ZurFischer-Indol-Umlagerung sterisch gehinderter Systeme, 6. Mitt.: Reaktionen mit cyclischen Oxalylverbindungen, 22. Mitt.

The N,N-diphenylhydrazones1 and7 combine with oxalyl chloride yielding the corresponding 2,3-dihydropyrrole-2,3-diones (2), the indeno[1,2—b]pyrrol-2,3-dion derivative8 a and the 1-diphenylamino-4,5-tetrahydrobenz[g]indol-2,3-dione (8 b).2 can be rearranged into the pyrrolo[2,3—b]indole systems3 by thermolysis in decaline. Heating of3 a gives ethyl 1,2-diphenyl-indole-3-carboxylate5, while3 b under the same conditions is converted into the (indolyl-)glyoxylic acid derivative4. The diaza-propellanes9 are synthesized by thermolysis of8 in decaline. Oxidative hydrolysis of9 leads to the indole derivatives10, which on the other hand are made byFischer indole synthesis starting with7.     

Synthesen von Heterocyclen, 98. Mitt.: Zur Chemie der Ketenimine

Zusammenfassung Diaryl-ketenimine reagieren mit monosubstit. Malonsäurechloriden unter Abgabe von 2 HCl zu 2-Oxo-chromeno-[3,2-b]pyrrolen (1–7), Dialkyl-ketenimine dagegen zu 4,5-Dihydro-5-oxo-2H-furo[3,2-b]pyrrolen (11–12).

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Diaryl ketenimines react with monosubstituted malonyl chlorides to 2-oxo-chromeno[3.2-b]pyrroles (1–7), and dialkyl ketenimines to 4.5-dihydro-5-oxo-2H-furo[3.2-b]pyrroles (11–12).

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Herrn Prof. Dr.F. Asinger mit den besten Wünschen zum 60. Geburtstag gewidmet.     

Synthese von indenothiophenen, 2. Mitt.

The synthesis of 5,6-dihydro-4H-indeno[5,4–b]thiophene (2 b) is described.     

2-Amino-2-Deoxytetrose Derivatives. 2. Preparation from d-Glyceraldehyde Acetonide: A Reinvestigation

Abstract

A diastereomeric mixture of nitriles 1a,b was prepared by a Strecker synthesis from D-glyceraldehyde acetonide and benzylamine. The reported selective hydrolysis of the acetonide group of 1a could not be accomplished. Nitrile diastereomers 1a,b were carried forward as a mixture to amines 3a,b where the diastereomers were readily separable. The hydrochloride of 3a was transformed via sequential debenzylation, N-acetylation, reduction, and exhaustive acetylation to the 2-amino-2-deoxy-D-threose derivatives 5 and 6. The corresponding 2-amino-2-deoxy-D-erythrose derivatives 10a and 11 were prepared similarly from amine 3b.     

Umwandlung von Phthalidisochinolinalkaloiden in Benzazepinalkaloide, 1. Mitt.

Zusammenfassung Als Modell für die geplante Umformung von Phthalidisochinolinalkaloiden in natürliche Benzazepinalkaloide (Rhoeadinalkaloide) wird das aus (–)-Narcotin zugängliche Nornarcein2a oder dessen Äthylester2b ² in das Rheadan8b ¹ übergeführt. Ein Rheadan mit dem aromatischen Substitutionsmuster von8b wurde bisher in der Natur noch nicht aufgefunden.

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Conversion of Phthalideisoquinolines into Benzazepine Alkaloids

As a model for the planned conversion of phthalideisoquinoline alkaloids into natural benzazepine alkaloids (rhoeadine type), nornarceine2a or its ethyl ester2b [obtained from (–)-narcotine,1]² have been transformed into the rheadane8b ¹. The aromatic substitution pattern of8b has not yet been observed in nature.

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Herrn Prof. Dr.O. Kratky zum 70. Geburtstag gewidmet.     

