β-Fur-2-yl-α-halogenacrylonitrile. VII. Reaktionen von β-(5-Brom-fur-2-yl)-α-bromacrylonitril mit Mercaptan,Thioharnstoff und Thioharnstoffderivaten

β-Fur-2-yl-α-halogenacrylonitriles. VII. Reactions of β-(5-Bromo-fur-2-yl)-α-bromoacrylonitriles with Mercaptans, Thiourea and Thiourea Derivatives β-(5-Bromo-fur-2-yl)-α-bromoacrylonitrile 1 reacts with ethylmercaptan to yield β-(5-bromo-fur-2-yl) β-ethylthioacrylonitrile 3 . With thiourea β,β′-thio-bis[β-(5-bromo-fur-2-yl)]-acrylonitrile 2 is formed. The pyrimidines 4 and 5 have been prepared by the reaction of 1 with s-methylthiourea and 2-aminothiazole, respectively. The structure of the new compounds were determined by means of x-ray analysis, ¹H-n.m.r., ¹³C-n.m.r. and mass-spectroscopy.     

Radikalreaktionen von N-Heterocyclen. I. Synthese und Struktur eines N,N-verknüpften Bipyrazols

Radical Reactions of N-Heterocyclic Compounds. I. Synthesis and Structure of an N,N-Linked Bipyrazole 5(3)-Amino-3(5)-(phenylamino)-pyrazole-4-carboxylic acid ethyl ester ( 1 ), which is a very good antioxidant, reacts under mild reaction conditions with dibenzoyl peroxide or with tert.-butoxy radicals under formation of a bipyrazole 4 . Evidence of the structure of 4 is given by ¹H-n.m.r., ¹³C-n.m.r., i.r. and u.v. spectroscopic measurements, respectively and especially by ¹⁵N-n.m.r. measurements of ¹⁵N labelled compounds 1 and 4 . The bispyrazole 4 reacts with Pb(IV)-acetate, the product isolated was the 5-amino-e-anilino-1-(1-anilino-2-cyano-2-ethoxycarbonylethenyl-azo)-pyrazole-4-carboxylic acid ethyl ester (7). The formation of this substance is a chemical proof of the structure of 4 .     

Reaktionen mit N-Acylimino-dithiokohlensäurediestern

Reactions with N-Acylimino-dithiocarbonic-acid-diesters . Reactions of N-acylimino-dithiocarbonic-acid-S,S-diesters 1 with nucleophilic com-pounds present new possibilities to synthesize heterocycles. With amines 1a reacts by mono- and disubstitution, respectively, of methylthio-groups to isothioureas 2 and guanidines 3 , with 1,2-bi-nucleophilic arenes to benzoheterocycles 4 , with aliphatic diamines to imidazolidines 5 , pyrimidines 6 , diazepines 7 and the hexamethylene-diamine-derivatives 8. 1a reacts also with hydrazines to 1,2,4-triazoles 9 and with hydrazides to the thiosemicarbazones 10 or 1,3,4-oxadiazoles 11 . Heterocyclisations of 1 with guanidines, thiourea, salts of thiourea and amidines give the 1,3,5-triazines 12, 14, 15 and 16 . N-benzoyl-dithiocarbonic-acid-methylester -amid reacts with CH-acidic compounds to thiazoles 17 . The structures of the final products are determined by i.r.-, ¹H-n.m.r.-, u.v.- and mass-spectras.     

