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DE2113343A1 - Indolo- (2,3) - quinolones - prepd by reaction of keto-indoles and anthranilates, followed by dehydration - Google Patents

Indolo- (2,3) - quinolones - prepd by reaction of keto-indoles and anthranilates, followed by dehydration

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Publication number
DE2113343A1
DE2113343A1 DE19712113343 DE2113343A DE2113343A1 DE 2113343 A1 DE2113343 A1 DE 2113343A1 DE 19712113343 DE19712113343 DE 19712113343 DE 2113343 A DE2113343 A DE 2113343A DE 2113343 A1 DE2113343 A1 DE 2113343A1
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indolo
alkyl
quinolones
mol
oxindole
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Helmar Dobinsky
Eiden Fritz Prof Dr
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THIEMANN CHEM PHARM FAB
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THIEMANN CHEM PHARM FAB
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D471/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04Ortho-condensed systems

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  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Indole Compounds (AREA)

Abstract

Indolo- 2,3-b -quinolones of formula (I): (where R1 is H or alkoxy; R2 is H, alkyl or acyl and R3 is H or alkyl) have C.N.S. activity and can be used as antibiotics and cytostatics. They are prepd. by reacting ketoindoles of formula (II): with anthranilates of formula (III): (where R is alkyl) in presence of an alkali hydride, e.g. NaH, and in a solvent, and treating the intermediate 3-(21-aminobenzoyl)-ketoindoles (IV): with dehydrating agents. (I; where R2 = H or alkyl) may be acylated to (I; where R2 = acyl) in presence of a solvent with acid halides and alkali hydride; (I; where R2 = H) may be alkylated by standard methods.

Description

Indolo [2.3 - b3 chinolone. und Verfahren zu ihrer Herstellung Gegenstand der Erfindung sind Indolo r2.3 - b3 chinolone und Verfahren zu ihrer Herstellung. Die Verbindungen besitzen eine gewisse Wirksamkeit auf das Zentralnervensystem und können als Antibiotikum und Cystostaticum zur Anwendung gelangen.Indolo [2.3 - b3 quinolones. and process for their manufacture subject of the invention are indolo r2.3 - b3 quinolones and processes for their preparation. The compounds have a certain effectiveness on the central nervous system and can be used as an antibiotic and cystostatic.

Die erfindungsgemässe Verbindung besitzt die folgende Struktur worin R1 ein H-Atom oder eineO-Alkylgruppe, R2-ein H-Atom, ein Alkyl- oder Acyl-Rest und R3 ein H-Atom oder eine Alkvl-Gruppe sein können. Als Alkyl-Rest kommen vor allem solche nlit 1 - 4 C-Atonen und die Benzyl-Gruppe in Frage; als Acyl-Rest dienen die Acetyl-Gruppe sowie vor allem die Benzoyl-Gruppe, gegebenenfalls substituiert mit llalogen und/oder Alkyl oder O-Alkyl-Gruppen, z.B. also die p-Chlorbenzoyl- oder die Methoxybenzoyl-Gruppe.The compound of the present invention has the following structure where R1 can be an H atom or an O-alkyl group, R2 can be an H atom, an alkyl or acyl radical and R3 can be an H atom or an alkyl group. Particularly suitable alkyl radicals are those having 1-4 carbon atoms and the benzyl group; the acetyl group and, above all, the benzoyl group, optionally substituted by halogen and / or alkyl or O-alkyl groups, for example the p-chlorobenzoyl or methoxybenzoyl group, serve as the acyl radical.

Es wurde nun gefunden, dass diese neuen Verbindungen dadurch erhalten werden, dass Oxindole (I)2 der weiter unten aufgeführten STruktur-Formel, worin R² und R² die vorstehend genannte Bedeutung besitzen, mit einem Anthranilsäureester (II), worin R3 die vorstehend angegebene Bedeutung besitzt, und R einen beliebigen Alkyl-Rest darstellt, in Gegenwart von Alkalihydrid in einem Lösungsmittel wie folgt umgesetzt und die gebildeten 3-(2'-Amino-benzoyl)-oxindole (III) mit wasserabspaltenden Mitteln behandelt werden. It has now been found that these new compounds are obtained by treating oxindoles (I) 2 of the structure formula given below, in which R² and R² have the abovementioned meaning, with an anthranilic acid ester (II) in which R3 has the abovementioned meaning and R is any alkyl radical, reacted in the presence of alkali hydride in a solvent as follows and the 3- (2'-amino-benzoyl) -oxindoles (III) formed are treated with dehydrating agents.

