Reactions of N- and C-alkenylanilines: VI. Synthesis of 6-methyl-2-[(E or Z)-1-propenyl]anilines and the corresponding anilides and their reaction with bromine

Article abstract of DOI:10.1007/s11178-005-0096-z

Isomerization of 2-allyl-6-methylaniline by the action of potassium hydroxide at 300°C afforded cis and trans isomers of 2-methyl-6-(1-propenyl) aniline which were converted into the corresponding carbamates by treatment with ethyl chloroformate. Ethyl 2-

Full text of DOI:10.1007/s11178-005-0096-z

Russian Journal of Organic Chemistry, Vol. 40, No. 12, 2004, pp. 1764–1768. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004,
pp. 1815–1818.
Original Russian Text Copyright © 2004 by Afon’kin, Sotnikov, Gataullin, Spirikhin, Abdrakhmanov.
Reactions of N- and C-Alkenylanilines:
VI.* Synthesis of 6-Methyl-2-[(E or Z)-1-propenyl]anilines
and the Corresponding Anilides and Their Reaction
with Bromine
I. S. Afon’kin, A. M. Sotnikov, R. R. Gataullin, L. V. Spirikhin, and I. B. Abdrakhmanov
Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: chemorg@anrb. ru
Received June 18, 2002
Abstract—Isomerization of 2-allyl-6-methylaniline by the action of potassium hydroxide at 300°C afforded cis
and trans isomers of 2-methyl-6-(1-propenyl)aniline which were converted into the corresponding carbamates
by treatment with ethyl chloroformate. Ethyl 2-methyl-6-(1-propenyl)phenylcarbamates reacted with bromine
to give mixtures of 4-(1-bromoethyl)-8-methyl-1,4-dihydro-2H-3,1-benzoxazin-2-one and ethyl 2-methyl-6-
(1,2-dibromopropyl)phenylcarbamates. Treatment of the same compounds with N-bromosuccinimide resulted
in formation of 2-ethoxy-4H-3,1-benzoxazine derivatives. The reaction of N-{6-methyl-2-[(Z)-1-propenyl]-
phenyl}methanesulfonamide gave a mixture of stereoisomeric N-[6-methyl-2-(1,2-dibromopropyl)-phenyl]-
methanesulfonamides.
double bond in IV and V was accompanied by intra-
molecular cyclization with formation of 4H-3,1-benz-
oxazin-2-one derivatives. The cyclization of trans
isomer V was characterized by lower stereoselectivity,
as compared to cis isomer IV. From cis isomer IV,
we obtained a mixture of threo-1,2-dibromopropyl
derivative VI and threo-(1-bromoethyl)-8-methyl-1,4-
Some benzoxazine derivatives exhibit a high bio-
logical activity. In this respect, 3,1-benzoxazin-2-ones
[2] and 2-amino-3,1-benzoxazines [3] are the most
interesting. These compounds are synthesized from
aminobenzyl alcohol derivatives or anthranilic acid. In
continuation of our studies [4] on the synthesis of
benzoxazinones, in the present work we prepared cis
dihydro-2H-3,1-benzoxazin-2-one (VII) at a ratio of
and trans-o'-(1-propenyl) derivatives of o-toluidine
5:2 in an overall yield of about 90%. The bromination
and examined their reactions with bromine.
of trans isomer V resulted in formation of erythro-di-
Isomerization of 2-allyl-6-methylaniline (I) by the
action of potassium hydroxide at 300°C afforded cis
and trans isomers of 2-methyl-6-(1-propenyl)aniline II
and III in 17 and 80% yield, respectively (Scheme 1).
Compounds II and III were treated with ethyl chloro-
formate to obtain N-substituted carbamates IV and V,
respectively. The addition of bromine at the exocyclic
bromopropyl derivative VIII, erythro-(1-bromoethyl)-
8-methyl-1,4-dihydro-2H-3,1-benzoxazin-2-one
(VIII), and benzoxazine VII at a ratio of ~12:4:1
(overall yield ~90%) (Scheme 2). N-Methylsulfonyl
derivative X reacted with bromine to give a mixture of
stereoisomeric dibromides XI and XII (Scheme 3);
isomer XI was isolated in the pure state by recrystal-
Scheme 1.
NH2
NH2
NH2
CH2
Me
Me
Me
Me
KOH, 300°C
+
Me
I
II
III
* For communication V, see [1].
