Synthesis of hybrid compounds derived from diterpene alkaloid lappaconitine

Full text of DOI:10.1134/S0012500810010076

ISSN 0012ꢀ5008, Doklady Chemistry, 2010, Vol. 430, Part 1, pp. 27–31. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.E. Romanov, E.E. Shul’ts, M.M. Shakirov, G.A. Tolstikov, 2010, published in Doklady Akademii Nauk, 2010, Vol. 430, No. 3, pp. 337–341.
CHEMISTRY
Synthesis of Hybrid Compounds Derived
from Diterpene Alkaloid Lappaconitine
V. E. Romanov, E. E. Shul’ts, M. M. Shakirov, and Academician G. A. Tolstikov
Received April 13, 2009
DOI: 10.1134/S0012500810010076
There has been growing interest in the design and therapeutics for the treatment of Alzheimer’s and Parꢀ
synthesis of dimeric bases of different alkaloids after
the structure and important pharmacological properꢀ
ties of dimeric alkaloids of isoquinoline (plant metabꢀ
olites of genera Thalictrum and Berberis) [1] and
kinson’s diseases and other problems of ageꢀrelated
neurodegeneration [11, 12]. To obtain dimeric comꢀ
pounds containing lappaconitine and indolizine fragꢀ
ments, we used the transformations of compound
product of the crossꢀcoupling of 5'ꢀiodolappaconitine
) with 5ꢀvinylꢀ2ꢀmethylpyridine [13]. Pyridinium
salts prepared by the reaction of compound with
3, a
indole types (from plants of genera Vinca, Strychnos,
Iboga, and Catharantus [2, 3]) were established.
Examples for modifications of morphinan alkaloids
A–X are described that enable junction with the secꢀ
ond molecule of alkaloid (A) through a linker (X) to
form bivalent opioid ligands A–X–A. The latter show
high selectivity in binding to receptors as compared
with monovalent ligands A–X. Studies are in progress
to transform semisynthetic alkaloid anhydrovinblasꢀ
tine [5], which differs from vinblastine by the modifiꢀ
cation of catharanthine unit and shows considerably
larger cytotoxicity in human lung tumor cells Hꢀ460
and antitumor activity against certain kinds of carciꢀ
noma in animals [6]. The promise of hybrid molecules
containing fragments of natural alkaloids as leader
compounds for the development of pharmacologically
valuable agents has been discussed [7].
(
2
4
–6
3
phenacetyl bromide, 4ꢀmethoxyphenacetyl bromide,
or 3,4ꢀdichlorophenacetyl bromide were subjected to
1,3ꢀdipolar cycloaddition with dimethyl acetylenediꢀ
carboxylate in the presence of triethylamine. The
reaction leads to compounds
(Scheme 1).
7–9 in 50–55% yield
The composition and structure of compounds 7–9
were confirmed by elemental analysis data and IR,
UV, and NMR spectra. The compounds show UV
spectra typical for indolizines conjugated with benꢀ
zene ring. For example, the spectrum of compound
shows absorption bands with maxima at 234, 250, 300,
and 384 nm. The configuration of the linking double
bond in indolizinolappaconitines was established
7
E
Lappaconitine (1) used as hydrobromide as antiarꢀ
7–9
rhythmic remedy [8] is one of promising alkaloids for
synthetic transformations. The modification of lappaꢀ
conitine molecule led to an increase in antiarrhythmic
activity [9, 10].
by 1H NMR data. The protons of the double bond (Hꢀ
1a, Hꢀ1b) show resonances as doublets with spin–spin
coupling constant of 15–17 Hz. A characteristic feaꢀ
ture of the 1H NMR spectra of these compounds is the
downfield shift of the signals of the Hꢀ1b proton (for
In this paper, we describe the synthesis of hybrid
alkaloids containing lappaconitine and indolizine
fragments. It should be noted that substituted indolizꢀ
ines behave as agonists of neuronal acetylcholine
receptors (NꢀAChRs) and are good candidates for
example, for compound
with its position in the spectrum of pyridineꢀsubstiꢀ
tuted lappaconitine derivative 6.99 ppm).
