Lactone, 10. Mitt. Zur Synthese N-heterocyclisch substituierter γ,γ-Diphenyl-γ-butyrolactone

Lactones, X: Synthesis of γ,γ-Diphenyl-γ-butyrolactones Substituted by N-Heterocycles Starting from 3 and 16 , syntheses of γ,γ-diphenyl-γ-butyrolactones with N-heterocycles at the α-position are described. Scope and limitation of the syntheses, tautomerism and stereochemistry of the products as well as spectroscopic results which are inconsistent with data from the literature are discussed.     

Lactone, 3. Mitt.1) Zur Synthese von α-Aminoalkyl-γ-lactonen

Lactones, III: Synthesis of α-Aminoalkyl-β-lactones Alkylation of α-acetyl-β-lactones with α-aminoethyl and -propyl chlorides, followed by in situ cleavage of the acetyl group with an excess of ethanolate is a general synthetic route to α-aminoethyl- and α-aminopropyl-β-lactones. The yields are limited by side reactions.     

Lactone, 1. Mitt. Synthese dihydroxylierter Diphenylethylamine über α-Amino-γ-lactone

Lactones, I: Synthesis of Dihydroxylated Diphenylethanamines via α-Amino-γ-lactones Treatment of α-amino-γ-lactones with phenyllithium yields the 2-amino-1,1-diphenylalkane-1,4-diols 2a–f which can be classified as dihydroxylated diphenylethanamines.     

Lactone, 11. Mitt. Synthese von 4.9-Dihydropyrano[3.4-b]indol-1(3H)-onen aus α-Ethoxalyl-γ-lactonen

Lactones, XI: Syntheses of 4.9-Dihydropyrano[3.4-b]-indol-1(3H)-ones from α-Ethoxalyl-γ-lactones Cleavage and decarboxylation of the α-ethoxalyl-γ-lactones 1a-d followed by treatment with phenylhy-drazines yield the hydrazones 4a-l , which can be rearranged to the indololactones 5a-m. Starting from the δ-lactones 6 and 10 , the same reactions lead to indoles without lactone ring closure.     

Lactone, 16. Mitt.: Synthese von 4,9-Dihydropyrano[3,4-b]indol-1(3H)-onen aus α-Ethoxalyl-δ-valerolacton

Lactones, XVI: Synthesis of 4,9-Dihydropyrano[3,4-b]indol-1(3H)-ones from α-Ethoxalyl-δ-valerolactone Treatment of α-ethoxalyl-δ-valerolactone (1) with diazotized anilines and indolization of the intermediate hydrazones 4 leads to the pyranoindolones 5 . Compared to the recently reported reaction of α-ethoxalyl-γ-butyrolactone with arylhydrazines²⁾, this synthesis is more versatile with regard to variation of substituents at the aromatic ring. Stereochemistry and reactivity of the α-arylhydrazonolactones are discussed.     

Indole, 12. Mitt. β-Carboline aus Lactonen - Zur Synthese von Liganden am Norharman-Rezeptor

Indoles, XII: β-Carbolines from Lactones - Synthesis of Ligands of the Norharmane Receptor Starting from α-ethoxalyl-δ-valerolactone ( 1 ) 6-substituted β-carbolines were synthesized in 5 steps to enable investigations at the norharmane binding sites in rat liver and in pig brain. The Pd-catalyzed aromatization of N-benzyl-tetrahydro-β-carbolines with debenzylation was optimized with 5a→6a and then used for the preparation of other derivatives. Additional hydrogenolyses occur with 5d,h . Bromination of 1a gives 6d which can be transferred to the radioligand ³H-norharmane.     

Imidazolsynthesen, 7. Mitt.: Imidazole aus Iminoestern, α-Amino- oder α-Acylaminoketonen und flüssigem Ammoniak

Imidazoles from Iminoesters and α-Amino-or α-Acylaminoketones and Liquid Ammonia Substituted imidazoles 4 are obtained from iminoesters 1 and α-amino- 2 or α-acylaminoketones 3 in liquid ammonia under pressure.     

Lactone, 4. Mitt. Synthese dihydroxylierter Diphenylalkylamine über Aminoalkyl-γ-lactone

Lactones, IV: Synthesis of Dihydroxylated Diphenylalkanamines via Aminoalkyl-γ-lactones Excess of phenyllithium reacts with the aminoalkyl-γ-lactones 1 – 3 , 10 , 13 to yield the 1,1-diphenyl-propan- 4 , -butan- 5 , and -pentanamines 6 , 14 . The reaction can be considered as a general method for the synthesis of dihydroxylated 1,1-diphenylalkanamines, which is limited only by the poor crystallizability of the end products.     

