AFM, SPM
A. Azizov N.S. Nabiyev
R.M. Alosmanov
I.A. Bunyad-zadeh r_alosmanov@rambler.ru
Reaction of oxidative chlorophosphorylation can be used as simple preparation method of the phosphorus-groups containing polymers. In publications devoted to olefin type polymers have been reported that phosphorus containing group directly adds to matrix with phosphorus-carbon bonds formation, and in case of diene polymers both the addition by pointed type and through oxygen took place. It is known that this reaction proceeds by chain-radical mechanism in the presence of atomic chlorine as initiator. Future radicals interaction with PCI3 or O2 can be explained by initial radicals stability: more stable radical reacts with oxygen and as a result of this interaction phosphorus-containing group adds to polymer through oxygen.
In present work the electron distribution of the intermediate radical obtained as a result of attack of macromolecule with chlorine by the quantum chemical analysis has been presented.
The quantum chemical analysis have been done with AM 1 and RM 3 semiempirical methods. The calculated models on the basis of chemical structure with application of the component atoms covalent radiuses have been constructed. The atoms coordinates corresponding to pre-optimized geometric structure of the compounds have been used under electron structure optimization. It have been established that the effective charges of macro radicals R1 and R2 are - 0.126 and -0.111 respectively.
Hence, R2 has more sensitivity to oxygen than R1, that has been established by NMR investigations of the solid phase.
1. Theoretical Organic Chemistry: Poster presentation P-10 THE INFLUENCE OF MOLECULAR DYNAMICS
SIMULATIONS ON THE STRUCTURE OF
SOLVATION OF MOLECULE IN SOLVENT AND ITS MANIFESTATION ON NMR SPECTRA
1 - E.K. Zavoisky Physical-Technical Institute, Quantum Dinamics and Informatics Laboratory, Kazan, Russia
2 - Kazan Federal University, Physics Institute, Kazan, Russia 3 - SGT, Kazan, Russia
E.R. Martynchuk1 R.M. Aminova2
S.L. Martynchuk3 baisupova@mail.ru
Problem of the dynamical processes influence on the structure and chemical shifts of the solute molecule in solvent is very actual.
It is important to construct the initial structure of solvation shell containing the solvent molecules. For this purpose in this work the program for construction of initial structure of solvation shell has been elaborated by using the program language JAVA. This program was used for construct of the initial structure of solvent molecules (acetone) around ((CH3)3P and (CH3)3PCS2) molecules. Direct molecular dynamics method has been implemented for optimization of solvation shell structures obtained with using of this program. This approach was applied for the dynamics study of the molecular cluster structures of ((CH3)3P and (CH3)3PCS2) molecules with acetone molecules and chemical shifts calculations. For molecular configurations extracted from molecular dynamic simulations the calculations of magnetic shielding constants of 31P nuclei were carried out within the framework of UB3LYP/6-31(d,p) method with gauge-including atomic orbitals.
It has been carried out the comparison of the dynamical processes simulation results of (CH3)3P and (CH3)3PCS2 molecules in the acetone with data obtained by using a different methods of cluster structure modelling – molecular mechanic method, quantum mechanics/molecular mechanic method and density functional theory method (DFT) with different functionals [1].
References:
1. R.M. Aminova, E.R. Baisupova, A.V. Aganov. – Appl. Magn. Reson. 40, 147-170 (2011).
1. Theoretical Organic Chemistry: Poster presentation P-11 THE REACTION OF 4-NITRO- AND 4-
METHOXYPHENYLACETYLENES WITH 4,7- DI(TERT-BUTYL)BENZO-1,3,2-
DIOXAPHOSPHOLES. INFLUENCE OF
SUBSTITUENT’S NATURE IN THE PHENYL MOIETY ON THE STABILITY OF OXAPHOSPHORINE CYCLE 1 - A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan, Russia
2 - Institute of Chemical Kinetics and Combustion, Novosibirsk, Russia
3 - G.A. Razuvaev Institute of Organometallic Chemistry, Nizhnii Novgorod, Russia
A.S. Aniskin1 A.V. Nemtarev1
V.F. Mironov1 D.S. Baranov2 S.F. Vasilevsky2 N.O. Druzhkov3
V.K. Cherkasov3 nemtarev@iopc.ru
The reaction of 2,2,2-trihalogenbenzo-1,3,2-dioxaphospholes with acetylenes is known to lead to the formation of benzo[e]-1,2-oxaphosphorines which exhibit a considerable resistant to the action of various reagents.
Herein, the reaction of 4,7-di(tert-butyl)-2,2,2-trichlorobenzo-1,3,2-dioxaphosphole with substituted phenylacetylenes are discussing. 2,6-Dichloro-1,2-dihydro-5,8-di(tert-bytyl)benzo[e]- 1,2-oxaphosphorin-2-oxide (2) is formed in reaction dioxaphosphole (1) with 4-nitrophenyl- acetylene. Hydrolysis of compound (2) leads to the opening of oxaphosphorine’s cycle and gives phosphonic acid (2).
