Synthesis of 1,5-disubstituted (E)-pent-2-en-4-yn-1-ones

Article abstract of DOI:10.1134/S1070428013090030

The condensation of 3-arylpropynals with aryl methyl ketones in the presence of sodium hydroxide in 50% aqueous ethanol at 0°C (Claisen-Schmidt reaction) afforded up to 89% of the corresponding (E)-1,5-diarylpent-2-en-4-yn- 1-ones. The E configuration of the double C=C bond and cis conformation of the enone fragment in the products in crystal and CDCl₃ solution were determined by X-ray analysis and ¹H NMR spectroscopy.

Full text of DOI:10.1134/S1070428013090030

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 9, pp. 1264–1269. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.A. Golovanov, D.R. Latypova, V.V. Bekin, V.S. Pisareva, A.V. Vologzhanina, V.A. Dokichev, 2013, published in Zhurnal
Organicheskoi Khimii, 2013, Vol. 49, No. 9, pp. 1282–1286.
Synthesis of 1,5-Disubstituted (E)-Pent-2-en-4-yn-1-ones
A. A. Golovanova, D. R. Latypovab, V. V. Bekina, V. S. Pisarevaa,
A. V. Vologzhaninac, and V. A. Dokichevb
a Togliatti State University, Belorusskaya ul. 14, Togliatti, 445667 Russia
b Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: dokichev@anrb.ru
c Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
Received March 27, 2013
Abstract—The condensation of 3-arylpropynals with aryl methyl ketones in the presence of sodium hydroxide
in 50% aqueous ethanol at 0°C (Claisen–Schmidt reaction) afforded up to 89% of the corresponding
(E)-1,5-diarylpent-2-en-4-yn-1-ones. The E configuration of the double C=C bond and cis conformation of the
enone fragment in the products in crystal and CDCl3 solution were determined by X-ray analysis and 1H NMR
spectroscopy.
DOI: 10.1134/S1070428013090030
The present work was aimed at synthesizing
a wider series of 1,5-disubstituted pent-2-en-4-yn-1-
ones and studying how the structure of initial acety-
lenic aldehydes IIIa–IIIc and methyl ketones IVa–IVj
affects the yield and structure of products of their base-
catalyzed condensation. Initial phenyl-, 4-methyl-
phenyl-, and 4-bromophenylprop-2-ynals IIIa–IIIc
were prepared by hydrolysis of propynal diethyl
acetals IIa–IIc, which were synthesized in turn by
successive reactions of arylacetylenes Ia–Ic with
ethylmagnesium bromide and triethyl orthoformate in
diethyl ether.
In recent years pentenynones, conjugated vinyl-
acetylenic ketones, have attracted appreciable interest
as promising biologically active compounds and build-
ing blocks ensuring selective modification of C=C,
C≡C, or C=O bonds to pyrazole [1, 2], furan [3–5],
pyran [6–8], dihydrothiopyranone [7–9], and other
pharmacophoric fragments [10]. 1,5-Disubstitued pent-
2-en-4-yn-1-ones are also interesting as initial com-
pounds for the synthesis of new PI3K inhibitors which
possess a huge potential for the treatment of cardio-
vascular, inflammatory, and autoimmune diseases, as
well as of cancer and AIDS [5]. New compounds of
this series are extensively synthesized; they are gener-
ally prepared by the Claisen–Schmidt condensation
[11, 12], catalytic vinylation of iodoacetylenes [13], or
base-catalyzed isomerization of 1,5-disubstituted
penta-2,4-diynyl silyl ethers [14].
The condensation of aldehydes III with methyl
ketones IV was carried out at 0°C in aqueous ethanol,
the molar ratio III–IV–NaOH being 1:1:0.5. In all
cases, the reaction did not stop at the aldolization step
and resulted in selective formation of E isomers Va–
Scheme 1.
