2,5-Bis(vinyloxyalkylamino)-1,4-benzoquinones

Full text of DOI:10.1134/S1070428011080264

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 8, pp. 1259−1260. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © B.F. Kukharev, V.K. Stankevich, G.R. Klimenko, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 8, pp. 1239−1240.
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2,5-Bis(vinyloxyalkylamino)-1,4-benzoquinones
B. F. Kukharev, V. K. Stankevich, and G. R. Klimenko
Faworsky Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences
Irkutsk, 664033 Russia
e-mail: irk_inst_chem@irioch.irk.ru
Received August 24, 2010
DOI: 10.1134/S1070428011080264
Vinyl ethers of amino alcohols and their derivatives
exhibit versatile biological action and also are used as
monomers for the synthesis of polymers with practically
useful properties [1]. In particular, 2,5-bis(vinyloxyethyl)
amino-1,4-benzoquinone [2] formerly described by us
was recently suggested as a comonomer in the synthesis
of redoxites [3, 4].
of the reaction product is low (62%).
We carried out the reaction with a dispersion of
benzoquinone in anhydrous ethanol at the stoichiometric
ratioofthereagents.Thereactionwithvinyloxyalkylamines
Ia, Ib proceeded with a slight self-heating (to 32–40°C).
In the case of less reactive vinyl ethers Ic, Id the reaction
mixture was heated at this temperature (see the scheme).
For the investigation of redoxite characteristics mono-
mers were synthesized underlain by vinyloxyethylamine
and various 1,4-quinones [5]. At the same time the data
on the character of the fragment of the vinyl ether of the
aminoalcohol in the aminoquinone were totally absent.
The vinyl ether of 2-amino-2-methyl-1-propanol did
not react with 1,4-benzoquinone even at boiling the reac-
tion mixture apparently due to the steric hindrance at the
amino group preventing in the first stage the addition of
the amine to quinine.
In this study aiming at further application of the
products synthesized for redoxites production and at the
elucidation of their biological activity we investigated the
effect of the structure of vinyl ethers of aminoalcohols
on their reaction with 1,4-benzoquinone.
2,5-Bis(vinyloxyalkyl)-1,4-benzoquinones IIa–IId.
General procedure. To a dispersion of 0.06 mol of ben-
zoquinone in 70 ml of anhydrous ethanol was added at
stirring 0.04 mol of vinyl ether Ia–Id, and the mixture
was heated at 40°C over 4 h. On cooling the precipitated
crystals were recrystallized from ethanol.
In the synthesis of 2,5-bis(vinyloxyethyl)amino-
1,4-benzoquinone [3] a dilute solution of quinone in
dioxane (0.26 mol l−1) and nearly 10-fold excess of
vinyloxyethylamine is used with the subsequent dilution
of the reaction mixture with water. As a result the yield
2,5-Bis(3-vinyloxypropylamino)-1,4-benzoquinone
(IIa). Yield 79%, mp 114–115°C. IR spectrum, ν, cm–1:
3250 (NH), 3105, 3070, 3010 (=CH), 1615, 1600, 1540
(C=C–C=O, C=C). 1H NMR spectrum, δ, ppm: 2.01 m
Scheme.
O
O
O
NHROCH CH2
+2H2NROCH CH2
3
_2 n-C6H4(OH)2
H2C CHORHN
Iа_Id
O
IIа_IId
R = (CH2)3 (a), (CH2)4 (b), trans-1,2-cyclo-C6H10 (c), 1,2-C6H4 (d).
1259