Als Lösungsmittel eignen sich z.B. Dioxan, Tetrahydrofuran, Dimethylformamid und höher siedende äther, wie insbesondere der Diisoamyläther. Wasserabspaltende Mittel sind bekanntlich starke Säuren, wie Chlorwasserstoff/Methanol, Schwefelsäure/ Eisessig und Polyphosphorsäure.Suitable solvents are, for example, dioxane, tetrahydrofuran, dimethylformamide and higher-boiling ethers, such as diisoamyl ether in particular. Dehydrating agents Agents are known to be strong acids such as hydrogen chloride / methanol, sulfuric acid / Glacial acetic acid and polyphosphoric acid.

Nach einer Variante des Verfahrens lassen sich die Indolo [2.3 - b3 chinolone mit R2 = Acyl und R3 = Alkyl auch dadurch herstellen, dass erfindungsgemässe Verbindungen (Formel IV) mit R2 = H und R3 = Alkyl mit Säurehalogeniden und Alkalihydrid in Gegenwart eines Lösungsmittels, z.B. Dioxan, Tetrahydrofuran, Dimethylformamid, höher siedende Äther und dergleichen umgesetzt werden.According to a variant of the process, the indolo [2.3 - b3 Quinolones with R2 = acyl and R3 = alkyl also produce that according to the invention Compounds (formula IV) with R2 = H and R3 = alkyl with acid halides and alkali hydride in the presence of a solvent, e.g. dioxane, tetrahydrofuran, dimethylformamide, higher boiling ethers and the like are implemented.

Weiterhin ist es möglich, in die Indolo r2.3 - b3 chinolone mit R2 = H durch Alkylierung, z.B. mittels Alkyl-Halogeniden und Alkali-Alkoholat die Alkylgruppe R² nachträglich einzuführen.It is also possible to convert quinolones into the indolo r2.3 - b3 with R2 = H by alkylation, e.g. by means of alkyl halides and alkali alcoholate the alkyl group R² to be introduced subsequently.

Die Herstellung der einzelnen erfindungsgemässen Verbindungen und der zu diesen Verbindungen führenden Zwischenprodukte sei anhand der Beispiele näher erläutert: Beispiel 1 3-(2dAmino-benzoyl)-oxindol 6,65 g Oxindol (0,05 Mol) werden zu einer Suspension von 4,8 g Natriumhydrid (0,2 Mol) in 70 ml absolutem Dioxan gegeben. Nach Zugabe von 2 Tropfen abs. Methanol wird 7,55 g Anthranilsäuremethylester (0,05 Mol) zugetropft und das Gemisch 8 Stdn.The preparation of the individual compounds according to the invention and the intermediates leading to these compounds are explained in more detail using the examples illustrated: Example 1 3- (2d-amino-benzoyl) -oxindole 6.65 g of oxindole (0.05 mol) become to a suspension of 4.8 g of sodium hydride (0.2 mol) in 70 ml of absolute dioxane given. After adding 2 drops of abs. Methanol becomes 7.55 g of anthranilic acid methyl ester (0.05 mol) was added dropwise and the mixture for 8 hours.

rückfliessend erhitzt. Anschliessend wird zur Trockene eingeengt, der Rückstand in Äther suspendiert und abgesaugt. Das Natriumsalz wird in kalte 5 %ige Schwefelsäure gegeben und das Produkt mit Äther extrahiert. Der Extrakt wird zur Entfernung von Anthranilsäure mit 5tiger NaHCO3-Lösung anschliessend ntit 5 @iger Na2CO3 -Lösung ausgeschüttelt. Nach Ansäuern fällt das 3-(2'-Arnino-benzoyl)-oxindol aus.heated to reflux. It is then concentrated to dryness, the residue suspended in ether and filtered off with suction. The sodium salt is in cold Given 5% sulfuric acid and extracted the product with ether. The extract will to remove anthranilic acid with 5% NaHCO3 solution then ntit 5 @iger Na2CO3 solution shaken out. After acidification, the 3- (2'-amino-benzoyl) -oxindole precipitates the end.

