CS214985B1 - A method of preparing a bis (triphenylphosphane oxide) tribromo ferric complex - Google Patents
A method of preparing a bis (triphenylphosphane oxide) tribromo ferric complex Download PDFInfo
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- CS214985B1 CS214985B1 CS842180A CS842180A CS214985B1 CS 214985 B1 CS214985 B1 CS 214985B1 CS 842180 A CS842180 A CS 842180A CS 842180 A CS842180 A CS 842180A CS 214985 B1 CS214985 B1 CS 214985B1
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Abstract
Sposob přípravy bis(trifenylfosfánoxid) tribromoželezitého komplexu spadá do odboru organickéj syntézy. Rieši sposob přípravy bis(trifenylfosfánoxidjtribromoželezitého komplexu tak, že bromid železitý FeBr3 reaguje s trifenylfosfánom PPh3 v mólovom pomere 1:2 v roztoku acetonitrilu za privádzania molekulárneho kyslíka pri teplotách 15 až 80 °C, dalej sa ochladením vzniknuté kryštáliky odsajú, prekryštalizujú a sušia.The method of preparation of bis(triphenylphosphane oxide) tribromoferric complex belongs to the field of organic synthesis. It deals with the preparation method of bis(triphenylphosphane oxide) tribromoferric complex so that iron bromide FeBr3 reacts with triphenylphosphane PPh3 in a molar ratio of 1:2 in a solution of acetonitrile with the introduction of molecular oxygen at temperatures of 15 to 80 °C, then the formed crystals are sucked off by cooling, recrystallized and dried.
Description
Vynález sa týká sposobu přípravy bis(trifenylfosfánoxid) tribromoželezitého komplexu vzorca FeBr3(OPPh3)2, kde Ph značí fenyl. Táto zlúčenina sa používá ako katalyzátor pri oxidácii triíenylfostánu molekulárnym kyslíkom podía čsl. autorského osvedčenia č. 205 483 a zároveň je potenciálnym katalyzátorom oxidácle různých substrátov ako trifenylarzánu, olefínov, alkylbenzénov. Zlúčenina zloženia FeBr3 (OPPh3j2 sa doteraz připravuje podía J. Chem. Soc. (A) 1971, 859 pTiamou reakciou FeBr3 s trifenylfosfánoxidom OPPh3, kde Ph zde i ďalej značí fenyl. Nevýhodou tohto sposobu přípravy je použitie OPPh3l ktorý je nutné připravit oxidáclou PPh3, ako je popísané v publikáciách Handbuch der práparativen Chemie, Stuttgard 1937 aleho J. Amer. Chem. Soc. 84, 3093 (1962); 95, 4847 (1973) a dalších.The present invention relates to a process for the preparation of bis (triphenylphosphane oxide) of a tribromocarbon complex of formula FeBr 3 (OPPh 3) 2, wherein Ph is phenyl. This compound is used as a catalyst in the oxidation of trienylphosphane by molecular oxygen. At the same time, it is a potential catalyst for the oxidation of various substrates such as triphenylarzane, olefins, alkylbenzenes. The compound of the composition FeBr3 (OPPh3j2 is still prepared according to J. Chem. Soc. (A) 1971, 859 by the reaction of FeBr3 with triphenylphosphine oxide OPPh3, where Ph is further referred to as phenyl. The disadvantage of this preparation is the use of OPPh3l which is to be prepared by oxidation of PPh3, as described in Handbuch der práparativen Chemie, Stuttgard 1937 but J. Amer Chem Soc., 84, 3093 (1962); 95, 4847 (1973) and others.
