General procedure for the synthesis of ortho-vinylbenzyl-substituted amines, ethers, and sulfides

Article abstract of DOI:10.1134/S1070428013090145

A convenient procedure has been proposed for the synthesis ortho-vinylbenzyl-substituted ethers, amines, and sulfides via reaction of o-(2-bromoethyl)benzyl bromide with various nucleophiles.

Full text of DOI:10.1134/S1070428013090145

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 9, pp. 1329–1334. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © N.M. Shcheglova, V.D. Kolesnik, R.V. Ashirov, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 9,
pp. 1344–1349.
General Procedure for the Synthesis of ortho-Vinylbenzyl-
Substituted Amines, Ethers, and Sulfides
N. M. Shcheglova, V. D. Kolesnik, and R. V. Ashirov
NIOST Ltd., ul. Kuzovlevskii trakt 2/270, Tomsk, 634067 Russia
e-mail: schnm@niost.ru
Received June 15, 2012
Abstract—A convenient procedure has been proposed for the synthesis ortho-vinylbenzyl-substituted ethers,
amines, and sulfides via reaction of o-(2-bromoethyl)benzyl bromide with various nucleophiles.
DOI: 10.1134/S1070428013090145
In recent time, substituted styrenes having an elec-
tron-donating group in the ortho position have attract-
ed much interest as chelating ligands for carbene ruthe-
nium complexes [1] which catalyze metathesis reac-
tions. Therefore, development of a general procedure
for the synthesis of styrenes with donor substituents is
an important problem.
benzyl bromide can be synthesized from isochroman
which is readily available from 2-phenylethanol [3]
(Scheme 1). The known procedure for the synthesis of
dibromide I by treatment of isochroman with 40% HBr
in acetic acid [4] is very sensitive to moisture and is
complicated due to formation of acetates.
We have found that passing of gaseous HBr through
isochroman yields a mixture of dibromide I with
2-(2-bromomethylphenyl)ethanol; treatment of this
mixture with bromine in the presence of red phospho-
rus gives target product I in an overall yield of 63%.
We now propose a general method for the prepara-
tion of ortho-vinylbenzyl-substituted amines, ethers,
and sulfides using o-(2-bromoethyl)benzyl bromide (I)
[2] as the key intermediate product. o-(2-Bromoethyl)-
Scheme 1.
(1) HBr, 70°C
(2) P, Br2, CH2Cl2
Br
O
Br
I
RR'NH, dioxane, MW
CH2
Br–
N
R
NRR'
R'
IIa–IIe
IIIa–IIIe
t-BuOK, t-BuOH
85°C
MePhNLi, THF
CH2
Br–
Me
N
N
N
Ph
Me
Ph
IIf
IIIf
(1) H2N(CH2)6NH2
dioxane
(2) K2CO3, 70°C
(1) MeI
(2) t-BuOK, t-BuOH, Δ
CH2
N
( )3
( )3
Me
2
2
IV
V
R = R′ = Et (a); RR′ = (CH2)5 (b), (CH2CH2)2O (c); R = R′ = cyclo-C6H11 (d), HOCH2CH2 (e).
1329

SHCHEGLOVA et al.
1330
Scheme 2.
RONa, ROH
CH2
OR
VIa–VId
Na2S, MeOH, Δ
MeI
t-BuOK, t-BuOH, Δ
CH2
I
I–
S
S
SMe
Me
VII
VIII
BuSH, K2CO3, THF
CH2
SBu
X
t-BuOK, THF, 35°C
CH2
Br
Me
N
IX
MeNH2·HCl
H2C
CH2
XI
R = Et (a), i-Pr (b), Ph (c), 4-t-BuC6H4 (d).
The reactions of dibromide I with excess secondary
amines led to the formation of tetrahydroisoquino-
linium bromides IIa–IIe (Scheme 1). Microwave ac-
tivation considerably accelerated the process and in-
creased its selectivity. Ammonium salts IIa–IIe can
readily be converted into the corresponding amino-
styrenes IIIa–IIIe by the action of potassium tert-
butoxide in tert-butyl alcohol or via Hofmann
elimination.
ment with a base afforded 2-(methylsulfanylmethyl)-
styrene (VIII). Dibromide I is readily converted into
2-bromomethylstyrene (IX) by the action of potassium
tert-butoxide under mild conditions. The reactions of
bromide IX with nucleophiles also gave targeted
ortho-substituted styrenes X and XI (Scheme 2).
Thus we have proposed a general and convenient
procedure for the synthesis of a wide series of ortho-
substituted styrenes with the use of readily accessible
o-(2-bromoethyl)benzyl bromide as key intermediate
product.
