Anticorrosion properties of products of N-(2-Vinyloxyethyl)-1,2- ethylenediamine condensation with carbonyl compounds

Article abstract of DOI:10.1134/S1070427210090302

N-(2-Vinyloxyethyl)-N′-cyclohexylidene-1,2-ethylenediamine and N,N′,N′-tris-[2-(2-vinyloxyethyl)-aminoethyl]hexahydro-1,3, 5-triazine were synthesized by reactions of N-(2-vinyloxyethyl)-1,2- ethylenediamine with cyclohexanone and formaldehyde with yields

Full text of DOI:10.1134/S1070427210090302

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 9, pp. 1666–1667. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © B.F. Kukharev, V.K. Stankevich, G.R. Klimenko, N.A. Lobanova, E.N. Kovalyuk, A.Yu. Negoda, V.V. Stankevich, E.V. Bragin, 2010,
published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 9, pp. 1570–1571.
BRIEF
COMMUNICATIONS
Anticorrosion Properties of Products
of N-(2-Vinyloxyethyl)-1,2-ethylenediamine
Condensation with Carbonyl Compounds
B. F. Kukharev, V. K. Stankevich, G. R. Klimenko, N. A. Lobanova,
E. N. Kovalyuk, A. Yu. Negoda, V. V. Stankevich, and E. V. Bragin
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Received December 24, 2009
Abstract―N-(2-Vinyloxyethyl)-N'-cyclohexylidene-1,2-ethylenediamine and N,N',N"-tris-[2-(2-vinyloxyethyl)-
aminoethyl]hexahydro-1,3,5-triazine were synthesized by reactions of N-(2-vinyloxyethyl)-1,2-ethylenedi-
amine with cyclohexanone and formaldehyde with yields of 91 and 90%, respectively. The IR and 1H and 13C
NMR spectral data and the results of studying their anticorrosion properties are given.
DOI: 10.1134/S1070427210090302
Nitrous bases [1, 2], in particular some vinyl ethers
of amino alcohols and their derivatives [3, 4], are
known to exhibit anticorrosion properties.
The condensation was carried out at boiling of an
equimolar mixture of reagents in toluene with azeo-
tropic distilling off water. As a result imine (IV) was
obtained from cyclohexanone (II) and amine (I) with a
yield of 91%. As it is known for imines, which are
derivatives of formaldehyde [5], imine (V) formed
intermediately in the reaction of formaldehyde (III)
with amine (I) is trimerized into triazine (VI). The
yield of triazine (VI) was 90%:
To detect anticorrosion properties of vinyl ether N-(2-
amino-ethyl)-1,2-aminoethanol (I) and its derivatives,
in the present work we have carried out the condensa-
tion of this ether with carbonyl compounds, which are
accessible large-tonnage products: cyclohexanone and
formaldehyde (in the form of paraformaldehyde).
CH2=CHOCH2CH2NHCH2CH2N=CR2
CH2=CHOCH2CH2NHCH2CH2NH2 + R2C=O
−H2O
I
II, III
IV, V
R = H
(CH2)2NH(CH2)2OCH=CH2
N
H2C=CHO(CH2)2NH(CH2)2N
N(CH2)2NH(CH2)2OCH=CH2
VI
R2 = (CH2)5 (II), (IV); R = H (III, V).
The trimeric structure of product VI is confirmed
by the absence of signals of protons and of the carbon
atom of the =СН2 group from the 1Н and 13С NMR spec-
tra, the presence of signals of protons and of the car-
bon atom of the NCH2N group, and also by a high boiling
point essentially exceeding the boiling point of imine IV.
1666