Uvedená nevýhoda je odstraněná u tohto vynálezu sposobu přípravy bis (tríf enylf osfánoxldj tribromoželezitého komplexu FeBr3(OPPh3)2, ktorého podstatou je reakcla bromidu železitého FeBr3 s trifenylfosfánom PPh3 v mólovom pomere 1:2 za ich rozpustenia v acetonitrile a za privádzania molekulárneho kyslíka pri teplotách od 15 do 80 °C, ďalej sa roztok ochladí, kryštáliky sa odsajú a čistia rekryštalizáclou z benzénu a vysušia sa.This disadvantage is eliminated in the present invention by the preparation of bis (triphenylphosphinoxide) tribromo ferric complex FeBr3 (OPPh3) 2, which is based on the reaction of ferric bromide FeBr3 with triphenylphosphane PPh3 in a molar ratio of 1: 2, while dissolving them in acetonitrile and bringing molecular oxygen at temperatures from 15 to 80 ° C, the solution is further cooled, the crystals are filtered off with suction and purified by recrystallization from benzene and dried.
Pri koncentrácii bromidu železitého FeBr3 0,125 M v acetonitrile pri dodržení uvedeného mólového poměru sa dá získat komplex FeBr3 (OPPh3)2 v 200 cm3 objeme acetonitrilového roztoku pri intenzívnotm prebublávaní roztoku díkyslíkom už za 10 h. Vedfajšle produkty reakciou nevznikajú. Vylúčená látka sa čistí rekryštalizáciou z benzénu a odstránením rozpúšťadla vo vákuovej sušiarni.At a concentration of ferric bromide FeBr 3 0.125 M in acetonitrile while maintaining the indicated molar ratio, a complex of FeBr 3 (OPPh 3) 2 in 200 cm 3 volume of acetonitrile solution can be obtained in as little as 10 h by vigorous bubbling of the solution. The precipitate is purified by recrystallization from benzene and removal of the solvent in a vacuum oven.
Pri použití nadbytku trlfenylfosfánu vzniká okrem FeBr3(OPPh3)2 tiež nadbytečný OPPh3.Excess of triphenylphosphane also produces excess OPPh3 in addition to FeBr3 (OPPh3) 2.
Predmet vynálezu je popísaný v nasledujúcich príkladoch riešenia. Příklad 1The invention is described in the following examples. Example 1
Do reakčnej nádoby temperované) na teplotu 50 °C a vypláchnutej molekulárnym kyslíkom sa vloží 5.10-4 mólov bezvodého bromidu železitého Febr3 a po jej připojení k aparatúre na meranie spotřeby O2 pri konštantnom atmosferickom tlaku sa injekčnou striekačkou nadávkuje 10 cm3 10-1 M roztoku trlfenylfosfánu PPh3 v acetonitrile. Sledováním závislosti spotřeby molekulárneho kyslíka od času sa zistilo, že oxidácla PPh3 na OPPh3 prebehla za dve hodiny. Po ocihladení z reakčného roztoku vykrystalizovala zlúčenina, ktorú sme Identifikovali ako bis(trifenylfosfánoxid) trlbromoželezitý komplex zloženia FeBr3(OPPh3]2. Infračervenou spektroskopiou boli nájdené pásy charakteristické pre FeBr(OPPh3)2: o (P-Oj 1149 cm-1; v3 (FeBr)4- 290 cm-1. Uvedené vlnočky charakteristických pásov sú zhodné s hodnotami najdenými v litera túře J. Chem. Soc. (A) 1971, 859 a J. Chem. Soc. (A), 1970, 1352. Příklad 25.10-4 moles of anhydrous ferric bromide Febr3 are placed in a reaction vessel tempered at 50 ° C and rinsed with molecular oxygen and, after being connected to an apparatus for measuring the O2 consumption at constant atmospheric pressure, 10 cm 3 of a 10-1 M solution of triphenylphosphane is injected with a syringe PPh 3 in acetonitrile. By monitoring the dependence of molecular oxygen consumption from time to time, it was found that OPh33 PPh3 oxidation took place in two hours. After smoothing from the reaction solution, the compound that we identified as bis (triphenylphosphane oxide) crystallized the ferric iron complex of the FeBr 3 (OPPh 3) 2 composition. The bands characteristic of FeBr (OPPh 3) 2: 0 (P-O 11 1149 cm -1; v3 (found by infrared spectroscopy) were found. These bands of characteristic bands are identical to those found in the literature of J. Chem Soc. (A) 1971, 859 and J. Chem. Soc. (A), 1970, 1352. Example 2