Cyclofunktionalisierung von 2-Allyl-phenolen mit Schwefelchloriden 2,3-Dihydrobenzofurfurylthioether aus 2-Allyl-phenolen und aromatischen Sulfenylchloriden

Cyclofunctionalization of 2-Allyl-phenols with Sulfur Chlorides. Synthesis of 2,3-Dihydrobenzofurfuryl Thioethers by the Reaction of 2-Allyl-phenols with Aromatic Sulfenyl Chlorides Reactions of different substituted 2-allyl-phenols ( 2a – h ) with either phenylsulfeny chloride ( 3 ) or 4-methyl phenylsulfenyl chloride ( 4 ) yield the products of a cyclofunctionali zation 2-phenylthiomethyl 2,3-dihydrobenzofuranes ( 6a – h ) or 2-(4′-methylphenyl) 2,3-dihydrobenzofurane ( 7a – g ), respectively. The identification of the products was carried out by mass spectroscopy and ¹H-n.m.r.-spectroscopy. Isomeric compounds, i.e. 3-phenylthio 2,3-dihydrobenzopyranes ( 10 ) were not obtained. The reaction is Markovnilov-directed. In the case of the treatment of 2-allyl-phenols with 2-nitro phenylsulfenyl chloride ( 5 ) we have obtained mixtures of 2-(2′-nitrophenyl) thiomethyl 2,3-dihydrobenzofuranes ( 8a – d ) and of simple Markovnikov adducts, so-called β-chlorothioethers. The mixtures were identified by ¹H-n.m.r.- and mass spectroscopic ( 9a – d ) methods.     

Zur Molekülverknüpfung mit Schwefelchloriden. X. Bis(arylamino-chloralkyl)-sulfane aus N-β-Methallyl-N-tosyl-anilinen und Schwefeldichlorid

Molecule Linkage by Sulfur Chlorides. X. Bis(arylamino-chloroalkyl)-sulfanes from N-β-Methallyl-N-tosyl-anilines and Sulfur Dichloride Reactions of differently substituted N-β-methallyl-N-tosyl-anilines 1 with sulfur dichloride yield bis(arylamino-chloroalkyl)-sulfanes 2 and 3 and dihydrobenzo-1,4-thiazines 4 . The structural assignment of the products 2 and 3 was carried out by mass spectroscopy and ¹H-n.m.r.-spectroscopy.     

Reaktionen geminaler Dithiolate mit (Z)-1,4-Dichlor-but-2-en

Reactions of Geminal Dithiolates with (Z)-1,4-Dichloro-but-2-ene Geminal dithiolates 2 and 7 react with (Z)-1,4-dichloro-but-2-ene either to give 4-vinyl-1,3-dithiolanes 3 or 4, 7-dihydro-1,3-dithiepines 4 and 8 , respectively. Another method for the synthesis of 4 and 8 is the reaction of ketene dichlorides 5 or isocyanide dichloride 9 with the disodium salt of (Z)-but-2-ene-1,4-dithiol. The formation of the corresponding 1,3-dithiolanes can be excluded in these cases. ¹H- and ¹³C-n.m.r. spectra are in accordance with the structures and are discussed.     

Synthese neuer, 3-substituierter 2H-Thiopyran-Derivate via [4+2]-Cycloaddition mittels acceptorsubstituierter Enaminothione

Synthesis of New 3-Substituted 2H-Thiopyran Derivatives via [4+2] Cycloaddition Reactions using Acceptor Substituted Enaminothiones 3- and 4-Nitro acetophenones as well as 3- and 4-trifluoromethyl acetophenones react with POCl₃/DMF (Vilsmeier reagent) to give dimethyliminium perchlorates 1a–d after addition of perchloric acid to the reaction mixture. Substitution of the chloro atom in 1 by using sodium sulfide nonahydrate occurs under mild conditions (in case of nitro compounds at −5°C) leading to enaminothiones 2a–d . Reactions with acroleine and methylvinylketone in refluxing benzene give exclusively 2H-thiopyran derivatives 4a–h , which were isolated in good yields after spontaneous fast elimination of dimethylamine. In contrast, the introduction of 1-nitro-2-phenylethene as the dienophile allows stepwise reaction to give stable adducts 3k and 3l , respectively, and also 3m under mild conditions (reaction at room temperature). ¹H n.m.r. spectroscopic data as well as the elimination of dimethylamine to 4k–m permit the elucidation of the structure of adducts 3k–m .     