Gel alu Nadeln; Ausbeute 30 %, Schmp. 136-37 (aus Isopropanol und Ligroin) C15H12N202 (252,3) JR (KBr) : 3475/3380 cm-1 # (NH), 3170 cm-1 (NH), 1650-1600 cm-1 # (C = o u. C = C); NMR (CDCl3): 9,4 ppm (s) (NH); 6,5 - 7,7 (m) (arom.H, NH2, OH); 5,4 (s) (-CO - CH - CO); 1 :) 10 :<1.Gel aluminum needles; Yield 30%, m.p. 136-37 (from isopropanol and ligroin) C15H12N202 (252.3) JR (KBr): 3475/3380 cm-1 # (NH), 3170 cm-1 (NH), 1650-1600cm-1 # (C = o & C = C); NMR (CDCl3): 9.4 ppm (s) (NH); 6.5 - 7.7 (m) (arom. H, NH2, OH); 5.4 (s) (-CO-CH-CO); 1 :) 10: <1.

UV (Dioxan): # max = 370 / 314 / 266 / 231 nm (log # = 3,89/3,88/ 4,10/4,37) Beispiel 2 1-Methyl-3-(2-amino-benzoyl)-oxindol Die Darstellung erfolgt analog 3-(2-Amino-benzovl)-oxindol, als Lösungsmittel wird abs. Xylol verwendet.UV (dioxane): # max = 370/314/266/231 nm (log # = 3.89 / 3.88 / 4.10 / 4.37) Example 2 1-Methyl-3- (2-aminobenzoyl) -oxindole The representation takes place analogous to 3- (2-amino-benzovl) oxindole, abs. Xylene used.

Eingesetzte Mengen: 7,35 g N-Methyloxindol (0,05 Mol) 7,55 g Anthranilsäuremethylester (0,05 Mol) 4,8 g NaH (0, 2 Mol) 70 ml abs Xylol Gelbe Nadeln; Ausbeute 40 %; Schmp. : 172-73° (aus Methanol und Ligroin) C16H14N2O2 (266,3) JR (KBr) : 3465/3345 cm-1 (NH), 1640-1610 (C=O), 1595 (C=C).Amounts used: 7.35 g of N-methyloxindole (0.05 mol), 7.55 g of methyl anthranilate (0.05 mol) 4.8 g NaH (0.2 mol) 70 ml abs xylene yellow needles; Yield 40%; M.p. : 172-73 ° (from methanol and ligroin) C16H14N2O2 (266.3) JR (KBr): 3465/3345 cm-1 (NH), 1640-1610 (C = O), 1595 (C = C).

NMR (CDCl3) : 6,7 - 7,6 (m) (arom.H, Nil2, OH) 5,4 (s) (-CO-CH-CO-) 3,38 und 3,26 (s/s) (NCH3) UV (Dioxan) : # max 363 / 313,314 / 267,268 / nm (log # = = 3,92 / 3,95 / 4,18).NMR (CDCl3): 6.7 - 7.6 (m) (arom. H, Nil2, OH) 5.4 (s) (-CO-CH-CO-) 3.38 and 3.26 (s / s) (NCH3) UV (dioxane): # max 363 / 313.314 / 267.268 / nm (log # = = 3.92 / 3.95 / 4.18).

Beispiel 3 3-(2-Methylamino-benzoyl)-oxindol Die Darstellung erfolgt analog (3-(2'-Amino-benzoyl)-oxindol. Example 3 3- (2-Methylamino-benzoyl) -oxindole The representation takes place analogous to (3- (2'-amino-benzoyl) -oxindole.

Eingesetzte Mengen: 6,65 g Oxindol (0,05 Mol) 8,25 g N-Methylanthranilsäuremethylester (0,05 Mol) 4,8 g NaH (0,2 Mol) 70 ml Tetrahydrofuran Gelbe Nadeln; Ausbeute 75 t Schmp. 160-61° (aus Methanol) C16H14N202 (266,3) JR (KBr) : 3425 cm-¹ (RN-CH3), 3195 (NH), 1650 - 1600 (C=O u. C-C), NMR (CDCl3) ; 9,13 ppm (s) (NH) ; 6,6 - 7,7 (m) (arom.H, H3C - NH-, OH) ; 5,45 (s) (-CO - CH - CO) ; 2,88 (s) (NCH3) 1 : > 9 : < 1 : 3 DV (Dioxan) : # max = 380 / 311 / 233 nm (log # = 3,88 / 3,89 / 4,39).Amounts used: 6.65 g of oxindole (0.05 mol), 8.25 g of N-methylanthranilic acid methyl ester (0.05 mol) 4.8 g NaH (0.2 mol) 70 ml tetrahydrofuran Yellow needles; Yield 75 t M.p. 160-61 ° (from methanol) C16H14N202 (266.3) JR (KBr): 3425 cm-1 (RN-CH3), 3195 (NH), 1650-1600 (C = O & C-C), NMR (CDCl3); 9.13 ppm (s) (NH); 6.6 - 7.7 (m) (arom.H, H3C - NH-, OH); 5.45 (s) (-CO-CH-CO); 2.88 (s) (NCH3) 1:> 9: <1: 3 DV (dioxane): # max = 380/311/233 nm (log # = 3.88 / 3.89 / 4.39).

