Synthesis of functional derivatives of aryl trichlorovinyl (trichloroallyl) ketones via consecutive transformations of the carbonyl group

Article abstract of DOI:10.1134/S1070428014100042

An efficient procedure have been developed for the selective reduction of the carbonyl group in phenyl trichlorovinyl ketone and aryl trichloroallyl ketones by the action of NaBH₄ in propan-2-ol to obtain the corresponding alcohols. The hydroxy

Full text of DOI:10.1134/S1070428014100042

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 10, pp. 1412–1421. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © V.I. Potkin, S.K. Petkevich, A.V. Kletskov, E.A. Dikusar, I.B. Rozentsveig, G.G. Levkovskaya, 2014, published in Zhurnal
Organicheskoi Khimii, 2014, Vol. 50, No. 10, pp. 1430–1439.
Synthesis of Functional Derivatives of Aryl Trichlorovinyl
(Trichloroallyl) Ketones via Consecutive Transformations
of the Carbonyl Group
V. I. Potkina, S. K. Petkevicha, A. V. Kletskova, E. A. Dikusara,
I. B. Rozentsveigb, and G. G. Levkovskayab
a Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus,
ul. Surganova 13, Minsk, 220072 Belarus
e-mail: potkin@ifoch.bas-net.by
b Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
Received April 23, 2014
Abstract—An efficient procedure have been developed for the selective reduction of the carbonyl group in
phenyl trichlorovinyl ketone and aryl trichloroallyl ketones by the action of NaBH4 in propan-2-ol to obtain the
corresponding alcohols. The hydroxy group in the latter was converted into amino by the Ritter reaction.
Treatment of the alcohols and amines with 5-phenylisoxazole-3-carbonyl chloride and 4,5-dichloroisothiazole-
3-carbonyl chloride gave the corresponding esters and amides, and condensation of the amines with aromatic
aldehydes afforded Schiff bases.
DOI: 10.1134/S1070428014100042
Unsaturated chlorinated ketones, especially chloro-
vinyl ketones (chloroenones), are widely used in
organic synthesis due to their high synthetic potential
which is determined by the presence in their molecules
of several reactive fragments, carbonyl group, chlorine
atoms, and C=C double bond [1–3]. Preparative proce-
dures for the synthesis of various useful compounds,
including biologically active substances, have been
developed on the basis of reactions of such ketones
[4, 5]. An important problem related to efficient use of
accessible chloroenones consists of selective modifica-
tion of different reactive centers in their molecules in
order to ensure desired transformations and avoid side
processes. Convenient methods for the synthesis of
unsaturated chloro ketones from accessible lower
chloroalkenes have been developed at the Institute of
Physical Organic Chemistry, National Academy of
Sciences of Belarus, and Favorskii Irkutsk Institute of
Chemistry, Siberian Branch, Russian Academy of
Sciences [2, 6–8].
and aryl trichloroallyl ketones with retention of the
other reaction centers. The products of these reactions
attract interest as substrates for further transformations,
as well as for biological testing. As starting compounds
we used 2,3,3-trichloro-1-phenylprop-2-en-1-one (I)
and 1-aryl-3,4,4-trichlorobut-3-en-1-ones II–V which
were prepared as described in [2, 6].
In the first step of our study we tried to develop
an efficient procedure for the selective reduction of the
carbonyl group, not involving chlorine atoms and C=C
bond. Various reagents and reagent systems have been
proposed for the reduction of carbonyl group, e.g.,
metallic sodium in alcohol, LiAlH4, NaBH(AcO)3,
NaBH4, and others. In our case, neither metallic
sodium in alcohol nor sodium tetrahydridoborate can
be used because of concurrent reactions involving the
chlorine atoms and C=C double bond, which lead to
complex mixtures of products. The reaction with
sodium triacetoxyhydridoborate in anhydrous benzene
in the presence of acetic acid was relatively slow, and
the target alcohols were formed in low yield.
The goal of the present work was to find rational
synthetic approaches to chlorinated unsaturated alco-
hols, amines, and Schiff bases via successive trans-
formations of the carbonyl group in aryl trichlorovinyl
The optimal procedure for the reduction of ketones
I–V was their treatment with a slight excess of NaBH4
in propan-2-ol. In this case, the reaction involved
1412

SYNTHESIS OF FUNCTIONAL DERIVATIVES OF ARYL TRICHLOROVINYL ...
1413
exclusively the carbonyl group and was complete in
4 h, and the desired chlorinated alcohols VI–X were
obtained in high yield (91–94%; Scheme 1). The IR
spectra of VI–X lacked carbonyl absorption bands, but
a broadened band was present in the region 3374–
3384 cm–1 due to stretching vibrations of the hydroxy
determined on the basis of their elemental analyses and
1
IR and H and 13C NMR spectra. Like the initial al-
cohols, compounds XII–XV and XVII–XX were race-
mates, and the CH2 protons gave rise to multiplet
signals in the 1H NMR spectra.
Alcohols VII–X underwent dehydration by the
action of sulfuric acid in the absence of acetonitrile.
By treatment of 3,4,4-trichloro-1-(4-methylphenyl)but-
3-en-1-ol (VIII) with H2SO4 we obtained 87% of
3,4,4-trichloro-1-(4-methylphenyl)buta-1,3-diene
1
group. In the H NMR spectra of VI–X, the hydroxy
proton resonated as a broadened singlet at δ 2.38–
3.57 ppm. Signals from the CH and CH2 protons in the
spectra of VII–X appeared as multiplets since these
alcohols were formed as racemic mixtures. The isotope
ratios of the molecular ion clusters in the mass spectra
of VI–X indicated the presence of three chlorine atoms
(and one bromine atom in X) [9].
1
(XXI) which was identified by the IR and H NMR
spectra (Scheme 3). Diene XXI was formed as
Z isomer, as followed from the coupling constants of
the CH=CH protons (3J = 7.1 Hz) [11].
Scheme 1.
Scheme 3.
Cl
O
Cl
OH
Cl
NaBH4, i-PrOH
Cl
Cl
Cl
Me
( )n
( )n
Ar
Ar
H2SO4
Cl
VIII
Cl
Cl
I–V
VI–X
XXI
I, VI, n = 0, Ar = Ph; II, VII, n = 1, Ar = Ph; III, VIII,
n = 1, Ar = 4-MeC6H4; IV, IX, n = 1, Ar = 2,5-Me2C6H3;
V, X, n = 1, Ar = 4-BrC6H4.
Further modification of the synthesized alcohols
and amines involved introduction into their molecules
of pharmacophoric isoxazole and isothiazole fragments
with a view to obtaining biologically active com-
pounds. There are numerous published data indicating
a broad spectrum of biological activity of isothiazole
and isoxazole derivatives [12, 13]. Moreover, we
found previously that esters and amides derived from
4,5-dichloroisothiazole-3-carboxylic acid show syner-
gistic effect in compositions with pyrethroid and neo-
nicotinoid insecticides against potato beetle larvae and
that some derivatives enhance the effect of cyper-
methrin against fleas [14, 15].
By acylation of alcohols VI and VIII and amine
XVI with 5-phenylisoxazole-3-carbonyl chloride and
4,5-dichloroisothiazole-3-carbonyl chloride in the
presence of triethylamine we synthesized the corre-
sponding esters XXII–XXIV and amides XXV and
XXVI (Scheme 4) which were identified by IR and
NMR spectroscopy. The products are now being tested
as cypermethrin synergists against the oriental rat flea
Xenopsylla cheopis (carriers of plague and other
diseases) at the Irkutsk Research Anti-plague Institute
(Russian Federal Service for Surveillance on Con-
sumer Rights Protection and Human Wellbeing).
The hydroxy group in alcohols VI–X was con-
verted into amino according to the approach based on
the Ritter reaction [10]. The reaction of VI–X with
acetonitrile in the presence of concentrated sulfuric
acid gave the corresponding acetamides XI–XV whose
hydrolysis with HCl in aqueous ethanol produced
2,3,3-trichloro-1-phenylprop-2-en-1-amine (XVI) and
1-aryl-3,4,4-trichlorobut-3-en-1-amine hydrochlorides
XVII–XX (Scheme 2). The formation of amines as hy-
drochlorides hampered further reactions with participa-
tion of chlorine atoms in the aliphatic residue. The
structure of amides XI–XV and amines XVI–XX was
Scheme 2.
