1536
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 6, June, 2005
Kutyreva et al.
and concentrated in vacuo to an oily product (1.71 g), which was
used unpurified for the next step.
dioxane. The reaction mixture was stirred at this temperature for
2 h. The solution was decanted and the precipitate was repeatꢀ
edly washed with dioxane until a neutral reaction and dried
in vacuo. The yield of a brown product was 0.13 g (96%).
Found (%): C, 86.30; H, 2.36; Cl, 3.65. C65H13ClN2•C4H8O2.
Calculated (%): C, 87.60; H, 2.22; Cl, 3.75. UV (DMSO),
1ꢀ(tertꢀButoxycarbonyl)aminopropanꢀ2ꢀone (2). Oxalyl chloꢀ
ride (0.98 mL, 11.45 mmol) was dissolved in CH2Cl2 (25 mL)
and cooled to –78 °C and anhydrous DMSO (1.7 mL,
23.9 mmol) in CH2Cl2 (5 mL) was added. The solution was
stirred at –73 °C for 2 min and Bocꢀaminopropanol (1.71 g,
9.71 mmol) in CH2Cl2 (10 mL) was added dropwise, while
preventing the temperature from rising above –50 °C. Then the
reaction mixture was stirred at the same temperature for 15 min,
triethylamine (6.9 mL, 49.8 mmol) was added, and stirring was
continued for an additional 5 min at –50 °C. The mixture was
warmed to room temperature, diluted with CH2Cl2 (50 mL),
and washed with water (4×50 mL). The organic layer was sepaꢀ
rated off and dried over Na2SO4. The solvent was removed
in vacuo and the residue was fractionated to collect a light liquid
with b.p. 80—85 °C (0.1 Torr), which then crystallized (m.p.
44—46 °C). The yield of compound 2 was 1.38 g (80%).
Found (%): C, 55.31; H, 8.51. C8H15NO3. Calculated (%):
λ
max/nm: 340, 430. 1H NMR (DMSOꢀd6), δ: 1.62 (s, 3 H,
NMe); 2.86 (s, 3 H, C—Me); 3.57 (s, 8 H, H of dioxane); 3.80,
4.37 (both d, 1 H each, CH2NH3+, J = 13.3 Hz); 4.41, 4.70
(both d, 1 H each, CH2, J = 10.5 Hz); 6.98 (s, NH3+). The
integral intensity of the signal at δ 6.98 is lower than the exꢀ
pected value, probably, because of the isotope exchange with
the solvent.
This work was financially supported by the Council on
Grants of the President of the Russian Federation (Proꢀ
gram for State Support of Leading Scientific Schools of
the Russian Federation, Grant NShꢀ1652.2003.3).
1
C, 55.49; H, 8.67. H NMR (CDCl3), δ: 1.42 (s, 9 H, Me3C);
References
2.16 (s, 3 H, MeC(O)); 4.00 (d, 2 H, CH2, J = 4.6 Hz); 5.23
(br.s, 1 H, NH).
1ꢀtertꢀButoxycarbonylaminomethylꢀ1,2ꢀdimethyl[60]fulleꢀ
reno[c]pyrrolidine (3). Sarcosine (1) (0.25 g, 2.80 mmol) and
Bocꢀaminopropanꢀ2ꢀone 2 (0.4 g, 2.31 mmol) were added to a
solution of fullerene (1 g, 1.38 mmol) in toluene (600 mL). The
reaction mixture was refluxed with stirring for 8 h, cooled
to ~20 °C, and filtered. The resulting solution was separated by
column chromatography on silica gel with toluene and toluꢀ
ene—chloroform (2 : 3) as the eluents for the unreacted fullerene
and the major product, respectively. Polyadducts were eluted
with chloroform. The solvents were removed in vacuo to give a
redꢀbrown solid (0.11 g, 60% with respect to the consumed
fullerene), m.p. >400 °C. Found (%): C, 90.80; H, 2.37.
C70H20N2O2. Calculated (%): C, 91.30; H, 2.17.
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0.16 mmol) was added at 0 °C to a solution of 4 M HCl (2 mL) in
Received December 24, 2004;
in revised form April 20, 2005