EtMgBr
(EtO)3CH
R2
OEt
OEt
R1
MeC(O)R2 (IVa–IVj)
H+
R1
CH
R1
R1
CHO
O
Ia–Ic
IIa–IIc
IIIa–IIIc
Va–Vr
I–III, R1 = Ph (a), 4-MeC6H4 (b), 4-BrC6H4 (c); IV, R2 = Ph (a), 4-MeC6H4 (b), 4-i-PrC6H4 (c), 4-MeOC6H4 (d), 4-EtOC6H4 (e),
4-ClC6H4 (f), 3-BrC6H4 (g), 4-BrC6H4 (h), 3-H2NC6H4 (i), 2-furyl (j); V, R1 = R2 = Ph (a); R1 = Ph, R2 = 4-MeC6H4 (b), 4-i-PrC6H4 (c),
4-MeOC6H4 (d), 4-EtOC6H4 (e), 4-ClC6H4 (f), 3-BrC6H4 (g), 4-BrC6H4 (h), 3-H2NC6H4 (i), 2-furyl (j); R1 = 4-MeC6H4, R2 = Ph (k),
4-MeC6H4 (l), 4-ClC6H4 (m), Ph (n), 4-BrC6H4 (o), 2-furyl (p).
1264

SYNTHESIS OF 1,5-DISUBSTITUTED (E)-PENT-2-EN-4-YN-1-ONES
1265
O1
Vp in 10–89% yield (Scheme 1). The products were
isolated as light yellow or yellow needles or plates.
According to published data, base-catalyzed isomer-
ization of 1,5-disubstituted penta-2,4-diynyl silyl
ethers yields mixtures of E- and Z-isomeric pent-2-en-
4-yn-1-ones [14].
C17
C1
C3
C16
C11
C5
C12
C13
C2
C6
C7
C4
C10
C9
C15
C14
The nature of both aldehyde and acetophenone
components exerts a considerable effect on the yield of
the condensation products. The reactions of meta-sub-
stituted acetophenones IVg and IVi with phenylprop-
2-ynal (IIIa) were accompanied by tarring, and the
yield of pent-2-en-4-yn-1-ones Vg and Vi was as poor
as 30 and 10%, respectively. Introduction of a methyl
group or bromine atom into the para position of the
aromatic ring of phenylprop-2-ynal led to reduction of
the yield of Vk–Vp to 20–68%.
C8
Va
O1
C17
C16
C15
C1
C3
C11
C5
C12
C13
C10
C2
O1
C18
C4
C9
C6
C14
C19
C7
C8
1
The product structure was confirmed by the H and
1
13C NMR spectra. The H NMR spectra of pent-2-en-
Ve
C3
O1
C1
4-yn-1-ones Va–Vp contained two doublets at δ 6.90–
7.14 (2-H) and 7.39–7.45 ppm (3-H) from protons at
the double C2=C3 bond. The vicinal coupling constant
3J = 15.4–15.6 Hz indicated E configuration of that
bond. The E configuration of the C=C bond and s-cis
conformation of the enone fragment in molecules V in
crystal were unambiguously determined by X-ray
analysis of 1,5-diphenylpent-2-en-4-yn-1-one (Va),
1-(4-ethoxyphenyl)-5-phenylpent-2-en-4-yn-1-one
(Ve), and 5-(4-bromophenyl)-1-phenylpent-2-en-4-yn-
1-one (Vn). The structures of molecules Va, Ve, and
Vn are shown in figure. The torsion angles C1C2C3C4
(–176.2 to –178.0°) and OC1C2C3 (2.6–7.1°) corre-
spond to the E-s-cis configuration of the O=C1–
C2=C3–C4 enone fragment. Molecules Va, Ve, and Vn
are planar, which implies conjugation of the lone
electron pair on the oxygen atom with the unsaturated
bond system. It should be noted that the C3–C4 bond in
Va, Ve, and Vn is appreciably shorter than analogous
bond in vinylacetylene (1.45 Å) [15] (Table 1). The
other bond lengths and bond angles in molecules Va,
Ve, and Vn almost coincide with the corresponding
standard values.
C17
C5
C11
C16
C15
C6
C7
C12
C13
C2
C4
C10
C9
C8
C14
Vn
Structures of the molecules of 1,5-diphenylpent-2-en-4-yn-1-
one (Va), 1-(4-ethoxyphenyl)-5-phenylpent-2-en-4-yn-1-one
(Ve), and 5-(4-bromophenyl)-1-phenylpent-2-en-4-yn-1-one
(Vn) according to the X-ray diffraction data.
internal reference. The IR spectra were measured on
an FSM 1201 spectrometer with Fourier transform.