1070-4280/04/4012-1764 © 2004 MAIK “Nauka/Interperiodica”

REACTIONS OF N- AND C-ALKENYLANILINES: VI.
1765
Scheme 2.
EtOCO
Br
Me
O
NHCOOEt
NH
Br
Me
Me
Br
EtOCOCl
Br2, CCl4
II
+
Me
Me
N
O
H
Me
IV
VI
NH
VII
Br
EtOCO
Me
Me
NHR
Br
EtOCOCl
or MeSO2Cl
Me
Me
Br
Br2, CCl4
O
III
+
Me
N
O
H
Me
V, X
VIII
IX
V, R = EtOCO; X, R = MeSO2.
lization from ethanol. The reactions of carbamates IV
and V with N-bromosuccinimide in chloroform gave
stereoisomeric 4-(1-bromoethyl)-2-ethoxy-8-methyl-
4H-3,1-benzoxazines XIII and XIV (Scheme 4). Pre-
sumably, the stability of cyclic imidates XIII and XIV
is ensured by weak acidity of succinimide, which
makes elimination of the ethyl group impossible [5].
coupling constants between the 4-H and 1'-H protons
in benzoxazine VII (J = 4.2 Hz) corresponds to its
threo configuration [6, 7]; the coupling constant be-
tween 4-H and 1'-H in erythro isomer IX is 5.5 Hz.
The configuration of compounds VII and IX is con-
sistent with the trans-addition mechanism in halo-
cyclization reactions [8]. Dibromide VI obtained from
cis isomer IV also belongs to the threo series, for the
coupling constant between 1'-H and 2'-H is equal to
6.0 Hz. Correspondingly, compound VIII is an erythro
isomer (J = 10.5 Hz), in keeping with the known
mechanism of trans-addition of bromine at a double
bond [7]. The large 1'-H–2'-H coupling constant in
sulfonamide XI (J = 10.8 Hz) indicates erythro
configuration of the 1,2-dibromopropyl group therein.
The steric structure of the products was determined
1
by analysis of their H NMR spectra. The smaller
Scheme 3.
Br
Me
Br
Me
Br2, CH2Cl2
Br
Br
X
+
NHSO2Me
NHSO2Me
Me
Me
EXPERIMENTAL
XI
XII
The IR spectra were recorded on a UR-20 instru-
1
ment. The H and 13C NMR spectra were obtained
Scheme 4.
Br
Me
on a Bruker AM 300 spectrometer at 300.13 and
75.7 MHz, respectively; the chemical shifts were
measured relative to tetramethylsilane as internal refer-
ence. The elemental compositions were determined on
an M-185B CHN analyzer. The reaction mixtures and
products were analyzed by GLC on a Chrom-5 chro-
matograph equipped with a flame ionization detector;
carrier gas helium (flow rate 50 ml/min); stationary
phases SE-30 (5%) on Chromaton N-AW DMCS
(1200×3-mm column, oven temperature 50–300°C)
and PEG-6000 (5%) on Chromaton AW DMCS
(2400×3-mm column, oven temperature 50–200°C).
Silica gel LS 40/100 µm and Silpearl (Czechia) was
used for column chromatography. Qualitative TLC
NBS, CHCl3
O
IV
N
OEt
Me
XIII
Br
Me
NBS, CHCl3
O
V
+
XIII
N
OEt
Me
XIV
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

AFON’KIN et al.
1766
analysis was performed using Silufol UV-254 and
UV-254/366 plates (Czechia); eluent benzene–ethyl
acetate (6:1); spots were visualized under UV light
(λ 254 nm) and by treatment with iodine vapor.
Synthesis of anilines II and III. A mixture of 10 g
of 2-allyl-6-methylaniline (I) and 10 g of potassium
hydroxide was heated for 1 h at 300°C. The mixture
was cooled, the liquid phase was separated by decant-
ing, and the isomeric products were separated by frac-
tional distillation under reduced pressure (aniline III).
The fraction with bp 85–89°C (3 mm) was additionally
subjected to column chromatography on silica gel
using benzene as eluent to isolate aniline II.
and the hexane extract was evaporated to obtain car-
bamate IV or V.
