US1091881A - Arseno-metal preparations and process of making same. - Google Patents

Description

l unieron PAUL EHRLICH,

TEE-MAIN, AND .SSIGNORS '2O FREIE 1 THE-MEIN, GERMANY.

MESTER LU' GURI? TLTION Gl GERMANY.

FFQE

nru, snniueirn' ARSENO-METL BREARTNS- ND PROCESS GF .MAKING SAME.

nemesi..

lo Drawing.

S ecfzcston of Lettere Eateuc,

epplcation filed Y.: sanary E25, 1913.

Serial H0. *f-$25225.

Bc il lmou'n that we fliifn lfliiunici-i, lf). professor of n'ieiliuincI a siti-en of the Empire of (crinunij7 residing el lf' forhonulxcelluin, Germany, BA1-#rior Tina. llli. L. chemist.y a citizen oit the linipire ol minion). residing at lloeiisbcnhewhen combined with salts of met-,ils such, los instance. as gold, platinum, palladium, copi sili'fer, forni addition products in thc metal iirnily coupled,

. prawess in question consists in coinliini g said. urseno compounds with Inemliic'salts in solution, rthe new compounds thus produced separate directly, or they my he isolated 'oy precipitation, or obtained j cx'agoration. The new products constiuif; preparations ot great value for thereunitc the action oi ,e :u'seno compounds with that of the salts and thereby become more elllous. "The erseno compounds which. con he used this process comprise not only the cle- \tives of the arsenolienzene, but also 'loose which contain the radical nliove infliconihincil hy the its with in o.li or inorganic residue.vl mul which con procluceili'or instance lo; .i'eilucii'ig u inizin rc oi" un aromatic m'sinio acid, or :in uro matic u 'cnoXiiL :unil un aliphatic ui'sinic ueiil, or en inorganic', arsenic compound, 'lliure nl: i" he obtained with urseuious zie-lil7 for iiistm. W, compounds contuining two zuul inoie utou oi' :ii-senil, f lfheso ronpouniils,ure heren culled iiolieziiseno coinpouiuls (sce 'ne follou'ing llxuniplcs XV-XV).

mi Jell politic purposes,V as they j purpose the compounds The nie/tal compounds cenlic obtained by carrying out the u'iuiuitucture of 'the er seno-metal preparations and oi' the urseno cinupounds in u single ope ation For this from which the j urs/eno compounds are obtained hy reduci 1 l l l l l 1 i l tion, are reduced in presence of the metal maiis (sce Exen'iplcs XVlll-XQ given puller).

i he new products in general, are reacisoluble inv Water, methyl alcohol, di- .eil allto'lis und hydrochloric acid, but insoluhle or scarcely soluble in ether and oennoue.

1the

following4 examples illustrate more f'jcularly the invention, but in no way vuple 2 cc. of en aqueous solution oi vi olilorid of l per cent. strength are in il into cc. of an aqueous solution o; cent. strength of the dihydrochlorid el lioxy 3.81 diaminoursenobcnzenc. 'lhus clear dark-brown solution vof :ieicl reaction is formed, from which, on addition of ot alkali, no auric hydroxicl scp arat'es'snfl from which, after 'treatment with elle li, no gold conbe isolated either by "formaldehyde or by hyclrosullte. By evnporating solution in a Vacuum, or by adding to it a :nii-:ture olf alcohol and ether, or of alcohol and acetone, solid products are obtained which, on addition of water, yield clear solutions having properties similar to those of the original solution.

Exemple 2 cc. of a solution of the sodium salt of murio oxid of l0 per cent strength are introduced into 5 cc, of an aqueous solution of 5 per cent. strength of the (lismlium salt of diaminodioxyarsenolocurene,x .whereby dark-brown solution of un n lkgiline reaction is formeel, wherein the lfgohl cannot be precipitated by a reducing; ugent, or precipitated by sodium sullcl. By cvai'uuating the 'solution in u vacuum or sliding to it u considerable quantity of alv eohol or of Aeilcohol und ethera solid products :ire olituincd readily soluble in Water.

