Targeted synthesis of diaryl-substituted 8-amino-1-imino-6-morpholino-2-oxa7-azaspiro[4.4]nona-3,6,8-triene-9-carbonitriles
M.Yu. Belikov, M.Yu. Ievlev, I.V. Belikova
Chuvash State University, Moskovskiy pr.15, Cheboksary 428015, Russia
E-mail: belikovmil@mail.ru
The synthesis of diarylethenes (DAE) is the actual problem, because of their practically
important photochromic properties. It is known, that photochromic DAE can be useful for creating
information processing systems, imaging of biological processes etc. The synthesis of compounds
with spiro-fused ethene «bridge» is insufficiently explored. The presence of such moiety is able to
affect on practically useful properties of DAE, to increase quantum yield of direct photochemical
reaction for example [1].
It is known, that 4-oxoalkane-1,1,2,2-tetracarbonitriles can be transformed into spirocompounds under action of basic reagents [2,3]. With the aim to obtain new representatives of
spiro-fused diarylethenes, 3,4-diaryl-4-oxobutane-1,1,2,2-tetracarbonitriles 2a-c were synthesized
and their interaction with morpholine was studied. It was found, that diarylethene-contained spirocompounds – 8-amino-1-imino-6-morpholino-2-oxa-7-azaspiro[4.4]nona-3,6,8-triene-9-carbonitriles
3a-c are the result of these processes.
The structure of spirans 3a-c established using the data of IR-, 1H NMR,
13
C NMR-
spectroscopy and mass-spectrometry.
Found that compounds 3a-c have no photochromic properties. It may be related with the
steric problems caused by spatial closeness of aryl substitutes and morpholine moiety, that
complicates the process of photocyclization
This work was financially supported by a grant of the President of the Russian Federation
MK-97.2014.3.
Literature
[1] K. Morinaka, T. Ubukata, Y. Yokoyama, Org. Lett. 2009, 11, 3890-3893.
[2] M.Yu. Belikov, O.V. Ershov, I.V. Lipovskaya, S.V. Fedoseev, O.E. Nasakin, Rus. J. Org. Chem. 2013, 6, 864–866.
[3] S.V. Fedoseev, O.V. Ershov, M.Yu. Belikov, K.V. Lipin, I.N. Bardasov, O.E. Nasakin, V.A. Tafeenko, Tetrahedron
Lett. 2013, 17, 2143-2145.