Synthesis of 4-Bromo-1,1′:4′,1″-terphenyl and 4-Methyl-1,1′:4′,1″-terphenyl

Article abstract of DOI:10.1134/S1070428020100115

Abstract: Possible synthetic routes to 4-bromo-1,1′:4′,1″-terphenyl and 4-methyl-1,1′:4′,1″-terphenyl have been studied. Stevens rearrangement of quaternary ammonium salts containing 3-phenylprop-2-en-1-yl and 3-(4-bromo- or 4-methylphenyl)prop-2-yn-1-yl

Full text of DOI:10.1134/S1070428020100115

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 10, pp. 1738–1743. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Organicheskoi Khimii, 2020, Vol. 56, No. 10, pp. 1564–1571.
Synthesis of 4-Bromo-1,1′:4′,1″-terphenyl
and 4-Methyl-1,1′:4′,1″-terphenyl
E. H. Chukhajiana, L. V. Ayrapetyana,*, K. G. Shahkhatunia, and El. H. Chukhajiana
a Institute of Organic Chemistry, Scientific Technological Center of Organic and Pharmaceutical Chemistry,
National Academy of Sciences of Armenia, Yerevan, 0014 Armenia
*e-mail: shhl@mail.ru
Received June 23, 2020; revised July 6, 2020; accepted July 18, 2020
Abstract—Possible synthetic routes to 4-bromo-1,1′:4′,1″-terphenyl and 4-methyl-1,1′:4′,1″-terphenyl have
been studied. Stevens rearrangement of quaternary ammonium salts containing 3-phenylprop-2-en-1-yl and
3-(4-bromo- or 4-methylphenyl)prop-2-yn-1-yl groups gave 1-(4-bromophenyl)-N,N-dimethyl-4-phenylhex-5-
en-1-yn-3-amine, 1-(4-bromophenyl)-N,N-diethyl-4-phenylhex-5-en-1-yn-3-amine, 1-(4-bromophenyl)-4-
phenyl-N,N-dipropylhex-5-en-1-yn-3-amine, 1-[1-(4-bromophenyl)-4-phenylhex-5-en-1-yn-3-yl]piperidine,
4-[1-(4-bromophenyl)-4-phenylhex-5-en-1-yn-3-yl]morpholine, 1-[1-(4-methylphenyl)-4-phenylhex-5-en-1-yn-
3-yl]piperidine, and 4-[1-(4-methylphenyl)-4-phenylhex-5-en-1-yn-3-yl]morpholine. Vacuum distillation of the
resulting amines, by analogy with structurally related compounds, was accompanied by deamination with the
formation of 4-bromo-1,1′:4′,1″-terphenyl and 4-methyl-1,1′:4′,1″-terphenyl in high yields. This transformation
is a domino reaction involving β-elimination of secondary amine to form conjugated dienyne, electrocyclization
of the latter to cyclic allene intermediate, and fast 1,3- or 1,5-hydride shift.
Keywords: deamination, dienynes, Stevens rearrangement, β-elimination, electrocyclic reactions
DOI: 10.1134/S1070428020100115
Stevens rearrangement discovered as early as 1928
[1] occupies a particular place among numerous molec-
ular rearrangements of organic compounds. This reac-
tion generates intermediate ammonium ylides that are
capable of undergoing various transformations. Stevens
rearrangement makes it possible to obtain amines and
quaternary ammonium salts which are widely used in
medicine, technology, and manufacture of cleaning
agents. Stevens rearrangements of new unsaturated
ammonium salts could give rise to new potentially
biologically active tertiary amines, and studies in this
field seem to be important.
proposed. Apart from the fundamental importance,
these studies are also significant from the practical
viewpoint, since they open the way to new p-terphenyl
derivatives [3, 4]. Each newly discovered reaction
would lose its significance if it had no further exten-
sions and general character.