7
δ
7.53 ppm) as compared
3
(
δ
Thus, in this work we obtained hybrid molecules
containing fragments of diterpene and indolizine
alkaloids interesting as biologically active comꢀ
pounds.
Vorozhtsov Institute of Organic Chemistry, Siberian Branch,
Russian Academy of Sciences, pr. Lavrent’eva 9, Novosibirsk,
630090 Russia
27

28
ROMANOV et al.
13
OCH3
OCH3
16
OCH3
12
OCH3
OCH3
17
HO
HO
9
14
1
1
OCH3
15
1) 10% H SO ,
2 4
21
11
8
N
N
2) ICl, AcOH,
5
3
22
3) Ac O
2
OH
OH
7
19
O
O
7'
C
C
O
O
1'
2'
5'
5'
AcNH
AcHN
I
AcHN
AcNH
1
2
OCH3
OCH3
OCH3
OCH3
OCH3
H3CO
HO
O
HO
O
H3C
N
O
H3C
N
CH2
H
O
OH
CH2
OH
Br
N
H3C
2''
Ar
O
Pd(dba) , P(o-Tol) , Et N, DMF
2
3
3
C
+
C
1'
1''
C
5''
N
O
5'
C
H
C
2'
–
Br
NHAc
NHAc
H
H3C
C
R2
N
H
3
R1
4–6
OCH3
OCH3
OCH3
HO
O
H3C
N
O
CH2
OH
7''
6''
CO Me
CO Et
2
2
H
5''
8''
C
1a
1'
C t,e,Et N
COO2EM E3t N
2 3
H3C
O
4''
C
C
5'
6'''
5'''
9''
1b
R1 = R2 = H (4, 7);
N
H
2'
NHAc
R1 = OCH , R2 = H (5, 8);
2
CO2CH3
R1
3''
1''
1'''
R
3
4'''
2''
R1 = R2 = Cl (6, 9).
3'''
H3CO2C
1
R2
R
7–9
Scheme 1.
EXPERIMENTAL
of standard Bruker software. IR spectra were recorded
on a VECTORꢀ22 spectrophotometer as KBr pellets.
Melting points were determined with a Kofler hotꢀ
stage apparatus. UV absorption spectra were recorded
on a HP 8453 UV/Vis spectrophotometer in ethanol
solutions.
1H and 13C NMR spectra were recorded on a
Bruker AVꢀ300 spectrometer operating at 300.13 and
75.47 MHz, respectively, in CDCl3 solutions. Signal
multiplicity in 13C NMR spectra was determined by
standard procedures in the
(JMOD). The 2D NMR 1H–1H (COSY) and 13C–1H
(COSY 125 Hz, COLOC 7 Hz) spectra of the comꢀ
Jꢀmodulation mode
1
Signal assignment of hydrogen atoms in H NMR
spectra and carbon atoms in 13C NMR spectra was
made by comparison with the corresponding spectra
J
J
pounds were obtained on a Bruker DRXꢀ500 specꢀ
1
trometer operating at 500.13 and 125.76 MHz for H
of lappaconitine (
difficult to assign all signals in the NMR spectra of
1) [14] as a key compound. since it is
and 13C, respectively, in CDCl3 solutions with the use
DOKLADY CHEMISTRY Vol. 430
Part 1
2010

SYNTHESIS OF HYBRID COMPOUNDS
29
compounds
We failed to obtain H and 13C NMR spectra of salts
of quality acceptable for assignment because of
7–9, only characteristic signals are given. 1086, 1147, 1219, 1270, 1376, 1412, 1450, 1515, 1587,
1
1692, 2822, 2928, 3401.
4–6
For C48H54Cl2BrN3O9 anal. calcd. (%): N, 4.73; Cl
7.99.
low solubility of the salts.
The reaction course and purity of the obtained
compounds was monitored by TLC on Silufol UVꢀ254
plates using the chloroform–ethanol (20 : 1) system.
Found (%): N, 4.84; Cl 8.88.
