Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 10, pp. 1780−1784.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
Yu.B. Baranova, A.N. Gafarov, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 10, pp. 1628−1632.
STUDIES IN THE FIELD OF CHEMISTRY OF NITRO COMPOUNDS
(TO 100TH BIRTHDAY ANNIVERSARY OF S. S. NOVIKOV)
Sulfo- and Aminomethylation of 4-Isononylphenol
Yu. B. Baranova and A. N. Gafarov
Kazan State Technological University, Kazan, Tatarstan, Russia
Received July 21, 2009
Abstract—Possibility of synthesizing sulfo- and aminomethyl derivatives of 4-isononylphenol (I) was examined
and the anticorrosion activity of the compounds obtained was determined.
The problem of corrosion control to protect industrial
apparatus is rather topical. At present, corrosion inhibitors
(CIs) are widely used for protection of equipment from the
corrosive effect of the medium. The protective effect of
CIs is caused, depending on the chemical nature of their
active components, by formation of a hydrophobizing
film on the surface of metals or by suppression of
electrochemical corrosion processes .
It is known that alkylated phenols and their func-
tionally substituted derivatives possess antioxidant and
anticorrosive properties and are used as active components
of protective additives and corrosion inhibitors . The
presence of a nucleophilic hydroxy group and ahydrophobic
alkyl substituent in the alkylphenol molecule predetermines
their ability to form complexes with atoms and ions of
a metal and to hydrophobize its surface.
Of interest as chemical processes improving the
anticorrosive properties of alkylphenols are reactions
of functional methylation. In particular, high protective
properties were found for sulfomethyl and aminomethyl
derivatives of alkylphenols.
In order to synthesize active components of corrosion
inhibitors, we studied the reactions of sulfo and amino
methylation of 4-isononylphenol.
Attempts to sulfomethylate 4-isononylphenol with
paraform as a source of formaldehyde and sodium sulﬁ te
at an equimolar component ratio in the temperature range
It was found that the sulfomethylation of 4-isononyl-
phenol occurs only in the presence of water. For this
reason, the reaction was carried out with formalin (40%
aqueous solution of formaldehyde), which supplies in the
given case not only formaldehyde, but also the aqueous
phase. It was also found that the sulfomethylation
of 4-isononylphenol only occurs under the alkaline
hydrolysis conditions. The presence of an alkaline
medium may be due to partial hydrolysis of sodium sulﬁ te
in its dissolution in water:
Possibly, the originally formed ortho-oxymethyl-4-
isononylphenol (II) is converted in the alkaline medium
to an active electrophilic reagent, 3-methylydene-4-
hydroxyisononylbenzyl (III). The sodium sulfonate
methyl derivative of para-isononylphenol (IV) is formed
via nucleophilic addition of a sodium sulﬁ te anion to III
Sodium-3-methylene sulfonate-4-isononylphenol (IV)
was obtained by performing the process in the course of
25 h at a temperature of 90–95°C. The compound exhibits
properties of an anion-active surfactant and possesses an
anticorrosion activity (84.7%) that compares well with
that of the active components of standard formulations.
Aminomethylated derivatives of alkylphenols are
cation-active oil-soluble surfactants. The wide use of
these compounds as active components of antioxidant
additives and corrosion inhibitors is primarily attributed to
their ability to form ammonium ions, which interact with
negatively charged areas of the metal to give poorly soluble
complex compounds of the type of double salts .
In this context, we studied the possibility of condensation
of I with formaldehyde and monoethanolamine. The
choice of monoethanolamine as the amine component