Untersuchungen an ß-Sultonen, 4. Mitt. Zur Reaktion von vicinalen Polycarbonylverbindungen mit Alkansulfonylhalogeniden und Triethylamin2,3), Teil 1

Investigations of ß-Sultones, IV:¹⁾ On the Reaction of Vicinal Polycarbonyl Compounds with Alkanesulfonyl Halides and Triethylamine^2,3), Part 1 The vicinal tricarbonyl compounds 1 and 5 react with alkanesulfonyl halides and triethylamine via the postulated β-sultones 3 or 6 to yield 4a or mixtures of the 2-chloro-1.3-dioxoindan-2-yl alkanesulfonates 7 and the 1,3,4-dioxathiane-2,6-dispiro compounds 8 . Reactions of 7 and 8 with nitrogenous bases afford the 2-(aminomethylidene)-1,3-indanediones 20 among other compounds. The chlorine in compounds 7 is difficult to replace by nucleophiles. With nitrogenous bases only exchange of the sulfonate base occurs. Thioureas on the other hand yield the isothioureas 9 .     

Untersuchungen an β-Sultonen, 5. Mitt. Zur Reaktion von vicinalen Polycarbonylverbindungen mit Alkansulfonylhalogeniden und Triethylamin,Teil 2

Investigations of β-Sultones, V ¹⁽: On the Reaction of Vicinal Polycarbonyl Compounds with Alkanesulfonyl Halides and Triethylamin 2,3), part 2 The 2-chloro-1,3-dioxoindane-2-yl methanesulfonates 1 , whose synthesis was described in part 1, react with phosphorus pentachloride to yield the sulfonyl chlorides 2 , the decomposition product 3 and the diacylketene dichloride 7 . With amines, compounds 2 afford the 2-(aminomethylidene)-l,3-indanediones 10, rather than the sulfonamides 9 .     

Synthese von Carbazolderivaten, 1. Mitt.: Über die Reaktion von 3-(2-Nitroethenyl)indol-2-malonestern mit Michael-Akzeptoren

Synthesis of Carbazole Derivatives, I: Reaction of 3-(2-Nitroethenyl)-indole-2-malonic Acid Esters with Michael-Acceptors Michael-type reactions of compounds of type 9 were studied. Addition reactions with acrolein and methyl vinyl ketone, respectively, lead — depending on the conditions — to pyridoindoles of type 16 and 14 and/or to tetrahydrocarbazoles of type 17 and 15 . With Triton B compounds 15 undergo retro-Michael-type elimination of the nitromethyl group, followed by hydrolysis/decarboxylation and dehydrogenation, leading to the disubstituted carbazoles 20 . In the case of 17a , the primary elimination product 18 could be isolated. The synthetic potential of these reaction types is discussed. Some of the described compounds and derivatives of them show antimycobacterial activity.     

Über Mannichbasen, 15. Mitt. Reaktion von Hexamethylentetramin mit 1-Naphthol und 2-bzw. 4-substituierten Derivaten

Mannich Bases, XV: Reaction of Hexamethylenetetramine with 1-Naphthol and its 2- and 4-Substituted Derivatives The product from the reaction of hexamethylenetetramine with 1-naphthol described by Duff and Bills does not show the N,O-acetal structure 1 that was claimed by the authors. Rather, the product is polycondensated material, which probably forms in reactions of the 2- and 4-positions of 1-naphthol. This assumption is confirmed by model experiments with 1-naphthol derivatives which carry substituents at positions 2 or 4.     

Untersuchungen an 1,3-Thiazinen, 12. Mitt. Reaktionen von 4-Oxo-2-thioxo- und 2,4-Dioxo-tetrahydro-1,3-thiazinen mit einigen Nucleophilen,Teil 1

1,3-Thiazines, XII: Reactions of 4-Oxo-2-thioxo- and 2,4-Dioxo-tetrahydro-1,3-thiazines with some Nucleophiles, I 4-Oxo-2-thioxo- and 2,4-dioxo-tetrahydro-1,3-thiazines 1 and 2 were investigated with regard to their behaviour in alcoholysis, in hydrolysis at various pH values and in reactions with phenol and thiols. The differences between 1 and 2 and the influences of substituents are described.     

