Synthesis of 7-hydroxy-6-alkoxy derivatives of 3,4-dihydroisoquinoline by ritter reaction

Article abstract of DOI:10.1134/S1070428012020169

1-Substituted 6,7-dialkoxy-3,4-dihydroisoquinolines containing in the position 7 of the isoquinoline ring propoxy- or butoxy groups in the course of maintaining in the concentrated sulfuric acid are converted into 1-substituted 6-alkoxy-7-hydroxy-3,4-dihydroisoquinolines. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070428012020169

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 2, pp. 257−267. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © Yu.V. Shklyaev, T.S. Vshivkova, O.A. Maiorova, A.A. Gorbunov, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48,
No. 2, pp. 267−276.
Synthesis of 7-Hydroxy-6-alkoxy Derivatives
of 3,4-Dihydroisoquinoline by Ritter Reaction
Yu. V. Shklyaev, T. S. Vshivkova, O. A. Maiorova, and A. A. Gorbunov
Institute of Technical Chemistry, Ural Branch, Russian Academy of Sciences, Perm, 614013 Russia
е-mail: shklyaev@itch.perm.ru
Received May 10, 2011
Abstract—1-Substituted 6,7-dialkoxy-3,4-dihydroisoquinolines containing in the position 7 of the isoquinoline
ring propoxy- or butoxy groups in the course of maintaining in the concentrated sulfuric acid are converted into
1-substituted 6-alkoxy-7-hydroxy-3,4-dihydroisoquinolines.
DOI: 10.1134/S1070428012020169
The simplest synthesis of 1-substituted deriva-
ties of 7-hydroxy-6-methoxy-3,3-dimethyl-3,4-
dihydroisoquinoline, analogs of natural alkaloids, consists
in the reaction of 1-(4-benzyloxy-3-methoxyphenyl)-2-
methyl-1-propanol with nitriles in concentrated sulfuric
acid [1] where the cyclization proceeds simultaneously
with the removal of the benzyl protection, and this is
rather unusual. The removal of the alkoxy group occurs
as a rule at heating the corresponding aromatic-aliphatic
ethers in hydrohalogenic acid [2–7]. The goal of this
research is the investigation of the effect of the substitu-
ents in the position 4 of 1-(4-alkoxy-3-methoxyphenyl)-
2-methyl-1-propanol on the character of compounds
formed in the course of Ritter heterocyclization. Carbinols
and styrenes used in the study were obtained from the
corresponding derivatives of vanillin or isovanillin and
isopropylmagnesium bromide in THF [8].
In the reaction of 1-(3-methoxy-4-ethoxyphenyl)-
2-methylpropan-1-ol (Iа) with nitriles 1-substituted
3,3-dimethyl-6-methoxy-7-ethoxy-3,4-dihydroiso-
quinolines IIa, IIb were obtained (Scheme 1).
The subsequent increasing the length of the substituent
in the position 4 of styrenes III, IV led to the formation
of a mixture of 6-methoxy-7-alkoxy-substituted Vа,
Vb, VIа, VIb and 3,3-dialkyl-6-methoxy-7-hydroxy-
3,4-dihydroisoquinolines VIIа, VIIb (Scheme 2). Char-
acteristics of compounds VIIа, VIIb were given in [1].
The reactions of alcohols VIII, IX having propoxy or
butoxysubstituentsintheposition3andamethoxygroupin
the position 4 furnished only 6,7-dialkoxy derivatives Xа,
Xb, XIа, XIb. The absence of 3,4-dihydroisoquinolines
having an ОН group was proved by the GC-MS investi-
gation of the reaction mixture. The reaction of isobutyric
aldehyde with 1,2-diethoxybenzene and nitriles (ethyl
Scheme 1.
MeO
EtO
R = CH2COOEt
NH
OH
MeO
EtO
H2SO4
+
RCN
IIa
IIb
COOEt
MeO
EtO
R = SMe
Ia
N
SMe
257

SHKLYAEV et al.
258
Scheme 2.
MeO
HO
MeO
R' = CH2COOEt
+
NH
NH
RO
MeO
RO
H2SO4
+
R'CN
COOEt
COOEt
+
Va, VIa
VIIa
VIIb
MeO
RO
MeO
HO
R' = SMe
III, IV
N
N
SMe
Vb, VIb
SMe
R = Pr (III, V), Bu (IV, VI).
R1 = Et (XIIа, XIIb), Pr (VIII, X), Bu (IX, XI); R2 = Me (VIII, Xа, Xb, XIа, XIb), Et (XIIа, XIIb).
cyanoacetate, methyl thiocyanate) resulted in correspond-
ing derivatives of 3,4-dihydroisoquinoline XIIa, XIIb
(Scheme 3) [9].
band is present in the region 3300–3340 cm–1 (ОН).
The position of the hydroxy group in ethyl [6-butoxy-
7-hydroxy-3,3-dimethyl-3,4-dihydroisoquinolin-1(2Н)-
ylidene]ethanoate (XVIIa) was established with the help
of the 2D spectrum. The position of the butoxy group at
the atom С6 is indicated by the presence in the НMВС
The reaction with о-dipropoxy- or о-dibutoxybenzene,
with α-branched aldehydes and nitrile within the mini-
mal possible time (~2 min) afforded the correspond-
ing 6,7-dialkoxy-3,4-dihydroisoquinolines XIIIа,
XIIIb, XIVа, XIVb, XVа and the reaction with the
о-dialkoxybenzenes within 20 min gave the correspond-
ing 6,7-dialkoxy-substituted compounds XIIIа, XIIIb,
XIVа, XIVb, XVа and 3,3-dialkyl-6-alkoxy-7-hydroxy-
3,4-dihydroisoquinolines XVIa, XVIIа, XVIIb, XVIIIа
(Scheme 4) which were isolated by the fractional crystal-
lization.
spectrum of the cross-peak С6/НОCH –C H (148.1/4.04
ppm). In the 2D NMR spectrum 13С–1Н (HMBC) also
appeared cross-peaks corresponding to the assumed
structure: С1/Н8 (155.3/7.22 ppm), С6/Н8 (148.1/7.22
ppm), С7/Н5 (144.2/6.57 ppm), С4а/Н8 (127.8/7.22 ppm),
С8а/Н5 (121.0/6.57 ppm), С8а/НNH (121.0/8.91 ppm),
С4/Н5 (41.6/6.57 ppm). At keeping compounds XIIIa,
XIVа, XIVb, XVа in concn. sulfuric acid for 2 h at
room temperature compounds XVIa, XVIIа, XVIIb,
XVIIIа formed in 49–71% yields.
2
3 7
The structure of compounds obtained was con-
1
firmed by Н and 13С NMR, IR, and mass spectra. In
1
Evidently the primary formed 6,7-dialkoxy-substi-
tuted 3,4-dihydroisoquinoline in the concn. sulfuric acid
is protonated at the oxygen atom in the position 7 caus-
the Н NMR spectra of compounds XVIa, XVIIа,
XVIIb, XVIIIа a singlet is observed in the region
5.47–5.82 ppm, and in the IR spectrum an absorption
Scheme 3.
OH
R1O
R1O
R2O
R3 = CH2COOEt
NH
R2O
R3CN, H2SO4
VIII, IX
Xa_XIIa
COOEt
R1O
EtO
EtO
R3 = SMe
+
CHO
N
R2O
Ib
SMe
Xb_XIIb
R1 = Et (XIIа, XIIb), Pr (VIII, X), Bu (IX, XI); R2 = Me (VIII, Xа, Xb, XIа, XIb), Et (XIIа, XIIb).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

SYNTHESIS OF 7-HYDROXY-6-ALKOXY DERIVATIVES
259
Scheme 4.
R1O
R1O
HO
R2
R2
R2
R2
R3 = CH2COOEt
+
NH
NH
R1O
XIIIa_XVa
R1O
R1O
R2
R2
H2SO4
R3CN
+
+
COOEt
XVIa_XVIIIa
R1O
COOEt
CHO
R2
R2
R1O
R2
R2
R3 = SMe
+
N
N
R1O
HO
SMe
XVIIb
SMe
XIIIb, XIVb
R2 = Me, R1 = Pr (XIII, XVI), Bu (XIV, XVII); R1 = Bu , R2,R2 = (CH2)5 (XV, XVIII).
Scheme 5.
MeO
O
MeO
MeO
HO
_C3H+7
N
N
N
O
H
B
A
ing the cleavage of a propyl (or butyl) cation and the
formation of the 7-hydroxy-3,4-dihydroisoquinoline
(Scheme 5).
Scheme 6.
R1O
R1O
R2O
XIXa_XIXj
H+
The calculation performed by the semiempirical
method РM3 (HyperChem 7.01) demonstrated that
the protonation of oxygen atom in the position 7 is
more favorable by energy than the protonation in the
position 6. The difference is 20 kJ mol−1. The transition
А → B is accompanied by the enthalpy decrease by
8 kJ mol−1. Analogous calculations for 6-methoxy-7-
ethoxy-substituted 3,4-dihydroisoquinoline showed
that the protonation by positions 6 and 7 can occur
virtually with equal probability, and the cleavage of
ethyl cation is unfavorable by energy (increase in the
enthalpy by ~48 kJ mol−1).
NH
COOEt
N
R2O
R1O
R2O
R1O
H+
N
NH
R2O
SMe
O
XXа_XXh
R1 = Me, R2 = Et (a), Pr (b), Bu (c); R2 = Me, R1 = Pr
(d), Bu (e); R1 = R2 = Et (f), Pr (g), Bu (h); R2 = OH,
R1 = Pr (i), Bu (j).
