz), 5.00 d.d.d (1H, 2-H,
3JHH = 11.3, JPH = 8.6, JPH = 9.0 Hz), 6.60–6.70 m
(3H, o-H, p-H in PhCH), 6.9–8.0 m (22H, Harom).
13C NMR spectrum, δC, ppm: 17.25 and 17.29 (Me),
2
3
Tertiary bis-phosphine oxides IVa–IVc (general
procedure) (Table 2, run nos. 4–6). Diphenylphosphine
oxide (I), 1 mmol, was added to a suspension of
0.5 mmol of acetylenic ketone IIa–IIc and 0.2 mmol
of KOH·0.5H2O (water content 15%) in 6 ml of THF.
The mixture was stirred under argon at room tempera-
ture, and the precipitate was filtered off, washed with
diethyl ether and water, and dried under reduced pres-
1
2
44.02 (Me2CH), 45.68 d.d (C1, JPC = 62.5, JPC
=
3.0 Hz), 54.46 d (C2, JPC = 54.7 Hz), 127.04–128.33,
1
2
130.48–132.87 (Ph), 209.35 d.d (C=O, JPC = 1.5,
3JPC = 3.0 Hz). 31P NMR spectrum, δP, ppm: 24.59 d
(3JPP = 41.5 Hz), 32.79 d (3JPP = 41.5 Hz). Found, %:
C 74.75; H 6.11; P 10.53. C36H34O3P2. Calculated, %:
C 74.99; H 5.94; P 10.74.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010

REACTION OF SECONDARY PHOSPHINE OXIDES WITH ACYLACETYLENES
489
Tertiary phosphine oxides VIa–VIc (general
procedure) (Table. 3, run nos. 3–5). A mixture of
0.5 mmol of bis(2-phenylethyl)phosphine oxide (V),
0.5 mmol of acetylenic ketone IIa–IIc, and 0.1 mmol
of KOH·0.5H2O (water content 15%) in 4 ml of THF
was stirred for 35 h under argon at room temperature.
The suspension was passed through a thin layer of
aluminum oxide, the solvent was removed under
reduced pressure, the residue was ground with 5 ml of
diethyl ether, and the precipitate was filtered off and
dried under reduced pressure.
(C≡C), 1144 (P=O). 1H NMR spectrum, δ, ppm: 1.23 d
3
3
(3H, Me, JHH = 6.3 Hz), 1.25 d (3H, Me, JHH
=
6.0 Hz), 2.11–2.40 m (4H, PCH2), 2.88–3.20 m (5H,
CH2Ph, OH), 7.2–7.4 m (15H, Harom). 13C NMR spec-
3
trum, δC, ppm: 17.04 d (Me, JPC = 4.8 Hz), 18.37 d
3
(Me, JPC = 1.8 Hz), 27.79 s (PhCH2), 28.01 d (PCH2,
2
1JPC = 61.9 Hz), 34.74 d (CH, JPC = 2.6 Hz), 74.38 d
1
2
(C3, JPC = 77.0 Hz), 85.71 d (C2, JPC = 1.0 Hz),
89.27 d (C1, JPC = 7.4 Hz), 121.47 (Ci in PhC≡),
3
125.92, 126.03 (Co in CH2Ph), 127.66–128.54 (Cm, Cp
in CH2Ph, PhC≡), 131.32 (Co in PhC≡), 140.80,
141.11 (Ci in CH2Ph). 31P NMR spectrum (CDCl3):
δP 52.91 ppm. Found, %: C 78.30; H 7.32; P 7.61.
C28H31O2P. Calculated, %: C 78.12; H 7.26; P 7.19.
2-[Bis(2-phenylethyl)phosphoryl]-4-phenylbut-3-
yn-2-ol (VIa) (Table 3, run no. 3). Yield 0.135 g
(67%), white powder, mp 103–105°C (decomp.). IR
spectrum, ν, cm–1: 3131 (OH), 2225 w (C≡C), 1158
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 07-03-00562).
1
(P=O). H NMR spectrum, δ, ppm: 1.90 d (3H, Me,
3JPH = 12.4 Hz), 2.1–2.6 m (4H, CH2P), 2.9–3.2 m
(4H, CH2Ph), 5.63 br.s (1H, OH), 7.2–7.4 m (15H,
Harom). 13C NMR spectrum, δC, ppm: 24.69 d (Me,
2JPC = 3.6 Hz), 26.90 d (CH2P, 1JPC = 60.8 Hz), 27.65 d
REFERENCES
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2
1. Noyori, R., Ohkuma, T., Kitamura, M., Takaya, H.,
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(CH2P, JPC = 57.2 Hz), 28.19 d (CH2Ph, JPC
=
2
3.6 Hz), 28.26 d (CH2Ph, JPC = 2.8 Hz), 67.96 d
(C2, JPC = 80.0 Hz), 87.75 d (PhC≡, JPC = 7.2 Hz),
1
3
2. Hayashi, M., Takezaki, H., Hashimoto, Y., Takaoki, K.,
88.33 d (PhC≡C, JPC = 2.0 Hz), 121.97 (Ci in PhC≡),
2
and Saigo, K., Tetrahedron Lett., 1998, vol. 39, p. 7529.
