AFM, SPM
OF 2-(E)-(THIENYL-2)VINYLDERIVATIVES OF FLUORINATED BENZAZINES
1 - Ural Federal University named after the First President of Russia Boris N. Yestsin, Yekaterinburg, Russia
2 - I.Ya. Postovskiy Institute of Organic Synthesis, Ural Division of the Russian Academy of Sciences, Yekaterinburg, Russia
Т.V. Trashakhova1 E.V. Nosova1
N.A. Malih1 М.S. Valova2 G.N. Lipunova2
V.N. Charushin2 ten786@mail.ru
Organic molecules that contain styryl moiety are an important fluorescent class and show a number of attractive photophysical and electro-optical properties. It is known that replacing of aryl fragment by π-excessive thiophene leads to large red-shift in absorbtion and emission spectra.
The synthesis of 3-phenyl-2-(E)-(2-thienyl)vinylquinazolin-4-ones 1a,b was achieved by refluxing of correspondent 2-methylquinazoline with thiophen-2-carbaldehyde and sodium acetate in acetic acid during 12-36 h in 36-70% yield. Novel trans-2-(2- thienyl)vinyl-6,7-difluorobenzazines 2а-c have been synthesyzed by condensation of 6,7- difluoroquinaldine, 2-methyl-6,7-difluoroquinolin-4-carboxylic acid or 2-methyl-6,7- difluoroquinoxaline with thiophen-2-carbaldehyde under reflux in glacial acetic acid in the presence of AcONa during 6-12 h.
N X F
F
S N
N O
S Y
Y
1a,b 2а-c
1: Y=H (a), F(b); 2: X=CH (а), С-СООН (b), N (c).
Upon photoexcitation, compounds 1, 2 display photoluminescence in MeCN solution and demonstrate emission wavelength 439-502 nm. Derivative 2c has the largest value of quantum yield (0.016). At decrease in temperature with 273 to 77 K intensity of emission increases in 77-143 times.
This work was supported by the Russian Foundation for Basic Research (grant 11-03-00718), the Grant of the Progressive Scientific Schools NSh-65261.2010.3 and State Contract GK- 02.740.11.0260.
3. Advanced Methods of Organic Synthesis: Poster presentation P-88 REACTIONS OF PERFLUOROCARBOXYLIC ACIDS
WITH MONOTERPENS
St. - Petersburg State Technological University of Plant Polymers, Department of Organic Chemistry, St. - Petersburg, Russia
Yu.G. Trishin M.V. Shafeeva
L.A. Tamm M.A. Yazvenko E.A. Artemenko
G.V. Votintseva
A.I. Medvedeva trish@YT4470.spb.edu
Addition of perfluorocarboxylic acids (PFCA) to the olefins is one of the important methods of esters RFC(O)OR synthesis. The properties such esters vastly differ from characteristic anfluorinated analogues. Such compounds containing as R residue of terpens are very interesting as perspective biologically active material. We found that selectivity of addition PFCA to monoterpens is mainly defined the structure of monoterpens in reaction with electrofilic reagents undergo the different rearrangements.
Perfluoroacylation of camphene by carboxylic perfluoroaliphatic acids is chemo- and stereoselective and result in isobornylperfluoroacylates (yield 85-90%). In reaction of such acids with limonene according to conditions participate only exocyclic or both bonds C=C.
As a result are formed terpinylperfluoroacylates or terpinylbisperfluoroacylates (yield 70- 85%). It was found that rate these reactions decrease with an increase of carbon acid chain.
However addition of perfluorobenzoic and 2,3,4,5-tetrafluorobenzoic acids to camphene and limonene occurs only in the hard conditions (heating, catalyst - a sulfuric acid) and is accompanied by the partial isomerization of monoterpens.
The interaction PFCA with α- and β-pinenes, α- and γ-terpinenes is characterized variety of rearrengements of the intermediates. This processes do not allow to get terpenilperfluoroacylates with predominance one of the isomers.
Addition of PFCA to endocyclic bond of cycloalkenes investigated in detail by the example of cyclohexene.
All new compounds were characterized by 1H, 13C, 19F NMR, IR spectrometry.
