2-benzazepines. 10 [1]. New d-fused 2-benzazepines

Pyrano[3,2-d][2]benzazepines were synthesized by reaction of the beta-dimethylamino unsaturated ketone 1 with malonic ester or the anion of t-butyl acetate. Conversion of the pyrano derivative to the pyrido[3,2-d]-[2]benzazepine was achieved in low yield. A pyrrolo[3,2-d][2]benzazepine was prepared via an oxazepino-[6,7-d][2]benzazepine which was obtained by reaction of 1 with the anion of ethyl isocyanoacetate.     

Chemistry of thienopyridines. XXXVIII. Diels-Alder reactions of thienopyridine sulfones. Part 2

Thieno[3,2-b]pyridine 1,1-dioxide ( 2 ) undergoes Diels-Alder condensation with the dienophiles cyclopentadiene, anthracene, and naphthacene in a manner analogous to its isomer thieno[2,3-b]pyridine 1,1-dioxide ( 1 ). Compound 2 dimerizes in refluxing xylene with the loss of sulfur dioxide plus either the loss or transfer of hydrogen to give a small yield (ca. 2%) of pyrido[2′,3′:4,5]thieno[3,2-f]quinoline 7,7-dioxide ( 7 ) and its 5,6-dihydro derivative 12 . Formation of 7 and 12 are compared and contrasted with products reported from dimerization of 1 and of benzo[b]thiophene 1,1-dioxide and its derivatives.     

Über die Synthese von 1-Aryl-und 1-Alkyl-2, 3-dimethyl-chinoxalinium-perchloraten. 2. Mitteilung. Synthese und 1H-NMR.-Spektren von 2,3-Dimethyl-1-phenyl-6-X-chinoxalinium-perchloraten

On the Synthesis of 1-Aryl- and-1-Alkyl-2, 3-dimethyl-quinoxalinium Perchlorates. 2nd Communication

1 1. Mitt.: [1].

. Synthesis and ¹ H-NMR. Spectra of 2, 3-Dimethyl-1-phenyl-6-X-quinoxlinium Perchlorates The synthesis of the title compounds ( 5 ) which have been useful as precursors for a lot of conventional and new-type dyes [2-8] has yet been limited to examples with X?H [2] [3] [11] [15] and with electron-donating [4] [12] or at best slightly electron-accepting [1] [6] substituents X and R. We now describe a method suitable even for compounds 5 with strongly electron-accepting substituents: N-monosubstituted o-phenylendiamines 4 , were condensed with 2, 3-butanedione and perchloric acid in mixed solvents containing an excess of diethyl ether. The products - mostly substituted at position 6 of the quinoxalinium ring - are chracterized by ¹H-NMR. spectra, elemental analyses and in most cases by isolation of the corresponding bases 6 . Correlations of chemical shifts with Hammett's σ_p [18] are given by equations (1)-(5).     

11. Anil-Synthese. 16. Mitteilung. Über die Herstellung von styryl-derivaten des 2-phenyl-imidazo [1,2-a]pyridins

Preparation of styryl derivatives of 2-phenyl-imidazo [1, 2-a]pyridine 2-(p-Tolyl)-imidazo [1, 2-a]pyridines and 7-methyl-2-phenyl-imidazo [1,2-a]-pyridines can be converted, in dimethylformamide, on reaction with anils of aromatic aldehydes in the presence of potassium hydroxide or potassium t-butoxide, into the corresponding 2-(stilben-4-yl)- and 2-phenyl-7-styry1-imidazo [1, 2-a]-pyridines (‘Anil-Synthesis’). The 2-(p-tolyl)-imidazo [1,2-a]pyridines react far less readily than the 7-methyl-2-phenyl-imidazo[1,2-a]pyridines.     

Synthesen von Chinoxalonderivaten, 2.Mitt.

Zusammenfassung Es wird die Synthese verschiedener Benzo[f]chinoxalone beschrieben.The synthesis of several benzo[f]quinoxalones is described.1. Mitt.:M. Pailer, G. Pruckmayr, H. Zellner undGertraud Zellner, Mh. Chem93, 1005 (1962).     

