Synthesis and alkylation of new 3-functionally substituted carbo[c]fused pyridin-2-ones(thiones)

Article abstract of DOI:10.1134/S1070428013020139

By condensation of 2-acyl-1-(morpholin-4-yl)cycloalkenes with CH-acids new 3-functuinally substituted carbo[c]fused pyridin-2-ones(thiones) were synthesized. N, 1-Diphenyl-5, 6, 7, 8-tetrahydroisoquinoline-3-thione under the action of acrylonitrile and alkyl halides suffered a selective S-alkylation.

Full text of DOI:10.1134/S1070428013020139

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 2, pp. 259−267. © Pleiades Publishing, Ltd., 2013.
Original English Text © I.V. Dyachenko, M.V. Vovk, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 2, pp. 268−275.
Synthesis and Alkylation of New 3-Functionally Substituted
Carbo[c]fused Pyridin-2-ones(thiones)
I. V. Dyachenkoa and M. V. Vovkb
aTaras Shevchenko Lugansk National University, Lugansk, 91011 Ukraine
e-mail: ivladya87@e-mail.ua
bInstitute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
Received May 30, 2012
Abstract—By condensation of 2-acyl-1-(morpholin-4-yl)cycloalkenes with СН-acids new 3-functuinally
substituted carbo[c]fused pyridin-2-ones(thiones) were synthesized. N, 1-Diphenyl-5, 6, 7, 8-tetrahydroisoquinoline-
3-thione under the action of acrylonitrile and alkyl halides suffered a selective S-alkylation.
DOI: 10.1134/S1070428013020139
The interest to the derivatives of carbo[c]fused
pyridines originates from the presence in their series of
compounds with wide range of biological actions: anti-
corosolic [1], analgesic [2], cardiotonic [3], fungicidal [4],
and antimicrobial [5]. Compounds of this type are inhibi-
tors of cytomegalovirus [6] and HIV-1 reverse transcrip-
tase [7], antagonists of neutral acetylcholine receptors [8],
and also can be applied as chromophores in manufactur-
ing light-sensitive diodes [9]. The preparation of versatile
carbo[c]fused pyridines is performed by the condensation
of 1-acylcyclohexanones with cyano(thio)acetamides
[10], by the recyclization of 6-amino-3, 4-tetramethylene-
2-thioxothiopyrans with amines [11], by the reaction
of 4, 6-dimethyl-3-cyanopyridine-2(1Н)-thione with
tetracyanoethylene [12], of cycloalkylidenecyanoacetic
ester with aromatic aldehydes and ammonium ac-
etates [13], or of cycloalkylidenemalononitriles with
arylmethylidene(cyano)thioacetamides[14].
Most probably the transformation sequence includes the
corresponding intermediates of the nucleophilic vinyl
substitution [16] А and B that undergo the intramolecular
cyclization into the target products (Scheme 1).
The advantage of this method is the use of more
available than 1-acylcycloalkanones[17] еnaminoketones
I[18], and also the mild reaction conditions not requiring
elevated temperature.
The heterocyclization of intermediate B occurs che-
moselectively; the nitrogen atom of the thioamide and
not the amide fragment plays the role of the nucleophilic
site. This fact is confirmed both by the complex of the
spectral data and by the chemical reactions. In particular,
the cyanoethylation of compound Vg with acrylonitrile
in boiling ethanol in the presence of triethylamine
afforded N, 1-diphenyl-3-(2-cyanoethylsulfanyl)-5,
6, 7, 8-tetrahydroisoquinoline-4-carboxamide (VI)
(Scheme 2).
We report here on the new approach to the synthesis of
previously unknown 3-functionally substituted carbo[c]
fused pyridines underlain by the cyclocondensation
involving enamines of 2-acylcycloalkenes. 2-Acyl-1-
(morpholin-4-yl)cycloalkenes Iа–Ig [15] cleanly react
with N-(furan-2-ylmethyl)-2-cyanoacetamide (IІ) and
N-substituted monothiomalonodiamides ІІІа–IIIe at
room temperature in anhydrous ethanol in the presence
of sodium ethylate leading to the formation of carbo[c]
fused 2-oxopyridine-3-carbonitriles IVа–IVd and
3-carbamoylpyridine-2-thiones Vа–Vk in high yields.
The alkylation of 2-thioxo-N, 1-diphenyl-2, 3, 5, 6, 7,
8-hexahydroisoquinoline-4-carboxamide (Vg) with alkyl
halides VIIа, VIIb provided the corresponding thioethers
VIIIа, VIIIb.
The reaction with allyl bromide was ambiguous:
A mixture formed of S-(IХ) and N-(X) allyl derivatives
in the ratio 3 : 1. This conclusion was derived from the
1
date of Н NMR and mass spectra and the chromato-
1
graphic findings: Н NMR spectra contains double set
of signals of protons from S(N)CH2 and NH groups, in
259

DYACHENKO, VOVK
260
Scheme 1.
R2
R2
H
N
n
n
O
CN
CN
O
CN
O
O
II
_H2O
. .
R2
R1
N
R1
O
HN
A
n
O
O
N
IVа_IVd
O
_ O
R1
O
R2
R2
NH
S
O
Iа_Ig
O
S
H2N
NHR3
IIIа_IIIe
O
S
NHR3
NHR3
_H2O
. .
H2N
R1
O
R1
N
H
Vа_Vk
B
I, n = 0, R1 = Ph, R2 = H (a); n = 1: R1 = Me, R2 = H (b), R1 = i-Pr, R2 = H (c); R1 = Ph, R2 = H (d); R1 = 2-ClC6H4, R2 = H
(e);R1 = Ph, R2 = Me (f); R1 = R2 = Me (g); III, R3 = PhCH2 (a), cyclo-C3H5 (b), Ph (c), 2-MeC6H4 (d), furan-2-ylmethyl
(e); IV, n = 0, R1 = Ph, R2 = H (a); n = 1 : R1 = Ph, R2 = H (b); R1 = 2-ClC6H4, R2 = H (c); R1 = Ph, R2 = Me (d); V, R1 =
Me, R2 = H, R3 = cyclo-C3H5 (a); R1 = Me, R2 = H, R3 = Ph (b); R1 = R2 = Me, R3 = PhCH2 (c); R1 = R2 = Me, R3 = Ph
(d); R1 = i-Pr, R2 = H, R3 = furan-2-ylmethyl (e); R1 = Ph, R2 = H, R3 = PhCH2 (f); R1 = Ph, R2 = H, R3 = Ph (g); R1 = Ph,
R2 = H, R3 = 2-MeC6H4 (h); R1 = Ph, R2 = H, R3 = furan-2-ylmethyl (i); R1 = Ph, R2 = Me, R3 = Ph (j); R1 = Ph, R2 = Me,
R3 = furan-2-ylmethyl (k).