In this work we studied the Stevens rearrangement
of dialkyl [1-(4-bromophenyl)prop-2-yn-1-yl](3-phe-
nylprop-2-en-1-yl)ammonium bromides 2a–2c,
1-[1-(4-bromophenyl)prop-2-yn-1-yl]-1-(3-phenyl-
prop-2-en-1-yl)piperidinium bromide (2d),
4-[1-(4-bromophenyl)prop-2-yn-1-yl]-4-(3-phenyl-
prop-2-en-1-yl)morpholinium bromide (2e),
1-[1-(4-methylphenyl)prop-2-yn-1-yl]-1-(3-phenyl-
prop-2-en-1-yl)piperidinium bromide (2f), and
4-[1-(4-methylphenyl)prop-2-yn-1-yl]-4-(3-phenyl-
prop-2-en-1-yl)morpholinium bromide (2g) and de-
amination of the resulting 1-(4-bromophenyl)-N,N-di-
methyl-4-phenylhex-5-en-1-yn-3-amine (3a),
1-(4-bromophenyl)-N,N-diethyl-4-phenylhex-5-en-1-
yn-3-amine (3b), 1-(4-bromophenyl)-4-phenyl-N,N-di-
propylhex-5-en-1-yn-3-amine (3c), 1-[1-(4-bromo-
phenyl)-4-phenylhex-5-en-1-yn-3-yl]piperidine (3d),
We previously found [2] that vacuum distillation of
N,N-diakyl-1,4-diphenylhex-5-en-1-yn-3-amines,
namely 1-(1,4-diphenylhex-5-en-1-yn-3-yl)pyrrolidine,
1-(1,4-diphenylhex-5-en-1-yn-3-yl)piperidine,
4-(1,4-diphenylhex-5-en-1-yn-3-yl)morpholine,
1-[1-(4-chlorophenyl)-4-phenylhex-5-en-1-yn-3-yl]-
piperidine, and 1-[1-(4-chlorophenyl)-4-phenylhex-5-
en-1-yn-3-yl]morpholine, is accompanied by their
deamination with the formation of 1,1′:4′,1″-terphenyl
and 4-chloro-1,1′:4′,1″-terphenyl in high yields.
A plausible mechanism of their formation was also
1738

SYNTHESIS OF 4-BROMO-1,1′:4′,1″-TERPHENYL AND 4-METHYL-1,1′:4′,1″-TERPHENYL
1739
Scheme 1.
R
R
R
N
R
N
R
N
R
HO–
PhCH=CHCH2Br
Br–
–HBr
X
X
X
1a–1g
2a–2g
CH2
HO–
R2N
X
3a–3g
1–3, X = Br, R = Me (a), Et (b), Pr (c), R2N = piperidin-1-yl (d), morpholin-4-yl (e); X = Me, R2N = piperidin-1-yl (f), morpholin-4-yl (g).
4-[1-(4-bromophenyl)-4-phenylhex-5-en-1-yn-3-yl]-
morpholine (3e), 1-[1-(4-methylphenyl)-4-phenylhex-
5-en-1-yn-3-yl]piperidine (3f), and 4-[1-(4-methyl-
phenyl)-4-phenylhex-5-en-1-yn-3-yl]morpholine (3g)
during vacuum distillation. Quaternary ammonium
salts 2a–2g were synthesized by alkylation of the cor-
responding N,N-dialkyl-1-(4-R-phenyl)prop-2-yn-1-
amines 1a–1g, with 3-bromo-1-phenylprop-1-ene [2]
in acetonitrile (Scheme 1).
3a–3e (cf. [2]) started at 55–57°C (1–2 mm Hg) with
vigorous evolution of the corresponding secondary
amine; the temperature was then raised to 75–85°C
(1–2 mm Hg), and final product 4 condensed in the
arm of the Claisen adapter. The reactions were com-
plete in ~15–20 min. The deamination of 3f and 3g
required heating to 75–85°C (1–2 mm Hg) for 8–
10 min, and prolonged heating was necessary for the
subsequent intramolecular cyclization of intermediate
dienyne A. Terphenyls 4 and 5 were mechanically
pulled out from the Claisen adapter. In addition, we
isolated a small amount of an amine product which
could not be identified.
The rearrangement of 2a–2g by the action of
2 equiv of potassium hydroxide in the presence of
a few drops of methanol was accompanied by vigorous
evolution of heat, and the corresponding amines 3a–3g
were formed in 70–75% yield. The IR spectra of 3a–3g
characteristically showed absorption bands at 3030,
730, and 690 cm–1 due to vibrations of the monosub-
stituted benzene ring and at 810 and 840 cm–1 due to
para-substituted benzene ring. In addition, terminal
C=C bond stretchings were observed at 1645–
As shown in Scheme 2, thermal intramolecular
cyclization of intermediate A gives a tricyclic structure
with an allene moiety in the middle ring. Such inter-
mediates are short-lived, and they rapidly isomerize to
terphenyl 4 or 5 via 1,3- or 1,5-hydride shift.
