Reactions of Amines. XIV. An Oxidative Rearrangement of Amides<sup>1,2</sup>

Baumgarten, Henry E.; Staklis, Andris

doi:10.1021/ja01083a042

Cited by 52 publications

(10 citation statements)

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“…T solution (activating solution): 10 mM ATP, 12 mM MgCl2, 5 mM EGTA, 5 mM CaCl2, 20 mM imidazole hydrochloride, 5 mM NaNg, 5 mM phosphoenol pyruvate, 20 U/mL pyruvate kinase, pH 6.7, at 22 °C. M solution (relaxing solution): identical in composition with T solution with the exception of no added CaCl2, pH 6.7,…”

Section: Methodsmentioning

confidence: 99%

5-Methyl-6-phenyl-1,3,5,6-tetrahydro-3,6-methano-1,5-benzodiazocine-2,4- dione (BA 41899): Representative of a Novel Class of Purely Calcium-Sensitizing Agents

Herold¹,

Herzig²,

Wenk³

et al. 1995

J. Med. Chem.

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BA 41899 (5-methyl-6-phenyl-1,3,5,6-tetrahydro-3,6-methano-1,5- benzodiazocine-2,4-dione, 6) is a structurally novel 1,5-benzodiazocine derivative and represents the prototype of a hitherto unknown class of positive inotropic Ca(2+)-sensitizing agents. It is completely devoid of phosphodiesterase (PDE) III inhibitory activity or any other known inotropic mechanism. BA 41899 (6) exhibits a pharmacological in vitro profile comprising Ca(2+)-sensitizing, positive inotropic, and negative chronotropic effects. CGP 48506 ((+)-6), the (+)-enantiomer of BA 41899 (6), enantiospecifically carries Ca2+ sensitization by up to a full pCa unit and a corresponding positive inotropic effect. Conversely, the negative chronotropic action resides in the corresponding (-)-enantiomer, CGP 48508 ((-)-6). All the effects are exerted in the low micromolar range. The positive inotropic action of CGP 48506 ((+)-6) is associated with a decelerating effect on contraction and, more prominently, relaxation dynamics in isolated guinea pig atria. In contrast to Ca(2+)-sensitizing PDE inhibitors, CGP 48506 ((+)-6) does not increase maximum Ca(2+)-activated force in myocardial skinned fibers.

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Section: Methodsmentioning

confidence: 99%

5-Methyl-6-phenyl-1,3,5,6-tetrahydro-3,6-methano-1,5-benzodiazocine-2,4- dione (BA 41899): Representative of a Novel Class of Purely Calcium-Sensitizing Agents

Herold¹,

Herzig²,

Wenk³

et al. 1995

J. Med. Chem.

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“…Als Oxydationsmittel erschien Bleitetraacetat aus mehreren Grunden besonders vorteilhaft : 1) Es lost sich gut in organischen Losungsmitteln und erlaubt daher homogene Reaktionsbedingungen ; 2) das als Reduktionsprodukt anfallende Bleidiacetat ist dort unloslich und kann daher leicht entfernt werden; 3) es l a s t sich ein attraktiver Mechanismus zur Uberfiihrung der H,N-Gruppe in ein Nitren-Stickstoffatom uber eine wie bei sekundaren Aminen (vgl. 9) [8] angenommene [9] formulieren; 4) schliesslich hatte sich Bleitetraacetat schon fruher fur die Oxydation der H,N-Gruppe primarer Amine, Amide und Hydrazine bewahrt [%lo]. (11) in inerten Losungsmitteln.…”

Section: ;unclassified

“…9) [8] angenommene Blei-Stickstoff-Verbindung (vgl. 10) [9] formulieren; 4) schliesslich hatte sich Bleitetraacetat schon fruher fur die Oxydation der H,N-Gruppe primarer Amine, Amide und Hydrazine bewahrt [%lo]. (11) in inerten Losungsmitteln.…”

Section: ;unclassified

Phthalimido‐nitren I. Bleitetraacetat‐Oxydation von N‐Aminophthalimid in inerten Lösungsmitteln. Bildung und Eigenschaften von trans‐1,4‐Bisphthaloyl‐2‐tetrazen

