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Yusupova Lola A., Nurmanov Suvon E., National university of Uzbekistan after name M. Ulug'bek.
E-mail: [email protected]
QUANTUM-CHEMICAL CALCULATIONS AND MATHEMATICAL MODELATION OF SYNTHESIS OF ACETYLENICAL DIOLS
Abstract: structural-dinamical and elektronical properties of new synthesised acetylenic diols: butin-2-diol-1,4; it's mono- end divinyl ethers by using of calculated computeral programm Hyper-Chem by semi- emperical quantum - chemical method RMZ have bem: ivestigated. Geometrical structures, distribution of charges and electonical density of molecules of synthesised compounds were determined. By quantum- chemical method calculation of such parameters of synthesised compounls as: energy of band, full energy, elctronical energy and charge on oxygen atomes have been calculated. Also mathematical treatment of experimental data btained at carring out of chemical reactions was carried out becourse at presence tima the mathematical modelation and mathematical treatment of experimental date are used wide in modern investigation (particully also method of the least squares).
Keywords: acetylenic alcohols, homogeneous synthesis, catalysis, mathematical modeling, quantum chemical calculations of a molecule.
Introduction
At presence time calculated methods of quantum chemistry are developed in great degree owing to which possibility of calculation of geometry of molecules of different reagents and products and value of stability of intermediate products and transitional states in chemical reaction has appeared. The experimental obtain of such data for different reactions is bounded by difficulties caused by many - staging of processes, sinhronical carring out of elemental stages and very small time of living of intermediate products. Development of calculated methods of quantum chemistry and appearance of powerful computeral means has allowed to calculated some important characteristic of complex organical compounds. Percition and trustworthiness of such calculations are very satisfactory. By this reason quantum-chemical and molecular dynamical calculations at present time are used as one of physico-chemical methods of investigations for obtain data necessary for deter-
mination some regularities of mechanisms of formation of different organical compounds. Quantum chemistry has allowed to explain experimental data about reactional ability of organical compounds and to predict possible ways of carring out of different reactions. The base of quantum chemistry is aquation of Sckredinger which is decided in adiabatical process for stacionaral states.
Objects and methods of investigation. Synthesised acetylenical alcohols and their derivatives were object of this sentifical invertigation. In this work calculated computeral programm HyperChem and semi-emperical quantum-chemical method RMZ were used.
Results and their discussion. At present time methods of quantum chemistry are more accessible, inexpensive and universal methods of investigation of electronical structure of molecules of different compounds [1; 2]. But also it is necessary to understand that it is impossible to refuse from some experimental methods of investigation of compounds.
Investigation of geometrical structure of monovinyl ether of butin-2-diol-1,4 (Fig. 4) has shown that vinyl group has plane structure and hybridization of carlon atom in it is sp 2. Distribution of electronical density and charge in molecule of this compound (Fig. 5) has shown a changing of charge of hydrogen atom of hydroxylic group (+0,186) at formation of above mentioned monovinyl ether. Obviously an hydrogen atom of hydroxylic group of diol is more active that is vinylation of one hydroxylic group has carried out to passivation of second hydroxylic group. Synthesis of divinyl ether was carried out throught formation of monovinyl ether. Limitation stage of all process is a vinylation of second hydroxylic group.
In this work an geometrical structures, distribution of charges and electronical density in molecules of following compounds: acetylene; methanale; butin-2-diol-2,4; it's mono- and divinyl ethers; benzene-1,3-diol; 3,6-dimethyloctin-4-di-ol-3,6 and it's mono- and divinyl ethers with using of program "Hyper Chem" by quantum-chemical method RMZ [5; 6]
As example low results of investigation of geometry and electronical structure of molecules butin-2-diol-1,4; butin-diol-1,4; benzene-1,3-diol and it's mono- and divinyl ethers are presented.