Synthesen von Heterocyclen, 146. Mitt.: Zur Synthese polymerer Indigofarbstoffe mit potentiellen Halbleitereigenschaften

Zusammenfassung Die Darstellung von polymeren Indigofarbstoffen (PI) nach dem Verfahren vonZiegler undKappe ^{2, 3} wird beschrieben. Ausgehend von Benzidin (1 a) und Tolidin (1 b) erhält man so diePI 6 a bzw.6 b. In analoger Weise wird aus Tetrahydrochinoxalin (7), der N,N-überbrücktePI 12 gewonnen.

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Syntheses of heterocycles, CXLVI: The synthesis of polymeric indigos with potential semiconductor properties

The synthesis of polymeric indigos (PI) according to the procedure ofZiegler andKappe ^{2, 3} is described. Starting with benzidine (1 a) or tolidine (1 b) thePI 6 a and6 b, resp., are obtained. In a similar way the N,N-bridgedPI 12 is synthesized from tetrahydroquinoxaline (7).

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Aus den Dissertationen vonH. G. Foraita undL. F. Werner, Universität Graz, Januar bzw. Juni 1963.     

Zur Kenntnis cyclischer Acylale, 18. Mitt.: Über die Einwirkung von Diazomethan auf substituierte Benzylidenmeldrumsäuren und ähnliche Verbindungen

Zusammenfassung Es wird die Reaktion der Kondensationsprodukte (1–3) vonMeldrumsäuren mit Diazomethan in Methanol/Äther beschrieben, die zu den Cyclopropanverbindungen1 b-3 b führt. Diese Reaktionsweise ist bekannt und auch nach quantenchemischen Berechnungen des einen von uns (P. Schuster) zu erwarten.Eine neue, bisher nicht beobachtete Reaktion wurde bei der Verbindung4 gefunden. Bei verschiedenen Temperaturen führt die Reaktion mit CH₂N₂ in Methanol/Äther (außer zu den Verbindungen4 a und4 b) zu4 c. In CHCl₃ entsteht nur4 b neben viel allem Anschein nach hochmolekularen Produkten.

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The reaction is described of the condensation products ofMeldrum's acid with aldehydes1–3 ² with diazomethane in methanol/ether, which leads to the cyclopropane compounds1 b-3 b. This is a known mode of reaction and is predicted by quantum chemical calculations ofP. Schuster.A reaction hitherto unobserved was found in the case of the compound4. The reaction with CH₂N₂ in methanol/ether at various temperatures yields the compound4 c as well as4 a and4 b. In CHCl₃ the reactions yields only4 b in addition to many other high molecular weight products.

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Mit 1 Abbildung

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Herrn Prof. Dr.F. Asinger zum 60. Geburtstag gewidmet.     

Zur Struktur der Tetrahydro-4-phenylspiro([1]benzopyran-2,4′(1′H)-pyrimidin)-2′(3′H)-one bzw.-thione über Heterocyclen, 49. Mitt

The structures of tetrahydro-4-phenylspiro([1]benzopyran-2,4(1H)-pyrimidin)-2(3H)-ones and-thiones4 a, b resp., are proved by synthesis. 3-(2-methoxy-3,5-dimethylphenyl)-3-phenylpropionic acid11 b is prepared from 3,4-dihydro-6,8-dimethyl-4-phenylcoumarin10. The lithium salt of11 b reacts with isobutenyl-lithium to 1-(2-methoxy-3,5-dimethylphenyl)-5-methyl-1-phenyl-4-hexen-3-on12 a. 12 a is transferred with urea in acid medium and NH₄CNS resp. in a mixture of dihydro-6-[2-(2-methoxy-3,5-dimethylphenyl)-2-phenyläthyl]-4,4-dimethyl-2(1H)-pyrimidinone and-thione13 a, b and tetrahydro-6-[2-(2-methoxy-3,5-dimethylphenyl)-2-phenyläthyliden]-4,4-dimethyl-2(1H)-pyrimidinone and-thione14 a, b resp.14 b leads to13 a, b with H₂O₂. Heating of13 a, 14 a and14 b resp. with pyridin-HCl leads to the spiro compounds4 a, b.     