3. Advanced Methods of Organic Synthesis: Poster presentation P-89 SOME NEW PHOSPHORYLATION REACTIONS OF
5,7-DICHLORO-4,6-DINITROBENZOFUROXAN 1 - Kazan Federal University, A.M. Butlerov Chemical Institute, Kazan, Russia
2 - Kazan State Technological University, Kazan, Russia E.V. Tudriy1
I.V. Galkina1 O.N. Kataeva1 L.M. Yusupova2
V.I. Galkin1 tev_25@mail.ru
In continuation of our systematic investigations of phosphorylation of 5,7-dichloro- 4,6-dinitrobenzofuroxan by various tertiary phosphines we report about some new results in this field.
N O N Cl O2N
Cl
NO2
O
2 PhP(NEt2)2
N O N O2N O
O2N
O
P(NEt2)2 Ph
HCl EtCl EtOH
N O N Cl O2N
Cl
NO2
O
2 P(C6H4F-p)3
Cl N
O N
P(C6H4F-p)3 Cl
O O
P(C6H4F-p)3 O
{ 2NO } _
EtOH
N O N Cl O2N
Cl
NO2
O
2 P(C6H4OCH3-p)3
OH
Cl O2N
N O N
P(C6H4OCH3-p)3 EtOH O
EtCl; NO (p. CH3OC6H5)3P
O
The structure of obtained products has been confirmed by X-ray analysis, mass- spectrometry, elemental analysis, NMR 31P, IR, EPR, TG/DSC analysis.
Synthesized products showed high antibacterial biological activity.
The research is supported by grants of Academy of Sciences of Tatarstan Republic.
3. Advanced Methods of Organic Synthesis: Poster presentation P-90 UNUSUAL INTERACTION OF
2-METHYLRESORCINOL AND PYROGALLOL WITH PHOSPHORYLATED AMINOACETALS
1 - A.E. Arbusov Institute of Organic and Physical Chemistry Kazan Scientific Center of the Russian Academy of Science, Department of Organoelemental Chemistry, Kazan, Russia
2 - A.E. Arbusov Institute of Organic and Physical Chemistry Kazan Scientific Center of the Russian Academy of Science, Department of Physical-chemistry Research, Kazan, Russia
L.I. Vagapova1 A.R. Burilov1 D.R. Sharafutdinova2
J.K. Voronina2
M.A. Pudovik1 vagapovan@mail.ru
Aminophosphonates and their peptidic analogues are mostly recognized as the biologically active compounds with variety of useful activities ranging from inhibitors of many metalloenzymes to herbicides. Thus the availability of new derivatives of aminophosphonates is still very important.
Early it was shown that condensation of (P/N)-containing acetals with resorcinol and its derivatives can lead, depending on experimental conditions, to the formation of calix[4]resorcinols or diarylmethane compounds containing on the lower rim organoelemental fragments.
In order to obtain new aminophosphonates derivatives we have investigated the condensation of 2-methylresorcinol, pyrogallol with phosphorylated aminoacetals 1. It has appeared that this reaction leads to the formation of two products: diarylmethane (2) and piperazine (3) derivatives, containing in its structure phosphonate groups.
The structures of synthesized compounds were proved by means 1H, 31P NMR spectroscopy, RCA, MALDI-TOF mass spectroscopy.
HO R"
OH HO
R"
OH
NH2 O P O R' O
R' Cl
HO OH
R"
+(MeO)2CHCH2NHCH2P O OR'
OR'
N N P O O
R' O R'
P O
O O R'
R' OH
R'' HO
OH R"
OH HA
-2MeOH
-4MeOH
1a-b
R"=Me, OH R'=H, Et
A-=Br, Cl, CF3COO
2
3
The influence of experimental conditions (the nature of acids, solvents, stoichiometric ratio of the starting reagents) on the result of this reaction will be discussed.
This work was supported by the Russian Foundation for Basic Research (grant 11-03-00416а)
3. Advanced Methods of Organic Synthesis: Poster presentation P-91 REACTIONS OF 3 CYANO-1-ETHYL-5-(HET)ARYL-
2-(1H)-PYRAZINONES
I.Ya. Postovsky Institute of Organic Synthesis (Ural Division of the Russian Academy of Sciences), Ekaterinburg, Russia
E.V. Verbitskiy E.M. Cheprakova
P.A. Slepukhin O.N. Zabelina M.G. Pervova M.A. Samorukova
G.L. Rusinov V.N. Charushin
Verbitsky@ios.uran.ru
2(1H)-Pyrazinones 2 are easily accessible from corresponding from 5-(het)aryl-substituted 1-ethyl-2,3-dicyano-1,4-diazinium salts 1 through acidic hydrolysis.