The X-ray diffraction data for compounds Va, Ve, and
Vn were acquired on a Bruker Smart Apex2 CCD
diffractometer. The structures were solved by the direct
Table 1. Bond lengths in the pent-2-en-4-yn-1-one fragment
of compounds Va, Ve, and Vn
Bond length d, Å
Bond
Thus the condensation of 3-arylpropynals with
acetophenones afforded 1,5-disubstituted (E)-pent-2-
en-4-yn-1-ones whose yield was largely determined by
the nature of the initial compounds.
Va
Ve
Vn
O1–C1
C1–C2
C1–C12
C2–C3
C3–C4
C4–C5
C5–C6
1.224(3)
1.478(4)
1.484(4)
1.324(4)
1.419(4)
1.204(4)
1.427(4)
1.227(2)
1.490(2)
1.481(2)
1.317(2)
1.425(2)
1.199(2)
1.442(2)
1.223(12)
1.514(15)
1.461(15)
1.328(16)
1.414(15)
1.197(15)
1.451(15)
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on
a Bruker AM-300 spectrometer at 300.13 and
75.47 MHz, respectively, using tetramethylsilane as
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

GOLOVANOV et al.
1266
Table 2. Principal crystallographic parameters of pent-2-en-4-yn-1-ones Va, Ve, and Vn and details of X-ray diffraction
experiments
Parameter
Va
Ve
Vn
CCDC entry no.
Formula
922718
C17H12O
232.27
925324
C19H16O2
276.36
925325
C17H11BrO
311.17
Molecular weight
Temperature, K
100(2)
100(2)
100(2)
Irradiation wavelength, Å
0.71073
Rhombic
P212121
0.71073
Rhombic
P212121
1.54178
Monoclinic
P21
Crystal system
Space group
Unit cell parameters:
a, Å
05.459(4)
13.641(9)
016.245(11)
90
5.3536(7)
10.9497(14)
24.370(3)00
90
4.9937(2)
23.1953(10)
5.7760(2)
98.496(3)
661.69(5)
2
b, Å
c, Å
β, deg
V, Å3
1209.6(13)
4
1428.6(3)
4
Z
F(000)
488
584
312
Crystal habit, mm
dcalc, g/cm3
0.36×0.12×0.09
1.275
0.42×0.38×0.08
1.285
0.16×0.14×0.03
1.562
μ, mm–1
0.078
0.082
4.123
Number of independent reflections (Rint)
Number of measured reflections/parameters
R, % [I > 2σ(I)]
1695 (0.10)
1218/163
0.045
2216 (0.034)
1931/191
0.037
1946 (0.074)
1748/172
0.068
Rw, %
0.097
0.093
0.161
Goodness of fit
1.000
1.010
1.000
method. All non-hydrogen atoms were localized by
difference syntheses of electron density, and their
positions were refined against F2hkl in anisotropic
approximation. All calculations were performed using
SHELXTL 5.10 [16]. Selected bond lengths in mole-
cules Va, Ve, and Vn are given in Table 1, and
parameters of X-ray diffraction experiments and final
divergence factors are collected in Table 2. The sets of
crystallographic data for compounds Va, Ve, and Vn
(CIF files) were deposited to the Cambridge Crystallo-
graphic Data Centre (http://ccdc.cam.ac.uk/).
tylene Ia–Ic in 15 ml of anhydrous diethyl ether was
added dropwise to the Grignard compound prepared
from 2.01 g (0.085 mol) of magnesium and 9.30 g
(0.085 mol) of ethyl bromide in 100 ml of anhydrous
diethyl ether on cooling, and the mixture was heated
for 2 h under reflux with stirring and was left to stand
for 10 h. A solution of 15 g (0.101 mol) of triethyl
orthoformate in 30 ml of diethyl ether was added under
vigorous stirring to the resulting precipitate of Iotsitch
compound, and the mixture was left to stand for 10 h
and was then heated under reflux for 4.5 h. The mix-
ture was treated with a solution of 26 g of ammonium
chloride in 74 ml of water on cooling with ice. The
organic phase was separated, the aqueous phase was
extracted with diethyl ether (3×10 ml), the extracts
were combined with the organic phase, dried over
MgSO4, and evaporated on a water bath, and the
residue was distilled under reduced pressure.