Cl
OH
Cl
NHAc
Ar
H2SO4, MeCN
Cl
Cl
( )n
( )n
Ar
Cl
Cl
VI–X
20% HCl, H2O–EtOH
XI–XV
Cl
NH2·HCl
Cl
( )n
Ar
Cl
XVI–XX
Amine hydrochlorides XVI–XX were also brought
into condensation with substituted benzaldehydes in
anhydrous ethanol in the presence of sodium hydrogen
carbonate to obtain the corresponding Schiff bases. As
VI, XI, XVI, n = 0, Ar = Ph; VII–X, XII–XV, XVII–XX,
n = 1; VII, XII, XVII, Ar = Ph; VIII, XIII, XVIII, Ar =
4-MeC6H4; IX, XIV, XIX, Ar = 2,5-Me2C6H3; X, XV, XX,
Ar = 4-BrC6H4.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 10 2014

POTKIN et al.
Scheme 4.
1414
Cl
OH
Cl
Ar
O
ZC(O)Cl, NEt3, Et2O
Cl
Cl
( )n
( )n
Ar
O
Z
Cl
Cl
VI, VIII
XXII–XXIV
Cl Ph
Cl
NH2·HCl
O
ZC(O)Cl, NEt3, CH2Cl2
Cl
Cl
( )n
( )n
Ph
N
Z
H
Cl
Cl
XVI
XXV, XXVI
VI, XXII, XXV, XXVI, n = 0, Ar = Ph; VIII, XXIII, XXIV, n = 1, Ar = 4-MeC6H4; XXII, XXIII, XXV, Z = 5-phenyl-
1,2-oxazole-3-yl; XXIV, XXVI, Z = 4,5-dichloro-1,2-thiazol-3-yl.
Scheme 5.
Cl
NH2·HCl
Cl
Ar
NaHCO3, MeOH
Cl
Cl
+
Ar'CHO
( )n
( )n
Ar
N
Ar'
Cl
Cl
XVI–XX
XXVII–XLI
XVI, XXVII–XXX, n = 0, Ar = Ph; XXVII, Ar′ = 4-MeOC6H4; XXVIII, Ar′ = 4-HOC6H4; XXIX, Ar′ = 3-MeO-4-HOC6H3; XXX,
Ar′ = 3-HO-4-MeOC6H3; XVII, XXXI–XXXIV, n = 1, Ar = Ph; XVIII, XXXV–XXXVII, n = 1, Ar = 4-MeC6H4; XIX, XXXVIII,
XXXIX, n = 1, Ar = 2,5-Me2C6H3; XX, XL, XLI, n = 1, Ar = 4-BrC6H4; XXXI, XXXV, XXXVIII, XL, Ar′ = 4-MeOC6H4; XXXII,
XXXVI, Ar′ = 4-HOC6H4; XXXIII, XXXVII, XXXIX, XLI, Ar′ = 3-MeO-4-HOC6H3; XXXIV, Ar′ = 3-HO-4-MeOC6H3.
aldehyde components we used 4-hydroxybenzalde-
hyde, 4-methoxybenzaldehyde, 4-hydroxy-3-methoxy-
benzaldehyde (vanillin), and 3-hydroxy-4-methoxy-
benzaldehyde (isovanillin) (Scheme 5). Schiff bases
attract persistent interest and are widely used in
organic synthesis due to their high synthetic potential.
In addition, they possess a variety of useful properties,
including a broad spectrum of biological activity [16].
Schiff bases derived from vanillin attract particular
interest since some vanillin derivatives were found to
XXXII, XXXVI–XXXVIII) or thin films (VI–X,
XXIII, XXIV, XXVII–XXXI, XXXIII–XXXV,
1
XXXIX–XLI). The H and 13C NMR spectra were
recorded on a Bruker Avance-500 spectrometer from
solutions in CDCl3 (VI–XV, XXI–XXIV, XXVII–
XXXV, XXXVII–XLI), acetone-d6 (XXV, XXVI,
XXXVI), or DMSO-d6 (XVI–XX); the chemical shifts
were determined relative to to the residual proton and
carbon signals of the deuterated solvent (CHCl3,
δ 7.26 ppm; CDCl3, δC 77.2 ppm; acetone-d5,
inhibit DNA protein kinase and regulate repair of DNA δ 2.05 ppm; δC 30.2 ppm; DMSO-d5, δ 2.50 ppm,
damage according to the NHEJ (non-homologous
DNA end-joining) mechanism; they also showed syn-
ergistic effect on the activity of neonicotinoid insec-
ticide imidacloprid [14, 17].
Schiff bases XXVII–XLI were identified on the
basis of their elemental analyses and IR and 1H and 13C
NMR spectra. In the 1H NMR spectra of XXVII–XLI,
the HC=N proton resonated as a singlet at δ 8.16–
8.38 ppm, which is typical of E configuration of the
azomethine fragment; the corresponding signal of Z
isomers is usually located in a weaker field due to
deshielding by the benzene ring [18].
δC 40.1 ppm). The mass spectra of alcohols VI–X
(electron impact, 70 eV) were obtained using
a Hewlett Packard HP 5890/5972 GC/MS system
(HP-5MS capillary column, 30 m×0.25 mm, film
thickness 0.25 μm; injector temperature 250°C).
Reduction of ketones I–V (general procedure).
Ketone I–V, 10 mmol, was dissolved in 50 mL of an-
hydrous propan-2-ol, 10 mmol of sodium tetrahydrido-
borate was added, and the mixture was stirred for 4 h
at room temperature and poured into 300 mL of water.
The product was extracted into chloroform, the extract
was dried over sodium sulfate, and the solvent was
removed under reduced pressure. Alcohols VI–X thus
isolated required no additional purification.
EXPERIMENTAL
2,3,3-Trichloro-1-phenylprop-2-en-1-ol (VI).
Yield 94%, oily substance. IR spectrum, ν, cm–1: 3374
(OH), 3064, 3032, 2924, 2851 (C–H), 1592, 1495,
The IR spectra were recorded on a Nicolet Protege-
460 spectrometer with Fourier transform from samples
prepared as KBr pellets (XI–XXII, XXV, XXVI,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 10 2014

SYNTHESIS OF FUNCTIONAL DERIVATIVES OF ARYL TRICHLOROVINYL ...
1415
1452 (C=C), 1108, 1046 (C–O), 921, 846 (C–Cl).
1H NMR spectrum, δ, ppm: 3.57 br.s (1H, OH), 6.12 s
(1H, CH), 7.41 m (5H, Harom). 13C NMR spectrum, δC,
ppm: 71.88 (CH), 125.79 (2C, CHarom), 128.68 (2C,
CHarom), 128.52 (CHarom), 119.77, 134.61, 138.88.
Found, %: C 45.65; H 2.88; Cl 44.64. Mass spectrum:
m/z 236 [M]+. C9H7Cl3O. Calculated, %: C 45.51;
H 2.97; Cl 44.78. M 237.51.
1593, 1487, 1427 (C=C), 1191, 1050 (C–O), 922, 825
1
(C–Cl), 546 (C–Br). H NMR spectrum, δ, ppm:
2.67 br.s (1H, OH), 2.77–3.09 m (2H, CH2), 5.97 m
3
(1H, CH), 7.22 d and 7.47 d (2H each, Harom, J =
8.4 Hz). 13C NMR spectrum, δC, ppm: 45.48 (CH2),
71.36 (CHOH), 127.59 (2C, CHarom), 131.80 (2C,
CHarom), 120.13, 122.07, 128.86, 141.57. Found, %:
C 36.28; H 2.51; Hlg 56.40. Mass spectrum: m/z 328
[M]+. C10H8BrCl3O. Calculated, %: C 36.35; H 2.44;
Hlg 56.37. M 330.43.
3,4,4-Trichloro-1-phenylbut-3-en-1-ol (VII).
Yield 94%, oily substance. IR spectrum, ν, cm–1: 3383
(OH), 3087, 3064, 2971, 2916, 2868 (C–H), 1603,
1494, 1454, 1430 (C=C), 1193, 1046 (C–O), 923, 769
Acetamides XI–XV (general procedure). Alcohol
VI–X, 100 mol, was dissolved in 25 mL of anhydrous
acetonitrile, 1 mL of concentrated sulfuric acid was
added, and the mixture was stirred for 5 h at 20°C and
poured into 250 mL of water. The product was
extracted into chloroform, the extract was dried over
CaCl2, the solvent was removed under reduced pres-
sure, and the residue was recrystallized from
70% aqueous methanol (XII, XIII, XV) or hexane–
chloroform (2:1) (XI, XIV).