Exemple lll: 3 cc. of un aqueous solution of plfxtnio clilorid of l0 per cent. strength are introduced into ce. of a solution of 5 per cent. strength of dihydrochlorid of iliaini ncflioxyarsenoben zene, whereby u lght brown solution is produced which behaves' toward precipitating agents like the solution described in Example I.

Example IV: 2 cc. of a solution of platinic dissolved in a small quantity of water, are mixed with 0.7 part of cupric chlorid CuCl2.2H2O, also dissolved in water. On pouring the mixture into a mixture of alcohol and ether, the addition-product is precipitated in the form of a yellow voluminous powder, dissolving in water to a yellowish-red solution. In this compound the copper cannot be detected by means of the usual reagents, and itis only by boiling that the compound is gradually decom osed.

Example V'I: 3 parts of sodium ormaldehyde sulfoxylate of dia-minodioxyarsenobenzene are dissolved in a small quantity of water and there is then gradually added while continually stirring, a solution oi 0.77 part of silver nitrate, in 2O parts of` water. By adding a mixture of alcohol and ether, the compound., is precipitated in the form of a black powder, which dissolves in water to a clear solution. The aqueous solutions sliow an intense fluorescence.

Example VII: A diluted aqueous solution of about 0.25gra1n of auric chlorid is introduced drop by drop into a solution of 1.5 grams of arsenophenylglycin of the formula:

q/Nuomcoon in water until a precipitate is formed. To

this mixture is added alcohol and ether, whereupon the addition compound precipitates in the form of a grayish-yellow powder. It is readily soluble in water and alltalis, thegold being very 'rmly bound Exam le VIII: 0.8 gram of auric chlorid dissolve in 5 cc.4 of water are in troduoed into a concentrated aqueous solution of 1 gram of the sodium salt of 4.41-dioxyarsenoenzene. On evaporating the solution in a vacuum, or addin alcohol and ether, a brownish-black addition-product is obtained which readily dissolves to a brownish-red solution.v

Example IX: 1 am of hydrochlorid of 3.31 diamino 4.41 'oxyarsenobenzene dissolved in 10 cc. of methyl alcohol is mixed with some drops of met-hylalcohol solution of` hydrochloric acid and then 'combined with a solutionl of 0.56 gram of corrosive sublimate in 10 cc. of methyl alcohol. The

.color of the solution turns from light-yellow to dark-orange. By adding ether the addition compound is precipitated in the form of a light-yellow powder. It is very readily soluble in glycerin, ethylene gl col, methyl alcohol; also soluble in acidiie solution of potassium iodid. It is decomposedby water, particularly easily when warmed. Y

Example X: 1 gram of hydrochloridof `diamino-dioxyasenobenzene, dissolved inl() cc. of methyl-alcohol, is mixed with a solution of 0.36 gram of silver nitratein methyl alcohol, whereby a reddish-brown solution is obtained. On adding ether, the addition product is precipitated in the form of a rownish-yellow powder. It is very readily soluble in water, methyl alcohol, glycerin, etc. The solutions do not show any traces of silver ions, and by addingl a reducing agent no silver is isolated. T e com ound contains one molecular proportion of iaminodioxyarsenobenzene to vone molecular proportion of silver nitrate.

Exanle XI: 1 gram of hydrochlorid of diamin ioxyarsenobenzene is combined, as

vindicated in Example X, with 0.72 gram of silver nitrate. The precipitate thus produced is of a dark-brown color and dissolves in water to an intense-reddish-brown .solution. -The compound contains one molecular proportion of diaminodioxyarsenobenzene to 2 molecular proportions of silver nitrate.

, Example XII: A solution of 3 grams of hydrochlorid of dialninodioxyarsenobenzene in l5 cc. of methyl alcohol is' acidified with a few drops of hydrochloric acid dissolved in methyl alcohol, and into the solution is introduced a solution of 1.07grams of cupric chlorid, CuCl22H2O, in 10 cc. of meth l alcohol. red color, and after a short time the addition-product crystallizes. When dry, it forms an orange-yellow powder, readily soluble in water, glycerin and ethylene glycol. By addition of caustic alkali to the cold aqueous solution, cupric hydroxidis precipitated, and it is only on heating that 'l ble compound can dry,

incassi ular proportion of cupric'chlorid.