Synthese und Reaktionen von 1,3-Azaphosphorinan-2-thionen

Synthesis and Reactions of 1,3-Azaphosphorinane-2-thiones Aminopropylphosphines, R P(H) (CH₂)₃ NH₂, react with carbon disulfide to give 1,3-azaphosphorinane-2-thiones. In presence of strong bases the title compounds are converted by alkyl halides into 2-alkylthio-3, 4, 5, 6-tetrahydro-1, 3-azaphosphorines whereas in absence of bases quaternization at the phosphorus atom occurs to give 2-thiono -1,3-azaphosphorinanium salts. The structures of the compounds prepared are elucidated by IR. ¹H-n.m.r. and mass spectra.     

Organoarsen-Verbindungen. XXVIII [1]. Reaktionen 2-aminofunktioneller Arsine mit Acetylenen

Organo-arsenic Compounds. XXVIII. Reactions of 2-Aminofunctional Arsines with Acetylenes Phenylacetylene and isopropenylacetylene add secondary 2-aminoethylarsines or o-aminophenylarsines to give mixtures of the cis- and trans-styrylarsines and of the trans-4,3-(90%) and 4,1-adducts (10%) to the enine, resp. ¹H-n.m.r.-and i.r.-data of the compounds are recorded.     

Synthese und Reaktionen von 2-[Bis-(alkylthio)-methyliden]-indan-1,3-dionen

Synthesis and Reactions of 2-[Bis-(alkylthio)-methyliden]-indan-1,3-diones The 2-[bis-(alkylthio)-methyliden]-indan-1,3-diones 3 and especially the methyl-compound 3a react with nucleophiles by substitution of the CH₃ S group. The reaction with amines are yields the S,N or N,N-acetales 7 and 8 , respectively. Diamines, amino hydroxy- or amino-mercapto compounds as dinucleophiles give the cyclic compounds 9 or the condensed heterocycles 12 and 16 , where the carbonyl group has been integrated in the cyclisation. Also carbanions react with 3a under substitution. The structures of the final products are determined with ir-, ¹H-n.m.r.- and ms-spectra.     

Synthese und Reaktionen carbocyclischer Acyl-keten-S,S-acetale

Synthesis and Reactions of Carbocyclic Acyl-ketene-S,S-acetales Cyclohexanone, tetralone(1) and indanone(1) react with CS₂ in the presence of bases and after methylation to 2-[bis(methylthio)-methyliden]-cyclohexanones 1,4 -tetralones(1) 2,5 and -indanones(1) 3,6 . In some cases thiophenes 8 and 9 are formed. The dimethyl-S,S-acetales 1, 2a and 3a react with mono or dinucleophiles to S,N- or N,N-acetales, with hydrazines to indazolone 22 or the pyrazole 23 . Oxidation with H₂O₂ yield disulfones 25 and 27 . The structure of products are determined by ir- and ¹H-n.m.r.-spectroscopy.     

Cyclofunktionalisierung von 2-Allyl-phenolen mit Schwefelchloriden. 2-Arylthiomethyl-2,3-dihydrobenzofurane aus 2-Allyl- und 2-Methallyl-phenolen und Arylsulfenylchloriden

Cyclofunctionalization of 2-Allyl-phenols with Sulfur Chlorides: Synthesis of 2-Arylthiomethyl-2,3-dihydrobenzofurans by Reaction of 2-Allyl- and 2-Methallyl-phenols, Respectively, and Arylsulfenyl Chlorides Reactions of acetylamino substituted 2-allyl-phenols ( 1 and 2 ), and 2-methallyl-phenol ( 6 ), respectively, with different arylsulfenyl chlorides ( 3a—d ) yield the products of a cyclofunctionalization 5- or 7-acetylamino-2-arylthiomethyl-2,3-dihydrobenzofurans ( 4a–d ) or ( 5a–d ) and 7-acetylamino-2-arylthiomethyl-2-methyl-2,3-dihydrobenzofurans ( 7a–d ). The compounds 7 are the first examples of cyclofunctionalization of 2-methallylphenols by means of sulfur chlorides. The identification of the products was carried out by mass spectrometry, ¹H-n.m.r. spectroscopy and elemental analysis.     