Figure 1. Geometrical structure of molecule butin-2-diol-1,4
On (Fig. 1) geometrical structure of butin-2-di- state; carbon atoms C2 and C3 have an linear struc-ol-1,4 is presented. It is shown that in it carbon at- ture with sp - hybridization. Owing to this carbom oms C1 and C4 have sp 3-hybridization in tetraedrical chair of molecule has formed an linear structure:
Figure 2. Distribution of charges in molecule butin-2-diol-1,4.
On (Fig. 2) distribution of charges in molecule butin-2-diol-1,4 is presented. It is shown that both hydroxylic groupa have the same position and also that atoms of hydrogen of these groups possessed by the same charge (+0,184). This also was shown at calculation of distribution of electronical density in molecule of this compound.
Comparasium of values of electronical charges in this molecule has shown that the great quantity of negative charge was concentrated on the oxygen atom. Obviously by this reason namely atom of oxygen is an
reaction center by which catalytical vinylation by acetylene has carried out in the presence of high-basecal system KOH-DMSO (dimethyl sulfoxide).
By this reason the selectivity of catalytical systems wasn't high and in all cases mixture of mono-and divinyl ethers of investigated diol has been obtained. Molecular-dinamical characteristices of divinyl ether of butin-2-diol-1,4 were investigated (Fig. 6). It was observed that with formation of divinyl ether charges on carbon atoms in molecule butin-2-diol-4 have been decreased; there carbon at-
oms C1; C2; C3 and C4 have a charges 0,023; -0,165; -0,165 and 0,223 correspendenly. With formation of divinyl ether these values have changed and were equelid correspendenly: 0,206; -0,163; -0,163 and
0,206. It is possible to suppose that character of triple bond in molecules of butin-2-diol-1,4 and it's divinyl ether is the same (without accounting of stretical factor)
Figure 3. Distribution of electronic density by atoms in molecule of butin-2-diol-1,4
Figure 4. Geometrical structure of monovinyl ether of butin-2-diol-1,4 (vinyloxy-butin-2-ol-1
Figure 5. Distribution of electronical density by atoms in molecule of monovinyl ether of butin-2-diol-1,4
(a)
b)
c)
Figure 6. Geometrical structure (a); distribution of charges (b) and electronical density (c) in molecule of divinyl ether of butin-2-diol-1,4
Investigation of geometrical structure; distribu- tity of negative charge and at this electronical density
tion of charges and electronical density by atoms in have concentrated on atoms of oxygen and at this
molecule 3,6-dimethyloctin-4-diol-3,6 (Fig. 7) has they have possessed by the same activity in reaction
shown that this molecule has symmetry, the quan- of basical vinylation by acetylene.
a)
b)
c)
Figure 7. Geometrical structure (a); distribution of charges (b) and electronical density (c) in molecule 3,6-dimethyloctin-4-diol-3,6
Also were obtained results by investigation of structure, distribution of charges and electronical density for some others compounds such as: methanale (Fig. 2); monovinyl ether of 3,6-dimethyloc-tin-4-diol-3,6 (Fig. 3); divinyl ether of 3,6-dimethyl-octin-4-diol-3,6 (Fig. 4); resorzin (Fig. 5); it's mono - (Fig. 6) and divinyl (Fig. 7) ethers.