The heating of esters of isoquinolylideneacetic acids
or thiolactim esters in dilute acids results in 1-methyl
derivatives of 3,4-dihydroisoquinoline XIXа–XIXj
and ketones XXа–XXh respectively (Scheme 6) with
the conservation of the substituents in the aromatic part
of the isoquinoline structure.
EXPERIMENTAL
Melting points were measured on a PTPdevice. 1Н and
13С NMR spectra were registered on a spectrometer
Varian Mercury plus 300 in CDCl3 at 300 and 75 MHz
respectively, internal reference HMDS. IR spectra were
Compounds XIXd, XIXe, XIXh were isolated in
the form of hydrochlorides XXIа–XXIc respectively.
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SHKLYAEV et al.
260
recorded on a spectrophotometer Specord M80 from
mulls in mineral oil. Elemental analysis was carried out
on an analyzer CHNS-932 Leco Corporation. The reac-
tion progress was monitored and the purity of compounds
obtained was checked by TLC on Sorbfil plates, devel-
opment with 0.5% solution of chloranil in toluene. Mass
spectra were obtained on a GC-MS instrument Agilent
6890N/5975B (EI, 70 eV).At the analysis of compounds
Va, VIa, XIa, XIIIa the products of their decarboethoxyl-
ation were registered formed as a result of the thermolysis
of the compounds in the vaporizer, identical to compounds
XIXb, XIXc, XIXe, XIXg respectively. Mass spectra
of compounds IIa, Xa, XIIa, XIVa, XVIa, XVIIa were
registered on a mass spectrometer Finnigan MAT.
cm–1: 3250, 1648, 1600, 1570, 1520. 1Н NMR spectrum,
δ, ppm: 1.27 s (6Н, 2Mе), 1.29 m (3Н, ОСН2Mе), 1.46 t
(3Н, Mе, J 7.1 Hz), 2.74 s (2Н, СН2), 3.89 s (3Н, ОMе),
4.12 m (4Н, 2ОСН2Mе), 5.00 s (1Н, СН=), 6.60 s
(1Нarom), 7.12 s (1Нarom), 8.92 br.s (1Н, NH). 13С NMR
spectrum, δ, ppm: 14.6 (Mе), 14.7 (Mе), 28.4 (С3CH3),
41.6 (С4), 49.3 (С3), 55.8 (ОСН3), 58.3 (ОСН2), 64.5
(ОСН2), 76.4 (СН=), 109.5 (С8), 111.4 (С5), 120.6 (С8а),
128.7 (С4а), 146.9 (С7), 151.5 (С6), 155.4 (С1), 171.0
(С=О). Mass spectrum, m/z (Irel, %): [M]+ 319 (49),
[M – Mе]+ 304 (20), [M – OC2H5]+ 274 (17), 258 (100),
247 (32), 232 (32). Found, %: С 67.40; Н 7.79; N 4.37.
C18H25NO4. Calculated, %: С 67.69; Н 7.89; N 4.39.
3,3-Dimethyl-1-methylsulfanyl-6-methoxy-7-
ethoxy-3,4-dihydroisoquinoline (IIb). Yield 0.84 g
(30%), mp 79–80°С (EtOH). IR spectrum, cm–1: 1596,
1-Substituted 3,4-dihydroisoquinolines V, VI, X,
XI. а. A mixture of 0.01 mol of an appropriate alcohol
or alkenylbenzene and 0.01 mol of nitrile was added
dropwise to 5 ml of concn. H2SO4 cooled to 5–10°С.
The mixture was stirred at 20–25°С for 20 min. The
reaction mixture was poured into water and neutralized
with sodium carbonate to рН 8. The reaction product was
extracted into СН2Сl2, the extract was washed with water,
dried with anhydrous MgSO4, the solvent was distilled
off, the residue was recrystallized.
1
1566, 1514. Н NMR spectrum, δ, ppm: 1.16 s (6Н,
2Mе), 1.43 t (3Н, Mе, J 6.9 Hz), 2.38 s (3Н, SMе), 2.58 s
(2Н, СН2), 3.85 s (3Н, ОMе), 4.08 q (2Н, ОСН2), 6.59 s
(1Нarom), 7.14 s (1Нarom). 13С NMR spectrum, δ, ppm:
12.2 (Mе), 14.8 (SMе), 28.3 (С3CH3), 38.9 (С4), 55.7
(С3), 55.9 (ОMе), 64.5 (ОСН2), 109.6 (С8), 111.0 (С5),
121.3 (С8а), 129.3 (С4а), 146.6 (С7), 151.3 (С6), 159.4
(С1). Mass spectrum, m/z (Irel, %): [M]+ 279 (25), [M –
Mе]+ 264 (100), 250 (14), 162 (10). Found, %: С 64.00;
Н 7.44; N 5.00; S 11.16. C15H21NO2S. Calculated, %:
С 64.48; Н 7.58; N 5.01; S 11.48.
1-Substituted 3,4-dihydroisoquinolines XIIIa–
XVIIIa, XIIIb, XIVb, XVIIb. b. A mixture of 0.01 mol
of arene, 0.72 g (0.01 mol) of isobutyric aldehyde, and
0.01 mol of nitrile was added dropwise to 5 ml of concn.
H2SO4 at 5–10°С. Further workup was carried out as in
procedure а.
2-Methoxy-4-(2-methylprop-1-enyl)-1-propoxy-
benzene (III). Yield 60%, bp 124–143°С (2 mm Hg).
1Н NMR spectrum, δ, ppm: 1.02 t (3Н, Mе, J 7.5 Hz),
1.81–1.87 m (8Н, 2Mе + СН2), 3.84 s (3Н, ОMе), 3.96 t
(2Н, ОСН2, J 6.8 Hz), 6.19 s (1Н, СН), 6.74–6.83 m
(3Нarom). Mass spectrum, m/z (Irel, %): [M]+ 220 (96), 179
(12), 178 (100), 163 (32), 147 (12), 131 (38).
1,3,3-Trimethyl-3,4-dihydroisoquinolines XIXа–
XIXj. c. Compounds XIXа–XIXj were obtained by
heating the corresponding ethyl 3,4-dihydroisoquinolin-
1(2Н)-ideneacetates in 20% H2SO4 within 2.5 h. Further
workup was carried out as in procedure а.
1-Butoxy-2-methoxy-4-(2-methylprop-1-enyl)-
benzene (IV). Yield 58%, bp 115–135°С (2 mm Hg).
1Н NMR spectrum, δ, ppm: 0.94–1.00 m (3Н, Mе),
1.44–1.52 m (2Н, СН2), 1.79–1.88 m (8Н, 2Mе + СН2),
3.84 s (3Н, ОMе), 4.00 t (2Н, ОСН2, J 6.9 Hz), 6.19 s (1Н,
СН), 6.74–6.84 m (3Нarom). Mass spectrum, m/z (Irel, %):
[M]+ 234 (70), 179 (12), 178 (100), 163 (25), 131 (28).
6,7-Dialkoxy-3,3-dimethyl-3,4-dihydroisoquinolin-
1(2Н)-ones XXа–XXh. d. Compounds IIb, Vb, VIb,
Xb–XIVb were heated in 80% СН3СООН for 2 h in the
presence of a catalytic quantity of sodium acetate. Further
workup was carried out as in procedure а.
Hydrochlorides XXIа–XXIc were obtained by
passing gaseous HCl thorough the ethyl acetate solution
of compounds XIXd, XIXe, XIXh respectively. The
separated precipitate was filtered off and recrystallized.
Ethyl [3,3-dimethyl-6-methoxy-7-propoxy-3,4-
dihydroisoquinolin-1(2Н)-ylidene]ethanoate (Va).
Yield 1.40 g (42%), mp 134–135оС (EtOH). IR spectrum,
cm–1: 3265, 1652, 1598, 1574, 1520. 1Н NMR spectrum,
δ, ppm: 1.04 t (3Н, Mе, J 7.5 Hz), 1.27 s (6Н, 2Mе),
1.29 m (3Н, ОСН2Mе), 1.86 m (2Н, СН2), 2.73 s (2Н,
СН2), 3.88 s (3Н, ОMе), 3.96 t (2Н, ОСН2, J 6.8 Hz),
Ethyl [3,3-dimethyl-6-methoxy-7-ethoxy-3,4-
dihydroisoquinolin-1(2Н)-ylidene]ethanoate (IIa).
Yield 1.12 g (35%), mp 136–138°С (EtOH). IR spectrum,
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SYNTHESIS OF 7-HYDROXY-6-ALKOXY DERIVATIVES
261
4.15 q (2Н, ОСН2Mе), 5.00 s (1Н, СН=), 6.60 s (1Нarom),
7.13 s (1Нarom), 8.93 br.s (1Н, NH). 13С NMR spectrum,
δ, ppm: 10.4 (ОСН2СН2СН3), 14.6 (ОСН2СН3), 22.4
(ОСН2СН2Mе), 28.4 (С3CH3), 41.6 (С4), 49.3 (С4),
55.8 (ОMе), 58.3 (ОСН2Me), 70.7 (ОСН2СН2Me), 76.4
(СН=), 109.7 (С8), 111.5 (С5), 120.6 (С8а), 128.6 (С4а),
147.2 (С7), 151.6 (С6), 155.5 (С1), 171.0 (С=О). Found,
%: С 68.60; Н 7.84; N 4.19. C19H27NO4. Calculated, %:
С 68.44; Н 8.16; N 4.20.
