R. Ott

Untersuchungen über Chinone. 2. Mitt.: Azinbildung durch Umsetzung von p-Chinonen mit o-Diaminen

Die in der 1. Mitteilung1 beim Dibenzpyrenchinon beobachtete Phenazinbildung tritt allgemein bei der Reaktion von p-chinoiden Verbindungen mit o-Diaminen ein, wie die Umsetzungen von 2,8-Chrysenchinon, 1,4-Naphthochinon und seiner Sulfonsaure sowie p-Benzochinon mit o-Phenylendiamin und 1,2-Naphthylendiamin zeigen. Zum Unterschied von der bekannten Reaktion der o-Chinone entstehen jedoch stets Hydroxy-derivate. Als Nebenreaktion tritt die Oxydation der o-Diamine zu o-Diaminophenazinen mehr oder weniger in Erscheinung, je nach Redoxpotential des Chinons, pH-Wert der Reaktionslosung und Oxydierbarkeit des Amins. Der Reaktionsmechanismus wird erortert.

Zur Kenntnis des Coronens

o-Coronenchinon wird durch Kalilauge und Luft (oder H2O2 oder Na2O2) zur 1,12-Benzperylen-6,7-dikarbonsaure aufgespalten, von der auch Derivate dargestellt wurden. Neben der Saure entstehen noch Coronen und eine sauerstoffhaltige Verbindung, uber deren Struktur noch keine endgultige Aussage gemacht werden kann. Sie bildet sich auch bei der Destillation des Chinons mit Bleioxyd neben Coronen und aus der Saure und ihren Derivaten. Diese eigenartigen Reaktionen werden auf den raumlichen Bau dieser Verbindungen zuruckgefuhrt und im Zusammenhang damit stereochemische Betrachtungen uber peri-kondensierte Ringsysteme, wie Furoperylen und 1,12-Perylencycloperoxyd, angestellt.

Untersuchungen über Chinone, 10. Mitt. Zur Reaktion vonp-Benzochinon mit sekundären aliphatischen Aminen

Summaryp-Benzoquinone (1) reacts with dialkylamines2a-d to 2-dialkylamino-p-benzoquinones3, 2,5-bis-dialkylamino-p-benzoquinones4, 2-dialkylamino-8-hydroxydibenzofuran-1,4-quinones5, and in pyridine also to 2-dialkylamino-5-p-hydroxy-phenoxy-p-benzoquinones6. A method affording almost exclusively3 has been developed which is also applicable to compounds2e-h.

Zur Synthese und Struktur derp-Indazolchinone und ihrer Methylierungsprodukte Untersuchungen über Chinone, 8. Mitt.

SummaryThep-benzoquinones5e-j react with diazomethane (after dehydrogenation) to 6-anilino-2e, dimethylamino-2h, phenylthio-2i, and methylthioindazolquinone2j. Methylation with dimethylsulfate of these as well as of the already known indazolquinones 6-toluidino-2f, 6-methylanilino-2g, 5-tert.butyl-2m, 5,6-methyl- (isomer mixture)2l,n, and benz-indazolquinone2o yield the 1-and 2-N-methyl derivatives3 and4. The structure of the 2-methyl derivatives is established by reaction of the corresponding benzoquinones with 3-methylsydnon in the case of4e,4g. UV/VIS-, IR- and1H-NMR-spectroscopy (in CDCl3 andDMSO) were used for structure determination. Comparison of the UV/VIS-spectra of2–4 shows that the indazolquinones are existing as 2 H-4,7-diones. For the structure elucidation of the 1- rs. 2-methylderivatives (whichh can be attributed to the methylation products) NMR-spectroscopy is well suited even without knowing the second isomer (solvent-effect). The course of the reaction of quinones with diazomethane and of the methylation reactions of the indazolquinones is discussed.

Reaktion von 2-(N-Alkyl-p-hydroxyanilino)-1,4-benzochinonen Diazomethan. N-(Alkyl-p-hydroxyanilino)-4,7-indazolchinone und ihre isomeren N-Methylderivate

The reaction of N-alkyl-p-hydroxyanilinobenzoquinones1 a–d, its acetylderivatives11–c1 and the methoxyderivative1 a2 with diazomethan yields in dependence on the reaction-conditions the indazolquinones2 a–d, 2 a1–c1 or2a2, the1-methylindazolquinones3 a–d and31–c1, and finally the methoxy-1-methylindazolquinones5 a–d. The 2-methyl-isomeres6 a–d are formed only in small amounts. Methylation of2 a with dimethylsulfate gives5 a and6 a in the ratio of appr 2 to 1. Acetylation of2 a–d with acetanhydride leads to the N−O-acetylderivatives, which are easily hydrolyzed to2 a1–d1 during work up;3 a d yields3 a1–d1. The structures are established by the described crossexperiments and by spectroscopy (UV/VIS, IR, NMR).