Synthese des 4-Hydroxy-6,6-dimethyl-5,6-dihydro-2H-thiopyran-2-thions bzw. -ons und der entsprechenden Tautomeren

The tautomers 4-hydroxy-6,6-dimethyl-5,6-dihydro-2H-thiopyran-2-thione (4 a) and 2-mercapto-6,6-dimethyl-5,6-dihydro-4H-thiopyran-4-one (4 b) resp. were synthesized by hydrolysis of 4-amino-5,6-dihydro-2H-thiopyranthiones6,8. On methylation of4 a,b only the S-methyl product7 is formed. Hydrolysis of 4-amino-2-methylthiothiopyranyliden iodides11 leads—depending on the amino group of11—either to the thiopyranone7 or to the 4-imino-thiopyranes12 and to -amino-,,,-unsaturated-methyldithio carboxylates13. On reaction of4 a,b with hydrogenperoxyd the tautomers 4-hydroxy-5,6-dihydro-2H-thiopyran-2-one5 a and 5,6-dihydro-2H-thiopyran-2,4(3H)diones5 b resp. are formed.4 a,b and5 a,b undergo an aminolysis with prim. and sec. amines to the corresponding 4-amino-2H-thiopyran-2-thiones6,8 and -ones10 resp. On heating in alcohols the 4-alkoxy-thiopyrane-2-thiones and -ones9,14 are formed from4 a,b and5 a,b resp.

     

Beiträge zur Chemie schwefelhaltiger Heterocyclen, 2. Mitt.

Zusammenfassung 6-Nitro-benzo[b]thiophen-1,1-dioxid wurde unter verschiedenen Bedingungen hydriert. Das durchSkraupsche Synthese aus 2,3-Dihydro-6-amino-benzo[b]thiophen-1,1-dioxid gewonnene Produkt konnte auf Grund des NMR-Spektrums als 2,3-Dihydrothieno[2,3-f]chinolin-1,1-dioxid identifiziert werden.

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6-Nitro-benzo[b]thiophene-1,1-dioxide was hydrogenated under various conditions. The product prepared from 2,3-dihydro-6-amino-benzo[b]thiophene-1,1-dioxide by theSkraup synthesis was identified by nmr as 2,3-dihydro-thieno[2,3-f]quinoline-1,1-dioxide.

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1. Mitt.:F. Sauter, Mh. Chem.99, 1507 (1968).     

3-Alkyl- bzw. 3-Aryl-3,4-dihydro-6-methyl-2(1H)-pyrimidinthione durchDimrothumlagerung von 2-Amino-4H-1,3-thiazinen

The 3,4-dihydro-3,4,4,6-tetramethyl- and 4,4,6-trimethyl-3-phenyl-2(1H)-pyrimidinethione (1 c, d), resp. as well as the corresponding trimethyl compound1 e are formed byDimroth rearrangement of 2-methylamino- and 2-amino-4,6,6-trimethyl-6H-1,3-thiazine (2 a, b) and of 3,6-dihydro-4,6,6-trimethyl-2-phenylimino-2H-1,3-thiazine (3 b), resp. The rearrangement takes place under thermal heterolysis of the 1–6 bond of2 a, b and3 b. The reactive behaviour1 c, d is almost equal to1 e, but the pyrimidine ring of1 d is more labile than those of1 c, e.     

Transformation of 5-Oxo Substituted Fused Pyran-2-ones. Lactam Versus Hydrazone Formation

6, 7-Dihydrocyclopenta[b]pyran-2, 5-dione 1 was converted with hydrazines to fused pyridine-2(1H)-ones of type a. In contrast, 2H-1-benzopyran-2, 5-diones 2–4 gave under the same reaction conditions 5-hydrazonobenzopyrans of type b. Calculated heats of formation matched experimental findings.     