1
(C–Cl). H NMR spectrum, δ, ppm: 2.72 br.s (1H,
OH), 2.72–3.15 m (2H, CH2), 5.02 m (1H, CH),
7.37 m (5H, Harom). 13C NMR spectrum, δC, ppm:
45.52 (CH2), 71.94 (CH), 125.85 (2C, CHarom), 128.23
(CHarom), 128.68 (2C, CHarom), 119.77, 121.87, 142.60.
Found, %: C 47.88; H 3.55; Cl 42.08. Mass spectrum:
m/z 250 [M]+. C10H9Cl3O. Calculated, %: C 47.75;
H 3.61; Cl 42.28. M 251.54.
3,4,4-Trichloro-1-(4-methylphenyl)but-3-en-1-ol
(VIII). Yield 94%, oily substance. IR spectrum, ν,
cm–1: 3382 (OH), 3050, 3024, 2971, 2922, 2862
(C–H), 1612, 1514, 1430 (C=C), 1180, 1044 (C–O),
N-(2,3,3-Trichloro-1-phenylprop-2-en-1-yl)acet-
amide (XI). Yield 63%, mp 141–143°C. IR spectrum,
ν, cm–1: 3261 (N–H), 3032, 2948, 2926 (C–H), 1650
(C=O), 1595, 1537, 1496, 1453 (C=C, δN–H), 916,
1
1
921, 818 (C–Cl). H NMR spectrum, δ, ppm: 2.42 s
837 (C–Cl). H NMR spectrum, δ, ppm: 2.03 s (3H,
3
(3H, Me), 2.69 br.s (1H, OH), 2.69–3.17 m (2H, CH2),
Me), 6.55 d (1H, CH, J = 8.3 Hz), 6.81 d (1H, NH,
5.02 m (1H, CH), 7.22 d and 7.30 d (2H each, Harom
,
3J = 8.3 Hz), 7.34 m (5H, Harom). 13C NMR spectrum,
δC, ppm: 22.95 (Me), 54.31 (CH), 126.47 (2C, CHarom),
128.46 (CHarom), 128.98 (2C, CHarom), 120.77, 131.91,
136.64, 169.79 (C=O). Found, %: C 47.40; H 3.77;
Cl 38.05; N 5.05. C11H10Cl3NO. Calculated, %:
C 47.43; H 3.62; Cl 38.18; N 5.03.
3J = 8 Hz). 13C NMR spectrum, δC, ppm: 21.25 (Me),
45.45 (CH2), 71.80 (CH), 125.81 (2C, CHarom), 129.33
(2C, CHarom), 119.61, 121.69, 137.92, 139.69. Found,
%: C 49.79; H 4.25; Cl 39.94. Mass spectrum: m/z 264
[M]+. C11H11Cl3O. Calculated, %: C 49.75; H 4.18;
Cl 40.05. M 265.56.
N-(3,4,4-Trichloro-1-phenylbut-3-en-1-yl)acet-
amide (XII). Yield 78%, mp 93–96°C. IR spectrum, ν,
cm–1: 3287 (N–H), 3065, 2986, 2926, 2853 (C–H),
1650 (C=O), 1601, 1542, 14983, 1445, 1425 (C=C,
3,4,4-Trichloro-1-(2,5-dimethylphenyl)but-3-en-
1-ol (IX). Yield 91%, oily substance. IR spectrum, ν,
cm–1: 3381 (OH), 3044, 3020, 2970, 2923, 2869
(C–H), 1619, 1502, 1446 (C=C), 1204, 1045 (C–O),
1
δN–H), 926, 867 (C–Cl). H NMR spectrum, δ, ppm:
1
923, 812 (C–Cl). H NMR spectrum, δ, ppm: 2.32 s
1.94 s (3H, Me), 2.98–3.09 m (2H, CH2), 5.36 m (1H,
CH), 6.91 d (1H, NH, 3J = 8.2 Hz), 7.28 m (5H, Harom).
13C NMR spectrum, δC, ppm: 23.28 (Me), 42.49 (CH2),
51.78 (CH), 126.60 (2C, CHarom), 127.99 (CHarom),
128.79 (2C, CHarom), 119.63, 129.34, 140.22, 169.86
(C=O). Found, %: C 49.19; H 4.22; Cl 36.09; N 4.78.
C12H12Cl3NO. Calculated, %: C 49.26; H 4.13;
Cl 36.35; N 4.79.
and 2.35 s (3H each, Me), 2.38 br.s (1H, OH), 2.70–
3.18 m (2H, CH2), 5.28 m (1H, CH), 7.06 m (2H,
H
arom), 7.38 s (1H, Harom). 13C NMR spectrum, δC,
ppm: 18.56 (Me), 21.20 (Me), 44.65 (CH2), 68.55
(CH), 125.94 (CHarom), 128.60 (CHarom), 130.59
(CHarom), 119.61, 121.73, 131.24, 136.05, 140.71.
Found, %: C 51.43; H 4.60; Cl 38.08. Mass spectrum:
m/z 278 [M]+. C12H13Cl3O. Calculated, %: C 51.55;
H 4.69; Cl 38.04. M 279.59.
N-[3,4,4-Trichloro-1-(4-methylphenyl)but-3-en-
1-yl]acetamide (XIII). Yield 65%, mp 129–132°C. IR
spectrum, ν, cm–1: 3272 (N–H), 3086, 2972, 2922,
2856 (C–H), 1650 (C=O), 1600, 1558, 1517, 1440,
1-(4-Bromophenyl)-3,4,4-trichlorobut-3-en-1-ol
(X). Yield 91%, oily substance. IR spectrum, ν, cm–1:
3384 (OH), 3050, 3030, 2971, 2916, 2854 (C–H),
1
1423 (C=C, δN–H), 933, 818 (C–Cl). H NMR spec-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 10 2014

POTKIN et al.
1416
trum, δ, ppm: 1.96 s (3H, Me), 2.33 s (3H, Me), 2.98–
H
arom), 9.64 br.s (3H, NH3+). 13C NMR spectrum, δC,
3.13 m (2H, CH2), 5.35 m (1H, CH), 6.41 d (1H, NH,
ppm: 54.96 (CH), 127.49 (2C, CHarom), 129.59 (2C,
CHarom), 129.95 (CHarom), 122.54, 129.80, 133.87.
Found, %: C 39.55; H 3.40; Cl 52.02; N 5.10.
C9H9Cl4N. Calculated, %: C 39.60; H 3.32; Cl 51.95;
N 5.13.
3
3J = 8 Hz), 7.14 d and 7.20 d (2H each, Harom, J =
8.1 Hz). 13C NMR spectrum, δC, ppm: 21.23 (Me),
23.41 (Me), 42.42 (CH2), 51.59 (CH), 126.53 (2C,
CHarom), 129.55 (2C, CHarom), 119.56, 129.51, 137.17,
137.81, 169.58 (C=O). Found, %: C 50.88; H 4.72;
Cl 34.44; N 4.50. C13H14Cl3NO. Calculated, %:
C 50.92; H 4.60; Cl 34.69; N 4.57.
3,4,4-Trichloro-1-phenylbut-3-en-1-amine
hydrochloride (XVII). Yield 82%, mp 191–193°C
(decomp.). IR spectrum, ν, cm–1: 3178–2626 (NH3+),
3038, 2888 (CH), 1595, 1515, 1497, 1459, 1435 (C=C,
N-[3,4,4-Trichloro-1-(2,5-dimethylphenyl)but-3-
en-1-yl]acetamide (XIV). Yield 75%, mp 132–135°C.
IR spectrum, ν, cm–1: 3265 (N–H), 3079, 2946, 2923,
2856 (C–H), 1650 (C=O), 1563, 1504, 1427 (C=C,
1
δN–H), 920, 769 (C–Cl). H NMR spectrum, δ, ppm:
3.24–3.59 m (2H, CH2), 4.47 m (1H, CH), 7.40 m (3H,
H
arom), 7.59 m (2H, Harom), 9.13 br.s (3H, NH3+).
1
δN–H), 925, 814 (C–Cl). H NMR spectrum, δ, ppm:
13C NMR spectrum, δC, ppm: 40.53 (CH2), 53.04 (CH),
128.41 (2C, CHarom), 129.19 (2C, CHarom), 129.72
(CHarom), 120.10, 128.73, 136.08. Found, %: C 41.69;
H 3.93; Cl 49.33; N 4.90. C10H11Cl4N. Calculated, %:
C 41.85; H 3.86; Cl 49.41; N 4.88.