General procedure for the preparation of comꢀ
pounds 7–9. A solution of 0.22 mmol of dimethyl
acetylenedicarboxylate and 0.5 mL of triethylamine in
10 mL of methylene chloride was added dropwise to a
solution of 0.2 mmol of appropriate pyridinium salt
4–6) in 10 mL of dry methylene chloride over 10 min.
The resulting dark red solution was stirred for 1 h at
ambient temperature, treated with aqueous ammonia
Silica gel precoated with 1% of Kꢀ35 fluorescent
indicator was used as a looseꢀlayer sorbent for preparꢀ
ative TLC. The plate size was 30 30 cm with 2ꢀmmꢀ
×
(
thick sorbent layer.
General procedure for the preparation of pyridinium
salts (4–6). A solution of 355 mg (0.5 mmol) of comꢀ
to pH
centrated sulfuric acid to pH
10 min, aqueous ammonia was added again to pH
~
11 and stirred for 10 min, treated with conꢀ
pound
3 and 0.55 mmol of appropriate phenacetyl
~
3 and stirred for
bromide in 20 mL of dry acetone was stirred at ambiꢀ
ent temperature for 48 h. The resulting precipitate was
filtered off, washed with dry acetone, and dried in air
to constant weight.
~
11. The organic layer was separated and dried with
MgSO4. The solvent was removed, the residue was
chromatographed on a SiO2 plate (chloroform–ethaꢀ
nol as eluent), and the yellowꢀorange zone showing
intense fluorescence in UV light was collected. The
substance was extracted with ethanol. The solvent was
removed, and the residue as a brown powder was dried
in vacuum to constant weight.
(
E
)ꢀ5''ꢀ{2'ꢀAcetamidoꢀ1'ꢀ[(8,9ꢀdihydroxyꢀ
1α
,14 ,16 ꢀtrimethoxyꢀ20ꢀethylaconitanꢀ4 ꢀyl)oxyꢀ
α
β
β
carbonyl]styrꢀ5'ꢀyl}ꢀ2''ꢀmethylꢀ1''ꢀ(2ꢀoxoꢀ2ꢀphenylꢀ
ethyl)pyridinium bromide (4). According to the general
procedure, the reaction of 351 mg (0.5 mmol) of comꢀ
pound
mide afforded 330 mg (73% yield) of compound
235–237 . IR (
, cm–1): 570, 689, 760, 784, 853,
970, 1040, 1083, 1129, 1206, 1231, 1300, 1371, 1410,
1450, 1523, 1588, 1631, 1694, 2046, 2842, 2938, 3411.
3
and 110 mg (0.5 mmol) of phenacetyl broꢀ
(
E
)ꢀ8''ꢀ{2'ꢀAcetamidoꢀ1'ꢀ[(8,9ꢀdihydroxyꢀ
4
, mp
1α
,14 ,16 ꢀtrimethoxyꢀ20ꢀethylaconitanꢀ4 ꢀyl)oxyꢀ
α
β
β
carbonyl]styrꢀ5'ꢀyl}ꢀ3''ꢀbenzoylꢀ1'',2''ꢀdimethoxycarꢀ
bonylꢀ5''ꢀmethylindolizin (7). According to the above
procedure, the reaction of 250 mg (0.28 mmol) of
°
С
ν
compound
ylenedicarboxylate gave 147 mg (55%) of compound
, mp 142–143 , ppm, , Hz):
. 1H NMR (CDCl3,
1.12 (t, 3H, Hꢀ22, = 2), 2.22 (s, 3H, CH3CO), 2.33
(s, 3H, CH3 at Cꢀ5''), 3.01 (s, 1H, Hꢀ17), 3.28 and
3.29 (both s, 6H, OCH3 at Cꢀ1 and Cꢀ14, respecꢀ
tively), 3.38 (m, 6H, OCH3 at Cꢀ16 and COOCH3 at
Cꢀ1'' or Cꢀ2''), 3.81 (s, 3H, COOCH3 at Cꢀ1'' or
4 and 44 mg (0.31 mmol) of dimethyl acetꢀ
For C48H56BrN3O9 anal. calcd. (%): N, 3.11.
Found (%): N, 2.80.