The reaction of dibromide I with N-methylaniline
under microwave irradiation gave no expected tetrahy-
droisoquinolinium salt, while the isolated product was
N-phenyltetrahydroisoquinoline. With a view to obtain
salt IIf dibromide I was treated with lithium N-meth-
ylanilide without microwave irradiation (Scheme 1).
EXPERIMENTAL
Microwave-assisted reactions were carried out in a
CEM MARS 5 chemical microwave furnace at an ir-
1
radiation power of 400 W. The H and 13C NMR spec-
The described approach is also applicable to the
synthesis of bis-amines (Scheme 1). For example,
treatment of hexane-1,6-diamine with 2 equiv of di-
bromide I afforded 2,2′-hexamethylenediisoquinoline
(IV) whose alkylation with methyl iodide, followed by
treatment with a base, led to the formation of N,N′-bis-
(2-vinylbenzyl)-N,N′-dimethylhexane-1,6-diamine (V).
tra were measured at 25°C on a Bruker Avance III 400
spectrometer operating at 400.1 and 100.6 MHz, re-
spectively; CDCl3 and DMSO-d6 [for 2-(phenoxy-
methyl)styrene] were used as solvents, and tetra-
methylsilane, as internal reference. The mass spectra
were obtained on an Agilent 7890A–5975S GC/MS
system (HP-5MS column, 30 m×0.25 mm; electron
impact, 70 eV). The high-resolution mass spectra were
recorded on an Agilent 1200-6210 mass spectrometer
(electrospray ionization, time-of-flight detector).
The reactions of I with oxygen-centered nucleo-
philes (alcohols and phenols) produced ortho-vinyl-
benzyl-substituted ethers VIa–VId in one step
(Scheme 2). Dibromide I reacted with sodium sulfide
in methanol to give thioisochroman (VII), and the sub-
sequent alkylation of VII with methyl iodide and treat-
2-(2-Bromoethyl)benzyl bromide (I). Anhydrous
hydrogen bromide [5] was passed over a period of 2 h
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

GENERAL PROCEDURE FOR THE SYNTHESIS OF ortho-VINYLBENZYL-SUBSTITUTED
1331
through 5.00 g (37.31 mmol) of isochroman [3] heated
to 70°C. A mixture of dibromide I and 2-(2-bromo-
methylphenyl)ethanol at a ratio of 5:2 was formed.
The mixture was cooled, 15 ml of methylene chloride
and 0.32 g (10.20 mmol) of red phosphorus were
added, and a solution of 2.46 g (15 mmol) of bromine
in methylene chloride was added dropwise under
stirring. The mixture was stirred for 1 h, poured into
ice water, and extracted with petroleum ether. The
extract was dried over anhydrous sodium sulfate and
evaporated under reduced pressure. Yield 63%, light
brown oily substance which solidified on storage.
1H NMR spectrum, δ, ppm: 3.28 t (2H, CH2CH2Br, J =
8.0 Hz), 3.62 t (2H, CH2CH2Br, J = 8.0 Hz), 4.53 s
(2H, CH2), 7.18–7.38 m (4H, Harom) [6].
(4H, 2′-H, 6′-H), 3.5 s (2H, ArCH2), 5.23 d.d (1H,
=CH2, J = 10.8, 1.6 Hz), 5.60 d.d (1H, =CH2, J = 19.2,
1.6 Hz), 7.21–7.29 m (4H, Harom, CH=), 7.55 m (1H,
H
arom). 13C NMR spectrum, δC, ppm: 24.5 (C4′), 26.1
(C3′, C5′), 54.6 (C2′, C6′), 61.3 (ArCH2), 115.0 (=CH2),
125.6 (C6), 127.1 (C5), 127.3 (C4), 130.3 (C2), 135.0
(C3), 136.0 (CH=), 137.8 (C1). Mass spectrum, m/z
(Irel, %): 202 (7.9) [M + H]+, 201 (59.1) [M]+, 200
(89.0), 187 (14.2), 186 (97.6), 172 (18.9), 158 (15.0),
145 (9.4), 144 (13.4), 130 (8.7), 119 (7.9), 118 (55.9),
117 (100), 116 (26.0), 115 (71.7), 98 (26.8), 91 (23.6),
84 (27.6). Found: m/z 202.15952 [M + H]+. C14H19N.
Calculated: [M + H]+ 202.15957.