Example X111: A solution of 3 grams of hydrochlorid of diaminodioxyarsenobenzene in cc. or' methyl alcohol is run into a solution ot' 1:24: gra-ms of cuprous chlorid in hydrochloric acid dissolved vin methyl alcohol, and the addition-product is precipitated by adding ether. The compound thus ob tained/forms a brick-colored powder, readily soluble in water, and contains one molecular proportion of diaminodioxyarsenobenzene toone molecular proportion of cuprous chlorid. l

Example XIV: 1.5 grains of hydrochlorid or dianiinodioxyarsenobenzene dissolved in methyl alcohol are introduced into a soluion of 0.55 gram of silver nitrate in methyl alcohol and there is then added a solution of 1 grain ofk auric chlorid in methyl alcohol. On addition of ether the compound is precipitated as a brownish-red powder. 1t is readily soluble in water, glycerin, etc., and contains one molecular proportion of diaminodioxyarsenobenzene to one molecular proportion oli silver nitrate and to one molecular proportion of auric chlorid.

A poly-arseno compound, such as has been referred to above and as used in the iollowing examples, is obtained by reducing a solution of 23.3 grams of At-aniino-oxyphenylarsinic acid and 13 grams oi sodium arsenite by means of sodium hydrosuliite in diluted aqueous. solution; it is an orangeyellovv powder readily soluble in diluted caustic soda lye as 'well as in diluted hydrochloric acid. lt contains about 49 of arsenic, the arsenic atom of the arsenite being linked to he arsenic atom of the arsinic acid, thus rorming the group:

into the clear liquid is introduced a solution of 1 gram of cuprous'chlorid in 2.5 cc. of

hydrochloric acid (of gravity 1.12) and 20 cc. of methyl alcohol. The liquid becomes deep dark-red, and on pouring it into several-times its volume ot ether, the dou-- be precipitated. When it forms a light-brown powder soluble in methylalcohol and Water. The .solution can be made alkaline with caustic soda lye without'precipitation of cuprous oXid. O

' adding sulfuric acid, a diicultly-soluble sul- The compound thus va deep dark broWmsh-orangecolor; there is thus precipitated is per cent.

-grams of stannous fate is precipitated from' the aqueous solution of the substance. I

Example-XVI: 3 grams of the aforesaid poly-arseno compound are dissolved in cc. of methyl alcohol and 1.5-2 cc. of hydrochloric acid (of spec. gravity 1.12), and into the clear liquid is introduced a solution of 2.? grams'of mercurio chlorid in 20 cc. of methyl alcohol, *whereupon the liquid becomes at once an orange magma ol the compound. 'ln order to facilitate its filtration, some ether is added, and after filtration, the mass is Washed with ether and dried. Thus an orange powder is obtained, which 'is insoluble in Water and methylv alcohol and on adding aqueous caustic soda lye decomposes While becoming black.

Example XVII: 3 grams of the aforesaid poly-arseno compound i are dissolved in G0 cc. of methyl alcohol and-.1.52 cc. ot' hy drochloric acid (of spec. gravity 1.12) and to the clear liquid a solutionof 0.85 gram of silver nitrate in 5 cc. of Water and 20 cc: of methyl alcohol is added. The mixture is of no substantial precipitation of silver chlorid and vno reduction of the silver salt. After having liltered any very small precipitate which may have formed, the liquid is poured into about 50G cc. of ether. The compound iiltered, Washed With ether and dried. lt forms a brown powder, readily soluble in methyl alcoholv and soluble in Water; its aqueous solution can be rendered alkaline by adding caustic soda lye Without any precipitation.