ОMе), 4.02 t (2Н, ОСН2), 6.61 s (1Нarom), 7.16 s
(1Нarom). 13С NMR spectrum, δ, ppm: 12.0 (Mе), 13.7
(SMe), 19.1(ОСН2СН2СН2Mе), 28.2 (С3CH3), 31.1
(ОСН2СН2СН2Mе), 38.8 (С4), 55.6 (С3), 55.8 (ОMе),
68.9 (ОСН2), 109.8 (С8), 111.0 (С5), 121.2 (С8а), 129.1
(С4а), 146.8 (С7), 151.4 (С6), 159.3 (С1). Mass spectrum,
m/z (Irel, %): [M]+ 307 (20), [M – Mе]+ 292 (100), 250
(15), 236 (11), 162 (10). Found, %: С 66.17; Н 8.16;
N 4.54; S 10.21. C17H25NO2S. Calculated, %: С 66.41;
Н 8.20; N 4.56; S 10.43.
3,3-Dimethyl-1-methylsulfanyl-6-methoxy-7-
propoxy-3,4-dihydroisoquinoline (Vb). Yield 0.79 g
(27%), mp 72–74°С (EtOH). IR spectrum, cm–1: 1702,
1600, 1568, 1518. 1Н NMR spectrum, δ, ppm: 1.04 t (3Н,
Mе, J 7.7 Hz), 1.18 s (6Н, 2Mе), 1.85 m (2Н, СН2), 2.41 s
(3Н, SMе), 2.60 s (2Н, СН2), 3.87 s (3Н, ОMе), 3.98 t
(2Н, ОСН2, J 7.7 Hz), 6.61 s (1Нarom), 7.16 s (1Нarom).
13С NMR spectrum, δ, ppm: 10.4 (Mе), 12.1 (SMe), 22.4
(ОСН2СН2Me), 28.3 (С3CH3), 38.9 (С4), 55.7 (С3), 55.9
(ОMе), 70.8 (ОСН2), 109.9 (С8), 111.1 (С5), 121.2 (С8а),
129.2 (С4а), 146.8 (С7), 151.4 (С6), 159.4 (С1). Mass
spectrum, m/z (Irel, %): [M]+ 293 (24), [M – Mе]+ 278
(100), 250 (15), 236 (11), 162 (11). Found, %: С 65.61;
Н 7.82; N 4.85; S 10.88. C16H23NO2S. Calculated, %:
С 65.49; Н 7.90; N 4.77; S 10.93.
2-Methyl-1-(4-methoxyphenyl-3-propoxy)propan-
1-ol (VIII). Yield 55%, mp 66–67°С (hexane). 1Н NMR
spectrum, δ, ppm: 0.77 d (3Н, Mе, J 6.9 Hz), 0.99–1.05 m
(6Н, Mе + ОСН2СН2Mе), 1.80–1.95 m (4Н, ОН + СН +
СН2), 3.85 s (3Н, ОMе), 3.97 t (2Н, ОСН2, J 7.1 Hz),
4.25 d (1Н, СН, J 7.2 Hz), 6.81 s (2Нarom), 6.87 s (1Нarom).
Mass spectrum, m/z (Irel, %): [M]+ 238 (12), 220 (19), 195
(100), 163 (14), 125 (38).
2-Butoxy-1-methoxy-4-(2-methylprop-1-enyl)
benzene (IX). Yield 65%, bp 130°С (2 mm Hg). 1Н NMR
spectrum, δ, ppm: 0.93–0.98 m (3Н, Mе), 1.41–1.54 m
(2Н, СН2), 1.73–1.89 m (8Н, 2Mе + СН2), 3.83 s (3Н,
ОMе), 4.00 t (2Н, ОСН2, J 6.8 Hz), 6.18 s (1Н, СН),
6.70–6.82 m (3Нarom).
Ethyl [7-butoxy-3,3-dimethyl-6-methoxy-3,4-
dihydroisoquinolin-1(2Н)-ylidene]ethanoate (VIa).
Yield 1.25 g (36%), mp 92–93°С (EtOH). IR spectrum,
Ethyl [3,3-dimethyl-7-methoxy-6-propoxy-3,4-
dihydroisoquinolin-1(2Н)-ylidene]ethanoate (Xa).
Yield 1.17 g (35%), mp 122–123°С (EtOH). IR spectrum,
cm–1: 3265, 1641, 1596, 1568, 1509. 1Н NMR spectrum,
δ, ppm: 1.04 t (3Н, Mе, J 7.4 Hz), 1.26 s (6Н, 2Mе),
1.29 t (3Н, ОСН2Mе), 1.87 m (2Н, СН2), 2.73 s (2Н,
СН2), 3.87 s (3Н, ОMе), 3.99 t (2Н, ОСН2, J 6.8 Hz),
4.15 q (2Н, ОСН2Mе), 5.03 s (1Н, СН=), 6.60 s (1Нarom),
7.12 s (1Нarom), 8.93 br.s (1Н, NH). 13С NMR spectrum, δ,
ppm: 10.3 (Mе), 14.6 (ОСН2СН3), 22.3 (ОСН2СН2Me),
28.4 (С3CH3), 41.5 (С4), 49.3 (С3), 56.0 (ОMе), 58.3
(ОСН2Me), 70.3 (ОСН2), 76.3 (СН=), 108.3 (С8), 112.3
(С5), 120.4 (С8а), 128.6 (С4а), 147.8 (С6), 150.8 (С7),
155.5 (С1), 171.0 (С=О). Mass spectrum, m/z (Irel, %):
[M]+ 333 (51), [M – Mе]+ 318 (18), [M – OC2H5]+ 288
(19), 273 (18), [M – OOC2H5]+ 272 (100), 261 (30),
246 (40), 230 (12). Found, %: С 68.13; Н 7.85; N 4.06.
C19H27NO4. Calculated, %: С 68.44; Н 8.16; N 4.20.
1
cm–1: 1646, 1602, 1576, 1516. Н NMR spectrum, δ,
ppm: 1.12 t (3Н, Mе), 1.41 s (6Н, 2Mе), 1.42 t (3Н,
ОСН2Mе), 1.63 m (2Н, ОСН2СН2СН2Mе), 1.96 m (2Н,
ОСН2СН2СН2Mе), 2.88 s (2Н, СН2), 4.01 s (3Н, ОMе),
4.14 t (2Н, ОСН2), 4.29 q (2Н, ОСН2Mе), 5.15 s (1Н,
СН=), 6.73 s (1Нarom), 7.27 s (1Нarom), 8.92 br.s (1Н, NH).
13С NMR spectrum, δ, ppm: 13.7 (ОСН2СН2СН2СН3),
14.6 (ОСН2СН3), 19.1 (ОСН2СН2СН2Mе), 28.4
(С3CH3), 31.2 (ОСН2СН2СН2Mе), 41.6 (С4), 49.3 (С3),
55.8 (ОMе), 58.3 (ОСН2Me), 68.9 (ОСН2СН2СН2Mе),
76.4 (СН=), 109.7 (С8), 111.5 (С5), 120.5 (С8а), 128.6
(С4а), 147.2 (С7), 151.6 (С6), 155.4 (С1), 171.0 (С=О).
Found, %: С 69.03; Н 8.47; N 3.98. C20H29NO4.
Calculated, %: С 69.14; Н 8.41; N 4.03.
7-Butoxy-3,3-dimethyl-1-methylsulfanyl-6-
methoxy-3,4-dihydroisoquinoline (VIb). Yield 0.77 g
(25%), mp 69–70°С (EtOH). IR spectrum, cm–1:
3,3-Dimethyl-1-methylsulfanyl-7-methoxy-6-
propoxy-3,4-dihydroisoquinoline (Xb). Yield 1.11 g
(38%), mp 71–72.5°С (EtOH). IR spectrum, cm–1: 1597,
1
1600, 1566, 1516. Н NMR spectrum, δ, ppm: 0.97 t
(3Н, Mе, J 7.4 Hz), 1.18 s (6Н, 2Mе), 1.49 m (2Н,
ОСН2СН2СН2Mе), 1.82 m (2Н, ОСН2СН2СН2Mе),
2.40 s (3Н, SMе), 2.60 s (2Н, СН2), 3.87 s (3Н,
1
1566, 1511. Н NMR spectrum, δ, ppm: 1.04 t (3Н,
Mе, J 7.4 Hz), 1.18 s (6Н, 2Mе), 1.87 m (2Н, СН2),
2.41 s (3Н, SMе), 2.60 s (2Н, СН2), 3.88 s (3Н, ОMе),
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4.00 t (2Н, ОСН2), 6.62 s (1Нarom), 7.16 s (1Нarom).
13С NMR spectrum, δ, ppm: 10.3 (Mе), 12.1 (SMe), 22.3
(ОСН2СН2Mе), 28.2 (С3CH3), 38.8 (С4), 55.6 (С3), 56.2
(ОMе), 70.3 (ОСН2), 108.5 (С8), 112.0 (С5), 121.1 (С8а),
129.2 (С4а), 147.5 (С7), 150.6 (С6), 159.4 (С1). Mass
spectrum, m/z (Irel, %): [M]+ 293 (39), 279 (18), [M – Mе]+
278 (100), 236 (24). Found, %: С 65.27; Н 7.93; N 4.72;
S 10.85. C16H23NO2S. Calculated, %: С 65.49; Н 7.90;
N 4.77; S 10.93.
(6Н, 2Mе), 2.67 s (2Н, СН2), 4.04 m (6Н, 2ОСН2 +
ОСН2Mе), 4.95 s (1Н, СН=), 6.54 s (1Нarom), 7.08 s
(1Нarom), 8.87 br.s (Н, NH). Mass spectrum, m/z (Irel,
%): [M]+ 333 (57), [M – Mе]+ 318 (20), [M – OC2H5]+
288 (17), 272 (100), 261 (31), 248 (34), 232 (13). Found,
%: С 68.37; Н 8.21; N 4.25. C19H27NO4. Calculated, %:
С 68.44; Н 8.16; N 4.20.
