Dihydroisochinolinumlagerung, 37. Mitt. Synthese von Isochinoliniumsalzen mit sperrigen C-1-Substituenten als Vorstufen für 1,2-Dihydroisochinoline

Rearrangement of Dihydroisoquinolines, XXXVII: Syntheses of Isoquinolinium Salts with Bulky C-1-Substituents as Precursors of 1,2-Dihydroisoquinolines The Reissert compound 1 is alkylated to give the compounds 2a-2d . From these by saponification the isoquinolines 3a-3d are obtained which are reacted with methyl iodide to yield the iminium iodides 4a-4d.     

Reaktionen von elektronenreichen Heterocyclen mit Orthocarbonsäure-Derivaten, 2. Mitt. Säurekatalysierte Reaktionen von 3-substituierten Indolen mit Orthoameisensäuretriethylester

Reactions of Electron-Rich Heterocycles with Derivatives of Carboxylic Ortho Acids, II: Acid Catalysed Reactions of 3-Substituted Indoles with Ethyl Orthoformate The indoles la and lb react with the diethoxycarbenium ion 2b , generated in an acidic medium, to yield the di- und triindolylmethanes 3 , 4 , 5 and 7 . Compound 5a is oxidized to the cyanine 6a . Tryptamine ( 8a ) undergoes formylation with 2b . When the nucleophilicity of the amino group in 8a is reduced, formation of triindolylmethane is favored, as shown in the reaction of 8b with 2b .     

Reaktionen mit Sulfamid, 3. Mitt. Säure- und basenkatalysierte Reaktionen von Chromon-3-carbaldehyd mit Sulfamid

Acid and Base Catalyzed Reactions of Chromone-3-carbaldehyde with Sulfamide Chromone-3-carbaldehyde ( 1 ) and sulfamide ( 2a ) react with acid catalysis to give bis(chromonyl)-dithiatetrazocine 3 and bis(chromonylidene)sulfamide 4 . Benzopyrano [4,3-d]thiadiazine 6 is obtained by base catalyzed condensation of 1 and 2a .     

Dihydroisochinolinumlagerung, 39. Mitt. 6,7-Dimethoxy-2-methyl-1-phenylpropargyl-1,2-dihydroisochinolin

Dihydroisoquinoline Rearrangement, XXXIX: 6,7-Dimethoxy-2-methyl-1-(phenylpropargyl)-1,2-dihydroisoquinoline The title compound 7 was obtained in 66 % yield by reaction of the isoquinolinium iodide 6 with (phenylpropargyl) magnesium bromide. Compound 7 is an ethinylogous 1-benzyl-1,2-dihydroisoquinoline and, therefore, was expected to show the dihydroisoquinoline rearrangement with acids. With dilute hydrochloric acid 7 yielded a mixture of rearrangement products, which could not be separated. Spectroscopic data suggest that 7 rearranges to yield the expected 1,2-dihydroisoquinoline.     

Diindolylmethane, 4. Mitt. Säure-katalysierte Kondensation von 3-Methylindol und Tryptophanmethylester mit sterisch anspruchsvollen aromatischen Aldehyden

Diindolylmethanes, IV: Acid Catalyzed Condensation of 3-Methylindole and Methyl Tryptophanate with Sterically Hindered Aromatic Aldehydes The 3-substituted indoles 1 and 2 react with 2,6-dimethoxybenzaldehyde ( 3a ) to yield the diindolylmethanes 4 and 6 by acid catalysis. The reaction of 2 with 3a also yields the tetrahydro-β-carboline 7 . The sterically hindered mesitylaldehyde ( 3b ) reacts only with the indole 1 to give the 2,2′-diindolylmethane 5 , while the tryptophane methyl ester 2 yields the tetrahydro-B-carboline 8 only.     