Scheme 2.
O
NHPh
CN
CN
Ph
Ph
Ph
N
N
S
VI
O
RX
VIIа, VIIb
NHPh
R
Vg
S
VIIIа, VIIIb
O
S
O
Br
NHPh
NHPh
+
Ph
N
N
S
IX
X
VII, R = Me, X = I (а); R = PhCH2, X = Cl (b); VIII, R = Me (а), PhCH2 (b).
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SYNTHESIS AND ALKYLATION
261
Scheme 3.
N
CN
NH
CN
N
H
CN
. .
XI
Ph
O
N
Ph
N
N
_H2O
C
XII
B
Id
_ O
NH
H2N
OH
XIII
N
OH
H
Ph
O
XIV
the GC-MS spectrum a single peak of the molecular ion
[M + 1]+ is observed, and the chromatogrphy indicates
the presence of two compounds. The assignment of the
proton signals of the SCH2 group was done accounting
for the data of [19] where an S-allyl pyridine derivative
had been characterized.
broadened singlets of the protons of NH and ОН groups
in the region δ 9.64 and 13.39 ppm. In the 13С NMR
spectrum of compound XIV all signals of carbon atoms
are present taking into account the superposition of two
pairs of symmetric carbon atoms of the phenyl substituent
in the region 126.76 and 128.39 ppm.
Bringing into the SNVin reaction with enaminok-
etone Id of 2-(1Н-benz[d]imidazol-2-yl)acetonitrile
(XI) rуsulted in the formation of 11-phenyl-7, 8, 9,
10-tetrahydrobenzo[4, 5]imidazole[1, 2-b]isoquinoline-
6-carbonitrile (XII), most probably via intermediate C
(Scheme 3).
EXPERIMENTAL
IR spectra of compounds obtained were recorded on
a spectrophotometer FIR-spectrometer Spectrum One
(Perkin Elmer) from pellets with KBr, 1Н NMR spectra
were registered on a spectrometer Bruker DR-500
(500.13 MHz) in DMSO-d6, internal reference TMS.
13С NMR spectra were taken on a spectrometer Varian
VXR-300 (125.74 MHz) in DMSO-d6, internal reference
TMS. Mass spectra were registered on instruments
Varian L GC/MS (70 eV) with a direct admission of
the sample into the ion source (compound XII) and
HP Chrommass GC/MC 5890/5972, column HP-5 MS
(70 eV), eluent CH2Cl2. Melting points were measured
on a Koeffler heating block. The reaction progress
was monitored and the purity of compounds obtained
was checked by TLC on Silufol UV-254 plates, eluent
acetone–hexane, 3 : 5, development in iodine vapor and
under UV irradiation.
Taking into consideration the data on the possibility
to use m-aminophenol XIII as the СН-component in the
Michael reaction [20] we carried out its condensation with
enaminoketone Id by boiling in anhydrous ethanol in the
presence of sodium ethylate. However this reaction result-
ed in transamination giving [2-(3-hydroxyphenylamino)
cyclohex-1-enyl]phenylketone (XIV).
Spectral characteristics confirm the structure of com-
pounds XII, XIV. IR spectrum of compound XII contains
the absorption band of the stretching vibrations of the
conjugated cyano group in the region 2223 cm–1. In the
1Н NMR spectrum proton signals of the tetramethylene
fragment and of the aromatic substituents are observed. In
the IR spectrum of enaminoketone XIV the characteristic
absorption bands of the stretching vibrations of ОН, NH,
and С=О groups are present at 3154, 2934, and 1713
cm–1. 1Н NMR spectrum contains the proton signals of
cyclohexene ring and of aromatic substituents, and also
2-Acyl-1-(N-morpholinyl)cycloalkenes Iа–Ig were
obtained by procedure [15]. Compound Ia, yield 71%,
orange oily substance, bp 180–190°С (6–7 mm Hg).
Compound Ib, yield 83%, orange oily substance, bp
120–130°С (1–2 mm Hg) {bp 90–110°С (0.2–0.3 mm Hg)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 2 2013

DYACHENKO, VOVK
262
Calculated, %: C 57.67; H 5.81; N 13.45. М 208.284.
[15]}. Compound Ic, yield 79%, yellow oily substance, bp
128–135°С (2 mm Hg). Compound Id, yield 77%, orange
oily substance, bp 160°С (2 mm Hg). Compound Ie,
yield 64%, orange oily substance, bp 200°С (2 mm Hg).
Compound If, yield 73%, orange oily substance, bp
180–190°С (6–7 mm Hg). Compound Ig, yield 70%,
yellow oily substance, bp 140°С (2 mm Hg).
3-Amino-3-thioxo-N-(furan-2-ylmethyl)propan-
amide (IIIe). Yield 14.67 g (74%), light-yellow crystals,
1
mp 89–91°С (EtОН) (mp 130–132°С [18]). Н NMR
spectra, δ, ppm: 3.50 s (2Н, СH2), 4.28 d (2Н, NСH2,
J 5.0 Hz), 6.29 s (1Н, furan), 6.40 s (1Н, furan), 7.58
s (1Н, furan), 8.51 br.s (1Н, СОNН), 9.31 br.s and
9.61 br.s (1H each, NH2). Mass spectrum, m/z(Irel, %):
199 (100) [M + 1]+. Found, %: C 48.30; H 4.95; N 14.02.
C8H10N2O2S. Calculated, %: C 48.47; H 5.09; N 14.13.
М 198.245.
Monothiomalonodiamides IIIа–IIIe were obtained
by method [21].
3-Amino-N-benzyl-3-thioxopropanamide (IIIa).
Yield 16.70 g (80%), colorless crystals, mp 98°С (EtОН)
(mp 110–111°С [22]). 1Н NMR spectra, δ, ppm: 3.53 s
(2H, CH2), 4.32 d (2Н, NСH2, J 6.0 Hz), 7.21–7.43 m
(5Н, Ph), 8.49 br.s (1Н, СОNН), 9.29 br.s and 9.55 br.s
(1H each, NH2). 13С NMR spectra, δ, ppm: 42.25, 51.55,
126.73, 127.18 (2С), 128.17 (2С), 139.04, 166.62, 200.00.
