Cationic β-cyclodextrin derivatives containing 2-(4-isobutylphenyl)- and 2-(3-benzoylphenyl)propionic acid residues

Article abstract of DOI:10.1007/s11172-019-2497-0

Cationic β-cyclodextrin derivatives containing residues of pharmacologically important acids linked by spacers of different lengths were obtained by treatment of mono-6-iodo-6-deoxy- and mono-6-tosyl-β-cyclodextrin with nucleophilic agents with terminal m

Full text of DOI:10.1007/s11172-019-2497-0

Russian Chemical Bulletin, International Edition, Vol. 68, No. 4, pp. 862—866, April, 2019
862
Cationic β-cyclodextrin derivatives containing
2-(4-isobutylphenyl)- and 2-(3-benzoylphenyl)propionic acid residues*
D. A. Shipilov,а M. A. Malenkovskaya,а N. V. Kutyasheva,а G. I. Kurochkina,а
A. A. Sergievich,b and M. K. Grachevа
аMoscow State University of Education, Institute of Biology and Chemistry,
6/2 ul. Kibalchicha, 129164 Moscow, Russian Federation.
Е-mail: shda90@mail.ru
bFar-Eastern Federal University,
8 ul. Sukhanova, 690950 Vladivostok, Russian Federation
Cationic -cyclodextrin derivatives containing residues of pharmacologically important
acids linked by spacers of different lengths were obtained by treatment of mono-6-iodo-6-deoxy-
and mono-6-tosyl--cyclodextrin with nucleophilic agents with terminal mono- and dimethyl-
amino groups.
1
Key words: -cyclodextrin, cationic derivatives, regiodirected functionalization, H and
13С NMR spectroscopy.
One of the most important problems of medicinal
phine in aqueous ammonia to obtain amino derivatives.6,7
However, this method has limitations since it is applicable
only for the production of primary alkylammonium de-
rivatives of cyclodextrins.
In addition, it is known that for the cyclodextrin-based
structures, the efficiency of drug delivery in biological
systems can be enhanced by the regulation of the spacer
length linking cyclodextrin and the drug residue via bet-
ter incorporation into the lipid matrix (the so-called
"membrane anchor"), which causes its smaller structural
changes.8,9
Earlier, we investigated the synthesis of -cyclodextrin
cationic compounds based on its per-, oligo-, and mono-
halodeoxy10 and tosyl11,12 derivatives. But, in contrast to
the traditional alkylation of amines with alkyl halides, the
hydrophobic cyclodextrin cavity has a specific (supra-
molecular) effect on the course of alkylation, which re-
quires an individual approach to the synthesis of cationic
-cyclodextrin derivatives. Below are the structural for-
mulas of monoiododeoxy (1) and monotosyl -cyclo-
dextrin (2).
The purpose of the present work is the synthesis of
monoiododeoxy (1) and monotosyl (2) -cyclodextrin-
based cationic derivatives containing residues of some
pharmacologically important acids, namely, 2-(4-iso-
butylphenyl)propionic acid (HO—Y) (an active ingredient
of Ibuprofen) and 2-(3-benzoylphenyl)propionic acid
(HO—Z) (an active ingredient of Ketoprofen). Note that
the drug moieties are linked to the cationic fragment by
the above-mentioned spacers, among which we selected
the residues of 2-(dimethylamino)ethanol (3), 3-(di-
chemistry is the low solubility and bioavailability of
pharmaceutical compounds.1 Cyclodextrins, natural and
readily available cyclic oligosaccharides, have long firmly
occupied their niche in medicine, food technology, ana-
lytical chemistry, and biotechnology.2 Among the plethora
of -cyclodextrin compounds, its cationic derivatives car-
rying a positive charge on the cyclodextrin matrix have
found wide application in pharmacology due to their in-
creased water solubility and other practically important
properties. Such alkylammonium ("charged") amphiphilic
cyclodextrins can be embedded and penetrate biological
barriers and also serve as carriers for the delivery ("vector-
ization") of DNA in gene therapy.3 Such amphiphilic
cationic cyclodextrins as heptakis-[2-(-aminooligoethyl-
ene glycol)-6-deoxy-6-hexylthio]--cyclodextrin and
heptakis-[2-(-aminooligoethylene glycol)-6-deoxy-6-
hexadecylthio]--cyclodextrin were assessed for plasmid
DNA condensation and cell transfection.4 These deriva-
tives can self-organize into cationic vesicles or nanopar-
ticles and, unlike their amphiphilic non-aminated analogs,
form lipoplexes with DNA, which efficiently transfect
COS-7 cells.