The results of our study confirm that previously
observed deamination of amines during vacuum
distillation is a unique process in organic chemistry.
An accessible method has been developed for the syn-
thesis of 4-bromo-1,1′:4′,1″-terphenyl and 4-methyl-
1,1′:4′,1″-terphenyl that are difficult to obtain by other
chemical methods. Their formation proves that the
Stevens rearrangement of ammonium salts 2a–2g is
accompanied by isomerization of the migrating group.
1
1640 cm–1. According to the IR and H NMR spectra,
amines 3a–3g had the structure with a terminal C=C
bond; i.e., the Stevens rearrangement of 2a–2g in-
volved isomerization of the migrating group.
Unlike N,N-dialkyl-1-phenylhex-5-en-1-yn-3-
amines, N,N-dimethyl-1-phenylhept-5-en-1-yn-3-
amines [5], and their methallyl analogs [6], amines 3a–
3g, like their analogs reported in [2], underwent
deamination during vacuum distillation to afford
4-bromo-1,1′:4′,1″-terphenyl and 4-methyl-1,1′:4′,1″-
terphenyl in 60–62% yield (Scheme 2). Regardless of
the substituents on the nitrogen atom, deamination of
p-Terphenyl is known as a high-temperature heat
carrier and starting material for the synthesis of poly-
phenyls [3, 4]. p-Terphenyl is also an organic scintil-
lator and is often used as a standard scintillator for
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

CHUKHAJIAN et al.
1740
Scheme 2.
NR2
CH2
Δ
–R2NH
CH2
X
X
3a–3g
A
X
X
[1,3]- or [1,5]-H shift
H
4, 5
3, X = Br, R = Me (a), Et (b), Pr (c), R2N = piperidin-1-yl (d), morpholin-4-yl (e); X = Me, R2N = piperidin-1-yl (f),
morpholin-4-yl (g); 4, X = Br; 5, X = Me.
evaluation of new scintillators [7]. As recently shown
[8], p-terphenyls are new HIV inhibitors that suppress
Rev-RRE function and viral replication. Alkyl-
substituted terphenyls are used as heat carriers in
nuclear power stations [9], as well as in the synthesis
of monomers for heat-resistant polymeric materials
[10], photosensitive materials [11], biologically
active compounds, and medicines [12].
tion of dienynes A (Scheme 2) occur at relatively low
temperatures, and the reactions were complete in ~15–
20 min (except for amines 3f and 3g), regardless of the
substituents on the nitrogen atom. The presence of
a bromine atom in the benzene ring of 3a–3e favored
these processes. Presumably, the bromine atom (unlike
chlorine) exerts no positive mesomeric effect, so that
the acidity of the CH protons in the 4-position of
3 increases, and β-elimination of secondary amine is
facilitated. On the other hand, the bromine atom does
not hamper counterclockwise cyclization of dienyne A
to form a six-membered ring, and both processes are
complete in a short time (~15–20 min; Scheme 2).
Deamination of 3f and 3g required a relatively higher
temperature (75–85°C at 1–2 mm Hg), and the overall
reaction time was ~30–35 min. This may be due to the
presence of a piperidine or morpholine ring and methyl
group in molecules 3f and 3g, which reduce the acidity
of the CH protons in the 4-position and hence hamper
β-elimination of secondary amine. On the other hand,
electronic effect of the methyl group in the para posi-
tion of benzene ring hampers cyclization of interme-
diate dienyne A (Scheme 2) [13].
Known methods of synthesis of p-terphenyl and its
derivatives are characterized by a large number of
steps, low yields, high costs, increased expenditures for
auxiliary materials, long reaction times, high tempera-
ture, sophisticated equipment, and the use of difficulty
accessible and/or hazardous compounds [7–12]. There-
fore, development of accessible methods for the syn-
thesis of p-terphenyl and its derivatives is an important
problem.
Analysis of published data on the synthesis of p-ter-
phenyls and their derivatives showed that the proposed
method for the preparation of compounds 4 and 5 via
deamination of N,N-dialkyl-1,4-diarylhex-5-en-1-yn-3-
amines 2a–2g is very simple and convenient. The ob-
served deamination of 2a–2g during vacuum distilla-
tion is a domino reaction, and it has a general character
and practical significance for the synthesis of new
important terphenyl derivatives.