Ethyl 2-methyl-6-[(Z)-1-propenyl]phenylcarba-
mate (IV). Yield 1.3 g (60%). Rf 0.55. IR spectrum, ν,
cm–1: 3400 (NH). 1H NMR spectrum (CDCl3), δ, ppm:
1.30 t (3H, CH3, J = 6.2 Hz), 1.77 d (3H, CH3, J =
7.0 Hz), 2.30 s (3H, CH3), 4.19 q (2H, CH2O, J =
6.2 Hz), 5.87 d.q (1H, 2'-H, J1 = 7.0, J2 = 11.4 Hz),
6.31 br.s (1H, NH), 6.44 d (1H, 1'-H, J = 11.4 Hz),
7.10–7.21 m (3H, Harom). 13C NMR spectrum, δC, ppm:
14.2 (C3'), 14.4 (CH3), 18.2 (CH3), 61.1 (CH2), 126.2
(C4), 126.6 (C3), 127.3 (C2'), 128.0 (C6), 129.1 (C1'),
133.2 (C2), 134.6 (C5), 135.7 (C1'), 155.1 (C=O).
Found, %: C 70.93; H 7.68; N 6.17. C13H17NO2. Cal-
culated, %: C 71.21; H 7.81; N 6.39.
Ethyl 2-methyl-6-[(E)-1-propenyl]phenylcarba-
mate (V). Yield 1.49 g (68%). Rf 0.58. IR spectrum, ν,
cm–1: 3390 (NH). 1H NMR spectrum (CDCl3), δ, ppm:
1.24 t (3H, CH3, J = 6.2 Hz), 1.90 d (3H, CH3, J =
6.5 Hz), 2.26 s (3H, CH3), 4.22 q (2H, CH2O, J =
6.2 Hz), 6.18 d.q (1H, 2'-H, J1 = 15.1, J2 = 6.5 Hz),
6.59 d (1H, 1'-H, J1 = 15.1 Hz), 6.76 br.s (1H, NH),
7.08–7.18 m (2H, 4-H, 5-H), 7.34 d (1H, 3-H, J =
6.6 Hz). 13C NMR spectrum, δC, ppm: 14.3 (CH3), 18.0
(C3'), 18.5 (CH3), 60.3 (CH2), 123.4 (C4), 126.7 (C3),
126.9 (C2'), 127.5 (C6), 128.7 (C1'), 131.9 (C2), 135.6
(C5), 136.0 (C1), 154.58 (C=O). Found, %: C 71.02;
H 7.72; N 6.07. C13H17NO2. Calculated, %: C 71.21;
H 7.81; N 6.39.
6-Methyl-2-[(Z)-1-propenyl]aniline (II). Yield
1.7 g (17%). bp 85–87°C (3 mm). IR spectrum, ν,
1
cm–1: 3350, 3470 (NH2). H NMR spectrum (CDCl3),
δ, ppm: 1.80 d (3H, CH3, J = 6.8 Hz), 2.24 s (3H,
CH3), 3.75 br.s (2H, NH2), 5.95 d.q (1H, 2'-H, J1 = 7.0,
J2 = 11.2 Hz), 6.38 d (1H, 1'-H, J = 11.2 Hz), 6.75 t
(1H, 4-H, J = 7.5 Hz), 7.02 d (1H, 5-H, J = 7.5 Hz),
7.04 d (1H, 3-H, J = 7.5 Hz). 13C NMR spectrum, δC,
ppm: 14.5 (C3'), 17.7 (CH3), 117.5 (C4), 122.0 (C2),
122.6 (C6), 126.2 (C2'), 127.6 (C3), 128.6 (C5), 129.0
(C1'), 142.0 (C1). Found, %: C 81.34; H 8.80; N 9.42.
C10H13N. Calculated, %: C 81.59; H 8.90; N 9.51.
6-Methyl-2-[(E)-1-propenyl]aniline (III). Yield 8 g
(80%). bp 89–91°C (3 mm). IR spectrum, ν, cm–1:
1
3360, 3470 (NH2). H NMR spectrum (CDCl3), δ,
ppm: 2.06 d (3H, CH3, J = 6.6 Hz), 2.26 s (3H, CH3),
3.75 br.s (2H, NH2), 6.19 d.q (1H, 2'-H, J1 = 6.6, J2 =
15.5 Hz), 6.56 d (1H, 1'-H, J1 = 15.5 Hz), 6.80 t (1H,
4-H, J = 7.5 Hz), 7.08 d (1H, 5-H, J = 7.5 Hz), 7.23 d
(1H, 3-H, J = 7.5 Hz). 13C NMR spectrum, δC, ppm:
17.5 (CH3), 18.8 (CH3), 118.1 (C4), 122.26 (C2), 124.
(C6), 125.3 (C5), 127.0 (C2'), 127.7 (C3), 129.0 (C1'),
141.5 (C1). Found, %: C 81.30; H 8.72; N 9.40.