1.96 s (3H, Me), 2.32 s (6H, Me), 2.92–3.15 m (2H,
CH2), 5.63 m (1H, CH), 6.09 d (1H, NH, 3J = 7.9 Hz),
13
7.0 m (1H, Harom), 7.06 m (2H, Harom). C NMR spec-
trum, δC, ppm: 18.94 (Me), 21.23 (Me), 23.38 (Me),
41.84 (CH2), 48.00 (CH), 125.99 (CHarom), 128.70
(CHarom), 130.95 (CHarom), 119.43, 129.66, 132.87,
135.93, 138.19, 169.35 (C=O). Found, %: C 52.64;
H 5.00; Cl 33.00; N 4.33. C14H16Cl3NO. Calculated,
%: C 52.44; H 5.03; Cl 33.17; N 4.37.
3,4,4-Trichloro-1-(4-methylphenyl)but-3-en-
1-amine hydrochloride (XVIII). Yield 67%, mp 193–
195°C (decomp.). IR spectrum, ν, cm–1: 3188–2596
(NH3+), 3033, 2922 (C–H), 1603, 1518, 1500, 1435
1
(C=C, δN–H), 918, 817 (C–Cl). H NMR spectrum, δ,
N-[1-(4-Bromophenyl)-3,4,4-trichlorobut-3-en-
1-yl]acetamide (XV). Yield 65%, mp 141–144°C. IR
spectrum, ν, cm–1: 3228 (N–H), 3065, 2926, 2851
(CH), 1652 (C=O), 1603, 1541, 1488, 1433 (C=C,
ppm: 2.30 s (3H, Me), 3.21–3.56 m (2H, CH2), 4.43 m
3
(1H, CH), 7.22 d and 7.45 d (2H each, Harom, J =
8.1 Hz), 9.02 br.s (3H, NH3+). 13C NMR spectrum, δC,
ppm: 21.43 (Me), 40.36 (CH2), 52.76 (CH), 128.31
(2C, CHarom), 129.61 (2C, CHarom), 119.95, 128.04,
133.05, 139.06. Found, %: C 43.92; H 4.48; Cl 47.03;
N 4.62. C11H13Cl4N. Calculated, %: C 43.89; H 4.35;
Cl 47.11; N 4.65.
1
δN–H), 924, 823 (C–Cl), 554 (C–Br). H NMR spec-
trum, δ, ppm (racemic mixture): 1.96 s (3H, Me),
2.95–3.08 m (2H, CH2), 5.31 m (1H, CH), 6.50 d (1H,
3
NH, J = 7.9 Hz), 7.17 d and 7.44 d (2H each, Harom
,
3J = 8.2 Hz). 13C NMR spectrum, δC, ppm: 23.39 (Me),
42.24 (CH2), 51.41 (CH), 128.35 (2C, CHarom), 132.01
(2C, CHarom), 120.11, 122.00, 128.90, 139.29, 169.73
(C=O). Found, %: C 38.66; H 3.08; Hlg 50.33; N 3.72.
C12H11BrCl3NO. Calculated, %: C 38.80; H 2.98;
Hlg 50.14; N 3.77.
3,4,4-Trichloro-1-(2,5-dimethylphenyl)but-3-en-
1-amine hydrochloride (XIX). Yield 67%, mp 195–
197°C (decomp.). IR spectrum, ν, cm–1: 3180–2610
(NH3+), 3005, 2923 (C–H), 1601, 1509, 1477 (C=C,
1
δN–H), 919, 813 (C–Cl). H NMR spectrum, δ, ppm:
2.28 s (3H, Me), 2.30 s (3H, Me), 3.28–3.54 m (2H,
CH2), 4.51 m (1H, CH), 7.09 m (2H, Harom), 7.66 s
Amines XVI–XX (general procedure). A mixture
of 10 mmol of acetamide XI–XV, 90 mL of 20% aque-
ous HCl, and 10 mL of ethanol was heated for 10 h
under reflux. After cooling, the aqueous layer was
separated, ethanol and water were removed under
reduced pressure, and the residue was dried in
a vacuum over P2O5.
+
(1H, Harom), 8.99 br.s (3H, NH3 ). 13C NMR spectrum,
δC, ppm: 19.18 (Me), 21.34 (Me), 40.26 (CH2), 48.24
(CH), 126.38 (CHarom), 128.35 (CHarom), 130.98
(CHarom), 119.99, 128.78, 133.29, 134.20, 136.00.
Found, %: C 45.89; H 4.78; Cl 45.21; N 4.41.
C12H15Cl4N. Calculated, %: C 45.75; H 4.80; Cl 45.01;
N 4.45.
2,3,3-Trichloro-1-phenylprop-2-en-1-amine
hydrochloride (XVI). Yield 98%, mp 186–188°C
(decomp.). IR spectrum, ν, cm–1: 3177–2586 (NH3+),
3048, 3036, 2924 (C–H), 1589, 1519, 1499, 1456
1-(4-Bromophenyl)-3,4,4-trichlorobut-3-en-
1-amine hydrochloride (XX). Yield 65%, mp 191–
193°C (decomp.). IR spectrum, ν, cm–1: 3089–2602
(NH3+), 3043, 3026, 2920, 2856 (C–H), 1594, 1512,
1493, 1417 (C=C, δN–H), 920, 824 (C–Cl), 540
1
(C=C, δN–H), 921, 818 (C–Cl). H NMR spectrum, δ,
ppm: 5.81 s (1H, CH), 7.46 m (3H, Harom), 7.56 m (2H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 10 2014

SYNTHESIS OF FUNCTIONAL DERIVATIVES OF ARYL TRICHLOROVINYL ...
1417
1
(C–Br). H NMR spectrum, δ, ppm: 3.21–3.55 m (2H,
(3H, Harom), 7.80 m (2H, Harom). 13C NMR spectrum,
δC, ppm: 21.21 (CH3), 42.73 (CH2), 74.86 (CH),
100.04 (C4), 125.96 (2C, CHarom), 126.63 (2C, CHarom),
129.19 (2C, CHarom), 129.51 (2C, CHarom), 130.91
(CHarom), 120.72, 123.17, 127.85, 134.73, 138.90,
156.59, 159.00, 171.83 (C=O).
CH2), 4.51 m (1H, CH), 7.56 d and 7.63 d (2H each,
3
H
arom, J = 8.1 Hz), 9.09 br.s (3H, NH3+). 13C NMR
spectrum, δC, ppm: 40.28 (CH2), 52.32 (CH), 130.68
(2C, CHarom), 132.09 (2C, CHarom), 120.24, 123.01,
128.46, 135.46. Found, %: C 32.95; H 2.88; Hlg 60.48;
N 3.79. C10H10BrCl4N. Calculated, %: C 32.82;
H 2.75; Hlg 60.60; N 3.83.
3,4,4-Trichloro-1-(4-methylphenyl)but-3-en-1-yl
4,5-dichloro-1,2-thiazole-3-carboxylate (XXIV).
Yield 84%, oily substance. IR spectrum, ν, cm–1: 3098,
3053, 3026, 2977, 2951, 2923, 2863 (C–H), 1738
(C=O), 1607, 1515, 1483, 1403 (C=C), 1216, 1082
(C–O), 923, 883, 817, 761 (C–Cl). 1H NMR spectrum,
δ, ppm: 2.35 s (3H, Me), 3.15–3.49 m (2H, CH2),
3,4,4-Trichloro-1-(4-methylphenyl)buta-1,3-di-
ene (XXI). Yield 87%, mp 66–67°C. IR spectrum, ν,
cm–1: 3048, 3023, 2920, 2855 (C–H), 1604, 1513,
1496 (C=C), 1167, 1072, 960 (C–C), 928, 802 (C–Cl).
1H NMR spectrum, δ, ppm: 2.39 s (3H, CH3), 7.13 d
3
(3H, CH=CH, Harom), 7.19 d (1H, CH=CH, J =
6.34 m (1H, CH), 7.16 d and 7.40 d (2H each, Harom,
7.1 Hz), 7.38 d (2H, Harom, 3J = 8.1 Hz).
3J = 8 Hz). 13C NMR spectrum, δC, ppm: 21.19 (Me),
42.51 (CH2), 75.08 (CH), 126.70 (2C, CHarom), 129.43
(2C, CHarom), 120.62, 123.10, 127.79, 134.58, 138.83,
150.60, 153.84, 157.98 (C=O).
Esters XXII–XXIV (general procedure). A solu-
tion of 5 mmol of triethylamine in 5 mL of anhydrous
diethyl ether was slowly added dropwise to a solution
of 5 mmol of 5-phenylisoxazole-3-carbonyl chloride or
4,5-dichloroisothiazole-3-carbonyl chloride and
5 mmol of alcohol VI or VII in 40 mL of anhydrous
diethyl ether. The mixture was stirred for 4 h at 20°C
and treated with water, and the organic layer was
separated, dried over sodium sulfate, and evaporated.