The cationic derivatives most often are synthesized by
the addition of various quaternary ammonium, phos-
phonium, and sulfonium salts5 or by treatment of cyclo-
dextrin 6-azido-6-deoxy derivatives with triphenylphos-
* Based on the materials of the V All-Russian Organic Chemistry
Conference (ROCC-V) (September 10—14, 2018, Vladikavkaz,
Russia).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0862—0866, April, 2019.
1066-5285/19/6804-0862 © 2019 Springer Science+Business Media, Inc.

Cationic -cyclodextrin derivatives
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 4, April, 2019
863
X = I (1), Ts (2)
methylamino)propan-1-ol (4), and 2-(methylamino)-
ethanol (5). Earlier, we have shown the principal possibil-
ity of obtaining such cationic derivatives.10 The advantage
of the proposed approach is the absence of the necessity
of protection of secondary hydroxyls and subsequent re-
moval of protective groups, so that the "wide" part of the
cyclodextrin framework remains free to accept various
guests, including those with other biological action, which
broadens the pharmacological possibilities of such struc-
tures. The starting mono derivatives 1 and 2 were obtained
according to the improved by us procedure.13 Nucleophilic
agents 7—11 to be alkylated with halogen 1 and tosyl 2
derivatives were obtained by treatment of the correspond-
ing dimethylaminoalcohol 3 or 4 or sodium methyl-
aminoethoxide 6 with the corresponding acyl chloride
Cl—Y(Z) (Scheme 1).
(Scheme 2). The corresponding cationic -cyclodextrin
derivatives 12—16 containing the residues of the mentioned
pharmacologically important acids linked with spacers of
different lengths (n = 2, 3) were isolated in 32—52% yields
(see Experimental).
The structure and purity of compounds 7—16 were
confirmed by NMR spectroscopy, TLC, and elemental
analysis. Additionally, to integrate the signals of carbon
nuclei, 13C NMR spectra of compounds 7—16 were re-
corded with a long delay between pulses (8 s). The
13C NMR spectra of compounds 12—16 exhibit signals for
unsubstituted C(6) atoms at C 57.5—64.5 and characteristic
weak signals for C(6´) carbon atoms bearing an N sub-
stituent at C 57.5—64.5 (see Experimental). The correct-
ness of the signal assignment was further confirmed by the
analysis of 2D NMR spectra of homo- (HOMOCOR
{1Н—1Н}) and heteronuclear (HETCOR {1Н—13С}) cor-
relations, recording the DEPT spectrum of the solution, and
also recording the spectrum of the solution at 20 and 80 C
for reliable assignment of signals for hydroxyl protons.
Dimethylaminoalkyl ethers 7—10 were alkylated with
iodo derivative 1 in DMF solution at 100—110 С for 30 h,
while the substitution of tosyl derivative 2 with ether 11
having an N-methyl group was carried out at 80 С for 6 h
Scheme 1
R = Y (7, 8), Z (9, 10)
n = 2 (3, 7, 9), 3 (4, 8, 10)

864
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 4, April, 2019
Shipilov et al.
Scheme 2
X = I (1), Ts (2)
Compound
7, 12
R´
Me
Me
Me
Me
n
2
3
2
3
2
R
Y
Y
Z
Z
Y
Hal
I
I
I
I
—
8, 13
9, 14
10, 15
11 , 16
H, Me
Compounds 8—10 were obtained similarly.