Do temperovanej reakčnej nádobky (teplota 80 °C) sa vloží 2,5.10-2 mólov bezvodého FeBr3, přidá sa 5.10- 2 mólov PPh3 a 200 cm3 acetonitrilu a za stálého miešania sa zavedie prúd dikyslíka. Oxidácla PPh3 na OPPh3 kvantitativné prebehne cca za 10 h. Vzniknutý FeBr3 (OPPh3)2 po ochladení roztoku vykrystalizoval v podobě hnedočervených kryštálikov, ktoré sa vyčistili rekryštalizáciou z benzénu a odstránením rozpúšťadla vo vákuovej sušiarni. Čistota preparátu sa zisťovala elementárnou analýzou a teplotou topenia. Výsledky analýzy FeBr3(OPPh3]2:2.5.10-2 moles of anhydrous FeBr 3 are charged into a tempered reaction vessel (temperature 80 ° C), 5.10-2 moles of PPh 3 and 200 cm 3 of acetonitrile are added, and an oxygen stream is introduced while stirring. OPh33 PPh3 oxidation quantitatively occurs after about 10 h. The resulting FeBr3 (OPPh3) 2 crystallized as a brown-red crystal upon cooling the solution, which was purified by recrystallization from benzene and removal of the solvent in a vacuum oven. The purity of the preparation was determined by elemental analysis and melting point. Results of FeBr3 (OPPh3) 2 analysis:
Fe — vyp. 6,55 %; naj. 6,49 °/o;Fe - off. 6.55%; naj. 6.49 ° / o;
Br — vyp. 28,13 °/o; naj. 28,26 °/o; C — vyp. 50,74 %; naj. 51,12 %; H — vyp. 3,55 %; naj. 3,80 %.Br - Off 28.13 ° / o; naj. 28.26 ° / o; C - off. 50.74%; naj. 51.12%; H - off. 3.55%; naj. 3.80%.
Teplota topenia: 174—175 °C Výťažok bol 75 %-ný.Melting point: 174-175 ° C The yield was 75%.
Zlúčenina vzorca FeBr3(OPPh3)2 připravená spůsobom podía vynálezu je čistá a využívá sa ako katalyzátor při oxidácii trlfenylfosfánu dikyslíkom.The compound of formula FeBr 3 (OPPh 3) 2 prepared by the process of the invention is pure and is used as a catalyst in the oxidation of triphenylphosphane by the oxygen.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS842180A CS214985B1 (en) | 1980-12-03 | 1980-12-03 | A method of preparing a bis (triphenylphosphane oxide) tribromo ferric complex |
| CS816839A CS218199B1 (en) | 1980-12-03 | 1981-09-16 | A method of preparing a bis / triphenylphosphane oxide / tritio-cyanate iron complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS842180A CS214985B1 (en) | 1980-12-03 | 1980-12-03 | A method of preparing a bis (triphenylphosphane oxide) tribromo ferric complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS214985B1 true CS214985B1 (en) | 1982-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS842180A CS214985B1 (en) | 1980-12-03 | 1980-12-03 | A method of preparing a bis (triphenylphosphane oxide) tribromo ferric complex |
| CS816839A CS218199B1 (en) | 1980-12-03 | 1981-09-16 | A method of preparing a bis / triphenylphosphane oxide / tritio-cyanate iron complex |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS816839A CS218199B1 (en) | 1980-12-03 | 1981-09-16 | A method of preparing a bis / triphenylphosphane oxide / tritio-cyanate iron complex |
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| Country | Link |
|---|---|
| CS (2) | CS214985B1 (en) |
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1980
- 1980-12-03 CS CS842180A patent/CS214985B1/en unknown
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1981
- 1981-09-16 CS CS816839A patent/CS218199B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS218199B1 (en) | 1983-02-25 |
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