5-(Het)aryl-1-ethyl-3-cyano-2(1H)-pyrazinones 2 have been found to undergo intermolecular hetero-Diels-Alder reaction with acetylenes under controlled microwave irradiation.
In case of symmetric acetylenes, for example dimethylacetylenedicarboxylate, these Diels-Alder reaction leads to a mixture of pyridone 3 and pyridine 4 products. It should be noted that the formation of 2(1H)-pyridone 3 is a predominant cycloaddition reaction. On the other hand, reactions with terminal acetylenes have been found to result in the formation of a mixture 4- (het)aryl- 5 and 5-(het)arylsubstituted 6 2(1H)-pyridones without of the corresponding pyridine derivatives. Regioselectivity of these processes have been studied by NMR spectroscopy and GC/MS data.
Also, 3,6-bis(2-(1H)-pyrazinon-3-yl)-1,4-dihydro-1,2,4,5-tetrazines 7 can be prepared by the reaction of 5-(het)aryl-1-ethyl-3-cyano-2(1H)-pyrazinones 2 with hydrazine hydrate in the presence of hydrochloric acid.
N N NC
NC Ar
Et
N N O
NC Ar
Et
COOR ROOC
N O
NC COOR
Et COOR
N
ROOC
COOR
NC Ar
R'
N O NC
Et R'
O N
NC R'
Et
N N N N N
N N
N H
H Ar O
O Ar
Et
Et +
H2O, H MeCN + BF4
_
1 2
MW, Ionic liquid +
MW, Ionic liquid
3 4
5
major minor
+
6
major minor
7
Ar= Ph, 4-X-Ph, thiophen-2-yl, thiophen-3-yl, ...
X= OAlk, Hal, ...
NH2-NH2
Compounds obtained are of interest as ligands for the synthesis of complexes.
This work was supported by the Programs of Ural Division of RAS 09-И-3-2004, 09-П-3-1015, 09- Т-3-1022, State Contract № 02.740.11.0260., the Russian Foundation for Basic Research (grant no.
09-03-12242-ofi_m) and the State Program for Supporting Leading Scientific of the Russian Federation (grant no. NSh-65261.2010.3)
3. Advanced Methods of Organic Synthesis: Poster presentation P-92 FIRST MACROBICYCLIC COMPLEXES WITH
INHERENT NITRILE SUBSTITUENTS AND UNEXPECTED DEHALOGENATION – REDUCTION
REACTION AT A CLATHROCHELATE FRAMEWORK
1 - Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, Russia
2 - Vernadskii Institute of General and Inorganic Chemistry NANU, Kiev, Ukraine
Y.Z. Voloshin1 A.S. Belov1 O.A. Varzatskii2
Z.A. Starikova1
E.G. Lebed1 voloshin@ineos.ac.ru
The monoribbed-substituted mono- and difunctionalized iron(II) macrobicycles with inherent nitrile substituents were obtained for the first time by the reaction of the iron(II) diiodoclathrochelate with copper(I) cyanide – triphenylphosphine complex under the mild conditions (Scheme 1).
Scheme 1
The target dinitrile clathrochelate is a minor product of this reaction, whereas the major product contains one cyano group in its molecule. The single crystals suitable for the X-ray crystallography were obtained only in the case of the crystallization from a mixture of the products and their unit cell contains one dinitrile and one mononitrile molecules (Scheme 1). The mechanism of the dehalogenation – reduction reaction that resulted in substitution of iodine atoms by cyano group and hydrogen atom (Scheme 2) includes the anion-radical hydrodehalogenation of the diiodoclathrochelate with acetonitrile as a source of hydrogen atom, whereas the product underwent a substitution with cyano group only.
The copper(I) cyanide – triphenylphosphine – acetonitrile system is proposed as a tool for the synthesis of nitrile derivatives of the electron-withdrawing heterocycles starting from their halogen-containing precursors.