4-(2-Ethenylbenzyl)morpholine (IIIc) was isolat-
ed by chromatography on silica gel using ethyl
acetate–petroleum ether (1:9) as eluent. Yield 45%,
Aminomethylstyrenes IIIa–IIId (general proce-
dure). A solution of 2 g (7.2 mmol) of dibromide I and
21.6 mmol of the corresponding secondary amine in
15 ml of dioxane was heated for 1 h at 120–130°C
under microwave irradiation. The mixture was cooled
and evaporated, the residue was treated with diethyl
ether, and the precipitate was filtered off and dried on
a filter. The yellow powder thus isolated was dissolved
in 40 ml of tert-butyl alcohol, 2.50 g (22 mmol) of
potassium tert-butoxide was added, and the mixture
was heated for 1 h under reflux, cooled, and evapo-
rated under reduced pressure. The residue was treated
with water and extracted with diethyl ether, and the
extract was dried over anhydrous sodium sulfate,
filtered, and evaporated.
1
colorless transparent liquid. H NMR spectrum, δ,
ppm: 2.47 t (4H, NCH2CH2O, J = 4.3 Hz), 3.54 s (2H,
ArCH2), 3.71 m (4H, OCH2), 5.33 d.d (1H, =CH2, J =
12.4, 1.6 Hz), 5.68 d.d (1H, =CH2, J = 17.6, 1.6 Hz),
7.19–7.30 m (4H, Harom, CH=), 7.55 m (1H, Harom).
13C NMR spectrum, δC, ppm: 53.6 (NCH2CH2O), 61.1
(ArCH2), 67.1 (CH2O), 115.3 (=CH2), 125.7 (C6),
127.3 (C5), 127.5 (C4), 130.5 (C2), 134.8 (C3), 136.8
(CH=), 137.9 (C1). Mass spectrum, m/z (Irel, %): 203
(24.5) [M]+, 202 (26.5), 188 (26.1), 174 (7.9), 172
(11.1), 159 (9.5), 158 (23.3), 146 (21.7), 145 (22.1),
144 (33.2), 131 (7.9), 130 (11.1), 129 (7.9), 119 (6.3),
118 (49.8), 117 (100), 116 (36.4), 115 (77.5), 100
(11.1), 91 (26.1), 86 (11.9), 56 (14.2). Found:
m/z 204.13877 [M + H]+. C13H17NO. Calculated:
[M + H]+ 204.13883.
N-(2-Ethenylbenzyl)-N-ethylethanamine (IIIa)
was isolated by vacuum distillation. Yield 52%, color-
less transparent oily substance, bp 90–95°C (3 mm)
N-Cyclohexyl-N-(2-ethenylbenzyl)cyclohexan-
amine (IIId) was isolated by chromatography on silica
gel using chloroform–petroleum ether (1:10) as eluent.
Yield 42%, light yellow oily substance. 1H NMR spec-
trum, δ, ppm: 0.85–1.35 m (8H, Cy), 1.61 m (4H, Cy),
1.78 m (8H, Cy), 2.56 m (2H, NCH), 3.83 s (2H,
ArCH2), 5.26 d.d (1H, =CH2, J = 16.0, 1.6 Hz),
5.59 d.d (1H, CH=CH2, J = 20.0, 1.6 Hz), 7.18–7.29 m
(3H, Harom, CH=), 7.46 m (1H, Harom), 7.58 m (1H,
1
[2]. H NMR spectrum, δ, ppm: 1.00 t (6H, CH2CH3,
J = 7.2 Hz), 2.49 q (4H, CH2CH3, J = 7.2 Hz), 3.55 s
(2H, ArCH2), 5.24 d.d (1H, =CH2, J = 10.8, 1.6 Hz),
5.60 d.d (1H, =CH2, J = 17.6, 1.6 Hz), 7.12–7.25 m
(3H, Harom, CH=), 7.30–7.34 m (1H, Harom), 7.4–7.51 m
(1H, Harom). 13C NMR spectrum, δC, ppm: 11.6 (CH3),
46.7 (CH2CH3), 55.5 (CH2), 114.9 (=CH2), 125.5 (C6),
127.0 (C5), 127.3 (C4), 130.1 (C3), 134.9 (C2), 137.0
(CH=), 137.6 (C1). Mass spectrum, m/z (Irel, %): 189
(16.7) [M]+, 188 (21.2), 175 (7.6), 174 (51.5), 161
(8.3), 160 (18.2), 118 (15.2), 117 (100), 116 (13.6),
115 (49.2), 91 (14.40), 86 (9.1). Found: m/z 190.15892
[M + H]+. C13H19N. Calculated: [M + H]+ 190.15957.