Zur Struktur der Tetrahydro-4-phenylspiro([1]benzopyran-2,4′(1′H)-pyrimidin)-2′(3′H)-one bzw.-thione Über Heterocyclen, 49. Mitt

The structures of tetrahydro-4-phenylspiro([1]benzopyran-2,4(1H)-pyrimidin)-2(3H)-ones and-thiones4 a, b resp., are proved by synthesis. 3-(2-methoxy-3,5-dimethylphenyl)-3-phenylpropionic acid11 b is prepared from 3,4-dihydro-6,8-dimethyl-4-phenylcoumarin10. The lithium salt of11 b reacts with isobutenyl-lithium to 1-(2-methoxy-3,5-dimethylphenyl)-5-methyl-1-phenyl-4-hexen-3-on12 a. 12 a is transferred with urea in acid medium and NH₄CNS resp. in a mixture of dihydro-6-[2-(2-methoxy-3,5-dimethylphenyl)-2-phenyläthyl]-4,4-dimethyl-2(1H)-pyrimidinone and-thione13 a, b and tetrahydro-6-[2-(2-methoxy-3,5-dimethylphenyl)-2-phenyläthyliden]-4,4-dimethyl-2(1H)-pyrimidinone and-thione14 a, b resp.14 b leads to13 a, b with H₂O₂. Heating of13 a, 14 a and14 b resp. with pyridin-HCl leads to the spiro compounds4 a, b.     

Beiträge zur Chemie der Pyrrolpigmente, 78. Mitt.: Die Eigenschaften desb-Nor-bilatrien-abc-b-Nor-biladien-ac-Systems

The redox coupleb-nor-biladiene-ac (2)/b-nor-bilatriene-abc (3) exhibits an oxidative half wave potential of 800 mV in acetonitrile solution. It is demonstrated that it can be used as an extremely efficient electron carrier through bulk membranes. Whereas2 is not suitable as a ligand in carrier mediated cation transport,3 is a medium suited carrier for Cu(II) or Zn(II) ions, however, it is the most efficient one found so far for transport of Hg(II) ions. A 1:1 zinc chelate of3 is isolated and characterized. it is deduced to represent a polymer consisting of about 73 monomer units.

     

On the condensation of 2,2-difluoro-4-methyl-benzo[d]-1,3,2-dioxaborines with cyano acetic acid derivatives. Formation and transformation of 3-cyano-4-methyl-benzo[b]pyran-2-ones and their 2-imine precursors

Summary By condensation of 2,2-difluoro-4-methyl-benzo[d]-1,3,2-2H-dioxaborines (12) with cyano acetic acid derivatives in presence of weak bases, 3-cyano-4-methyl-benzo[b]pyran-2-ones (13) or their 3-cyano-4-methyl-benzo[b]pyran-2-imine precursors (14) are available in satisfactory yields.

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Zur Kondensation von 2,2-Difluor-4-methyl-benzo[d]-1,3,2-2H-dioxaborinen mit Cyanessigsäure- Derivaten. Bildung und Umwandlung von 3-Cyano-4-methyl-benzo[b]pyran-2-onen und ihrer 2-Imino-Vorstufen

Zusammenfassung Durch Kondensation von 2,2-Difluor-4-methyl-benzo[d]-1,3,2-2H-dioxaborinen (12) mit Cyanessigsäure-Derivaten in Gegenwart von Hilfsbasen entstehen in befriedigenden Ausbeuten 3-Cyan-4-methyl-benzo[b]pyran-2-one (13) oder ihre 3-Cyan-4-methyl-benzo[b]pyran-2-imino-Vorstufen (14).

     

Insect growth regulators. XVI Syntheses of juvenoids with the 3,3-dimethylcyclohexane system

New cyclic juvenoids containing the 3,3-dimethylcyclohexane (esters16,18,22,26, and ethers28 a, b) or the 5,5-dimethyl-2-cyclohexene system (esters15,17,21,25, and ethers27 a,b) have been obtained by a several-step synthesis starting from dimedone (1). The compounds obtained exhibited morphogenetic activity against larvae ofDysdercus cingulatus and they were inactive on pupae ofTenebrio molitor.