Beispiel 4 l-Methyl-3- (2-methylamino-benzoyl) -oxindol Die Darstellung erfolgt analog 3-(2-Amino-benzoyl)-oxindol. Example 4 1-Methyl-3- (2-methylamino-benzoyl) -oxindole The illustration takes place analogously to 3- (2-amino-benzoyl) -oxindole.

Eingesetzte Mengen: 2,94 g N-Methyloxindol (0,02 Mol) 3,3 g N-Methylanthranilsäuremethylester (0,02 Mol) 1,44 g KH (0,06 Mol) 30 ml Dimethylformamid Gelbe Nadeln; Ausbeute 41 % Schmp. 157-58° (aus Methanol) C17H16N2O2 (280,3) IR (KBr): 3380 cm-1 (NH), 1630 - 1610 (C = O), 1590 (C = C) NMR (CDCl3) : 6,7 - 8,0 (m) (arom.H, -NH-, OH), 5,4 (s) (-CO-CH-CO-); 3,37 und 3,25 (s/s) (NCH3); 2,85 (s) (-HN-CH3) > 9 : <1 : 3 : 3 UV (Dioxan):# max = 380 / 312 / 269 / 232 nm (log # = 3,85 / 3,93 / 4,19 / 4,39) Beispiel 5 3-(2-Methylamino-benzoyl]-5-methoxy-oxindol Die Darstellung erfolgt analog den in 5-Stellung unsubstituierten Oxindolderivaten.Amounts used: 2.94 g of N-methyloxindole (0.02 mol), 3.3 g of N-methylanthranilic acid methyl ester (0.02 mol) 1.44 g KH (0.06 mol) 30 ml dimethylformamide yellow needles; Yield 41 % M.p. 157-58 ° (from methanol) C17H16N2O2 (280.3) IR (KBr): 3380 cm-1 (NH), 1630 - 1610 (C = O), 1590 (C = C) NMR (CDCl3): 6.7-8.0 (m) (arom.H, -NH-, OH), 5.4 (s) (-CO-CH-CO-); 3.37 and 3.25 (s / s) (NCH3); 2.85 (s) (-HN-CH3)> 9: <1 : 3: 3 UV (dioxane): # max = 380/312/269/232 nm (log # = 3.85 / 3.93 / 4.19 / 4.39) Example 5 3- (2-Methylamino-benzoyl) -5-methoxy-oxindole Die Representation is analogous to the oxindole derivatives unsubstituted in the 5-position.

Eingesetzte Mengen: 4,9 g 5-Methoxyindol (0,03 Mol) 4,95 g N-Methylanthranilsäuremethylester (0,03 Mol) 2,88 g NaH (0,12 Mol) 100 ml Diisoamyläther Gelbe Nadeln; Ausbeute: 62 % Schmp. 138-39° (aus Methanol) C17Hl6N203 (296,3) JR (KBr) : 3440 cm-¹ (-NH-CH3), 3170 - 3150 (NH), 1650 - 1610 (C = 0).Amounts used: 4.9 g of 5-methoxyindole (0.03 mol) 4.95 g of N-methylanthranilic acid methyl ester (0.03 mol) 2.88 g NaH (0.12 mol) 100 ml diisoamyl ether yellow needles; Yield: 62 % M.p. 138-39 ° (from methanol) C17Hl6N203 (296.3) JR (KBr): 3440 cm-1 (-NH-CH3), 3170-3150 (NH), 1650-1610 (C = 0).

NMR (CDCl3): 9,25 ppm (s) (NH) ; 7,6 - 6,5 ppm (m) (arom.H,-NH-OH) ; 5,4 (s) (-CO-CH-CO-) ; 3,69 u. 3,60 (s/s) $OCH3); 2,85 (s) (NCH3); 1 : 8 : < 1 : 3 : 3.NMR (CDCl3): 9.25 ppm (s) (NH); 7.6 - 6.5 ppm (m) (arom. H, -NH-OH) ; 5.4 (s) (-CO-CH-CO-); 3.69 & 3.60 (s / s) $ OCH3); 2.85 (s) (NCH3); 1: 8: < 1: 3: 3.