3-(Dimethylamino)propyl (RS)-2-(4-isobutylphenyl)pro-
In conclusion, we investigated new possibilities for the
synthesis of cationic -cyclodextrin derivatives containing
covalently bonded residues of specified pharmacologically
important acids, which are of interest to biomedical re-
search in different directions.
pionate (8) was obtained from (RS)-2-(4-isobutylphenyl)pro-
pionyl chloride (5.00 g, 22.25 mmol) and 3-(dimethylamino)-
propan-1-ol (4) (2.90 g, 22.25 mmol). The yield was 5.51 g (85%),
m.p. 110—112 C, Rf = 0.40 (А). 1H NMR, : 0.80 (d, 6 H,
CH(CH3)2, J = 6.5 Hz); 1.31 (d, 3 H, CHCH3, J = 7.1 Hz); 1.62
(m, 2 H, NCH2CH2); 1.75 (m, 1 H, CHMe2); 2.10 (s, 6 H,
NMe2); 2.20 (t, 2 H, NCH2); 2.37 (d, 2 H, CHCH2, J = 7.3 Hz);
3.72 (q, 1 H, CHC(O), J = 7.1 Hz); 4.07 (t, 2 H, CH2O, J = 5.7 Hz);
7.04 (d, 2 H, m-H, J = 7.9 Hz); 7.14 (d, 2 H, o-H, J = 7.9 Hz).
13C NMR, : 19.1 (CHCH3), 22.7 (CH(CH3)2), 25.9
(NCH2CH2), 30.2 (CHMe2), 40.0 (CHC(O)), 44.7 (CHCH2),
46.3 (NMe2), 55.3 (NCH2), 62.7 (OCH2), 127.6 (m-C), 129.3
(o-C), 138.5 (ipso-C), 140.3 (p-C), 174.4 (C=O). Found (%):
C, 74.53; H, 6.86; N, 5.01. C18H29NO2. Calculated (%): C, 74.18;
H, 7.03; N, 4.81.
Experimental
1Н and 13C NMR spectra were recorded on a JEOL ECX-400
spectrometer (399.78 and 100.53 МHz, respectively) in DMSO-d6,
with 1Н and 13C chemical shifts being reported relative to SiMe4.
Elemental analysis was performed on a FlashEA 1112HT ana-
lyzer. Thin-layer chromatography was carried out aluminum
plates precoated with silica gel (Silufol UV-254), eluents: benz-
ene—dioxane, 3 : 1 (А), n-butanol—ethanol—water, 5 : 4 : 3 (B).
-Cyclodextrin was purchased from Wacker (USA).
2-(Dimethylamino)ethyl (RS)-2-(3-benzoylphenyl)propionate
(9) was obtained from (RS)-2-(3-benzoylphenyl)propionyl chlor-
ide (5.00 g, 18.33 mmol) and 2-(dimethylamino)ethanol (3) (1.63 g,
18.33 mmol). The yield was 5.93 g (82%), m.p. 100—102 C
2-(Dimethylamino)ethyl (RS)-2-(4-isobutylphenyl)propionate
(7). 2-(Dimethylamino)ethanol (3) (1.98 g, 22.25 mmol) in
benzene (25 mL) was added dropwise to a solution of (RS)-2-
(4-isobutylphenyl)propionyl chloride (5.00 g, 22.25 mmol) in
benzene (10 mL) with stirring. After stirring at 20 С for 3 h,
benzene (30 mL) was added and the stirring was continued for
24 h at 20 С. Then, saturated aqueous NaHCO3 (10 mL) was
added to the reaction mixture with stirring, the benzene layer was
separated, dried with СaCl2, the solvent was evaporated, the
residue was evacuated (1 Torr) at 60 С for 5 h. The yield was
1
(decomp.), Rf = 0.45 (А). H NMR, : 1.35 (d, 3 H, CHCH3,
J = 7.0 Hz); 2.10 (s, 6 H, NMe2); 3.33 (t, 2 H, NCH2); 3.77
(m, 1 Н, СНСН3); 4.08 (t, 2 H, CH2O, J = 5.6 Hz); 7.53—7.68
(m, 9 H, Ar). 13C NMR, : 19.0 (CHCH3), 45.0 (CHMe),
45.3 (NMe2), 57.2 (NCH2), 62.2 (OCH2), 128.8—133.3
(Ar), 175.6 (CHC=O), 195.9 (PhC=O). Found (%): C, 74.02;
H, 7.06; N, 4.21. C20H23NO3. Calculated (%): C, 73.82; H, 7.12;
N, 4.30.