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Insekten-Wachstumsregulatoren. XVI. Synthesen von Juvenoiden mit dem 3,3-Dimethylcyclohexan-System

Zusammenfassung Ausgehend von Dimedon (1) wurden in mehrstufigen Synthesen neue, cyclische Juvenoide hergestellt, die das 3,3-Dimethylcyclohexan- (Ester16,18,22,26 und Ether28 a, b) oder 5,5-Dimethyl-2-cyclohexen-System (Ester15,17,21,25 und Ether27 a, b) enthalten. Die erhaltenen Verbindungen zeigen morphogenetische Aktivität gegenüber Larven vonDysdercus cingulatus und sind inaktiv gegenüber Puppen vonTenebrio molitor.

     

Reaktionen mit cyclischen Oxalylverbindungen, 26. Mitt. Cyclokondensation von 4,5-substituierten Thiophen- bzw. N-Alkylpyrrol-2,3-dionen mito-Phenylendiamin

4-Benzoyl-5-phenylthiophene-2,3-dione (1) reacts witho-phenylendiamine to give the quinoxaline derivative2 which cyclizes either to the furo[2,3-b]quinoxaline4 or to the thieno[2,3-b]quinoxaline5 depending on the reaction conditions. On the other hand, the pyrrol-2,3-diones6 ando-phenylendiamine combine yielding the pyrrolidino[2,3-b][1,5]benzodiazepine derivatives7. The structures of all compounds were confirmed by IR and¹³C NMR spectroscopic measurements based on X-ray structure determinations of4/5 (mixed crystal) as well as7 b.4/5 crystallize triclinically in the space group P1 (Nr. 2) with two molecules per cell, while7 b crystallizes monoclinically in space group P2₁/a (Nr. 14) with four molecules7 b and four moleculesDMSO per cell. The reaction pathways leading to the compounds2,4,5, and7 are briefly discussed.

Herrn em. Univ.-Prof. Dr.E. Ziegler zur Vollendung des 75. Lebensjahres mit besten Wünschen gewidmet.     

Prototropic acetylene-allene isomerization in planarly chiral ferrocenes. Intramolecular acymmetric induction in the course of the formation of chiral axis

Racemic 2-trimethylsilyl- and 2-trimethylstannyl-1-(3-phenyl-2-propynyl)ferrocene (rac-1a,b) as well as the dextrorotatory specimen of the latter, (+)-1b, were synthesized in two steps from racemic 1-formyl-2-trimethylsilyl- and 1-formyl-2-trimethylstannylferrocenes (2a,b) or from the levorotatory specimen of the latter, (–)-2b, respectively. On the contact with strongly alkaline alumina compounds1a,b and (+)-1b undergo diastereoselective prototropic acetylene-allene rearrangement to give predominantly one of the two possible stereoisomers of 2-trimethylsilyl- or 2-trimethylstannyl-1-(3-phenyl-1,2-propadienyl)ferrocenes,rac-4a,b or (+)-4b, depending on the starting material (d. e. 30–40 %). The extent of intramolecular asymmetric induction in the formation of the axially chiral fragment during the transformation of (+)-1b to (+)-4b is estimated at 38 %.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1111– 1115, June, 1994.The work was carried out with financial support from the Russian Fundamental for Basic Research (Project No.93-03-5827).     

Derivate des Methylendioxybenzols, 24. Mitt.

Zusammenfassung Es wird die Synthese des isomerenfreien 2,3-Methylendioxyallylbenzols (o-Safrols) (1 d) durch Einwirkung von Chlorbrommethan auf 2,3-Dihydroxy-allylbenzol (1 b) beschrieben.Durch Behandlung des 4-Hydroxy-3-methoxy-allylbenzols (3 a) mit Kaliumnitrosodisulfonat, Reduktion des entstehenden 3-Methoxy-5-allyl-o-benzochinons (4) mit Natriumdithionit und Methylenierung des 3-Methoxy-5-allyl-brenzcatechins (5) bildet sich Myristicin (3 b) in guter Ausbeute.