C10H13N. Calculated, %: C 81.59; H 8.90; N 9.51.
Reaction of carbamates IV and V with bromine.
A solution of 0.3 g (1.65 mmol) of bromine in 3 ml of
carbon tetrachloride was added dropwise under stirring
to a solution of 0.36 g (1.63 mmol) of carbamate IV or
V, the mixture was left to stand for 1 h at 20°C and
evaporated, and the residue was subjected to column
chromatography on silica gel using benzene as eluent.
Ethyl (1'RS,2'RS)-2-(1,2-dibromopropyl)-6-
methylphenylcarbamate (VI). Yield 0.37 g (60%).
Ethyl 2-methyl-6-(1-propenyl)phenylcarbamates
IV and V. Potassium carbonate, 4 g (30 mmol), was
added to a solution of 1.47 g (10 mmol) of aniline II or
III in 20 ml of methylene chloride, and a solution of
1.6 g (15 mmol) of ethyl chloroformate in 15 ml of
methylene chloride was added dropwise under stirring
at 20°C. The mixture was stirred for 2 h and was left to
stand for 18 h at 20°C. The precipitate (inorganic
material) was filtered off and washed with methylene
chloride (2×10 ml), and the filtrate was washed in
succession with a 10% aqueous solution of sodium
hydrogen carbonate (until CO2 no longer evolved) and
water and dried over magnesium sulfate. The solvent
was removed, the residue was treated with hot hexane,
1
Rf 0.6. IR spectrum, ν, cm–1: 3400 (NH). H NMR
spectrum (CDCl3), δ, ppm: 1.36 t (3H, CH3, J =
6.7 Hz), 1.69 d (3H, CH3, J = 6.8 Hz), 2.27 s (3H,
CH3), 4.21 q (2H, CH2O, J = 6.7 Hz), 4.66 d.q (1H,
2'-H, J1 = 6.8, J2 = 6.0 Hz), 5.52 d (1H, 1'-H, J =
6.0 Hz), 6.62 br.s (1H, NH), 7.20–7.30 m (2H, Harom),
7.45 d (1H, 3-H, J = 6.4 Hz). 13C NMR spectrum,
δC, ppm: 14.5 (CH3), 18.3 (CH3), 23.5 (C3'), 53.2
(C2'), 54.9 (C1'), 61.6 (CH2), 127.3 (C4), 127.4 (C5),
131.1 (C3), 132.6 (C6), 136.0 (C2), 137.2 (C1), 154.3
(C=O). Found, %: C 40.92; H 4.40; Br 41.93; N 3.54.
C13H17Br2NO2. Calculated, %: C 41.19; H 4.52;
Br 42.16; N 3.69.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

REACTIONS OF N- AND C-ALKENYLANILINES: VI.
1767
tallized from ethanol. Yield 2.2 g (72%). mp 103–
105°C. IR spectrum, ν, cm–1: 3350 (NH). Found, %:
C 58.30; H 6.55; N 6.10; S 14.30. C11H15NO2S. Cal-
culated, %: C 58.64; H 6.71; N 6.22; S 14.23.
(4RS,1'RS)-4-(1-Bromoethyl)-8-methyl-1,4-di-
hydro-2H-3,1-benzoxazin-2-one (VII). Yield 0.13 g
(30%). mp 127–129°C. Rf 0.4. IR spectrum, ν, cm–1:
1
3410 (NH). H NMR spectrum (CDCl3), δ, ppm:
1.80 d (3H, CH3, J = 6.8 Hz), 2.32 s (3H, CH3),
4.39 d.q (1H, 2'-H, J1 = 4.2, J2 = 6.8 Hz), 5.42 d (1H,
4-H, J = 4.2 Hz), 6.96–7.17 m (3H, Harom), 8.57 s (1H,
NH). 13C NMR spectrum, δC, ppm: 16.6 (CH3), 21.8
(C2'), 51.1 (C1'), 82.6 (C4), 117.3 (C8), 122.8 (C6),
123.0 (C4a), 123.1 (C5), 131.1 (C7), 133.4 (C8a), 151.3
(C2). Found, %: C 48.47; H 4.36; Br 29.34; N 4.94.
C11H12BrNO2. Calculated, %: C 48.91; H 4.48;
Br 29.58; N 5.19.
