Folgeprodukte halogenierter Aldehyde. XIV [1]. Synthesen mit 1,2,2,2-Tetrachlorethylisocyanat

Derivatives of Halogenated Aldehydes. XIV. Reactions of 1,2,2,2-Tetrachloroethyl Isocyanate 1,2,2,2-Tetrachloroethyl isocyanate 2 reacts with alcohols or phenols to form the N-tetrachloroethyl-O-alkyl(aryl) urethanes 3–6 . With thioalcohols and thiophenols the corresponding thiourethanes 11–12 are obtained. In these compounds the chlorine in position 1 can be substituted by treatment with a nucleophilic compound in the presence of a base by way of an elimination addition mechanism. In these reactions the compounds 7–10 and 13–14 are formed. Amines attack 2 at both active centres to give the substituted ureas 15–18 . Diphenyl amine, some carboxylic acid amides and benzazoles, however, react only with the isocyanate group to form the compounds 19–25 . Reactions of 2-amino-benzazoles, 2-amino-pyridine and amidines with 2 yield the heterocyclic compounds 26–31 .     

Folgeprodukte halogenierter Aldehyde. XVI [1]. Untersuchungen über Chloralammoniak

Derivatives of Halogenated Aldehydes. XVI. Investigations of Chloralammonia N-(1,2,2,2-Tetrachloroethyl)trichloroacetaldimine 8 is formed by heating of chloral-ammonia 2 with thionyl chloride. The reaction of 2 with phosphorus pentachloride in ether leads to a mixture of aldimine 8 , 1,2,2,2-tetrachloroethyl-phosphorodichloridate 5 , N-(1,2,2,2-tetrachloroethyl)-phosphorimidic acid trichloride 6 and N-(1,2,2,2-tetrachloroethyl)-phosphoramidic acid dichloride 7 . From compound 7 , the phosphoramidic acid ester 9 , the substituted phosphoric acid triamide 10 and the N-dichlorophosphoryl trichloroacetaldimine 11 are obtained on treatment with methanol, isopropyl amine or triethyl amine, respectively. Compound 9 is also formed from 6 by reaction with methanol. The data of i. r. spectra are concordant with the assigned structures of the compounds 6–11 .     

Folgeprodukte halogenierter Aldehyde. VI [1]. Die Addition von Phosphorpentachlorid an Chloral

Derivatives of Halogenated Aldehydes. VI. The Addition of Phosphorus Pentachloride to Chloral 1,2,2,2-Tetrachloroethoxy-phosphorus-tetrachloride 1 is obtained by reaction of chloral with an excess of phosphorus pentachloride in carbon tetrachloride at 35–40°C. Hydrolysis of 1 with water yields 1,2,2,2-tetrachloroethyl-phosphorodichloridate 2 . Compound 1 is reduced with white phosphorus to give 1,2,2,2-tetrachloroethyl-phosphorodichloridite 3 . The structures of 1, 2 , and 3 are determined by i. r. and n.m.r. analysis.     

Folgeprodukte halogenierter Aldehyde. X. Die Synthese von O-Polyhalogenalkyl-dichlorphosphaten und O,O-Dialkyl-O-polyhalogenalkyl-phosphaten

Derivatives of Halogenated Aldehydes. X. The Synthesis of O-Polyhalogenoalkyl Phosphorodichloridates and O,O-Dialkyl-O-polyhalogenoalkyl Phosphates The phosphorodichloridates 2a – e are prepared by reaction of halogenated aldehydes or of glyoxylic acid n-butyl ester with phosphorus pentachloride or PCl₃Br₄ and subsequent treatment with sulfur dioxide. The compounds 2a – e give the phosphates 3a – i by reaction with alcohols.     

Folgeprodukte halogenierter Aldehyde. XIII. [1] Eine Neue Synthese für O,O-Dialkyl-O-polyhalogenalkyl-thionophosphorsäureester

Derivatives of Halogenated Aldehydes. XIII. A New Synthesis of O,O-Dialkyl-O-poly-halogenoalkyl-thionophosphates O-Polyhalogenoalkyl-thionophosphoric acid ester dichlorides 2 are obtained by treatment of polyhalogenoalkoxy-phosphorus tetrachlorides with hydrogen sulphide. The reactions of 2 with alcohols lead to the O, O-dialkyl-O-polyhalogenoalkyl-thionophosphates 4 .     

