DE488892C - Process for the preparation of aminoalkylamino substitution products of the xanthene series - Google Patents

Process for the preparation of aminoalkylamino substitution products of the xanthene series

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Publication number
DE488892C
DE488892C DEI27081D DEI0027081D DE488892C DE 488892 C DE488892 C DE 488892C DE I27081 D DEI27081 D DE I27081D DE I0027081 D DEI0027081 D DE I0027081D DE 488892 C DE488892 C DE 488892C
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DE
Germany
Prior art keywords
derivatives
substitution products
xanthene
preparation
aminoalkylamino
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Expired
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DEI27081D
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German (de)
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IG Farbenindustrie AG
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IG Farbenindustrie AG
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Priority to DEI27081D priority Critical patent/DE488892C/en
Priority to DEF56868D priority patent/DE486079C/en
Application granted granted Critical
Publication of DE488892C publication Critical patent/DE488892C/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/40—Nitrogen atoms attached in position 8
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C07D215/42—Nitrogen atoms attached in position 4
    • C07D215/46—Nitrogen atoms attached in position 4 with hydrocarbon radicals, substituted by nitrogen atoms, attached to said nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

Verfahren zur Darstellung von Aminoalkylaminosubstitutionsprodukten der Xanthenreihe Zusatz zum Patent 4860791 Durch das Hauptpatent 486 079 ,ist .ein Verfahren zur Herstellung von -AminoalkyT aminosubstitutionsprodukten der Chinolinreihe usw. geschützt, die in vorzüglicher Weise gegen Blutparasiten wirken. Das Verfahren besteht darin, daß man Aminosubsttutionsprodukte des Chinolins als solche oder über geeignete Zwischenprodukte hinweg in Polyaminderivate bestimmter Art überführt.A process for the preparation of the xanthene Aminoalkylaminosubstitutionsprodukten additional patent 4860791 by the main patent 486,079, is .a method for producing the quinoline -AminoalkyT aminosubstitutionsprodukten protected, etc., which act in an excellent manner against blood parasites. The process consists in converting amino substitution products of quinoline as such or via suitable intermediates into polyamine derivatives of a certain type.

Es wurde nun gefunden., daß man zu therapeutisch ebenso wirksamen neuen Heilmitteln auch dadurch gelangen kann, daß man Aminoderivate der Xanthenreihe, ihre Abkömmlinge, Kernsubstitutionsprodukte oder Äquivalente in solche stärker basischen Polyaminderivate überführt, welche die neueingeführten Stickstoffatome mit Hilfe aliphatischer Reste an den aromatischen Aminogruppen gebunden enthalten.It has now been found that one can also be therapeutically effective new remedies can also be achieved by using amino derivatives of the xanthene series, their derivatives, core substitution products or equivalents to those more basic Polyamine derivatives transferred, which the newly introduced nitrogen atoms using contain aliphatic radicals bonded to the aromatic amino groups.