Example XVl: l0 grams of B-amino- --oxyphenyl-l-arsinic acid are dissolved in' 100 cc'. of Water and 43 cc. of 2N hydrochloric acid. There are then added 3.611 grams vof cupric chlorid CuCl2-2H2O dissolved in a small quantity of Water, and the Whole is heated to about 50 C. lnto this mixture isA introduced a solution, heated to 50o C., of 50 grams of hydrosulte in 150 oc. of Water, and after adding 43er.. of 2N. caustic soda lye, the mixture is stirred for several hours at 50 C. The brownish-red precipitate thus produced is filtered and well Washed with Water. The product is readilyv soluble in diluted hydrochloric acid and caustic Example XIX: G `grams of S-ainino-Lloxypnenylarsenozrid are dissolved in an eX- f cess of hydrochloric acid and 2.5 grams of cupric chlorid CuClT2H2O added, and this mixture is mixed with a solution of chlorid in concentrated hydrochloric acid, whereupon the hydrochlorid of the metal-salt compound immediately separates.

Example XX: 3 grains of S-amino-Ll-oxyphenylarsenoxid are'dissolved in thc calculated quan'tity of diluted hydrochloric acid.

and there are added, rst a solution of 2.25l 130.

15.0.91 ,eel f grams of auric chlorid in water, and then in a single dose, a solution of SOIgraIns of hydrosulfite. The metal-salt compound of 3.3l-diarninc-4A-dioxyarsenobenzen of a goldenyellow precipitate.

EXainplefXXI: 2 grams of pamino plienylarsenoxid are dissolved in the calcu.

lated quantity of diluted hydrochloric acid, and there are addechrst l gram of pla'- Ytinic chlorid dissolved, in water, and then inia single dose/a solution of 30 grams of seno-metal preparations, which. consists incombining arseno compounds containing the radical with salts o'f-heavy metals.

metal preparations, which consists in combining arseno compoundscontaining the ,with saltsiof `heavy metals in solutions in conjunction wi @an aromatic complex of atoms coupled wltfthe arsenic atom AsII withauric chlorid separates at once 1n the forn Y 4; The process of manufacturing an `arseno preparation, which consists in -combin ing the hydro-chlorid of 3.31-diamino-4A 'dioxyarseno'benzene with cuprous chlorid.

5. As new products, arseno-metal preparations containing the'radical and a heavy metal, said metal being boundv in the form of a complex salt and not being detectable bythe usual analytical reagents; the preparations being readily soluble in water, methyl alcohol, diluted alkalis and `hydrochloric acid, but substantially insoluble in ether and benzene.

6. As' a new product, a preparation con-y taining the radical ,and copper, the copper being bound in the. form -of a complex salt and not being de Qtectablefby the usual analyticall reagents, vsaid repara-tion being readily soluble in, water, methyl alcohol, diluted alkalis and hydr'jchloric acid, but substantially insolu-` ble in ether and benzene.

7 As a new product, a preparation consisting of 3.31-diamino-4-41dioxyarsenobenzene combined with cuprous chlorid, in a complex form, the coplper not being detectable by the usual ana ytical reagents, said preparation being read1ly `soluble in water, methyl alcohol, diluted alkals and hydro chloric acid, but insoluble `or scarcely soluble in ether and benzene.

In testimony whereof, We aiix our signatures in presence of two witnesses.

PAUL EHRLICH. BAPTIST REUTER. PAUL KARRER.

"Witnesses:

JEAN Gann D, CARL GRUND Aas Correction in Letters Paelnt No. 1,091,881.

.1 improvement in Arsenol-Metal Preparations and Processes 0f Making' Sinne,"

l l 1 I1 It is hereby Vcertified that in Letters Patent No. 1,091,881, granted March 31, 1914, upon the application 0f Paul Ehrlich, of' Frankfort-0hthe-Main, Baptist Reut-er, of

,i Hchstenthe-Mam, and Paul Kurrer, of Frankfort-on-the-Ma1n,'(iernmny. 101' :1n

errorlippe/dereI in the printed speeiication requiring' corree'tion as follows: Page v3. i line 1T, for the werd grains resul (/rmns.' und that the said Letiiers Patent should be read with this' correction therein 4than; the szinierniay conformi to the record 0l' tlie case in the Patent Olice.

Signed and ealed this 6th day Of'July, A. D., 19153 [SEAL] R, F. VVHITEHEAD7V Actng Lhmmz'ssa'aner of Paens.