Synthesis of New Methanofullerenes with Phthalimide Fragment

Article abstract of DOI:10.1134/S1070363220020139

Abstract: Bromo- and chloromethyl ketones based on N-phthalyl-substituted amino acids have been synthesized via the Arndt–Eistert reaction. The products [2+1] cycloaddition to the fullerene scaffold has afforded the monoadducts of fullerene C₆₀.

Full text of DOI:10.1134/S1070363220020139

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 2, pp. 244–248. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 2, pp. 268–273.
Synthesis of New Methanofullerenes with Phthalimide Fragment
I. M. Sakhautdinova,*, G. F. Sakhautdinovaa, and A. G. Mustafina
a Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences, Ufa, 450054 Russia
*e-mail: ioh039@mail.ru
Received July 12, 2019; revised July 23, 2019; accepted July 25, 2019
Abstract—Bromo- and chloromethyl ketones based on N-phthalyl-substituted amino acids have been synthesized
via theArndt–Eistert reaction. The products [2+1] cycloaddition to the fullerene scaffold has afforded the monoad-
ducts of fullerene C60.
Keywords: phthalimide, amino acids, [2 + 1] cycloaddition reactions, Bingel reaction, fullerene
DOI: 10.1134/S1070363220020139
Over the recent 15 years, organic photovoltaics has
grown into a high-priority research field. The related
studies have been mainly devoted to the synthesis and
investigation of properties of photoactive and electro-
conductive organic substances. In this instance, materials
containing fullerenes in combination with polyconjugated
macromolecular species are important, since they exhibit
enhanced efficiency of light conversion [1]. Hence, The
studies on preparation on novel materials based on С60
fullerene for the application in solar cells have emerged.
Primary functionalization of the С60 scaffold can be
easily and efficiently performed via the Bingel–Hirsch
approach: [2+1]-cycloaddition at the fullerene scaffold
affording the methanofullerenes [2, 3].
different amino acids (glycine, γ-aminobutyric acid,
5-aminovaleric acid, valine, or leucine [6]). The Arndt–
Eistert reaction of the carboxylic acids 1a–1e (via the
corresponding acyl chloride) afforded the diazo ketones
which were introduced (without isolation or purification)
in the reaction with hydrochloric or hydrobromic acid
to yield chloromethyl ketones 2a–2e and bromomethyl
ketones 3a–3e (Scheme 1).
Structure of halomethyl ketones 2 and 3 was confirmed
by physico-chemical methods. The chloromethyl group
in compounds 2a–e appeared in the 13С NMR spectra as
characteristic signal at 46.0–48.2 ppm (4.0–4.2 ppm in the
1Н NMR spectra). The NMR spectra of the bromomethyl
ketones 3a–e showed the signals of the СН2Br group at
36.5–37.7 and 3.9–4.0 ppm, respectively.
Extending the studies of [2+1]-cycloaddition of ha-
lomethyl ketones at the fullerene scaffold [4, 5], herein
we prepared novel fullerene conjugates based on bromo-
and chloromethyl ketones prepared from N-phthalyl-
substituted amino acids.
The Bingel reaction of the halomethyl ketones 2a–2e
and 3a–3e with the С60 fullerene in toluene in the pres-
ence of diazabicyclo[4.2.0]undec-7-ene (DBU) gave
methanofullerenes 4a–4e (Scheme 2).
The N-phthalyl-substituted amino acids 1a–1e were
13С NMR spectra of compounds 4a–4e contained
synthesized via direct fusion of phthalic anhydride with
the signals of different multiplicity corresponding to the
Scheme 1.
O
O
(1) SOCI2
(2) CH2N2
(3) HCl
R
R
X
N
N
n
n
OH
O
O
O
O
ꢀɚ
ꢀ1e
ꢁɚꢀ2e,ꢂꢃɚꢀ3e
R = H, n = 1 (ɚ), 3 (b), 5 (c); R = CH(CH ) , n = 1 (d, e);
3 2
R = CH CH(CH ) , n = 1 (ɚ); X = Cl (2), Br (3).
2
3 2
244

SYNTHESIS OF NEW METHANOFULLERENES WITH PHTHALIMIDE FRAGMENT
245
Scheme 2.