Mass spectrum, m/z(Irel, %): 209 (100) [M + 1]+. Found,
%: C 57.58; H 5.06; N 13.33. C10H12N2OS. Calculated,
%: C 57.67; H 5.18; N 13.45. М 208.284.
Compounds IVа–IVd. General procedure. To a
mixture of 10 mmol of an appropriate enaminoketone
Iа–Ig and 1.64 g (10 mmol) of N-(furan-2-ylmethyl)-2-
cyanoacetamide (II) in 15 ml of anhydrous ethanol was
added while stirring at 20°С a solution obtained from
0.23 g (10 mmol) of sodium and 10 ml of anhydrous
ethanol, the mixture was stirred for 1 h and left standing
for 24 h. The formed precipitate was filtered off, washed
with ethanol and hexane.
3-Amino-3-thioxo-N-cyclopropylpropanamide
(IIIb). Yield 10.92 g (69%), white crystalline powder,
mp 143–145°С (EtОН). 1Н NMR spectra, δ, ppm: 0.38–
0.45 m (2Н, СH2 cyclopropyl), 0.58–0.66 m (2Н, СH2
cyclopropyl), 2.54–2.62 m (1Н, С1H cyclopropyl), 3.34 d
(2Н, СH2, 2J 12.6 Hz), 8.12 br.s (1Н, СОNН), 9.28 br.s
and 9.58 br.s (1H each, NH2). Found, %: C 45.41; H 6.20;
N 17.68. C6H10N2OS. Calculated, %: C 45.55; H 6.37;
N 17.71.
3-Oxo-1-phenyl-2-(furan-2-ylmethyl)-3, 5, 6,
7-tetrahydro-2Н-cyclopenta[c]pyridine-4-carbo-
nitrile (IVа). Yield 2.2 g (69%), dark-brown crystals
of cubic form, under UV irradiation fluoresce, mp
191–193°С (АсОН). IR spectrum, ν, cm–1: 2213(C≡N),
1660 (C=O). 1Н NMR spectra, δ, ppm: 1.81–2.12 m (2Н,
СН2), 2.36–2.48 m (2Н, СН2), 2.84–3.15 m (2Н, СН2),
4.92 s (2Н, NСН2), 5.97 br.s (1H, C3H furan), 6.32 br.s
(1H, C4H furan), 7.26–7.58 m (6H, Ph and C5H furan).
13С NMR spectra, δ, ppm: 24.48, 30.56, 33.84, 40.30,
42.76, 97.47, 108.66, 111.03, 116.08, 123.04, 128.62,
129.35, 130.31, 132.99, 142.81, 148.54, 149.47, 160.11,
167.48. Mass spectrum, m/z(Irel, %): 315 (100) [M –
1]+. Found, %:C 75.85; H 9.99; N 8.71. C20H16N2O2.
Calculated, %: C 75.93; H 5.10; N 8.85. М 316.354.
3-Amino-3-thioxo-N-phenylpropanamide (IIIc).
Yield 15.0 g (77%), light-brown crystals, mp 105–107°С
1
(АсОН) (mp 96–98°С [18]). Н NMR spectra, δ, ppm:
3.68 s (2Н, СН2), 7.05 t (1Н, Ph, J 7.5 Hz), 7.29 t (2Н,
Ph, J 7.5 Hz), 7.61 d (2Н, Ph, J 8.0 Hz), 9.33 br.s and
9.60 br.s (1H each, NH2), 10.05 br.s (1Н, СОNН). Mass
spectrum, m/z(Irel, %): 195 (100) [M + 1]+. Found, %:
C 55.49; H 5.06; N 14.37. C9H10N2OS. Calculated, %:
C 55.65; H 5.19; N 14.42. М 194.256.
3-Oxo-1-phenyl-2-(furan-2-ylmethyl)-2, 3, 5, 6, 7,
8-hexahydroisoquinoline-4-carbonitrile (IVb). Yield
2.54 g (77%), orange crystals, under UV irradiation
fluoresce, mp 165–167°С (АсОН). IR spectrum, ν,
3-Amino-3-thioxo-N-(2-methylphenyl)
propanamide (IIId). Yield 14.6 g (70%), yellow crystals,
mp 102–105°С (EtОН). 1Н NMR spectra, δ, ppm: 2.28
s (3Н, Mе), 3.73 s (2Н, СH2), 7.10 t (1Нarom, J 7.5 Hz),
7.18 t (1Нarom, J 7.5 Hz), 7.22 d (1Нarom, J 7.5 Hz), 7.46 d
(1Нarom, J 8.0 Hz), 9.45 br.s and 9.70 br.s (1H each, NH2),
9.53 br.s (1Н, СОNН). 13С NMR spectra, δ, ppm: 17.76,
51.97, 124.51, 125.09, 125.81, 130.17, 131.36, 135.99,
165.28, 200.01. Mass spectrum, m/z(Irel, %): 209 (100) [M
+ 1]+. Found, %:C 57.50; H 5.75; N 13.30. C10H12N2OS.
1
cm–1: 2216(C≡N), 1663 (C=O). Н NMR spectra, δ,
ppm: 1.55 m (2H, СН2), 1.67 m (2H, СН2), 1.97 t (2Н,
CH2, J 6.0 Hz), 2.85 t (2H, СН2, J 6.0 Hz), 4.90 s (2Н,
NСН2), 6.00 d (1H, C3H furan, J 2.4 Hz), 6.32 br.s (1H,
C4H furan), 7.27 d (1H, C5H furan, J 3.2 Hz), 7.48–7.59 m
(5H, Ph). 13С NMR spectra, δ, ppm: 20.64, 21.64, 25.90,
28.86, 42.66, 100.66, 108.09, 110.50, 114.96, 115.52,
128.08, 128.92, 129.59, 132.28, 142.21, 148.68, 151.57,
158.69, 159.71. Mass spectrum, m/z(Irel, %): 331 (100) [M
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SYNTHESIS AND ALKYLATION
263
+ 1]+. Found, %: C 76.21; H 5.29; N 8.35. C21H18N2O2.