7
°
С
δ
J
J
(
E
)ꢀ5''ꢀ{2'ꢀAcetamidoꢀ1'ꢀ[(8,9ꢀdihydroxyꢀ
1
α
,14 ,16 ꢀtrimethoxyꢀ20ꢀethylaconitanꢀ4 ꢀyl)oxyꢀ
α
β
β
carbonyl]styrꢀ5'ꢀyl}ꢀ1''ꢀ[2ꢀ(4'''ꢀmethoxyphenyl)ꢀ2ꢀ
oxoethyl]ꢀ2''ꢀmethylpyridinium bromide (5). Accordꢀ
ing to the general procedure, the reaction of 701 mg
Cꢀ2''), 6.68 (d, 1H, Hꢀ6'',
= 17.0), 7.32 (d, 1H, Hꢀ7'',
Hꢀ3''', Hꢀ5'''), 7.53 (d, 1H, Hꢀ1b,
1H, Hꢀ4'''), 7.75 (dd, 1H, Hꢀ4',
J
= 8.0), 6.96 (d, 1H, Hꢀ1a,
= 8.0), 7.47 (m, 2H,
= 17.0), 7.55 (m,
= 7.5, 2.3), 7.89 (d,
= 8.2), 7.95 (d, 1H, Hꢀ6', = 2.3),
= 7.5), 11.07 (s, 1H, NH at Cꢀ2').
, ppm): 13.45 (Cꢀ22), 22.60
NHCOCH3), 24.07 (Cꢀ6), 25.49 (CH3 at Cꢀ5''),
(1 mmol) of compound
4ðmethoxyphenacetyl bromide afforded 654 mg (70%
yield) of compound , mp 216–217 . IR (
, cm–1):
3 and 252 mg (1.1 mmol) of
J
J
J
5
°
С
ν
J
567, 696, 790, 837, 970, 1023, 1082, 1128, 1173, 1206,
1240, 1369, 1422, 1460, 1514, 1600, 1630, 1685, 2822,
2930, 3410.
2H, Hꢀ2''', Hꢀ6''',
8.70 (d, 1H, Hꢀ3',
J
J
J
13C NMR (CDCl3,
δ
For C49H58BrN3O10 anal. calcd. (%): N, 3.01.
Found (%): N, 3.35.
(
25.80 (Cꢀ12), 26.70 (Cꢀ2), 31.75 (Cꢀ3), 36.19 (Cꢀ13),
44.67 (Cꢀ15), 47.51 (Cꢀ7), 47.87 (Cꢀ5), 48.91 (Cꢀ21),
49.78 (Cꢀ10), 50.90 (Cꢀ11), 51.78 (COOCH33 at Cꢀ1''
or Cꢀ2''), 52.65 (COOCH3 at Cꢀ1'' or Cꢀ2''), 55.44 (Cꢀ
19), 56.03 (OCH3 at Cꢀ16), 56.49 (OCH3 at Cꢀ1),
(6). 57.84 (OCH3 at Cꢀ14), 61.46 (Cꢀ17), 75.52 (Cꢀ8),
(E
)ꢀ5''ꢀ{2'ꢀAcetamidoꢀ1'ꢀ[(8,9ꢀdihydroxyꢀ
,14 ,16 ꢀtrimethoxyꢀ20ꢀethylaconitanꢀ4 ꢀyl)oxyꢀ
carbonyl]styrꢀ5'ꢀyl}ꢀ1''ꢀ[2ꢀ(3''',4'''ꢀdichlorophenyl)ꢀ
2ꢀoxoethyl]ꢀ2'''ꢀmethylpyridinium bromide
According to the general procedure, the reaction of
351 mg (0.5 mmol) of compound and 147 mg (0.55
mmol) of 2ꢀbromoꢀ3',4'ꢀdichloroacetophenone
afforded 337 mg (70% yield) of compound , mp 243–
245 . IR (
, cm–1): 556, 676, 751, 834, 966, 1032, 128.51 (Cꢀ7''), 129.61 (Cꢀ6'), 129.61 (Cꢀ3''', Cꢀ5'''),
1α
α
β
β
78.47 (Cꢀ9), 82.78 (Cꢀ16), 83.11 (Cꢀ1), 84.95 (Cꢀ4),
90.01 (Cꢀ14), 107.33 (Cꢀ1''), 115.88 (Cꢀ1'), 115.92
(Cꢀ1a), 120.61 and 121.02 (Cꢀ3', Cꢀ6''), 132.53
(Cꢀ3''), 123.97 (Cꢀ1b), 126.18 (Cꢀ5'), 128.31 (Cꢀ8''),
3
6
°
С
ν
DOKLADY CHEMISTRY Vol. 430
Part 1
2010

30
ROMANOV et al.
