Dinitroaniline in kabachnik-fields reaction

Article abstract of DOI:10.1080/10426507.2010.523034

Simple conditions for the Kabachnik-Fields reaction of 2,4-dinitroaniline with arylaldehydes and triphenyl phosphite were found. Several diphenyl N-2,4- dinitrophenylaminobenzylphosphonates have been synthesized. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426507.2010.523034

This article was downloaded by: [University of Chicago Library]
On: 11 October 2014, At: 10:45
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the
Related Elements
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gpss20
Dinitroaniline in Kabachnik–Fields
Reaction
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) Dinitroaniline in Kabachnik–Fields
Reaction, Phosphorus, Sulfur, and Silicon and the Related Elements, 186:4, 778-779, DOI:
10.1080/10426507.2010.523034
To link to this article: http://dx.doi.org/10.1080/10426507.2010.523034
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Phosphorus, Sulfur, and Silicon, 186:778–779, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.523034
DINITROANILINE IN KABACHNIK–FIELDS REACTION
Alexey L. Chuiko and Miron O. Lozinskiy
Institute of Organic Chemistry, NAS of Ukraine, Kyiv, Ukraine
Abstract Simple conditions for the Kabachnik–Fields reaction of 2,4-dinitroaniline
with arylaldehydes and triphenyl phosphite were found. Several diphenyl N-2,4-
dinitrophenylaminobenzylphosphonates have been synthesized.
Keywords α-Aminophosphonates; Kabachnik–Fields reaction
INTRODUCTION
The Kabachnik–Fields reaction of an amine, a carbonyl compound, and a
phosphorus component is a well-known method implemented for the synthesis of
α-aminophosphonates.1 2,4-Dinitroaniline has not been utilized in this reaction, probably
because of its low nucleophilicity. The only example was published in 2007,2 where
magnesium perchlorate was used as a catalyst.
At the same time, it is known that poorly nucleophilic amides can undergo a three-
component Kabachnik–Fields type condensation that is particularly effective for triphenyl
phosphite.3
RESULTS AND DISCUSSION
We have found that N-2,4-dinitrophenylaminobenzylphosphonates can be easily ob-
tained in conditions described previously for amides, namely, a short reflux in acetic acid.
Other anilines used as substrates are acylated under such conditions, thus, application of
4-nitroaniline leads to N-acetyl-4-nitroaniline with a good yield.
Target phosphonates were formed in the reaction mixture with 58–84% yield while
refluxing an equimolar ratio of the starting aldehyde, 2,4-dinitroaniline, and 15% molar
excess of (PhO)3P in acetic acid (Table 1). In most cases, they crystallized after dilu-
tion of the reaction mixture with alcohol. Yields of separated crystalline products varied
in range 50–75%. Starting 2,4-dinitroaniline was found as the only admixture in some
cases. The crude materials were then purified by recrystallization from acetonitrile or an
acetone/alcohol mixture.
Received 17 August 2010; accepted 8 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
778

DINITROANILINE IN KABACHNIK–FIELDS REACTION
779
Table 1 Conditions of the reaction: CH3COOH, reflux, 1 h; Formation in the reaction mixture calculated
according to the 31P NMR spectra
R
NO2
O
PO3Ph2
H
NH2
N
P(OPh)3
+
+
R
O2N
NO2
O2N
Formed in the
31P
R
reaction mixture
Yield
[DMSO-d6]
p-Me
p-OMe
p-Cl
84%
71%
71%
66%
64%
59%
63%
75%
50%
64%
60%
51%
57%
14.8
15.1
14.2
14.2
13.1
13.0
14.8∗
p-F
m-NO2
p-NO2
p-OH
No crystallization
∗Data from NMR of the reaction mixture.
REFERENCES
1. http://en.wikipedia.org/wiki/Kabachnik-Fields reaction.
2. Bhagat, S.; Chakraborti, A. K. J. Org. Chem. 2007, 72, 1263–1270.
3. Oleksyszyn, J.; Subotkowska, L.; Mastalerz, P. Synthesis 1979, 985–986.