Calculated, %: C 76.34; H 5.49; N 8.48. М 330.389.
with 10% hydrochloric acid till рН 5 and left standing
for 48 h. The formed precipitate was filtered off, washed
with ethanol and hexane.
3-Oxo-2-(furan-2-ylmethyl)-1-(2-chlorophenyl)-2,
3, 5, 6, 7, 8-hexahydroisoquinoline-4-carbonitrile
(IVc). Yield 2.5 g (68%), white powder, under UV
irradiation fluoresce, mp 131–133°С (АсОН). IR
1-Methyl-3-thioxo-N-cyclopropyl-2, 3, 5, 6, 7,
8-hexahydroisoquinoline-4-carboxamide (Vа). Yield
1.7 g (64%), dark-brown powder, mp 215–218°С
(АсОН). IR spectrum, ν, cm–1: 3300(NН), 1664
(CONН), 1155 (C=S). 1Н NMR spectra, δ, ppm: 0.52 m
(2Н, СН2 cyclopropyl), 0.62 m (2Н, СН2 cyclopropyl),
1.51–1.79 m (4Н, 2СН2), 2.28 s (3Н, Mе), 2.51 m (4Н,
2СН2), 2.61–2.79 m (1Н, NСН), 7.90 br.s (1Н, CONН),
13.09 br.s (1Н, NН). 13С NMR spectra, δ, ppm: 5.45,
15.91, 21.16, 21.58, 22.25, 23.85, 26.57, 120.31, 136.70,
145.57, 146.22, 167.58, 169.71. Mass spectrum, m/z(Irel,
%): 263 (100) [M + 1]+. Found, %: C 63.95; H 6.80;
N 10.52. C14H18N2OS. Calculated, %: C 64.09; H 6.91;
N 10.68. М 262.375.
1
spectrum, ν, cm–1: 2222(C=N), 1658 (C=O). Н NMR
spectra, δ, ppm: 1.42–1.61 m (2H, СН2), 1.65–1.74 m
(2H, СН2), 1.82–1.98 m (2H, СН2), 2.83–2.94 m (2H,
2
СН2), 4.70 d and 5.08 d (1H each, NCH2, J 15.2 Hz),
5.96 d (1Н, C3H furan, J 2.4 Hz), 6.31 d (1Н, C5H furan,
J 1.2 Hz), 7.36 d (1Harom, J 7.6 Hz), 7.47 br.s (1H, C4H
furan), 7.52 t (1Harom, J 7.6 Hz), 7.66 t (1Harom, J 7.6 Hz),
7.66 d (1Harom, J 7.6 Hz). 13С NMR spectra, δ, ppm:
20.60, 21.44, 25.06, 28.79, 42.17, 101.48, 108.52, 110.52,
115.26, 115.39, 127.90, 129.78, 130.56, 130.70, 131.85,
131.91, 142.41, 148.15, 148.17, 158.73, 160.00. Mass
spectrum, m/z(Irel, %): 365 (100) [M + 1]+. Found, %:
C 69.02; H 4.58; N 7.57. C21H17ClN2O2. Calculated, %:
C 69.14; H 4.70; N 7.68. М 364.834.
1-Methyl-3-thioxo-N-phenyl-2, 3, 5, 6, 7, 8-hexa-
hydroisoquinoline-4-carboxamide (Vb). Yield 2.15 g
(72%), gray powder, mp 235–238°С (BuОН). IR
spectrum, ν, cm–1: 3444, 2945(NН), 1673 (CONН),
1255 (C=S). 1Н NMR spectra, δ, ppm: 1.65–1.71 m (4Н,
2СН2), 2.33 s (3Н, Mе), 2.57–2.68 m (4Н, 2СН2), 7.06 t
(1Н, Ph, J 6.8 Hz), 7.32 t (2Н, Ph, J 7.6 Hz), 7.68 t (2Н,
Ph, J 7.8 Hz), 10.12 br.s (1Н, CONН), 11.33 br.s (1Н,
NН). 13С NMR spectra, δ, ppm: 15.97, 21.10, 21.53,
23.86, 26.76, 119.19, 120.50, 123.07, 128.50, 136.88,
139.53, 145.72, 146.70, 165.02, 169.72. Mass spectrum,
m/z(Irel, %): 299 (100) [M + 1]+. Found, %: C 68.33;
H 5.95; N 9.18. C17H18N2OS. Calculated, %: C 68.43;
H 6.08; N 9.39. М 298.409
6-Methyl-3-oxo-1-phenyl-2-(furan-2-ylmethyl)-2,
3, 5, 6, 7, 8-hexahydroisoquinoline-4-carbonitrile
(IVd). Yield 2.9 g (84%), yellow crystals, under UV
irradiation fluoresce, mp 149–151°С (АсОН). IR
1
spectrum, ν, cm–1: 2212(C≡N), 1656 (C=O). Н NMR
spectra, δ, ppm: 1.01 d (3Н, Mе, J 4.0 Hz), 1.13–1.24 m
(1H, СНMе), 1.65–1.81 m (2Н, СН2), 1.82–2.18 m (2Н,
СН2), 2.42 d.d (1Н, СН2, J 8.0 and 20.0 Hz), 2.97 d.d (1Н,
СН2, J 4.0 and 16.0 Hz), 4.87 d and 4.94 d (2Н, NСН2,
2J 16.0 Hz), 6.99 d (1H, C3H furan, J 4.0 Hz), 6.32 m (1H,
C4H furan), 7.21–7.32 m (2Н, Ph), 7.41–7.62 m (4H,
Ph and C5H furan). 13С NMR spectra, δ, ppm: 21.62,
26.33, 27.54, 30.33, 37.53, 43.20, 101.03, 108.69, 111.05,
115.04, 116.08, 128.38, 128.83, 129.48, 129.50, 130.15,
132.90, 142.76, 149.22, 152.09, 159.30, 159.99. Mass
spectrum, m/z(Irel, %): 345 (100) [M + 1]+. Found, %:
C 76.61; H 5.72; N 8.00. C22H20N2O2. C22H20N2O2.
Calculated, %:C 76.72; H 5.85; N 8.13. М 344.416.
N-Benzyl-1, 6-dimethyl-3-thioxo-2, 3, 5, 6, 7,
8-hexahydroisoquinoline-3-carboxamide (Vc). Yield
2.6 g (79%), white powder, mp 270–272°С (BuОН).