UV (Dioxan) : 2 max = 388 / 315 / 276 nm (log # = 3,95 / 3,94 / 4,27) Beispiel 6 Indolo [2,3 - b] chinolon Eine Lösung von 2,52 g 3-(2'-Amino-benzoyl)-oxindol (0,01) in 80 ml Chlorwasserstoff gesättigtem Methanol wird 15 Stdn. rückfliessend erhitzt. Die Lösung wird anschliessend auf ca. 50 ml eingeengt. Beim Erkalten fiel die gewünschte Verbindung auso Farblose Kristalle: Ausbeute 86 % Schmp. >360° (aus Isopropanol) C15H10N2O (234,3 Ber.: 76,91 % C 4,30 % H 11,96 % N Gef. : 76,90 % C 4,12 % H 11,87 % N JR (KBr) : 3200 cm-1 (NH), 1630 - 1600 (C = O), UV (Dioxan): max = 345 / 329 / 298 / 247 / 228 (log # = 4,43 / 4,31 / 4,09 / 4,74 / 4,70).UV (dioxane): 2 max = 388/315/276 nm (log # = 3.95 / 3.94 / 4.27) example 6 Indolo [2,3 - b] quinolone A solution of 2.52 g of 3- (2'-amino-benzoyl) -oxindole (0.01) in 80 ml of saturated hydrogen chloride is refluxed for 15 hours heated. The solution is then concentrated to approx. 50 ml. When it cooled down, it fell the desired compound from Colorless crystals: yield 86% mp> 360 ° (from isopropanol) C15H10N2O (234.3 calc .: 76.91% C 4.30% H 11.96% N found: 76.90 % C 4.12% H 11.87% N JR (KBr): 3200 cm-1 (NH), 1630 - 1600 (C = O), UV (dioxane): max = 345/329/298/247/228 (log # = 4.43 / 4.31 / 4.09 / 4.74 / 4.70).

Beispiel 7 6-Methyl-indolo [2,3 - b] chinolon Die Darstellung erfolgt analog Indolo C2,3 - b3 chinolon. Example 7 6-methyl-indolo [2,3 - b] quinolone The representation takes place analogous to indolo C2,3 - b3 quinolone.

Eingesetzte Mengen: 2,66 g 1-Methyl-3-(2-amino-benzoyl)-oxindol (0,01 Mol) 80 ml HCl-gesättigtes Methanol 15 Stdn. Erhitzen unter Rückfluss.Amounts used: 2.66 g of 1-methyl-3- (2-aminobenzoyl) oxindole (0.01 Mol) 80 ml of HCl-saturated methanol for 15 hours. Heating under reflux.

Farblose Nadeln; Ausbeute 53 % Schmp. 337-38° (aus Isopropanol C16H12N20 (248,3 Ber.: 77,40 % C 4,87 % H 11,28 % N Gef.: 76,94 % C 5,00 % H 11,32 % N JR (KBr): 3000 - 2810 cm 1 (NH), 1650-1630 (C=O), 1605 (C=C).Colorless needles; Yield 53%, melting point 337-38 ° (from isopropanol C16H12N20 (248.3 calc .: 77.40% C 4.87% H 11.28% N found: 76.94% C 5.00% H 11.32% N JR (KBr): 3000-2810 cm -1 (NH), 1650-1630 (C = O), 1605 (C = C).

NMR (CF3COOH): 8,56 - 8,23 / 8,06 - 7,12 ppm (m/m) (arom.H); 4,1 (s) (NCH3).NMR (CF3COOH): 8.56-8.23 / 8.06-7.12 ppm (m / m) (arom.H); 4.1 (s) (NCH3).

UV (Dioxan) : max = 347 / 331 / 298 / 251 / 231 nm (log # = 4,41 / 4,32 / 4,07 / 4,75 / 4,62 Beispiel 8 5-Methyl-indolo [2,3 - b] chinolon Die Darstellung erfolgt analog Indolo [2,3 - b] chinolon.UV (dioxane): max = 347/331/298/251/231 nm (log # = 4.41 / 4.32 / 4.07 / 4.75 / 4.62 Example 8 5-methyl-indolo [2,3 - b] quinolone The representation is analogous to indolo [2,3 - b] quinolone.

