PL779B1 - Method for the preparation of complex gold salts, thiophenols and their derivatives. - Google Patents

Method for the preparation of complex gold salts, thiophenols and their derivatives. Download PDF

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Publication number
PL779B1
PL779B1 PL779A PL77920A PL779B1 PL 779 B1 PL779 B1 PL 779B1 PL 779 A PL779 A PL 779A PL 77920 A PL77920 A PL 77920A PL 779 B1 PL779 B1 PL 779B1
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Poland
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gold
thiophenols
derivatives
preparation
gold salts
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PL779A
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Polish (pl)
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Publication of PL779B1 publication Critical patent/PL779B1/en

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Wykryto, ze tiofenole i ich pochodne, jaik :np. kwas tiofeinolokarbomowy i aimiino- tiofen-ole dzialainiean dwuchlorowców zlota zamieniaja sie na zlozone siole zlota, które posiadaja wybitna wartosc terapeutyczna.WTiadomo, ze tiokwaisy organicizne, szcze¬ gólniej tiokwais salicylowy, lacza sie z* meta¬ lami ciezkiemi. Z zachowania sie innych me¬ talów: ciezkich nie mozna bylo wywniosko¬ wac, ze zloto zachowywac sie bedzie podob¬ nie, poniewaz kruszec ten pod wielu wzgle¬ dami zachowuje sie odmiennie, niz inne me¬ tale ciezkie. Szczególnie- ma. to miejsee w sto¬ sunku do wytwarzania zwiazków zlozonych z kwiaisalmi organiiczinieoiii, ze tylko wspo- minlilmy kwas grtoimowy, kltóiry liaitiwio wytwairza zwiazki zlozone, ale ze zlotem w zwyklych warunkach zwiazków tych nie daje. Chlo¬ rowce zlota sluza ogólnie do charakterysty¬ ki zasad organicznych, z któremi tworza cha- rakterystycizne sole podwójne. Wiadomo nadto (Berichte der deutseh. chem. Geselisch. 45, 1912, strona 1735), ze dzialanie soli zlota na kwas aminosulfonowy przejawia sie w ten sposób, iz zloto laczy sie z grupa ami¬ nowa. Bylo przeto niespodzianka, ze dwu- chlorowce zlota przemieniaja sie z tiofeno- lami oraz ich poehodnemi, wlaczinie z po- chodneini amlnowemi tak, ze tworza sie zlo¬ zone tiofenolany zlota.Nowe zwiazki oidiznaiczaija sie tern, ze nie daja zadnych reakcyj jonowych zlota, np. nie bywaja stracane przez siarkowodór. Na tej stalosci zwiazków zlozonych polegaja ich wybitne wlasnosci lecznicze. Nie stracaja one bialka w obiegu krwi i dostaja sie w ten sposób nie rozlozone do ogniska choroby,, gdzie dzialaja gojaco./ : ,, Przyklady. 1. Tiofenolam zlota: Do 4,4 g tioifemolii, rolzpusiziczonego z 100 cm3 aJKkiohoilu metylo¬ wego dodajemy czesnie, 5,92 g zlotobrojiaku 'potaisu, rozpu¬ szczonego w 10 cm3 alkoholu metylowego.Przy zuipelnem odbarwieniu wydziela sie' osad, który przesaczamy, przemywamy, mie¬ szajac w 500 cm3 alkoholu w ciagu 5 godzin, nastepnie znowu przesaczamy i suszymy w prózni.Dróbno. sproszkowany tiofenolan zlota jest ja&no-zóltym proszkiem o stai yn skladzie, cdpowiadajacym wizorowi C6H5S Au. Zawartosc zlpta wynosi: obliczona 64,38°/0, znaleziiona Q3,95°/0. 