ANTICORROSION PROPERTIES OF PRODUCTS
1667
To estimate inhibiting properties of initial vinyl
ether of amino alcohol I and compounds IV and VI
obtained from it, we have studied their effect on the
corrosion of St.20 steel in 20% hydrochloric acid. The
rate of metal dissolution was determined by a
gravimetric method using 2×20×6 mm steel samples
according to GOST 9.505-86 at 20°С and exposure
time of 3 h. At the concentration of compounds I and
IV 10–2 M and of compound VI 3.33×10–3 M the
following protective effect Z (%) was obtained: 97.5
(IV), 94.4 (VI), and 34.9 (I). Thus, it has been shown
that though N-(2-vinyloxyethyl)-1,2-ethylenediamine
(I) itself does not inhibit the acid corrosion process, the
products of its condensation with carbonyl compounds
IV and VI possess a good protective effect. It shows
searching for new corrosion inhibitors among such
compounds is promising.
N,N',N"-Tris-[2-(2-vinyloxyethyl)aminoethyl]-
hexahydro-1,3,5-triazine (VI). Similarly to the
previous synthesis from 25.6 g (90%) of compound VI,
bp 175–178°С (3 mm Hg), d420 1.0218, nD20 4960, was
obtained from 26 g (0.2 mol) of N-(2-vinyloxyethyl)-
1,2-ethylenediamineа (I) and 6 g (0.2 mol) of para-
formaldehyde (III). IR spectrum, ν, cm–1: 1605, 1625,
3025, 3075, 3110, 3280. 1Н NMR spectrum, δ, ppm (J,
3
3
Hz): 6.43 d.d (OCH=C, 1H, Jcis 6.9, Jtrans 14.3), 4.10
2
3
d.d (trans-CH=C, 1H, Jhem 1.8, Jtrans 14.3), 3.93 d.d
2
3
(cis-CH=C, 1H, Jhem 1.8, Jcis 6.9), 3.44 s(NCH2N,
2H), 3.73 t (ОCH2, 2H, 3J 5.6), 3.01 t (NHCH2CH2N,
3
3
2H, J 7.1), 2.73 t (NHCH2CH2O, 2H, J 5.6), 2.62 t
(NHCH2CH2N, 2H, J 7.1), 1.83 br.s (NH, 1H). 13C
3
NMR spectrum, δ, ppm: 151.60 (OCH=), 86.34
(=CH2), 75.32 (NCH2N), 66.66 (OCH2), 53.54
(NCH2CH2NH), 52.69 (NCH2CH2NH), 50.39
(NHCH2CH2O). Found, %: C 59.33, Н 10.03, N 19.51.
C21H42N6O3. Calculated, %: C 59.12, Н 9.92, N 19.70.
EXPERIMENTAL
Commercial paraformaldehyde (purity of 98.3%)
and cyclohexanone purified by fractionation up to a
base material content of no less than 99.8% were used
for the synthesis. N-(2-Vinyloxyethyl)-1,2-ethylenedi-
amine was obtained by a procedure described in [6].
CONCLUSIONS
(1) It has been shown that products of N-(2-
vinyloxyethyl)-1,2-ethylenediamine condensation with
cyclohexanone and formaldehyde have the imine and
symmetrical triazine structures, respectively.
N-(2-Vinyloxyethyl)-N'-cyclohexylidene-1,2-ethyl-
enediamine (IV). A mixture of 26 g (0.2 mol) of N-
(2) In the case of steel acid corrosion the protective
effect N-(2-vinyloxyethyl)-N'-cyclohexylidene-1,2-ethyl-
enediamine and N,N',N"-tris-[2-(2-vinyloxyethyl)amino-
ethyl]hexahydro-1,3,5-triazine is 94.4–97.5%.
(2-vinyloxyethyl)-1,2-ethylenediamine (I), 19.6
g
(0.2 mol) of cyclohexanone, and 100 ml of toluene
were boiled with a Dyne–Stark trap up to the termina-
tion of water separation. The reaction mixture was
cooled and distilled. Yield of compound IV 38.2 g
(91%), bp 119–121°С (3 mm Hg), nD20 1.500. IR spec-
trum, ν, cm–1: 1605, 1615, 1660, 3040, 3065, 3100,
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3
3
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RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 9 2010