[2 + 2]-Cycloadditions to Strained Bridgehead Olefins. II. Diphenylketene

The strained bridgehead olefins bicyclo [3.3.1]non-1-ene ( 1 ), bicyclo [4.2.1 ]non-1(8)-ene ( 2 ), and bicyclo [4.2.1]non-1-ene (3), and the comparable monocyclic (E)-1-methylcyclooctene ( 4 ) react with diphenylketene ( 6 ) to give a single cycloadduct 7 , 8 , 9 and 10 , respectively, in which the diphenyl-substituted C-atom is bound to the bridgehead. The structure of the cyclobutanone 8 has been determined by X-ray analysis of a twin crystal obtained by crystallization with spontaneous enrichment of enantiomers.     

Über Reaktionen von Nitrosophenolen, 2. Mitt.: Reaktion von 1-Nitroso-2-naphthol mit Orein

Zusammenfassung In der vorliegenden Arbeit wurde die Reaktion von 1-Nitroso-2-naphthol mit Orcin in Äther bei Anwesenheit von HNO₃ studiert. Als Reaktionshauptprodukte wurden 11-Methylbenzo[a]-phenoxazon-(9) (1) sowie dessen 12-Oxid (2) isoliert. Der Reaktionsmechanismus und die Konstitution der erhaltenen Substanzen werden diskutiert. Ferner wurden auch 11-Methyl-5-hydroxy-benzo[a]phenoxazon-(9) (6), 11-Methyl-5-äthoxybenzo[a]phenoxazon-(9), 11-Methyl-5-methoxybenzo[a]phenoxazon-(9) (4), 11-Methyl-5-aminobenzo[a]phenoxazon-(9) (7) und 11-Methyl-5-anilinobenzo[a]phenoxazon-(9) (8) dargestellt.

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In this paper the reaction of 1-nitroso-2-naphthol with orcin in an ether medium in presence of HNO₃ is described. As main products 11-methylbenzo[a]phenoxazone-(9) (1) as well as its 12-oxide (2) were isolated. The reaction mechanism is presented. Identity of the reaction products is verified. 11-methyl-5-hydroxybenzo[a]phenoxazone-(9) (5), 11-methyl-5-methoxybenzo[a]phenoxazone-(9) (4), 11-methyl-5-aminobenzo[a]phenoxazone-(9) (7) and 11-methyl-5-anilinobenzo[a]phenoxazone-(9) (8) are prepared.

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Mit 2 Abbildungen     

Condensed Pyridazines. Part I. Synthesis of 2-Oxo-2H-pyrano[2,3-D]-pyridazine and 2-Oxo-2H-pyrano[2,3-c] pyridazine

The reaction of 4,7-diehlorofuro[2,3-d]pyridazine (1) with potassium cyanide in DMSO gave two products, (E)-3,6-diehloro-5-(2-cyanovinyl)-4-hydroxypyridazine (II) and 5,8-dichloro-2-oxo-2H-pyrano[2,3-d]pyridazine (III) as a result of ring opening or ring expansion. A new ring system, 2-oxo-2H-pyrano[2,3-c]pyridazines (IX, XII, XIII) was obtained from 5,8-dichloro-3-methyl-2-oxo-2H-pyrano[2,3-d]pyridazine (VI).     

Saturated heterocycles. 57. Synthesis of 4-substituted-9,10-dialkoxy-1,6,7,11b-tetrahydro-2H-pyrimido[6,1-a]isoquinolin-2-ones

A large number of 4-substituted-9,10-dialkoxy-1,6,7,11b-tetrahydropyrimido[6,1-a]isoquinolin-2-ones were prepared by the reaction of 1-(ethoxycarbonylmethyl)-6,7-dialkoxy-1,2,3,4-tetrahydroisoquinolines with iminoethers. Reaction of the corresponding isoquinoline-1-acetic acid derivatives with iminoethers led to the formation of N-acyl-1,2,3,4-tetrahydroisoquinolin-1-acetamides. In the hydrolysis of the prepared 4-substituted-pyrimido[6,1-a]isoquinolin-2-ones, the corresponding N-acyl-1,2,3,4-tetrahydroisoquinolin-1-acetamides were obtained. While reduction of the 4-phenyl derivative resulted in the corresponding 1,3,4,6,7,11b-hexahydropyrimidinone. The steric structures of the tetrahydro- and hexahydropyrimido[6,1-a]isoquinolines were determined by nmr spectroscopy.     

Spirocyclohexadienones. 7. Three-component condensation of 1- or 2-methoxynaphthalene with isobutyraldehyde and nitriles

1-R-3,3-Dimethylbenzo[i]-2-azaspiro[4.5]deca-1,6-dien-8-ones or 1-R-3,3-dimethylbenzo[i]-2-azaspiro[4.5]deca-1,7-dien-6-ones were synthesized by three-component condensation of 1- or 2-methoxynaphthalene, isobutyraldehyde (or isobutylene oxide), and nitrile RCN in concentrated sulfuric acid.     

