Chloracylierung und Bromacylierung von Carbonylverbindungen. III. Lage des Gleichgewichts

Chloroacylation and Bromoacylation of Carbonyl Compounds III. Reactant/Product Equilibria Aliphatic, α, β-unsaturated and aromatic aldehydes 1 as well as aliphatic ketones react with acyl halides 2 to α-haloalkyl esters 3 . In the presence of Lewis acids there is an equilibrium between reactants and product. The position of the equilibrium depends on the nature of the carbonyl compound as well as that of the acyl halide: The products 3 are favoured in the case of aldehydes, cyclobutanone and cyclohexanone, and the equilibrium constant increases in the series F < Cl < Br < I. Low reaction temperature, nonpolar solvents as well as high reactant concentrations favour the product 3 .     

Chloracylierung und Bromacylierung von Carbonylverbindungen. II. Analyse der Nebenprodukte

Chloroacylation and bromoacylation of carbonyl compounds II. Structure of the by-products The structures of the by-products formed in the reaction between paraformaldehyde and acetyl chloride as well as between acetaldehyde and acetyl chloride are elucidated. Optimum conditions for a high yield of the (α-chloroalkyl) ester 1 were obtained by variation of structure and reaction parameters. A speculative reaction scheme of the formation of by-products is discussed.     

Chloracylierung und Bromacylierung von Carbonylverbindungen: Eine in Vergessenheit geratene Carbonylreaktion. I. Präparative Anwendungsbreite

Chloroacylation and bromoacylation of carbonyl compounds: A forgotten carbonyl reaction. I. Scope of the reaction Aliphatic, α,β-unsaturated and aromatic aldehydes as well as aliphatic ketones react with acyl halides to (α-haloalkyl)esters. These bifunctional derivates contain two leaving groups of different reactivity. The scope of this scarcely of this scarcely known carbonyl reaction is discussed.     

Herstellung und Solvolyse von 3-substituierten p-Toluolsulfonsäure-(1-adamantyl)estern

The Preparation and Solvolysis of 3-substituted 1-Adamantyl Toluenesulfonates Methods for the preparation of some hitherto unknown 3-iubstitutetl 1-adamantyl toluenesulfonates are evaluated. Their solvolysis products in dioxane/water 70:30 are reported.     

Synthese und Hydrolyse von 6endo-substituierten p-Toluolsulfonsäure-[2endo-norbornyl]estern. Norbornanreihe, 9. Mitteilung

The Synthesis and Hydrolysis of 6endo-Substituted 2endo-Norbornyl p-Toluenesulfonates The hydrolysis products of the p-toluenesulfonates of several hitherto unknown 6endo-substituted 2endo-norbornanols have been determined.     

Die Synthese von 6exo-substituierten p-Toluolsulfonsäure-[2exo-norbornyl]estern. Norbornanreihe, 1. Mitteilung

The Synthesis of 6 exo -Substituted 2 exo -Norbornyl p -Toluenesulfonates A number of hitherto unknown 6exo-substituted 2exo-norbornanols and their p-toluenesulfonates have been prepared by functionalization of intermediate norbornenes.     

Die Synthese von 6exo-substituierten p-Toluolsulfonsäure-[2endo-norbornyl]estern. Norbornanreihe, 2. Mitteilung

The synthesis of 6 exo -Substituted 2 endo -Norbornyl p -Toluenesulfonates The preparation of hitherto unknown p-toluenesulfonates of 6exo-substituted 2endo-norbornanols is described.     

Über Chalkogenolate. 133. Untersuchungen über Ester von Halogenoameisensäuren 1. Chloroameisensäure-, Chloromonothioameisensäure- und Chlorodithioameisensäurealkylester

On Chalcogenolates. 133. Studies on Esters of Haloformic Acids. 1. Alkyl Esters of Chloroformic, Chloromonothioformic, and Chlorodithioformic Acids The prepared esters RO? CO? Cl, RS? CO? Cl, RO? CS? Cl, and RS? CS? Cl with R = alkyl have been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra.     

1H-NMR-Spektroskopische Untersuchungen zur Konformation von Cyclohexandicarbonsäure-(1,2)-anhydriden

¹H NMR chemical shifts of 18 methyl substituted cyclohexane-1,2-dicarboxylic anhydrides were determined. In compounds with asymmetric substitution vicinal coupling constants were measured. In the series of trans-anhydrides it can be deduced from the NMR data, that the 6-membered ring has a chair-like conformation. Additionally, in the series of the cis-anhydrides a twisted chair conformation is favoured for the most part.     

Zur thermolyse von methantriearbon-bzw-tetraearbonsäure-(N-α-naphthylamiden)

Thermolysis of Methanetricarboxylic Acid and Teracarboxylic Acid-(N-α-Naphtylamides). By the thermolysis of methanetricarboxylic acid and tetracarboxylic acid-(N-αnaphthylamides) under reduced pressure, 1- and 1,3-substituted 4-hydroxy-2-oxo-1,2-dyhydrobenzo[h]quinolines have been obtained in good yield.     