2. Do 10 g tiokwalsu isaililcyiioiwego, drob¬ ino sproszkowanego, rolzpuis;ziczolneigo pa:'zy • mieszaniu w 250 cm3 estru octowego i cizyisto przesaczonego, dodajemy kroplami miesza¬ jac jednotczesnie, 10,5 g zlotobroniku potasu w 125 cm3 estru octowego. W krótkim czasie naistepuje stopniowo odbarwienie przy jed- noczesnem oddzieleniu sie bronizowego pro¬ duktu w proszku. Po' 24-o godzinineim odsta- n'ilu, odsaczamy plyn old osaldlu i dlo silaibo za- batrwiilonego inia kloiioir zóiltoi-brazotwy pirzeisa- oziu, dodajemy aikloholu aibsioikutmego. Naftych- mialst wydziela sie 'ciezki, blraiiCMZ,óilltiy osad — kwiais 'zloitotiofealiiicyliowy^ Pio pólgodzintnem staniu oidlewiamiy górny klajrfOfwmy plyn, & osad odisaeza sie nia: twalrdjym saczku, i przemywa sie allkohloleml. Osald ta, wysu- sizooy, pirzieidJstlawia sLe jako •zliiaimMiy zól- talwy prostek o stiaiymi sklaldziie AuSC6H4 CÓOH. Zloto: oibliioziolnK) 56,23%, zinaiteizibino 55,71 %. Dla oltrzymatnia solu. plOtasowej roiz- pujsMzsajmy 10 g kwiaisu izl'0(tloltiiois)a(liicylowego w 40 cm3 ailfooholu. Op&ldaJ zóitiOHbialy oisad, który sie odsacza, i susizy w elksikiaitoirze. 3. Kwas 4-amino^2-tiiofenolo-l-karbono- Vy. Lejemy jia 6,2 g kwasu 4-amino-2-tio- fenoloHl-karbonoWego 60 cm3 rozcienczonego kwasu solnego, rozpuszczamy go przez do¬ danie 440 cm3 wody i saczymy az do zupel¬ nej klarownosci przesaczu. Mieszajac, wie-- warny kroplami*'5,3^ zlotobromku potasu, roizpuiSizcizonego w 200 cm3 wody i mieszamy 3 godziny. W krótkim czasie nastepuje od¬ barwienie przy jednoiczesinem wytworzeniu sie osadu slabo na zólto^zabarwionego1. Osad. zbieramy na twardym saczku i suszymy, na¬ stepnie drobno proszkujemy, przemywamy prizy -jedno*czeisnem mieszaniu ^'alkoholem w ilosci 500 cm3 w ciagu 5 godzin, odsacza¬ my i suszymy w prózni.. . Kwat3 4-!ajnirno:-3h-jzlotiOitiofenolo-!karbono- wy, majacy wzór C7H502NSAuH207 drobno roztarty prizedistawia sie jako zóltawy pro¬ szek, nierozpuszczalny w rozcizynnikaJch or¬ ganicznych.Zloto: obliczane 51,44%, Enaleiztone . 50,98%.¦ Sól sicidowa citirzympjeniy priz^z ro»zpfu- sziczeinie 4,9 g kwaisiii aimiilnióiziloftjotlijofenololkajr- bonowego w 20 cm3 20°/0-go lugu wodnego sddowego i dodanie do roiz!czly|n!u 500 cm3 ^alkoholu. Osad odsacza sie i suszy w prózni.Sól siodlowa, dlroibnoi rote&tairtaJ, jest piro^ sizlkiiem, 'ziabairwtonyim n&J kollolr jaismo-zólty, bardzo latwo rozpuszczajacym sie w* wodzie i dajacym reakcje obojetna. Zawartosc zlota wynosi, odpowiednio do wzoru: C7H^02NS AuNa, H20: obliczona — 48,64°/0, 'znalezio¬ na ¦— 48,23%. PL PL PLThiophenols and their derivatives, such as thiophenolcarbolic acid and ammonium thiophenols, have been found to convert gold dihalogenates into complex gold compounds, which possess outstanding therapeutic value. It is known that organic thioacids, particularly salicylic thioacid, combine with heavy metals. From the behavior of other heavy metals, it could not be concluded that gold would behave similarly, because this metal behaves differently from other heavy metals in many respects. Particularly. this is in relation to the production of complex compounds with organic flowers, since we only mentioned grotoimic acid, the plant produces complex compounds, but with gold it does not produce these compounds under ordinary conditions. Gold halides are generally used to characterize organic bases, with which they form characteristic double salts. It is also known (Berichte der deutseh. chem. Geselisch. 