Ortho-Effekte in 1-(o-Aminomethylaryl)-(buten(1)-3-onen und ihren Hydrierungsprodukten, 3. Mitt. o-Aminomethyl-benzalacetone und ihre Hydrierungsprodukte,Teil 2

Ortho-effects in 1-(2-Aminomethylaryl)-1-buten-3-ones and Their Hydrogenation Products, III: 2-(Aminomethyl)phenylmethylenacetones and Their Hydrogenation Products, II The preparations of the phenylmethylenacetones and their (deuterated) hydrogenation products (compounds 2 – 28 ) are described; anomalies in some of the ¹³C-NMR spectra are explained by increment calculations.     

Die Reaktion von 3-Benzoylchromon mit Diphenylketen. 28. Mitt. über Untersuchungen an 4-Pyronen

The Reaction of 3-Benzoylchromone with Diphenylketene By action of diphenylketene on 3-benzoylchromone ( 3 ) two products are obtained. The result depends on the reaction conditions: 1,4-cycloaddition yields 2-oxo-2H-pyrano-chromanone 6 , while decarboxylation gives triphenylethenyl-chromone 11 , which can be converted into the corresponding 4-thiochromone 15 or into an acetophenone derivative 16 .     

Reaktionen von 1,4-Pentadien-3-onen, 15. Mitt. Zur Reaktion alkylsubstituierter Pentadienone mit Phenylacetonitrilen

Reactions of 1,4-Pentadien-3-ones, XV:. - The Reaction of Alkylated Pentadienones with Phenylacetonitriles The base-catalysed reaction of dialkylpentadienones 1 with phenylacetonitriles 2 selectively yields 3e,5e-dialkyl-1e,2e,6e-triaryl-4-oxocyclohexane-1a-carbonitriles 3 . Likewise 3a may be obtained from the tetrahydropyrane 4 . On the other hand, monoalkylpentadienones 5 give 3e-alkyl-1e,2a,6e-triaryl-4-oxo-cyclohexane-1a-carbonitriles 6 , which may be converted to the 2e-compounds 7 . A possible mechanism of isomerization is discussed.     

Untersuchungen an 1,3-Dicarbonyl-Verbindungen, 24. Mitt. 1,4-Dihydropyridine und 1,2,3,4-Tetrahydropyrimidine,III. Zur Reaktion von Acetylaceton mit 2-Nitrobenzaldehyd und Ammoniak

1,3-Dicarbonyl Compounds, XXIV: 1,4-Dihydropyridines and 1,2,3,4-Tetrahydropyrimidines, III; The Reaction of Acetylacetone with 2-Nitrobenzaldehyde and Ammonia Depending on the reaction conditions either the 1,4-dihydropyridine 1 or the 1,2,3,4-tetrahydropyrimidine 2 , with the indole 4 and the pyrimidine 5 as by-products, are obtained by Hantzsch synthesis. Compounds 1, 2 and 4 were characterized by chemical and spectroscopic methods. A mechanism leading to 4 is proposed.     

Untersuchungen an 1,3-Thiazinen, 19. Mitt. Darstellung von und Cyclisierungsversuche mit N-monosubstituierten S-Prop-2-inyl-thiolurethanen

1,3-Thiazines, XIX: Preparation of N-monosubstituted Prop-2-ynyl Carbonamidothioates and Attempts to Cyclize these Products The preparation of novel N-monosubstituted prop-2-ynyl carbonamidothioates 1 and their aminolysis to N,N'-disubstituted ureas is described. The failure of cyclizing the thioesters to 3,6-dihydro-1,3-thiazin-2-ones 2 is reported.     

