DD276480A1 - PROCESS FOR THE PREPARATION OF NAPHTHO / 2,1-B / FUR-2-YLCHINOXALINES - Google Patents
PROCESS FOR THE PREPARATION OF NAPHTHO / 2,1-B / FUR-2-YLCHINOXALINES Download PDFInfo
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- DD276480A1 DD276480A1 DD32107588A DD32107588A DD276480A1 DD 276480 A1 DD276480 A1 DD 276480A1 DD 32107588 A DD32107588 A DD 32107588A DD 32107588 A DD32107588 A DD 32107588A DD 276480 A1 DD276480 A1 DD 276480A1
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Abstract
Die Erfindung betrifft ein neues Verfahren zur Herstellung der bisher nicht zugaenglichen Naphtho&2,1-b!fur-2-ylchinoxaline (Formel II), die als Zwischenprodukte zur Zubereitung biologisch aktiver Praeparate oder als Pigmentfarbstoffe mit intensiver Fluoreszenz anwendbar sind. Die Herstellung der erfindungsgemaessen Verbindungen erfolgt durch zweistufige Synthese aus 2-(Halogenmethyl)chinoxalin und 2-Hydroxy-naphthalen-1-carbaldehyd unter Zugabe einer Base, wobei in der ersten Stufe 2-(Chinoxalin-2-ylmethoxy)naphthalen-1-carbaldehyde gebildet werden, die mit oder ohne Isolierung in der zweiten Stufe cyclisiert werden.The invention relates to a novel process for the preparation of the previously inaccessible naphtho & 2,1-b! Fur-2-ylquinoxalines (formula II), which can be used as intermediates for the preparation of biologically active preparations or as pigmentary dyes with intense fluorescence. The preparation of the compounds according to the invention is carried out by two-stage synthesis of 2- (halomethyl) quinoxaline and 2-hydroxy-naphthalene-1-carbaldehyde with the addition of a base, wherein in the first stage 2- (quinoxalin-2-ylmethoxy) naphthalene-1-carbaldehyde which are cyclized with or without isolation in the second stage.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Naphtho|2,1-b)fur-2-ylchinoxf,iinon, die alt Zwischenprodukte zur Zubereitung biologisch aktiver Präparate oder als Pigmentfarbstoffe mit intensiver Fluoreszenz anwendbar sind.The invention relates to a process for the preparation of naphtho | 2,1-b) fur-2-yl-quinoxf, iinone, which are applicable to intermediate intermediates for the preparation of biologically active preparations or as pigment dyes with intense fluorescence.
Ziel der Erfindung ist es, ein Verfahren zur Herstellung von Naphtho(2,1 -b]fur-2-ylchinoxalinen zu finden, da derartige Verbindungen bisher nicht zugänglich sind.The aim of the invention is to find a process for the preparation of naphtho (2,1-b] fur-2-ylquinoxalines, since such compounds are not previously available.
Aufgabe der Erfindung ist es, ein Verfahren zu finden, nach dem die bisher nicht zugänglichen Naphtho|2,1 -blfur-2-ylchinoxaline hergestellt werden können.The object of the invention is to find a method by which the hitherto inaccessible naphtho | 2,1-blur-2-ylquinoxalines can be prepared.
Erfindungsgemäß wird die Aufgabe dadurch gelöst, daß 2-(Halogenmethyl)chinoxaline der allgemeinen Formel I, in der Hai = Halogen, bevoizugt Cl oder Br, und R = Alkyl oder Aryl, bevorzugt Methyl oder Phenyl, bedeuten, mit 2-Hydroxynaphthalen-1-carbaldehyd in zweistufiger Synthese zu den Naphtho|2,1-b)fur-2-ylchinoxalinen der allgemeinen Formel II, in der R die gleiche Bedeutung wie im eingesetzten 2-(Halogenmethyl)chinoxalin besitzt, umgesetzt werden. Die beiden Ausgangsstoffe werden dabei in genau oder annähernd äquimolarem Verhältnis eingesetzt. In der erston Synthesestufo werden 2-(Chinoxalin-2-ylmethoxy)nephthalen-1-carbaldehyde gebildet, die in 3-Stellung des Chinoxaline durch R, das die gleiche ' Bedeutung wie im eingesetzten 2-(Halogenmethyl)chinoxalin besitzt, substituiert sind. Diese in der ersten Synthesestufe gebildeten Zwischenprodukte können mit oder ohne Isolierung eis Ausgangsstoffe für die zweite Synthosestufe, bei der der Naphihofuran-Ringcchluß orfolgt, eingesetzt werden. In beiden Synthesestufen ist die Zugabe einer ausreichend starken Base, bevorzugt NaOH oder KOK, erforderlich. In der ersten Synthesestufe wird die Base dem 2-Hydroxy-naphtalen-i-carbaldehyd inAccording to the invention the object is achieved in that 2- (halomethyl) quinoxalines of the general formula I in which Hal = halogen, bevoizugt Cl or Br, and