Also quantum-chemical calculations of some other parameters (general anergy; energy of formation; heat of formation; energy of electron; energy of curn; dipole moment, charge on the oxygen atoms) have been carried out for following molecules: bu-tin-2-diol-1,4; resorzin; 3,6-di-ethyloctin-4-diol-3,6; methanale; monovinyl ether of butin-2-diol-2,4;
Table 1. - Quantum-chemical calculations of investigated compounds
Nature of compound Energy of bond (ccal/mole) The full energy (ccal/mole) The full energy (ccal/mole) Isolation of atomatic energy (ccal/mole) Electronical energy (ccal/mole) Interaction (ccal/mole) Heat of formation (ccal/mole) Gradient (ccal/mole) Charge of oxygen atom
Synthesized compounds
Resorzin -1524.5266444 -32068.8672664 -51.103972614 -30544.3406220 -129757.5445498 97688.6772834 -67.4566444 0.0100481 -0.227 -0.229
Butin-2-diol-l,4 -1156.7236304 -26570.9141924 -42.342601625 -25414.1905620 -88070.0518435 61499.1376512 -41.4336304 0.0068146 -0.297 -0.297
3,6-Dimethyloc-tin-4-diol-3,6 -2835.4623029 -50227.1087189 -80.040394540 -47391.6464160 -271772.8764646 221545.7677457 -69.6083029 0.0095789 -0.301 -0.304
Monovinyl ether of butin-2-diol-l,4 -1991.4560396 -38871.8525336 -61.945003260 -36880.3964940 -170830.3919642 131958.5394305 15.8019604 0.0097181 -0.191 -0.297
Divinyl ether of butin-2-diol-l,4 -2843.1886834 -47265.5468614 -75.320939537 44422.3581780 -269876.0436325 222610.4967712 -77.3346834 0.0184108 -0.192 -0.192
Monovinyl ether of resorzin -1938.9570685 -38216.4006565 -60.900495061 -36277.4435880 -175513.4723243 137297.0716677 -35.9030685 0.0093965 -0.130 -0.226
Divinyl ether of resorzin -2353.4005691 -44363.9471231 -70.697038346 -42010.5465540 -225838.6149920 181474.6678688 -4.3625691 0.0091260 -0.127 -0.129
Monovinyl ether of 3,6-dimethyloc- tin-4-diol-3,6 -3249.0876783 -56747.6097483 -53498.5220700 -334722.6583164 -334722.6583164 277975.0485681 -37.2496783 0.0093937
Divinyl ether of 3,6-dimethyloctin -4-diol-3,6 -3664.1100366 -63269.5077606 -100.824365421 -59605.3977240 -402851.2880456 339581.7802850 -6.2880366 0.0099521
1-ethyloxy -4-vi-nyloxybutin-2 -1850.0436328 -38708.5552378 -61.684777650 -36858.5116050 -156940.0477383 118231.4925005 -13.6756328 0.0015691 -0.121 -0.343
1-ethyloxy -4-vi-nyloxy-4-methyl-hexyn-2 -3106.2189350 -50696.6050490 -80.788569629 -47590.3861140 -305485.6005429 254788.9954939 -65.2709350 0.0098751 -0.192 -0.268
1 -Ethyloxy- 3 -vi-nyloxybenzol -2486.5999300 -45100.0993900 -71.870148234 -42613.499460 -236892.2477376 191792.1483476 -33.3579300 0.0092637 -0.128 -0.193
1-Methacry- loil-4-vinyloxybu- tin-2 -2556.6639195 -55631.3017485 -88.652352371 -53074.6378290 -263177.4924690 207546.1907205 -43.8629195 0.0097901 -0.190 -0.226 -0.337
l-Acryloil-3-vi-nyloxy -3-methy-lexyn-2 -3105.2192196 -58727.2904136 -93.586025851 -55622.0711940 -338612.3170070 279885.0265934 -42.2302196 0.0196108 -0.194 -0.235 -0.329
1-Vinyloxy -3-methacryloil- benzol -2904.0822408 -61536.4671918 -98.062644621 -58632.3849510 -326224.5301165 264688.0629247 -49.5012408 0.0099009 -0,241 -0,128 -0,325
3,6-dimethyloctin-4-diol-3,6; divinyl ether of bu-tin-2-diol-1,4 (table 1).
Such on the base of results of investigation of
structure, distribution of charges, electronical density and energetical characteristics of investigated molecules by semi-emperitical quantum-chemical method their reactional centers were determined and also some experimental data have been confirmed.
It is known that chemical processes have carried out on the base of different lows and regularities. Mathematical treatment of experimental data obtained at carring out chemical reactions has allowed to test and to value of their rightness.
