KUTYREVA et al.
1380
Thus, analysis of the IR spectra demonstrated struc-
11.2 Hz), 5.25 br.s (2H, COOH). 13C NMR spectrum
(CDCl3), δC, ppm: 17.78 (CH3), 49.91 (CCH3), 51.4
(CH3O), 66.70 (CH2O), 176.30 (C=O). Found, %:
C 48.24; H 5.77. C14H20O10. Calculated, %: C 48.28;
H 5.79.
tural similarity between low-molecular-weight com-
pounds 2–5 and functionalized derivatives of hyper-
branched polyesters polyols of the second and third
generations. The obtained derivatives of bis(hydroxy-
methyl)propionic acid (1) can be used to simulate
ionization and complexation behavior of amino and
carboxy derivatives of hyperbranched polyesters.
2-(Methoxycarbonyl)-2-methylpropane-1,3-diyl
diprop-2-enoate (4). Acryloyl chloride, 6.1 g
(67 mmol), was added dropwise to a solution of 5.0 g
(33 mmol) of ester 2, 6.8 g (67 mmol) of triethylamine,
and hydroquinone (1 wt %) in 20 mL of methylene
chloride on cooling to 0°C. The mixture was stirred at
room temperature in an inert atmosphere until the OH
stretching band (3400–3100 cm–1) disappeared from
the IR spectrum of the mixture. The mixture was
repeatedly treated with ethyl acetate, and the product
was isolated from the filtrate by drying under reduced
pressure. Yield 60%, light yellow oily material. IR
spectrum, ν, cm–1: 2986–2847 m (CH3, CH2), 1724
(C=O), 1635, 1618 w (C=C), 1407 m [δ(=CH2)],
1296–1138 s (C–O), 1059 w (C–O), 982, 808 m
EXPERIMENTAL
The IR spectra were recorded on a Perkin Elmer
Spectrum 400 with Fourier transform equipped with
a universal ATR accessory and a ZnSe prism (resolu-
tion 1 cm–1; number of scans 14; spectral range 4000–
1
400 cm–1). The H and 13C NMR spectra were mea-
sured on a Bruker Avance 400 spectrometer at 400 and
125.77 MHz, respectively, relative to the residual
proton and carbon signals of the deuterated solvent.
Methyl 2,2-di(hydroxymethyl)propanoate (2)
was synthesized according to the procedure described
in [14]. A solution of 50 g (373 mmol) of acid 1 in
methanol was cooled to 0°C, 64 g (560 mmol) of
thionyl chloride was added dropwise, and the mixture
was stirred for 18 h at 62°C. The product was isolated
by vacuum distillation. Yield 75%, bp 104°C
(0.2 mm). IR spectrum, ν, cm–1: 3418 br (OH, assoc.),
2975–2847 m (CH3, CH2), 1713 v.s (C=O), 1297–
1
[δ(CH=CH2)]. H NMR spectrum (CDCl3), δ, ppm:
1.25 s (3H, CH3), 3.69 s (3H, OCH3), 4.29 s and 4.30 s
(4H, CH2O), 5.81 d.d (2H, CH2=CH, 2JHH = 1.3, 3JHH
=
10.4 Hz), 6.06 q (2H, CH2=CH, 3JHH = 10.4, 17.3 Hz),
2
3
6.35 d.d (2H, CH2=CH, JHH = 1.3, JHH = 17.3 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 16.80 (CH3),
45.38 (CCH3), 51.38 (OCH3), 64.48 (OCH2), 126.84
(CH=CH2), 130.45 (=CH2), 172.18 [C(O)OCH3],
164.56 [C(O)CH=CH2]. Found, %: C 56.52; H 6.46.
C12H16O6. Calculated, %: C 56.25; H 6.29.
1
1130 m (C–O), 1030 s (C–O, δOH). H NMR spec-
trum (CDCl3), δ, ppm: 1.04 s (3H, CH3), 3.51 s (2H,
3
2-(Methoxycarbonyl)-2-methylpropane-1,3-diyl
bis[3-(diethylamino)propanoate] (5). Diethylamine,
1.7 g (23 mmol), was added to a solution of 3 g
(12 mmol) of bis-acrylate 4 in 13 mL of methylene
chloride, and the mixture was stirred for 13 h at room
temperature. The solvent was removed under reduced
pressure, and the light brown oily residue was washed
with diethyl ether and dried under reduced pressure.
Yield 62%. IR spectrum, ν, cm–1: 2970–2876 m (CH3,
CH2), 2810 m (NCH2), 1736 v.s (C=O), 1295–1135 s
CH2OH), 3.64 d (2H, CH2OH, JHH = 11.2 Hz), 3.70 s
3
(3H, OCH3), 3.80 d (2H, CH2OH, JHH = 11.2 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 17.8 (CH3),
49.9 (CCH3), 51.4 (OCH3), 66.7 (CH2OH), 176.3
(C=O). Found, %: C 48.90; H 8.26. C6H12O4. Calculat-
ed, %: C 48.64; H 8.16.
4,4′-[2-(Methoxycarbonyl)-2-methylpropane-1,3-
diylbis(oxy)]bis(4-oxobutanoic acid) (3). Succinic
anhydride, 3.4 g (33.8 mmol), was added to a solution
of 2.5 g (16.9 mmol) of ester 2 in 8 mL of 1,4-dioxane,
and the mixture was heated for 4 h at 80°C. The
product was purified by reprecipitation from ethyl
acetate–hexane (1:3) and dried under reduced pres-
sure. Yield 67%, white amorphous substance. IR spec-
trum, ν, cm–1: 3474 (OH, assoc.), 2984–2903 m (CH3,
CH2), 2766–2583 m (COOH, assoc.), 1731, 1709 v.s
(C=O), 1299–1145 s (C–O), 1024, 1002 w (C–O,
(C–O), 1047, 1014 w (C–O, C–N). 1H NMR spectrum
3
(CDCl3), δ, ppm: 0.99 t (12H, CH2CH3, JHH
=
=
7.2 Hz), 1.23 s (3H, CH3), 2.43 t [4H, C(O)CH2, 3JHH
7.7 Hz], 2.50 q (8H, NCH2CH3, JHH = 7.2 Hz), 2.77 t
3
3
(4H, CH2CH2N, JHH = 7.7 Hz), 3.70 s (3H, OCH3),
4.22, 4.23 d.s (4H, CH2O). 13C NMR spectrum
(CDCl3), δC, ppm: 11.01 (NCH2CH3), 15.87 (CH3),
31.02 (CH2CH2), 45.67 (CCH3), 46.97 (NCH2CH3),
52.3 (OCH3), 64.36 (CH2O), 171.27 [C(O)OCH2].
Found, %: C 59.38; H 9.76; N 7.02. C20H38N2O6. Cal-
culated, %: C 59.68; H 9.52; N 6.96.
1
δOH). H NMR spectrum (DMSO-d6), δ, ppm: 1.13 s
(3H, CH3), 2.56–2.60 m (8H, CH2CH2), 3.70 s (3H,
3
OCH3), 4.21–4.30 d.d (4H, CH2OC=O, JHH
=
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 10 2015