Einfache Darstellung von Bis(trimethylsilyl)estern der Mono-, Di- und Trischwefelsäure

A Simple Method of Preparing Bis(trimethylsilyl)esters of the Mono-, Di-, and Trisulfuric Acid Hexamethyl disiloxane 1 reacts with one mole sulfurtrioxide under insertion giving bistrimethylsilylsulfate 2 . Through further stepwise insertion of sulfur trioxide the silylester of disulfuric acid 3 and the silylester of trisulfuric acid 4 are obtainable.     

Die Hydrolyse von 7-anti-substituierten p-Toluolsulfonsäure-[2-endo-und 2-exo-norbornyl]estern. Norbornanreihe. 12. Mitteilung

The Hydrolysis of 7-anti-Substituted 2-endo- and 2-exo-Norbornyl p-Toluenesulfonates The hydrolysis products of the title compounds have been determined. The preparation of the hitherto unknown solvolysis products is described.     

Alkyl- und Arylkomplexe des Iridiums und Rhodiums. XIX. Reaktion von Carbonsäuren mit ausgewählten Organoverbindungen von Ir(I) und Rh(I): Bildung von Arylhydrido-, Carboxylatohydrido- und Carboxylato-Derivaten

Alkyl and Aryl Complexes of Iridium and Rhodium. XIX. Reaction of Carboxylic Acids with Selected Organo Compounds of Ir(I) and Rh(I): Formation of Arylhydrido, Carboxylatohydrido, and Carboxylato Derivatives cis-Arylhydridoiridium(III) complexes IrH(Ar)(O₂CR)(CO)(PPh₃)₂ (R = Me: Ar = C₆H₅, 4-MeC₆H₄; R = Et: Ar = 4-MeC₆H₄, 2,4-Me₂C₆H₃) could be prepared by oxidative addition of carboxylic acids to aryliridium(I) compounds Ir(Ar)(CO)(PPh₃)₂. Reaction of aliphatic carboxylic acids with alkyliridium(I) derivatives Ir(Alk)(CO)(PPh₃)₂ and Ir(Alk)[PhP(CH₂CH₂CH₂PPh₂)₂] (Alk = CH₂CMe₃, CH₂SiMe₃) lead to dicarboxylatoiridium(III) hydrides IrH(O₂CR)₂(CO)(PPh₃)₂ (R = Me, Et, i-Pr) and IrH(O₂CR)₂[PhP(CH₂CH₂CH₂PPh₂)₂] (R = Me, Et). Ir(4-MeC₆H₄CO₂)(CO)(PPh₃)₂ was obtained from Ir(CH₂SiMe₃)(CO)(PPh₃)₂ and 4-MeC₆H₄CO₂H. Interaction of organorhodium complexes Rh(R′)(CO)(PPh₃)₂ (R′ = CH₂SiMe₃, 4-MeC₆H₄) and Rh(R′)[PhP(CH₂CH₂CH₂PPh₂)₂] (R′ = CH₂CMe₃, 4-MeC₆H₄) with aliphatic and aromatic carboxylic acids yielded carboxylatorhodium(I) compounds Rh(O₂CR)(CO)(PPh₃)₂ (R = Me, t-Bu, 4-MeC₆H₄) and Rh(O₂CR)[PhP(CH₂CH₂CH₂PPh₂)₂] (R = Me, 4-MeC₆H₄).     

Komplexe mit aromatischen Carbonsäuren. I Darstellung und Struktur von Zinkpyromellitat-Heptahydrat

Complexes with Aromatic Carboxylic Acids. I. Synthesis and Crystal Structure of Zinc Pyromellitate Heptahydrate The crystal structure of zinc pyromellitate heptahydrate comprises features of ion exchangers, layer-like, and zeolitic structures. Single crystals of this compound were obtained by crystallization in aqueous silicagel. According to the structural properties Zn(H₂O)₅[ZnC₆H₂(COO)₄]·2H₂O is an appropriate formula. Zn(1) is coordinated tetrahedrally by four oxygen atoms of the carboxylate groups. Thus forming folded [ZnC₆H₂(COO)₄] layers to which Zn(2) is bound by only one carboxylate oxygen atom. The coordination sphere of Zn(2) is completed by five water molecules to yield a slightly distorted octahedron. Additional water is accomodated between the layers. The [ZnC₆H₂(COO)₄] layers possess channel-like cavities extending along [100] which are filled by water molecules. Hydrogen bonding is an important feature of this crystal structure.     

Gemischte Halogeno-Äthylendiamin-Komplexe von Osmium(III) und (IV)

Mixed Halogeno-Ethylendiamine Complexes of Osmium (III) and (IV) [OsCl₄en] or [OsBr₄en] and [OsCl₄en]- or [OsBr₄en]- are prepared by reaction of [Os(en-H)₂en]Br₂ with HCl or HBr. Whereas the chelate group behaves inert, the halogeno ligands become substituted easily, alltogether or partly. This enables the preparation of [OsI₄en], of complexes of the type [OsCl_nBr_4?en]-, n = 1–3, and of other compounds. The chemical properties and infrared spectra of the new complexes are discussed.