H
arom). 13C NMR spectrum, δC, ppm: 26.3 (C4′), 26.5
(C3′, C5′), 31.8 (C2′, C6′), 47.5 (ArCH2), 57.7 (C1′),
114.8 (=CH2), 125.4 (C6), 126.2 (C5), 127.4 (C4), 129.0
(C2), 135.0 (C3), 136.8 (CH=), 139.7 (C1). Mass spec-
trum, m/z (Irel, %): 297 (11.4) [M]+, 254 (12.6), 215
(6.7), 214 (26.8), 213 (92.1), 212 (100), 172 (9.4), 144
(5.9), 130 (9.8), 118 (9.4), 117 (64.2), 116 (11.0), 115
(35.0), 91 (11.4), 55 (15.7), 41 (8.7). Found:
m/z 298.25333 [M + H]+. C21H31N. Calculated:
[M + H]+ 298.25347.
1-(2-Ethenylbenzyl)piperidine (IIIb) was isolated
by chromatography on silica gel using ethyl acetate–
petroleum ether (1:10) as eluent. Yield 65%, colorless
transparent oily substance. 1H NMR spectrum, δ, ppm:
1.39 m (2H, 4′-H), 1.58 m (4H, 3′-H, 5′-H), 2.41 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

SHCHEGLOVA et al.
1332
2,2′-[(2-Ethenylbenzyl)imino]diethanol (IIIe).
H
arom), 6.95 d.d (1H, CH=, J = 11.2, 18.4 Hz), 7.19 m
(5H, Harom), 7.50 d (1H, Harom, J = 7.2 Hz). 13C NMR
spectrum, δC, ppm: 38.3 (Me), 54.5 (ArCH2), 112.2
(=CH2), 116.3 (2C, Carom), 116.8 (Carom), 126.1 (C6),
126.7 (C5), 127.0 (C4), 127.9 (C2), 129.2 (2C, Carom),
133.7 (C3), 135.3 (CH=), 136.4 (C1), 149.6 (Carom).
Mass spectrum, m/z (Irel, %): 224 (15.3) [M + 1]+, 223
(90.8) [M]+, 222 (50.0), 209 (7.6), 208 (46.9), 194
(13.7), 193 (19.8), 192 (38.5), 191 (7.6), 180 (6.1), 179
(13.0), 132 (6.9), 120 (30.5), 118 (21.4), 117 (100),
116 (26.0), 115 (90.8), 107 (26.7), 106 (16.0), 105
(7.6), 104 (13.0), 91 (36.6), 89 (6.1), 78 (6.1),
77 (29.0), 65 (8.4), 51 (9.9), 39 (6.0). Found:
m/z 224.14056 [M + H]+. C16H17N. Calculated:
[M + H]+ 224.14392.
A solution of 2.00 g (7.20 mmol) of dibromide I and
2.27 g (21.60 mmol) of diethanolamine in 15 ml of
dioxane was heated for 1 h at 120–130°C under micro-
wave irradiation. The mixture was cooled and evapo-
rated, the residue was washed with THF, and the
precipitate was filtered off and dried on a filter. The
product was dissolved in 40 ml of 50% isopropyl
alcohol, and the solution was applied to a column
charged with AV-17-8 anion exchanger (OH form).
The column was eluted with 50% ethanol until neutral
eluate, the eluate was evaporated, and the residue was
kept for 3 h at 100–180°C (4 mbar) and purified by
chromatography on silica gel using ethyl acetate as
1
eluent. Yield 46%, colorless oily substance. H NMR
spectrum, δ, ppm: 2.71 t (4H, CH2CH2OH, J =
4.4 Hz), 3.59 t (4H, CH2CH2OH, J = 4.4 Hz), 3.80 s
(2H, ArCH2), 5.37 d.d (1H, =CH2, J = 13.4, 1.6 Hz),
5.68 d.d (1H, =CH2, J = 16.8, 1.6 Hz), 7.16 d.d (1H,
CH=, J = 13.4, 16.8 Hz), 7.20–7.40 m (3H, Harom),
7.52 d (1H, Harom, J = 7.2 Hz). 13C NMR spectrum, δC,
ppm: 56.0 (CH2CH2OH), 58.2 (ArCH2), 59.8
(CH2OH), 115.7 (=CH2), 126.5 (C6), 127.8 (C5), 128.0
(C4), 130.6 (C2), 135.1 (C3), 135.7 (CH=), 137.6 (C1).
Mass spectrum, m/z (Irel, %): 191 (8.0), 190 (59.3), 118
(11.4), 117 (100), 116 (10.3), 115 (41.1), 91 (13.3).
Found: m/z 222.14911 [M + H]+. C13H19NO2. Calculat-
ed: [M + H]+ 222.14939.