130.18 (Cꢀ2''', Cꢀ6'''), 130.18 (Cꢀ4'''), 131.21 (Cꢀ2''), nol, λmax, nm (logε): 229 (4.55), 252 (4.29), 301
133.17 (Cꢀ1'''), 133.32 (Cꢀ4'), 135.30 (Cꢀ9''), 138.68
(Cꢀ5''), 141.14 (Cꢀ2'), 163.48 (COOCH3 at Cꢀ1'' or Cꢀ
(4.50), 382 (4.04).
For C55H61N3O14
·
CHCl3 anal. calcd. (%): C,
2''), 164.06 (COOCH3 at Cꢀ1'' or Cꢀ2''), 166.25 (Cꢀ
3
60.67; H, 5.60; N, 3.79.
Found (%): C, 60.21; H, 6.00; N, 3.93.
)ꢀ8''ꢀ{2'ꢀAcetamidoꢀ1'ꢀ[(8,9ꢀdihydroxyꢀ
,16 ꢀtrimethoxyꢀ20ꢀethylaconitanꢀ4 ꢀyl)oxyꢀ
7'), 167.13 (NHCOCH3), 188.11 (CO at Cꢀ3''). IR ( ,
ν
cm–1): 650, 696, 727, 754, 789, 839, 892, 914, 967,
1000, 1035, 1086, 1100, 1120, 1147, 1231, 1377, 1515,
1588, 1620, 1690, 1703, 1710, 2928, 2932, 3401.
(
E
1α
,14
α
β
β
carbonyl]styrꢀ5'ꢀyl}ꢀ3''ꢀ(3''',4'''ꢀdichlorobenzoyl)ꢀ
1'',2''ꢀdimethoxycarbonylꢀ5''ꢀmethylindolizin (9). The
UV (ethanol, λmax, nm (logε): 234 (4.40), 250
(4.40), 300 (4.21), 384 (3.88).
reaction of 550 mg (0.59 mmol) of compound
6 and
92 mg (0.65 mmol) of dimethyl acetylenedicarboxyꢀ
late gave 297 mg (52%) of compound , mp 155–
157 , ppm, , Hz): 1.12 (t, 3H,
C. 1H NMR (CDCl3
Hꢀ22, = 2), 2.23 (s, 3H, CH3СО), 2.30 (s, 3H, СН3
9
For C54H59N3O13
· CHCl3 anal. calcd. (%): C,
°
,
δ
J
61.25; H, 5.38; N, 3.90.
J
Found (%): C, 61.10; H, 5.77; N, 3.45.