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).     

2-benzopyrylium salts. 33. 4-1′-Dimerization of 2-benzopyrylium salts. Formation of benz [a] anthracenes

The conversion of 2-benzopyrylium salts to benz [a] anthracenes, which proceeds through prior dimerization of a new type, was observed. An intermediate dimer was isolated, its properties were studied, and assumptions regarding the mechanisms of its formation and conversion to benz [a] anthracenes, cenes were expressed.See [1] for Communication 32.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1185–1189, September, 1988.     

Cycloaddition in Condensed Isoindoles. 2. Method for Obtaining New Derivatives of 2-Phenylpyridine

The reaction of pyrido[2,1-a]isoindole with maleimide derivatives has been investigated. A new rearrangement has been found, the products of which are 2-[2'-(1-R-2,5-dioxopyrrolidinidene)-2'-(1-R-2,5-dioxopyrrolidinyl)methyl]phenylpyridines. A probable mechanism for the rearrangement has been proposed. The existence of atropoisomerism for the compounds obtained has been demonstrated by ¹H NMR spectra.     

Mass spectrometry of nitrogen heterocycles. 3. Thermal intramolecular cyclization of 2-azolylaminopyridines

Mass spectrometric fragmentation or decay of 2-azolylaminopyridines containing a carbonyl group in the ortho-position results in elimination of a neutral molecule (ammonia, ethanol, hydrogen sulfide). This decay process is accompanied by intramolecular cyclization to form an ion with a triazolo[1,5-a]pyrido[2,3-d]pyrimidine structure.For Communication 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 101–104, January, 1991.     

Dipyrrolo[1,2-a:2',1'-c]pyrazines. 8. Electrophilic Substitution in Dipyrrolo[1,2-a:2',1'-c]pyrazines and 5,6-Dihydrodipyrrolo[1,2-a:2',1'-c]pyrazines. Acylation of Dipyrrolo[1,2-a:2',1'-c]pyrazines

Esters, nitriles, and amides of dipyrrolo[1,2-a:2',1'-c]pyrazines have been synthesized by the acylation of dipyrrolo[1,2-a:2',1'-c]pyrazines and 5,6-dihydrodipyrrolo[1,2-a:2',1'-c]pyrazines with trichloroacetic acid chloride, p-tosyl isocyanate, and isocyanatophosphoric acid dichloride (Kirsanov isocyanate).     

Untersuchungen zum elektronischen Einfluß von Organoliganden. XIII. Synthese und Charakterisierung von 2-funktionalisierten Vinylrhodoximen

Studies on the Electronic Influence of Organoligands. XIII. Synthesis and Characterization of 2-Functionalized Vinyl Rhodoximes 2-Functionalized vinyl rhodoximes [Rh(dmgH)₂ (PPh₃)cis/trans-CH = CHZ] ([Rh]? CH = CHZ) ) ( 1 ) can be prepared with a wide variation of the substituent Z (cis: OEt ( 1 a ), OPh ( 1 b ), Cl ( 1 c ), Me ( 1 j ), Ph ( 1 k ), SMe ( 1 l ), SPh ( 1 m ); trans: SPh ( 1 d ), Me ( 1 e ), Ph ( 1 f ), CMe₃ ( 1 g ), SiMe₃ ( 1 h )) by oxidative addition of XCH = CHZ and/or by nucleophilic addition of HC?CZ and Me₃SiC?CZ, respectively, to [Rh]^?. 1 a is converted to [Rh]? CH₂CHO ( 2 ) already in a weakly acid medium. 1 l is isomerized to trans-[Rh]? CH = CHSMe ( 1 n ) in the presence of acids. The complexes 1 are characterized by microanalysis and by ¹H, ¹³C and ³¹P NMR spectroscopy. The magnitude of the coupling constants ¹J(¹⁰³Rh, ³¹P) reveals only a small effect of Z on the (NMR) trans influence of the vinyl ligands CH = CHZ. The molecular structures of cis-[Rh]? CH = CHSPh ( 1 m ) and trans-[Rh]? CH = CHSPh ( 1 d ) show a distorted octahedral coordination of Rh with a mutual trans position of triphenyl-phosphine and the 2-phenylmercaptovinyl ligands. Van der Waals interactions exist between the sulfur and the equatorial dimethylglyoximato ligands in the cis complex 1 m .     