Oily products XXIII and XXIV were dried under
reduced pressure, and crystalline compound XXII was
recrystallized from hexane.
2,3,3-Trichloro-1-phenylprop-2-en-1-yl 5-phenyl-
1,2-oxazole-3-carboxylate (XXII). Yield 76%,
mp 102–104°C. IR spectrum, ν, cm–1: 3151 (C–Hisox),
3079, 3062, 3041, 3013, 2967, 2925, 2856 (C–H),
1741 (C=O), 1611, 1591, 1572, 1497, 1455, 1443,
1422 (C=C), 1228, 1145 (C–O), 918, 806, 765 (C–Cl).
1H NMR spectrum, δ, ppm: 7.00 s (1H, CH), 7.31 s
(1H, 4-H), 7.44 m (3H, Harom), 7.50 m (3H, Harom),
7.58 m (2H, Harom), 7.83 m (2H, Harom). 13C NMR spec-
trum, δC, ppm: 74.05 (CH), 100.10 (C4), 126.04 (2C,
CHarom), 126.39 (2C, CHarom), 128.93 (2C, CHarom),
129.28 (2C, CHarom), 129.30 (CHarom), 131.07 (CHarom),
122.64, 126.50, 130.21, 134.79, 156.13, 158.54,
172.20 (C=O).
Amides XXV and XXVI (general procedure).
5-Phenylisoxazole-3-carbonyl chloride or 4,5-dichloro-
isothiazole-3-carbonyl chloride, 3 mmol, was added to
a suspension of 3 mmol of hydrochloride XVI in
25 mL of anhydrous methylene chloride, and 6.2 mmol
of triethylamine was then added dropwise. The mixture
was stirred for 4 h at 20°C and treated with water, the
organic layer was separated and dried over calcium
chloride, the solvent was distilled off under reduced
pressure, and the residue was recrystallized from
hexane– methylene chloride (2:1).
5-Phenyl-N-(2,3,3-trichloro-1-phenylprop-2-en-
1-yl)-1,2-oxazole-3-carboxamide (XXV). Yield 81%,
mp 92–93°C. IR spectrum, ν, cm–1: 3337 (N–H), 3154
(C–Hisox), 3085, 3060, 3026, 2977, 2943, 2856 (C–H),
1677 (C=O), 1613, 1599, 1591, 1574, 1523, 1494,
1
1450, 1425 (C=C), 932, 820, 764 (C–Cl). H NMR
spectrum, δ, ppm: 6.75 m (1H, CH), 7.26 s (1H, 4-H),
3
3
7.41 t (1H, Harom, J = 7.4 Hz), 7.46 t (2H, Harom, J =
3
7.4 Hz), 7.55 m (5H, Harom), 7.94 d (2H, Harom, J =
4
3
7.8, J = 1.9 Hz), 8.39 d (1H, NH, J = 7.8 Hz).
13C NMR spectrum, δC, ppm: 55.86 (CH), 100.61 (C4),
127.08 (2C, CHarom), 127.95 (2C, CHarom), 129.80
(CHarom), 130.19 (2C, CHarom), 130.49 (2C, CHarom),
132.07 (CHarom), 121.49, 133.50, 137.33, 159.63,
159.70, 160.11, 172.64 (C=O).
3,4,4-Trichloro-1-(4-methylphenyl)but-3-en-1-yl
5-phenyl-1,2-oxazole-3-carboxylate (XXIII). Yield
79%, oily substance. IR spectrum, ν, cm–1: 3133
(C–Hisox), 3093, 3057, 3027, 2977, 2952, 2923, 2865
(C–H), 1738 (C=O), 1612, 1593, 1572, 1515, 1446,
1422 (C=C), 1239, 1138 (C–O), 923, 817, 765 (C–Cl).
1H NMR spectrum, δ, ppm: 2.36 s (3H, Me), 3.16–
3.50 m (2H, CH2), 6.35 m (1H, CH), 6.92 s (1H, 4-H),
4,5-Dichloro-N-(2,3,3-trichloro-1-phenylprop-
2-en-1-yl)-1,2-thiazole-3-carboxamide (XXVI).
Yield 76%, mp 103–104°C. IR spectrum, ν, cm–1: 3410
(N–H), 3092, 3058, 3032, 2955, 2926, 2856 (C–H),
1697 (C=O), 1600, 1595, 1586, 1504, 1493, 1476,
3
1
7.18 d and 7.41 d (2H each, Harom, J = 8 Hz), 7.48 m
1449 (C=C), 919, 894, 827, 773 (C–Cl). H NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 10 2014

POTKIN et al.
1418
spectrum, δ, ppm: 6.71 m (1H, CH), 7.39 t (1H, Harom
,
oily substance. IR spectrum, ν, cm–1: 3407 (OH), 3084,
3063, 3028, 3008, 2973, 2938, 2857 (CH), 1638
(C=N), 1602, 1593, 1512, 1495, 1464, 1452, 1431
(C=C), 1285, 1160, 1021 (C–O), 979, 920 (C–Cl).
1H NMR spectrum, δ, ppm: 3.96 s (3H, OCH3), 5.54 s
3
3J = 7.4 Hz), 7.45 t (2H, Harom, J = 7.4 Hz), 7.51 d
(2H, Harom, 3J = 7.4 Hz), 8.47 d (1H, NH, 3J = 7.9 Hz).
13C NMR spectrum, δC, ppm: 55.58 (CH), 127.78 (2C,
CHarom), 129.77 (CHarom), 130.17 (2C, CHarom), 121.49,
125.17, 133.40, 137.31, 151.42, 158.10, 159.78 (C=O).
3
(1H, OH), 6.07 s (1H, CH), 6.98 d (1H, Harom, J =
3
4
8.1 Hz), 7.24 d.d (1H, Harom, J = 8.1, J = 1.8 Hz),
Schiff bases XXVII–XLI (general procedure).
A mixture of 1 mmol of amine hydrochloride XVI–
XX, 1 mmol of aromatic aldehyde, and 1.1 mmol of
sodium hydrogen carbonate in 20 mL of anhydrous
methanol was heated for 10 h under reflux. The
mixture was filtered, the solvent was removed from the
filtrate under reduced pressure, the residue was dis-
solved in 5 mL of diethyl ether, the solution was
filtered through a filter paper, the filtrate was evap-
orated under reduced pressure on a rotary evaporator,
and the residue was dried at 35–40°C under reduced
pressure.
7.41 m (3H, Harom), 7.48 m (2H, Harom), 7.59 d (1H,
4
H
arom, J = 1.8 Hz), 8.33 s (1H, CH=N). 13C NMR
spectrum, δC, ppm: 56.15 (OCH3), 72.53 (CH), 108.92
(CHarom), 114.34 (CHarom), 124.78 (CHarom), 127.38
(2C, CHarom), 128.00 (CHarom), 128.60 (2C, CHarom),
163.24 (C=N), 119.55, 128.55, 134.46, 139.53, 147.18,
149.14. Found, %: C 55.34; H 3.90; Cl 28.46; N 3.58.
C17H14Cl3NO2. Calculated, %: C 55.09; H 3.81;
Cl 28.69; N 3.78.
(E)-2-Methoxy-5-[(2,3,3-trichloro-1-phenylprop-
2-en-1-ylimino)methyl]phenol (XXX). Yield 75%,
oily substance. IR spectrum, ν, cm–1: 3364 (OH), 3085,
3062, 3028, 3004, 2958, 2936, 2907, 2841 (C–H),
1639 (C=N), 1614, 1584, 1511, 1495, 1453, 1441
(C=C), 1275, 1162, 1030 (C–O), 979, 919 (C–Cl).