O
O
R
R
X
N
C
60, DBU
20oC
n
N
n
O
O
O
O
2, 3
ꢄɚꢀ4e
R = H, n = n = 1 (ɚ), 3 (b), 5 (c); R = CH(CH ) , n = 1 (d); R=CH CH(CH ) , n = 1 (e).
3 2
2
3 2
Scheme 3.
O
O
R
R
O
O
C60
DBU
Cl
Cl
Cl
R
R
sp2 carbon atoms of the fullerene at 136.4–148.2 ppm,
whereas the signals of the sp3 carbon atoms appeared
at 71.3–72.1 ppm. The Н NMR spectra contained the
EXPERIMENTAL
Methylene chloride and ethyl acetate were distilled
over P2O5. Toluene, petroleum ether, and benzene were
refluxed and distilled over sodium. Thionyl chloride
(analytical pure grade) was used as received. The reaction
products were isolated via column chromatography using
Chemapol silica gel (particles size 40/100 μm).
1
signals of the cyclopropane moiety at 4.91–5.01 ppm.
The obtained data evidenced the effect of the halo-
gen nature on the reaction course: chloromethyl ketones
were preferable for the primary functionalization of С60
via the Bingel reaction (Scheme 3), likely due to higher
electronegativity of the chlorine atom which, being ac-
companied by the keto group effect, made the methylene
protons more labile and facilitated the formation of the
carbanions via the Bingel reaction (via proton elimina-
tion in the presence of a strong base) in comparison with
bromomethyl ketones.
IR spectra were recorded using an IR-Prestige-21
Shimadzu device (thin film or suspension in Vaseline
oil). NMR spectra were recorded using a Bruker-AM 500
operating at 500.13 (1Н) or 125.76 (13С) MHz with TMS
as internal reference. The NMR signals were assigned us-
ing the data of homo- and heteronuclear two-dimensional
correlation (COSY, NOESY, HSQC, and HMBC). The
reactions course was followed by means of thin-layer
chromatography (Sorbfil PTSKh-AF-Aplated developed
with iodine vapor or spaying with a ninhydrin solution
followed by heating at 100–120°С. Mass spectra were
obtained using an LCMS-2010EV Shimadzu chromato–
mass spectrometer (chemical ionization at atmospheric
pressure). Elemental analysis was performed using a
EURO EA-3000 CHN instrument. Melting points were
determined using a Boetius heating bench.
In summary, [2+1]-cyclofunctionalization of the С60
scaffold via the Bingel reaction with bromo- and chloro-
methyl ketones afforded novel monoadducts of the С60
fullerene containing phthalimide fragment. The highest
yields of the methanofullerenes were obtained using the
chloromethyl ketones during 20 min. Further increase
in the reaction duration reduced the yield of the mono-
methanofullerenes due to the formation of the polyaddi-
tion products. The methanofullerenes obtained from the
amino acids were poorly soluble in organic solvents, yet
the introduction of the methylene bridge in the structure
increased the solubility, thus extending the possibilities
of further transformations and the application of the С60
conjugates in solar energy conversion devices.
N-Phthalimide-substituted amino acids 1a–e were
prepared as described elsewhere [6]. Bromomethyl ke-
tones 3a, 3d were prepared as described elsewhere [7,
8]; their physico-chemical parameters coincided with
the reference data.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 2 2020

246
SAKHAUTDINOV et al.
Synthesis of chloromethyl ketones 2a–e and bro-
δ, ppm (J, Hz): 1.34 m (2Н, CH2), 1.67 m (4Н, CH2), 2.68 t
(2Н, CH2, J = 7.3), 3.66 t (2Н, CH2, J = 7.1), 4.04 s
momethyl ketones 3a–3e under the Arndt–Eistert
reaction conditions (general procedure). 30 mmol of
thionyl chloride was added to a solution of 10 mmol of
the corresponding N-phthalimide-substituted amino acid
in 30 mL of benzene. The reaction mixture was refluxed
during 3 h and then evaporated to dryness. The obtained
acyl chloride (without additional purification) was cooled
to –5°С, and a cooled solution of diazomethane prepared
from 60 mmol of nitrosourea was added in a single por-
tion. The mixture was stirred at –5°С during 2 h, and the
solvent was distilled off. The residue was dissolved in
6 mL of CH2Cl2, and 1 mL of 38% solution of HCl (or
1 mL of 48% solution of HBr) was added at stirring. Af-
ter the gas evolution had ceased, the mixture was stirred
during 1 h at room temperature, the organic layer was
separated, washed with 5% solution of NaHCO3 (20 mL),
vigorously shaken, and extracted with CH2Cl2 (3×40 mL).