IR spectrum, ν, cm–1: 3256, 3198(NН), 1668 (CONН),
1239 (C=S). 1Н NMR spectra, δ, ppm: 0.93 d (3Н, Mе,
J 6.5 Hz), 1.22 m (1Н, С6Н), 1.63 m (1Н, СН2), 1.82 m
(1Н, СН2), 2.05 d and 2.08 d (1Н, СН2, J 11.0 and
11.50 Hz), 2.30 s (3Н, Mе), 7.49 m (1Н, СН2), 2.57 m
(2Н, СН2), 4.41 d (2Н, NСН2, J 5.5 Hz), 7.24 t (1Н,
Ph, J 7.5 Hz), 7.32 t (2Н, Ph, J 7.5 Hz), 5.50 d (2Н, Ph,
J 8.0 Hz), 8.54 t (1Н, CONН, J 5.5 Hz), 13.24 br.s (1Н,
NН). 13С NMR spectra, δ, ppm: 16.06, 21.39, 23.82,
27.37, 29.71, 35.07, 42.17, 120.02, 126.55, 127.55,
127.95, 136.73, 139.52, 145.59, 146.30, 166.55, 169.75.
Mass spectrum, m/z(Irel, %): 327 (100) [M + 1]+. Found,
%: C 69.81; H 6.66; N 8.41. C19H22N2OS. Calculated,
%: C 69.90; H 6.79; N 8.58. М 326.463.
N, 1-Dialkyl(aryl, hetaryl)-3-thioxo-2, 3, 5, 6, 7,
8-hexahydroisoquinoline-4-carboxamides Vа–Vk.
General procedure. To a mixture of 10 mmol of an
appropriate enaminoketones Iа–Ig and 10 mmol of
monothiomalonodiamides IIIа–IIIe in 15 ml of anhy-
drous ethanol was added while stirring at 20°С a solution
obtained from 0.23 g (10 mmol) of sodium and 10 ml of
anhydrous ethanol, the mixture was stirred for 10 min and
left standing for 24 h. The reaction mixture was diluted
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DYACHENKO, VOVK
264
IR spectrum, ν, cm–1: 3419, 2928(NН), 1638(CONН),
1, 6-Dimethyl-3-thioxo-N-phenyl-2, 3, 5, 6, 7,
1250 (C=S). 1Н NMR spectra, δ, ppm: 1.57 m (2Н, СН2),
1.68 m (2Н, СН2), 2.33 t (2Н, СН2, J 6.0 Hz), 2.67 t (2Н,
СН2, J 6.0 Hz), 7.07 t (1Н, Ph, J 7.5 Hz), 7.33 t (2Н,
Ph, J 8.0 Hz), 7.41 m (1Н, Ph), 7.53 m (4Н, Ph), 7.72 d
(2Н, Ph, J 8.0 Hz), 10.31 br.s (1Н, CONН), 13.52 br.s
(1Н, NН). Mass spectrum, m/z(Irel, %): 361 (100) [M +
1]+. Found, %: C 73.19; H 5.41; N 7.68. C22H20N2OS.
Calculated, %:C 73.30; H 5.59; N 7.77. М 360.480.
8-hexahydroisoquinoline-4-carboxamide (Vd). Yield
2.12 g (68%), yellow powder, mp 285–287°С (BuОН).
IR spectrum, ν, cm–1: 3430, 2936(NН), 1668 (CONН),
1252 (C=S). 1Н NMR spectra, δ, ppm: 0.97 d (3Н, Mе,
J 6.5 Hz), 1.28 m (1Н, СН2), 1.70 m (1Н, СН2), 1.85 m
(1Н, СН2), 2.19 m (1Н, СН2), 2.34 s (3Н, Mе), 7.43 m
(1Н, СН2), 2.64 t (2Н, СН2, J 4.0 Hz), 7.07 t (1Н, Ph,
J 7.5 Hz), 7.31 t (2Н, Ph, J 7.5 Hz), 7.69 d (2Н, Ph,
J 8.0 Hz), 10.13 br.s (1Н, CONН), 13.35 br.s (1Н, NН).
13С NMR spectra, δ, ppm: 16.10, 21.34, 23.79, 27.35,
29.66, 34.99, 39.50, 119.20, 120.15, 123.12, 128.57,
136.82, 139.58, 145.51, 146.70, 165.04, 169.79. Mass
spectrum, m/z(Irel, %): 313 (100) [M + 1]+. Found, %:
C 69.01; H 6.32; N 8.85. C18H20N2OS. Calculated, %:
C 69.20; H 6.45; N 8.97. М 312.436.
N-(2-Methylphenyl)-3-thioxo-1-phenyl-2, 3, 5, 6, 7,
8-hexahydroisoquinoline-4-carboxamide (Vh). Yield
2.8 g (75%), yellow powder, mp 215–218°С (АсОН).
IR spectrum, ν, cm–1: 3435, 3283(NН), 1652 (CONН),
1269 (C=S). 1Н NMR spectra, δ, ppm: 1.62 m (2Н, СН2),
1.75 m (2Н, СН2), 2.37 m (5Н, СН2 and Mе), 2.80 m (2Н,
СН2), 7.12 t (1Нarom, J 7.5 Hz), 7.23 m (2Нarom), 2.43 m
(2Нarom), 7.54 m (3Нarom), 7.59 d (1Нarom, J 8.0 Hz),
9.58 br.s (1Н, СОNН), 13.37 br.s (1Н, NН). 13С NMR
spectra, δ, ppm: 18.13, 21.13, 21.66, 25.39, 26.68, 120.75,
125.15, 125.38, 125.65, 128.36, 129.07, 129.49, 130.13,
132.32, 132.37, 136.13, 138.64, 144.44, 145.70, 165.11,
172.15. Mass spectrum, m/z(Irel, %): 373 (100) [M –
1]+. Found, %: C 73.59; H 5.88; N 7.33. C23H22N2OS.
Calculated, %: C 73.76; H 5.92; N 7.48. М 374.507.