N,N′-Bis(2-ethenylbenzyl)-N,N′-dimethylhexane-
1,6-diamine (V). A solution of 0.23 g (2 mmol) of
hexane-1,6-diamine in 5 ml of dioxane was added to
a solution of 1.11 g (4 mmol) of dibromide I in 10 ml
of dioxane. The mixture was stirred for 1 h, 3.50 ml of
40% aqueous potassium carbonate was added, and the
mixture was heated for 1 h at 70°C and left to stand for
42 h. The mixture was then filtered, the filtrate was
added to 28.38 g (200 mmol) of methyl iodide, the
mixture was stirred for 24 h at room temperature, the
solvent was distilled off, the light yellow residue was
dissolved in 35 ml of tert-butyl alcohol, 0.68 g
(6.10 mmol) of potassium tert-butoxide was added,
and the mixture was heated for 1 h under reflux. After
cooling, the solvent was distilled off, the residue was
treated with 50 ml of water and extracted with diethyl
ether, the extract was dried over anhydrous Na2SO4,
filtered, and evaporated under reduced pressure, and
the residue was purified by chromatography on silica
gel using toluene–methanol–aqueous ammonia
(10:0.08:0.05) as eluent. Yield 20%, light yellow oily
N-Methyl-N-(2-ethenylbenzyl)aniline (IIIf). A so-
lution of 1.00 g (9.40 mmol) of N-methylaniline in
10 ml of THF was cooled to 0°C, 6.20 ml (9.92 mmol)
of 1.60 M n-butyllithium was added, and the mixture
was stirred for 30 min. A solution of 2.62 g
(9.42 mmol) of dibromide I in 10 ml of THF was then
added dropwise at 0°C, and the mixture was stirred for
15 min, treated with a saturated solution of ammonium
chloride, diluted with water, and extracted with diethyl
ether. The extract was dried over anhydrous Na2SO4,
filtered, and evaporated under reduced pressure. The
residue was a yellow powder which was dissolved in
20 ml of tert-butyl alcohol, 1.74 g (15.60 mmol) of
potassium tert-butoxide was added, and the mixture
was heated for 1 h under reflux. The mixture was
cooled and evaporated, 50 ml of water was added to
the residue, and the mixture was extracted with diethyl
ether. The extract was dried over anhydrous Na2SO4,
filtered, and evaporated under reduced pressure. Yield
50%, light yellow transparent oily substance. 1H NMR
spectrum, δ, ppm: 2.99 s (3H, Me), 4.55 s (2H,
ArCH2), 5.32 d.d (1H, =CH2, J = 11.2, 1.2 Hz),
5.65 d.d (1H, =CH2, J = 18.4, 1.2 Hz), 6.69 m (3H,
1
substance. H NMR spectrum, δ, ppm: 1.25 m (4H,
3′-H, 4′-H), 1.46 m (4H, 2′-H, 5′-H), 2.13 s (6H, Me),
2.32 m (4H, 1′-H, 6′-H), 3.45 s (4H, ArCH2), 5.23 d.d
(2H, =CH2, J = 11.0, 1.2 Hz), 5.60 d.d (2H, =CH2, J =
17.5, 1.2 Hz), 7.1–7.3 m (7H, Harom, CH=), 7.47 m
(2H, Harom). 13C NMR spectrum, δC, ppm: 27.3 (C3′,
C4′), 27.4 (C2′, C5′), 42.1 (Me), 57.7 (C1′, C6′), 60.6
(ArCH2), 114.9 (=CH2), 125.6 (C6), 127.2 (C5), 127.3
(C4), 130.4 (C2), 135.0 (C3), 136.4 (CH=), 137.8 (C1).
Mass spectrum, m/z (Irel, %): 260 (7.0), 259 (35.2), 161
(5.1), 160 (42.5), 146 (6.6), 144 (5.5), 118 (11.0), 117
(100), 116 (10.6), 115 (35.2), 112 (10.6), 91 (12.5).
Found: m/z 377.29603 [M + H]+. C26H36N2. Calculat-
ed: [M + H]+ 377.29513.