The combined organic phase was dried over anhydrous
MgSO4, and the solvent was distilled off. The residue
was separated via column chromatography on silica gel
(petroleum ether : ethyl acetate = 7 : 3).
(2Н, CH2), 7.68 m (2H, CHAr), 7.83 m (2H, CHAr). 13
С
NMR spectrum (CDCl3), δС, ppm: 23.00 (CH2), 26.22
(CH2), 28.29 (CH2), 37.52 (CH2), 39.40 (CH2), 48.15
(CН2), 123.18 (2CHAr), 132.10 (2CAr), 133.91 (2CHAr),
168.39 (2С=О), 202.39 (С=О). Mass spectrum, m/z: 294
[M + H]+, 293 [M]–. Found, %: С 61.33; H 5.48, N 4.75.
C15H16ClNO3. Calculated, %: С 61.33; H 5.49; Cl 12.07;
N 4.77; O 16.34.
2-(1-Chloro-4-methyl-2-oxopent-3-yl)isoin-
doline-1,3-dione (2d). Yield 2.23 g (80%), transparent
oil. IR spectrum, ν, cm–1: 724, 1380, 1458, 1653, 1718,
1736. 1Н NMR spectrum (CDCl3), δ, ppm (J, Hz): 0.84 m
(3Н, CH3), 1.06 m (3Н, CH3), 2.73 m (1Н, CH), 4.04 d
(2Н, CH2, J = 4.5), 4.74 d (1Н, CH, J = 7.9), 7.78 m (2H,
CHAr), 7.87 m (2H, CHAr). 13С NMR spectrum (CDCl3),
δС, ppm: 18.73 (CH3), 20.64 (CH3), 27.57 (CH), 46.46
(CН2), 61.09 (CH), 123.58 (2CHAr), 131.31 (2CAr),
134.60 (2CHAr), 167.78 (2С=О), 196.79 (С=О). Mass
spectrum, m/z: 280 [M + H]+, 279 [M]–. Found, %: С
60.03; H 5.09, N 4.98. C14H14ClNO3. Calculated, %: С
60.11; H 5.04; Cl 12.67; N 5.01; O 17.16.
2-(3-Chloro-2-oxopropyl)isoindole-1,3-dione (2a).
Yield 1.93 g (82%), white powder. IR spectrum, ν, cm–1:
713, 1378, 1418, 1465, 1718, 1747. 1Н NMR spectrum
(CDCl3), δ, ppm:4.21s(2Н, CH2), 4.75s(2Н, CH2), 7.72m
(2H, CHAr), 7.86 m (2H, CHAr). 13С NMR spectrum
(CDCl3), δC, ppm: 44.68 (CH2), 46.19 (CН2), 123.69
(2CHAr), 131.94 (2CAr), 134.35 (2CHAr), 167.38 (2С=О),
195.47 (С=О). Mass spectrum, m/z: 238 [M + H]+, 237
[M]–. Found, %: С 55.56; H 3.32, N 5.78. C11H8ClNO3.
Calculated, %: С 55.6; H 3.39; Cl 14.92; N 5.89; O 20.2.
2-(1-Chloro-5-methyl-2-oxohex-3-yl)isoin-
doline-1,3-dione (2e). Yield 2.2 g (75%), white powder.
IR spectrum, ν, cm–1: 724, 1063, 1383, 1464, 1713, 1738.