The formation of 4-bromo-1,1′:4′,1″-terphenyl and
4-methyl-1,1′:4′,1″-terphenyl indicates that the Stevens
rearrangement of ammonium salts 2a–2g involves
isomerization of the migrating group. An accessible
method has been developed for the synthesis of
valuable p-terphenyl derivatives, 4-bromo-1,1′:4′,1″-
terphenyl and 4-methyl-1,1′:4′,1″-terphenyl.
The structure of ammonium salts 2a–2g and amines
3a–3g was proved by IR and 1H NMR spectra, and the
structure of 4 and 5 was also confirmed by 13C NMR
spectra. The deamination and intramolecular cycliza-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

SYNTHESIS OF 4-BROMO-1,1′:4′,1″-TERPHENYL AND 4-METHYL-1,1′:4′,1″-TERPHENYL
1741
EXPERIMENTAL
CHPh, J = 10.8, 7.9, 1.6 Hz), 3.77 d (1H, NCH, J =
10.9 Hz), 4.95 d.d.d (1H, =CH2, J = 17.3, 1.5, 1.3 Hz),
5.01 d.d.d (1H, =CH2, J = 10.4, 1.5, 1.2 Hz), 6.15 d.d.d
(1H, =CH, J = 17.2, 10.3, 7.8 Hz), 7.02–7.06 m (2H,
C6H4), 7.14–7.33 m (5H, C6H5), 7.34–7.39 m (2H,
C6H4). Found, %: C 69.22; H 6.41; Br 21.05; N 3.78.
C22H24BrN. Calculated, %: C 69.11; H 6.33; Br 20.90;
N 3.66.
Initial amines 1a–1g and quaternary salts 2a–2g
were reported previously [13, 14]. The IR spectra were
recorded on a Specord 75 IR spectrometer (Analytik
Jena, Germany) from thin films (3) or solutions in
1
chloroform (4, 5). The H and 13C NMR spectra of 4
and 5 were recorded at 303 K on a Varian Mercury 300
VX spectrometer (USA) at 300 and 75 MHz, respec-
tively, using DMSO-d6–CCl4 (1:3) as solvent and tetra-
methylsilane as internal standard.
1-(4-Bromophenyl)-4-phenyl-N,N-dipropylhex-
5-en-1-yn-3-amine (3c). Yield 2.3 g (0.0056 mmol,
70%), syrupy material. IR spectrum, ν, cm–1: 3030,
720, 710 (Ph), 1645–1640 (C=C), 835, 810 (C6H4).
1H NMR spectrum, δ, ppm: 0.91 t (6H, CH3, J =
7.3 Hz), 1.80–1.90 m (4H, CH2CH3, J = 7.3 Hz), 2.43 t
(4H, NCH2, J = 7.3 Hz), 3.47 d.d.t (1H, CHPh, J =
10.9, 7.8, 1.5 Hz), 3.76 d (1H, NCH, J = 10.9 Hz),
4.96 d.d.d (1H, =CH2, J = 17.2, 1.5, 1.3 Hz), 5.02 d.d.d
(1H, =CH2, J = 10.3, 1.5, 1.1 Hz), 6.16 d.d.d (1H,
=CH, J = 17.2, 10.3, 7.8 Hz), 7.01–7.06 m (2H, C6H4),
7.14–7.32 m (5H, C6H5), 7.34–7.39 m (2H, C6H4).
Found, %: C 70.35; H 6.97; Br 19.62; N 3.54.
C24H28BrN. Calculated, %: C 70.24; H 6.88; Br 19.47;
N 3.41.
Stevens rearrangement of quaternary ammo-
nium salts 2a–2g (general procedure). A mixture of
powdered salt 2a–2g (8 mmol) and 1.46 g (16 mmol)
of potassium hydroxide was thoroughly stirred, and
a few drops of methanol were added. The reaction was
accompanied by evolution of heat. The mixture was
left to stand at room temperature for 30–40 min and
extracted with diethyl ether (2×50 mL). The combined
extracts were washed with water, and a sample of
the extract was treated with water and titrated with
0.1 N H2SO4 with shaking. According to the titration
data, the extract contained 5.6–6.0 mmol (70–75%)
of amine 3a–3g. The extract was acidified with
20% aqueous HCl, and the aqueous phase was separat-
ed, neutralized with a solution of potassium hydroxide,
and extracted with diethyl ether (3×40 mL). The extract
was washed with water, dried over MgSO4, and evapo-
rated, and the residue (amine 3a–3g) was subjected to
vacuum distillation.