Synthese und Polymerisation von 2-Aryl-5-methylen-1,3-dioxolan-4-onen und Arylbis(5-methylen-1,3-dioxolan-2-yl-4-on)en

Synthesis and Polymerization Behaviour of 2-Aryl-5-methylene-1,3-dioxolan-4-ones and Arylbis(5-methylene-1,3-dioxolan-2-yl-4-on)es Starting from 2,6-di(hydroxymethyl)-4-methylphen-ol-Na-salt-1-hydrate ( 1 ) a synthesis of 2-alkoxy-5-methyliso-phthaldialdehydes ( 3a,b ) is described via alkylation and oxidation. Condensation of aromatic aldehydes with 3-bromo-2-hydroxypropanoic acid (β-bromolactic acid) affords diastereoisomeric mixtures of new 2-aryl-5-bromomethyl-1,3-dioxolan-4-ones ( 6a–h ) as well as the corresponding bisdioxolanones ( 6i–l ). Dehydrobromination of 2-aryl-5-bromomethyl-1,3-dioxolan-4-ones ( 6a–d,i ) with DBU leads to 2-aryl-5-methylene-1,3-dioxolan-4-ones ( 8a–e ). Polymerization of compounds 8a , b , d and e proceed via opening of the dioxolanone ring.     

Folgeprodukte halogenierter Aldehyde IX. Die Synthese von Dialkyl-1,2,2,2-tetrachloräthyl- und Alkyl-phenyl-1,2,2,2-tetrachloräthyl-phosphaten

Derivatives of Halogenated Aldehydes. IX. The Synthesis of Dialkyl-1,2,2,2-tetrachloroethyl- and Alkyl-phenyl-1,2,2,2-tetrachloroethyl Phosphates Dialkyl-1,2,2,2-tetrachloroethyl- ( 3a – t ) and alkyl-phenyl-1,2,2,2-tetrachloroethyl phosphates 3u , v are prepared by reactions of 1,2,2,2-tetrachloroethyl phosphorodichloridate 1 with one mole of an alcohol or phenol to give alkyl(phenyl)-1,2,2,2-tetrachlorethyl phosphorochloridates 2a – k , followed by treatment of the latter with a second alcohol. The n.m.r. spectra of 2 and 3 are discussed.     

Folgeprodukte halogenierter Aldehyde. XV. Derivate der Aryl-(3,3,3-trichlor-2-hydroxy-propyl)-ketone

Derivatives of Halogenated Aldehydes. XV. Derivatives of Aryl 3,3,3-trichloro-2-hydroxy-propyl Ketones From aryl 3,3,3-trichloro-2-hydroxy-propyl ketones 1a – e , the oximes 6a – e , phenylhydrazones 5a – e , aryl 2,3,3,3-tetrachloro-propyl ketones 3b – d and aryl 3,3,3-trichloropropen(1)-yl ketones 2a – e are prepared. The phenylhydrazones 5a , b form the substituted Δ³-1,2,4-triazolines 4a , b by treatment with thiocyanic acid.     

Folgeprodukte halogenierter Aldehyde. XVII. Reaktionen des N-(1,2,2,2-Tetrachlorethyl)-trichloracetaldimins mit Alkoholen und Mercaptanen

Derivatives of Halogenated Aldehydes. XVII. Reactions of N-(1,2,2,2-Tetrachloroethyl)trichloroacetaldimine with Alcohols and Thioalcohols Reactions of N-(1,2,2,2-tetrachloroethyl)trichloroacetaldimine 1 with methanol lead to 1,2,2,2-tetrachloroethyl-(2,2,2-trichloro-1-methoxyethyl)amine 2a , N-(2,2,2-trichloro-1-methoxyethyl)trichloroacetaldimine 3a and bis-(2,2,2-trichloro-1-methoxyethyl)amine 5 . After the reaction of the aldimine 1 with ethanol or propanol only the N-(1-alkoxy-2,2,2,-trichloroethyl)trichloroacetaldimines 3b, c are isolated; with thioalcohols only the N-(1-alkylthio-2,2,2-trichloroethyl)-trichloroacetaldimines 4a–c are obtained. The aldimines 3a–c and 4b, c are decomposed on treatment with hydrochloric acid and an excess of an alcohol or thioalcohol to yield the amine hydrochlorides 6a–c, 7b, c , which are transformed into the amines 8a–c and 9b, c . From these amines the derivatives 10–15 are prepared.     