1Н NMR spectrum (CDCl3), δ, ppm (J, Hz): 0.89 d (3Н,
CH3, J = 6.6), 0.96 m (3Н, CH3, J = 6.6), 1.48 m (1Н,
CH), 1.93 m (1Ha, CH2), 2.27 m (1Hb, CH2), 4.19 d (2Н,
CH2, J = 2.8), 5.12 d (1Н, CH, J = 7.3), 7.77 m (2H,
CHAr), 7.88 m (2H, CHAr). 13С NMR spectrum (CDCl3),
δС, ppm: 21.03 (CH3), 23.26 (CH3), 25.05 (CH), 36.38
(CН2), 45.99 (CН2), 55.59 (CH), 123.75 (2CHAr), 131.62
(2CAr), 134.48 (2CHAr), 167.79 (2С=О), 197.76 (С=О).
Mass spectrum, m/z: 294 [M + H]+, 293 [M]–. Found, %:
С 61.3; H 5.49, N 4.78. C15H16ClNO3. Calculated, %: С
61.33; H 5.49; Cl 12.07; N 4.77; O 16.34.
2-(5-Chloro-4-oxopentyl)isoindoline-1,3-dione
(2b). Yield 2.1 g (78%), white powder. IR spectrum,
1
ν, cm–1: 725, 1038, 1373, 1463, 1709, 1772. Н NMR
spectrum (CDCl3), δ, ppm (J, Hz): 1.96 m (2Н, CH2),
2.63 t (2Н, CH2, J = 7.1), 3.71 t (2Н, CH2, J = 6.6), 4.09 s
2-(5-Bromo-4-oxopentyl)isoindoline-1,3-dione (3a).
Yield 2.35 g (76%), white powder. IR spectrum, ν, cm–1:
726, 1378, 1463, 1712, 1771. 1Н NMR spectrum (CDCl3),
δ, ppm (J, Hz): 1.97 m (2Н, CH2), 2.59 t (2Н, CH2, J =
7.1), 3.69 t (2Н, CH2, J = 6.6), 3.93 s (2Н, CH2), 7.66 m
(2H, CHAr), 7.82 m (2H, CHAr). 13С NMR spectrum
(CDCl3), δС, ppm: 22.81 (CH2), 34.31 (CH2), 36.76
(CH2), 36.84 (CН2), 123.23 (2CHAr), 131.92 (2CAr),
134.01 (2CHAr), 168.40 (2С=О), 200.91 (С=О). Mass
spectrum, m/z: 339 [M + H]+, 338 [M]–. Found, %: С
58.71; H 4.62; N 5.28. C13H12BrNO3. Calculated, %: С
50.34; H 3.90; Br 25.76; N 4.52; O 15.48.
(2Н, CH2), 7.71 m (2H, CHAr), 7.82 m (2H, CHAr). 13
С
NMR spectrum (CDCl3), δС, ppm: 22.57 (CH2), 36.67
(CH2), 36.87 (CH2), 48.21 (CН2), 123.28 (2CHAr), 131.97
(2CAr), 134.06 (2CHAr), 168.47 (2С=О), 201.56 (С=О).
Mass spectrum, m/z: 266 [M + H]+, 265 [M]–. Mass spec-
trum, m/z: 266 [M + H]+, 265 [M]–.Found, %: С 58.71;
H 4.62, N 5.28. C13H12ClNO3. Calculated, %: С 58.77;
H 4.55; Cl 13.34; N 5.27; O 18.07.
2-(7-Chloro-6-oxoheptyl)isoindoline-1,3-dione (2c).
Yield 2.2 g (75%), light yellow oil. IR spectrum, ν, cm–1:
725, 1403, 1463, 1709, 1772. 1Н NMR spectrum (CDCl3),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 2 2020

SYNTHESIS OF NEW METHANOFULLERENES WITH PHTHALIMIDE FRAGMENT
247
2-(7-Bromo-6-oxoheptyl)isoindoline-1,3-dione (3c).
Yield 2.66 g (79%), light yellow oil. IR spectrum, ν, cm–1:
723, 1048, 1373, 1464, 1709, 1769. 1Н NMR spectrum
(CDCl3), δ, ppm (J, Hz): 1.33 m (2Н, CH2), 1.65 m (4Н,
CH2), 2.62 t (2Н, CH2, J = 7.3), 3.66 t (2Н, CH2, J = 7.1),
3.87 s (2Н, CH2), 7.68 m (2H, CHAr), 7.72 m (2H, CHAr).