1-[1-(4-Bromophenyl)-4-phenylhex-5-en-1-yn-3-
yl]piperidine (3d). Yield 2.4 g (0.006 mmol, 75%),
syrupy materials. IR spectrum, ν, cm–1: 3030, 720, 710
1
(Ph), 1645–1640 (C=C), 835, 810 (C6H4). H NMR
spectrum, δ, ppm: 1.38–1.68 m (6H, β-H, γ-H, piperi-
dine), 2.40–2.48 m (2H, NCH2, α-H, piperidine), 2.63–
2.71 m (2H, NCH2, α-H, piperidine), 3.57 d.d.t (1H,
CHPh, J = 10.8, 7.5, 1.6 Hz), 3.70 d (1H, NCH, J =
10.8 Hz), 4.92 d.d.d (1H, =CH2, J = 17.2, 1.6, 1.4 Hz),
5.02 d.d.d (1H, =CH2, J = 10.3, 1.6, 1.2 Hz), 6.20 d.d.d
(1H, =CH, J = 17.2, 10.3, 7.5 Hz), 7.01–7.05 m
(2H, C6H4), 7.14–7.31 m (5H, C6H5), 7.34–7.38 m
(2H, C6H4). Found, %: C 70.19; H 6.24; Br 20.39;
N 3.69. C23H24BrN. Calculated, %: C 70.05; H 6.13;
Br 20.26; N 3.55.
1-(4-Bromophenyl)-N,N-dimethyl-4-phenylhex-
5-en-1-yn-3-amine (3a). Yield 2.1 g (0.058 mmol,
73%), syrupy material. IR spectrum, ν, cm–1: 3030,
730, 690 (Ph), 1645–1640 (C=C), 840, 810 (C6H4).
1H NMR spectrum, δ, ppm: 2.29 s (6H, NMe2),
3.47 d.d.t (1H, CHPh, J = 10.9, 7.8, 1.5 Hz), 3.76 d
(1H, NCH, J = 10.9 Hz), 4.96 d.d.d (1H, =CH2, J =
17.2, 1.5, 1.3 Hz), 5.02 d.d.d (1H, =CH2, J = 10.3, 1.5,
1.1 Hz), 6.16 d.d.d (1H, =CH, J = 17.2, 10.3, 7.8 Hz),
7.01–7.06 m (2H, C6H4), 7.14–7.32 m (5H, C6H5),
7.34–7.39 m (2H, C6H4). Found, %: C 67.93; H 5.72;
Br 22.77; N 3.83. C20H20BrN. Calculated, %: C 67.80;
H 5.69; Br 22.55; N 3.95.
4-[1-(4-Bromophenyl)-4-phenylhex-5-en-1-yn-3-
yl]morpholine (3e). Yield 2.3 g (0.059 mmol, 74%),
syrupy material. IR spectrum, ν, cm–1: 3030, 730, 690
1
(Ph), 1645–1640 (C=C), 840, 810 (C6H4). H NMR
spectrum, δ, ppm: 3.69–3.83 m [4H, O(CH2)2], 4.00–
4.15 m [4H, N(CH2)2], 3.59 d.d.t (1H, CHPh, J = 10.7,
7.6, 1.5 Hz), 3.72 d (1H, NCH, J = 10.8), 4.92 d.d.d
(1H, =CH2, J = 17.3, 1.5, 1.3 Hz), 5.01 d.d.d (1H,
=CH2, J = 10.4, 1.5, 1.2 Hz), 6.23 d.d.d (1H, =CH,
J = 17.2, 10.3, 7.5 Hz), 7.01–7.06 m (2H, C6H4), 7.14–
1-(4-Bromophenyl)-N,N-diethyl-4-phenylhex-5-
en-1-yn-3-amine (3b). Yield 2.3 g (0.006 mmol, 75%),
syrupy material. IR spectrum, ν, cm–1: 3015, 720, 700
(Ph), 1645–1640 (C=C), 835, 815 (C6H4). H NMR
spectrum, δ, ppm: 1.45 t (6H, CH3, J = 7.2 Hz),
3.61 br.q (4H, NCH2, J = 7.2 Hz), 3.49 d.d.t (1H,
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

CHUKHAJIAN et al.
1742
7.32 m (5H, C6H5), 7.34–7.38 m (2H, C6H4).