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Derivatives of methylenedioxy-benzene, XXIV: Synthesis of o-safrole and of myristicine

Preparation of 2.3-methylenedioxy-allylbenzene (o-safrole) (1 d) free of isomers by reaction of 2.3-dihydroxy-allylbenzene (1 b) with CH₂BrCl is described.Treating 4-hydroxy-3-methoxy-allylbenzene (3 a) with potassium nitrosodisulfonate gives 3-methoxy-5-allyl-o-benzoquinone (4) which ist reduced to 3-methoxy-5-allyl-pyrocatechol (5) with sodium dithionite. Methylenation of3 c gives myristicin with good yield.

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23. Mitt.:F. Dallacker, W. Edelmann undA. Weiner, Ann. Chem.,719, 112 (1968).     

Strukturelle Abwandlungen an partiell silylierten Kohlenhydraten mittels Triphenylphosphan-Azodicarbonsäureester, 5. Mitt.: Transformationen an Glykonolactonen

Reaction ofD-glucono-1,5-lactone1 with two equivalents oft-butyldimethylchlorosilane yields via a ringcontraction 2,6-bis-O-(t-BDMSi)-D-glucono-1,4-lactone2a as main product and a small amount of 5,6-bis-O-(t-BDMSi)-D-glucono-1,4-lactone2c. Under the same conditionsL-mannono-1,4-lactone3 is transformed to the derivatives 2,6-bis-O-(t-BDMSi)-L-mannono-1,4-lactone3a and 3,6-bis-O-(t-BDMSi)-L-mannono-1,4-lactone3c as the minor product. 2,6-bis-O-(t-BDMSi)-D-galactono-1,4-lactone4a and 2,6-bis-O-(t-BDMSi)-D-gulono-1,4-lactone5a are also prepared from the corresponding glyconolactones4 and5. Whereas the compounds2a, 2c, 4a and5a withAc ₂O-pyridine give the bisacetylderivatives2b, 2d, 4b and5b, 3c is converted by an accompanying migration of one silylgroup to the 5,6-bis-O-(t-BDMSi)-2,3-bis-O-acetyl-L-mannono-1,4-lactone3d. The gluconolactone derivative2a reacts easily withTPP/DEAD/HX to the 5-X-L-idono-1,4-lactone derivatives6a (X=N₃),6b (X=p-NO₂-C₆H₄COO) and6c (3-O-acetylderivative of6a). Treating6b with a second equivalentTPP/DEAD/HX leads to the unsaturated sugarlacton7b. Without an external nucleophile2a affords withTPP the mixture of 2,6-bis-O-(t-BDMSi)-3,5-carbonato-D-glucono-1,4-lactone2c, 3,5-anhydro-L-idono-1,4-lactone8 and 3,6-anhydro-D-glucono-1,4-lactone9. Analogous procedures applied to4a yield theL-altronolactonoderivatives10a, 10b and10c, the unsaturated sugarlactone11b on the one and the 3,5-carbonatogalactonolactone4c and the 2,6-bis-O-(t-BDMSi)-3-desoxy-5-ethoxycarbonyl-D-threo-hex-2-en-1,4-lactone12 on the other hand.Whereas the bis-silyletherderivative3a is transformed by the title system exclusively by an elimination process to13, the derivative5a affords withTPP/DEAD without any elimination the 3,6-anhydrosugar14. Partial desilylation of14 followed by acetylation gives the derivatives14a and14b.Structural elucidations were achieved by¹H-NMR-analysis. In some cases also CD-measurements allowed suitable correlations.

Mark, E., Zbiral, E., Brandstetter, H. H., 4. Mitt., Mh. Chem.111, 289 (1980).