Aza-Enamine. VI. Umsetzungen von N,N-Dialkylhydrazonen aromatischer Aldehyde mit Sulfonylisocyanaten

Aza-enamines. VI. Reactions of N,N-Dialkylhydrazones of Aromatic Aldehydes with Sulfonyl Isocyanates The electrophilic attack of the sulfonyl isocyanates 2 on the arylaldehyde-N,N-dialkylhydrazones 1 takes place in dependence upon the substitutents R¹ and NR₂ at the nitrogen or carbon of the azomethine-group giving the 5-amino-hexahydro-1,3,5-triazine-2,4-diones 3 , the phenylglyoxylic-acid-sulfonamide-N,N-dialkylhydrazones 4 and/or the imidazolidine-2,4-diones 5 . The preparation and the u.v.-, i.r.- and n.m.r.-spectroscopic dates of the compounds 3 – 5 are reported.     

Reactions of 2-arylhydrazones of 1,2,3-triketones with 1,2-diaminoethane. I. Synthesis and spectral characterization of 6-arylazo-2,3-dihydro-1H-1,4-diazepines and 3,10-diarylazo-4,9-dimethyl-5,8-diaza-3,9-dodecadiene-2,11-diones

Reactions of 3-arylhydrazones of 2,3,4-pentanetrione ( 1a–1e ) and 2-arylhydrazones of 1,3-diphenyl-1,2,3-propanetrione ( 1f–1l ) with 1,2-diaminoethane have been studied. It was found, that 3-arylhydrazones of 2,3,4-pentanetrione react with 1,2-diaminoethane with formation of 6-arylazo-2,3-dihydro-1,4-diazepines ( 2a–2e ) or the diarylazo derivatives of 4,9-dimethyl-5,8-diaza-3,9-dodecadiene-2,11-dione ( 3a–3e ). Analogous reactions of 2-arylhydrazones of 1,3-diphenyl-1,2,3-propanetrione yielded exclusively the derivatives of dihydrodiazepine. The structure of obtained products has been elucidated on the basis of i.r., m.s. and ¹H-n.m.r. spectra.     

Synthesen mit 1,3-Dithietanen. IX [1]. Reaktionen des 2,4-Bis-(äthoxycarbonyl-cyan-methylen)-1,3-dithietans und des 2-Cyan-3,3-bis-(methylmercapto)-acrylsäureäthylesters mit Carbonsäurehydraziden

Syntheses with 1,3-Dithietanes. IX. Reactions of 2,4-Bis(ethoxycarbonyl-cyano-methylene)-1, 3-dithietane and of Ethyl 2-cyano-3, 3-bis(methylmercapto)acrylate with Carboxylic Acid Hydrazides 2, 4-Bis(ethoxycarbonyl-cyano-methylene)-1, 3-dithietane 1 reacts with carboxylic acid hydrazides to yield ethyl 1-aroyl-5-imino-3-mercapto-Δ³-pyrazoline-4-carboxylates 4. 4 and hydrazin hydrate yield ethyl 1-aroyl-5-imino-3-hydrazino-Δ³-pyrazoline-4-carboxylates 5 which are transformed by heat to the ethyl 3(5)-amino-5(3)-(2-aroyl-hydrazino)pyrazole-4-carboxylates 6 . The reaction of ethyl 2-cyano-3,3-bis(methylmercapto)acrylate 8 with carboxylic acid hydrazides yield ethyl 1-aroyl-3-amino-5-methylmercapto-pyrazole-4-carboxylates 10 . Compounds 10 are compared with S-methyl derivatives of 4 .     

Über die Reaktionen von Benzimidazol-2-carbonsäurehydrazid mit Elektrophilen

About the Reactions of Benzimidazole-2-carbohydrazide with Electrophilic Compounds Benzimidazole-2-carbohydrazide ( 1 ) reacts with aldehydes and ketones to form N-alkylidene-benzimidazole-2-carbohydrazides( 2a–j ). With carbon disulfide, diphenyl carbonate and cyanates, ring closure takes place to afford 1,2,4-triazines and 1,3,4-oxadiazoles. Attempts to synthezise 2-isocyanato-benzimidazole failed. ¹H-n.m.r. and ¹³C-n.m.r. spectroscopic data of the compounds are given.     