Thion- und Dithioester, 38. Mitt. Zur Kondensation von 2-Amino-dithiooxalsäure-O-ester mit Cyanessigestern

Thiono- and Dithioesters, XXXVIII: Condensation of 2-Amino-dithio-O-oxalates with Cyanoacetic Esters By thiolysis of the cyano methanimidoates 2 cyano methanethioates 1 or 2-amino-2-thioxoethanethioates 3 are formed, depending on the reaction conditions. The thionoester group in 3 condenses with cyanoacetates in the presence of potassium methoxide to form the potassium salts 7 , which were S-alkylated to give the thioenol ethers 9 . Condensations of 9 with hydrazines lead to structurally different products 11–18 .     

Heterocyclisierungen an Ascorbinsäuren mit α, ß- ungesättigten Aldehyden und Ketonen, 2.Mitt.: Michael-Reaktionen von Ascorbinsäuren mit Acroleinderivatenstrukturelle und physikochemische Beobachtungen

Heterocyclisations of Ascorbic Acids with α, β-Unsaturated Aldehydes and Ketones, II: Michael Reactions of Ascorbic Acids with Acrolein Derivatives - Structural and Physicochemical Behaviour. The Michael reaction of ascorbic acids ( la – d ) with acrolein ( 2 ) and some derivatives ( 7 , 8 ) is reported. The pH-optimum of the reaction course is 4. Furthermore, solvents supporting ionisation are favourable. α- and β-subsituted acrolein derivatives react differently: Crotonaldehyde, a β-substituted derivative, reacts nearly quantitatively to the spiro compounds 3e and 3f , whereas α-ethyl-acrolein favours the formation of 4g and 4h .     

Michael-Additionen mit N-Acylaminosäureestern, 4. Mitt. Einstufensynthese von 1-Aryl-pyrrolizidin-3,5,7-trionen

Michael Additions with Esters of Acylamino Acids, IV: One-Step-Syntheses of 1-Arylpyrrolizidine-3,5,7-triones Michael additions between N-acylglycine ester and α,β-disubstituted ethyl acrylates yield stereoselectively, 1,8H-trans-1-arylpyrrolizidine-3,5,7-triones in a one-step reaction.     

Reaktionen von N-Alkoxycyclimoniumsalzen, 16. Mitt. Reaktionen von N-Methoxychinolinium-Verbindungen mit C- und ambidenten C-N-Nucleophilen

Reactions of N-Alkoxy Cyclimonium Salts, XVI: Reactions of N-Methoxyquinolinium Compounds with C- and Ambident C-N-Nucleophiles C-nucleophiles are added to the title compounds at C-2, in case of nucleophiles with high enolisation tendency followed by elimination of methanol. Ambident C-N-Nucleophiles are added to C-2 too, followed by methanol elimination and/or NH₂/OH substitution, depending on the solvent. The reaction products are mostly enolized.     

Barbitursäurederivate, 27. Mitt. Synthese der Enantiomere von 1-Methyl-5-alkyl-5-pentadeuteroethyl-barbitursäuren

Derivatives of Barbituric Acid, XXVII: Syntheses of the Enantiomers of 5-Alkyl-1-methyl-5-(pentadeuterioethyl)barbituric Acids Syntheses of the enantiomers of 1-methyl-5-(pentadeuterioethyl)-5-propylbarbituric acid ( 1 ) and of 5-ethyl-1-methyl-5-(pentadeuterioethyl)barbituric acid ( 2 ) are described. While the enantiomers of 1 are obtained in the usual manner, syntheses of the enantiomers of 2 required a detour. The narcotic activity of (-)- 1 is five times that of (+)- 1 . The 2 -enantiomer obtained from (-)- 10 is more narcotic by a factor of 2.5 than the enantiomer obtained from (+)- 10 .     

α-Thiotetronsäuren, 1. Mitt.: Synthese und Eigenschaften von γ-Alkyliden-α-thiotetronsäuren

α-Thiotetronic Acids, I: Synthesis and Properties of γ-Alkylidene α-Thiotetronic Acids We report on the synthesis of the alkylidene α-thiotetronic acids 11 and 12a and a variety of their derivatives, starting with 2,3-dimethoxysuccinic thioanhydride ( 4 ) or diethyl 3-thioxoglutarate. The rhodium(II)-catalysed decomposition of the diazoketone 26 furnishes the reductone 12p and the aminoreductone 12r with the thietanone 27 as one of the by-products.     