1
5.18 g (84%), m.p. 80—82 С, Rf = 0.45 (А). H NMR, : 0.81
(d, 6 H, CH(CH3)2, J = 6.4 Hz); 1.31 (d, 3 H, CHCH3, J = 7.0 Hz);
1.75 (m, 1 H, CHMe2); 2.09 (s, 6 H, NMe2); 2.36 (d, 2 H,
CHCH2, J = 7.3 Hz); 3.33 (t, 2 H, NCH2); 3.72 (q, 1 H, CHC(O),
J = 7.1 Hz); 4.07 (t, 2 H, CH2O, J = 5.6 Hz); 7.04 (d, 2 H, m-H,
J = 7.8 Hz), 7.14 (d, 2 H, o-H, J = 8.0 Hz). 13C NMR, : 19.2
(CHCH3), 22.7 (CH(CH3)2), 30.1 (CHMe2), 40.0 (CHC(O)),
44.6 (CHCH2), 45.3 (NMe2), 57.2 (NCH2), 62.2 (OCH2), 127.6
(m-C), 129.4 (o-C), 138.5 (ipso-C), 140.3 (p-C), 174.3 (C=O).
Found (%): C, 74.02; H, 9.56; N, 5.23. C17H27NO2. Calculat-
ed (%): C, 73.61; H, 9.81; N, 5.05.
3-(Dimethylamino)propyl (RS)-2-(3-benzoylphenyl)propionate
(10) was obtained from (RS)-2-(3-benzoylphenyl)propionyl
chloride (5.00 g, 18.33 mmol) and 3-(dimethylamino)propan-
1-ol 4 (2.39 g, 18.33 mmol). The yield was 6.27 g (83%), m.p.
1
123—125 C, Rf = 40 (А). H NMR, : 1.35 (d, 3 H, CHCH3,
J = 7.0 Hz); 1.62 (m, NCH2CH2); 2.10 (s, 6 H, NMe2); 2.20
(t, 2 H, NCH2); 3.77 (m, 1 Н, СНMe); 4.06 (t, 2 H, CH2O,
J = 5.6 Hz); 7.53—7.68 (m, 9 H, Ar). 13C NMR, : 19.0 (CHCH3),
25.9 (NCH2CH2), 45.0 (CHMe), 46.3 (NMe2), 55.3 (NCH2),
62.6 (OCH2), 128.8—133.3 (Ar), 175.6 (CHC=O), 195.9 (PhC=O).

Cationic -cyclodextrin derivatives
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 4, April, 2019
865
Found (%): C, 74.18; H, 7.49; N, 4.18. C21H25NO3. Calculated (%):
C, 74.31; H, 7.42; N, 4.13.
(CH(CH3)2), 26.0 (NCH2CH2), 30.1 (CHMe2), 40.0 (CHC(O)),
44.3—45.1 (NMe2, CHCH2), 55.4 (NCH2), 60.4 (C(6)), 62.7
(OCH2), 64.5 (C(6´)), 72.5—73.6 (C(5), C(2), C(3)), 82.0 (C(4)),
102.5 (C(1)), 127.6 (m-C), 129.6 (o-C), 138.5 (ipso-C), 140.3
(pC), 174.4 (C=O). Found (%): C, 47.04; H, 6.39; N, 0.89.
C60H98INO36. Calculated (%): C, 46.91; H, 6.43; N, 0.91.
