Sobolev, Vasily Igorevich

Suprunenko, V. D.

Electronic archive of Tomsk Polytechnic University

≠〉「〈′＜〔∴≦〈＜〔● ≠≦÷≦〈〉「＜〔● ＜〔′％＜〔● ＃±≦÷〔 た≠〉°≦〈≦÷≦］『● ∞∴≦〉±°『∴≦［〔＜『● ≠≦÷≦〈〉「＜≦］≦ ＜〔′％＜≦-『＜＜≦［〔¢『≦＜＜≦］≦ ∞∴≦♂°∴〔＜♂°［〔 ±〔± ≦♂＜≦［〔 ∞≦〈］≦°≦［±『 ♂≦［∴〉≠〉＜＜≦］≦ 『＜「〉＜〉∴〔だ  02-ヰヴ ０ＵＷＡＮｒ ヲヰヱヴ４く °ＳＰＸＬが ∴ＳＸＸＦｒ  111 ALKALINE AND ALKALINE-EARTH METALS FLUOROHALOGENATES IN  ORGANIC SYNTHESIS V.D. Suprunenko, V.I.Sobolev  ScientificSupervisor: PhD, Associate Professor  R.V. Ostvald Language Advisor:Senior teacher U.A. Smirnova Tomsk Polytechnic University, Russia, Tomsk, Lenin str., 30, 634050 E-mail:vladislav94ru@mail.ru  In recent years, threefluoridebromin is famous fluorinating  and bromating agent in chemistry of organic compounds . The main feature of threefluoridebromin is its feature of electrophylicbromating high- deactivatedaromatic compounds. It is known that nitrobenzene forms 3-bromo-nitro benzene with good output. However, threefluoridebromin  is a dangerous compound. In this way , using alkaline and alkaline-earth metals fluorohalogenates in organic synthesis is safer.  Tetrafluorobromates are white loose crystal substances, whichhave low reactivity. Degrading, they form threefluoridebromine which has low decomposition temperature, and posess good fluorinating, and bromating agents. Today  chair CTRE is a study on the methods of synthesis tetrafluorobromates and their properties and application. (expand) Equipment.  Spectrums of gas chromatography-mass-spectrometry (Gび-ぜS) of the interaction products were measured with the help of chromato-mass-spectrumeters TRACE DSQ on the base of  TPU Scientific and Analytical Center. The analysis was performed with the following parameters: expansion coil temperature– β80 °でν tСermostatic oven temperature   +40 °で - +γ00 °でν СОatТnР spООН– 10 °で/mТnν ranРО of mass sМannТnР– 33-350 a.u.m. Initialsubstances • Kalium tetrafluobromate, KBrF4. • Barium Tetrafluobromate, Ba(BrF4)2. . • p- Nitrobenzene diazonium tosylate • Nitrobenzene • Distilled water • Calcium chloride, C=0,7g/ml. solution was prepared immediately before the experiment. • Siliceous gel, Sigma-AlНrТМС SТlТМК РОl ШrКЧРО, ≥99%, 10087-2.5KG-R.  • Sodium fluoride, Sigma-AlНrТМС SШНТЮЦ ПlЮШrТНО, ≥98%, 71ηββ-500G.  Interaction of KBrF4 and NBDT in solid state was conducted at following molar ratio of reactants:  3:1; 1:1 and also  3:1:1 in the presence of one mole NaF as an inert diluents . The following reagent samples were used : KBrF4 - 183 mg ( 61mg for a molar ratio1:1); Ba (BrF4) 2 - 420 mg (140 mgr a molar ratio 1:1) p- nitrobenzenediazonium tosylate - 100mg ; NaF - 13 mg . • General experimental techniques for solid substrates are: ≠〉「〈′＜〔∴≦〈＜〔● ≠≦÷≦〈〉「＜〔● ＜〔′％＜〔● ＃±≦÷〔 た≠〉°≦〈≦÷≦］『● ∞∴≦〉±°『∴≦［〔＜『● ≠≦÷≦〈〉「＜≦］≦ ＜〔′％＜≦-『＜＜≦［〔¢『≦＜＜≦］≦ ∞∴≦♂°∴〔＜♂°［〔 ±〔± ≦♂＜≦［〔 ∞≦〈］≦°≦［±『 ♂≦［∴〉≠〉＜＜≦］≦ 『＜「〉＜〉∴〔だ  02-ヰヴ ０ＵＷＡＮｒ ヲヰヱヴ４く °ＳＰＸＬが ∴ＳＸＸＦｒ  112 • 1. Material samples are placed in an agate mortar and triturated gradually at room temperature in the given proportions. • 2. This technical product is poured  with distilled water and vigorously stirred until complete dispersion in water. • 3. A concentrated solution of CaCl2(C = 0,7 g \ ml ) is added into this slurry to precipitate the free F-ions as an insoluble precipitate of CaF2. • 4. 5ml of ethyl acetate is added into this mixture for extraction of organic substrates into organic phase. • 5. The aqueous and  organic phases are separated using a separatory funnel. • 6. The organic phase is purified by resinous impurities by filtration through silicagel.  Interaction of KBrF4 and  NBDT . In a 3:1 molar ratio active instantaneous emission of gaseous products is observed as white smoke formation and heating of brown oily substance mixture. The chromatogram of the products of interaction and one of the mass spectra of obtained substances  is presented in Figure 2. 0BrBrBrBrBrm/zだöÖÜïóöñ¿áÖí　 óÖöñÖïóçÖÜïöá, %4361 123 2038716624732640748630 90 150 210 270 330 390 450 510≠〉「〈′＜〔∴≦〈＜〔● ≠≦÷≦〈〉「＜〔● ＜〔′％＜〔● ＃±≦÷〔 た≠〉°≦〈≦÷≦］『● ∞∴≦〉±°『∴≦［〔＜『● ≠≦÷≦〈〉「＜≦］≦ ＜〔′％＜≦-『＜＜≦［〔¢『≦＜＜≦］≦ ∞∴≦♂°∴〔＜♂°［〔 ±〔± ≦♂＜≦［〔 ∞≦〈］≦°≦［±『 ♂≦［∴〉≠〉＜＜≦］≦ 『＜「〉＜〉∴〔だ  02-ヰヴ ０ＵＷＡＮｒ ヲヰヱヴ４く °ＳＰＸＬが ∴ＳＸＸＦｒ  113  Findings Kalium and barium tetrafluorobromates  show high reactivity feature in organic substances in the form of  aromatic diazonium salts. Degradation reactions of the diazonium salts to form nucleophylic substitution and electrophylicbromating is predominant over the interaction of reactants This reaction dominates with nitrobenzene, consequently kalium and barium tetrafluorobromate and threefluoridebromine react equally.   REFERENCES 1. Diachkova T.P. Khimicheskaia tekhnologia organicheskich veshestv. –   2007. – で. 37-44. 2. Orlov G.D., Saraev V.ん. Razrabotka Tehnologii, proizvodstvo i primenenie bromhladonov // Soedinenie ftora. – Sant-Petesberg: Teza. – 2009. – で. 41–44. 3. Maksimov B.N, Barabanov V.G. Promishlennie ftor organicheskie produkti //Sprav. izd. –  : Himiia. – 1990. –で. 221. 4. Plate N.A. Osnovi himii I tehnologii monomerov. – : Nauka. – 2002. – で. 199–210.      0            % time, min. 1 0 15 20 25 5 23,19 22,14 18,82 15,35 15,27 7,76 6,58 100 50 

Alkaline and alkaline-earth metals fluorohalogenates in organic synthesis

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Alkaline and alkaline-earth metals fluorohalogenates in organic synthesis

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