126.46 m (Co in CH2Ph), 128.15–128.95 (Cm, Cp in
CH2Ph, PhC≡), 131.70 (Co in PhC≡), 141.15–141.28
(Ci in CH2Ph). 31P NMR spectrum: δP 51.49 ppm.
Found, %: C 77.86; H 6.89; P 7.99. C26H27O2P. Cal-
culated, %: C 77.59; H 6.76; P 7.70.
3. Tolis, E.I., Vallianatou, K.A., Andreadaki, F.J., and
Kostas, I.D., Appl. Organomet. Chem., 2006, vol. 20,
p. 335.
4. Snee, P.T., Somers, R.C., Nair, G., Zimmer, J.P.,
Bawendi, M.G., and Nocera, D.G., J. Am. Chem. Soc.,
2006, vol. 128, p. 13320.
5. Paine, R.T., Bond, E.M., Parveen, S., Donhart, N.,
Duesler, E.N., Smith, K.A., and Nöth, H., Inorg. Chem.,
2002, vol. 41, p. 444.
3-[Bis(2-phenylethyl)phosphoryl]-1-phenylhex-
1-yn-3-ol (VIb) (Table 3, run no. 4). Yield 0.136 g
(63%), white powder, mp 117–119°C (decomp.). IR
spectrum, ν, cm–1: 3083 (OH), 2221 w (C≡C), 1145
1
6. Alguacil, F.J. and Alonso, M., Hydrometallurgy, 2004,
(P=O). H NMR spectrum, δ, ppm: 1.05 t (3H, Me,
3JHH = 7.0 Hz), 1.87 m (2H, MeCH2), 2.1–2.6 m (6H,
CH2P, EtCH2), 2.9–3.2 m (4H, CH2Ph), 4.32 br.s (1H,
OH), 7.2–7.4 m (15H, Harom). 13C NMR spectrum, δC,
vol. 74, p. 157.
7. Chan, Z., Yan-Zhao, Y., Tao Z., Jian, H., and Chang-
Hong, L., J. Radioanal. Nucl. Chem., 2005, vol. 265,
p. 419.
8. Plotnikova, G.V., Malysheva, S.F., Gusarova, N.K.,
Khaliullin, A.K., Udilov, V.P., and Kuznetsov, K.L.,
Zh. Prikl. Khim., 2008, vol. 81, p. 314.
3
ppm: 14.30 s (Me), 16.91 d (MeCH2, JPC = 7.9 Hz),
27.11 d (PCH2, 1JPC = 60.0 Hz), 27.60 d (PCH2, 1JPC
=
=
2
58.0 Hz), 28.23 s (PhCH2), 38.33 d (EtCH2, JPC
1
2.4 Hz), 71.40 d (C3, JPC = 79.5 Hz), 87.15 d (C2,
3
2JPC = 1.9 Hz), 88.72 d (C1, JPC = 7.6 Hz), 122.01 (Ci
9. Yin, J., Lin, Y., Cao, X., Yu, G.-A., Tu, H., and
in PhC≡), 126.39 m (Co in CH2Ph), 128.14–128.88
(Cm, Cp in CH2Ph, PhC≡), 131.73 (Co in PhC≡),
141.21–141.65 (Ci in CH2Ph). 31P NMR spectrum:
δP 51.45 ppm. Found, %: C 78.38; H 7.49; P 7.31.
C28H31O2P. Calculated, %: C 78.12; H 7.26; P 7.19.
Liu, S.H., Dyes Pigm., 2009, vol. 81, p. 152.
10. Subhan, M.A., Hasegawa, Y., Suzuki, T., Kaizaki, S.,
and Shozo, Y., Inorg. Chim. Acta, 2009, vol. 362,
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11. Gusarova, N.K., Arbuzova, S.N., Shaikhudinova, S.I.,
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naya, L.K., and Trofimov, B.A., Phosphorus, Sulfur,
Silicon Relat. Elem., 2001, vol. 175, p. 163.
3-[Bis(2-phenylethyl)phosphoryl]-4-methyl-1-
phenylpent-1-yn-3-ol (VIc) (Table 3, run no. 5). Yield
0.041 g (19%), white powder, mp 117–118°C
(decomp.). IR spectrum, ν, cm–1: 3132 (OH), 2225 w
12. Gusarova, N.K., Ivanova, N.I., Reutskaya, A.M., Arbu-
zova, S.N., Baikalova, L.V., Deryagina, E.N., Russav-
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