N-[2-(1,2-Dibromopropyl)-6-methylphenyl]-
methanesulfonamide (XI). A solution of 0.29 g
(1.8 mmol) of bromine in 5 ml of acetonitrile was
added dropwise under stirring to a solution of 0.415 g
(1.8 mmol) of compound X in 20 ml of acetonitrile.
The mixture was stirred for 3 h and evaporated under
reduced pressure, and the residue was recrystallized
from ethanol. Yield 0.32 g (45%). mp 155–157°C.
1
IR spectrum, ν, cm–1: 3380 (NH). H NMR spectrum
(CDCl3), δ, ppm: 2.10 d (3H, CH3, J = 6.4 Hz), 2.49 s
(3H, CH3), 3.20 s (3H, CH3), 4.7 d.q (1H, 2'-H, J1 =
10.8, J2 = 6.4 Hz), 5.69 d (1H, 1'-H, J = 10.8 Hz),
6.08 s (1H, NH), 7.27–7.37 m (2H, 4-H, 5-H), 7.50 d.d
(1H, 3-H, J1 = 7.6, J2 = 2.2 Hz). 13C NMR spectrum,
δC, ppm: 19.5 (CH3), 25.9 (CH3), 42.0 (CH3), 52.0
(C2'), 53.4 (C1'), 126.4 (C4), 129.0 (C3), 131.2 (C2),
131.6 (C5), 136.4 (C1), 140.5 (C6). Found, %: C 34.10;
H 3.59; Br 41.30; N 3.29; S 8.17. C11H15Br2NO2S. Cal-
culated, %: C 34.31; H 3.93; Br 41.50; N 3.64; S 8.33.
Evaporation of the mother liquor gave an additional
0.37 g of a mixture of dibromides XI and XII.
Ethyl (1'RS,2'SR)-2-(1,2-dibromopropyl)-6-
methylphenylcarbamate (VIII). Yield 0.36 g (60%).
mp 93–95°C. Rf 0.67. IR spectrum, ν, cm–1: 3380
(NH). 1H NMR spectrum (CDCl3), δ, ppm: 1.33 t (3H,
CH3, J = 7.0 Hz), 2.07 d (3H, CH3, J = 6.4 Hz), 2.30 s
(3H, CH3), 4.24 q (2H, CH2O, J = 7.0 Hz), 4.63 d.q
(1H, 2'-H, J1 = 10.4, J2 = 6.4 Hz), 5.44 d (1H, 1'-H, J =
10.4 Hz), 6.29 br.s (1H, NH), 7.20–7.30 m (2H, 4-H,
5-H), 7.40 d (1H, 3-H, J = 7.5 Hz). 13C NMR spec-
trum, δC, ppm: 14.4 (CH3), 18.1 (CH3), 25.2 (C3'), 50.2
(C2'), 54.1 (C1'), 61.3 (CH2), 125.5 (C4), 127.5 (C5),
130.6 (C3), 132.6 (C6), 136.9 (C2), 138.1 (C1), 154.36
(C=O). Found, %: C 41.08; H 4.35; Br 41.87; N 3.46.
C13H17Br2NO2. Calculated, %: C 41.19; H 4.52;
Br 42.16; N 3.69.
Reaction of carbamates IV and V with N-bromo-
succinimide. A solution of 0.2 g (0.91 mmol) of com-
pound IV or V and 0.195 g (1 mmol) of N-bromo-
succinimide in 20 ml of chloroform was kept for 8 h
at room temperature (the progress of the reaction was
monitored by TLC). The mixture was evaporated
under reduced pressure, the residue was dissolved in
10 ml of carbon tetrachloride, and the mixture was left
to stand for 4 h. The undissolved material (succin-
imide) was filtered off and washed with 3 ml of carbon
tetrachloride, and the filtrate was evaporated under
reduced pressure.
(4RS,1'SR)-4-(1-Bromoethyl)-8-methyl-1,4-di-
hydro-2H-3,1-benzoxazin-2-one (IX). Yield 0.11 g
(24%). mp 125–127°C. Rf 0.4. -IR spectrum, ν, cm–1:
1
3420 (NH). H NMR spectrum (CDCl3), δ, ppm:
1.78 d (3H, CH3, J = 6.7 Hz), 2.32 s (3H, CH3),
4.38 d.q (1H, 2'-H, J1 = 5.5, J2 = 6.7 Hz), 5.45 d (1H,
4-H, J = 5.5 Hz), 6.96–7.16 m (3H, Harom), 8.78 s (1H,
NH). 13C NMR spectrum, δC, ppm: 16.7 (CH3), 20.7
(C2'), 49.8 (C1'), 83.0 (C4), 117.2 (C8), 122.6 (C6),
123.2 (C4a), 124.3 (C5), 131 (C7), 133.3 (C8a), 154.3
(C2). Found, %: C 48.25; H 4.40; Br 29.34; N 4.94.