1-Isopropyl-3-thioxo-N-(furan-2-ylmethyl)-2,
3, 5, 6, 7, 8-hexahydroisoquinoline-3-carboxamide
(Ve). Yield 2.1 g (63%), white powder, mp 170–172°С
(АсОН). IR spectrum, ν, cm–1: 3329, 2955(NН), 1670
(CONН), 1199 (C=S). 1Н NMR spectra, δ, ppm: 1.27 d
(6Н, 2Mе, J 6.0 Hz), 1.54–1.79 m (4Н, 2СН2), 2.53–
2.77 m (4Н, 2СН2), 3.01–3.12 m (1Н, СНMе2), 4.41 d
(2Н, NСН2, J 7.96 Hz), 6.31 m (1Н, С4Н furan), 6.42 s
(1Н, С3Н furan), 7.59 s (1Н, С5Н furan), 8.85 br.s (1Н,
NН), 9.01 br.s (1Н, NН). Mass spectrum, m/z(Irel, %):
331 (100) [M + 1]+. Found, %: C 65.32; H 6.60; N 8.39.
C18H22N2O2S. Calculated, %: C 65.43; H 6.71; N 8.48.
М 330.452.
3-Thioxo-1-phenyl-N-(furan-2-ylmethyl)-2, 3, 5, 6,
7, 8-hexahydroisoquinoline-4-carboxamide (Vi). Yield
2.5г (66%), yellow powder, mp 225–227°С (АсОН).
IR spectrum, ν, cm–1: 3348, 2966 (NН), 1655 (CONН),
1250 (C=S). 1Н NMR spectra, δ, ppm: 1.38–1.55 m (2Н,
СН2), 1.56–1.71 m (2Н, СН2), 2.30 t (2Н, СН2, J 8.0 Hz),
2.58 t (2Н, СН2, J 8.0 Hz), 4.40 d (2Н, NСН2, J 4.0 Hz),
6.41 br.s (1Н, С3Н furan), 6.49 br.s (1Н, С4Н furan),
7.38–7.50 m (5Н, Ph), 7.57 br.s (1Н, С5Н furan), 8.59 br.s
(1Н, CONН), 13.19 br.s (1Н, NН). 13С NMR spectra, δ,
ppm: 21.57, 22.10, 25.82, 27.03, 36.33, 107.32, 110.90,
121.10, 128.83, 129.57, 129.95, 132.90, 138.87, 142.21,
146.26, 147.79, 152.80, 166.78, 171.76. Mass spectrum,
m/z (Irel, %): 365 (100) [M + 1]+. Found, %: C 69.07;
H 5.44; N 7.59. C21H20N2O2S. Calculated, %: C 69.21;
H 5.53; N 7.69. М 364.469.
N-Benzyl-3-thioxo-1-phenyl-2, 3, 5, 6, 7, 8-hexa-
hydroisoquinoline-4-carboxamide (Vf). Yield 2.73 g
(73%), yellow powder, mp 223–225°С (АсОН). IR
spectrum, ν, cm–1: 3336, 2926(NН), 1653(CONН), 1250
1
(C=S). Н NMR spectra, δ, ppm: 1.52 m (2Н, СН2),
1.73 m (2Н, СН2), 2.31 t (2Н, СН2, J 4.0 Hz), 2.60 t
(2Н, СН2, J 4.0 Hz), 4.46 d (2Н, NСН2, J 5.0 Hz), 7.25 t
(1Н, Ph, J 6.9 Hz), 7.36 t (2Н, Ph, J 8.1 Hz), 7.34 d (2Н,
Ph, J 8.1 Hz), 7.52 br.s (5Н, Ph), 8.57 br.s (1Н, CONН),
13.29 br.s (1Н, NН). 13С NMR spectra, δ, ppm: 21.04,
21.57, 25.29, 26.58, 42.14, 120.57, 126.50, 127.44,
127.93, 128.28, 129.04, 129.40, 132.35, 138.58, 139.38,
145.62, 147.19, 166.13, 172.14. Mass spectrum, m/z(Irel,
%): 375 (100) [M + 1]+. Found, %:C 73.68; H 5.88;
N 7.30. C23H22N2OS. Calculated, %: C 73.77; H 5.92;
N 7.48. М 374.507.
6-Methyl-N, 1-diphenyl-3-thioxo-2, 3, 5, 6, 7,
8-hexahydroisoquinoline-4-carboxamide (Vj). Yield
2.62 g (70%), yellow powder, mp 249–251°С (АсОН).
IR spectrum, ν, cm–1: 3318, 2911(NН), 1668 (CONН),
1248 (C=S). 1Н NMR spectra, δ, ppm: 0.97 d (3Н, Mе,
J 8.0 Hz), 1.16 m (1Н, С6Н), 1.74 m (2Н, СН2), 2.23 m
(2Н, СН2), 2.79 t (2Н, СН2, J 4.0 Hz), 7.09 t (1Н, Ph,
J 8.0 Hz), 7.34 t (2Н, Ph, J 8.0 Hz), 7.41 m (2Н, Ph),
2-Thioxo-N, 1-diphenyl-2, 3, 5, 6, 7, 8-hexahydro-
isoquinoline-4-carboxamide (Vg). Yield 2.52 g (70%),
yellow cotton-like substance, mp 260–262°С (BuОН).
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SYNTHESIS AND ALKYLATION
265
eral procedure. To a solution of 3.6 g (10 mmol) of
isoquinolinethione Vg in 15 ml of DMF was added in
succession at stirring 5.6 ml (10 mmol) of 10% water
solution of KОН and 10 mmol of an appropriate alkyl
halide VIIa, VIIb, the mixture was stirred for 1 h and
left standing for 24 h. The reaction mixture was diluted
with an equal volume of water, the formed precipitate
was filtered off, washed in succession with water, ethanol,
and hexane.
7.53 m (3Н, Ph), 7.72 d (2Н, Ph, J 8.0 Hz), 10.27 br.s (1Н,
CONН), 13.58 br.s (1Н, NН). Mass spectrum, m/z(Irel,
%): 375 (100) [M + 1]+. Found, %: C 73.65; H 5.80;
N 7.33. C23H22N2OS. Calculated, %: C 73.77; H 5.92;
N 7.48. М 374.507.