3,3-Dimethyl-1-methylsulfanyl-6,7-diethoxy-3,4-
dihydroisoquinoline (XIIb). Yield 1.17 g (40%), mp
71–73°С (EtOH). IR spectrum, cm–1: 1660, 1596, 1566,
Ethyl [6-butoxy-3,3-dimethyl-7-methoxy-3,4-
dihydroisoquinolin-1(2Н)-ylidene]ethanoate (XIa).
Yield 1.42 g (41%), mp 80–81°С (EtOH). IR spectrum,
cm–1: 3270, 1650, 1602, 1547, 1516. 1Н NMR spectrum,
δ, ppm: 0.97 t (3Н, Mе, J 15.3 Hz), 1.25 s (6Н, 2Mе), 1.28 t
(3Н, ОСН2Mе, J 7.7 Hz), 1.49 m (2Н, ОСН2СН2СН2Mе),
1.82 m (2Н, ОСН2СН2СН2Mе), 2.71 s (2Н, СН2), 3.85
s (3Н, ОMе), 4.02 t (2Н, ОСН2, J 6.9 Hz), 4.15 q (2Н,
ОСН2Mе), 5.03 s (1Н, СН=), 6.60 s (1Нarom), 7.12 s
(1Нarom), 8.92 br.s (1Н, NH). 13С NMR spectrum, δ, ppm:
13.7 (Mе), 14.6 (ОСН2СН3), 19.0 (ОСН2СН2СН2Mе),
28.3 (С3CH3), 31.0 (ОСН2СН2СН2Mе), 41.5 (С4), 49.2
(С3), 56.0 (ОMе), 58.2 (ОСН2Me), 68.5 (ОСН2), 76.4
(СН=), 108.4 (С8), 112.4 (С5), 120.4 (С8а), 128.6 (С4а),
147.9 (С6), 150.9 (С7), 155.4 (С1), 171.0 (С=О). Found,
%: С 69.07; Н 8.45; N 3.92. C20H29NO4. Calculated, %:
С 69.14; Н 8.41; N 4.03.
1
1514. Н NMR spectrum, δ, ppm: 1.17 s (6Н, 2Mе),
1.44 m (6Н, 2Mе), 2.40 s (3Н, SMе), 2.59 s (2Н, СН2),
4.09 m (4Н, 2ОСН2), 6.61 s (1Нarom), 7.16 s (1Нarom).
13С NMR spectrum, δ, ppm: 12.0 (SMe), 14.6 (Mе),
14.7 (Mе), 28.2 (С3CH3), 38.8 (С4), 55.6 (С3), 64.3
(ОСН2), 64.8 (ОСН2), 110.5 (С5), 112.4 (С8), 121.2
(С8а), 129.3 (С4а), 146.8 (С7), 150.9 (С6), 159.3 (С1).
Mass spectrum, m/z (Irel, %): [M]+ 293 (27), [M – Mе]+
278 (100), 265 (15). Found, %: С 65.65; Н 7.79; N 4.63;
S 10.74. C16H23NO2S. Calculated, %: С 65.49; Н 7.90;
N 4.77; S 10.93.
Ethyl [3,3-dimethyl-6,7-dipropoxy-3,4-
dihydroisoquinolin-1(2Н)-ylidene]ethanoate (XIIIa).
Yield 1.41 g (39%), mp 93–94°С (EtOH). IR spectrum,
1
cm–1: 1700, 1596, 1564, 1516. Н NMR spectrum, δ,
ppm: 1.04 t (6Н, 2Mе, J 7.5 Hz), 1.26 s (6Н, 2Mе), 1.27 t
(3Н, ОСН2Mе, J 7.5 Hz), 1.84 m (4Н, 2СН2),2.71 s (2Н,
СН2), 3.95 m (4Н, 2ОСН2), 4.14 q (2Н, ОСН2Mе), 5.00 s
(1Н, СН=), 6.59 s (1Нarom), 7.14 s (1Нarom), 8.92 br.s (1Н,
NH). 13С NMR spectrum, δ, ppm: 10.3 (2С, Mе), 14.6
(ОСН2СН3), 22.4 (ОСН2СН2Me), 22.6 (ОСН2СН2Me),
28.4 (С3CH3), 41.5 (С4), 49.3 (С3), 58.3 (ОСН2Me), 70.3
(ОСН2), 71.0 (ОСН2), 76.3 (СН=), 110.8 (С8), 113.0 (С5),
120.5 (С8а), 128.8 (С4а), 147.5 (С7), 151.5 (С6), 155.5
(С1), 171.0 (C=O). Found, %: С 69.89; Н 8.59; N 3.98.
C21H31NO4. Calculated, %: С 69.78; Н 8.64; N 3.87.
6-Butoxy-3,3-dimethyl-1-methylsulfanyl-7-
methoxy-3,4-dihydroisoquinoline (XIb). Yield 1.54 g
(50%), mp 53–55°С (EtOH). IR spectrum, cm–1:
1
1594, 1560, 1514. Н NMR spectrum, δ, ppm: 0.96 t
(3Н, Mе, J 7.4 Hz), 1.18 s (6Н, 2Mе), 1.48 m (2Н,
ОСН2СН2СН2Mе), 1.82 m (2Н, ОСН2СН2СН2Mе),
2.40 s (3Н, SMе), 2.59 s (2Н, СН2), 3.86 s (3Н, ОMе),
4.02 t (2Н, ОСН2, J 6.8 Hz), 6.62 s (1Нarom), 7.15 s
(1Нarom). 13С NMR spectrum, δ, ppm: 12.0 (Mе), 13.7
(SMe), 19.0 (ОСН2СН2СН2Me), 28.2 (С3CH3), 31.0
(ОСН2СН2СН2Me), 38.8 (С4), 55.6 (С3), 56.1 (ОMе),
68.5 (ОСН2), 108.3 (С8), 111.9 (С5), 120.9 (С8а), 129.1
(С4а), 147.4 (С7), 150.5 (С6), 159.3 (С1). Mass spectrum,
m/z (Irel, %): [M]+ 307 (25), [M – Mе]+ 292 (100), 250
(13), 236 (25), 162 (14). Found, %: С 66.11; Н 8.29;
N 4.62; S 10.21. C17H25NO2S. Calculated, %: С 66.41;
Н 8.20; N 4.56; S 10.43.
3,3-Dimethyl-1-methylsulfanyl-6,7-dipropoxy-
3,4-dihydroisoquinoline (XIIIb). Yield 1.06 g (33%),
mp 54–57°С (EtOH). IR spectrum, cm–1: 1596, 1564,
1
1516. Н NMR spectrum, δ, ppm: 1.03 t (6Н, 2Mе,
J 7.2 Hz), 1.17 s (6Н, 2Mе), 1.81 m (4Н, 2ОСН2СН2Mе),
2.39 s (3Н,SMе), 2.58 s (2Н, СН2), 3.96 t (4Н, 2ОСН2,
J 6.6 Hz), 6.60 s (1Нarom), 7.17 s (1Нarom). 13С NMR
spectrum, δ, ppm: 10.4 (2С, Mе), 12.0 (SMe), 22.5
(ОСН2СН2СН3), 22.6 (ОСН2СН2Me), 28.3 (С3CH3),
38.9 (С4), 55.7 (С3), 70.5 (ОСН2), 71.2 (ОСН2), 111.1
(С5), 112.9 (С8), 121.3 (С8а), 129.5 (С4а), 147.3 (С7),
151.4 (С6), 159.4 (С1). Mass spectrum, m/z (Irel, %): [M]+
Ethyl [3, 3-dimethyl-6, 7-diethoxy-3, 4-
dihydroisoquinolin-1(2Н)-ylidene]ethanoate (XIIa).
Yield 1.73 g (52%), mp 71–72°С (EtOH). IR spectrum,
cm–1: 1715, 1640, 1590, 1560, 1505. 1Н NMR spectrum,
δ, ppm: 1.20 s (6Н, 2Mе), 1.22 m (3Н, ОСН2Mе), 1.39 q
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SYNTHESIS OF 7-HYDROXY-6-ALKOXY DERIVATIVES
263
321 (26), [M – Mе]+ 306 (100), [M – C3H7]+ 278 (15),
264 (12), 222 (13). Found, %: С 66.92; Н 8.50; N 4.40;
S 9.77. C18H27NO2S. Calculated, %: С 67.25; Н 8.47;
N 4.36; S 9.97.
(2Н, СН2), 3.94 m (4Н, 2ОСН2), 4.11 q (2Н, ОСН2Mе),
4.96 s (1Н, СН=), 6.55 s (1Нarom), 7.07 s (1Нarom), 9.33 br.s
(1Н, NH). 13С NMR spectrum, δ, ppm: 13.6 (Mе), 13.7
(Mе), 14.6 (ОСН2СН3), 19.1 (ОСН2СН2СН2Me), 21.7
(С3СН2), 25.5 (С3СН2), 31.1 (ОСН2СН2СН2Me), 31.2
(ОСН2СН2СН2Me), 36.3 (С3СН2), 40.3 (С4), 50.9 (С3),
58.2 (ОСН2Me), 68.6 (ОСН2), 69.2 (ОСН2), 76.3 (СН=),
110.7 (С8), 113.1 (С5), 120.7 (С8а), 128.4 (С4а), 147.5
(С7), 151.5 (С6), 155.3 (С1), 171.1 (С=О). Mass spectrum,
m/z (Irel, %): [M]+ 429 (100), 386 (22), [M – OC2H5]+ 384
(10), [M – OC4H9]+ 357 (31), 341 (13), 340 (39), 328 (10),
327 (37). Found, %: С 72.75; Н 9.12; N 3.22. C26H39NO4.