13С NMR spectrum (CDCl3), δC, ppm: 23.27 (CH2), 26.19
(CH2), 28.29 (CH2), 34.26 (CН2), 37.68 (CH2), 39.52
(CH2), 123.18 (2CHAr), 132.10 (2CAr), 133.91 (2CHAr),
168.39 (2С=О), 201.82 (С=О). Mass spectrum, m/z: 339
[M + H]+, 338 [M]–. Found, %: С 53.23; H 4.75; N 4.16.
C15H16BrNO3. Calculated, %: С 53.27; H 4.77; Br 23.63;
N 4.14; O 14.19.
142.28, 142.38, 142.31, 142.77, 143.11, 143.73, 143.00,
144.50, 144.54, 144.63, 144.75, 145.08, 145.23, 145.43,
145.63, 145.67, 147.93, 147.99, 168.02 (C=O), 206.76
(C=O). Found, %: С 92.63; H 0.76, N 1.50. C71H7NO3.
Calculated, %: С 92.51; H 0.77; N 1.52; O 5.21.
4'-[1f,2f-Methanofulleren-5'-yl]-4'-oxobutyl-
phthalimide (4b). Yield 60 mg (45%) from 2b, 56 mg
(42%) from 3b, dark brown powder. IR spectrum, ν,
cm–1: 526, 720, 1187, 1377, 1464, 1709, 1768. 1H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 2.31 m (2Н, CH2),
3.29 t (2Н, CH2, J = 6.8), 3.93 t (2Н, CH2, J = 6.3), 5.00 s
13
(1Н, CH), 7.72 m (2H, CHAr), 7.87 m (2H, CHAr). C
NMR spectrum (CDCl3), δС, ppm: 22.67 (CH2), 37.36
(CH2), 41.77 (CH2), 45.20 (CН), 72.04 (C1f, C2f), 123.40
(2CHAr), 129.04 (2CAr), 134.08 (2CHAr), 136.37, 137.88,
140.38, 140.89, 141.14, 141.99, 142.09, 142.25, 142.45,
142.76, 142.97, 143.014, 143.32, 143.69, 143.96, 144.30,
144.53, 144.66, 145.02, 145.14, 145.26, 145.53, 145.84,
148.22, 168.68 (2С=О), 200.24 (С=О). Found, %: С 92.3;
H 1.16; N 1.49. C73H11NO3. Calculated, %: С 92.31; H
1.17; N 1.47; O 5.05.
6'-[1f,2f-Methanofulleren-7'-yl]-6'-oxohexyl-
phthalimide (4c) Yield 58 mg (42%) from 2c, 54 mg
(39%) from 3c, dark brown powder. IR spectrum, ν,
cm–1: 527, 720, 1377, 1455,1706, 1768. 1H NMR spec-
trum (CDCl3), δ, ppm (J, Hz): 1.56 m (2Н, CH2), 1.79 m
(2Н, CH2), 1.98 m (2Н, CH2), 3.18 t (2Н, CH2, J = 7.2),
3.72 t (2Н, CH2, J = 7.2), 5.01 s (2Н, CH2), 7.72 m (2H,
CHAr), 7.86 m (2H, CHAr). 13C NMR spectrum (CDCl3),
δ, ppm: 23.20 (CH2), 26.49 (CH2), 28.50 (CH2), 37.78
(CН2), 44.13 (CH2), 45.44 (CH), 72.06 (C1f, C2f), 123.26
(2CHAr), 132.17 (2CAr), 133.95 (2CHAr), 136.37, 140.28,
140.92, 141.14, 142.03, 142.08, 142.25, 142.44, 142.75,
142.96, 143.01, 143.13, 143.32, 143.95, 144.32, 144.53,
144.61, 144.65, 144.85, 145.02, 145.14, 145.25, 145.47,
145.92, 148.17, 168.46 (2С=О), 200.86 (С=О). Found,
%: С 92.15; H 1.56; N 1.41. C75H15NO3. Calculated, %:
С 92.11; H 1.55; N 1.43; O 4.91.
2-(1-Bromo-5-methyl-2-oxohex-3-yl)isoin-
doline-1,3-dione (3e). Yield 2.43 g (72%), white powder.