Folgeprodukte halogenierter Aldehyde. VII [1] Die Synthese von Di-(1,2,2,2-tetrachloräthyl)-chlorphosphat und Tri-(1,2,2,2-tetrachloräthyl)-phosphat

Derivatives of Halogenated Aldehydes. VII. The Synthesis of Di-(1,2,2,2-tetrachloroethyl) phosphorochloridate and Tri-(1,2,2,2-tetrachloroethyl) phosphate Reaction of phosphorus pentachloride with an excess of chloral in carbon tetrachloride yields a mixture of the tetrachloroethoxy-phosphorus-chlorides 1 — 4 . Following elimination of pentachloroethane by heating gives a mixture of phosphorus oxychloride, tetrachloroethyl phosphorodichloridate 6 , di-(tetrachloroethyl)phosphorochloridate 7 and tri-(tetrachloroethyl) phosphate 8 , which are separated by distillation in vacuo. The data of i.r., n.m.r. and mass spectra are concordant with the assigned structures.     

Photochemie substituierter Cycloheptatriene. XI [4]. Cyclisierung und Cycloreversion

Photochemistry of Substituted Cycloheptatrienes. XI. Cyclization and Cycloreversion The photo-valence-isomerization of 1-(p-dimethylaminophenyl)-4-aryl-cycloheptatrienes has been studied. The photoreactive state is assumed by a long wave emission state. The dependence of reaction quantum yields on solvents and substituents points out that the reactive state is not very polar contrary to the assumption in the literature. Reactivity indices from front orbitals cannot describe the ring closure. The parameters for thermically induced cycloreversion are discussed.     

Photochemie diarylsubstituierter 2H-Tetrazole. XI [1] Sydnone V [2]. Blitzlichtphotolytische Untersuchungen an 2,5-Diaryl-2H-tetrazolen und 3,4-Diarylsydnonen Absolute Cycloadditionsgeschwindigkeitskonstanten von Diarylnitriliminen an Dipolarophile

Photochemistry of Diarylsubstituted 2H-Tetrazoles, XI and Sydnones. V. Flashphotolytic Investigations with 2,5-Diaryl-2H-tetrazoles and 3,4-Diarylsydnones. Absolute Rate Constants of Cycloadditionreactions of Diarylnitrile Imines to Dipolarophils The flash photolysis of 2,5-Diaryl-2H-tetrazoles 1 and 3,4-Diarylsydnones 2 was investigated. The nitrile imines were detected spectroscopically as short living intermediates. Rate constants of the cycloaddition reaction of nitrile imines and dipolarophiles were determined and the influence of substituents in the dipolarophile as well as in the nitrile imine is discussed. The results agree quite well with SUSTMANN 'S theroetical classification of 1,3-dipolar cycloaddition reactions.     

Pyryliumverbindungen. 43 [1]. Arylsubstituierte 5-(2-Dialkylamino-thiazol-5-yl)-pentadienone aus 2,4,6-Triaryl-pyryliumsalzen und 2-Dialkylamino-4-arylthiazolen

Pyrylium Compounds. 43. Arylsubstituted 5-(2-Dialkylamino-thiazol-5-yl)-pentadienones from 2,4,6-Triarylpyrylium Salts and 2-Dialkylamino-4-aryl-thiazoles 2,4,6-Triarylpyrylium salts 1 react with 2-dialkylamino-4-aryl-thiazoles 7 (used in substance or prepared in situ from α-thiocyanato-acetophenones 9 ) in the presence of an appropriate acid-binding agent (e.g. piperidine acetate or sodium acetate) to give 5-(2-dialkylamino-4-aryl-thiazol-5-yl)-1,3,5-triaryl-penta-2,4-dien-1-ones 8 . As reaction medium aliphatic alcohols (ethanol, n-propanol), dipolar aprotic solvents (acetonitrile) or chlorinated hydrocarbons (methylene chloride, chloroform) can be used. On the other hand, under the same conditions 2-amino-4-phenyl-thiazole ( 10 ) reacts with salts of type 1 via pyrylium ring transformation yielding 2,4,6-triaryl-1-(4-phenyl-thiazol-2-yl)-pyridinium perchlorates 11 .