The structure of previously described compounds
IIa [17], IIIa [19], Va [22], Vd, Vf, and Vj [14] was
1
confirmed by their H and 13C NMR and IR spectra
which coincided with those reported in the literature.
3-Arylprop-2-ynal diethyl acetals IIa–IIc (gen-
eral procedure). A solution of 0.085 mol of arylace-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

SYNTHESIS OF 1,5-DISUBSTITUTED (E)-PENT-2-EN-4-YN-1-ONES
1267
3,3-Diethoxy-1-phenylpropyne (IIa). Yield 79%,
bp 121–122°C (1 mm), nD19 = 1.5191 [17].
ppm: 89.52, 104.28, 118.42, 126.31, 132.26, 134.57,
176.56 [21].
3,3-Diethoxy-1-(4-methylphenyl)propyne (IIb).
Reaction of 3-arylprop-2-ynals IIIa–IIIc with
methyl ketones IVa–IVj (general procedure). A solu-
tion of 0.01 mol of ketone IVa–IVj and 0.01 mol of
aldehyde IIIa–IIIc in 25 ml of 50% aqueous ethanol
was cooled to 0°C, and 0.8 ml of 20% aqueous sodium
hydroxide was added. After a solid separated, an ad-
ditional 0.6-ml portion of 20 aqueous sodium hy-
droxide was added, and the mixture was left to stand
for 10 h at room temperature. The precipitate was
filtered off, washed with 10 ml of cold 20% aqueous
ethanol, and recrystallized from 70–80% aqueous
ethanol.
Yield 54%, bp 135–136°C (5 mm), d20 = 0.985, nD20
=
1
1.5207. IR spectrum: ν 2238 cm–1 (C≡C). H NMR
3
spectrum (CDCl3), δ, ppm: 1.27 t (6H, CH2CH3, J =
6.0 Hz), 2.33 s (3H, C6H4CH3), 3.60–3.71 m and 3.78–
3.87 m (2H each, OCH2), 5.48 s (1H, CH), 7.05–
7.12 m and 7.32–7.40 m (2H each, Harom). 13C NMR
spectrum (CDCl3), δC, ppm: 15.58, 21.01, 62.52, 84.02,
86.01, 92.68, 120.02, 129.02, 130.83, 140.03 [18].
1-(4-Bromophenyl)-3,3-diethoxypropyne (IIc).
Yield 54%, bp 161–164°C (7 mm), d20 = 1.269, nD20.2
=
1.5503. IR spectrum: ν 2240 cm–1 (C≡C). H NMR
spectrum (CDCl3), δ, ppm: 1.16–1.23 m (6H,
CH2CH3), 3.55–3.61 m and 3.71–3.76 m (2H each,
OCH2), 5.40 br.s (1H, CH), 7.24–7.27 m and 7.34–
7.38 m (2H each, Harom). 13C NMR spectrum (CDCl3),
δC, ppm: 14.84, 60.67, 83.74, 85.42, 91.44, 120.56,
122.87, 131.28, 133.23. Found, %: C 51.62; H 4.46;
Br 31.29. C11H11O2Br. Calculated, %: C 51.79; H 4.35;
Br 31.32.
1
1,5-Diphenylpent-2-en-4-yn-1-one (Va). Yield
89% [22].
1-(4-Methylphenyl)-5-phenylpent-2-en-4-yn-1-
one (Vb). Yield 71%, mp 84–85°C. IR spectrum, ν,
1
cm–1: 2198, 1663, 1573. H NMR spectrum (CDCl3),
3
δ, ppm: 2.43 s (3H, CH3), 7.13 d (1H, 3-H, J =
15.6 Hz), 7.45 d (1H, 2-H, 3J = 15.6 Hz), 7.20–8.00 m
(9H, Harom). 13C NMR spectrum (CDCl3), δC, ppm:
21.53, 87.37, 99.85, 119.12, 125.28, 128.46, 128.61,
129.24, 131.93, 132.56, 133.07, 137.23, 139.78,
188.79. Found, %: C 87.62; H 5.86. C18H14O. Cal-
culated, %: C 87.74; H 5.74.
3-Arylprop-2-ynals IIIa–IIIc (general procedure).