IR spectrum, ν, cm–1: 721, 1060, 1385, 1468, 1709, 1774.
1Н NMR spectrum (CDCl3), δ, ppm (J, Hz): 0.89 d (3Н,
CH3, J = 6.6), 0.94 m (3Н, CH3, J = 6.6), 1.47 m (1Н, CH),
1.89 m (1Ha, CH2), 2.25 m (1Hb, CH2), 3.96 s (2Н, CH2,
J = 2.8), 5.14 d. d (1Н, CH, J = 11.3, 4.1), 7.76 m (2H,
CHAr), 7.85 m (2H, CHAr). 13С NMR spectrum (CDCl3),
δС, ppm: 20.98 (CH3), 23.21 (CH3), 25.05 (CH), 31.20
(CН2), 36.49 (CН2), 55.23 (CH), 123.68 (2CHAr), 131.58
(2CAr), 134.42 (2CHAr), 167.73 (2С=О), 197.41 (С=О).
Mass spectrum: m/z 339 [MH]+, 338 [M]–. Found, %: С
53.28; H 4.77, N 4.13. C15H16BrNO3. Calculated, %: С
53.27; H 4.77; Br 23.63; N 4.14; O 14.19.
Methanofullerenes 4a–e (general procedure). 0.21
mmol of chloromethyl ketone 2a–e (or bromomethyl
ketone 3a–e) and 0.21 mmol of DBU were added to a
solution of 0.14 mmol of С60 in 40 mL of toluene. The
reaction mixture was stirred at room temperature during
20 min (reaction course monitoring by TLC with toluene
as eluent) and filtered. The solution was washed with 5%
solution of HCl (30 mL) vigorously shaken, and extracted
with toluene (3×10 mL). The combined organic phase
was dried over anhydrous MgSO4, and half of the solvent
was distilled off. The residue was separated by column
chromatography on silica gel eluting with toluene.
2'-[1f,2f-Methanofulleren-3'-yl]-2'-oxoethylphthal-
imide (4a). Yield 64 mg (49.6%) from 2a, 50 mg (39%)
from 3a), dark brown powder. IR spectrum, ν, cm–1:
470 br, 1098 br, 1377, 1411, 1462, 1711,1718. 1H NMR
spectrum (CDCl3), δ, ppm: 5.21 s (2H, CH2), 5.02 s (1H,
CH), 7.79 m (2H, CHAr), 7.98 m (2H, CHAr). 13C NMR
spectrum (CDCl3), δС, ppm: 42.06 (CH2), 47.73 (CH),
71.31 (C1f, C2f), 123.86 (2CHAr), 132.05 (2CAr), 134.48
(2CHAr), 137.88, 140.60, 140.66, 140.92, 141.00, 141.98,
4'-[1f,2f-Methanofulleren-5'-yl]-4'-oxobutyl-
phthalimide (4d) Yield 77 mg (57%) from 2d, 48.6 mg
(36%) from 3d, dark brown powder. IR spectrum, ν,
1
cm–1: 527, 723, 1062, 1155, 1377, 1456, 1710 br. Н
NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.03 m (3Н,
CH3), 1.31 m (3Н, CH3), 3.14 m (1Н, CH), 4.91 s (1Н,
CH), 5.13 d (1Н, CH, J = 8.6), 7.78 m (2H, CHAr), 7.97 m
(2H, CHAr). 13C NMR spectrum (CDCl3), δС, ppm: 19.35
(CH3), 21.10 (CH3), 27.58 (CH), 64.99 (CH), 71.31 (C1f,
C2f), 124.05 (2CHAr), 131.56 (2CAr), 134.79 (2CHAr),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 2 2020

248
SAKHAUTDINOV et al.
136.43, 136.48, 137.82, 140.52, 140.87, 141.11, 142.01,
142.17, 142.27, 142.66, 142.71, 142.94, 142.99, 143.12,
143.31, 143.67, 144.02, 144.44, 144.63, 144.68, 144.85,
144.97, 145.03, 145.11, 145.19, 145.28, 145.48, 145.83,
147.88, 168.15 (2С=О), 195.68 (С=О). Found, %: С
92.22; H 1.36, N 1.44. C74H13NO3. Calculated, %: С
92.21; H 1.36; N 1.45; O 4.98.