6-Methyl-3-thioxo-1-phenyl-N-(furan-2-yl-
methyl)-2, 3, 5, 6, 7, 8-hexahydroisoquinoline-4-
carboxamide (Vk). Yield 3.26 g (86%), yellow powder,
mp 227–231°С (АсОН). IR spectrum, ν, cm–1: 3345,
2946(NН), 1653 (CONН), 1251 (C=S). 1Н NMR spectra,
δ, ppm: 1.00 d (3Н, Mе, J 8.0 Hz), 1.06–1.15 m (1Н,
СНMе), 1.58–1.71 m (2Н, СН2), 2.11–2.18 d.d (1Н,
СН2, J 8.0 and 16.0 Hz), 2.38–2.43 m (2Н, СН2), 2.68 d
(1Н, СН2, J 20.0 Hz), 4.42 d (2Н, NCH2, J 8.0 Hz),
6.33 s (1Н, С4Н furan), 6.46 с (1Н, С3Н furan), 7.36 с
(1Н, С5Н furan), 7.43–7.52 m (5Н, Ph), 8.4 br.s (1Н,
СОNН), 13.24 br.s (1Н, NН). 13С NMR spectra, δ, ppm:
22.10, 25.75, 27.93, 30.43, 35.51, 36.25, 107.33, 110.86,
120.53, 128.60, 128.81, 129.52, 129.87, 133.25, 138.64,
142.15, 145.96, 147.98, 152.87, 166.86, 171.75, 194.59.
Mass spectrum, m/z(Irel, %): 379 (100) [M + 1]+. Found,
%: C 69.70; H 5.92; N 7.34. C22H22N2O2S. Calculated,
%: C 69.81; H 5.86; N 7.40. М 378.496.
3-Methylsulfanyl-N, 1-diphenyl-5, 6, 7, 8-tetra-
hydroisoquinoline-4-carboxamide (VIIIа). Yield 2.8
g (75%), colorless crystals, mp 235–237°С (АсОН). IR
1
spectrum, ν, cm–1: 3300(NН), 1666(CONН). Н NMR
spectra, δ, ppm: 1.65 m (2Н, СH2), 1.74 m (2Н, СH2),
2.48 s (3Н, Mе), 2.67 t (2Н, СH2, J 5.6 Hz), 2.76 t (2Н,
СH2, J 6.0 Hz), 7.13 t (1Н, Ph, J 7.5 Hz), 7.37 t (2Н,
Ph, J 8.0 Hz), 7.45–7.57 m (5Н, Ph), 7.75 d (2Н, Ph,
J 7.5 Hz), 10.61 br.s (1Н, NH). 13С NMR spectra, δ,
ppm: 12.60, 21.26, 22.14, 25.97, 26.93, 119.46, 123.75,
126.46, 128.02, 128.70, 128.75, 130.80, 138.88, 139.82,
143.57, 150.60, 157.25, 162.18, 164.75. Mass spectrum,
m/z(Irel, %): 375 (100) [M + 1]+. Found, %:C 73.65;
H 5.81; N 7.32. C23H22N2OS. Calculated, %: C 73.76;
H 5.92; N 7.48. М 374.507.
N, 1-Diphenyl-3-(2-cyanoethylsulfanyl)-5, 6,
7, 8-tetrahydroisoquinoline-4-carboxamide (VI).
To a mixture of 3.6 g (10 mmol) of substituted
isoquinolinethione Vg and 0.66 ml (10 mmol) of
acrylonitrile in 20 ml of anhydrous ethanol was added 3
drops of triethylamine, and the mixture was boiled for 2 h.
After 24 h the formed precipitate was filtered off, washed
with ethanol and hexane. Yield 2.85 g (69%), colorless
needle crystals, mp 160–162°С (BuОН). IR spectrum, ν,
cm–1: 3434 (NН), 2252(С≡N), 1662(CONН). 1Н NMR
spectra, δ, ppm: 1.66 m (2Н, СH2), 1.76 m (2Н, СH2),
2.68 t (2Н, СH2, J 4.0 Hz), 2.77 t (2Н, СH2, J 4.0 Hz),
2.94 t (2Н, СH2, J 4.6 Hz), 3.73 t (2Н, СH2, J 4.6 Hz),
7.14 t (1Н, Ph, J 7.0 Hz), 7.37 t (2Н, Ph, J 8.0 Hz), 7.45–
7.57 m (5Н, Ph), 7.72 d (2Н, Ph, J 8.5 Hz), 10.64 br.s
(1Н, NH). 13С NMR spectra, δ, ppm: 17.98, 21.20, 22.08,
25.19, 26.08, 26.95, 119.33, 119.51, 123.90, 127.24,
128.11, 128.17, 128.74, 128.76, 130.94, 138.75, 139.60,
144.30, 148.79, 157.51, 164.39. Mass spectrum, m/z(Irel,
%): 414 (100) [M + 1]+. Found, %: C 72.50; H 5.49;
N 9.99. C25H23N3OS. Calculated, %: C 72.61; H 5.61;
N 10.16. М 413.545.
3-Benzylsulfanyl-N, 1-diphenyl-5, 6, 7, 8-tetra-
hydroisoquinoline-4-carboxamide (VIIIb). Yield 4.0 g
(89%), colorless cotton-like substance, mp 144–146°С
(АсОН). IR spectrum, ν, cm–1: 3322(NН), 1664(CONН).
1Н NMR spectra, δ, ppm: 1.66 m (2Н, СH2), 1.75 m
(2Н, СH2), 2.66 t (2Н, СH2, J 4.0 Hz), 2.79 t (2Н, СH2,
J 4.0 Hz), 4.40 s (2H, SCH2), 7.12 t (1Н, Ph, J 7.0 Hz),
7.21 t (1Н, Ph, J 6.5 Hz), 7.26 t (2Н, Ph, J 8.5 Hz), 7.35 m
(4Н, Ph), 7.48 m (1Н, Ph), 7.52 m (4Н, Ph), 7.71 d (2Н,
Ph, J 7.5 Hz), 10.56 br.s (1Н, NH). 13С NMR spectra, δ,
ppm: 21.20, 22.06, 26.01, 26.86, 33.14, 119.44, 123.78,
126.73, 126.82, 128.03, 128.05, 128.10, 128.70, 128.94,
130.42, 138.33, 138.77, 139.68, 143.68, 143.91, 149.75,
157.25, 164.53. Mass spectrum, m/z(Irel, %): 451 (100) [M
+ 1]+. Found, %: C 77.18; H 5.77; N 6.09. C29H26N2OS.
Calculated, %: C 77.30; H 5.82; N 6.22. М 450.606.