KUKHAREV et al.
1260
(4H, 2CCH2C), 3.30 t (4H, 2NCH2,3J6.0 Hz), 3.77 t (4H,
2CH2O, 3J 5.8 Hz), 4.03 d.d (2H, 2cis-CH=C, 2Jgem 1.8,
3Jcis 6.8 Hz), 4.19 d.d (2H, 2 trans-CH=C, 2Jgem 1.8, 3Jtrans
14.3 Hz), 5.32 s (2H, 2NC=CH), 6.48 d.d (2H, 2OCH=C,
3Jcis 6.8, 3Jtrans 14.3 Hz), 6.81 br.s (2H, 2NH). Found, %:
C 62.68; H 7.21; N 9.10. C16H22N2O4. Calculated, %:
C 62.73; H 7.24; N 9.14.
13.1 Hz), 7.12 m (6H, 2C4Harom, 2C5Harom, 2C6Harom),
7.40 m (2H, 2C3Harom), 8.29 br.s (2H, 2 NH). Found, %:
C 70.67; H 4.89; N 7.22. C22H18N2O4. Calculated, %:
C 70.58; H 4.85; N 7.48.
1H NMR spectra were registered on a spectrometer
Bruker DPX-400 (400 MHz) in DMSO-d6 at 50°C,
internal reference HMDS. IR spectra were recorded on
a spectrophotometer Specord 75IR in pellets with KBr.
2,5-Bis(3-vinyloxybutylamino)-1,4-benzoquinone
(IIb). Yield 74%, mp 138–139°C. IR spectrum, ν, cm–1:
3260 (NH), 3100, 3070, 3015 (=CH), 1615, 1600, 1540
(C=C–C=O, C=C). 1H NMR spectrum, δ, ppm: 1.75 m
Vinyl ethers of aminoalcohols were obtained by vinyl-
ation of the corresponding aminoalcohols with acetylene
by procedure [6].
3
(8H, 2CCH2CH2C), 3.21 t (4H, 2NCH2, J 6.1 Hz),
3.69 t (4H, 2CH2O, 3J6.0 Hz), 3.99 d.d (2H, 2cis-CH=C,
REFERENCES
3
2Jgem 1.7, Jcis 6.8 Hz), 4.17 d.d (2H, 2trans-CH=C,
2Jgem 1.7, 3Jtrans 14.2 Hz), 5.30 s (2H, 2NC=CH), 6.45 d.d
(2H, 2OCH=C, 3Jcis 6.8, 3Jtrans 14.2 Hz), 6.77 br.s (2H,
2NH). Found, %: C 64.28; H 7.89; N 8.26. C18H26N2O4.
Calculated, %: C 64.65; H 7.84; N 8.38.
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2,5-Bis(1S,2R)-(2-vinyloxycyclohexylamino)-1,4-
benzoquinone (IIc). Yield 67%, mp 199–200°C. IR
spectrum, ν, cm–1: 3260 (NH), 3100, 3000 (=CH), 1620,
1615, 1550 (C=C–C=O, C=C). H NMR spectrum, δ,
ppm: 1.35–2.06 m (16H, 2CH2CH2CH2CH2), 3.33 m (2H,
1
2NCH), 3.64 m (2H, 2CHO), 3.98 d.d (2H, 2cis-CH=C,
3
2Jgem 1.8, Jcis 6.7 Hz), 4.25 d.d (2H, 2trans-CH=C,
2Jgem 1.8, 3Jtrans 14.3 Hz), 5.41 s (2H, 2NC=CH), 6.33 d.d
(2H, 2OCH=C, 3Jcis 6.7, 3Jtrans 14.3 Hz), 6.62 br.s (2H,
2NH). Found, %: C 68.58; H 7.65; N 7.49. C22H30N2O4.
Calculated, %: C 68.37; H 7.82; N 7.25.
2,5-Bis(2-vinyloxyanilino)-1,4-benzoquinone (IId).
Yield 54%, mp 152–153°C. IR spectrum, ν, cm–1: 3330
(NH), 3110, 3040, 3010 (=CH), 1645, 1605, 1580, 1500
1
(C6H4, C=C–C=O, C=C). H NMR spectrum, δ, ppm:
4.48 d.d (2H, 2cis-CH=C, 2Jgem 1.7, 3Jcis 6.1 Hz), 4.77 d.d
2
3
(2H, 2trans-CH=C, Jgem 1.7, Jtrans 13.1 Hz), 6.11 s
(2H, 2NC=CH), 6.57 d.d (2H, 2OCH=C, 3Jcis 6.1, 3Jtrans
6. Phillips, A.P., J. Am. Chem. Soc., 1956, vol. 78, p. 4441.
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