Untersuchungen an 1,4-Naphthochinonen, 11. Mitt. Farbstoffsensibilisierte Photooxidation von 1-Naphtholen mit Alkyl- und Alkoholfunktionen in 2-Position

1,4-Naphthoquinones, XI: Dye-Sensitized Photooxygenation of 1-Naphthols with an Alkyl or Carbinol Function at C-2 The results of dye-sensitized photooxygenations of 2-alkylnaphthalene-1-ols depend on the length of the aliphatic chain and the extent of its branching. Photooxygenation of 1a yields 2 and, unexpectedly, 3 . While the primary alcohol 5a is oxidized to the parent naphthoquinone 8 , the secondary alcohol yields the ketone 7 rather than 6 . Two additional methods are presented for the independent synthesis of 7 .     

Untersuchungen zur Isolierung von Flavonoiden mit Hilfe der Oxide und Salze 2-wertiger Kationen, 1. Mitt. Untersuchungen an Reinsubstanzen chelatbildender Flavonoide

Investigations of Pure Chelating Flavonoids Flavonoids were adsorbed onto acid-soluble oxides or salts of 2-valent cations. After dissolution of the cation flavonoid complexes in dilute acids, the flavonoids could be extracted with organic solvents. The influence of the basicity of the sorption materials and of the concentration of the dilute acids on the stability of the flavonoids was investigated.     

Heterocyclische 1,4-Naphthochinonderivate, 1. Mitt.: Zur Reaktion von 2-Chlor-3-chloracetylamino-1,4-naphthochinon mit Anilin

Heterocyclic 1,4-Naphthoquinone Derivatives, I: Reaction of 2-Chloro-3-chloroacetylamino-1,4-naphthoquinone with Aniline. 2-Chloro-3-chloroacetylamino-1,4-naphthoquinone ( 3 ) reacts with aniline ( 4 ) in molar ratio 1:2 to give 2-anilino-3-chloroacetylamino-1,4-naphthoquinone ( 6 ). This is an intermediate at the molar rate 1:1 and undergoes acid catalyzed cyclization to give 2-chloromethyl-4,9-dihydro-1-phenyl-1H-naphtho[2,3-d]imidazole-4,9-dione ( 10 ). Base catalyzed reaction of morpholine ( 8 ) and 6 gives also 10 , which alkylates 8 to give 4,9-dihydro-2-(4-morpholinomethyl)-1-phenyl-1H-naphtho-[2,3-d]imidazole-4,9-dione ( 7 ).     

Thion- und Dithioester, 52. Mitt.: Zur Reaktion von Dithionmalonestern mit N,N-Dimethylformamidacetalen

Thiono and Dithio Esters, LII¹⁾: Reaction of Dithiono Malonates with N,N-Dimethylformamide Acetals The reaction of the dithiono malonates 1 with the formamide acetals 2 leads to the 2-dialkylaminomethylene dithionomalonates 4 and the thiono acrylates 6 . The condensation of 4 with hydrazines gives rise to the pyrazoles 7 and 8 , with hydroxylamine sulfonic acid to the isothiazoles 10 , and with amidines to the pyrimidines 11 - 13 .     

Synthesen von N-Lost-Derivaten, 2. Mitt. Reaktion von N-Bis(2-Chlorethyl)phosphorsäureamid-dichlorid mit 1-Aminopropan-2,3-diol

Synthesis of N-Lost Derivatives, II: Reaction of N,N-bis(2-Chloroethyl)phosphoramidic dichloride with 1-Aminopropane-2,3-diol The reaction between the phosphoramidic dichloride 1 and 1-aminopropane-2,3-diol ( 3 ) affords the five membered ring 9 and not the desired 5-hydroxycyclophosphamide 8 . The structural assignment was based on an independent synthesis of 9 via the benzyl ether 14 .     

Untersuchungen an 1,3-Thiazinen, 13. Mitt. Reaktionen von 4-Oxo-2-thioxo- und 2,4-Dioxo-tetrahydro-1,3-thiazinen mit einigen Nucleophilen,Teil 2

1,3-Thiazines, XIII: Reactions of 4-Oxo-2-thioxo- and 2,4-Dioxo-tetrahydro-1,3-thiazines with some Nucleophiles, II . 4-Oxo-2-thioxo- and 2,4-dioxo-tetrahydro-1,3-thiazines 1 and 2 were reacted with nitrogen bases, the basicity of which influenced the nature of the products. Nucleophilic attack occurred first at carbon 4 of 1 and 2 and in some cases was followed by attack at carbon 2.     

