W. J. De Klein

Reactions with Manganese (III) Acetate

Oxidations with manganese (III) acetate can be broadly divided into two classes: 1. Direct inner- or outer-sphere one-electron oxidation of the substrate after formation of an inner- or outer-sphere substrate-Mn(III) complex. Often subsequent oxidation of an intermediate radical is product determining. Numerous examples can be found in oxidations of alcohols, amino- and thio-compounds, carboxylic acids, and certain aromatics. 2. Indirect oxidation of the substrate after formation of an intermediate adduct free radical from interaction of manganese (III) acetate and an enolizable compound and subsequent addition or substitution of this radical to the substrate. Most examples here refer to aromatic substitution and oxidative addition of enolizable compounds to unsaturated systems.

Electrochemical synthesis of vicinal dithiocyanates from olefins and a thiocyanate salt in acidic media

Abstract The addition of electrochemically generated thiocyanogen to olefins is described. The effect of solvent and irradiation is briefly outlined. In acidic media the reaction takes place without irradiation. In acetic acid thiocyanogen adds smoothly to the double bond to produce the vicinal dithiocyanate. In methanol-HCl addition of both SCN and OCH3 takes place. An ionic mechanism analogous to halonium type addition reactions is proposed to account for the phenomena observed.

Telomer Acids: Monocarboxylic acids with long-chain branching; Their derivatives, properties and potential uses in lubricants

Telomer acids are synthesized by addition of acetic anhydride to α-olefins using managenese (III) acetate as a free radical initiator. The telomerization mechanism comprises initiation, propagation and termination steps. The reaction product consists of a mixture of acids having [xn+2] carbon atoms (n: number of carbon atoms of α-olefin: x:1, 2, 3, 4, ...). The “first telomer” (x=1) is a linear fatty acid. Under appropriate conditions, mainly telomer acid (x:2, 3, 4, ...) are obtained, being α- and γ-branched monocarboxylic acids, characterized by long-chain branches. Telomer acids derived from α-olefins up to n=14 are liquids at room temperature, despite the high molecular weight. Esters of telomer acids show interesting properties in lubricant applications: low pour point, high viscosity index, low viscosity as a function of molecular weight, good thermo-oxidative stability and a remarkably low elastomer swell. In amino amide derivatives, the telomer acid structure gives low viscosity properties, as is, for instance, found in significant viscosity reductions by using telomer acid as coreactant in polyisobutenyl succinic anhydride—tetraethylene pentamine condensation products. Dispersancy properties of these products are retained. Telomer acid metal salts exhibit quite different solubility characteristics and rheological properties than do fatty acid salts. Calcium salts of telomer acids are readily soluble in mineral oil: the rheology of these low viscosity solutions exhibits Newtonian behavior. Solvent-free magnesium salts which are liquid can be obtained. Neutral and overbased calcium salts show pour point depressing activity in paraffinic oils. For overbased calcium salts, decrease of coefficient of friction with increasing temperature has been observed.