1232
GORBOVOI et al.
Table 3. IR and 1H NMR spectra of 1-acryloyloxy-4-(2-thiocyanato-3-arylpropionyloxy)butanes II IV
1
IR spectrum, , cm
Comp.
no.
1H NMR spectrum, , ppm
SCN
2156
CH=CH2
1636
II
7.34 7.26 m (5H, Ph), 6.33 d.d (Hcis, =CH2, JHH 11 Hz), 6.16 d.d (1H, =CH , JHH 10 Hz),
5.93 d.d (Htrans, =CH2, JHH 14 Hz), 4.50 d.d (1H, CH, JHH 7 Hz), 4.11 t [4H, 2( OCH2)],
3.35 d.d (JHH 8 Hz), 3.13 d.d (2H, CH2Ph, JHH 8 Hz), 1.48 1.70 m (4H, CH2 CH2
)
III
2152
2152
1640
1640
7.36 7.26 m (4H, C6H4), 6.35 d.d (Hcis, =CH2, JHH 11 Hz), 6.18 d.d (1H, =CH , JHH
10 Hz), 5.97 d.d (Htrans, =CH2, JHH 14 Hz), 4.51 d.d (1H, CH, JHH 7 Hz), 4.12 t [4H,
2( OCH2)], 3.35 d.d. (JHH 8 Hz), 3.12 d.d (2H, CH2 C6H4, JHH 8 Hz), 2.35 s (3H, p-CH3
C6H4), 1.46 1.72 m (4H, CH2 CH2
)
IV
7.44 7.36 m (4H, C6H4), 6.36 d.d (Hcis, =CH2, JHH 11 Hz), 6.18 d.d (1H, =CH , JHH
10 Hz), 5.98 d.d (Htrans, =CH2, JHH 14 Hz), 4.53 d.d (1H, CH, JHH 7 Hz), 4.14 t [4H,
2( OCH2)], 3.37 d.d (JHH 8 Hz), 3.14 d.d (2H, CH2 C6H4, JHH 8 Hz), 1.47 1.69 m (4H,
CH2 CH2
)
EXPERIMENTAL
analyzed by HPLC to find that the latter fractions
contain exclusively the target product. The eluent was
removed by distillation and traces of solvents were
purged off with argon to obtain 24.2 g of compound
II.
The IR spectra of compounds II IV were obtained
on a Specord M-80 instrument for thin films. The H
NMR spectra were measured on a Varian Gemini
instrument in DMSO, working frequency 300 MHz,
internal reference HMDS.
1
Compound III and IV were obtained in a similar
way.
The purity of the synthesized compounds was es-
tablished by TLC on Silufol UV-254 plates (eluent he-
xane chloroform methanol diethyl ether, 5:3:3:1).
The mixtures were analyzed on a Milikhrom-4 liquid
chromatograph with a UV detector on a 80 2-mm
column packed with Separon SC-RP-S-Super C18
(average grain size 5 m). The detection was per-
formed at 220, 230, 254, 274, 284 nm. Eluent iso-
propanol water acetonitrile, 6:11:33. Measurement
time 0.02 s, recording scale 10. Regeneration volume
150 l, buffer volume 20 l, sample volume 5 l,
eluent rate 30 l/min.
REFERENCES
1. Grishchuk, B.D., Gorbovoi, P.M., Ganushchak, N.I.,
and Dombrovskii, A.V., Usp. Khim., 1994, vol. 63,
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2. Grishchuk, B.D. and Gorbovii, P.M., Naukovi Zapiski
Ternopil. Ped. Univ. im. V. Gnatyuka, Ser. Khim., 1998,
no. 2, pp. 3 16.
3. Grishchuk B.D. and Gorbovii P.M., Abstracts of Papers,
XVIII Ukrains’ka konferentsiya z organichnoi khimii
(XVIII Ukr. Conf. on Organic Chemistry), Dnipropet-
rovsk, 1998, p. 22.
1-Acryloyloxy-4-(2-thiocyanato-3-arylpropyonyl-
oxy)butane (II). Benzenediazonium tetrafluoroborate,
0.1 mol, was added over the course of 45 60 min to
0.12 mol of 1,4-bis(acryloyloxy)butane, 0.01 mol of
copper(II) tetrafluoroborate, and 0.13 mol of am-
monium thiocyanate in 200 ml of aqueous acetone
(1:2). Nitrogen evolution was observed at 5 to
10 C for 2 h. When nitrogen no longer evolved, the
reaction mixture was treated with 250 ml of diethyl
ether, and the extract was washed with water and
dried with magnesium sulfate. The ether was removed,
and the residue was subjected to column chromato-
graphy on Al2O3 (eluent hexane chloroform metha-
nol diethyl ether, 5:3:3:1). The fractions whose IR
spectra contained isothiocyanate, isothiocyanate and
thiocyanate, or thiocyanate absorption bands were
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Zh. Obshch. Khim., 1999, vol. 69, no. 2, pp. 283 285.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 8 2002