3-Allylsulfanyl-N, 1-diphenyl-5, 6, 7, 8-tetrahydro-
isoquinoline-4-carboxamide (IX) and 2-allyl-3-thioxo-
N, 1-diphenyl-2, 3, 5, 6, 7, 8-hexahydroisoquinoline-
4-carboxamide (X) were obtained analogously to
compounds VIIIa, VIIIb using 0.85 ml (10 mmol) of
allyl bromide. Yield 3.0 g (74%), white powder, mp
155–158°С (EtОН). IR spectrum, ν, cm–1: 3440(NН),
3-Alkylsulfanyl-1-phenyl-5, 6, 7, 8-tetrahydroiso-
quinoline-3-carboxamides VIIIa, VIIIb. Gen-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 2 2013

DYACHENKO, VOVK
266
[M + 1]+. Found, %: C 77.65; H 6.42; N 4.72. C19H19NO2.
Calculated, %: C 77.79; H 6.53; N 4.78. М 293.37.
1
1661(CONН), 1244(C=S). Н NMR spectra, δ, ppm:
1.66 m (2Н, СH2), 1.75 m (2Н, СH2), 2.67 m (2Н, СH2),
2.76 m (2Н, СH2), 3.58 d (0.6H, NCH2, J 7.0 Hz) and
3.81 d (1.4H, SCH2, J 6.5 Hz), 5.04 d (1Н, СН2=, Jcis
10.0 Hz), 5.22 d (1Н, СН2=, Jtrans 17.0 Hz), 5.90 m (1Н,
=СН), 7.13 m (1Н, Ph), 7.36 m (2Н, Ph), 7.39–7.55 m
(5Н, Ph), 7.72 d (2Н, Ph, J 7.5 Hz), 10.59 br.s (0.7Н,
СОNН), 10.67 br.s (0.3Н, СОNН). Mass spectrum,
m/z(Irel, %): 401 (100) [M +1]+. Found, %: C 74.88;
H 5.92; N 6.80. C25H24N2OS. Calculated, %: C 74.97;
H 6.04; N 6.99. М 400.546.
REFERENCES
1. Paronikyan, E.G., Noravyan, A.S., Akopyan, Sh.F., Dzha-
gatspanyan, I.A., Nazaryan, I.M., and Paronikyan, R.G.,
Khim.-Farm. Zh., 2007, vol. 41, no. 9, p. 14.
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and Alkaloids), Kartsev, V.G. and Tolstikov, G.A., IBS,
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zuki, T., Otsuka, K., Ito, T., Kamiya, J., and Maruyama, M.,
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4. Hunt, J.C.A., Briggs, E., Clarke, E.D., and Whitting-
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11-Phenyl-7, 8, 9, 10-tetrahydrobenzo[4, 5]im-
idazo[1, 2-b]isoquinoline-6-carbonitrile XII). To a
mixture of 2.71 g (10 mmol) of enaminoketone Id and
1.57 g (10 mmol) of benzimidazol-2-ylacetonitrile (ХІ)
in 15 ml of anhydrous ethanol was added while stirring a
solution obtained from 0.23 g (10 mmol) of sodium and
10 ml of anhydrous ethanol. Then the reaction mixture
was brought to boiling and left standing for 24 h. The
crystals precipitated on cooling were filtered off and
washed in succession with ethanol and hexane. Yield 3.0 g
(93%), yellow crystals, under UV irradiation fluoresce,
mp 353–355°С (АсОН), at 240°С undergo sublimation.
5. Issac, Y.A., Ali, M.S., and Eian, A.W., Sci. Pharm., 2000,
vol. 68, p. 389.
6. Chan, L., Stefanac, T., Turcotte, N., Hu, Z., Chen, Y., Be-
dard, J., May, S., and Jin, H., Bioorg. Med. Chem. Lett.,
2000, vol. 10, p. 1477.
IR spectrum, ν, cm–1: 2223(С≡N). Н NMR spectra, δ,
1
ppm: 1.51–1.99 m (4Н, 2СH2), 3.09–3.34 m (4Н, 2СH2),
5.98–6.17 m (1Нarom), 6.81–7.02 m (1Нarom), 7.27–7.86 m
(7Нarom). Mass spectrum, m/z(Irel, %): 324 (21) [M + 1]+,
323 (100) [M]+, 322 (11) [M – 1]+, 294 (10), 231 (2), 165
(4), 140 (13), 102 (8), 77 (21) [Ph]+, 75 (7), 41 (5). Found,
%: C 81.66; H 5.22; N 13.12. C22H17N3. Calculated, %:
C 81.71; H 5.30; N 12.99. М 323.4.
7. Elgemeie, G.E.H.,Attia,A.M.E., and Fathy, N.M., Nucleo-
sides, Nucleotides, 1997, vol. 16, p. 485.
8. Vernier, J.-M., Holsenback, H., Cosford, N.D.P., Whit-
ten, J.P., Menzaghi, F., Reid, R., Rao, T.S., Sacaan, A.I.,
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Freeman, F., Farquhar, D.K., and Walker, R.L., J. Org.
Chem., 1968, vol. 33, p. 3648.
[2-(3-Hydroxyphenylamino)cyclohex-1-enyl]-
(phenyl)methanone (XIV). A mixture of 2.71 g
(10 mmol) of enaminoketone Id and 1.1 g (10 mmol)
of m-aminophenol (XIII) in 20 ml of anhydrous etha-
nol was boiled for 1 h. On cooling the reaction mixture
the separated precipitate was filtered off and washed in
succession with ethanol and hexane. Yield 2.3 g (77%),
light-red powder, mp 199–202°С (АсОН). IR spectrum,
1
ν, cm–1: 3154(ОН), 2934(NН), 1713(C=O). Н NMR
spectra, δ, ppm: 1.51 d (2Н, СH2, J 4.0 Hz), 1.56 d (2Н,
СН2, J 4.0 Hz), 2.18–2.27 m (2Н, СH2), 3.34–3.49 m (2Н,
СH2), 6.52–6.68 m (3Нarom), 7.18 t (1Нarom, J 8.0 Hz),
7.39 br.s (5Н, Ph), 9.64 br.s (1Н, NH), 13.39 br.s (1Н,
ОН). 13С NMR spectra, δ, ppm: 21.74, 23.14, 27.57,
27.94, 101.95, 112.06, 112.94, 115.87, 126.76 (2С),
128.39 (2С), 129.09, 130.37, 139.87, 142.77, 158.53,
161.79, 194.97. Mass spectrum, m/z (Irel, %): 294 (100)
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