AFM, SPM
N. M. Surin 2
Fig. 1 Absorption and fluorescence emission spectrum 3 a-c in THF
3. Advanced Methods of Organic Synthesis: Poster presentation P-45 SYNTHESIS AND FLUORESCENCE OF
ALKOXYSYLIL DERIVATIVES OF
DIBENZOYLMETHANATE OF BORON DIFLUORIDE 1 - N.S. Enikolopov Institute of Synthetic Polymer Materials of RAS, Laboratory of the Synthesis of Organoelement Polymers, Moscow, Russia
2 - N.S. Enikolopov Institute of Synthetic Polymer Materials of RAS, Laboratory of Thermostable Plastics, Moscow, Russia
Y.N. Kononevich1 I.B. Meshkov1 N.V. Voronina1
3. Advanced Methods of Organic Synthesis: Poster presentation P-46 A SYNTHETIC APPROACH TO SULFUR-
CONTAINING DERIVATIVES OF 3-PYRROLIN-2-ONE
1 - A.M. Butlerov Chemical Institute at Kazan Federal University, Kazan, Russia
2 - A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan, Russia
L.S. Kosolapova1 M.F. Valiev1 A.R. Kurbangalieva1
O.A. Lodochnikova2 E.A. Berdnikov1
G.A. Chmutova1 Almira.Kurbangalieva@ksu.ru
A convenient and efficient approach to the synthesis of various sulfur-containing derivatives of 5-hydroxy-3-pyrrolin-2-one 2-8 was developed via reactions of corresponding thioethers of 5-alkoxy-2(5H)-furanones 1 with different nitrogen-containing mono- and binucleophilic reagents. Bis-thioethers with -SCH2CH2S- chain, connecting two lactam units 5 were obtained from the reaction of corresponding 5-methoxyderivatives of 2(5H)- furanone with ammonia and benzylamine. Products of the reactions with aminoalcohols 2g, 2h under acidic conditions undergo an intramolecular dehydratation to give novel fused bicyclic compounds 6. The utilization of N,N-binucleophilic reagents in amination reactions allowed us to obtain novel heterocyclic compounds of different structural types, e.g.
bis-pyrrolinone 8 that combines -CH2CH2- moiety and two lactam fragments bridged through their nitrogen atoms. Novel compounds of the 3-pyrrolin-2-one series have been characterized in detail by NMR spectroscopy and single crystal X-ray diffraction.
1 O O
H OCH3 Cl
CH3 S
NH2R
NR O
H OH Cl
S CH3
Et2O, EtOH
a R = H f R = CH(CH3)C6H5
b R = CH2C6H5 g R = CH2CH2OH c R = CH2C6H4CH3-p h R = CH2CH2CH2OH d R = CH2CH(CH3)2 i R = OH
e R = CH(CH3)2 j R = NH2
2
NH OH O
H
RN O
HO H S Cl
S
NR Cl
O
H OH
Cl N O
H O
N O
H OH Cl
p-TolS
N O
H HO
Cl N
H O
O n Cl
NH OH O
H S S
3 4
7
5 a R = H, b R = CH2C6H5
6 a n = 1, b n = 2 8
CH3 S
S CH3
CH3 S CH3 S STol-p
The financial support from the Ministry of Science and Education of Russian Federation within FTP "Scientific and scientific-pedagogical personnel of the innovative Russia" (Governmental Contract No 14.740.11.1040) is gratefully acknowledged.
3. Advanced Methods of Organic Synthesis: Poster presentation P-47 SYNTHESIS AND PROPERTIES OF COMPOUNDS
ON THE BASIS OF 5-ARYL-3-ARYLIMINO-3H- FURAN-2-ONES
1 - Perm State Pharmaceutical Academy, Perm, Russia 2 - Perm State University, Perm, Russia
V.J. Kozhukhar1 N.A. Pulina1
A.E. Rubtsov2 slavaperm@inbox.ru
One of the fundamental problems of preparative organic chemistry is the synthesis of new compounds that have a practical application as biologically active compounds or building blocks for the construction of new compounds. For this purpose, there is a significant interest in 5-aryl-3-arilimino-3H-furan-2-ones. Analysis of published data demonstrates that iminofuranones represent a promising class of furan derivatives, as their structure determines rich synthetic possibilities.