Zur Herstellung dieser Verbindungen kann man in der Art verfahren., daß man die Aminoderivate der obengenannten Körperklasse mit Salzen von Halogenalkylaminen verschmilzt oder nach den üblichen Methoden den Aminoalkylrest anfügt, beispielsweise durch Umsetzung mit Halogenalkylaminen oder ihren Substitutionsprodukten, wie Halogenalkylphthalirnid, unter nachheriger Abspaltung des Phthalsäurerestes. Man kann natürlich auch in der Weise verfahren, da.ß man diese Aminoalkylreste nacheinander in die Aminosubstitutionsprodukte einführt, beispielsweise so, daß man diese Aminoderivate zunächst mit Äthylenoxyd oder halogenierten Alkoholen in Reaktion bringt und die auf diese Weise entstehenden Oxyalkylami;nod.erivate in üblicher Weise über die Halogenide hinweg in Polyaminderivate umwandelt, oder auch derart, daß man reaktionsfähige Abkömmlinge der genannten Körperklassen, z. B. das Fluoreszeinchlorid, mit aliphatischen Diaminen umsetzt. Selbstverständlich kann man auch so vorgehen, daß man geeignete Zwischenprodukte zur Herstellung der Aminoxanthene nach einer der eben angedeuteten öder nach sonstigen üblichen. Methoden in Polyaminderivate überführt und die so erhaltenen Zwischenprodukte dann in die Polyaminderivate umwandelt. Der Umwandlung in Polyaminderivate können sowohl primäre oder sekundäre Aminoderivate unterworfen werden. Ebenso ist es möglich, Amine zur Anwendung zu bringen, die die Aminogruppe nicht nur einmal, sondern mehrfach enthalten; die den gleichfalls ,einmal oder öfter vorhanden sein könnenden aliphatischen Stickstoff tragenden Seitenketten können gerade *) Frühere Zusatzpatente 486771, 488 8go, 488945. oder verzweigt sein und das aliphatische Stickstoffatom in (3- oder in y-Stellung oder noch weiter entfernt von den Aminogruppen der genannten Körper enthalten. Natürlich können an Stelle der hier beschriebenen Polyamine auch andere ähnlicher Konstitution, z. B. auch Piperidinverbindungen, verwendet werden. Beispiel i Zur Darstellung von m-Oxy-N-diäthylaminoäthylä.thylani,hn werden i o2 g m-Oxy-N-äthylaniEn in i 5o ccm Benzol auf dem Wasserbad gelöst, ioog Diiäthylaminoäthylchlorid in i 5 o ccm Benzol zugegeben und einen Tag zum Sieden erhitzt. Man löst nach Abgießen des Benzols in Wasser, macht mit Kaliumcarbonat die Base frei und nimmt mit Benzol auf. Nach Entfernung des Benzols siedet die neue Base bei 18o bis i82° (unter q. mm Druck) ; sie ist ein stark lichtbrechendes, in, der Kälte zähflüssiges cal, das nach mehrtägigem Stehen zur weißten Kristallnasse erstarrt.To prepare these compounds one can proceed in such a way that one fuses the amino derivatives of the abovementioned body class with salts of haloalkylamines or adds the aminoalkyl radical by the usual methods, for example by reaction with haloalkylamines or their substitution products, such as haloalkylphthalimide, with subsequent cleavage of the phthalic acid radical . One can of course also proceed in such a way that these aminoalkyl radicals are introduced one after the other into the amino substitution products, for example in such a way that these amino derivatives are first reacted with ethylene oxide or halogenated alcohols and the oxyalkylamino; nod.erivate resulting in this way are usually reacted Way converts over the halides into polyamine derivatives, or in such a way that reactive descendants of the body classes mentioned, eg. B. the fluorescein chloride, reacts with aliphatic diamines. It is of course also possible to proceed in such a way that suitable intermediates for the preparation of the aminoxanthenes are used according to one of the just indicated or according to other customary ones. Methods converted into polyamine derivatives and the intermediate products thus obtained are then converted into polyamine derivatives. Both primary and secondary amino derivatives can be subjected to the conversion into polyamine derivatives. It is also possible to use amines which contain the amino group not just once but several times; the side chains carrying the aliphatic nitrogen, which can also be present once or more often, can be straight *) previous additional patents 486771, 488 8go, 488945. or branched and the aliphatic nitrogen atom in (3 or y position or even further away from the amino groups Of course, instead of the polyamines described here, other similar constitution, for example also piperidine compounds, can be used To prepare m-Oxy-N-diethylaminoäthylä.thylani, hn, 10.2 g of m-Oxy-N-ethylaniEn are dissolved in 15o cc of benzene on a water bath, 10o of diethylaminoethyl chloride in 15o cc of benzene is added and the mixture is heated to the boil for one day . After the benzene has been poured off, it is dissolved in water, the base is released with potassium carbonate and taken up with benzene. After removal of the benzene, the new base boils at 180 to 182 ° (under q. Mm pressure); it is a strongly refractive cal, which is viscous in the cold and which solidifies to a white, crystalline liquid after standing for several days.