At presence time for mathematical modelation and mathematical treatment of experimental data the method of the least quadrants has used. This method in comparasion with some others methods is characterized by fact that obtained results are more precisious. We have used this method to reaction of vinylation of investigated compounds. As example the mathematical treatment of experimental data of vinylation reaction of butin-2-diol-1,4 is presented:
q Y
q Y
q2 y2
Yn
According to method of the least quadrants the best values of parameters a, b and c are values for which the sum of quadrants of deviations is minimal:
F = £e* =£\Y - YMM(q )] =
i-1 i-i
n
=Z\y ++c )
(2)
= min
For obtain of minimal value of function F values of private derivatives by coefficient a, b and c must to equale to nought:
^ = 0, ^ = 0, ^ = 0. (3) da db da
Then private derivatives F (a, b, c) of changing parameters a, b, c have been determined. At this the best value of these parameters are these at which private derivatives of this function by changing parameters converted in naught:
dF = 2Z [Y - (aqi + bq< + c))(-q2 ) = 0,
i=i
da
db=Y -(2+h+c )] - H ) -o,
^[Y-(( + bqt + c )]•(-!)
(-1) = 0.
dF_
da i=i ■
From these equations for determination of values didn't determined coefficients a, b and c the system of algebraic quations was formed:
n n n n
Zqf • a + •b + • c = • Yi,
i-i
i -i
i -i
where: Y._yield of vinyl ether; to each q (i = 1,n) Yi (i = 1, n) is corresponded which is determined by experimentally. Such it is possible to proposed that q - factor influencing on the yield of vinyl ether of butin-2-diol-1,4.
For determination ofprecission of experimental data of vinylation it was proposed that dependence of value of yield of the mathematical treatment has appearance of secondary.
YMM = aq2 + bq + c (1);
where a, b and c are unknown coefficients.
Zq3 • a+Zqf •b• c = Zqi Y, (4)
i=i i=i i=i i =i
n n n
Z q2 •a+Z qi •b+n •c=ZY
i=i
i=i
i=i
Low as example experimental data obtained at vinylation of butin-2-diol-1,4 are presented:
T Y
100 35.7
120 46
130 48.1
150 47
where: Y - yie.
d of product-vinyl ether of butin-2-di-
ol-1,4 forming in reaction of butin-2-diol-1,4 with
acetylene at temperature T. (one from influencing factor). This dependence is presented as multimember YMM = aT2 + bT + c. For this in system of equations (4) sum of participated factors and values of coefficients a, b and c are determined with using lined system of equations:
1099220000a+8300000b+63800c = 2889790, 8300000a+63800b+500c =22393, (5) 63800a+500b+4c =176,8.
a = -0.0095, b = 2.6 and c = -129.323 Obviously that dependence of yield vinyl of ether butin-2-diol-1,4 (Y, %) from temperature of process (T, °C) at duration (t) 8 hours is presented by equation YMM = -0,0095T2 + 2.6T -129.323. Values ofyield of vinyl ether of butin-2-diol-1,4 obtained by mathematical treatment (YMM.) and also their experimental values are presented in (table 2).
Table 2. - Values of experimental data and obtained by mathematical treatment of vinylation of butin-2-diol-1,4
T 1 Y 1 YMM Ti 2 Ti Y T3 T 4 T2 Y
100 35,7 35,677 10000 3570 1000000 100000000 357000
120 46 45,877 14400 5520 1728000 207360000 662400
130 48,1 48,127 16900 6253 2197000 285610000 812890
150 47 46,927 22500 7050 3375000 506250000 1057500
n IT = i=1 n Ж = i=1 N b-T n YJi Y = i i i=1 n У T.3 = / 11 1 i=1 n Et 4 = i=1 N b-T
= 500 = 176.8 =63800 =22393 = 8300000 =1099220000 = 2889790
Figure 8. Comparasional data of values of yield of vinyl ether of butin-2-diol-1,4: Y-experimental; YMM-calculated
From it's it is shown that values of experimental yield of vinyl ether of butin-2-diol-1,4 and obtained by mathematical treatment are coincided.
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