Found, %: C 66.79; H 5.71; Br 20.25; N 3.69.
C22H22BrNO. Calculated, %: C 66.67; H 5.59;
Br 20.16; N 3.53.
H 4.23; Br 25.67. C18H13Br. Calculated, %: C 69.90;
H 4.21; Br 25.89.
4-Methyl-1,1′:4′,1″-terphenyl (5). Yield 0.9 g
(3.6 mmol, 60%), yellowish crystals, mp 185–187°C
(from xylene). IR spectrum, ν, cm–1: 1580 (C=Carom),
820 (C6H4), 720, 680 (Ph). 1H NMR spectrum, δ, ppm:
2.40 s (3H, CH3), 7.22 m (2H), 7.50 m (2H, C6H4CH3),
7.31 t.t (1H, p-H, J = 7.3, 2.2 Hz), 7.42 m (2H, m-H),
7.60 m (2H, o-H), 7.63 s (4H, C6H4). 13C NMR spec-
trum, δC, ppm: 121.7, 126.3 (2C, CH), 126.7 (2C, CH),
126.8 (CH), 128.2 (4C, CHarom), 126.9 (2C, CH), 127.8
(2C, CH), 128.2 (2C, CH), 128.3 (2C, CH), 132.5 (2C,
CH), 137.9, 138.0, 139.6. Found, %: C 92.96; H 6.42.
C19H16. Calculated, %: C 93.44; H 6.56.
1-[1-(4-Methylphenyl)-4-phenylhex-5-en-1-yn-3-
yl]piperidine (3f). Yield 1.97 g (0.006 mmol, 75%),
syrupy material. IR spectrum, ν, cm–1: 3025, 720, 700
1
(Ph), 1645–1640 (C=C), 835, 820 (C6H4). H NMR
spectrum, δ, ppm: 1.35–1.66 m (6H, β-H, γ-H, piperi-
dine), 2.35 s (3H, CH3), 2.42–2.48 m (2H, NCH2, α-H,
piperidine), 2.64–2.71 m (2H, NCH2, α-H, piperidine),
3.56 d.d.t (1H, CHPh, J = 10.7, 7.6, 1.5 Hz), 3.73 d
(1H, NCH, J = 10.8 Hz), 4.92 d.d.d (1H, =CH2, J =
17.3, 1.6, 1.3 Hz), 5.02 d.d.d (1H, =CH2, J = 10.2, 1.5,
1.1 Hz), 6.23 d.d.d (1H, =CH, J = 17.3, 10.4, 7.6 Hz),
7.02–7.06 m (2H, C6H4), 7.16–7.32 m (7H, C6H4,
C6H5). Found, %: C 87.61; H 8.38; N 4.37. C24H27N.
Calculated, %: C 87.49; H 8.26; N 4.25.
CONFLICT OF INTEREST
The authors declare the absence of conflict of interest.
REFERENCES
4-[1-(4-Methylphenyl)-4-phenylhex-5-en-1-yn-3-
yl]morpholine (3g). Yield 1.99 g (0.006 mmol, 75%),
syrupy material. IR spectrum, ν, cm–1: 3040, 720, 680
1. Stevens, T.S., Greighton, B.M., Gordon, Q.B., and
MacNikol, M., J. Chem. Soc., 1928, p. 3193.
https://doi.org/10.1039/JR9280003193
1
(Ph), 1645–1640 (C=C), 830, 820 (C6H4). H NMR
spectrum, δ, ppm: 2.32 s (3H, CH3), 2.46–2.56 m (2H,
NCH2), 2.66–2.74 m (2H, NCH2), 3.58–3.71 m [4H,
O(CH2)2], 3.58 d.d.t (1H, CHPh, J = 10.8, 7.7, 1.6 Hz),
3.75 d (1H, NCH, J = 10.8 Hz), 4.95 d.d.d (1H, =CH2,
J = 17.2, 1.6, 1.2 Hz), 5.03 d.d.d (1H, =CH2, J = 10.3,
1.6, 1.0 Hz), 6.21 d.d.d (1H, =CH, J = 17.2, 10.3,
7.7 Hz), 7.03–7.05 m (2H, C6H4), 7.16–7.31 m (7H,
C6H4, C6H5). Found, %: C 83.46; H 7.73; N 4.35.
C23H25NO. Calculated, %: C 83.35; H 7.60; N 4.23.