A mixture of 38 mmol of acetal IIa–IIc, 10 ml of 5%
sulfuric acid, and 10 ml of glacial acetic acid was
heated for 1 h on a boiling water bath. Ethanol
liberated during the hydrolysis process was distilled
off under reduced pressure (water-jet pump). The still
residue was cooled, combined with the distillate, and
treated with NaHCO3 until neutral reaction. The prod-
uct was extracted into diethyl ether (3×10 ml), the
combined extracts were dried over MgSO4 and evapo-
rated on a water bath, and the residue was distilled
under reduced pressure.
1-(4-Isopropylphenyl)-5-phenylpent-2-en-4-yn-1-
one (Vc). Yield 64%, mp 49–50°C. IR spectrum, ν,
1
cm–1: 2198, 1662, 1571. H NMR spectrum (CDCl3),
3
δ, ppm: 1.29 d (6H, CH3, J = 7.0 Hz), 2.99 sext (1H,
3
J = 6.9 Hz), 7.12 d (1H, 3-H, J = 15.5 Hz), 7.45 d
3
(1H, 2-H, J = 15.5), 7.20–8.00 m (9H, Harom). Found,
%: C 87.38; H 6.77. C20H18O. Calculated, %: C 87.54;
H 6.63.
3-Phenylprop-2-ynal (IIIa). Yield 94%, bp 105–
107°C (13 mm), nD22 = 1.6027 [19].
1-(4-Methoxyphenyl)-5-phenylpent-2-en-4-yn-1-
one (Vd). Yield 50% [14].
3-(4-Methylphenyl)prop-2-ynal (IIIb). Yield
75%, bp 126–128°C (12 mm), nD19.5 = 1.6066. IR spec-
1-(4-Ethoxyphenyl)-5-phenylpent-2-en-4-yn-1-
1
trum, ν, cm–1: 2186 (C≡C), 1657 (C=O). H NMR
one (Ve). Yield 76%, mp 110–111°C. IR spectrum, ν,
1
cm–1: 2198, 1659, 1575. H NMR spectrum (CDCl3),
spectrum (CDCl3), δ, ppm: 2.35 s (3H, CH3), 7.12–
7.20 m and 7.42–7.50 m (2H each, Harom), 9.37 br.s
(1H, CHO). 13C NMR spectrum (CDCl3), δC, ppm:
21.52, 88.28, 95.65, 116.05, 129.35, 133.10, 141.99,
176.55 [20].
3
δ, ppm: 1.46 t (3H, CH3, J = 7.0 Hz), 4.13 q (2H,
3
3
CH2, J = 7.0 Hz), 7.11 d (1H, 3-H, J = 15.5 Hz),
3
7.45 d (1H, 2-H, J = 15.5 Hz), 6.90–8.10 m (9H,
Harom). Found, %: C 82.54; H 5.82. C19H16O2. Calculat-
ed, %: C 82.57; H 5.85.
3-(4-Bromophenyl)prop-2-ynal (IIIc). Yield 90%,
mp 91–93°C (from EtOH). IR spectrum, ν, cm–1: 2246
1-(4-Chlorophenyl)-5-phenylpent-2-en-4-yn-1-
one (Vf). Yield 89% [14].
1
(C≡C), 1652 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 7.40–7.48 m and 7.51–7.60 m (2H each, Harom),
1-(3-Bromophenyl)-5-phenylpent-2-en-4-yn-1-
one (Vg). Yield 30%, mp 58–59°C. IR spectrum, ν,
9.41 s (1H, CHO). 13C NMR spectrum (CDCl3), δC,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

GOLOVANOV et al.
1268
1
cm–1: 2198, 1675, 1666, 1568. H NMR spectrum
5-(4-Bromophenyl)-1-phenylpent-2-en-4-yn-1-
one (Vn). Yield 54%, mp 86–87°C. IR spectrum, ν,
cm–1: 2199, 1667. 1H NMR spectrum (CDCl3), δ, ppm:
7.09 d (1H, 3-H, J = 15.4 Hz), 7.27 d (1H, 2-H, J =
15.4 Hz), 7.30–8.10 m (9H, Harom). 13C NMR spectrum
(CDCl3), δC, ppm: 87.68, 99.88, 122.08, 125.64,
128.31, 128.37, 128.49, 129.47, 129.97, 130.13,
131.82, 132.02, 132.14, 132.35, 135.91, 187.65.