Eingesetzte Mengen: 2,66 g 3-(2-Methylamino-benzoyl)-oxindol (0,01 Mol) 80 ml Tripolyphosphorsäure 15 Stdn. Erhitzen unter Rückfluss, Umkristallisation aus Isopropanol.Amounts used: 2.66 g of 3- (2-methylaminobenzoyl) oxindole (0.01 Mol) 80 ml of tripolyphosphoric acid for 15 hours. Heating under reflux, recrystallization from isopropanol.

Farblose Kristalle; Ausbeute: 79 % ab 320° Zersetzung C16H12N2O (248,3) Ber.: 77, 40 % C 4,87 % H 11,28 % N Gef.: 77,36 % C 4,87 % H 11,46 % N JR (KBr): 3230 - 3180 (NH), 1625 - 1595 (C = 0), NMR (CF3COOH): : 8,23 - 7,16 ppm (m) (arom.H); 4,08 (s) (NCH3).Colorless crystals; Yield: 79% from 320 ° decomposition C16H12N2O (248.3) Calc .: 77, 40% C 4.87% H 11.28% N Found: 77.36% C 4.87% H 11.46% N JR (KBr): 3230-3 180 (NH), 1625-1595 (C = 0), NMR (CF3COOH):: 8.23-7.16 ppm (m) (arom.H); 4.08 (s) (NCH3).

UV (Dioxan):#max = 348 / 331 / 299 / 251 / 228 nm (log # = 4,37 / 4,26 / 4,05 / 4,73 / 4,65).UV (dioxane): # max = 348/331/299/251/228 nm (log # = 4.37 / 4.26 / 4.05 / 4.73 / 4.65).

Beispiel 9 5,6-Dimethyl-indolo g2,3 - b] chinolon 2,8 g 1-Methyl-3-(2-methylamino-benzoyl)-oxindol (0,01 Mol) werden 15 Stdn. in 80 ml chlorwasserstoffgesättigtem Methanol rtckfliessend erhitzt. Die Lösung wurde nach Erkalten in Eiswasser gegossen, der Niederschlag abgesaugt, getrocknet und aus Tetrachlorkohlenstoff und anschliessend aus Äthanol umkristallisiert. Example 9 5,6-Dimethyl-indolo g2,3 - b] quinolone 2.8 g of 1-methyl-3- (2-methylamino-benzoyl) -oxindole (0.01 mol) are refluxed for 15 hours in 80 ml of methanol saturated with hydrogen chloride heated. After cooling, the solution was poured into ice water, the precipitate sucked off, dried and made from carbon tetrachloride and then from ethanol recrystallized.

Farblose Blättchen; Ausbeute 83,5 % Schmp. 2350 (aus Tetrachlorkohlenstoff und Äthanol C17H14N2O (262,3) Ber.: 77,84 % C 5,38 % H 10,68 % N Gef.: 78,20 % C 5,64 % H 11,09 % N JR (KBr): 1635 cm %lt;- (C = 0). Colorless leaflets; Yield 83.5% m.p. 2350 (from carbon tetrachloride and ethanol C17H14N2O (262.3) calc .: 77.84% C 5.38% H 10.68% N found: 78.20% C 5.64% H 11.09% N JR (KBr): 1635 cm% lt; - (C = 0).

NMR (CF3COOD): 8,57 - 8,3 / 8,11 - 7,1 ppm (m/m) (arom.H), 4,0 / 3,93 (s/s) (NCH3 / NCH3).NMR (CF3COOD): 8.57-8.3 / 8.11-7.1 ppm (m / m) (arom.H), 4.0 / 3.93 (s / s) (NCH3 / NCH3).

UV (Dioxan): #max = 349 / 333 / 300 / 253 / 232 nm (log # = 4,38 / 4,29 / 4,04 / 4,76 / 4,61) Beispiel 10 5-Methyl-9-methoxy-indolo [2,3 -b] chinolon Die Darstellung erfolgt analog Indolo 52,3 - b3 chinolon.UV (dioxane): #max = 349/333/300/253/232 nm (log # = 4.38 / 4.29 / 4.04 / 4.76 / 4.61) Example 10 5-methyl-9-methoxy-indolo [2,3 -b] quinolone The representation is analogous to indolo 52,3 - b3 quinolone.

