КОНФОРМАЦИОННОЕ СОСТОЯНИЕ АЦЕТИЛЕНОВЫХ АМИНОГЛИКОЛЕЙ ПО ДАННЫМ ПМР И КВАНТОВО-ХИМИЧЕСКИХ РАСЧЕТОВ

Admin bo'lib kirish (www.admin.slib.uz)

Tizim sinov (TEST) rejimida ishlamoqda! Murojat uchun @slib_support

Eski talqinga o'tish link

13 декабр 2019

Asosiy til:O'zbek

КОНФОРМАЦИОННОЕ СОСТОЯНИЕ АЦЕТИЛЕНОВЫХ АМИНОГЛИКОЛЕЙ ПО ДАННЫМ ПМР И КВАНТОВО-ХИМИЧЕСКИХ РАСЧЕТОВ

Fan yo'nalishi:

5df306fb58276.pdf

PDF

Илмий хабарнома - Научный вестник

Maqola chop etish see more

MAQOLA ANNOTATSIYASI

The article presents data relating to the combined use of the PMR method and quantum chemical calculations to obtain information on the effect of the Air Force on the conformational state of acetylene amino glycols, which are derivatives of acetylene glycerols. To realize these goals, comparative analysis of the conformational state and the nature of intramolecular hydrogen bonds (IHB) in acetylene aminoglycols using the PMR spectra and quantum chemical calculations using the «Gaussian» program was carried out. Based on the presented model using the semi-empirical method according to the Mc. Konnel equation, the anisotropic chemical shift (∆δ) and the difference of chemical shifts of the geminal methyl groups was calculated. According to the obtained data, the dependence of the calculated values of the anisotropic chemical shift ∆δ of each of the geminal methyl groups on the angles θ1 and θ2 formed by a straight line coming from the center of the acetylene bond to the edge of the sphere bounded by the protons of these groups was constructed. According to molecular models, the distances between donor-acceptor groups forming the air force are measured. It is noted that, in the shielded conformation, these groups are brought closer to a distance of 1.6Ао, at 30o this distance is 1.8Ао, and at 60o - 2.0Ао. By using quantum chemical calculations, data concerning to the minimum energy and angular distribution were obtained, wich allowed to evaluate the effect of the effective volume of the substituent on the conformational and energy stability of aminoglycols, the dependence of the influence of intramolecular hydrogen bonds (IHB) on the molecular energy and rotation of the carbon – carbon bond of the glycol fragment was constructed. The difference between the calculated minimum energy values obtained for aminoglycols and their acylatedanalogues is used to calculate the energy contribution of the structural organization of molecules. There is a consistency in the results of the semi-empirical calculation of the anisotropic chemical shift for geminal methyl groups and quantum chemical calculations, which indicate that the structural fragment, in the presence of the IHB, is characterized mainly by the gauche conformation, and the φ values are within 50.00о - 56.00o. It was noted, that the blocking of hydroxyl groups by acylation leads to an increase in the minimum energy, which can be attributed to the absence of IHB in the molecules of amino glycol diacetate. From the difference in the calculated minimum energy values obtained for aminoglycols and their acylated analogues, the energy contribution of the structural organization of molecules was calculated and the dependence of the dihedral angle φ depending on the “adding weigh” of the alkyl group for mono- and diacyl- derivatives was constructed.

MUALIFLAR

Teglar

# ички молeкуляр водород боғланиш # вицинал системалар# конформация# кимёвий силжиш# квант-кимёвий ҳисоблаш# внутримолекулярная водородная св# вицинальные системы# химические сдвиги# квантово-химический расчет# intramolecular hydrogen bond (IH# vicinal systems# conformation# chemical shifts# quantum-chemical calculation

Maqolani baholang

0

0 ta

Maqola idintifikatorlari

ROI:

https://eroi.uz/11.0049/A1219-0240

DOI:

Mavjud emas

Foydalanilgan adabiyotlar

1. A.S.1128548 SSSR., (1984) 6,7-dimetil-2-undeken-4-in-1,6,7-triol, obladayushchiy zhelchegonnoy aktivnost'yu / Sabirov S.S., Fayzilov I.U.,KhaydarovK.Kh., Alidzhonov U. [Certificate of authorship.1128548 USSR., 6,7-dimethyl-2-undecene-4-in-1,6,7-triol, with choleretic activity / Sabirov S.S., Fayzilov I.U., Khaidarov K.Kh., Alijonov U.] P. 6. 2. Isobaev, M.D., Wenger, E.F., Glazunova, E.M. (1984) Vliyanie vnutri molekulyarnykh vodorodnykh svyazey na konformacionnoe sostoyanie khiralnykh aminoglikoley atsetilenovogo ryada [The effect of molecular hydrogen bonds on the conformational state of chiral amino glycols of the acetylene series]. Russian Journal of Organic Chemistry. Vol.20, Issue 11. pp. 2302 – 2306. 3. Isobaev, M.D., Wenger, E.F., Glazunova, E.M. (1986) YaMR khiralnykh molekul. III. Vzaimodeystvie geminalnykh metilnykh grupp v atsetilenovom aminoglikole [The interaction of geminal methyl groups with a vasilethylene aminoglycol]. Russian Journal of Organic Chemistry.Vol. 22. Issue 5. pp. 983 – 986. 4. Isobayev, M.D., Fayzilov, I.U., Sabirov, S.S. (1990) Konformaciya izomernykh Z, E yeninovykh triolov i dioksialdegidov [Conformation of isomeric Z, E enin triols and dioxaldehydes]. Teoreticheskaya i eksperimentalnaya khimiya. Issue 6. pp. 681 – 681. 5. Terentyev, V.A. (1973) Termodinamika vodorodnoy svyazi. [Thermodynamics of hydrogen bonding]. Saratov: Saratov University Press. 6. Isobaev, M.D., Glazunova, E.M., Grigina, I.N. (1987) Temperaturnye gradienty khimicheskikh sdvigov gidroksilnykh grupp v atsetilenovom triole [Temperature gradients of chemical shifts of hydroxyl groups in acetylene triol]. Russian Journal of Organic Chemistry. Vol.23. Issue 2. pp. 302 – 305. 7. Isobaev, M.D., Wenger, E.F., Abdullaev, T.Kh.,Glazunova, E.M. (1991) Vnutri molekulyarnye vzaimodeystviya v vitsinalnykh sistemakh Inside molecular interactions in vicinal systems]. Teoreticheskaya organicheskaya khimiya. Tezisy dokladov 1-oy Vsesoyuznoy konferentsii [Theoretical Organic Chemistry. Thesiss report I-st. All-Union Conference]. Volgograd. P. 64. 8. Isobaev, M.D., Wenger, E.F., Abdullaev, T.Kh., Glazunova, E.M. (1991). Vnutri molekulyarnye i anizotropnye vzaimodeystviya v vitsinalnykh sistemakh [Inside molecular and anisotropic interactions in vicinal systems]. Reports of Academy Sciences of the Republic of Tajikistan. Vol. 37. Issue 7 – 8. pp. 35 – 41. 9. Abdullaev, T.Kh. (1997). Razdeleniye 3-metil-3-aminopentina-1 naenantiomery, sintez i biologicheskaya aktivnost'ikh proizvodnykh [Separation of 3-methyl-3-aminopentine-1 into enantiomers, synthesis and biological activity of their derivatives]. Dissertation PhD in chemical sciences. Dushanbe. P. 130. 10. McConnell, H.M. (1957) Theory of nuclear magnetic shielding in molecules. Long-range dipolar shielding of protons. Journal Chemistry of Physics, Vol. 27. Issue 1.pp. 226 – 229. 11. Serba, P.V., Miroshnichenko, S.P., Blinov, Yu.F. (2012) Kvantovo-khimicheskiye raschety v programme GAUSSIAN. Po kursu ‘Fizika nizkorazmernykh struktur’ [Quantum-chemical calculations in the GAUSSIAN program for the course ‘Physics of Low-Dimensional Structures’]. Taganrog: TTI SFU. 12. Frisch, M.J. etc. Gaussian Inc., Wallingford CT, 2009. URL: researchgate.net/publication/220020584_Gaussian_Gaussian_Inc_Walingford_CT.