1H NMR spectrum, δ, ppm: 3.91 s (3H, OCH3), 5.54 s
(E)-2,3,3-Trichloro-N-(4-methoxybenzylidene)-1-
phenylprop-2-en-1-amine (XXVII). Yield 80%, oily
substance. IR spectrum, ν, cm–1: 3088, 3063, 3031,
3002, 2955, 2935, 2908, 2835 (C–H), 1638 (C=N),
1606, 1578, 1512, 1494, 1466, 1451, 1422 (C=C),
1
3
1251, 1031 (C–O), 983, 919 (C–Cl). H NMR spec-
(1H, OH), 6.05 s (1H, CH), 6.89 d (1H, Harom, J =
3
4
trum, δ, ppm: 3.86 s (3H, OCH3), 6.06 s (1H, CH),
8.3 Hz), 7.30 d.d (1H, Harom, J = 8.3, J = 1.9 Hz),
3
6.98 d (2H, Harom, J = 8.8 Hz), 7.40 m (3H, Harom),
7.39 m (3H, Harom), 7.48 m (2H, Harom), 7.58 d (1H,
3
4
H
arom, J = 1.9 Hz), 8.32 s (1H, CH=N). 13C NMR
7.50 m (2H, Harom), 7.85 d (2H, Harom, J = 8.8 Hz),
8.38 s (1H, CH=N). 13C NMR spectrum, δC, ppm:
55.44 (OCH3), 72.63 (CH), 114.14 (2C, CHarom),
127.34 (2C, CHarom), 127.95 (CHarom), 128.56 (2C,
CHarom), 130.44 (2C, CHarom), 162.77 (C=N), 119.30,
128.77, 134.60, 139.66, 162.32. Found, %: C 57.76;
H 4.06; Cl 28.63; N 3.80. C17H14Cl3NO. Calculated,
%: C 57.57; H 3.98; Cl 29.99; N 3.95.
spectrum, δC, ppm: 56.04 (OCH3), 72.52 (CH), 110.33
(CHarom), 113.78 (CHarom), 122.38 (CHarom), 127.36
(2C, CHarom), 127.94 (CHarom), 128.54 (2C, CHarom),
162.87 (C=N), 119.28, 129.57, 134.57, 139.64, 146.04,
149.67. Found, %: C 55.37; H 3.94; Cl 28.26; N 3.52.
C17H14Cl3NO2. Calculated, %: C 55.09; H 3.81;
Cl 28.69; N 3.78.
(E)-4-[(2,3,3-Trichloro-1-phenylprop-2-en-1-yl-
imino)methyl]phenol (XXVIII). Yield 78%, oily sub-
stance. IR spectrum, ν, cm–1: 3346 (OH), 3087, 3062,
3028, 2977, 2945, 2877 (CH), 1637 (C=N), 1606,
1585, 1515, 1494, 1450 (C=C), 1278, 1028 (C–O),
(E)-3,4,4-Trichloro-N-(4-methoxybenzylidene)-
1-phenylbut-3-en-1-amine (XXXI). Yield 74%, oily
substance. IR spectrum, ν, cm–1: 3085, 3063, 3029,
3005, 2958, 2932, 2918, 2838 (C–H), 1642 (C=N),
1606, 1578, 1512, 1494, 1454, 1422 (C=C), 1252,
1
1
982, 920 (C–Cl). H NMR spectrum, δ, ppm: 5.55 s
1030 (C–O), 924, 832 (C–Cl). H NMR spectrum, δ,
3
(1H, OH), 6.07 s (1H, CH), 6.83 d (2H, Harom, J =
ppm: 3.04–3.36 m (2H, CH2), 3.85 s (3H, OCH3),
3
8.6 Hz), 7.40 m (3H, Harom), 7.47 m (2H, Harom), 7.73 d
(2H, Harom, 3J = 8.6 Hz), 8.35 s (1H, CH=N). 13C NMR
spectrum, δC, ppm: 72.60 (CH), 115.97 (2C, CHarom),
127.42 (2C, CHarom), 128.64 (2C, CHarom), 128.84
(CHarom), 130.82 (2C, CHarom), 163.67 (C=N), 119.69,
127.74, 134.25, 139.33, 159.83. Found, %: C 56.78;
H 3.62; Cl 30.91; N 3.86. C16H12Cl3NO. Calculated,
%: C 56.42; H 3.55; Cl 31.22; N 4.11.
4.71 m (1H, CH), 6.95 d (2H, Harom, J = 8.8 Hz),
7.39 m (3H, Harom), 7.53 m (2H, Harom), 7.77 d (2H,
3
H
arom, J = 8.8 Hz), 8.27 s (1H, CH=N). 13C NMR
spectrum, δC, ppm: 45.50 (CH2), 55.42 (OCH3), 72.20
(CH), 114.04 (2C, CHarom), 127.08 (2C, CHarom),
127.55 (CHarom), 128.64 (2C, CHarom), 130.11 (2C,
CHarom), 160.21 (C=N), 119.70, 129.19, 129.87,
142.63, 161.86. Found, %: C 58.95; H 4.47; Cl 28.61;
N 3.54. C18H16Cl3NO. Calculated, %: C 58.64; H 4.37;
Cl 28.85; N 3.80.
(E)-2-Methoxy-4-[(2,3,3-trichloro-1-phenylprop-
2-en-1-ylimino)methyl]phenol (XXIX). Yield 82%,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 10 2014

SYNTHESIS OF FUNCTIONAL DERIVATIVES OF ARYL TRICHLOROVINYL ...
1419
C19H18Cl3NO2. Calculated, %: C 57.24; H 4.55;
Cl 26.68; N 3.51.
(E)-4-[(3,4,4-Trichloro-1-phenylbut-3-en-1-yl-
imino)methyl]phenol (XXXII). Yield 68%, mp 188–
189°C. IR spectrum, ν, cm–1: 3415 (OH), 3077, 3062,
3030, 3008, 2961, 2925, 2865 (C–H), 1629 (C=N),
1607, 1594, 1518, 1495, 1443 (C=C), 1285, 1046
(E)-3,4,4-Trichloro-N-(4-methoxybenzylidene)-1-
(4-methylphenyl)but-3-en-1-amine (XXXV). Yield
75%, oily substance. IR spectrum, ν, cm–1: 3073, 3050,
3023, 3008, 2958, 2932, 2838 (C–H), 1641 (C=N),
1606, 1578, 1512, 1463, 1441, 1422 (C=C), 1253,
1
(C–O), 927, 833 (C–Cl). H NMR spectrum, δ, ppm:
3.03–3.30 m (2H, CH2), 4.66 m (1H, CH), 5.33 s (1H,
3
1
OH), 6.80 d (2H, Harom, J = 8.6 Hz), 7.36 m (3H,
1033 (C–O), 923, 832 (C–Cl). H NMR spectrum, δ,
3
Harom), 7.47 m (2H, Harom), 7.63 d (2H, Harom, J =
ppm: 2.40 s (3H, CH3), 3.07–3.40 m (2H, CH2), 3.84 s
8.6 Hz), 8.21 s (1H, CH=N). 13C NMR spectrum, δC,
ppm: 42.41 (CH2), 72.26 (CH), 115.83 (2C, CHarom),
126.61 (2C, CHarom), 128.32 (2C, CHarom), 129.06 (2C,
CHarom), 130.40 (CHarom), 160.70 (C=N), 119.67,
129.25, 130.13, 142.61, 169.92. Found, %: C 57.40;
H 4.06; Cl 29.50; N 3.48. C17H14Cl3NO. Calculated,
%: C 57.57; H 3.98; Cl 29.99; N 3.95.
3
(3H, OCH3), 4.72 m (1H, CH), 6.97 d (2H, Harom, J =
3
8.8 Hz), 7.23 d (2H, Harom, J = 8.0 Hz), 7.45 d (2H,
3
3
Harom, J = 8.0 Hz), 7.80 d (2H, Harom, J = 8.8 Hz),
8.29 s (1H, CH=N). 13C NMR spectrum, δC, ppm:
21.16 (CH3), 45.32 (CH2), 55.28 (OCH3), 71.88 (CH),
113.94 (2C, CHarom), 126.90 (2C, CHarom), 129.25 (2C,
CHarom), 130.02 (2C, CHarom), 159.98 (C=N), 119.48,
121.16, 129.14, 137.03, 139.55, 161.76. Found, %:
C 60.02; H 4.88; Cl 27.39; N 3.40. C19H18Cl3NO. Cal-
culated, %: C 59.63; H 4.74; Cl 27.79; N 3.66.
(E)-2-Methoxy-4-[(3,4,4-trichloro-1-phenylbut-
3-en-1-ylimino)methyl]phenol (XXXIII). Yield 71%,
oily substance. IR spectrum, ν, cm–1: 3357 (OH), 3085,
3063, 3029, 3005, 2969, 2936, 2853 (C–H), 1640
(C=N), 1602, 1589, 1513, 1495, 1465, 1453, 1430
(C=C), 1284, 1160, 1032 (C–O), 923, 818 (C–Cl).