Eingesetzte Mengen: 2,96 g 3-(2-Methylamino-benzoyl)-5-methoxy-oxindol (0,01 Mol) 80 ml HCl-gesätigtes Äethanol Schwach gelbe Nadeln; Ausbeute: 75% Schmp. 274° C17H14N2O2 (278,3) Ber.: 73,37 % C 5,07 % H 10,06 % N Gef.: 72,46 % C .5,13 % H 9,36 % N JR(KBr): 3225 - 3180 cm 1 (NH), 1620 - 1600 (C = O).Amounts used: 2.96 g of 3- (2-methylamino-benzoyl) -5-methoxy-oxindole (0.01 mol) 80 ml of HCl-saturated ethanol. Pale yellow needles; Yield: 75% m.p. 274 ° C17H14N2O2 (278.3) calc .: 73.37% C 5.07% H 10.06% N found: 72.46% C. 5.13 % H 9.36% N JR (KBr): 3225-3 180 cm -1 (NH), 1620-1600 (C = O).

NMR (CF3COOH): 8,33 - 7,03 ppm (m) (arom.H); 4,2 (s) (OCH3); 4,06 (s) (NCH3).NMR (CF3COOH): 8.33-7.03 ppm (m) (arom.H); 4.2 (s) (OCH3); 4.06 (s) (NCH3).

UV (Dioxan):# = 355 / 339 / 308 / 254 / 230 nm (log # = 4,42 / 4,32 / 4,08 / 4,61 / 4,67).UV (dioxane): # = 355/339/308/254/230 nm (log # = 4.42 / 4.32 / 4.08 / 4.61 / 4.67).

Beispiel 11 5,6-Dimethyl-9-methoxy-indolo [2,3 - b] chinolon 5-Methyl-9-methoxy-indolo C2,3 - b] chinolon (0,01 Mol) wird mit Methyljodid (0,03 Mol) und Natriumäthanolat (0,01 Mol) 4 Stdn. rückfliessend erhitzt. Das beim Erkalten ausfallende Produkt wird abgesaugt und aus Äthanol umkristallisiert: Schwach gelbe Nadeln; Ausbeute: 81 % Schmp. 225 - 260 C18H16N2O2 (292,3) Bex.: 73,95 % C 5,52 % H 9,58 % N Gef.: 74,09 % C 5-,78 % H 9,38 % N JR(KBr): 1625 cm (C = 0) NMR (CCDC13): 8,17 - 7,84 / 7,5 - 6,92 (m/m) (arom.H); 3,92 (s) (NCH3 u. OCH3); 3,65 (s) (NCH3). Example 11 5,6-Dimethyl-9-methoxy-indolo [2,3-b] quinolone 5-methyl-9-methoxy-indolo C2,3-b] quinolone (0.01 mol) is treated with methyl iodide (0.03 mol) and sodium ethanolate (0.01 mol) heated to reflux for 4 hours. The product that precipitates when it cools is suctioned off and recrystallized from ethanol: pale yellow needles; Yield: 81% m.p. 225 - 260 C18H16N2O2 (292.3) Ex .: 73.95% C 5.52% H 9.58% N Gef .: 74.09% C 5, 78% H 9.38% N JR (KBr): 1625 cm (C = 0) NMR (CCDC13): 8.17-7.84 / 7.5 - 6.92 (m / m) (arom.H); 3.92 (s) (NCH3 &OCH3); 3.65 (s) (NCH3).

UV (Dioxan): #max = 358 / 341 / 309 / 257 / 232 nm (log # = 4,38 / 4,31 / 4,06 / 4,62 / 4,61).UV (dioxane): #max = 358/341/309/257/232 nm (log # = 4.38 / 4.31 / 4.06 / 4.62 / 4.61).

Beispiel 12 5-Methyl-6-(p-Chlorbenzoyl)-9-methoxy-indolo [2,3 - b] chinolon 1,39 g 5-Methyl-9-methoxnr-indolo [2,3 - b] chinolon (0,005 Mol) werden zu einer Suspension von 120 mg NaH (0,005 Mol) in 50 ml abs. Dioxan gegeben. Es wird einige Zeit bei Zimmertemperatur gerührt, dann zum Sieden erhitzt. Die Suspension wird 30 Min. Example 12 5-Methyl-6- (p-Chlorobenzoyl) -9-methoxy-indolo [2,3 - b] quinolone 1.39 g of 5-methyl-9-methoxnr-indolo [2,3 - b] quinolone (0.005 moles) to a suspension of 120 mg of NaH (0.005 mol) in 50 ml of abs. Given dioxane. It is stirred for some time at room temperature, then heated to the boil. The suspension will be 30 min.