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GENERAL PROCEDURE FOR THE SYNTHESIS OF ortho-VINYLBENZYL-SUBSTITUTED
1333
2-(Ethoxymethyl)styrene (VIa). Dibromide I,
5.0 g (18 mmol), was added to a solution of 0.99 g
(43 mmol) of metallic sodium in 70 ml of ethanol. The
mixture was heated for 1 h under reflux, the solvent
was removed under reduced pressure, and the residue
was treated with 250 ml of water and extracted with
ethyl acetate. The extract was dried over anhydrous
Na2SO4, filtered, and evaporated under reduced pres-
sure, and the residue was distilled in a vacuum. Yield
54%, colorless transparent viscous liquid, bp 70–90°C
7.45 d (1H, Harom, J = 7.6 Hz), 7.63 d (1H, Harom, J =
7.6 Hz). 13C NMR spectrum (DMSO-d6), δC, ppm:
67.3 (ArCH2), 114.6 (2C, Carom), 116.4 (=CH2), 120.7
(Carom), 125.4 (C3), 127.7 (C6), 128.4 (C5), 129.4 (2C,
C
arom), 129.4 (C4), 133.4 (C1), 133.7 (CH=), 136.5
(C2), 158.2 (Carom). Mass spectrum, m/z (Irel, %): 210
(9.5) [M]+, 118 (9.9), 117 (100.0), 116 (27.5), 115
(56.4), 91 (17.6), 65 (8.4), 39 (5.3). Found:
m/z 211.12362 [M + H]+. C15H14O. Calculated:
[M + H]+ 211.11229.
1
(4 mm). H NMR spectrum, δ, ppm: 1.30 t (3H, Me,
2-(4-tert-Butylphenoxymethyl)styrene (VId) was
synthesized in a similar way from 4-tert-butylphenol.
Yield 78%, light yellow transparent oily substance.
1H NMR spectrum, δ, ppm: 1.32 s (9H, t-Bu), 5.08 s
(2H, CH2), 5.34 d.d (1H, =CH2, J = 10.8, 1.6 Hz),
5.71 d.d (1H, =CH2, J = 17.2, 1.6 Hz), 6.95 m (2H,
J = 7.0 Hz), 3.60 q (2H, CH2CH3, J = 7.0 Hz), 4.60 s
(2H, ArCH2), 5.37 d.d (1H, =CH2, J = 11.2, 1.6 Hz),
5.72 d.d (1H, =CH2, J = 17.6, 1.6 Hz), 7.05–7.13 d.d
(1H, CH=, J = 17.6, 11.2 Hz), 7.28–7.32 m (2H,
H
H
arom), 7.40 d (1H, Harom, J = 7.2 Hz), 7.59 d (1H,
arom, J = 7.2 Hz). 13C NMR spectrum, δC, ppm: 15.3
H
arom), 7.01 d.d (1H, CH=, J = 10.8, 17.2 Hz), 7.27–
(Me), 65.8 (CH2CH3), 70.8 (ArCH2), 115.9 (=CH2),
125.8 (C6), 127.6 (C5), 128.0 (C4), 129.1 (C2), 134.2
(C3), 135.8 (CH=), 137.1 (C1). Mass spectrum, m/z
(Irel, %): 162 (22.6) [M]+, 134 (13.5), 133 (100), 119
(7.1), 118 (55.5), 117 (72.7), 116 (41.6), 115 (89.5),
106 (6.2), 105 (65.0), 103 (17.4), 102 (5.3), 91 (30.9),
89 (8.3), 79 (18.6), 78 (6.7), 77 (22.6), 65 (7.1), 63
(7.1), 51 (7.1). Found: m/z 163.11252 [M + H]+.
C11H14O. Calculated: [M + H]+ 163.11229.
7.38 m (4H, Harom), 7.44 d (1H, Harom, J = 7.2 Hz),
7.58 d (1H, Harom, J = 7.2 Hz). 13C NMR spectrum, δC,
ppm: 31.5 (Me), 34.1 [C(CH3)3], 68.2 (ArCH2), 114.2
(2C, Carom), 116.6 (=CH2), 125.9 (C6), 126.2 (2C,
C
arom), 127.9 (C5), 128.6 (C4), 129.2 (C3), 133.6
(Carom), 133.7 (CH=), 137.1 (C1), 143.8 (C2), 156.5
(Carom). Mass spectrum, m/z (Irel, %): 266 (15.4) [M]+,
150 (6.6), 135 (27.8), 118 (10.3), 117 (100.0), 116
(23.8), 115 (39.6), 91 (16.8). Found: m/z 267.12143
[M + H]+. C19H22O. Calculated: [M + H]+ 267.12020.
2-(Isopropoxymethyl)styrene (VIb) was synthe-
sized in a similar way from propan-2-ol. Yield 85%,
colorless viscous liquid, bp 100–110°C (7 mm). The
spectral parameters of VIb were identical to those
reported previously [7].