6-[{2-[2-(3-(Benzoylphenyl)propionyloxy]ethyl}(dimethyl)-
ammonio]-6-deoxy--cyclodextrin iodide (14) was obtained from
-cyclodextrin iodo derivative 1 (1.00 g, 0.80 mmol) and ether 9
(1.30 g, 4.00 mmol). The yield was 0.59 g (47%), m.p. 246—248 C
(with decomp.), Rf = 0.45 (А). 1H NMR, : 1.35 (d, 3 H, CHCH3,
J = 7.0 Hz); 2.10 (s, 6 H, NMe2); 3.23—3.61 (m, 44 H, С(2)
H—С(5)H, C(6)H2, NCH2); 3.79 (m, 1 Н, СНMe); 4.08 (t, 2 H,
CH2O, J = 5.6 Hz); 4.47 (br.s, 6 H, C(6)OH); 4.79 (br.s, 7 H,
C(1)H); 5.71 (br.s, 14 H, C(2)OH, C(3)OH); 7.53—7.68 (m, 9 H,
Ar). 13C NMR, : 19.0 (CHCH3), 45.0 (CHMe), 45.3 (NMe2),
57.2 (NCH2), 60.4 (C(6)), 62.2 (OCH2), 64.5 (C(6´)), 72.5—73.6
(C(5), C(2), C(3)), 82.0 (C(4)), 102.5 (C(1)), 128.8—133.3 (Ar),
175.6 (CHC=O), 195.9 (PhC=O). Found (%): C, 47.53; H, 5.85;
N, 0.92. C62H92INO37. Calculated (%): C, 47.42; H, 5.91; N, 0.89.
6-[{3-[2-(3-(Benzoylphenyl)propionyloxy]propyl}(dimethyl)-
ammonio]-6-deoxy--cyclodextrin iodide (15) was obtained from
-cyclodextrin iodo derivative 1 (1.00 g, 0.80 mmol) and ether
10 (1.36 g, 4.00 mmol). The yield was 0.57 g (45%), m.p.
2-(Methylamino)ethyl (RS)-2-(4-isobutylphenyl)propionate
(11). Sodium hydride (1.07 g, 44.50 mmol) was added to a solu-
tion of 2-(methylamino)ethanol 6 (1.67 g, 22.25 mmol) in DMF
(30 mL) with stirring. The solution was stirred at 20 С for 1 h,
methanol (30 mL) was added and the stirring was continued for
1 h at 20 С. A precipitate formed was filtered off, (RS)-2-(4-
isobutylphenyl)propionyl chloride (5.00 g, 22.25 mmol) in
benzene (30 mL) was added dropwise to the filtrate. After 24 h,
a precipitate was filtered off, the filtrate was concentrated to 2 mL
and diluted with diethyl ether (10 mL). An oil formed was dis-
solved in benzene (5 mL), the solvent was evaporated, the residue
was evacuated (1 Torr) at 60 С for 5 h. The yield was 1.64 g
(28%), m.p. 78—80 С (decomp.), Rf = 0.40 (А). 1H NMR,
: 0.81 (d, 6 H, CH(CH3)2, J = 6.9 Hz); 1.27 (d, 3 H, CHCH3,
J = 6.5 Hz); 1.75 (m, 1 H, CHMe2); 2.36 (d, 2 H, CHCH2,
J = 7.3 Hz); 2.73 (m, 2 H, NCH2); 3.49 (m, 3 H, NMe); 3.72
(q, 1 H, CHC(O), J = 7.1 Hz); 3.97 (m, 2 H, CH2O); 7.02 (d, 2 H,
m-H, J = 7.8 Hz); 7.14 (d, 2 H, o-H, J = 8.0 Hz). 13C NMR, :
19.6 (CHCH3), 22.7 (CH(CH3)2), 30.1 (CHMe2), 33.7 (NMe),
40.0 (CHC(O)), 44.5 (CHCH2), 52.2 (NCH2), 58.1 (OCH2),
127.7 (m-C), 129.2 (o-C), 129.6 (ipso-C), 138.8 (p-C), 175.4
(C=O). Found (%): C, 73.12; H, 9.50; N, 5.29. C16H25NO2.
