NIKOLAEV et al.
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8400S spectrometer from samples pressed with KBr.
SCH2), 5.23 s (2H, OCH2), 7.33 m (5H, C6H5).
13C NMR spectrum (CDCl3), δC, ppm: 25.27
[(CH3)2S], 35.69 (SCH2), 67.91 (OCH2), 128.00‒
129.00 (Co, Cm, Cp), 134.97 (Ci), 164.35 (C=O). Mass
spectrum, m/z (Irel, %): 211.0789 (100) [M ‒ Br]+,
501.0766 (60) [M + Br + M]+.
1
The H and 13C NMR spectra were recorded on
a Bruker Avance-400 spectrometer at 400 and
100 MHz, respectively. The mass spectra (MALDI)
were obtained on a Bruker Daltonics UltrafleXtreme
MALDI TOF/TOF instrument, and the ESI mass
spectra were taken on a Bruker Maxis 4G spectrometer
(Germany).
[2-(Diphenylmethoxy)-2-oxoethyl](dimethyl)-
sulfanium bromide (3d). Yield 70%, white crystals,
mp 111‒113°C. IR spectrum: ν 1736 cm–1 (C=O).
1H NMR spectrum (CDCl3), δ, ppm: 2.15 s, 2.17 s, and
2.67 s [6H, (CH3)2S]; 3.30 s and 3.95 s (2H, SCH2),
6.94 s (1H, OCH), 7.39 m (10H, Harom). 13C NMR
spectrum (CDCl3), δC, ppm: 25.97 [(CH3)2S], 35.95
(SCH2), 77.70‒78.72 (CH), 127.12‒128.61 (Co, Cm,
Cp), 139.34‒139.88 (Ci), 166.19 (C=O). Mass spec-
trum, m/z (Irel, %): 287.1100 (100) [M ‒ Br]+, 653.1389
(60) [M + Br + M]+.
Fullerene C60 with a purity of 99.7‒99.8%
(NeoTekProdakt, St. Petersburg, Russia), bromoacetic
acid, benzhydrol, methylene chloride, ethanol, tert-
butyl alcohol, benzyl alcohol, acetonitrile, chloroform,
hexane, dimethyl sulfide, o-dichlorobenzene, p-tolu-
enesulfonic acid monohydrate, sodium hydroxide,
potassium carbonate, toluene, pyridine, dioxane, and
silica gel (grain size 0.06‒0.2 mm, pore diameter 60 Å;
Acros) were commercial products.
Ethyl 2-(dimethyl-λ4-sulfanylidene)acetate (4a).
Alkyl bromoacetates 2a [5], 2b, 2c [6], and 2d [7]
were synthesized by known methods. IR spectrum:
ν 1742 cm–1 (C=O). 1H NMR spectrum of 2d (CDCl3),
δ, ppm: 3.97 s (2H), 7.09 s (1H), 7.40‒7.54 m (10H,
Yield 90%, yellowish oil. IR spectrum: ν 1626 cm–1
1
(C=O). H NMR spectrum (CDCl3), δ, ppm: 1.01 t
(3H, CH3CH2), 3.76 q (2H, CH2CH3), 2.56 s [7H,
(CH3)2SCH]. 13C NMR spectrum (CDCl3), δC, ppm:
16.45 (CH3CH2), 30.80 [(CH3)2S], 32.76 (SCH), 59.72
(OCH2), 170.13 (C=O).
H
arom). 13C NMR spectrum (CDCl3), δC, ppm: 26.20
(CH2), 78.81 (CH), 127.30‒128.79 (Co, Cm, Cp),
139.57 (Ci), 166.29 (C=O).
tert-Butyl 2-(dimethyl-λ4-sulfanylidene)acetate
Compounds 3a–3d and 4a–4d were synthesized
according to the procedures described in [8].
(4b). Yield 92%, white amorphous solid. IR spectrum:
1
ν 1610 cm–1 (C=O). H NMR spectrum (CDCl3), δ,
(2-Ethoxy-2-oxoethyl)(dimethyl)sulfanium
bromide (3a). Yield 60%, white crystals, mp 82‒84°C;
published data [12]: mp 85‒87°C. IR spectrum:
ppm: 1.30 s [9H, (CH3)3C], 2.60 s [7H, (CH3)2SCH].
13C NMR spectrum (CDCl3), δC, ppm: 28.95
[(CH3)3C], 30.69 [(CH3)2S], 33.00 (SCH), 76.55
[C(CH3)3], 170.42 (C=O).
1
ν 1730 cm–1 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 1.16 t (3H, CH3CH2), 3.33 s [6H, (CH3)2S],
4.12 q (2H, CH2CH3), 4.93 s (2H, SCH2). 13C NMR
spectrum (CDCl3), δC, ppm: 14.21 (CH3CH2), 25.20
[(CH3)2S], 36.51 (SCH2), 63.43 (OCH2), 163.76
(C=O). Mass spectrum, m/z (Irel, %): 149.0630 (100)
[M ‒ Br]+, 374.0778 (60) [M + Br + M]+.
Benzyl 2-(dimethyl-λ4-sulfanylidene)acetate (4c).
Yield 96%, white amorphous solid. IR spectrum:
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ν 1620 cm–1 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 2.50 s [6H, (CH3)2S], 2.90 s (1H, SCH), 5.00 s
(2H, OCH2), 7.24 m (5H, C6H5). 13C NMR spectrum
(CDCl3), δC, ppm: 30.37 [(CH3)2S], 32.68 (SCH),
63.71 (OCH2), 127.30‒128.30 (Co, Cm, Cp), 138.51
(Ci), 169.67 (C=O).
(2-tert-Butoxy-2-oxoethyl)(dimethyl)sulfanium
bromide (3b). Yield 75%, white crystals, mp 112‒
114°C. IR spectrum: ν 1719 cm–1 (C=O). H NMR
1
Diphenylmethyl 2-(dimethyl-λ4-sulfanylidene)-
spectrum (CDCl3), δ, ppm: 1.45 s [9H, (CH3)3C],
3.44 s [6H, (CH3)2S], 5.00 s (2H, SCH2). 13C NMR
spectrum (CDCl3), δC, ppm: 25.25 [(CH3)2S], 27.97
[(CH3)3C], 36.97 (SCH2), 85.88 [OC(CH3)3], 163.31
(C=O). Mass spectrum, m/z (Irel, %): 177.0946 (100)
[M ‒ Br]+, 433.1075 (60) [M + Br + M]+.
acetate (4d). Yield 96%, white amorphous solid. IR
1
spectrum: ν 1620 cm–1 (C=O). H NMR spectrum
(CDCl3), δ, ppm: 2.70 s [6H, (CH3)2S], 3.10 s (1H,
SCH), 6.89 s (1H, OCH), 7.30‒7.40 m (10H, Harom).
13C NMR spectrum (CDCl3), δC, ppm: 30.40
[(CH3)2S], 32.61 (SCH), 74.29 (OCH), 127.12‒128.27
(Co, Cm, Cp), 142.52 (Ci), 169.18 (C=O).
(2-Benzyloxy-2-oxoethyl)(dimethyl)sulfanium
bromide (3c). Yield 82%, white crystals, mp 78‒80°C.
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IR spectrum: ν 1737 cm–1 (C=O). H NMR spectrum
Alkyl 3′H-cyclopropa[1,9](C60-Ih)[5,6]fullerene-
3′-carboxylates 5a–5d (general procedure). A 2-L
(CDCl3), δ, ppm: 3.36 s [6H, (CH3)2S], 5.18 s (2H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 7 2016