Found, %: C 65.94; H 3.61. C17H11BrO. Calculated, %:
C 65.61; H 3.57.
(CDCl3), δ, ppm: 2.38 s (3H, CH3), 7.14 d (1H, 3-H,
3J = 15.6 Hz), 7.37 d (1H, 2-H, J = 15.6 Hz), 7.15–
3
3
3
8.00 m (8H, Harom). Found, %: C 66.02; H 3.75.
C17H11BrO. Calculated, %: C 65.61; H 3.57.
1-(4-Bromophenyl)-5-phenylpent-2-en-4-yn-1-
one (Vh). Yield 76%, mp 96–97°C. IR spectrum, ν,
cm–1: 2198, 1664, 1568. H NMR spectrum (CDCl3),
1
3
δ, ppm: 7.14 d (1H, 3-H, J = 15.4 Hz), 7.39 d (1H,
2-H, J = 15.4 Hz), 7.20–8.00 m (9H, Harom). Found,
%: C 65.85; H 3.85. C17H11BrO. Calculated, %:
C 65.61; H 3.57.
3
1,5-Bis(4-bromophenyl)pent-2-en-4-yn-1-one
(Vo). Yield 30%, mp 130–134°C. IR spectrum, ν, cm–1:
2199, 1679, 1664. 1H NMR spectrum (CDCl3), δ, ppm:
3
1-(3-Aminophenyl)-5-phenylpent-2-en-4-yn-1-
one (Vi). Yield 10%, mp 62–63°C. IR spectrum, ν,
cm–1: 2196, 1663. 1H NMR spectrum (CDCl3), δ, ppm:
3.87 s (2H, NH2), 6.89 d (1H, Harom, J = 6.4 Hz),
7.09 d (1H, 3-H, J = 15.6 Hz), 7.20–7.60 m (9H,
7.09 d (1H, 3-H, J = 15.6 Hz), 7.20–8.00 m (9H,
Harom, 2-H). Found, %: C 52.52; H 2.71. C17H10Br2O.
Calculated, %: C 52.34; H 2.59.
3
5-(4-Bromophenyl)-1-(2-furyl)pent-2-en-4-yn-1-
one (Vp). Yield 20%, mp 129–130°C. IR spectrum, ν,
cm–1: 2197, 1661. 1H NMR spectrum (CDCl3), δ, ppm:
6.50–7.70 m (3H, Fu), 7.11 d (1H, 3-H, 3J = 15.6 Hz),
3
Harom, 2-H). Found, %: C 82.28; H 5.58. C17H13NO.
Calculated, %: C 82.56; H 5.31.
3
1-(2-Furyl)-5-phenylpent-2-en-4-yn-1-one (Vj).
7.29 d (1H, 2-H, J = 15.6 Hz), 7.30–7.60 m (4H,
Yield 69% [14].
H
arom). Found, %: C 60.19; H 2.86. C15H9BrO2. Cal-
culated, %: C 59.85; H 3.02.
5-(4-Methylphenyl)-1-phenylpent-2-en-4-yn-1-
one (Vk). Yield 50%, mp 70–71°C. IR spectrum, ν,
cm–1: 2196, 1664. 1H NMR spectrum (CDCl3), δ, ppm:
This study was performed in the framework of the
state problem of the Ministry of Education and Science
of the Russian Federation (project no. 3.1168.2011).
3
2.38 s (3H, CH3), 7.14 d (1H, 3-H, J = 15.6 Hz),
3
7.42 d (1H, 2-H, J = 15.6 Hz), 7.16–8.05 m (9H,
Harom). 13C NMR spectrum (CDCl3), δC, ppm: 21.61,
87.81, 98.93, 122.26, 124.54, 128.43, 128.63, 129.27,
129.36, 131.94, 133.08, 134.61, 144.08, 188.20.
Found, %: C 87.40; H 5.98. C18H14O. Calculated, %:
C 87.74; H 5.74.
REFERENCES
1. Sukhova, L.N., Ostroumov, I.G., Bel’skii, V.K., Gali-
shev, V.A., and Maretina, I.A., Zh. Org. Khim., 1994,
vol. 30, p. 46.