2. Chukhajian, E.O., Shahkhatuni, K.G., Chukhajian, El.O.,
Ayrapetyan, L.V., and Panosyan, G.A., Russ. J. Org.
Chem., 2017, vol. 53, p. 178.
https://doi.org/10.1134/S1070428017020063
3. Chemistry of Carbon Compounds, Rodd, E.H., Ed.,
Amsterdam: Elsevier, 1956, vol. 3, p. 1049.
4. Ullmann’s Encyclopedia of Industrial Chemistry,
Weinheim: Wiley-VCH, 1977, 4th ed., vol. 14, p. 683.
5. Babayan, A.T., Ananyan, E.S., and Chukhadzhyan, E.O.,
Vacuum distillation of amines 3a–3g (general
procedure). Amines 3a–3g (6 mmol) were subjected to
vacuum distillation in a Claisen flask. Compound 4 or
5 crystallized in the Claisen adapter arm, and the
crystals were mechanically pulled out therefrom. The
still residue was washed off from the flask with xylene.
Compounds 4 and 5 were recrystallized from xylene.
Arm. Khim. Zh., 1969, vol. 22, p. 894.
6. Atomyan, A.V., Chukhadzhyan, E.O., and Babayan, A.T.,
Arm. Khim. Zh., 1983, vol. 36, p. 639.
7. Vardanyan, S.A. and Vardanyan, A.G., Izv. Akad. Nauk
Arm. SSR, 1964, no. 4, p. 428.
8. Gonzalez-Bulnes, L., Ibanez, I., Bedoya Luis, M.,
Beltran, M., Catalan, S., Alcami, J., Fustero, S., and
Gallego, J., Angew. Chem., Int. Ed., 2013, vol. 52,
p. 13405.
4-Bromo-1,1′:4′,1″-terphenyl (4). Yield 1.2 g
(3.72 mmol, 62%), white crystals, mp 220–222°C
(from xylene). IR spectrum, ν, cm–1: 1580 (C=Carom),
820 (C6H4), 720, 680 (Ph). 1H NMR spectrum, δ, ppm:
7.32 t.t (1H, p-H, J = 7.3, 1.3 Hz), 7.39–7.46 m (2H,
m-H), 7.57 s (4H, C6H4), 7.59–7.63 m (4H, o-H),
7.66 s (4H, C6H4). 13C NMR spectrum, δC, ppm: 120.7,
126.2 (2C, CH), 126.6 (2C, CH), 126.8 (CH), 126.9
(2C, CH), 128.0 (2C, CH), 128.2 (2C, CH), 131.3
(2C, CH), 137.9, 138.8, 139.7. Found, %: C 69.68;
https://doi.org/10.1002/anie.201306665
9. Kagan, S.Z. and Chechetkin, A.V., Organicheskie
vysokotemperaturnye teplonositeli i ikh primenenie v
promyshlennosti (High-Temperature Organic Heat
Carriers and Their Industrial Uses), Moscow:
Goskhimizdat, 1951.
10. Ivanova, V.M., Seina, Z.N., and Naryshkin, G.P.,
Monomery dlya termostoikikh polimerov (Monomers for
Heat-Resistant Polymers), Moscow: NIITEKh, 1985.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

SYNTHESIS OF 4-BROMO-1,1′:4′,1″-TERPHENYL AND 4-METHYL-1,1′:4′,1″-TERPHENYL
1743
11. Krasovitskii, B.M. and Bolotin, B.M., Organicheskie
lyuminofory (Organic Luminophores), Moscow:
Khimiya, 1976.
Tamazyan, R.A., J. Heterocycl. Chem., 2008, vol. 45,
p. 687.
https://doi.org/10.1002/jhet.5570450309
12. Stepanov, B.I., Vvedenie v khimiyu i tekhnologiyu
organicheskikh krasitelei (Chemistry and Technology of
Organic Dyes. An Introduction), Moscow: Khimiya,
1977.
14. Chukhajian, E.O., Ayrapetyan, L.V., Chukhajian, El.O.,
and Panosyan, H.A., Chem. Heterocycl. Compd., 2012,
vol. 48, p. 1314.
https://doi.org/10.1007/s10593-012-1138-4
13. Chukhajian, E.O., Nalbandyan, M.K., Gevorkyan, H.R.,
Chukhajian, El.O., Panosyan, H.A., Ayvazyan, A.G., and
15. Kocharyan, S.T., Doctoral (Chem.) Dissertation,
Yerevan, 1986.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020