Calculated, %: С 72.69; Н 9.15; N 3.26.
Ethyl [6,7-dibutoxy-3,3-dimethyl-3,4-
dihydroisoquinolin-1(2Н)-ylidene]ethanoate (XIVa).
Yield 0.47 g (12%), mp 72–73°С (EtOH). IR spectrum,
cm–1: 1648, 1602, 1572, 1516. 1Н NMR spectrum, δ, ppm:
0.92 t (6Н, 2Mе, J 7.2 Hz), 1.21 s (6Н, 2Mе), 1.24 t (3Н,
ОСН2Mе, J 7.7 Hz), 1.44 m (4Н, 2ОСН2СН2СН2Mе),
1.74 m (4Н, 2ОСН2СН2СН2Mе), 2.67 s (2Н, СН2),
3.94 m (4Н, 2ОСН2), 4.09 q (2Н, ОСН2Mе), 4.95 s (1Н,
СН=), 6.54 s (1Нarom), 7.08 s (1Нarom), 8.88 br.s (1Н,
NH). 13С NMR spectrum, δ, ppm: 13.7 (2C, Mе), 14.6
(ОСН2СН3), 19.1 (2C, ОСН2СН2СН2Me), 28.3 (С3CH3),
31.1 (ОСН2СН2СН2Me), 31.2 (ОСН2СН2СН2Me), 41.5
(С4), 49.2 (С3), 58.2 (ОСН2Me), 68.6 (ОСН2), 69.2
(ОСН2), 76.3 (СН=), 110.7 (С8), 113.0 (С5), 120.5 (С8а),
128.7 (С4a), 147.6 (С7), 151.5 (С6), 155.5 (С1), 171.0
(C=O). Mass spectrum, m/z (Irel, %): [M]+ 389 (66), [M –
Mе]+ 374 (24), [M – OC2H5]+ 344 (16), 328 (100), [M –
COOC2H5]+ 317 (48), [M – OC4H9]+ 316 (12), 302 (30),
272 (16). Found, %: С 70.85; Н 9.10; N 3.57. C23H35NO4.
Calculated, %: С 70.92; Н 9.06; N 3.60.
Ethyl [7-hydroxy-6-propoxy-3,3-dimethyl- 3,4-di-
hydroisoquinolin-1(2Н)-ylidene]ethanoate (XVIa).
Yield 0.10 g (3%), mp 132–141°С (EtOH). IR spectrum,
cm–1: 3300, 3210, 1628, 1575. 1Н NMR spectrum, δ, ppm:
0.99 t (3Н, Mе, J 7.5 Hz), 1.20 s (6Н, 2Mе), 1.23 t (3Н,
ОСН2СН3, J 7.5 Hz), 1.80 m (2Н, ОСН2СН2Mе), 2.66 s
(2Н, СН2), 3.96 m (2Н, ОСН2), 4.07 q (2Н, ОСН2Mе),
4.96 s (1Н, СН=), 5.51 br.s (1Н, ОН), 6.52 s (1Нarom),
7.17 s (1Нarom), 8.86 br.s (1Н, NH). 13С NMR spectrum, δ,
ppm: 10.4 (Mе), 14.7 (ОСН2СН3), 22.5 (ОСН2СН2Me),
28,5 (С3СН3), 41.9 (С4), 49,4 (С3), 58.4 (ОСН2Me), 70.5
(ОСН2), 77.0 (СН=), 111.3 (С8), 111.3 (С5), 121.4 (С8а),
127.9 (С4а), 144.4 (С7), 148.0 (С6), 155.3 (С1), 171.4
(С=О). Mass spectrum, m/z (Irel, %): [M]+ 319 (56), [M –
Mе]+ 304 (26), [M – OC2H5]+ 274 (17), 258 (100), 232
(41). Found, %: С 67.81; Н 7.93; N 4.34. C18H25NO4.
Calculated, %: С 67.69; Н 7.89; N 4.39.
6,7-Dibutoxy-3,3-dimethyl-1-methylsulfanyl-3,4-
dihydroisoquinoline (XIVb). Yield 0.52 g (15%), mp
41–43°С (EtOH). IR spectrum, cm–1: 1585, 1550, 1505.
1Н NMR spectrum, δ, ppm: 0.97 t (6Н, 2Mе, J 7.4 Hz),
1.17 s (6Н, 2Mе), 1.50 m (4Н, 2ОСН2СН2СН2Mе),
1.80 m (4Н, 2ОСН2СН2СН2Mе), 2.40 s (3Н, SMе), 2.59 s
(2Н, СН2), 4.00 t (4Н, 2ОСН2, J 5.9 Hz), 6.60 s (1Нarom),
7.15 s (1Нarom). Mass spectrum, m/z (Irel, %): [M]+ 349
(23), [M – Mе]+ 334 (100), [M – C4H9]+ 292 (18), 278
(16), 222 (15). 13С NMR spectrum, δ, ppm: 11.9 (Mе),
13.7 (SMe), 19.1 (2С, ОСН2СН2СН2Me), 28.2 (С3CH3),
31.1 (ОСН2СН2СН2Me), 31.2 (ОСН2СН2СН2Me), 38.8
(С4), 55.5 (С3), 68.6 (ОСН2), 69.2 (ОСН2), 110.9 (С8),
112.7 (С5), 121.2 (С8а), 129.3 (С4а), 147.2 (С6), 151.3
(С7), 159.3 (С1). Found, %: С 68.82; Н 8.78; N 4.08;
S 9.06. C20H31NO2S. Calculated, %: С 68.72; Н 8.94;
N 4.01; S 9.17.
Ethyl [6-butoxy-7-hydroxy-3,3-dimethyl-
3,4-dihydroisoquinolin-1(2Н)-ylidene]ethanoate
(XVIIa). Yield 0.07 g (2%), mp 141–145°С (EtOH).
IR spectrum, cm–1: 3340, 3292, 1684, 1636, 1594.
1Н NMR spectrum, δ, ppm: 0.97 t (3Н, Mе, J 7.4 Hz),
1.24 s (6Н, 2Mе), 1.27 m (3Н, ОСН2СН3), 1.44–
1.54 m (2Н, ОСН2СН2СН2Mе), 1.74–1.84 m (2Н,
ОСН2СН2СН2Mе), 2.69 s (2Н, СН2), 4.04 t (2Н, ОСН2,
J 6.6 Hz), 4.09–4.16 q (2Н, ОСН2Mе), 5.01 s (1Н, СН=),
5.82 br.s (1Н, ОН), 6.57 s (1Нarom), 7.22 s (1Нarom),
8.91 br.s (1Н, NH). 13С NMR spectrum, δ, ppm: 13.7
(Mе), 14.6 (ОСН2СН3), 19.1 (ОСН2СН2СН2Me), 28.3
(С3СН3), 31.0 (ОСН2СН2СН2Me), 41.6 (С4), 49.3 (С3),
58.3 (ОСН2Me), 68.5 (ОСН2), 76.6 (СН=), 111.1 (С8),
111.2 (С5), 121.0 (С8а), 127.8 (С4а), 144.2 (С7), 148.1
(С6), 155.3 (С1), 171.2 (С=О). Mass spectrum, m/z (Irel,
%): [M]+ 333 (45), [M – Mе]+ 318 (21), [M – OC2H5]+ 288
(18), 272 (100), 260 (11), 246 (34). Found, %: С 68.35;
Ethyl [6,7-dibutoxy-3,3-pentamethylene-3,4-
dihydroisoquinolin-1(2Н)-ylidene]ethanoate (XVa).
Yield 0.39 g (9%), mp 97–100°С (EtOH). IR spectrum,
cm–1: 3244, 3124, 1722, 1634, 1600, 1570, 1514. 1Н NMR
spectrum, δ, ppm: 0.92 t (6Н, 2Mе, J 7.7 Hz), 1.25 t (7Н,
ОСН2Mе + 2ОСН2СН2СН2Mе, J 7.1 Hz), 1.38–1.55 m
(10Н, 5СН2), 1.75 m (4Н, 2ОСН2СН2СН2Mе), 2.68 s
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1
Н 8.07; N 4.24. C19H27NO4. Calculated, %: С 68.44;
Н 8.16; N 4.20.
1628, 1606, 1574, 1516. Н NMR spectrum, δ, ppm:
1.04 t (3Н, Mе, J 7.2 Hz), 1.17 s (2Н, 2Mе), 1.85 m
(2Н, ОСН2СН2Mе), 2.32 s (3Н, Mе), 2.59 s (2Н, СН2),
3.88 s (3Н, ОMе), 3.97 t (2Н, ОСН2, J 6.8 Hz), 6.62 s
(1Нarom), 6.99 s (1Нarom). 13С NMR spectrum, δ, ppm:
10.3 (ОСН2СН2СН3), 22.7 (ОСН2СН2Mе), 23.1 (Mе),
28.0 (С3СН3), 38.8 (С4), 53.6 (С3), 56.1(ОMе), 71.7
(ОСН2), 112.0 (С5), 112.3(С8), 121.8 (С8а), 130.4 (С4а),
147.2 (С7), 152.1 (С6), 160.4 (С1). Mass spectrum, m/z
(Irel, %): [M]+ 261 (100), [M – Mе]+ 246 (99), [M – C3H7]+
219 (43), 204 (95). Found, %: С 73.41; Н 8.95; N 5.29.