Synthese von Phosphorsäurephenylesterdiamiden, 1. Mitt.

Synthesis of Phenyl Phosphorodiamidates, I Two procedures are described for the synthesis of phenyl phosphorodiamidates in high yields. These compounds can be represented by the general formula 6 and are used for cyclisation reactions leading to phosphabarbituric acids.     

Intramolekulare Umsetzung von Iminiumverbindungen mit Carbonsäuren

Intramolecular Reactions of Iminium Compounds with Carboxylic Acids 5-Nitrobenzoic acids which are substituted at C-2 with cyclic amines are dehydrogenated with mercury EDTA. The piperidine and perhydroazepine derivatives yield tricyclic oxazinones with a small amount of decarboxylated product. The pyrrolidine compound reacts in unusual solvents only, mainly with loss of the carboxy group and to a small degree with dehydrogenation. Comparative experiments were made in order to explain these results.     

Stereochemie substituierter Glutarsäuren, 2. Mitt. Synthese kernfluorierter,mehrfach substituierter Glutarsäuren

Stereochemistry of Substituted Glutaric Acids, II: Syntheses of Substituted 3-(4-Fluorophenyl)-glutaric Acids The stereoselective syntheses of (±)erythro- and (±) threo-3-(4-fluorophenyl)-2-methyl-glutaric acids (9), (10) by Michael addition of dimethyl malonate (2) to methyl E-2-methyl-4′-fluorocinnamate (1) via the subst. trimethylbutanetricarboxylates 3,4 and the subst. butanetricarboxylic acids 7,8 are described. 3 and 4 have been alkylated with methyl bromoacetate to the subst. tetramethylpentanetetracarboxylates 5 and 6 . Attempts towards saponification of 5 and 6 are reported.     

Aminolyse von trans-3-Phenylglycidsäure-Derivaten mit aromatischen Aminen, 4. Mitt

Aminolysis of Derivatives of trans-3-Phenylglycidic Acid with Aromatic Amines, IV Treatment of derivatives of 3-phenylglycidic acid with aromatic amines which differ in basicity and steric properties leads to derivatives of 3-amino-2-hydroxy-3-phenylpropanecarboxylic acid by nucleophilic oxiran ring cleavage. Acid, ester, amide and anilide react in the same way, as is shown by the interconversion of the products 2a, 4a, 6a and 8 . Hydrogenolysis of the compounds of type 4 to 3-phenyllactic amide confirms the structures of the products.     

Stereochemie substituierter Glutarsäuren, 1. Mitt. (±)-threo- und erythro-2-Methyl-3-phenylglutarsäuren

Stereochemistry of Substituted Glutaric Acids, I: (±)-threo- and erythro-2-methyl-3-phenylglutaric Acids Syntheses of (±)-threo-and erythro-2-methyl-3-phenylglutaric acids ( 5,6 ) via the (±)-threo- and erythro-2-phenylbutane-1,1,3-tricarboxylic acids ( 3, 4 ) is described. The configurations of the products were determined.     

Wirkung neuer Iminiumverbindungen gegen ausgewählte Bakterien- und Pilzstämme, 9. Mitt. Synthese von 1,2-Dimethyl- und 1-Butyl-3-(n-alkylthiomethyl)imidazoliumchloriden

Activities of New Iminium Compounds on Selected Strains of Bacteria and Fungi, IX: Synthesis of 1,2-Dimethyl- and 1-Butyl-3-(n-alkylthiomethyl)imidazolium Chlorides Syntheses of the imidazolium compounds 1 and 2 were performed by reaction of chloromethyl n-alkyl sulfide with 1,2-dimethyl- and 1-butylimidazole. Antimicrobial activities of the products were tested against 13 strains of bacteria and fungi. Compounds with a dodecyl or octyl chain showed the best antibacterial properties.