C11H12BrNO2. Calculated, %: C 48.91; H 4.48;
Br 29.58; N 5.19.
(4RS,1'RS)-4-(1-Bromoethyl)-2-ethoxy-8-methyl-
4H-3,1-benzoxazine (XIII). Yield 0.22 g (80%).
Rf 0.7. 1H NMR spectrum (CDCl3), δ, ppm: 1.37 t (3H,
CH3, J = 7.1 Hz), 1.70 d (3H, CH3, J = 6.8 Hz), 2.35 s
(3H, CH3), 4.28 d.q (1H, 1'-H, J1 = 6.8, J2 = 5.1 Hz),
4.42 q (2H, CH2O, J = 7.1 Hz), 5.34 d (1H, 4-H, J =
5.1 Hz), 6.87 d (1H, 5-H, J = 7.5 Hz), 6.97 t (1H, 6-H,
J = 7.5 Hz), 7.29 d (1H, 7-H, J = 7.5 Hz). 13C NMR
spectrum, δC, ppm: 14.0 (CH3), 16.6 (CH3), 21.5 (C2'),
50.9 (C1'), 64.4 (CH2O), 82.1 (C4), 120.1 (C8), 122.3
(C5), 123.3 (C6), 130.5 (C7), 131.7 (C4a), 138.8 (C8a),
154.1 (C2). Found, %: C 51.41; H 5.24; Br 26.62;
N 7.54. C13H16BrNO2. Calculated, %: C 52.37; H 5.41;
Br 26.80; N 4.70.
N-{6-Methyl-2-[(Z)-1-propenyl]phenyl}methane-
sulfonamide (X). Methanesulfonyl chloride, 2.34 g
(20.4 mmol), was added under stirring to a solution of
2 g (13.6 mmol) of compound III in 15 ml of pyridine,
and the mixture was kept for 24 h at 20°C. The mixture
was evaporated under reduced pressure, the residue
was dissolved in 100 ml of methylene chloride, the
solution was washed in succession with 5% hydro-
chloric acid (2×25 ml) and a 10% solution of NaOH
(2×25 ml) and evaporated, and the residue was recrys-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

AFON’KIN et al.
2. Gûtschow, M., Sci. Pharm., 1999, vol. 67, p. 524; Ref.
1768
(4RS,1'SR)-4-(1-Bromoethyl)-2-ethoxy-8-methyl-
Zh., Khim., 2000, no. 19Zh280.
4H-3,1-benzoxazine (XIV). Yield 0.14 g (50%).
Rf 0.7. 1H NMR spectrum (CDCl3), δ, ppm: 1.38 t (3H,
CH3, J = 7.0 Hz), 1.64 d (3H, CH3, J = 6.7 Hz), 2.30 s
(3H, CH3), 4.28 d.q (1H, 1'-H, J1 = 6.7, J2 = 5.5 Hz),
4.39 q (2H, CH2O, J = 7.07 Hz), 5.43 d (1H, 4-H, J =
5.5 Hz), 6.91–7.12 m (2H, 5-H, 6-H), 7.29 d (1H, 7-H,
J = 7.4 Hz). 13C NMR spectrum, δC, ppm 14.5 (CH3),
16.6 (CH3), 19.6 (C3'), 50.0 (C1'), 64.7 (CH2O), 82.6
(C4), 120.2 (C8), 123.4 (C5), 125.7 (C6), 130.7 (C7),
131.2 (C4a), 138.2 (C8a), 154.5 (C2). Found, %:
C 51.54; H 5.20; Br 26.55; N 7.47. C13H16BrNO2. Cal-
culated, %: C 52.37; H 5.41; Br 26.80; N 4.70.
3. Pierce, M.E., Parsons, R.L., Radesca, L.A., Lo, Y.S.,
Silverman, St., Moore, J.R., Islam, Q., Choudhury, A.,
Fortunak, J.M.D., Nguyen, D., Luo, C., Morgan, S.G.,
Davis, W.P., Confalone, P.N., Chen, C., Tillyer, R.D.,
Frey, L., Tan, L., Xu, F., Zhao, D., Thomson, A.S.,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004