Reactions of 2-aminooxazoles and 2-aminothiazoles with dienophiles. Isolation of stable diels-alder adducts

Room temperature reaction of 2-aminooxazole 1 and its 4- and 4,5-substituted derivatives, with dimethyl acetylenedicarboxylate gave good yields of Diels-Alder adducts 2 , isolated as stable crystalline compounds. A competing process produced oxazole[3,2-a]pyrimidines 3 , also in good yield. Minor products were also identified. 2-Amino-4-methylthiazole ( 6 ) reacted in a similar manner and gave the Diels-Alder adduct 7 and a thia-zolo[3,2-a]pyrimidine 8 as main products with a lesser amount of a thiazole [3,2-d][1:3]diazepine ( 9 ). The aminooxazoles reacted with olefinic dienophiles to give pyridine derivative, formed by breakdown of the original unstable adducts.     

Pyridinethiones. VI. The synthesis of 2H-Thiopyrano[2,3-b]pyridin-2-ones

A general and versatile method for the preparation of 2H-thiopyrano[2,3-b]pyridin-2-ones is described. The starting materials, the β, β-disubstituted vinyl-1-t-butyl-2-(1H)pyridinethiones were prepared from the synthon 3-formyl-1-t-butyl-2-(1H)pyridinethione by condensation. ¹³H nmr spectra showed the vinyl double bond of the condensation products to have the trans configuration with the smallest group close to the sulfur atom. Some reactions of these new azaanalogues of thiocoumarins are reported.     

Electrospray-Ionization Mass Spectrometry. Part 2. Neighboring-Group Participation in the Mass-Spectral Decomposition of 4-Hydroxycinnamoyl-spermidines

The three mono substituted N-[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]spermidines 1–3 have been studied by positive-ion electrospray-ionization tandem mass spectrometry (ESI-MS/MS). Because of the neighboring-group participation, the MS/MS of [ 1 + H]⁺ and [ 2 + H]⁺ are essentially similar, while compound 3 can be easily distinguished from 1 and 2 because of the characteristic ions at m/z 218. However, with the source collision-induced dissociation (source-CID) MS/MS technique, the compounds 1 and 2 can be unambiguously distinguished by the signal of the pyrrolidinium ion (m/z 72) from their daughter ion (m/z 275). The source-CID MS/MS of the labeled compound N-(4-aminobutyl)-N-(3-aminopropyl)-N-[3-(4- hydroxyphenyl)prop-2-en[¹⁵N]amide] ([¹⁵N(4)]- 2 ) provide more information on the decomposition mechanisms and proved the occurrence of a partial transamidation reaction 2→1 during the measurement.     

Studies on ketene and its derivatives. CXI . Photoreaction of diketene with 2(1H)-quinolone derivatives

Photoreaction of diketene with 4-methyl-2(1H)-quinolone and 1,4-dimethyl-2(1H)-quinolone gave 2R*,2aR*,SbR*- and 2R*,2aS*8bS*-8b-methyl-3-oxo-1,2,2a,3,4,8b-hexahydrocyclobuta[c]quinoline-2-spiro-2′-(oxetan)-4′-one ( 6a and 6b ), and their 4-methyl derivatives 7a and 7b , respectively. Thermolysis of compounds 6 and 7 afforded 2aR*,8bS*-8b-methyl-2-methylene-3-oxo-1,2,2a,3,4,8b-hexahydrocyclobuta[c]quinoline ( 8 ) and its 4-methyl derivatives 9 , respectively. Similarly, photolysis of diketene and 4-acetoxy-2(1H)-quinolone gave 1R*,2aS*,8bS*- and 1R*,2aR*,8bR*-8b-acetoxy-3-oxo-1,2,2a,3,4,8b-hexahydrocyclobuta[c]-quinoline ( 11a and 11b ). Alcoholysis of compounds 11a and 11b with hydrogen chloride in methanol gave 1-hydroxy-1-(methoxycarbonyl)methylcyclobuta[c]quinoline derivative 12 and 13 which were transformed to 4-acetyl-3-methyl-2(1H)-quinolone ( 15 ) by further alcoholysis. Photoreaction of diketene with 2(1H)-quinolone derivatives gave the corresponding cyclobuta[c]quinoline spirooxetanone derivatives 18 and 23 , which, by thermolysis, were transformed to 2-methylenecyclobuta[c]quinoline 23 and 25 , respectively.