Lactone, 23. Mitt.: Synthese und Stereochemie „γ-lactonisierter”︁ Neuroleptika vom Butyrophenon-Typ

Lactones, XXIII: Synthesis and Stereochemistry of ?γ-Lactonized”? Butyrophenone-type Neuroleptics ?γ-Lactonized”? neuroleptics ( 1,2a-c ) can be obtained by reaction of α-formyl, α-carboxy- and α-methylene-lactones 5-7a,b with amines 8a - c . 6a, 1a-c were cis/trans-mixtures with predominating cis-compounds, 6b, 2a cis/trans-mixtures with predominating trans-compounds and 2b , c were isolated as pure trans-isomeres.     

β-Substituierte Enamine, 11. Mitt. Kondensationsprodukte aus γ-Chloracetessigester und primären aromatischen oder heteroaromatischen Aminen

β-Substituted Enamines, XI. Condensation Products from Reactions of γ-Chloroacetoacetic Ester with Primary Aromatic and Heteroaromatic Amines γ-Chloroacetoacetic ester ( 1a ) reacts with aniline via an α-(chloromethyl)enamine 2a to yield 4-anilino-5H-furan-2-one ( 4 ). It undergoes condensation reactions with heterocycles having primary aminogroups in position 2, e. g. 2-aminopyridine ( 6 ). 2-aminothiazole ( 9 ), 2-aminobenzimidazole ( 10 ), 2-aminobenzothiazole ( 11 ). Products are the fused chloromethylpyrimidones 8, 12, 13 and 14 .     

Untersuchungen an 1,3-Thiazinen, 31. Mitt. 3-Carbazoylthio-propionsäuren aus Hydrazinderivaten,Carbonylsulfid und β-Propiolactonen

1,3-Thiazines XXXI¹⁾: 3-(Hydrazinocarbonylthio)propionic Acids from Hydrazine Derivatives, Carbon Oxide Sulfide and β-Propiolactones Hydrazine, N-mono- and N,N-disubstituted hydrazines, N-aminoheterocycles and N-4-phenylthio-semicarbazide were reacted with carbon oxide sulfide and triethylamine to yield the unstable hydrazinecarbothioates 3 , which were 2-ethoxycarbonylated with β-propiolactones to give the novel pharmacologically active (hydrazinocarbonylthio)propionic acids 4 .     

Neue Substanzen aus ätherischen Ölen verschiedener Artemisia-Species, 3. Mitt. α-Cadinol aus Beifußkrautöl

New Substances from the Essential Oils of Artemisia-Species^*), III: α-Cadinol α-Cadinol is a tertiary sesquiterpenic alcohol. For the first time it has now been found in the volatile oil of Artemisia vulgaris L. var. vulgatissima. Its identity was established by physicochemical and spectroscopic methods.     

Lactone, 24. Mitt.: „γ-Lactonisierte”︁ Neuroleptika - Synthese,Stereochemie und Affinität am D2-Rezeptor

Lactones, XXIV: ?γ-Lactonized”? Neuroleptics - Synthesis, Stereochemistry and Affinity at the D₂ Receptor Addition of piperidines 15a-d to methylene lactones 8,14a gives the ?γ-lactonized”? diphenylbutylpiperidine-type neuroleptics 3a,b,d,4a-d. 8 can be produced by cyclization or - as well as 14 - from the corresponding α-carboxylactone. ¹H- and ¹³C-nmr data give evidence for the equatorial position of the aminomethyl group in all derivatives of 3 and 4 and bisequatorial-trans-configuration in 4a - d . ³H-spiroperidole displacement at the D₂ receptor in rat brain by 3,4 and the ?γ-lactonized”? butyrophenone neuroleptics 1,2a-c was investigated. Some compounds show moderate up to high ( 3b ) activity.     

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.     

Lactone, 14. Mitt.: Synthese lactonverbrückter 1,1-Diarylethylamine

Lactones, XIV: Synthesis of Lactone-Bridged 1,1-Diarylethanamines Reaction of the 5,5-diaryl-2(5H)-furanones 4a–d with excess of amines gives the aminoamides 5a–k , which are transformed into the desired 4-amino-5,5-diaryl-4,5-dihydro-2(3H)-furanones 6a–k by hydrolysis and ring closure.     

Über Dialkyl-[β,β,β-trichlor-bzw. β,β,β-triphenyl-äthyl]-amine. 34. Mitt. über α-halogenierte Amine

Dialkyl-[β,β,β-trichloro- or β,β,β-triphenyl-ethyl]-amines Reactions of α-halo amines 2 with trichloromethyllithium give dialkyl-[β,β,β-triphenyl-ethyl]-amines 1 , with triphenylmethyllithium dialkyl-[β,β,β-triphenyl-ethyl]-amines 3 .