6'-[1f,2f-Methanofulleren-7'-yl]-6'-oxohex-
ylphthalimide (4e). Yield 55 mg (40%) from 2e, 37
mg (27%) from 3e, dark brown powder. IR spectrum, ν,
cm–1: 526, 720, 1377, 1462, 1709 br. 1H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 0.99 d (3Н, CH3, J = 6.6), 1.12
m (3Н, CH3, J = 6.6), 1.68 m (1Н, CH), 2.33 m (1Ha,
CH2), 2.62 m (1Hb, CH2), 4.99 s (1Н, CH), 5.48 m (1Н,
CH), 7.79 m (2H, CHAr), 7.96 m (2H, CHAr). 13C NMR
spectrum (CDCl3), δС, ppm: 21.43 (CH3), 23.29 (CH3),
25.42 (CH), 36.59 (CН2), 58.46 (CH), 71.71 (C1f, C2f),
123.92 (2CHAr), 131.75 (2CAr), 134.63 (2CHAr), 136.45,
140.16, 140.96, 141.21, 142.06, 142.14, 142.28, 142.95,
143.03, 143.18, 144.01, 144.39, 144.56, 144.62, 144.70,
145.05, 145.20, 145.29, 145.72, 168.07 (2С=О), 199.56
(С=О). Found, %: С 92.12; H 1.56; N 1.42. C75H15NO3.
Calculated, %: С 92.11; H 1.55; N 1.43; O 4.91.
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
REFERENCES
1. Troshin, P.A., Troshina, O.A., Lyubovskaya, R.N.,and
Razumov, V.F., Funktsional’nye proizvodnye fullerenov:
metody sinteza i perspektivy ispol’zovaniya v organiches-
koi elektronike i biomeditsine (Functional Derivatives of
Fullerenes: Synthesis Methods and Prospects For Use
in Organic Electronics and Biomedicine). Ivanovo: Iva-
novsk. Gos. Univ., 2010.
2. Nierengarten, J.F. and Nicoud, J.F., Tetrahedron Lett.,
1997, vol. 38, no. 44, p. 7737.
https://doi.org/10.1016/S0040-4039(97)10066-1
3. Camps, X. and Hirsch, A., J. Chem. Soc. Perkin Trans. 1,
1997, p. 1595.
https://doi.org/10.1039/a702055d
4. Sakhautdinov, I.М. and Mukhamet’yanova, А.F., Russ. J.
Gen. Chem., 2018, vol. 88, no. 12, p. 2011.
https://doi.org/10.1134/S1070363218120125
5. Sakhautdinov, I.M., Malikova, R.N., Nugumanov, T.R.,
Biglova, Yu.N., Atangulov, A.B., and Yunusov, M.S.,
Chem. Nat. Compd., 2018, vol. 54, no. 3, p. 481.
https://doi.org/10.1007/s10600-018-2384-1
6. Grinshtein, J. and Vinits, M., Chemistry of Aminoacids
and Peptide, Moscow: Mir, 1965.
FUNDING
7. Tolstikov, G.A., Galin, F.Z., and Lakeev, S.N., Izv. Akad.
Nauk, Ser. Khim., 1989, no. 5, p. 1209.
This study was performed in the scope of the plan of re-
search for Ufa Institute of Chemistry, RAS according to the
topic “Creation of materials with predefined functional proper-
ties: electroconductivity, anticorrosive and biological activity”
(state registration no.AAAA-A19-119020890014-7). Spectral
part of the study was performed using the equipment of the
Center for Collective Usage “Chemistry”, Ufa Institute of
Chemistry, Russian Academy of Sciences.
8. Khimiya i biologicheskaya aktivnost’ sinteticheskikh i
prirodnykh soedinenii. Azotistye geterotsikly i alkaloidy
(Chemistry and Biological Activity of Synthetic and
Natural Compounds. Nitrogen Heterocycles and Alka-
loids), Kartsev, V.G. and Tolstikov, G.A., Eds., Moscow:
IRIDIUM-PRESS, 2001, vol. 1, p. 262.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 2 2020