1H NMR spectrum, δ, ppm: 3.09–3.39 m (2H, CH2),
3.84 s (3H, OCH3), 4.73 m (1H, CH), 6.90 d (1H,
(E)-4-{[3,4,4-Trichloro-1-(4-methylphenyl)but-
3-en-1-ylimino]methyl}phenol (XXXVI). Yield 65%,
mp 177–178°C. IR spectrum, ν, cm–1: 3423 (OH),
3063, 3027, 3008, 2922, 2882, 2855 (C–H), 1637
(C=N), 1610, 1574, 1514, 1450 (C=C), 1241, 1032
3
3
4
1
H
arom, J = 8.1 Hz), 7.14 d.d (1H, Harom, J = 8.1, J =
(C–O), 922, 830 (C–Cl). H NMR spectrum, δ, ppm:
1.6 Hz), 7.38 m (3H, Harom), 7.41 (1H, OH), 7.53 m
(3H, Harom), 8.22 s (1H, CH=N). 13C NMR spectrum,
δC, ppm: 45.11 (CH2), 55.74 (OCH3), 71.95 (CH),
109.06 (CHarom), 114.70 (CHarom), 124.13 (CHarom),
126.21 (CHarom), 127.07 (2C, CHarom), 128.57 (2C,
CHarom), 160.76 (C=N), 119.56, 128.38, 129.88,
142.32, 147.43, 149.19. Found, %: C 56.48; H 4.35;
Cl 27.09; N 3.26. C18H16Cl3NO2. Calculated, %:
C 56.20; H 4.19; Cl 27.56; N 3.64.
2.30 s (3H, CH3), 3.00–3.32 m (2H, CH2), 4.68 m (1H,
CH), 6.91 d (2H, Harom, 3J = 8.3 Hz), 7.16 d (2H, Harom
,
3
3J = 7.8 Hz), 7.39 d (2H, Harom, J = 7.8 Hz), 7.70 d
3
(2H, Harom, J = 8.3 Hz), 8.28 s (1H, CH=N), 8.94 br.s
(1H, OH). 13C NMR spectrum, δC, ppm: 21.46 (CH3),
46.26 (CH2), 72.90 (CH), 116.59 (2C, CHarom), 128.06
(2C, CHarom), 130.20 (2C, CHarom), 131.27 (2C,
CHarom), 161.23 (C=N), 119.92, 129.01, 129.49,
131.67, 137.89, 141.10. Found, %: C 58.96; H 4.53;
Cl 28.31; N 3.44. C18H16Cl3NO. Calculated, %:
C 58.64; H 4.37; Cl 28.85; N 3.80.
(E)-2-Methoxy-5-[(3,4,4-trichloro-1-phenylbut-
3-en-1-ylimino)methyl]phenol (XXXIV). Yield 72%,
oily substance. IR spectrum, ν, cm–1: 3358 (OH), 3084,
3063, 3029, 3003, 2956, 2935, 2839 (C–H), 1641
(C=N), 1602, 1586, 1512, 1495, 1454, 1441 (C=C),
(E)-2-Methoxy-4-{[3,4,4-trichloro-1-(4-methyl-
phenyl)but-3-en-1-ylimino]methyl}phenol
(XXXVII). Yield 71%, mp 119–121°C. IR spectrum,
ν, cm–1: 3342 (OH), 3068, 3024, 3008, 2973, 2936,
2852 (C–H), 1640 (C=N), 1601, 1593, 1514, 1464,
1453, 1431 (C=C), 1287, 1158, 1032 (C–O), 921, 818
1
1277, 1130, 1029 (C–O), 923, 802 (C–Cl). H NMR
spectrum, δ, ppm: 3.03–3.32 m (2H, CH2), 3.82 s (3H,
OCH3), 4.69 m (1H, CH), 5.35 s (1H, OH), 6.83 d (1H,
3
3
4
1
H
arom, J = 8.3 Hz), 7.22 d.d (1H, Harom, J = 8.3, J =
(C–Cl). H NMR spectrum, δ, ppm: 2.34 s (3H, CH3),
1.7 Hz), 7.36 m (3H, Harom), 7.50 m (3H, Harom), 8.19 s
(1H, CH=N). 13C NMR spectrum, δC, ppm: 45.23
(CH2), 55.78 (OCH3), 72.01 (CH), 110.29 (CHarom),
113.86 (CHarom), 121.72 (CHarom), 126.97 (2C, CHarom),
127.42 (CHarom), 128.49 (2C, CHarom), 160.36 (C=N),
119.54, 129.74, 131.23, 142.40, 146.01, 149.42.
Found, %: C 57.56; H 4.70; Cl 26.33; N 3.35.
3.05–3.36 m (2H, CH2), 3.87 s (3H, OCH3), 4.69 m
3
(1H, CH), 6.91 d (1H, Harom, J = 8.1 Hz), 7.13 d.d
3
4
(1H, Harom, J = 8.1, J = 1.6 Hz), 7.17 d (2H, Harom
,
3J = 7.9 Hz), 7.37 d (2H, Harom, J = 7.9 Hz), 7.49 d
(2H, Harom, 4J = 1.6 Hz), 8.19 s (1H, CH=N). 13C NMR
spectrum, δC, ppm: 21.20 (CH3), 44.87 (CH2), 55.94
(OCH3), 71.66 (CH), 109.08 (CHarom), 114.33 (CHarom),
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 10 2014

POTKIN et al.
1420
124.29 (CHarom), 127.04 (2C, CHarom), 129.33 (2C,
CHarom), 160.82 (C=N), 119.56, 128.65, 129.99,
137.25, 139.13, 147.19, 148.82. Found, %: C 57.48;
H 4.72; Cl 26.10; N 3.29. C19H18Cl3NO2. Calculated,
%: C 57.24; H 4.55; Cl 26.68; N 3.51.
2.99–3.26 m (2H, CH2), 3.80 s (3H, OCH3), 4.64 m
3
(1H, CH), 6.93 d (2H, Harom, J = 8.7 Hz), 7.39 d (2H,
3
3
H
arom, J = 8.4 Hz), 7.49 d (2H, Harom, J = 8.4 Hz),
3
7.75 d (2H, Harom, J = 8.7 Hz), 8.23 s (1H, CH=N).
13C NMR spectrum, δC, ppm: 45.26 (CH2), 55.29
(OCH3), 71.35 (CH), 113.99 (2C, CHarom), 128.73 (2C,
CHarom), 130.05 (2C, CHarom), 131.57 (2C, CHarom),
160.44 (C=N), 119.85, 121.23, 128.76, 129.35, 141.49,
161.88. Found, %: C 48.67; H 3.54; Hlg 41.18; N 2.80.
C18H15BrCl3NO. Calculated, %: C 46.64; H 3.26;
Hlg 41.61; N 3.13.
(E)-3,4,4-Trichloro-1-(2,5-dimethylphenyl)-
N-(4-methoxybenzylidene)but-3-en-1-amine
(XXXVIII). Yield 74%, mp 90–91°C. IR spectrum, ν,
cm–1: 3067, 3040, 3016, 2957, 2921, 2838 (C–H),
1641 (C=N), 1608, 1579, 1511, 1443, 1423 (C=C),
1
1251, 1031 (C–O), 925, 812 (C–Cl). H NMR spec-
(E)-4-{[1-(4-Bromophenyl)-3,4,4-trichlorobut-3-
en-1-ylimino]methyl}-2-methoxyphenol (XLI). Yield
88%, oily substance. IR spectrum, ν, cm–1: 3358 (OH),
3070, 3026, 3006, 2973, 2934, 2856 (C–H), 1640
(C=N), 1601, 1594, 1513, 1487, 1464, 1430 (C=C),
trum, δ, ppm: 2.41 s (3H, CH3), 2.48 s (3H, CH3),
2.90–3.47 m (2H, CH2), 3.87 s (3H, OCH3), 4.96 m
3
(1H, CH), 6.99 d (2H, Harom, J = 8.8 Hz), 7.05 d (1H,
3
4
3
Harom, J = 7.7, J = 1.1 Hz), 7.12 d (1H, Harom, J =
3
7.7 Hz), 7.62 s (1H, Harom), 7.80 d (2H, Harom, J =
1
8.8 Hz), 8.27 s (1H, CH=N). 13C NMR spectrum, δC,
ppm: 19.06 (CH3), 21.28 (CH3), 44.47 (CH2), 55.39
(OCH3), 68.56 (CH), 114.01 (2C, CHarom), 127.96
(CHarom), 128.01 (CHarom), 130.11 (2C, CHarom), 130.64
(CHarom), 159.91 (C=N), 119.57, 121.25, 129.37,
131.63, 135.87, 140.61, 161.81. Found, %: C 60.92;
H 5.14; Cl 26.38; N 3.26. C20H20Cl3NO. Calculated,
%: C 60.55; H 5.08; Cl 26.81; N 3.53.