2-(Methylsulfanylmethyl)styrene (VIII). Methyl
iodide, 22.79 g (160.55 mmol), was added to 1.95 g
(13.00 mmol) of isothiochroman (VII) [8], and the
mixture was kept for 24 h. The precipitate was filtered
off, washed with diethyl ether, and dried over Na2SO4,
40 ml of tert-butyl alcohol and 2.45 g (21.80 mmol) of
potassium tert-butoxide were added, and the mixture
was heated for 1 h under reflux. The mixture was
cooled and evaporated under reduced pressure, the
residue was treated with 150 ml of water and extracted
with diethyl ether, the extract was dried over anhy-
drous Na2SO4, filtered, and evaporated, and the residue
was purified by chromatography on silica gel using
ethyl acetate–petroleum ether (1:5) as eluent. Yield
2-(Phenoxymethyl)styrene (VIc). A solution of
7.20 mmol of phenol in 5 ml of THF was added to
a suspension of 0.32 g (7.90 mmol) of sodium hydride
(60 wt %) in 20 ml of THF. The mixture was stirred for
5 min, a solution of 1.00 g (3.60 mmol) of dibromide I
in 5 ml of THF was added, the mixture was stirred for
3 h at 50°C, 0.96 g (8.60 mmol) of potassium tert-
butoxide was added, and the mixture was heated for
2 h under reflux. The mixture was cooled, poured into
100 ml of brine, and extracted with diethyl ether. The
extract was washed with 10% aqueous sodium hydrox-
ide, dried over anhydrous Na2SO4, filtered, and evapo-
rated, and the residue was purified by chromatography
on silica gel using chloroform–petroleum ether (1:20)
as eluent. Yield 72%, light yellow transparent oily sub-
1
70%, light brown transparent oily substance. H NMR
spectrum, δ, ppm: 2.00 s (3H, Me), 3.70 s (2H, CH2),
5.31 d.d (1H, =CH2, J = 12.0, 1.2 Hz), 5.64 d.d (1H,
=CH2, J = 20.0, 1.2 Hz), 7.02–7.10 d.d (1H, CH=, J =
12.0, 20.0 Hz), 7.10–7.30 m (3H, Harom), 7.47 d (1H,
H
arom, J = 8.0 Hz). 13C NMR spectrum, δC, ppm: 15.2
1
stance. H NMR spectrum (DMSO-d6), δ, ppm: 5.13 s
(Me), 35.9 (CH2S), 116.0 (=CH2), 126.3 (C4), 127.5
(C6), 127.6 (C5), 130.2 (C3), 134.3 (CH=), 134.9 (C1),
137.1 (C2). Mass spectrum, m/z (Irel, %): 164 (43.7)
[M]+, 149 (35.5), 134 (4.9), 118 (9.4), 117 (78.8), 116
(2H, CH2), 5.34 d.d (1H, =CH2, J = 11.2, 1.6 Hz),
5.78 d.d (1H, =CH2, J = 17.6, 1.6 Hz), 6.93–6.98 m
(1H, Harom), 6.99–7.06 m (4H, Harom, CH=), 7.25–
7.34 m (2H, Harom), 7.37 t (1H, Harom, J = 7.6 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013

SHCHEGLOVA et al.
1334
(40.9), 115 (100.0), 91 (23.6), 89 (7.4), 65 (6.1), 63
(6.9). Found: m/z 165.07484 [M + H]+. C10H12S. Cal-
culated: [M + H]+ 165.07325.
silica gel using methylene chloride–petroleum ether
(1:15) as eluent. Yield 57%, light yellow transparent
oily substance. 1H NMR spectrum, δ, ppm: 2.13 s (3H,
Me), 3.53 s (4H, ArCH2), 5.19 d.d (2H, =CH2, J =
11.0, 1.4 Hz), 5.60 d.d (2H, =CH2, J = 17.5, 1.4 Hz),
7.03–7.13 d.d (2H, CH=, J = 11.0, 17.5 Hz), 7.51 m
(2H, Harom), 7.16–7.28 m (6H, Harom). 13C NMR spec-
trum, δC, ppm: 42.1 (Me), 60.2 (ArCH2), 114.8
(=CH2), 125.5 (C6), 127.4 (C5), 127.5 (C4), 130.8 (C2),
134.9 (C3), 136.1 (CH=), 137.8 (C1). Mass spectrum,
m/z (Irel, %): 263 (5.3) [M]+, 262 (14.7), 248 (13.9),
220 (7.7), 160 (7.3), 159 (6.6), 158 (53.5), 148 (7.7),
147 (8.8), 146 (59.3), 145 (19.0), 144 (65.2), 132
(11.7), 131 (21.2), 130 (11.0), 119 (13.2), 118 (25.6),
117 (100.0), 116 (35.9), 115 (83.5), 105 (7.0), 103
(5.5), 91 (33.3), 89 (5.3), 77 (7.0), 65 (6.2), 42 (7.3),
39 (5.1). Found: m/z 264.17148 [M + H]+. C19H21N.
Calculated: [M + H]+ 264.17522.