)ꢀ8''ꢀ{2'ꢀAcetamidoꢀ1'ꢀ[(8,9ꢀdihydroxyꢀ
,14 ,16 ꢀtrimethoxyꢀ20ꢀethylaconitanꢀ4 ꢀyl)oxyꢀ
carbonyl]styrꢀ5'ꢀyl}ꢀ3''ꢀ(4'''ꢀmethoxybenzoyl)ꢀ1'',2''ꢀ
at Cꢀ5''), 3.00 (s, 1H, Hꢀ17), 3.28 and 3.29 (both s,
6H, OCH3 at Cꢀ1 and Cꢀ14, respectively), 3.39 (s, 3H,
OCH3 at Cꢀ16), 3.51 (s, 3H, COOCH3 at Cꢀ1'' or Cꢀ
2''), 3.82 (s, 3H, COOCH3 at Cꢀ1'' or Cꢀ2''), 6.72 (d,
(E
1α
α
β
β
1H, Hꢀ6'',
(d, 1H, Hꢀ7'',
7.54 (d, 1H, Hꢀ5''',
7.2, 2.2), 7.74 (dd, 1H, Hꢀ4',
J
= 6.8), 6.97 (d, 1H, Hꢀ1a,
= 8.0), 7.53 (d, 1H, Hꢀb,
= 7.2), 7.71 (dd, 1H, Hꢀ6''',
= 7.8, 2.0), 7.95 (d,
= 2.0), 8.03 (1H, Hꢀ2''', = 2.2), 8.71 (d,
= 7.8), 11.07 (s, 1H, NH at Cꢀ2'). 13C
, ppm): 13.37 (Cꢀ22), 22.67
H3), 23.99 (Cꢀ6), 25.17 (CH3 at Cꢀ5''),
J
= 16.0), 7.35
dimethoxycarbonylꢀ5''ꢀmethylindolizin (8). The reacꢀ
J
J
= 16.0),
tion of 550 mg (0.59 mmol) of compound
(0.65 mmol) of dimethyl acetylenedicarboxylate gave
5
and 92 mg
J
J =
J
1
297 mg (55%) of compound
8
, mp 155–157
°
С. H
1H, Hꢀ6',
1H, Hꢀ3',
J
J
J
NMR (CDCl3, , ppm, , Hz): 1.11 (t, 3H, Hꢀ22, J =
δ
J
2), 2.22 (s, 3H, CH3СО), 2.32 (s, 3H, СН3 at Cꢀ5''),
3.00 (s, 1H, Hꢀ17), 3.28 and 3.29 (both s, 6H, OCH3
at Cꢀ1 and Cꢀ14, respectively), 3.38 (s, 3H, OCH3 at
Cꢀ16), 3.44 (s, 3H, OCH3 at COOCH3 at Cꢀ1'' or Cꢀ
2''), 3.81 (s, 3H, COOCH3 at Cꢀ1'' or Cꢀ2''), 3.85 (s,
NMR (CDCl3,
(NHCO
δ
C
25.42 (Cꢀ12), 26.62 (Cꢀ2), 31.69 (Cꢀ3), 36.10 (Cꢀ13),
44.63 (Cꢀ15), 47.41 (Cꢀ7), 48.25 (Cꢀ5), 48.83 (Cꢀ21),
49.69 (Cꢀ10), 50.82 (Cꢀ11), 51.99 (COO
CH3 at Cꢀ1''
3H, OCH3 at Cꢀ4'''), 6.62 (d, 1H, Hꢀ6'',
(d, 2H, Hꢀ3''', Hꢀ5''', = 7.2), 6.96 (d, 1H, Hꢀa,
16.1), 7.26 (d, 1H, Hꢀ7'', = 7.4), 7.53 (d, 1H, Hꢀb,
= 16.1), 7.74 (dd, 1H, Hꢀ4', = 7.0, 2.0), 7.84 (d,
= 7.2), 7.94 (d, 1H, Hꢀ6', = 2.0),
= 7.0), 11.06 (s, 1H, NH at Cꢀ2').