1284, 1160, 1033 (C–O), 922, 822 (C–Cl). H NMR
spectrum, δ, ppm: 3.01–3.27 m (2H, CH2), 3.86 s (3H,
3
OCH3), 4.64 m (1H, CH), 6.90 d (1H, Harom, J =
3
7.8 Hz), 7.13 d (1H, Harom, J = 7.8 Hz), 7.31 d (1H,
3
3
H
arom, J = 7.8 Hz), 7.36 d (2H, Harom, J = 7.1 Hz),
7.46 m (3H, 2H, Harom, OH), 8.18 s (1H, CH=N).
13C NMR spectrum, δC, ppm: 45.03 (CH2), 55.91
(OCH3), 71.29 (CH), 109.03 (CHarom), 114.44 (CHarom),
124.28 (CHarom), 128.85 (2C, CHarom), 131.66 (2C,
CHarom), 161.07 (C=N), 119.92, 121.38, 128.46,
129.42, 141.28, 147.22, 148.92. Found, %: C 46.55;
H 3.35; Hlg 40.00; N 3.16. C18H15BrCl3NO2. Calculat-
ed, %: C 46.64; H 3.26; Hlg 40.18; N 3.02.
(E)-2-Methoxy-4-{[3,4,4-trichloro-1-(2,5-di-
methylphenyl)but-3-en-1-ylimino]methyl}phenol
(XXXIX). Yield 73%, oily substance. IR spectrum, ν,
cm–1: 3417 (OH), 3074, 3046, 3005, 2958, 2924, 2855
(C–H), 1632 (C=N), 1598, 1515, 1463, 1430 (C=C),
1
This study was performed under financial support
by the Belarusian Republican Foundation for Basic
Research (project no. Kh12SO-012) and by the
Siberian Branch, Russian Academy of Sciences
(project no. 21).
1284, 1167, 1035 (C–O), 925, 814 (C–Cl). H NMR
spectrum, δ, ppm: 2.33 s (3H, CH3), 2.41 s (3H, CH3),
2.89–3.43 m (2H, CH2), 3.90 s (3H, OCH3), 4.94 m
3
(1H, CH), 6.92 d (1H, Harom, J = 8 Hz), 7.02 s (1H,
OH), 7.07 d (1H, Harom, 3J = 8 Hz), 7.14 d.d (2H, Harom
,
4
3J = 8, J = 1.1 Hz), 7.40 s (1H, Harom), 7.50 d (2H,
REFERENCES
4
Harom, J = 1.1 Hz), 8.16 s (1H, CH=N). 13C NMR
spectrum, δC, ppm: 19.06 (CH3), 21.23 (CH3), 44.14
(CH2), 56.06 (OCH3), 68.05 (CH), 109.22 (CHarom),
114.34 (CHarom), 124.17 (CHarom), 127.96 (CHarom),
128.05 (CHarom), 130.65 (CHarom), 160.55 (C=N),
119.53, 121.44, 128.84, 131.84, 135.88, 140.10,
147.16, 148.75. Found, %: C 58.61; H 5.07; Cl 25.19;
N 3.04. C20H20Cl3NO2. Calculated, %: C 58.20;
H 4.88; Cl 25.77; N 3.39.
1. Pohland, A.E. and Benson, W.R., Chem. Rev., 1966,
vol. 66, p. 161.
2. Kaberdin, R.V., Potkin, V.I., and Petkevich, S.K., Vestsi
Nats. Akad. Navuk Belarusi, Ser. Khim. Navuk, 2006,
no. 2, p. 100.
3. Levkovskaya, G.G., Bozhenkov, G.V., and Mirsko-
va, A.N., Selected Methods for Synthesis and Modifica-
tion of Heterocycles, Kartsev, V.G., Ed., Moscow: IBS,
2003, vol. 2; Moiseev, I.K., Makarova, N.V. and
Zemtsova, M.N., Izv. Vyssh. Ucheb. Zaved., Ser. Khim.
Khim. Tekhnol., 2007, vol. 59, no. 1, p. 3.
4. Lemke, T.L., Review of Organic Functional Groups:
Introduction to Medicinal Organic Chemistry, Philadel-
phia: Wolters Kluwer/Lippincott Williams & Wilkins
Health, 2012, 5th ed., p. 198.
(E)-1-(4-Bromophenyl)-3,4,4-trichloro-N-(4-me-
thoxybenzylidene)but-3-en-1-amine (XL). Yield
75%, oily substance. IR spectrum, ν, cm–1: 3066, 3031,
3005, 2958, 2933, 2838 (C–H), 1642 (C=N), 1605,
1578, 1512, 1486, 1463, 1422 (C=C), 1254, 1032
1
(C–O), 923, 829 (C–Cl). H NMR spectrum, δ, ppm:
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SYNTHESIS OF FUNCTIONAL DERIVATIVES OF ARYL TRICHLOROVINYL ...
1421
5. Pilgram, K. and Hass, K., J. Med. Chem., 1975, vol. 18,
13. Clerici, F., Gelmi, M.L., Pellegrino, S., and Pocar, D.,
Bioactive Heterocycles III, Berlin: Springer, 2007,
vol. 9, p. 179.
14. Potkin, V.I., Zubenko, Yu.A., Bykhovetz, A.I., Zolo-
tar, R.M., and Goncharuk, V.M., Nat. Prod. Commun.,
2009, vol. 4, p. 1205.
15. Potkin, V.I., Bykhovets, A.I., Lakhvich, F.A.,
Nechai, N.I., Zolotar’, R.M., Goncharuk, V.M.,
Zubenko, Yu.S., and Vashkevich, E.V., Belarusian
Patent no. 12039, 2007; Ofits. Byull., 2009, no. 3, p. 42.
p. 1204.
6. Potkin, V.I., Kaberdin, R.V., Petkevich, S.K., and Kur-
man, P.V., Russ. J. Org. Chem., 2002, vol. 38, p. 1099.
7. Levkovskaya, G.G., Kobelevskaya, V.A., Rudyako-
va, E.V., Khanh, Q.H., Samultsev, D.O., and Rozen-
tsveig, I.B., Tetrahedron, 2011, vol. 67, p. 1844.
8. Savosik, V.A., Rudyakova, E.V., Albanov, A.I.,
Bozhenkov, G.V., and Levkovskaya, G.G., Russ. J. Org.
Chem., 2009, vol. 45, p. 617.
16. Azometiny. Stroenie, svoistva, primenenie (Schiff Bases.
Structure, Properties, and Application), Zhdanov, Yu.A.,
Ed., Rostov-on-Don: Rostov. Gos. Univ., 1974.
17. Dikusar, E.A., Potkin, V.I., and Kozlov, N.G., Benzal’-
degidy vanilinovogo ryada. Sintez proizvodnykh, prime-
nenie i biologicheskaya aktivnost’ (Benzaldehydes of
the Vanillin Series. Synthesis of Derivatives, Applica-
tion, and Biological Activity), Saarbrücken, Germany:
LAP LAMBERT Academic, 2012; Durant, S. and
Karran, P., Nucleic Acids Res., 2003, vol. 31, p. 5501.
18. Dyer, J.R., Applications of Absorption Spectroscopy of
Organic Compounds, Englewood Cliffs: Prentice–Hall,
1965. Translated under the title Prilozheniya absorb-
tsionnoi spektroskopii organicheskikh soedinenii,
Moscow: Khimiya, 1970, p. 92.
9. Takhistov, V.V., Prakticheskaya mass-spektrometriya
organicheskikh soedinenii (Practical Mass Spectrometry
of Organic Compounds), Leningrad: Leningr. Gos. Univ.,
1977; Takhistov, V.V., Rodin, A.A., and Maksimo-
va, B.N., Russ. Chem. Rev., 1991, vol. 60, no. 10, p. 1101.
10. Vatsuro, K.V. and Mishchenko, G.L., Imennye reaktsii v
organicheskoi khimii (Name Reactions in Organic
Chemistry), Moscow: Khimiya, 1976; Polla, E., Bull.
Soc. Chim. Belg., 1985, vol. 94, p. 81.
11. Brown, D.W., Floyd, A.J., and Sainsbury, M., Organic
Spectroscopy, Chichester: Wiley, 1988. Translated under
the title Spektroskopiya organicheskikh veshchestv,
Moscow: Mir, 1992, p. 169.
12. Shailaja, M., Manjula, A., and Vittal Rao, B., Indian J.
Chem., Sect. B, 2011, vol. 50, p. 214.
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