Zur Farbstoffbildung werden 40 g der Base mit 50 g Phthalsäureanhydrid 3 bis q. Stunden auf Nächstens 175° Ölbadtemp,eratur unter Rühren erhitzt. Die in der Kälte springharte Schmelze wird gepulvert und. zweckmäßig in Nitrobenzol bei 7o bis 8o° gelöst. Die noch q.o bis 50° warme Lösung wird zur Entziehung der Phthalsäure und Freimachen der Farbbase mit Natriumcarbonat mehrfach geschüttelt. Die nitrohenzolische Lösung wird getrocknet, mit Äther verdünnt und aus der Lösung. mit ätherischer Sal'zsiäure der Farbstoff als rotbraunes, hygroskopisches Pulver gefällt, das sich in Wiasser spielend leicht mit klarem Rhodamnton löst.To form the dye, 40 g of the base are mixed with 50 g of phthalic anhydride 3 to q. Hours heated to next 175 ° oil bath temperature with stirring. The melt, which is spring-hard in the cold, is powdered and. expediently dissolved in nitrobenzene at 7o to 8o °. The solution, which is still warm from qo to 50 °, is shaken several times with sodium carbonate to remove the phthalic acid and clear the color base. The nitrohenzene solution is dried, diluted with ether and out of the solution. the dye is precipitated with ethereal hydrochloric acid as a red-brown, hygroscopic powder, which easily dissolves in white water with a clear shade of rhodamn.

Zur Estehf zierurig der - Carboxylgruppe werden, i o. g dieses salzsauren .Salzes in 5o g absolutem _ Alkohol gelöst --und einen Tag unter Eiskühlung und einen Tag unter Kochen, gasförmige HCl eingeleitet. Das im Vakuum zur Trockne gebrachte Farbsalz unterscheidet sich, in Wasser gelöst, nur durch einen gering gelberen Ton vom Ausgangsstoff. Dagegen ist die spielende Leichtlöslichkeit der Farbbase in Nitrobenzol sowie ihre auffallend, stärker violette Lösungsfarbe in Nitrobenzol gegenüber der nicht 4-,stexif.-zierten Farbbase charakteristisch. Beispiel z Zur Farbstoffkondensation wird das im zweiten Zusatzpatent, Beispiel. q., beschriebene m-Oxy-N-diäthylaminoäthyhnethylaniUnverwendet. z Mol. dieser Base werden mit i Mo1. Formaldehyd und 11401. 5oproäentiger Oxalsäure in alkoholischer Lo-sung .unter Erwärmung zum Diphenyhnethanderivat kondensiert. VachAbdestillieren desAlkohols im Vakuum, Lösen des Rückstandes in Wasser, Fällen mit Kaliumcarbonat, Aufnehmen in Benzol und AbdestiMeren des Benzols erhält man die Verbindung als zähflüssiges Öl, das zum Xanthenringschluß vorsichtig in konzentrierte Schwefelsäure von 6o° B6 eingetragen und einige Stunden darin bei ungefähr 3o° belassen wird. Sodann verdünxnt man mit 6ogrädäg-er Säure auf einem Gesamtgehalt von 9o% H2S04 und oxydiert mit trockenem Natrinmnitrit bei etwa 3o" unter Rühren zum Farbstoff. Dieser, als Zinkdoppelsalz abgeschieden, wird durch konzentrierte Natronlauge vom Zink getrennt, die abfiltrierte Farbbase in Nitrobenzol aufgenommen und, wie oben, in das Hydrachlorid übergeführt.At the foot of the carboxyl group, 10 g of this hydrochloric acid salt are dissolved in 50 g of absolute alcohol - and gaseous HCl is introduced for one day while cooling with ice and one day while boiling. The colored salt, which has been brought to dryness in a vacuum, differs from the starting material in that it is dissolved in water only by a slightly more yellow shade. On the other hand, the easy solubility of the color base in nitrobenzene and its striking, more violet solution color in nitrobenzene are characteristic of the non-4, stexified color base. Example For dye condensation, this is described in the second additional patent, example. q., described m-Oxy-N-diethylaminoäthyhnethylaniUnused. z moles of this base are combined with i Mo1. Formaldehyde and 11401.5 percent oxalic acid in alcoholic solution. Condensed under heating to the diphenyhnethane derivative. After distilling off the alcohol in vacuo, dissolving the residue in water, precipitating with potassium carbonate, taking up in benzene and distilling off the benzene, the compound is obtained as a viscous oil, which is carefully added to concentrated sulfuric acid at 60 ° B6 to close the xanthene ring and then for a few hours at about 30 ° is left. Then it is diluted with 60 degrees of acid to a total content of 90% H2S04 and oxidized with dry sodium mnitrite at about 30 "with stirring to form the dye , as above, converted into the hydrochloride.