C16H23NO2. Calculated, %: С 73.53; Н 8.87; N 5.36.
6-Butoxy-3,3-dimethyl-1-methylsulfanyl-3,4-
dihydroisoquinolin-7-ol (XVIIb. Yield 0.03 g (1%), mp
95–100°С (EtOH). IR spectrum, cm–1: 1594, 1560, 1514.
1Н NMR spectrum, δ, ppm: 0.98 t (3Н, СН3, J 7.4 Hz),
1.17 s (6Н, 2Mе), 1.49 m (2Н, ОСН2СН2СН2Mе), 1.80 m
(2Н, ОСН2СН2СН2Mе), 2.58 s (2Н, СН2), 2.39 s (3Н,
SMе), 4.06 m (2Н, ОСН2), 5.50 br.s (1Н, ОН), 6.58 s
(1Нarom), 7.24 s (1Нarom). 13С NMR spectrum, δ, ppm:
12.2 (Mе), 13.8 (SMe), 19.2 (ОСН2СН2СН2Me), 28.3
(С3CH3), 31.2 (ОСН2СН2СН2Me), 39.1 (С4), 55.8 (С3),
68.7 (ОСН2), 110.9 (С5), 111.1 (С8), 121.8 (С8а), 128.4
(С4а), 144.0 (С7), 147.9 (С6), 159.9 (С1). Mass spectrum,
m/z (Irel, %): [M]+ 293 (37), [M – Mе]+ 278 (100), [M –
C4H9]+ 236 (9), 222 (35). Found, %: С 65.53; Н 7.87;
N 4.80; S 10.82. C16H23NO2S. Calculated, %: С 65.49;
Н 7.90; N 4.77; S 10.93.
7-Butoxy-1,3,3-trimethyl-6-methoxy-3,4-
dihydroisoquinoline (XIXc). Yield 2.45 g (89%),
mp 50–56°С (hexane). IR spectrum, cm–1: 1628,
1
1604, 1574, 1516. Н NMR spectrum, δ, ppm: 0.98
t (3Н, Mе, J 7.4 Hz), 1.18 s (2Н, 2Mе), 1.50 m (2Н,
ОСН2СН2СН2Mе), 1.80 m (2Н, ОСН2СН2СН2Mе), 2.33
s (3Н, Mе), 2.60 s (2Н, СН2), 3.88 s (3Н, ОMе), 4.01 t
(2Н, ОСН2, J 6.8 Hz), 6.62 s (1Нarom), 6.99 s (1Нarom).
13С NMR spectrum, δ, ppm: 13.8 (ОСН2СН2СН2СН3),
19.2 (ОСН2СН2СН2Me), 23.4 (Mе), 28.0 (С3СН3), 31.4
(ОСН2СН2СН2Me), 38.6 (С4), 53.5 (С3), 56.0 (ОMе),
69.4 (ОСН2), 111.3 (С8), 111.4 (С5), 121.6 (С8а), 130.1
(С4а), 146.9 (С7), 151.6 (С6), 160.6 (С1). Mass spectrum,
m/z (Irel, %): [M]+ 275 (100), [M – Mе]+ 260 (53), 233
(15), [M – C4H9]+ 218 (11), 204 (56). Found, %: С 74.01;
Н 9.11; N 5.12. C17H25NO2. Calculated, %: С 74.14; Н
9.15; N 5.09.
Ethyl [6-butoxy-7-hydroxy-3,3-pentamethylene-
3,4-dihydroisoquinolin-1(2Н)-ylidene]ethanoate
(XVIIIa). Yield 0.04 g (1%), mp 127–135°С (hexane).
1Н NMR spectrum, δ, ppm: 0.98 t (3Н, Mе, J 7.4 Hz),1.30
t (3Н, ОСН2Mе, J 6.9 Hz), 1.37–1.60 m (12Н, 5СН2 +
ОСН2СН2СН2Mе), 1.81 m (2Н, ОСН2СН2СН2Mе),
2.71 s (2Н, СН2), 4.05 t (2Н, ОСН2, J 6.6 Hz), 4.14 q
(2Н, ОСН2Mе), 5.02 s (1Н, СН=), 5.47 br.s (1Н, ОН),
6.56 s (1Нarom), 7.20 s (1Нarom), 9.25 br.s (1Н, NH). Mass
spectrum of thermolysis product, m/z (Irel, %): [M]+ 301
(48), [M – Mе]+ 286 (10), 258 (100), 245 (25). Found,
%: С 70.63; Н 8.41; N 3.71. C22H31NO4. Calculated, %:
С 70.75; Н 8.37; N 3.75.
1,3,3-Trimethyl-6,7-diethoxy-3,4-dihydroiso-
quinoline (XIXf). Yield 1.64 g (63%), mp 93–96°С
(hexane). IR spectrum, cm–1: 1602, 1560, 1505. 1Н NMR
spectrum, δ, ppm: 1.12 s (2Н, 2Mе), 2.53 s (2Н, СН2),
1.39 m (6Н, 2ОСН2СН3), 2.26 s (3Н, Me), 4.05 m (4Н,
2ОСН2), 6.57 s (1Нarom), 6.95 s (1Нarom). 13С NMR spec-
trum, δ, ppm: 14.4 (ОСН2СН3), 14.3 (ОСН2СН3), 22.8
(Mе), 27.5 (С3СН3), 38.1 (С4), 53.0 (С3), 64.8 (ОСН2),
63.9 (ОСН2), 111.8 (С5), 112.3 (С8), 121.0 (С8а), 129.8
(С4а), 146.4 (С7), 150.7 (С6), 160.0 (С1). Mass spectrum,
m/z (Irel, %): [M]+ 261 (100), [M – Me]+ 246 (47), [M –
C2H5]+ 232 (42), 219 (28), 204 (15), 190 (16). Found,
%: С 73.70; Н 8.81; N 5.42. C16H23NO2. Calculated, %:
С 73.53; Н 8.87; N 5.36.
1,3,3-Trimethyl-6-methoxy-7-ethoxy-3,4-di-
hydroisoquinoline (XIXa). Yield 1.63 g (66%), mp
80–82°С (hexane). IR spectrum, cm–1: 1622, 1606,
1
1572, 1516. Н NMR spectrum, δ, ppm: 1.18 s (2Н,
2Mе), 1.46 t (3Н, ОСН2СН3, J 6.9 Hz), 2.32 s (3Н, Mе),
2.60 s (2Н, СН2), 3.89 s (3Н, ОMе), 4.10 q (2Н, ОСН2),
6.62 s (1Нarom), 6.99 s (1Нarom). 13С NMR spectrum, δ,
ppm: 14.8 (ОСН2СН3), 23.2 (Mе), 27.9 (С3СН3), 38.6
(С4) , 53.5 (С3), 55.8 (ОMе), 64.9 (ОСН2), 111.1 (С8),
111.2 (С5), 121.4 (С8а), 130.1 (С4а), 146.5 (С7), 151.4
(С6), 160.6 (С1). Mass spectrum, m/z (Irel, %): [M]+ 247
(100), [M – Mе]+ 232 (74), [M – C2H5]+ 218 (11), 205
(36). Found, %: С 72.71; Н 8.63; N 5.61. C15H21NO2.
Calculated, %: С 72.84; Н 8.56; N 5.66.
1,3,3-Trimethyl-6,7-dipropoxy-3,4-dihydro-
isoquinoline (XIXg). Yield 1.71 g (59%), light-yellow
oily substance. IR spectrum, cm–1: 1636, 1600, 1560,
1516. Н NMR spectrum, δ, ppm: 1.04 t (6Н, 2Mе,
J 7.4 Hz), 1.17 s (6Н, 2Mе), 1.84 m (4Н, 2СН2), 2.32 s
1,3,3-Trimethyl-6-methoxy-7-propoxy-3,4-
dihydroisoquinoline (XIXb). Yield 2.11 g (81%),
mp 58–60°С (ethyl ether). IR spectrum, cm–1: 1768,
1
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SYNTHESIS OF 7-HYDROXY-6-ALKOXY DERIVATIVES
265
(3Н, Mе), 2.58 s (2Н, СН2), 3.97 q (4Н, 2ОСН2), 6.61
s (1Нarom), 7.00 s (1Нarom). Mass spectrum, m/z (Irel, %):
[M]+ 289 (100), [M – Mе]+ 274 (95), [M – C3H7]+ 246
(89), 232 (46), 204 (73), 190 (94). Found, %: С 74.55;
Н 9.47; N 5.00. C18H27NO2. Calculated, %: С 74.70;
Н 9.40; N 4.84.
1.29 s (6Н, 2Mе), 1.84 m (2Н, СН2), 2.83 s (2Н, СН2),
3.89 s (3Н, ОСН3), 4.02 t (2Н, ОСН2, J 6.8 Hz), 5.53
br.s (1Н, NH), 6.61 s (1Нarom), 7.55 s (1Нarom). 13С NMR
spectrum, δ, ppm: 10.3 (Mе), 22.3 (ОСН2СН2Me), 28.7
(С3CH3), 41.2 (С4), 52.0 (С3), 55.9 (ОMе), 70.4 (ОСН2),
110.4 (С8), 111.5 (С5), 120.3 (С8а), 131.0 (С4а), 147.3
(С7), 152.5 (С6), 165.5 (С1). Mass spectrum, m/z (Irel,
%): [M]+ 263 (81), [M – Mе]+ 248 (62), 206 (100), 164
(44). Found, %: С 68.29; Н 8.11; N 5.27. C15H21NO3.
Calculated, %: С 68.42; Н 8.04; N 5.32.