1 O
PCl3
O H2O
2 3 8 8a 7
6
5 4a CH2Cl2 , 20oC
NO2
4 3 C6H4NO2
Cl P O O
C6H4NO2 OH O P OH
OH
Cl Cl
The geometry of molecule (2) was determined by XRD (Z-configuration of C3=C4 bond).
Dioxaphosphole (1) gives with para-methoxyphenylacetylene benzophosphorine (4) with the same substituents set in the phenylene fragment. Oxaphosphorine cycle of compound (4) is resistant to disclosure even upon hydrolysis when heated. Thus, the result revealed a clear dependence of the substituents nature in the phenyl fragment, situated in the fourth position of the heterocycle, on the stability of oxaphosphorine’s cycle in the reaction with nucleophiles. Electron withdrawing groups favor to the disclosure of the oxaphosphorine cycle.
1
H2O
4 8 8a 7
6
5 4a CH2Cl2 , 20oC
4 3 C6H4OMe
Cl P O O
Cl H2NBu-t
OCH3 8 8a
7 6
5 4a 4
3 C6H4OMe
O P O O
Cl
_ H3NBu-t+
5
This work was supported by Russian Foundation of Basic Research (№ 10-03-00525).
1. Theoretical Organic Chemistry: Poster presentation P-12 USE OF THE THEORETICAL-INFORMATION TOPOLOGICAL INDICES FOR CALCULATION OF
ACIDIC IONIZATION CONSTANT OF CYCLIC CIS- AND TRANS-DICARBOXYLIC ACIDS Institute of Polymer Materials of Azerbaijan National Academy of Sciences, Sumgayit, Azerbaijan
M.S. Salakhov O.T. Greckina
B.T. Bagmanov salahov_mustafa@mail.ru
We have carried out the search of the possibilities of use of discriminating capacities of the theoretical-information indices of ICk, TICk, SICk, CICk (k = 0 - 3) on an example of configuration cis- and trans-stereoisomer 4-cyclohexene-1, 2-dicarboxylic acids (4 – CHDA) (I, II), 1-methyl-4-CHDA (III, IV), 3-methyl-4-CHDA (V – VIII), 4-methyl-4- CHDA (IX, X), 1, 2-dimethyl-4-CHDA (XI) and 4, 5-dimethyl-4-CHDA (XII) synthesized by us with the aim of finding of possible correlations f (TI) - рКα for a series of cis- and trans-configurations of the studied acids. Our calculations showed that the values of IC0, TIC0, SIC0, CIC0 indices, calculated without account of hydrogen atoms in molecule for (III – X) and (XI, XII) are equal among themselves thereupon that at k=0 ICk, TICk, SICk, CICk
indices are not able to distinguish the isomer forms of the same compound. So, IC1, TIC1, SIC1, CIC1 indices for isomers (III – X), and also IC2, TIC2, SIC2, CIC2 indices for (III – VIII) owing to the small discriminating ability are equal among themselves. However, IC3, TIC3, SIC3, CIC3, indices can be apparently used for establishment of dependence between structure and properties of the studied compounds, as they differ isomers of methyl- and dimethyl-4-CHDA depending on position of methyl groups in cyclohexene ring. It has been revealed depending on removal of methyl group on carboxyl groups in molecules of monomethylsubstituted 4-CHDA IC3 value is decreased. Owing to the fact that TICk, SICk
and СICk have been connected with ICk simple functional ratios, TIC3 and SIC3 value is also decreased and СIC3 value correspondingly grows. In spite of the fact that the topological indices do not consider the stereochemical peculiarities of molecules, nevertheless using IC3, TIC3, SIC3, CIC3 indices in a series of monomethylsubstituted correspondingly cis- and trans isomers of methyl-4-CHDA we have revealed that рК1 value for cis-isomers of methyl-4-CHDA grows with removal of methyl group from carboxyl groups and рК2 and ΔрК values are correspondingly decreased. The рК1 value of trans- isomers of methyl-4-CHDA is analogously changed. Taking into account above-mentioned, one can conclude that correspondingly for cis- and trans-isomers of methyl-4-CHDA there is a dependence of рК1 values on IC3, TIC3, SIC3 and CIC3, and also рК2 and ΔрК on IC3,
TIC3, SIC3 and CIC3 for cis-isomers of methyl- 4-CHDA.
1. Theoretical Organic Chemistry: Poster presentation P-13 KINETIC ISOTOPE EFFECT OF THE REACTION OF
TERTIARY PHOSPHINES WITH UNSATURATED CARBOXYLIC ACIDS AND THEIR DERIVATIVES Kazan Federal University, Department of Chemistry, Kazan, Russia A.V. Salin