1,4-Carbazolchinone ausp-Benzochinon und primären aliphatischen Aminen. Das vermeintliche und das wahre 2-Methylamino-benzochinon

The compound which is obtained in the reaction of 1,4-benzoquinone with methylamine in chloroform was supposed to be 2-methylaminobenzoquinone; actually it is 6-hydroxy-9-methyl-3-methylamino-1,4-carbazolquinone. The structure is proved by spectroscopic methods, through derivates, zinc dust distillation and via synthesis from 2,5,2′,5′-biphenyl-diquinone. A second main product, 2,5-bis(methylamino)quinone, is obtained; varying the reaction conditions shows especially the influence of the solvent. One of the intermediate products is the true 2-methylamino-1,4-quinone. Other substituted 9-alkyl-3-alkylamino-6-hydroxy-1,4-carbazolquinones can be prepared by reaction with the corresponding primary amines.

2-(N-Alkyl-p-hydroxyanilino)-1,4-benzochinone ausp-Benzochinonen und primären aliphatischen Aminen

In acetic (aqueous or chloroform) solutionp-benzoquinones yield with primary aliphatic amines mainly 2-(N-alkyl-p-hydroxy-anilino)-1,4-benzoquinones besides the 2-alkylamino- and 2,5-bis(alkylamino)-quinones. The methyl-, ethyl-,n-propyl-,n-butylhomologues ofp-benzoquinone and the isomer methylderivatives of toluquinone are described. Their structure were established by spectroscopic (UV/VIS, IR, NMR) methods and by synthesis of the methylderivative3 a fromp-benzoquinone andp-hydroxy-N-methylaniline. The influence of other acids on the reaction was studied.

Phenazine, 3. Mitt.: N-(o-Aminophenyl)-benzo[a]phenazin-5-amin, das vermeintliche “Dihydronaphthodiphenazin”Kehrmanns, und seine Derivate

The “dihydronaphthodiphenazine” ofKehrmann, which is according toBadger andPettit reported to be “14-o-aminophenyl-13,14-dihydro-5,8,13,14-tetraaza-6,7-benzopentaphene”, is N-(o-aminophenyl)-benzo[a]phenazin-5-amine. This was proved by chemical and spectroscopic investigations. The structures of the derivatives prepared byBadger andPettit are also corrected and the acetylation processes are cleared up.

Zur Umsetzung von 8a-Methoxy-3,4-dihydro-2H-1,4-benzoxazin-6(8aH)-onen mit Diazoalkanen, 2. Mitt.

Summary8a-Methoxy-3,4-dihydro-2H-1,4-benzoxazin-6(8aH)-ones2 undergo regio- and stereospecific 1,3-dipolar cycloaddition reactions with diazomethane or diazoethane to yield 3,4,6a,9,9a,9b-hexahydro-pyrazolo[3,4-h][1,4]benzoxazin-6(2H)-ones3, which slowly isomerize in solution to give the 3,4,8,9,9a,9b-hexahydro-pyrazolo[3,4-h][1,4]benzoxazin-6(2H)-ones5. The carbon of the diazoalkane dipole is attached to carbon C-8 of the benzoxazinone. The structures of the obtained products were determined by1H- and13C-NMR spectroscopy. An X-ray crystal structure analysis of3 a was carried out at room temperature:C11H15N3O3,Mr=237.26, orthorhombic, Pc21n,a=9.173 (5),b=9.133 (4),c=13.281 (6),V=1112.6 (9) Å3,Z=4,dx=1.416 g/cm−3, μ=0.93 cm−1,R=4.33%,Rw=3.95% (919 observations, 168 parameters).

Umsetzung von 2-substituierten p-Naphthochinonen mit 0-Phenylendiamin: Phenazine II

The reaction of 2-substituted p-naphthoquinones with o-phenylenediamine proceeds either with elimination of the substituent and formation of benzo[a]phenazin-5-ol (path A) or by addition and oxidation to 6-substituted benzo[a]phenazin-5-ols (pathB). The relationship between reaction path and electronic effect of the substituent, expressed by the redox potential of the quinones, and other factors which influence the reaction are indicated, and reaction mechanisms are discussed.Zusammenfassung2-substituiertep-Naphthochinonesetzen sich mito-Phenylendiamin entweder unter Eliminierung des Substituenten zu Benzo[a]phenazin-5-ol (WegA) oder unter Addition und Oxydation zu 6-substituierten Benzo[a]phenazin-5-olen (WegB) um. Ein Zusammenhang zwischen Reaktionsweg und elektronischer Wirkung der Substituenten (ausgedrückt durch das Redoxpotential der Chinone) sowie weitere die Reaktion beeinflussende Faktoren werden aufgezeigt, Mechanismen für den Ablauf der Reaktion diskutiert.