1,3,3-Trimethyl-6-propoxy-3,4-dihydro-
isoquinolin-7-ol (XIXi). Yield 0.05 g (2%), mp 145–
153°С (hexane). 1Н NMR spectrum, δ, ppm: 0.99 t (3Н,
Mе, J 7.4 Hz), 1.14 s (6Н, 2Mе), 1.80 m (2Н, СН2),
2.25 s (3Н, Mе), 2.54 s (2Н, СН2), 4.05 t (2Н, ОСН2),
6.55 s (1Нarom), 7.04 s (1Нarom). 13С NMR spectrum, δ,
ppm: 10.4 (Mе), 22.5 (ОСН2СН2Me), 23.3 (Me), 28.0
(С3CH3), 38.8 (С4), 53.7 (С3), 70.5 (ОСН2), 111.2 (С5),
112.0 (С8), 121.9 (С8a), 129.0 (С4a), 147.8 (С6), 144.1
(С7), 159.8 (С1). Mass spectrum, m/z (Irel, %): [M]+
247 (95), [M – Mе]+ 232 (33), [M – C3H7]+ 204 (100),
190 (47), 163 (34). Found, %: С 72.94; Н 8.39; N 5.71.
C15H21NO2. Calculated, %: С 72.84; Н 8.56; N 5.66.
7-Butoxy-3,3-dimethyl-6-methoxy-3,4-dihydro-
isoquinolin-1(2Н)-one (XXc). Yield 1.55 g (56%),
mp 150–153°С (EtOH). IR spectrum, cm–1: 3180,
1
1654, 1602, 1516. Н NMR spectrum, δ, ppm: 0.96 t
(3Н, Mе, J 7.4 Hz), 1.29 s (6Н, 2Mе), 1.47 m (2Н,
ОСН2СН2СН2Mе), 1.82 m (2Н, ОСН2СН2СН2Mе),
2.83 s (2Н, СН2), 3.89 s (3Н, ОMе), 4.06 t (2Н,
ОСН2, J 6.8 Hz), 5.53 br.s (1Н, NH), 6.61 s (1Нarom),
7.55 s (1Нarom). 13С NMR spectrum, δ, ppm: 13.6
(Mе), 19.0 (ОСН2СН2СН2Me), 28.6 (С3CH3), 31.0
(ОСН2СН2СН2Me), 41.1 (С4), 51.9 (С3), 55.8 (ОMе),
68.6 (ОСН2), 110.3 (С8), 111.4 (С5), 120.3 (С8а), 130.9
(С4а), 147.3 (С7), 152.4 (С6), 165.5 (С1). Mass spectrum,
m/z (Irel, %): [M]+ 277 (72), [M – Mе]+ 262 (39), [M –
C4H9]+ 220 (47), 206 (100), 192 (10), 164 (56). Found,
%: С 69.19; Н 8.42; N 5.01. C16H23NO3. Calculated, %:
С 69.29; Н 8.36; N 5.05.
6-Butoxy-1,3,3-trimethyl-3,4-dihydroisoquinolin-
7-ol (XIXj). Yield 0.05 g (2%), mp 91–110°С (hexane).
1
IR spectrum, cm–1: 1620, 1580, 1512. Н NMR spec-
trum, δ, ppm: 0.92 t (3Н, Mе, J 7.4 Hz), 1.14 s (6Н,
2Mе), 1.43 m (2Н, ОСН2СН2СН2Mе), 1.74 m (2Н,
ОСН2СН2СН2Mе), 2.29 s (3Н, Mе), 2.53 s (2Н, СН2),
3.97 t (2Н, ОСН2), 6.59 s (1Нarom), 6.88 s (1Нarom).
Mass spectrum, m/z (Irel, %): [M]+ 261 (42), [M – Mе]+
246 (18), [M – C4H9]+ 204 (45), 190 (37), 163 (34), 149
(25). Found, %: С 73.44; Н 8.91; N 5.42. C16H23NO2.
Calculated, %: С 73.53; Н 8.87; N 5.36.
6-Propoxy-3,3-dimethyl-7-methoxy-3,4-
dihydroisoquinolin-1(2Н)-one (XXd). Yield 0.10 g
(38%), mp 173–174°С (EtOH). IR spectrum, cm–1:
1
3217, 1659, 1604, 1512. Н NMR spectrum, δ, ppm:
3,3-Dimethyl-6-methoxy-7-ethoxy-3,4-
dihydroisoquinolin-1(2Н)-one (XXa). Yield 1.99 g
(80%), mp 196–198°С (EtOH). IR spectrum, cm–1:
1.05 t (3Н, Mе, J 7.4 Hz), 1.31 s (6Н, 2Mе), 1.89 m (2Н,
ОСН2СН2Mе), 2.82 s (2Н, СН2), 3.91 s (3Н, ОMе),
4.01 t (2Н, ОСН2, J 6.6 Hz), 6.27 br.s (1Н, NH), 6.63 s
(1Нarom), 7.55 s (1Нarom). 13С NMR spectrum, δ, ppm:
10.3 (Mе), 22.2 (ОСН2СН2Me), 28.7 (С3CH3), 41.1 (С4),
52.1 (С3), 56.0 (ОMе), 70.3 (ОСН2), 110.2 (С8), 111.1
(С5), 120.0 (С8а), 131.1 (С4а), 148.0 (С7), 151.7 (С6),
165.6 (С1). Mass spectrum, m/z (Irel, %): [M]+ 263 (48),
[M – Mе]+ 248 (38), 206 (100), 164 (22), 136 (23). Found,
%: С 68.31; Н 7.99; N 5.30. C15H21NO3. Calculated, %:
С 68.42; Н 8.04; N 5.32.
1
1662, 1604, 1516. Н NMR spectrum, δ, ppm: 1.29 с
(6Н, 2Mе), 1.44 t (3Н, Mе, J 7.2 Hz), 2.83 s (2Н, СН2),
3.90 s (3Н, ОMе), 4.14 q (2Н, ОСН2), 5.54 br.s (1Н,
NH), 6.61 s (1Нarom), 7.55 s (1Нarom). 13С NMR spectrum,
δ, ppm: 14.7 (Mе), 28.8 (С3CH3), 41.3 (С4), 52.1 (С3),
56.0 (ОMе), 64.4 (ОСН2), 110.3 (С8), 111.4 (С5), 120.3
(С8а), 131.0 (С4а), 147.2 (С7), 152.5 (С6), 165.5 (С1).
Mass spectrum, m/z (Irel, %): [M]+ 249 (82), [M – Mе]+
234 (100), [M – C3H7]+ 206 (23), 192 (74). Found, %:
С 67.59; Н 7.62; N 5.66. C14H19NO3. Calculated, %:
С 67.45; Н 7.68; N 5.62.
6-Butoxy-3,3-dimethyl-7-methoxy-3,4-
dihydroisoquinolin-1(2Н)-one (XXe). Yield 1.80 g
(65%), mp 138–139°С (EtOH). IR spectrum, cm–1:
3,3-Dimethyl-6-methoxy-7-propoxy-3,4-dihydro-
isoquinolin-1(2Н)-one (XXb). Yield 2.24 g (85%), mp
182–185°С (EtOH). IR spectrum, cm–1: 1660, 1606, 1516.
1Н NMR spectrum, δ, ppm: 1.02 t (3Н, Mе, J 7.2 Hz),
1
3165, 1656, 1599, 1511. Н NMR spectrum, δ, ppm:
0.97 t (3Н, Mе, J 7.4 Hz), 1.31 s (6Н, 2Mе), 1.49 m (2Н,
ОСН2СН2СН2Mе), 1.84 m (2Н, ОСН2СН2СН2Mе),
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266
2.82 s (2Н, СН2), 3.90 s (3Н, ОMе), 4.04 t (2Н,
ОСН2, J 6.6 Hz), 6.56 br.s (1Н, NH), 6.64 s (1Нarom),
7.55 s (1Нarom). 13С NMR spectrum, δ, ppm: 13.7
(Mе), 19.0 (ОСН2СН2СН2Me), 28.6 (С3CH3), 30.9
(ОСН2СН2СН2Me), 41.1 (С4), 52.0 (С3), 56.0 (OMe),
68.5 (ОСН2), 110.2 (С8), 111.1 (С5), 120.0 (С8a), 131.1
(С4a), 147.9 (С7), 151.8 (С6), 165.6 (С1). Mass spectrum,
m/z (Irel, %): [M]+ 277 (59), [M – Mе]+ 262 (38), [M –
C4H9]+ 220 (43), 206 (100), 164 (38). Найdе-но, %:
С 69.36; Н 8.32; N 4.99. C16H23NO3. Calculated, %:
С 69.29; Н 8.36; N 5.05.
