Neue Derivate des 2‐Aminomethyl‐tetrahydro‐chinolins und ‐tetrahydro‐isochinolins

Abstract

Helv. 10, 167 (1927) Sur quelques acides polym6thyhe-dicarboniques mono-methylis Chuit, Bolsing, et quelques-uns de leurs derives. Hausser, Xalet Helv. 12, 463 (1929) Sur les acides-alcools polyrn6thylhe-carboniques de 8 L 21 atomes Chuid et Hausser de carbone. Helv. 12, 850 (1929) Reduction des ethcrs dimkthyliques des acides polymkthylbne-Chuit e t Hausser dicarboniques de 15 L 21 atomes de carbone, par le sodium e t l'alcool. Helv. 12, 1906 (1929) Preparation de quelques acides polymethylknc-dicarboniques di-Chuit, Bolsing, methyles et de quelques-uns de leurs d6rives. Malet Recherches dans la serie undecylkuique e t de ses homologues. 152. Neue Derivate des 2-Aminomethyl-tetrahydro-ehinolins und -tetrahydro-isoehinolins von Alois Gassmann und H. Rupe.(28. VIII. 39.) Zur weiteren Charakterisierung der von uns beschriebenen A m i nb a s e n des T e t r a h y d r o -c h i n olins und T e t r a h y d r o -i s o c h i n ol i n s wurde eine Reihe von Verbindungen dargestellt, welche zum Teil wegen ihrer pharmakologischen Eigenschaften von Interesse waren.Wir sind der Gesdlsehnft fur ehemische Induslrae in Basel, Pharmazeutische Abteilung, zu grosstem Dank verpflichtet dafiir, dass sie fur uns diese pharmakologischen Untersuchungen in ausgezeichneter Weise durchgefuhrt hat.Es zeigte sich, dass lange nicht alle Chinolinderivate sich bei der Behandlung mit Kaliumcyanid und Benzoylchlorid in eine dem ,,Reissert'schen KorpeF analoge Verbindung uberfuhren liessen. Nicht reagieren z. B., wie wir gefunden haben, Chinaldin, $Nitrochinolin, 5-Amino-chinolinl), 5-Acetamino-chinolin, 6-Dimethylamino-chinolin, 7-Nitro-chinolin7 8-Oxy-chinolin, 8-Methoxy-chinolin, 8-Benzoyloxy-chinolin und 8-Acetoxy-chinolin2).Dagegen wurde bei diesen Versuchen haufig das B i s -b e n z o y l c y a n i d von Wache3) und von Dzels und P d l o~~) in mehr oder weniger grosser Menge erhalten (Formel I).Nur mit 6-Methoxy-chinolin gelang es, eine d t m ,,Keissert'schen Korper" konforme Verbindung darzustellen. I) Dargestellt durch Reduktion von 5-Nitro-chinolin mit Kickel als Katalysator. z, Wurde erstmals krystallin erhalten. Nadeln vom Smp. 74-75O. 3, J. pr. [2] 39, 260 (1889). 4, B. 41, 1894 (1908). 4,163 mg Subst. gaben 10,130 mg CO, und 1,865 mg H,O 3,063 mg Subst. gaben 0,341 cm3 N, (20°, 745 m m ) ClsH,,O,Pi, Ber. C 66,84 H 5,30 K 13,0O% Gef. ,, 66,36 ,, 5,Ol ,, 12,83y0 N e b e n p r o d u k t : 2-Cyan-6-Methoxy-chinolin ( ? ) (IV). Bei der Aufarbeitung der Mutterlaugen des Reissert'schen Korpers aus 6-Methoxy-chinolin fie1 beim Einengen und Erkalten 3,212 mg Subst. gaben 0,395 cn13 S, (17,5O, 742 mm) Cl,H,oN,Q, Ber. N 13,8fi Gcf. N 14,11% Natriumcarbonatlosung; in konz. Sodalosung tritt voriibergehend Losung ein, dann fallt das Natriumsalz als dicker, fast farbloser Niederschlag aus. 4,467; 5,409 mg Subst. gaben 0,275; 0,336 em3 N, (24,5O, 739 mm; 20°, 739 mm) C,,H,O,N Ber. N 6,90 Gef. N 6,94; 7,04% H y d r i e r u n g z u m B e n z o y l -6 -m e t h o x y -t e t r a h y d r o -c h i n o l i n -2 -a m i n o -m e t h y l a m i n (VII). 150 g de...

The Chemistry of N-Acyldihydroquinaldonitriles and N-Acyldihydroisoquinaldonitriles (Reissert Compounds)

“…It has been emphasized (51) that an optimum yield of 1-benzoyl-l ,2-dihydroquinaldonitrile (I: R = C6H6) may be obtained only with pure quinoline. The yield of the product does not seem to be decreased significantly, however, if technical benzoyl chloride is employed (37). Also, for a reason which is not clear, the use of potassium cyanide appears to give better results than the use of sodium cyanide; in some instances use of the latter salt gives a product that is difficult to purify.…”

“…5,6-Benzoquinoline has been reported to give IX in good yield, whereas 7 , 8-benzoquinoline failed to undergo reaction, but inasmuch as this information mas contained only in a footnote of reference 22, reaction conditions were not specified. In those cases where substituted quinolines failed to give derivatives of I , considerable amounts of phenylglyoxylonitrile dimer (X) (59,93) were frequently formed (37). Clearly, the ease of formation of Reissert compounds is dependent upon steric as well as electronic factors, since the presence of substituents in the 2-and 8-positions of quinoline inhibits the formation of compounds of the general structure I.…”

“…The ability of quinoline to react with an acid chloride and a source of cyanide ion to form I is greatly affected by substituents present on the ring. 6-Methoxyquinoline (37), 6-chloroquinoline (35), 6-methylquinoline (35), and 7-methoxyquinoline (86) readily undergo reaction with benzoyl chloride and aqueous potassium cyanide to give the respective substituted derivatives of 1-benzoyl-l, 2-dihydroquinaldonitrile (I: R = C6H5), but when the substituent is the 5-nitro, 5-amino, 5-acetamido, 6-dimethylamino, 7-nitro, 8-hydroxy, 8-methoxy, 8benzoyloxy, 8-acetoxy, or 2-methyl group, the reaction fails (37). Reaction of benzoyl chloride and aqueous potassium cyanide with 2, 3'-biquinoline gives l-benzoyl-3-(2-quinolyl)-1,2-dihydroquinaldonitrile (VII) (48), while reaction with 6,6'-biquinoline gives 1,1'-dibenzoyl-1,1',2,2'-tetrahydro-6,6'-biquinaldonitrile (VIII) (91).…”

“…An unusual side reaction has been observed on treatment of 6-methoxyquinoline with benzoyl chloride and aqueous potassium cyanide solution. A significant amount of 6-methoxyquinaldonitrile was obtained in addition to 1benzoyl-6-methoxy-l, 2-dihydroquinaldonitrile (37).…”

“…Another reaction usually undergone by nitriles is their conversion to amidoximes by reaction with hydroxylamine. In the case of the only Reissert compound investigated, l-benzoyl-6-methoxy-l, 2-dihydroquinaldonitrile (LXXXV) gave the a midoxime XCV in a facile reaction (37). As part of an investigation of the effect of various amines on the preparation of N-phenylbenzimidyl cyanide, it was found that a reaction of V-phenylbenzimidyl chloride with anhydrous hydrogen cyanide in the presence of quinoline led to formation of an addition compound.…”