Calculated (%): C, 72.97; H, 9.57; N, 5.32.
1
251—253 C (with decomp.), Rf = 0.40 (А). H NMR, : 1.35
6-[(2-{2-[4-(Isobutyl)phenyl]propionyloxy}ethyl)(dimethyl)-
ammonio]-6-deoxy--cyclodextrin iodide (12). Ether 7 (1.11 g,
4.00 mmol) was added to a solution of -cyclodextrin iodo de-
rivative 1 (1.00 g, 0.80 mmol), obtained by the improved proce-
dure,13 in DMF (30 mL) with stirring. The solution was stirred
for 30 h at 100—110 С, concentrated to 5 mL, and filtered, fol-
lowed by the addition of acetone (30 mL). A precipitate formed
was collected by filtration, washed with acetone (2×5 mL), and
dried in vacuo (1 Torr) at 80 С for 4 h. The yield was 0.63 g
(52%), m.p. 260—262 C (with decomp.), Rf = 0.75 (B).
1H NMR, : 0.81 (d, 6 H, CH(CH3)2, J = 6.4 Hz); 1.31 (d, 3 H,
CHCH3, J = 7.0 Hz); 1.75 (m, 1 H, CHMe2); 2.10 (s, 6 H, NMe2);
2.35 (d, 2 H, CHCH2, J = 7.3 Hz); 3.23—3.61 (m, 44 H,
С(2)H—С(5)H, C(6)H2, NCH2); 3.85 (m, 1 H, CHC(O)); 4.07
(m, 2 H, CH2O); 4.47 (br.s, 6 H, C(6)OH); 4.79 (br.s, 7 H, C(1)H);
5.71 (br.s, 14 H, C(2)OH, C(3)OH); 7.05 (d, 2 H, m-H,
J = 7.8 Hz); 7.13 (d, 2 H, o-H, J = 8.0 Hz). 13C NMR, : 19.1
(CHCH3), 22.7 (CH(CH3)2), 30.1 (CHMe2), 40.0 (CHC(O)),
44.6 (CHCH2), 45.3 (NMe2), 57.3 (NCH2), 60.4 (C(6)), 62.4
(OCH2), 64.5 (C(6´)), 72.5—73.6 (C(5), C(2), C(3)), 82.0 (C(4)),
102.5 (C(1)), 127.6 (m-C), 129.6 (o-C), 138.3 (ipso-C), 140.3
(p-C), 174.4 (C=O). Found (%): C, 46.73; H, 6.31; N, 0.95.
(d, 3 H, CHCH3, J = 7.0 Hz); 1.62 (m, NCH2CH2); 2.15 (br.s,
6 H, NMe2); 2.20 (t, 2 H, NCH2); 2.46 (d, 2 H, CHCH2,
J = 7.3 Hz); 3.21—3.69 (m, 43 H, С(2)H—С(5)H, C(6)H2,
CHC(O)); 3.99 (m, 2 H, CH2O); 4.47 (br.s, 6 H, C(6)OH); 4.79
(br.s, 7 H, C(1)H); 5.70 (br.s, 14 H, C(2)OH, C(3)OH);
7.53—7.68 (m, 9 H, Ar). 13C NMR, : 18.9 (CHCH3), 26.0
(NCH2CH2), 45.0 (CHMe), 46.3 (NMe2), 55.4 (NCH2), 60.4
(C(6)), 62.6 (OCH2), 64.5 (C(6´)), 72.5—73.6 (C(5), C(2), C(3)),
82.0 (C(4)), 102.5 (C(1)), 128.8—133.3 (Ar), 175.6 (CHC=O),
195.9 (PhC=O). Found (%): C, 47.93; H, 5.93; N, 0.92.
C63H94INO37. Calculated (%): C, 47.76; H, 5.98; N, 0.88.