Hoesch¹,

Dreiding²

1975

Helvetica Chimica Acta

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Summary. Lead tetraacetate oxidation of N-aminophthalimide (11) in inert solvents gives as major products phthalimide (15) or truns-l.4-bisphthaloyl-2-tetrazene (12), the former (15) on slow, the latter (12) on fast addition of the oxidizing agent. As by-products are found: (a) in the presence of acetic acid : N-acetylamino-phthalimide (14). and (b) in its absence (especially at higher temperatures) : banzocyclobutenedione (13) along with N-phthalimido-phthalimide (16) as well as traces of phthalic anhydride (17).The tetrazene 12 and phthalimide (15) are considered to be formed by oxidation and fragmentation, respectively, of the intermediate 1,4-bisphthaloyl-tetrazane (18). Phthalimido-nitrene (22), or its conjugated acid 23, is postulated to be the species which initiates the major reactions, namely: (a) addition to the educt 11 to give the tetrazane 18 and (b) fragmentation with loss of N, to give the dione 13. The minor by-products 16 and 17 may be the result of cross-amidation of 11 with 15 and rearrangement-oxidation via phthalazine-1.4-dione (30), respectively.The structure of the tetraacyltetrazene 12 follows from its properties, among others a comparison of its UV. spectrum with that of the known 1,4-dimethoxycarbonyl-l,4-dimethyl-2-tetrazene (32). Methanolysis of 12 affords 1,4-di-(o-methoxycarbonyl-benzoyl)-2-tetrazene (33).The diacyltetrazene 33 is converted to methyl N-methoxycarbonyl-anthranilate (36), N, and phthalimide (15) on thermolysis, or to methyl N-acetylphthalamate (35), methyl N, N'-carbonyldianthranilate (37) and methyl N-acetyl-anthranilate (38) on acetylation in pyridine. The intermediate in these reactions, leading to 36, 37 and 38, probably is o-methoxycarbonyl-phenylisocyanate (34), itself the result of a Curtius-type rearrangement. Acetolysis of the tetrazene 12 gives phthalimide (15), N, and N-carboxyanthranilic anhydride (42) by a mechanism analogous to that of the methanolysis of 12.In the preparation of 1,4-dimethoxycarbonyl-1,4-dimethyl-Z-tetrazene (32), required for the above mentioned comparison, by zinc reduction of methyl N-methyl-N-nitro-carbamate (43), followed by bromine oxidation of methyl N-amino-N-methylcarbarnate (44), a deamination of 43 to methyl N-methyl-carbamate (45) was observed both in the reductive and in the oxidative step. Both formations of 45 can be formulated v i a a nitrene and a tetrazane, namely via 47 and 48.

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“…Table II Nmr Coupling Constants0 for 9-OxA-9a-AZONiABENZo [6] phenanthro [4,3-d] changeable hydrogens were missing. The chemical shifts of the pyridinium hydrogens were puzzling at first; the low-field shifts expected on introduction of the positive charge were observed but not in the expected manner.…”

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confidence: 99%

Overcrowded molecules. IV. Synthesis and properties of some highly strained 1-(2-pyridyl)-9-oxa-9a-azoniabenzo[b]phenanthro[4,3-d]furans

Fields¹,

Regan²,

Maier³

1973

J. Org. Chem.

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Oxidation of the overlapped pyridyl compounds 3 yields the even more highly overcrowded isoxazolium zwitterions, 4, whose spectral properties indicate them to be intramolecular charge transfer complexes. Unusual, largely unexplained, chemical shifts and coupling constants occur in the nmr spectra of 4. Reaction of 4 with several "hard" nucleophiles gives products resulting from addition at C-8a (BH4~, OH-, OMe-), or substitution at C-7 (CN-) via an apparent 1,6 addition-elimination. In contrast, reaction of the closely related deoxy isoxazolium salt 8 with nucleophiles gives products resulting from the more common reduction (BH4-), or substitution (CN-) of the pyridinium ring. The difference in reactivity is ascribed to the charge transfer character of the zwitterion.

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Reactions of Amines. XIV. An Oxidative Rearrangement of Amides^1,2

Cited by 52 publications

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5-Methyl-6-phenyl-1,3,5,6-tetrahydro-3,6-methano-1,5-benzodiazocine-2,4- dione (BA 41899): Representative of a Novel Class of Purely Calcium-Sensitizing Agents

5-Methyl-6-phenyl-1,3,5,6-tetrahydro-3,6-methano-1,5-benzodiazocine-2,4- dione (BA 41899): Representative of a Novel Class of Purely Calcium-Sensitizing Agents

Phthalimido‐nitren I. Bleitetraacetat‐Oxydation von N‐Aminophthalimid in inerten Lösungsmitteln. Bildung und Eigenschaften von trans‐1,4‐Bisphthaloyl‐2‐tetrazen

Overcrowded molecules. IV. Synthesis and properties of some highly strained 1-(2-pyridyl)-9-oxa-9a-azoniabenzo[b]phenanthro[4,3-d]furans

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Reactions of Amines. XIV. An Oxidative Rearrangement of Amides1,2

Cited by 52 publications

References 0 publications

5-Methyl-6-phenyl-1,3,5,6-tetrahydro-3,6-methano-1,5-benzodiazocine-2,4- dione (BA 41899): Representative of a Novel Class of Purely Calcium-Sensitizing Agents

5-Methyl-6-phenyl-1,3,5,6-tetrahydro-3,6-methano-1,5-benzodiazocine-2,4- dione (BA 41899): Representative of a Novel Class of Purely Calcium-Sensitizing Agents

Phthalimido‐nitren I. Bleitetraacetat‐Oxydation von N‐Aminophthalimid in inerten Lösungsmitteln. Bildung und Eigenschaften von trans‐1,4‐Bisphthaloyl‐2‐tetrazen

Overcrowded molecules. IV. Synthesis and properties of some highly strained 1-(2-pyridyl)-9-oxa-9a-azoniabenzo[b]phenanthro[4,3-d]furans

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Reactions of Amines. XIV. An Oxidative Rearrangement of Amides^1,2