Phosphonomethylation of dinitroaniline-substituted alkylamines

Article abstract of DOI:10.1080/10426507.2010.522637

It was found that aminoalkyl derivatives of 2,4-dinitroaniline can be phosphonomethylated at the terminal aliphatic amino group using a known method, whereas the aromatic part of the molecule and bound nitrogen atom remain unaffected. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426507.2010.522637

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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Phosphonomethylation of Dinitroaniline-
Substituted Alkylamines
Alexey L. Chuiko a & Miron O. Lozinskiy a
a Institute of Organic Chemistry , NAS of Ukraine , Kyiv , Ukraine
Published online: 25 Apr 2011.
To cite this article: Alexey L. Chuiko & Miron O. Lozinskiy (2011) Phosphonomethylation of
Dinitroaniline-Substituted Alkylamines, Phosphorus, Sulfur, and Silicon and the Related Elements,
186:4, 780-781, DOI: 10.1080/10426507.2010.522637
To link to this article: http://dx.doi.org/10.1080/10426507.2010.522637
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Phosphorus, Sulfur, and Silicon, 186:780–781, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.522637
PHOSPHONOMETHYLATION OF
DINITROANILINE-SUBSTITUTED ALKYLAMINES
Alexey L. Chuiko and Miron O. Lozinskiy
Institute of Organic Chemistry, NAS of Ukraine, Kyiv, Ukraine
Abstract It was found that aminoalkyl derivatives of 2,4-dinitroaniline can be phospho-
nomethylated at the terminal aliphatic amino group using a known method, whereas the
aromatic part of the molecule and bound nitrogen atom remain unaffected.
Keywords α-Aminophosphonates; phosphonomethylation
INTRODUCTION
N-Alkylated 2,4-dinitroanilines show a strong inhibition of plant growth and may be
used as contact herbicides.1 2,4-Dinitrophenylpiperazine derivatives are similarly active.2
The purpose of our study was the synthesis and evaluation of properties of analogous
compounds containing hydrophilic phosphonic groups in their structure.
Phosphonomethylation of alkylamines or ammonia by a mixture of formaldehyde
and phosphoric acid in strong acidic medium is a well known and widely used reaction.3
At the same time, we have not found examples of the use of this reaction for the synthesis
of aminophosphonates containing N-phenyl group in their structure. It is the result of the
undesired interaction of formaldehyde with the anilines in the reaction condition that results
in the formation of byproducts of polymeric character.
RESULTS AND DISCUSSION
The starting N-aminoalkyl derivatives of 2,4-dinitroaniline were synthesized in a
reaction of 2,4-dinitrochlorobenzene with an excess of a polyamine.
When refluxed in hydrochloric acid with phosphoric acid and formaldehyde, the
2,4-dinitrophenyl substituted amino group and the aromatic part of the molecule was not
modified in the title reaction, while the primary or secondary alkyl amine converted to
the corresponding bis (compound 1 and 3) or mono methylenephosphonate (compound 2),
respectively (Scheme 1). The products crystallized from the reaction mixture after partial
evaporation of hydrochloric acid and dilution the mixture with water.
Received 17 August 2010; accepted 7 September 2010.
Address correspondence to A. L. Chuiko, Institute of Organic Chemistry, NAS of Ukraine, Murmans’ka Str.
5, 02094 Kyiv, Ukraine. E-mail: chuikoal@yahoo.com
780

DINITROANILINE-SUBSTITUTED ALKYLAMINES
781
NO2
NO2
PO3H2
N
HClaq, reflux
N
O2N
N
NH2
H2C=O
H3PO3
+
+
H
O2N
H
PO3H2
1, 43%
NO2
NO2
PO3H2
PO3H2
N
N
N
N
N
PO3H2
O2N
O2N
3, 46%
2, 83%
Scheme 1 The products of phosphonomethylation of selected N-aminoalkyl derivatives of 2,4-dinitroaniline and
the obtained yields.
The products are bright yellow solids that decompose above 200◦С, and are insoluble
in water and in most organic solvents. They can be recrystallized from DMSO or acetic
acid. They form salts with alkali and alkylamines, and are well soluble in water and DMSO,
respectively.
REFERENCES
1. Britzun, V. M.; Shvartau, V. V.; Ozerova, L. V.; Lozinskiy, M. O. Patent UA 84947, 2008.
2. Private communication with A. Yu. Nyporko, 2008.
3. Moedritzer, K.; Irani, R. R. J. Org. Chem. 1966, 31, 1603–1607.