im Sieden gehalten. Nach Erkalten werden 0,88 g p-Chlorbenzoylchlorid (0,005 Mol) in 3 ml Dioxan zugetropft und das Gemisch 2 Stdn. rückfliessend erhitzt. Es wird heiss filtriert, das Filtrat zur Trockene eingeengt und aus Isopropanol umkristallisiert: Gelbe Blättchen; Ausbeute 60 z Schmp. 236 - 370 C24H17CIN2O3 (416,9 Ber.: 69,15 % C 4,11 % H 8,50 % Cl 6,72 % N Gef.: 69,31 % C 4,25 z H 8,19 % Cl 6,67 % N JR(KBr) : 1690 und 1635 cm-¹ (C = O).kept simmering. After cooling, 0.88 g of p-chlorobenzoyl chloride are obtained (0.005 mol) in 3 ml of dioxane are added dropwise and the mixture is heated under reflux for 2 hours. It is filtered hot, the filtrate is concentrated to dryness and extracted from isopropanol recrystallized: yellow leaflets; Yield 60 z m.p. 236-370 C24H17CIN2O3 (416.9 Calc .: 69.15% C 4.11% H 8.50% Cl 6.72% N Found: 69.31% C 4.25 z H 8.19% Cl 6.67 % N JR (KBr): 1690 and 1635 cm -1 (C = O).

NMR (CDCl3) : 8,14 - 6-,84 (m) (arom.H) 3,93 (s) (OCH3) ; 3,88 (s) (NCH3).NMR (CDCl3): 8.14-6.84 (m) (arom.H) 3.93 (s) (OCH3); 3.88 (s) (NCH3).

UV (Dioxan) : # max = 340 / 309 / 249 / 223 nm (log # = 4,18 / 4,14 / 4,73 / 4,67).UV (dioxane): # max = 340/309/249/223 nm (log # = 4.18 / 4.14 / 4.73 / 4.67).

Claims (4)

P a t e n t a n s p r ü c h eP a t e n t a n s p r ü c h e 1. Indolo [2.3 - b chinolone der allgemeinen Formel worin R1 ein H-Atom oder ein O-Alkyl-Rest, R2 ein H-Atom, ein Alkyl- oder Acyl-Rest und R3 ein H-Atom oder ein Alkyl-Rest hedeuten.1. Indolo [2.3 - b quinolones of the general formula where R1 is an H atom or an O-alkyl radical, R2 is an H atom, an alkyl or acyl radical and R3 is an H atom or an alkyl radical. 2. Verfahren zur Herstellung der Verbindung gemäss Anspruch 1, dadurch gekennzeichnet, dass gemäss der nachfolgenden Formeln Oxindole I, worin .R1 und R2 die in Anspruch 1 angegebene Bedeutung haben, mit einem Anthranilsäureester II, worin R3 die in Anspruch 1 angegebene Bedeutung hat, und R einen beliebigen Alkyl-Rest darstellt, in Gegenwart eines Alkalihydrids in einem Lösungsmittel zu 3-(2'-Amino-benzoyl)-oxindolen III umgesetzt und diese mit wasserabspaltenden Mitteln behandelt werden.2. Process for the preparation of the compound according to claim 1, characterized in that according to the following formulas Oxindoles I, in which .R1 and R2 have the meaning given in claim 1, with an anthranilic acid ester II, in which R3 has the meaning given in claim 1 and R is any alkyl radical, in the presence of an alkali hydride in a solvent to 3- (2'-Amino-benzoyl) oxindoles III implemented and these treated with dehydrating agents. 3. Abänderung des Verfahrens nach Anspruch 2, dadurch gekennzeichnet, dass Indolo E2.3 - b3 chinolone gemäss Anspruch 1, in denen R2 = H oder Alkyl bedeutet, in Gegenwart eines Lösungsmittels mit Säurehalogeniden und Alkalihydrid umgesetzt werden 3. Modification of the method according to claim 2, characterized in that that indolo E2.3 - b3 quinolones according to claim 1, in which R2 = H or alkyl, reacted in the presence of a solvent with acid halides and alkali hydride will 4. Weitere Abänderung des Verfahrens gemäss Anspruch 2, dadurch gekennzeichnet, dass Indolo [2.3 - b3 chinolone gemäss Anspruch 1, worin R = H bedeutet, in an sich bekannter Weise alkyliert werden.4. Further modification of the method according to claim 2, characterized in that that indolo [2.3 - b3 quinolones according to claim 1, wherein R = H, in per se be alkylated in a known manner.
DE19712113343 1971-03-19 1971-03-19 Indolo- (2,3) - quinolones - prepd by reaction of keto-indoles and anthranilates, followed by dehydration Pending DE2113343A1 (en)

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