2-(Butylsulfanylmethyl)styrene (X). Potassium
tert-butoxide, 1.61 g (14.40 mmol), was added to
a solution of 4.00 g (14.40 mmol) of dibromide I in
120 ml of THF, and the mixture was stirred for 2.5 h at
35°C. Compound IX was formed; its structure was
confirmed by mass spectrometry [9]. Butane-1-thiol,
2.21 g (24.50 mmol), and potassium carbonate, 3.38 g
(24.50 mmol), were added, and the mixture was stirred
for 24 h, poured into 50 ml of water, and 100 ml of
brine was added. The organic phase was separated, the
aqueous phase was extracted with ethyl acetate, the
extract was combined with the organic phase, dried
over anhydrous Na2SO4, filtered, and evaporated under
reduced pressure, and the residue was purified by
chromatography on silica gel using ethyl acetate–
petroleum ether (1 :5) as eluent. Yield 42%, light
REFERENCES
1
brown transparent oily substance. H NMR spectrum,
δ, ppm: 0.97 t (3H, Me, J = 7.3 Hz), 1.46 m (2H,
CH2CH3), 1.62 m (2H, SCH2CH2), 2.51 t (2H, SCH2,
J = 7.3 Hz), 3.80 s (2H, ArCH2), 5.39 d.d (1H, =CH2,
J = 11.0, 1.2 Hz), 5.73 d.d (1H, =CH2, J = 17.4,
1.2 Hz), 7.1–7.3 m (4H, Harom, CH=), 7.56 d (1H,
Harom, J = 7.0 Hz). 13C NMR spectrum, δC, ppm: 13.7
(Me), 22.1 (CH2CH3), 31.5 (SCH2CH2), 31.6 (SCH2),
34.0 (ArCH2), 116.0 (=CH2), 126.2 (C4), 127.4 (C6),
127.6 (C5), 130.1 (C3), 134.2 (CH=), 135.5 (C1), 136.9
(C2). Mass spectrum, m/z (Irel, %): 206 (22.6) [M]+, 151
(5.1), 149 (62.0), 135 (19.7), 134 (6.6), 118 (23.4), 117
(100), 116 (42.0), 115 (97.4), 91 (24.5), 89 (6.9), 65
(6.6), 39 (6.2). Found: m/z 207.11959 [M + H]+.
C13H18S. Calculated: [M + H]+ 207.12020.
1. Kolesnik, V.D., Ashirov, R.V., Shcheglova, N.M., Novi-
kova, E.S., Yakimov, R.V., Nosikov, A.A., Bogomolo-
va, M.N., and Cheremukhina, N.M., Russian Patent
no. 2409420, 2009; Byull. Izobret., 2011, no. 2.
2. Pogosyan, G.M., Khimiya nepredel’nykh soedinenii.
Sbornik statei (Chemistry of Unsaturated Compounds.
A Collection of Papers), Erevan: Akad. Nauk Arm. SSR,
1979, p. 169.
3. Reiche, A. and Schmitz, E., Chem. Ber., 1956, vol. 89,
p. 1254.
4. Colonge, J. and Boisde, P., Bull. Soc. Chim. Fr., 1956,
p. 1337.
5. Karyakin, Yu.V. and Angelov, I.I., Chistye khimicheskie
veshchestva (Pure Chemicals), Moscow: Khimiya, 1974,
p. 165.
N,N-Bis(2-ethenylbenzyl)methanamine (XI).
A solution of 1.67 g (24.90 mmol) of potassium
hydroxide in 50 ml of water was added to a mixture of
1.98 g (28.60 mmol) of methylamine hydrochloride
and 50 ml of isopropyl alcohol, the mixture was stirred
for 1 h, 1.0 g (3.6 mmol) of compound IX was added,
and the mixture was stirred for 24 h at room tempera-
ture and for 24 h at 50°C. The solvent was distilled off,
and the residue was purified by chromatography on
6. Hori, M., Kataoka, T., Shimizu, H., Tsutsumi, K.,
Hu, Y.-Zh., and Nishigiri, M., J. Chem. Soc., Perkin
Trans. 1, 1990, p. 39.
7. Hirao, A., Negishi, Y., Hayashi, M., Sako, K., Ryu, S.W.,
Loykulnant, S., Matsuo, A., and Sugiyama, K., Macro-
mol. Chem. Phys., 2001, vol. 202, p. 3590.
8. Holiman, F.G. and Mann, F.G., J. Chem. Soc., 1945, p. 37.
9. Oppolzer, W., Roberts, D.A., and Bird, T.G., Helv. Chim.
Acta, 1979, vol. 62, p. 2017.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013