(ОСН2СН2СН2Me), 31.1 (ОСН2СН2СН2Me), 41.0 (С4),
51.8 (С3), 68.6 (ОСН2), 68.8 (ОСН2), 111.8 (С8), 112.2
(С5), 120.2 (С8а), 131.0 (С4а), 147.6 (С7), 152.3 (С6),
165.6 (С1). Mass spectrum, m/z (Irel, %): [M]+ 319 (100),
[M – Mе]+ 304 (41), [M – C4H9]+ 262 (53), 248 (83), 220
(17), 207 (71), 192 (72). Found, %: С 71.56; Н 9.08; N
4.42. C19H29NO3. Calculated, %: С 71.44; Н 9.15; N 4.38.
1,3,3-Trimethyl-7-methoxy-6-propoxy-3,4-
dihydroisoquinoline hydrochloride (XXIa). Yield
1.04 g (35%), mp 183–186°С (ethyl acetate). IR spectrum,
1
cm–1: 1650, 1604, 1565, 1517. Н NMR spectrum, δ,
3,3-Dimethyl-6,7-diethoxy-3,4-dihydroiso-
quinolin-1(2Н)-one (XXf). Yield 1.97 g (75%), mp
192–193°С (EtOH). IR spectrum, cm–1: 1756, 1660,
ppm: 1.07 t (3Н, Mе, J 7.4 Hz), 1.59 s (6Н, 2Mе), 1.92 m
(2Н, ОСН2СН2Mе), 2.96 s (2Н, СН2), 2.98 s (3Н, Mе),
3.94 s (3Н, ОMе), 4.10 t (2Н, ОСН2), 6.77 s (1Нarom),
7.18 s (1Нarom), 14.37 s (1Н, HCl). 13С NMR spectrum,
δ, ppm: 10.2 (Mе), 19.2 (Me), 22.0 (ОСН2СН2Me),
25.8 (С3CH3), 39.3 (С4), 55.1 (С3), 56.4 (OMe), 70.9
(ОСН2), 111.4 (С5), 111.9 (С8), 116.6 (С8a), 131.8 (С4a),
148.7 (С6), 156.1 (С7), 171.9 (С1). Mass spectrum, m/z
(Irel, %): 261 [M – HCl]+ (100), 246 [M – HCl – Mе]+
(38), 219 (24), 218 (60), 204 (47), 177 (27). Found, %:
С 64.61; Н 8.08; N 4.64. C16H23NO2·HCl . Calculated,
%: С 64.53; Н 8.12; N 4.70.
1
1604, 1514. Н NMR spectrum, δ, ppm: 1.29 s (6Н,
2Mе), 1.46 q (6Н, 2ОСН2Mе), 2.81 s (2Н, СН2), 4.12 m
(4Н, 2ОСН2), 5.57 br.s (1Н, NH), 6.61 s (1Нarom), 7.53 s
(1Нarom). 13С NMR spectrum, δ, ppm: 14.6 (Mе), 14.7
(Mе), 28.8 (С3CH3), 41.2 (С4), 52.0 (С3), 64.4 (ОСН2),
64.5 (ОСН2), 111.7 (С8), 111.9 (С5), 120.2 (С8а), 131.0
(С4а), 147.4 (С7), 152.0 (С6), 165.6 (С1). Mass spectrum,
m/z (Irel, %): [M]+ 263 (99), [M – Mе]+ 248 (100), 220
(26), 206 (97), 178 (61). Found, %: С 68.35; Н 8.00;
N 5.29. C15H21NO3. Calculated, %: С 68.42; Н 8.04;
N 5.32.
6-Butoxy-1,3,3-trimethyl-7-methoxy-3,4-
dihydroоisoquinoline hydrochloride (XXIb). Yield
0.84 g (27%), mp 187–188°С (toluene). IR spectrum,
3,3-Dimethyl-6,7-dipropoxy-3,4-dihydro-
isoquinolin-1(2Н)-one (XXg). Yield 1.95 g (67%), mp
137–139°С (EtOH). IR spectrum, cm–1: 3180, 1660, 1606,
1
cm–1: 1596, 1560, 1514. Н NMR spectrum, δ, ppm:
1.00 t (3Н, Mе, J 7.4 Hz), 1.51 m (2Н, ОСН2СН2СН2Mе),
1.59 s (6Н, 2Mе), 1.89 m (2Н, ОСН2СН2СН2Mе), 2.94 s
(2Н, СН2), 2.96 s (3Н, Mе), 3.97 q (3Н, ОMе), 4.13 m
(2Н, ОСН2), 6.74 s (1Нarom), 7.14 s (1Нarom), 14.53 s
(1Н, HCl). 13С NMR spectrum, δ, ppm: 13.5 (Mе), 18.8
(ОСН2СН2СН2Me), 18.9 (ОСН2СН2СН2Me), 19.1 (Me),
25.8 (С3CH3), 30.6 (ОСН2СН2СН2Me), 39.3(С4), 55.1
(С3), 56.4 (OMe), 69.1 (ОСН2), 111.5 (С8), 111.9 (С5),
116.6 (С8a), 131.8 (С4a), 148.7 (С7), 156.2 (С6), 171.8
(С1). Mass spectrum, m/z (Irel, %): [M – HCl]+ 275 (100),
[M – HCl – Mе]+ 260 (36), 218 (60), 204 (47), 177 (30).
Found, %: С 65.39; Н 8.36; N 4.43. C17H25NO2·HCl.
Calculated, %: С 65.48; Н 8.40; N 4.49.
1
1560, 1516. Н NMR spectrum, δ, ppm: 1.03 m (6Н,
2Mе), 1.29 s (6Н, 2Mе), 1.84 m (4Н, 2ОСН2СН2Mе),
2.81 s (2Н, СН2), 3.99 m (4Н, 2ОСН2), 5.65 br.s (1Н,
NH), 6.61 s (1Нarom), 7.54 s (1Нarom). 13С NMR spectrum,
δ, ppm: 10.4 (Mе), 22.6 (ОСН2СН2Me), 29.0 (С3CH3),
41.4 (С4), 52.3 (С3), 70.7 (ОСН2), 70.8 (ОСН2), 112.2
(С8), 112.5 (С5), 120.2 (С8а), 131.1 (С4а), 148.0 (С7),
152.6 (С6), 165.6 (С1). Mass spectrum, m/z (Irel, %): [M]+
291 (69), [M – Mе]+ 276 (39), 234 (100), 192 (76). Found,
%: С 69.98; Н 8.73; N 4.78. C17H25NO3. Calculated, %:
С 70.07; Н 8.65; N 4.81.
6,7-Dibutoxy-3,3-dimethyl-3,4-dihydroisoquinolin-
1(2Н)-one (XXh). Yield 2.97 g (93%), mp 152–153°С
(EtOH). IR spectrum, cm–1: 3162, 1660, 1604, 1512.
1Н NMR spectrum, δ, ppm: 0.97 m (6Н, 2Mе),
1.29 s (6Н, 2Mе), 1.50 m (4Н, 2ОСН2СН2СН2Mе),
1.80 m (4Н, 2ОСН2СН2СН2СН3), 2.81 s (2Н,
СН2), 4.00 m (4Н, 2ОСН2), 6.60 s (1Нarom), 7.54 s
(1Нarom). 13С NMR spectrum, δ, ppm: 13.6 (2С, Mе),
18.9 (2С, ОСН2СН2СН2Me), 28.5 (С3CH3), 31.0
6,7-Dibutoxy-1,3,3-trimethyl-3,4-dihydroisoquin-
oline hydrochloride (XXIc). Yield 1.52 g (43%), mp
180–187°С (ethyl ether). IR spectrum, cm–1: 1636,
1
1600, 1558, 1516. Н NMR spectrum, δ, ppm: 0.99 t
(6Н, 2Mе, J 7.4 Hz), 1.51 m (4Н, 2ОСН2СН2СН2Mе),
1.59 s (6Н, 2Mе), 1.83 m (4Н, 2ОСН2СН2СН2Mе),
2.93 s (3Н, Mе), 4.01 t (2Н, ОСН2, J 6.5 Hz), 4.10 t
(2Н, ОСН2, J 6.5 Hz), 6.71 s (1Нarom), 7.16 s (1Нarom),
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SYNTHESIS OF 7-HYDROXY-6-ALKOXY DERIVATIVES
267
14.49 s (1Н, НCl). 13С NMR spectrum, δ, ppm: 13.6 (Mе),
18.9 (ОСН2СН2СН2Me), 19.0 (Me), 25.8 (С3CH3), 30.6
(ОСН2СН2СН2Me), 30.9 (ОСН2СН2СН2Me), 39.3 (С4),
55.1 (С3), 69.0 (ОСН2), 69.5 (ОСН2), 112.2 (С5), 113.5
(С8), 116.5 (С8a), 131.8 (С4a), 148.3 (С6), 156.8 (С7),
171.7 (С1). Mass spectrum, m/z (Irel, %): [M – HCl]+ 317
(100), [M – HCl – Mе]+ 302 (79), 275 (32), [M – HCl –
C4H9]+ 260 (77), 246 (39), 204 (71), 190 (77). Found, %:
С 67.95; Н 9.10; N 3.88. C20H31NO2·HCl. Calculated, %:
С 67.87; Н 9.11; N 3.96.
Geterotsikl. Soedin., 2009, p. 421.
2. Brossi A. and Teitel S., Helv. Chim. Acta, 1970, vol. 53,
p. 1779.
3. Charifson P.S., Wyrick S.D., Hoffmann A.J., Simmons
R.M.A., Bowen J.P., McDougald D.L., and Mailman R.B.,
J. Med. Chem., 1988, vol. 31, p. 1941.
4. Chen S., Liu X.-J., Lu Z.-X., Xie Q., and Ling N., J. Med.
Chem., 2001, vol. 44, p. 4001.
5. Bindra J.S. and Grodski A., J. Org. Chem., 1977, vol. 42,
p. 910.
6. White J.D. and Straus D.S., J. Org. Chem., 1967, vol. 32,
ACKNOWLEDGMENTS
p. 2689.
7. Grethe G., Toome V., Lee H.L., Uskokovic M., and
The study was carried out under the financial support
of the program of the Presidium of the RussianAcademy
of Sciences no. 21.
Brossi A., J. Org .Chem., 1968, vol. 33, p. 504.
8. Shklyaev Yu.V. and Nifontov Yu.V., Izv. Akad. Nauk, Ser.
Khim., 2002, p. 780.
9. Obshchii praktikum po organicheskoi khimii (General
Practocum on organic Chemsitry), Kost, A.N., Ed.,
Moscow: Mir, 1965.
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