Initially, (Z)-2-((4-(ethoxycarbonyl)phenyl)amino)-4-oxo-4-phenylbut-2-enoic acid (1) was obtained by the known method [1]. On the 2nd stage it was converted into (E)-3-((4- (1-ethoxycarbonyl)phenyl)imino)-5-phenylfuran-2(3H)-one (2) under the action of acetic anhydride.
Heterylamides of N-substituted 2-amino-4-aryl-4-oxobut-2-enoate acids (3) were obtained by interaction of iminofuranones (2) with a number of heteryl amines:
The structure of iminofuranone 2 and decyclized derivatives 3a-i proved by IR, 1H NMR spectroscopy, mass spectrometry and is in good agreement with published data for related structures.
References:
1. Zalesov, V.V. Synthesis, structure and chemical properties of N-substituted 2(3)-amino-2,3-dihydrofuran- 3(2)-ones (review) / V.V. Zalesov, A.E Rubtsov // Chemistry of Heterocyclic Compounds.- 2004.- №2.- Pp.
163-186.
This work is supported by RFBR (project № 11-03-00882).
N CH3
N
H2 S
N N
C2H4SH N
H2
S N N H2 S
N N
SH N
H2
N N
N NH2
CH3 N
H2
N NH
H
N H
NH N N N N H2
S N
NH2 OH
O N
O
H
O O
O N
O O O
(CH3COO)2O -2 CH3COOH
NR1R2
O N
O
H
O O
NHR1R2 = (a), (b), (c), (d),
(e), (f), (g), (h), (i).
2 3
1
NHR1R2
3. Advanced Methods of Organic Synthesis: Poster presentation P-48 REACTIVITY OF FLUORENES IN THE REACTION
OF CYANINE CONDENSATION
1 - Institute of Organic Chemistry National Academy of Sciences of Ukraine, Colour and Structure of Organic Compounds Department, Kiev, Ukraine
2 - Donetsk National Technical University, Physical and Organic Chemistry Department, Donetsk, Ukraine
I.V. Kurdyukova1 N.A. Derevyanko1 A.A. Ishchenko1
D.D. Mysyk2 Iryna_Kurdiukova@ukr.net
Fluorene has extended π-system, high electronic symmetry, and the methylene group potentially capable, due to conjugation with two benzene nuclei, to be active in the reaction of cyanine condensation. Therefore, the carbocyclic fluorene core is a promising terminal group of polymethine dyes. However, unsubstituted fluorene does not enter into this reaction even in the presence of such strong organic bases as sodium ethoxide, potassium tert-butoxide, DBU and "proton sponge" (N,N,N′,N′-tetramethylnaphthalene-1,8-diamine).
DFT//B3LYP/6-31G(d,p) quantum chemical calculations of fluorene anion showed that the electron density increases on excitation mainly in the positions 2, 4, 5 and 7.
Therefore, the acceptor substituents in these positions will have the largest influence on the dye colour. The fluorene acidity and the methylene group activity in the cyanine condensation increases with such substitution.
Really, even acceptors of medium strength in the positions 2 and 7 (see scheme) allowed to carry out the condensation in the presence of DBU. 2,7-Dinitrofluorene also reacts when DBU is used as a condensing agent. And only with 2,4,5,7-tetranitrofluorene the cyanine condensation takes place under its standard conditions.
R2
R1
R2
R1
R2
R1
R2
R1
n
R1
R1
R2
R2
N HN
Ph
Ph n
+
Cln = 1, 2 Ct+
H Base
+
1: n = 2, R1 = SO3Ph, R2 = H
2: n = 1, R1 = R2 = NO2
3: n = 2, R1 = R2 = NO2
A novel deeply coloured anionic polymethine dyes 1-3 containing only carbocycles as terminal groups have been synthesized by this method.
3. Advanced Methods of Organic Synthesis: Poster presentation P-49 NITRONORBORNENE DERIVATIVES IN THE REACTION OF 1,3-DIPOLAR CYCLOADDITION
ETHYL DIAZOACETATE
1 - St. Petersburg State Mining University, St. Petersburg, Russia 2 - Saint-Petersburg State Technological University of Plant Polymers, St. Petersburg, Russia