Synthese von Indolderivaten

Fischer, Emil; Hess, Otto

doi:10.1002/cber.188401701155

Cited by 243 publications

(83 citation statements)

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“…Gramine C H~ 6 methiodide 5 was also investigated in conjunction with the study of its N-methyl derivative 2 and proved to have quite different properties with DNA. Compounds 2 and 3 were prepared by known procedures involving the Fischer indole synthesis, followed by a Mannich reaction and quaternization (9)(10)(11)(12)(13). The literature preparation of gramine methiodide 5 was found to give substantial amounts of 7 as evidenced by the nmr spectrum (singlets at 2.85 and 7.30 6 in CDCI,) (14).…”

Section: Syt~thesis Of 2-and 3-itzclolylcarbitzyl Compoundsmentioning

confidence: 99%

Studies related to antitumor antibiotics. Part XIII. Reactivity of 2- and 3-indolylcarbinyl compounds as models for mitosane action

Lown¹,

Weir²

1978

Can. J. Chem.

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J. WILLIAM LOWN and GORDON L. WEIR. Can. J. Chern. 56, 249 (1978). The base-catalyzed methanolyses of 1-methylgramine methiodide 2, I-niethylisogramine lnethiodide 3, and 1-methylindol-2-ylmethyl N-fert-butylcarbamate 4 were studied in the temperature range 50-90°C in order to gain information about the relative reactivity of 2-and 3-indolylcarbinyl systems, analogous to the proposed reactive sites of the mitosane antitumor antibiotics when enzymatically reduced. The leaving groups were also analogous to those found in the mitosanes. The methanolysis of 2 proceeds with strict first-order kinetics in accord with indole nitrogen lone pair assistance of the displacement. The comparable reactions of 3 and 4 proceed with second-order kinetics in accord with a direct Ss2 process and the carbamate moiety is the better leaving group by a factor of 10. Gramine methiodide 5 undergoes a very + rapid elimination of the elements of (CH3),NH I-followed by addition of a nucleophile such as methanol at a rate which is too rapid to follow kinetically even at -78'C. In accord with the model for the mode of action of the mitosanes, 2.2 m M 5 alkylates and cross-links DNA to the extent of 71% at p H 7 and 37°C. The extent of cross-linking is proportional to the (G + C) content of DNA's as was found for the niitosanes and occurs at a position other than N-7 on guanine. The results suggest that in the reaction of the mitosane antibiotics with DNA the inherent greater reactivity of the 10-carbamate moiety towards nucleophilic displacement is more than offset by the rate enhancement of the 1 position due to relief of aziridine ring strain. Chem. 56, 249 (1978). On a ttudie la mCthanolyse, catalyske par les bases, de I'iodomethylate de nitithyl-1 grarnine (2), de I'iodomethylate de methyl-1 isogramine (3) et du N-trrf-butylcarbamate de methyl-l indolylmethyle-2 (4) a des temperatures allant de 50-90°C; on a realis6 ces etudes afin d'obtenir des inforniations concernant les rCactivitCs relatives des systenies indolylcarbinyles-2 et -3 qui, lorsqu'ils sont reduits d'une f a~o n enzymatique, sont des sites riactifs proposes pour les antibiotiques antitumoraux mitosanes. Les nucleofi~ges sont aussi analogues a ceux trouves dans les mitosanes. La rnethanolyse de 2 se produit d'apres line cinetique de preniier ordre strict tel que prevu si I'on fait I'hypothese que la paire d'ilectrons libres de I'azote de I'indole fournit ulie aide lors du deplacement. Les reactions cornparables de 3 et 4 se prod~lisent suivant des cinetiques du deuxieme ordre tel que I'on peut le supposer pour une reaction SN2; par opposition au groupe iodomethylate le groupe carbamate est un meilleur ~iuclCofiige par un + facteur de 10. L'iodomCthylate de gramine 5 subit une elirninatio~i tres rapide de (CH3),NH 1-qui est suivie par une addition de nuclCophiles, comlne le methanol, a une vitesse qui est trop rapide pour &tre mesurke mCme a -78°C. Tel qu'on peut le supposer en se basant sur le niodele pour le mode d'action des mitosanes, le compose 5, a des concentrations d...

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Section: Syt~thesis Of 2-and 3-itzclolylcarbitzyl Compoundsmentioning

confidence: 99%

Studies related to antitumor antibiotics. Part XIII. Reactivity of 2- and 3-indolylcarbinyl compounds as models for mitosane action

Lown¹,

Weir²

1978

Can. J. Chem.

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“…11 4-Hydrazinobenzoic acid 4 was reacted with 2-methyl-2-butanone (Fischer indole reaction) 22,23 to give indoline 5, which was alkylated with iodomethane to give the methylindole 6.…”

Section: Resultsmentioning

confidence: 99%

Crowned spiropyran fluoroionophores with a carboxyl moiety for the selective detection of lithium ions

2016

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“…Multivariate optimization achieved not only regiospecific synthesis of single indole regioisomers, 8 but almost quantitative yields in a single step (one-pot) reaction. 9 It is striking that the above result was achieved for a reaction, such as the Fischer indole synthesis 10 known for more than a century, and to which an entire book has been devoted. 11 In addition to statistical orthogonality, PPs derived from PCA multivariate characterizations have the advantage of being less influenced by measurement errors and system-specific variations than are single descriptors.…”

Section: Introductionmentioning

confidence: 91%

Principal properties (PPs) as solvent descriptors for multivariate optimisation in organic synthesis: specific PPs for ethers

Ballistreri¹,

Fortuna²,

Musumarra³

et al. 2002

Arkivoc

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Synthese von Indolderivaten

Cited by 243 publications

References 0 publications

Studies related to antitumor antibiotics. Part XIII. Reactivity of 2- and 3-indolylcarbinyl compounds as models for mitosane action

Studies related to antitumor antibiotics. Part XIII. Reactivity of 2- and 3-indolylcarbinyl compounds as models for mitosane action

Crowned spiropyran fluoroionophores with a carboxyl moiety for the selective detection of lithium ions

Principal properties (PPs) as solvent descriptors for multivariate optimisation in organic synthesis: specific PPs for ethers

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