, ppm): 13.45 (Cꢀ22), 22.19
NHCOCH3), 24.11 (Cꢀ6), 25.46 (CH3 at Cꢀ5''),
J = 7.4), 6.92
or Cꢀ2''), 52.66 (COO H3 at Cꢀ1'' or Cꢀ2''), 55.35 (Cꢀ
C
J
J =
19), 55.95 (OCH3 at Cꢀ16), 56.41 (OCH3 at Cꢀ1),
57.76 (OCH3 at Cꢀ14), 61.38 (Cꢀ17), 75.46 (Cꢀ8),
78.38 (Cꢀ9), 82.70 (Cꢀ16), 83.96 (Cꢀ1), 84.89 (Cꢀ4),
89.93 (Cꢀ14), 107.60 (Cꢀ1''), 115.80 (Cꢀ1'), 116.29
(Cꢀ1a), 120.54 (Cꢀ3'), 121.36 (Cꢀ6''), 122.62 (Cꢀ2''),
123.56 (Cꢀ1b), 124.01 (Cꢀ5'''), 128.42 (Cꢀ8''), 128.56
(Cꢀ7''), 129.90 (Cꢀ6'), 130.45 (Cꢀ6'''), 130.53 (Cꢀ3'''),
130.99 (Cꢀ5'), 131.00 (Cꢀ4'), 131.13 (Cꢀ2'''), 133.17
(Cꢀ3'''), 133.45 (Cꢀ1'''), 135.11 (Cꢀ9''), 137.80 (Cꢀ4'''),
J
J
J
2H, Hꢀ2''', Hꢀ6''',
8.70 (d, 1H, Hꢀ3',
13C NMR (CDCl3
J
J
J
,
δ
(
26.17 (Cꢀ12), 26.75 (Cꢀ2), 31.84 (Cꢀ3), 36.31 (Cꢀ13),
44.70 (Cꢀ15), 47.60 (Cꢀ7), 48.33 (Cꢀ5), 48.88 (Cꢀ21),
49.86 (Cꢀ10), 50.98 (Cꢀ11), 51.81 (COOCH3 at Cꢀ1''
or Cꢀ2''), 52.60 (COOCH3 at Cꢀ1'' or Cꢀ2''), 55.46
138.19 (Cꢀ5''), 141.15 (Cꢀ2'), 163.82 (
Cꢀ1''), 163.82 ( OOCH3 at Cꢀ2''), 167.02 (Cꢀ7'),
168.84 (NH OCH3), 185.29 (CO at Cꢀ3'').
COOCH3 at
C
(
ОCН3 at Cꢀ4'''), 55.51 (Cꢀ19), 56.03 (ОCН3 at
C
Cꢀ16), 56.43 (ОCН3 at Cꢀ1), 57.84 (ОCН3 at Cꢀ14),
61.41 (Cꢀ17), 75.53 (Cꢀ8), 78.50 (Cꢀ9), 82.85 (Cꢀ16),
83.10 (Cꢀ1), 85.02 (Cꢀ4), 90.08 (Cꢀ14), 107.27 (Cꢀ
1''), 113.82 (Cꢀ1a), 115.54 (Cꢀ6''), 115.97 (Cꢀ1'),
120.50 (Cꢀ7''), 120.64 (Cꢀ3'), 122.40 (Cꢀ2''), 124.06
(Cꢀ1b), 128.34 (Cꢀ8''), 129.01 (Cꢀ5'), 129.91 (Cꢀ6'),
130.14 (Cꢀ3''', Cꢀ5'''), 131.25 (Cꢀ4'), 131.30 (Cꢀ3''),
131.96 (Cꢀ2''', Cꢀ6'''), 132.17 (Cꢀ1'''), 132.70 (Cꢀ9''),
135.11 (Cꢀ5''), 141.14 (Cꢀ2'), 163.80 (COOCH3 at
Cꢀ1''), 163.80 (COOCH3 at Cꢀ2''), 166.46 (Cꢀ4'''),
167.15 (Cꢀ7'), 168.84 (NHCOCH3), 187.27 (CO at
IR (
, cm–1): 676, 751, 966, 1031, 1086, 1106,
1127, 1147, 1219, 1270, 1290, 1376, 1515, 1550, 1587,
1598, 1623, 1692, 1700, 2928, 3401.
ν
UV (ethanol, λmax, nm (log ): 225 (4.42), 257
ε
(4.30), 305 (4.14), 405 (3.62).
For C54H57ClN3O13 · CHCl3 anal. calcd. (%): C,
57.70; H, 5.19; N, 3.67; Cl, 15.52.
Found (%): C, 58.07; H, 5.55; N, 3.92; Cl, 15.31.
ACKNOWLEDGMENTS
Cꢀ3''). IR (
ν
, cm–1): 649, 755, 789, 838, 892, 916, 967,
1031, 1086, 1115, 1167, 1239, 1379, 1513, 1550, 1597,
This work was supported by the Russian Foundaꢀ
1620, 1630, 1690, 1710, 1723, 2928, 3437. UV (ethaꢀ tion for Basic Research (project no. 08–03–00340).
DOKLADY CHEMISTRY Vol. 430
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SYNTHESIS OF HYBRID COMPOUNDS
31
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DOKLADY CHEMISTRY Vol. 430
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