45, 1912, page 1735) that the action of gold salt on aminosulfonic acid is manifested in the way that gold combines with the amino group. It was therefore surprising that gold dichlorides react with thiophenols and their derivatives, including ammonium derivatives, to form complex gold thiophenolates. These new gold dichloride compounds are characterized by the fact that they do not produce any ionic reactions with gold; for example, they are not precipitated by hydrogen sulfide. This stability of complex compounds is the basis of their outstanding medicinal properties. They do not lose protein in the bloodstream and thus reach the site of illness undecomposed, where they have a healing effect. 1. Gold thiophenolate: To 4.4 g of gold thiophenolate dissolved in 100 cm3 of methyl alcohol, add simultaneously 5.92 g of potassium gold bromide dissolved in 10 cm3 of methyl alcohol. When the color is completely discolored, a precipitate separates, which is filtered, washed, and stirred in 500 cm3 of alcohol for 5 hours, then filtered again and dried in vacuo. Finely powdered gold thiophenolate is a light yellow powder of constant composition, corresponding to the C6H5S Au standard. The gold content is: calculated 64.38°/0, found 3.95°/0. 2. To 10 g of finely powdered isopropyl thioglycerol mixed in 250 cm3 of heavily filtered acetic ester, add dropwise, while stirring, 10.5 g of potassium gold hydroxide in 125 cm3 of acetic ester. Within a short time, gradual discoloration occurs, accompanied by the separation of the powdered product. After 24 hours, filter off the old liquid and precipitate, and to the yellow-brown clotted liquid, add alcohol. The kerosene was immediately separated by a heavy precipitate - a floriferous gold-tiophenolic acid. After standing for half an hour, we removed the upper liquid, and the precipitate became a hard particle and was washed with alcohol. This dried, soluble solid is formed as a yellowish solid with a solid composition of AuSC6H4COOH. Gold: oibliioziolnK) 56.23%, zinaiteizibino 55.71%. For a long life of salt. Let's dissolve 10 g of the lycylic acid in 40 cm3 of alcohol. Remove the yellow precipitate, which is filtered off, and dry it in an elksikiaitoir. 3. 4-amino^2-thiophenol-l-carbono-Vy acid. We pour 6.2 g of 4-amino-2-thiophenolHl-carbonic acid into 60 cm3 of dilute hydrochloric acid, dissolve it by adding 440 cm3 of water and filter the filtrate until the filtrate is completely clear, stirring it with drops of 5,34 potassium golden bromide. dissolve it in 200 cm3 of water and mix 3 hours. Discoloration occurs shortly thereafter, with the simultaneous formation of a faintly yellow precipitate. The precipitate is collected on a hard filter and dried, then finely pulverized, washed with 500 cm3 of alcohol while stirring for 5 hours, filtered, and dried in a vacuum. 4-aminophenol-3-carboxylic acid, having the formula C7H5O2NSAuH2O7, when finely ground, appears as a yellowish powder, insoluble in organic solvents. Gold: calculated 51.44%, Enamel: 50.98%. Salt Citirzympjeniy sicid by diluting 4.9 g of acidic acid in 20 cm3 of 20°C 300°C aqueous solution and adding 500 cm3 of alcohol to the solution. The precipitate is filtered off and dried in vacuo. Saddle salt, long-lasting, is a light-yellow pyrolyte, which dissolves very easily in water and gives a neutral reaction. The gold content is, according to the formula: C7H^02NS AuNa, H20: calculated - 48.64°/0, found on - 48.23%. PL PL PL

PL779A 1920-07-12 Method for the preparation of complex gold salts, thiophenols and their derivatives. PL779B1 (en)

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