Claims (1)

PATENTANSPRUCH: Weitere Ausbildung der durch Patent 486079 geschützten Erfindung, dadurch gekennzeichnet, daß man hier zwecks Darstellung von Aminoalkylaminosubstitu.-tionsprodwkten der Xanthenreihe Aminosubstitutionsprodukte dieser Körperklasse, ihre Abkömmlpnge, Kernsubstitutionsprodukte oder Äquivalente in solche stärker basischen Polyaminderivate überführt, die die neueingeführten Stickstoffatome mit Hilfe aliphatis@cher Reste an den aronma.-tischen Aminogruppen gebunden enthalten, oder daß man Am.noderivate geeigneter Zwischenverbindungen zur Herstellung dieser Körperklasse in Polyaminderivate -. der genannten Art überführt und diese dann nach den üblichen Methoden in Xanthenderivate umwandelt. PATENT CLAIM: Further development of the invention protected by patent 486,079 , characterized in that here, for the purpose of representing aminoalkylaminosubstitu.-tion products of the xanthene series, amino substitution products of this body class, their derivatives, nuclear substitution products or equivalents are converted into such more basic polyamine derivatives which use the newly introduced aliphatic atoms @cher contain residues bound to the aronma.-table amino groups, or that one Am.noderivate suitable intermediate compounds for the production of this body class in polyamine derivatives -. of the type mentioned and then converted into xanthene derivatives by the usual methods.
DEI27081D 1924-09-12 1924-09-12 Process for the preparation of aminoalkylamino substitution products of the xanthene series Expired DE488892C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DEI27081D DE488892C (en) 1924-09-12 1924-09-12 Process for the preparation of aminoalkylamino substitution products of the xanthene series
DEF56868D DE486079C (en) 1924-09-12 1924-09-12 Process for the preparation of N-substituted aminoquinolines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEI27081D DE488892C (en) 1924-09-12 1924-09-12 Process for the preparation of aminoalkylamino substitution products of the xanthene series
DEF56868D DE486079C (en) 1924-09-12 1924-09-12 Process for the preparation of N-substituted aminoquinolines

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DE488892C true DE488892C (en) 1930-01-23

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DEI27081D Expired DE488892C (en) 1924-09-12 1924-09-12 Process for the preparation of aminoalkylamino substitution products of the xanthene series
DEF56868D Expired DE486079C (en) 1924-09-12 1924-09-12 Process for the preparation of N-substituted aminoquinolines

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2477480A (en) * 1946-04-08 1949-07-26 Robert C Elderfield Antimalarial compounds and process of making them
US2464199A (en) * 1946-04-08 1949-03-15 Robert C Elderfield Alkylamino alkyl bromides

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DE486079C (en) 1929-12-02

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