Derivate des Phosphorsäure-o-phenylenesters. XII[1]. Reaktion von Orthosäurechloriden mit Äthylenoxid

Derivatives of o-Phenylene Phosphate. XII. Reaction of Ortho-acid Chlorides with Ethylene Oxide Ortho-acid chlorides react with ethylene oxide in dependence of their structure either to ortho-acid β-chloroethylester or by splitting off 1,2-dichloroethane to the corresponding carbonyl- and phosphoryl derivatives, respectively. Using this method i. a. pentacovalent P-derivatives (pentaoxyphosphoranes 14, 16 ) are available.     

Derivate des Phosphorsäure-o-phenylenesters. XVI. o-Phenylendioxyphosphonium-hexahalogenoantimonate

Derivatives of o-Phenylenphosphates. XVI. o-Phenylendioxyphosphonium-hexahalogenoantimonates Pentacoordinated o-phenylen-orthophosphate-trihalogenides 1 resp. bis-o-phenylenorthophosphate-chloride 3 can be transformed to stable quasiphosphoniumsalts 2 resp. 4 by reaction with SbCl₅ or SbBr₃/Br₂. The structures of 2 and 4 are confirmed by ³¹P-n.m.r.     

Derivate des Phosphorsäure-o-phenylenesters. XIX. Zum Ablauf der Bromierung von Phenyl-o-phenylenphosphit

Derivatives of o-Phenylene Phosphates. XIX. Bromination of Phenyl o-Phenylene Phosphite The bromination of phenyl o-phenylene phosphite does not yield the expected penta-coordinated phosphorus dibromide 3 but phosphorus tribromide, phenoxy-bis-(o-phenylendioxy)-phosphorane and tetraphenoxyphosphonium bromide. The mechanism of the reaction is discussed.     

Derivate des Phosphorsäure-o-phenylenesters. 23. Verhalten von Brenzkatechylphosphortrichlorid gegenüber O-funktionellen P(III)-Verbindungen

Derivatives of o-Phenylene Phosphates. 23. Behaviour of Catechyl Phosphorus Trichloride towards Phosphites and Phosphinites Catechyl phosphorus trichloride ( 1 ) reacts with triethyl phosphite ( 4 ), triphenyl phosphite ( 9 ), and the o-phenylene phosphites ( 16a–d ) by ligand exchange and with isopropyl diphenyl-phosphinite ( 21 ) by ligand exchange and oxidation.     

Synthese von Heterocyclen mit Hydroxymethylenketonen. XIV [1]. Zur Regioselektivität der Reaktion von Acetylacetaldehyd mit Tryptamin

Synthesis of Heterocyclic Compounds with Hydroxymethylene Ketones. XIV. Contribution to the Regioselectivity of the Reaction of Acetoacetaldehyde with Tryptamine The range of substitution products of tryptamine with acetoacetaldehyde as substituent at the basic or the indole nitrogen ( 2, 3 ) is completed by a product containing the substituent in the indole α-position ( 5 ). It is formed by ring opening of the tetrahydro-β-carboline 4 . The reaction conditions are commented and the ¹H-NMR spectra comparatively discussed. The synthesis of the azocino-indole 7 is described.     

Photochemie von Aminoketonen. IV [1]. Synthese von 3-Aryl-pyrrolidinolen-(3) durch Photocyclisierung von β-Amino-propiophenonen

Photochemistry of Aminoketones. IV. Synthesis of 3-Aryl-pyrrolidinols-(3) via Photocyclization of β-Amino-propiophenones Photolysis (λ_irr ≥ 300 nm) of N-benzyl-N-benzoyl-β-aminopropiophenones 6–9 in abs. ether affords a 47–50% yield of N-benzoyl-pyrrolidinols 12–18 . The relative configurations of the diastereomeric 12–18 are determined by ¹H-n.m.r. spectroscopy. The different behaviour of the N-acylated 6–9 in contrast to N,N-dialkyl-β-aminopropiophenones is explained by assumption of a dipol-dipol interaction between the keto and the amido carbonylgroups in the n,π*-excited state.     

Untersuchungen über Poly(arylenvinylen)e. XVIII [1]. Synthese von Poly(1,4-phenylen- 1 -phenylvinylen) durch Dehydrochlorierung

Investigations on Poly(arylenevinylene)s. XVIII. Synthesis of Poly(1,4-phenylene-1-phenylvinylene) by Dehydrochlorination Reaction Dehydrochlorination reaction has been applied successfully to the polycondensation of 4-chloromethylbenzhydryl chloride 2 with potassium tert-butoxide in hexamethylphosphoric triamide, whereby soluble poly(1,4-phenylene-1-phenylvinylene) 1 was obtained. Some properties of 1 are described.