Untersuchungen an 1,4-Napthochinonen, 24. Mitt.: Zur Dehalogenierung von 2-/3-Halogen-1,4-naphthochinon-derivaten

1,4-Naphthoquinones, XXIV: On the Dehalogenation of 2-/3-Halogen-1,4-naphthoquinone Derivatives Bu₃SnH is an effective reagent for the debromination of 2-bromonaphthoquinones but elimination of chlorine with 1c , e.g., only proceeds at 30%. With Et₃SiH dechlorination does not occur at all. Instead, with the 5-acetoxy derivatives 1a/1d as starting materials the cyclic acetales 3a – c are formed as selectively protected juglone derivatives. The bromo derivative 3a is obtained only at temp. < 10° and even at room temp. Br-Elimination occurs with low yield of 3b . An especially suitable reagent for the debromination of 1a – b leading to the natural compounds plumbagin ( 2a ) and isoplumbagin ( 2b ) is zinc-silver couple but Cl-elimination again occurs in traces only.     

Untersuchungen an 1,4-Naphthochinonen, 25. Mitt. Reaktion des Redox 5-Lipoxygenase-Inhibitors 2-(3,5-Di-tert-butyl-4-hydroxyphenyl)-3-hydroxy-1,4-naphthochinon mit O2•− und 3O2

1,4-Naphthoquinones, XXV: Reaction of the Redox 5-Lipoxygenase Inhibitor 2-(3,5-Di-tert-butyl-4-hydroxyphenyl)-3-hydroxy-1,4-naphthoquinone with O₂^?? and ³O₂ The 5-lipoxygenase inhibitor 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-3-hydroxy-1,4-naphthoquinone ( 2 ), its deoxygenation product 1 as well as the oxygenated species 3 are O₂^?? quenchers with different power in aqueous solution. In alcoholic solution the antioxidative capacity of 1 does not change, 2 indeed is still only a weak O₂^?? quencher while 3 shows prooxidative properties. This phenomenon was explored in the O₂^?? generating oxygenation system (OS) DMSO-CO₃^2-–O₂ by preparative techniques. The following reaction sequence could be proven: 3 ? 2 ? 4 (2,6-di-tert-butyl-1,4-benzoquinone). While the step 3 ? 2 would be O₂^?? dependent the transition 2 ? 4 occurs on two levels: 1. retro Michael reaction with release of 2,6-di-tert-butylphenol ( 5 ), 2. base catalysed oxygenation of 5 ? 4 by ³O₂. The diphenoquinone 6 occurring as byproduct is split with the OS – in contrast to the reaction with ¹O₂ – in considerable yield to give 4 .     

Ortho-Effekte in 1-(o-Aminomethylaryl)-buten(1)-3-onen und ihren Hydrierungsprodukten, 2. Mitt. o-Aminomethyl-benzalacetone und ihre Hydrierungsprodukte,Teil 1

Ortho effects in 1-(2-Aminomethylaryl)-1-buten-3-ones and Their Hydrogenation Products, II: 2-(Aminomethyl)phenylmethylenacetones and Their Hydrogenation Products, I The preparations of the compounds 3 – 13 are described.     

Untersuchungen an 1,4-Naphthochinonen, 19. Mitt.: 2-, 3- und 6-Methyljuglon aus Formylnaphtholen

1,4-Naphthoquinones, XIX: 2-, 3- and 6-Methyljuglone from Formylnaphthol Derivatives The methylnaphthol derivatives 9 and 10 are suitable compounds for the synthesis of plumbagin, 6-methyljuglone ( 14 ) and 3-methylnaphthazarine ( 12 ). 9 and 10 are derived from 5 and 6 which are synthesized by formylation of the naphthols 2 and 3 . As it was not possible to get the formylnaphthol 8 in the same way, isoplumbagin ( 18 ) was prepared by bromine-lithium exchange in the key compound 16 followed by methylation and oxidation.