2. Waldo, J.P., Mehta, S., and Larock, R.C., J. Org. Chem.,
1,5-Bis(4-methylphenyl)pent-2-en-4-yn-1-one
(Vl). Yield 40%, mp 92–93°C. IR spectrum, ν, cm–1:
2197, 1662. 13C NMR spectrum (CDCl3), δC, ppm:
21.40, 87.40, 99.40, 119.10, 124.60, 128.50, 129.10,
129.20, 131.80, 132.50, 134.50, 139.60, 143.90,
188.00. Found, %: C 87.89; H 6.16. C19H16O. Calculat-
ed, %: C 87.65; H 6.21.
2008, vol. 73, p. 6666.
3. Miki, K., Nishino, F., Ohe, K., and Uemura, S., J. Am.
Chem. Soc., 2002, vol. 124, p. 5260.
4. Miki, K., Yokoi, T., Nishino, F., Kato, Y., Washitake, Y.,
Ohe, K., and Uemura, S., J. Org. Chem., 2004, vol. 69,
p. 1557.
5. Du, X., Chen, H., Chen, Y., Chen, J., and Liu, Y.,
Synlett, 2011, p. 1010.
6. Iwasawa, N., Shido, M., Maeyama, K., and Kusama, H.,
J. Am. Chem. Soc., 2000, vol. 122, p. 10226.
7. Ohe, K., Miki, K., Yokoi, T., Nishino, F., and
Uemura, S., Organometallics, 2000, vol. 19, p. 5525.
8. Iwasawa, N., Shido, M., and Kusama, H., J. Am. Chem.
Soc., 2001, vol. 123, p. 5814.
1-(4-Chlorophenyl)-5-(4-methylphenyl)pent-2-
en-4-yn-1-one (Vm). Yield 68%, mp 112–113°C. IR
1
spectrum, ν, cm–1: 2196, 1663, 1571. H NMR spec-
trum (CDCl3), δ, ppm: 2.38 s (3H, CH3), 7.14 d (1H,
3
3
3-H, J = 15.6 Hz), 7.37 d (1H, 2-H, J = 15.6 Hz),
13
7.15–8.00 m (8H, Harom). C NMR spectrum (CDCl3),
δC, ppm: 21.64, 87.40, 100.46, 119.12, 125.95, 129.07,
129.36, 129.95, 132.06, 132.21, 135.69, 139.65,
140.03, 187.60. Found, %: C 76.85; H 4.62.
C18H13ClO. Calculated, %: C 76.98; H 4.68.
9. Rosiak, A. and Christoffers, J., Tetrahedron Lett., 2006,
vol. 47, p. 5095.
10. Oliva, C.G., Silva, A.M.S., Paz, F.A.A., and Cava-
leiro, J.A.S., Synlett, 2010, p. 1123.
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SYNTHESIS OF 1,5-DISUBSTITUTED (E)-PENT-2-EN-4-YN-1-ONES
1269
16. Sheldrick, G.M., Acta Crystallogr., Sect. A, 2008,
11. Utekhina, N.V., Cand. Sci. (Chem.) Dissertation,
vol. 64, p. 112.
Khar’kov, 1987.
17. Zeitler, K., Org. Lett., 2006, vol. 8, p. 637.
12. Korshunov, S.P., Doctoral (Chem.) Dissertation,
Nizhnii Novgorod, 1997.
18. Lemhadhi, M., Tetrahedron, 2005, vol. 61, p. 9839.
19. Belot, S., Adv. Synth. Catal., 2010, vol. 352, p. 667.
20. Lee, K., Tetrahedron Lett., 2004, vol. 45, p. 5043.
13. Jeffery, T., Synthesis, 1987, p. 70.
14. Chen, J., Fan, G., and Liu, Y., Org. Biomol. Chem.,
2010, vol. 8, p. 4806.
21. Belot, S., Angew. Chem., Int. Ed., 2009, vol. 48,
p. 8923.
15. Spravochnik khimika (Chemist’s Handbook), Nikol’-
skii, B.P., Ed., Moscow: Khimiya, 1966, vol. 1, p. 367.
22. Stetter, H., Chem. Ber., 1960, vol. 93, p. 1253.
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