Zur Molekülverknüpfung mit Schwefelchloriden. IX. Reaktion von Schwefeldichlorid mit N-Allyl-anilinen. Eine Synthese für 2-Chlormethyl-2,3-dihydro-1,4-benzothiazine

Molecule Linkage by Sulfur Chlorides. IX. The Addition Reaction of Sulfur Dichlorides with N-Allyl-anilines. A Synthesis for 2-Chloromethyl-2,3-dihydrobenzo-1,4-thiazines Reactions of different substituted N-allyl-anilines 1 with sulfur dichloride yield 2-chloromethyl-2,3-dihydrobenzo-1,4-thiazines 3a – i . The identification of the products was carried out by mass spectroscopy and ¹H-n.m.r.-spectroscopy. The seven-membered cyclic isomers of the S, N-heterocycles 3 , dihydro-benzo-1,5-thiazepanes 5 were not obtained.     

Cyclofunktionalisierung von 2-Allyl-phenolen mit Schwefelchloriden. III. 2-Arylthiomethyl-2,3-dihydrofuro[3,2-h]chinoline aus 7-Allyl- bzw. 7-Methallyl-8-hydroxychinolin und Aryl-sulfenylchloriden

Cyclofunctionalization of 2-Allyl-phenols with Sulfur Chlorides. III. 2-Arylthiomethyl-2,3-dihydrofuro[3,2-h] quinolins from 7-Allyl- and 7-Methallyl-8-hydroxyquinoline, respectively, and Arylsulfenyl Chlorides Reactions of 7-allyl- ( 3 ) and 7-methallyl-8-hydroxyquinoline ( 4 ) with selected arylsulfenyl chlorides ( 5a – d ) yield the products of cyclofunctionalization corresponding 2-arylthiomethyl-2,3-dihydrofuro[3,2-h]quinolins ( 6 and 7 ). The products are identified by ¹H-n.m.r.-spectroscopy, mass spectrometry and microanalyses.     

The reaction between trityl hexachloroantimonate and 1,2-dimethoxy-4-(1-propenyl)-benzene

Summary Reactions between triphenylmethyl hexachloroantimonate and 1,2-dimethoxy-4-(1-propenyl) benzene in methylene dichloride were studied by liquid chromatography, n.m.r. and visible spectroscopy. The system is characterised by slow initiation, shown to proceed through an addition reaction, and propagation only to the dimer stage, enabling simple analysis of the initiation kinetics. Similarities between this system and the anethole-trityl salt system were observed including initiation rate constants on the order of 10^–3dm³ · mol^–1 · sec^–1 and the development of a chromophore at 545 nm which is probably due to a side reaction of the propagating cation.     

Reaktionen von β-Chlorvinylaldehyden. IV [1]. Synthesen von 2-Formylmethylen-2H-1-benzopyranen und Benzopyrylocyaninfarbstoffen aus β-Chlorvinylaldehyden

Reactions of β-Chlorovinylaldehydes. IV. Syntheses of 2-Formylmethylene-2H-1-benzopyranes and Benzopyrylocyaninedyes from β-Chlorovinylaldehydes α-Alkyl-β-chlorocrotonaldehydes react with salicylaldehyde in methanolic solution of potassium hydroxide forming 2-formyl-methylene-2H-1-benzopyranes 1 . The corresponding benzopyryliumsalts 2 which are easily available from 1 and strong acids, exist in the enolic form. They react at room temperature in alcoholic solution with elimination of ethyl formiate, yielding dark blue compounds which were identified as 2,2′-benzopyrylotrimethincyanindyes 3 . The structure of 3 has been elucidated by means of ¹H-n.m.r.-spectra.