R = alkyl or aryl, preferably methyl or phenyl, mean with 2-hydroxynaphthalene-1 Carbaldehyde in a two-stage synthesis to the naphtho | 2,1-b) fur-2-ylchinoxalinen the general formula II in which R has the same meaning as in the used 2- (halomethyl) quinoxaline reacted. The two starting materials are used in exactly or approximately equimolar ratio. In the erston Synthesestufo 2- (quinoxalin-2-ylmethoxy) nephthalene-1-carbaldehyde are formed, which are substituted in the 3-position of the quinoxalines by R, which has the same 'meaning as used in 2- (halomethyl) quinoxaline. These intermediates formed in the first stage of the synthesis can be used with or without isolation of ice precursors for the second stage of the synthesis in which the naphihofuran ring closure occurs. In both steps of the synthesis, it is necessary to add a sufficiently strong base, preferably NaOH or KOK. In the first stage of the synthesis, the base is the 2-hydroxy-naphthalene-i-carbaldehyde in
äquimolarer Menge zugesetzt; sie bewirkt die Umwandlung der Hydroxylverbindung in das entsprechende Anion, das anschließend das 2-(Halogenmethyl)chinoxalin nucleophil angreifen kann. In der zweiten Synthesestufe wird die Bai e in Äquimolarer Menge oder im Überschuß zugesetzt; sie bewirkt die Cyctisierungsroaktion. Die Durchführung dor Reakiionen erfolgt in Suspension oder in Lösung unter Benutzung inerter Lösungsmittel, bevorzugt Methanol oder Ethanol, bei Temperaturen von O'C bis 250"C, bevorzugt bei der Siedetemperatur des Lösungsmittels.equimolar amount added; it causes the conversion of the hydroxyl compound into the corresponding anion, which can then attack the 2- (halomethyl) quinoxaline nucleophilic. In the second stage of the synthesis, the base is added in an equimolar amount or in excess; it causes the cyctivation action. The reactions are carried out in suspension or in solution using inert solvents, preferably methanol or ethanol, at temperatures of from 0 to 250 ° C., preferably at the boiling point of the solvent.
N^CH2HgIN, CH 2 HgI
2-Methyl-3-(naphtho|2,1-bIfur-2-yl)chlnoxalin2-methyl-3- (naphtho | 2,1-Bifur-2-yl) chlnoxalin
kocht erneut 2 Stunden unter Rückfluß. I 'ach dem Abkühlen wird obgesaugt, mit Wasser gewaschen und aus ΓοΙυβηumkristallisiert.Boil again for 2 hours under reflux. After cooling it is sucked up, washed with water and recrystallised from water.
2-(3-Methyl-chinoxalin-2-ylmethoxy)naphthalen-1 -carbaldehyd2- (3-methyl-quinoxalin-2-ylmethoxy) -naphthalene-1-carbaldehyde
17,2 TI. 2-Hydroxy-naphthalen-1 -carbaldehyd werden in 300 TI. Ethanol gelö3t und mit der Lösung von 5,6 TI. Kaliumhydroxid in100 TI. Ethanol vermischt. Anschließend fügt man 23,7 TI. 2-(Brommethyl)-3-methylchinoxalin hinzu und läßt 2 Stunden unter17.2 TI. 2-hydroxy-naphthalene-1-carbaldehyde are dissolved in 300 TI. Ethanol and dissolved with the solution of 5.6 TI. Potassium hydroxide in 100 TI. Ethanol mixed. Then add 23.7 TI. 2- (bromomethyl) -3-methylquinoxaline and allowed to 2 hours
2-Methyl-3-(naphtho|2,1-b]fur-2-yl)chinoxalin2-methyl-3- (naphtho | 2,1-b] fur-2-yl) quinoxaline
von 7 TI. Kaliumhydroxid in 100 TI. Ethanol hinzu und läßt 2 Stunden unter Rückfluß kochen. Nach dem Abkühlen wird abgesaugtund aus Toluen umkristallisiert.from 7 TI. Potassium hydroxide in 100 TI. Ethanol and allowed to reflux for 2 hours. After cooling, it is filtered off with suction and recrystallised from toluene.
2-(3-Phenyl-chinoxalin-2-ylmethoxy)naphthalen-1-carbaldehyd2- (3-Phenyl-quinoxaline-2-ylmethoxy) naphthalene-1-carbaldehyde
Belsr.el5:Bels r .el5:
'2-(Naphtho[2,1-b)fur-2-yl)-3phenyl-chinoxalin'2- (naphtho [2,1-b) fur-2-yl) -3phenyl-quinoxaline
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DD32107588A DD276480A1 (en) | 1988-10-26 | 1988-10-26 | PROCESS FOR THE PREPARATION OF NAPHTHO / 2,1-B / FUR-2-YLCHINOXALINES |
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DD32107588A DD276480A1 (en) | 1988-10-26 | 1988-10-26 | PROCESS FOR THE PREPARATION OF NAPHTHO / 2,1-B / FUR-2-YLCHINOXALINES |
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1988
- 1988-10-26 DD DD32107588A patent/DD276480A1/en not_active IP Right Cessation
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