6-[(2-{2-[4-(Isobutyl)phenyl]propionyloxy}ethyl)(methyl)-
ammonio]-6-deoxy--cyclodextrin iodide (16). Sodium carbonate
(0.067 g) and ether 11 (0.21 g, 0.80 mmol) in DMF (10 mL) were
added to a solution of -cyclodextrin monotosyl derivative 2
(1.00 g, 0.80 mmol) in DMF (20 mL) with stirring. The solution
was stirred at 80 С for 6 h, concentrated 5 mL, and filtered,
followed by the addition of acetone (30 mL). A precipitate formed
was collected by filtration, washed with acetone (2×5 mL) and
diethyl ether (2×5 mL), and dried in vacuo (1 Torr) for 4 h at
80 С. The yield was 0.35 g (32%), m.p. 297—299 С (with de-
1
comp.), Rf = 0.58 (B). H NMR, : 0.79 (d, 6 H, CH(CH3)2,
C
59H96INO36. Calculated (%): C, 46.55; H, 6.36; N, 0.92.
Compounds 13—15 were obtained similarly.
6-[(3-{2-[4-(Isobutyl)phenyl]propionyloxy}propyl)(dimethyl)-
J = 7.0 Hz); 1.25 (d, 3 H, CHCH3, J = 7.3 Hz); 1.74 (m, 1 H,
CHMe2); 2.33 (s, 3 H, NMe); 2.39 (d, 2 H, CHCH2, J = 7.3 Hz);
2.46 (br.s, 2 H, NCH2); 2.78 (m, 2 H, CH2O); 3.21—3.33
(m, 14 H, С(2)H, С(4)H); 3.42 (m, 1 H, CHC(O)); 3.47—3.65
(m, 28 H, С(3)H, С(5)H, C(6)H2); 3.98 (br.s, 20 H, C(2)OH,
C(3)OH, C(6)OH); 4.78 (br.s, 7 H, C(1)H); 7.00 (d, 2 H,
m-H, J = 7.5 Hz); 7.12 (d, 2 H, o-H, J = 7.6 Hz). 13С NMR, :
19.8 (CHCH3), 22.7 (CH(CH3)2), 30.2 (CHMe2), 33.5 (NMe),
40.0 (CHC(O)), 44.8 (CHCH2), 46.7 (OCH2), 51.6 (NCH2),
57.5 (C(6´)), 60.4 (C(6)), 72.5—73.6 (C(5), C(2), C(3)),
82.0 (C(4)), 102.5 (C(1)), 127.7 (m-C), 129.6 (o-C), 139.3
(ipso-C), 140.9 (p-C), 177.8 (C=O). Found (%): C, 50.63;
H, 6.84; N, 0.99. C58H93INO36. Calculated (%): C, 50.47;
H, 6.79; N, 1.01.
ammonio]-6-deoxy--cyclodextrin iodide (13) was obtained from
-cyclodextrin iodo derivative 1 (1.00 g, 0.80 mmol) and ether 8
(1.17 g, 4.00 mmol). The yield was 0.60 g (49%), m.p. 265—267 C
(with decomp.), Rf = 0.71 (B). 1H NMR, : 0.79 (d, 6 H,
CH(CH3)2, J = 6.4 Hz); 1.31 (d, 3 H, CHCH3, J = 7.0 Hz); 1.62
(m, 2 H, NCH2CH2); 1.75 (m, 1 H, CHMe2); 2.15 (br.s, 6 H,
NMe2); 2.20 (t, 2 H, NCH2); 2.46 (d, 2 H, CHCH2, J = 7.3 Hz);
3.21—3.69 (m, 43 H, С(2)H—С(5)H, C(6)H2, CHC(O)); 3.99
(m, 2 H, CH2O); 4.47 (br.s, 6 H, C(6)OH); 4.79 (br.s, 7 H, C(1)H);
5.70 (br.s, 14 H, C(2)OH, C(3)OH); 7.05 (d, 2 H, m-H, J = 7.8 Hz);
7.13 (d, 2 H, o-H, J = 8.0 Hz). 13C NMR, : 18.9 (CHCH3), 22.7

866
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This work was financially supported by the Russian
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