Addition von organomagnesium-verbindungen an nicht aktivierte CC-doppelbindungen : IV. Benzylmagnesiumchlorid und olefine

Benzylmagnesium chloride (I) adds to ethylene and 1-alkenes, to the strained CC double bonds in bicyclo[2.2.1]hept-2-ene and bicyclo[2.2.1]heptadiene and to 1,3-alkadienes if the reaction of the etherate of (I) with olefin is carried out in an apolar reaction medium between 60 and 130°. Reaction products of the mono-olefins are the 1,1-adducts; derivatives of divinylcyclohexane are formed with butadiene as 1,3-adducts. With bicyclo[2.2.1]heptadiene the addition of the magnesium compound is followed by an intramolecular MgC-addition to the second double bond forming 2-benzyltricyclo[2.2.1.0¹]hept-3-ylmagnesium chloride.     

Nickel-katalysierte Synthese von α-Nornicotin-Derivaten. Vorläufige Mitteilung

Nickel-catalysed Synthesis of α-Nornicotines Schiff's bases 1 and butadiene generally co-oligomerize on nickel catalysts to yield octatrienyl-substituted amines 2 and octadienyl-substituted imines 3 . Schiff's bases 4 and 5 , on the other hand, react with 1, 3-dienes to give new [3+2]-cycloadducts 6 . In addition to the appropriately functionalized α-nornicotine derivatives some higher oligomers are formed.     

Study of pyrolysis kinetic of green corn husk

In this paper, it was suggested the use of green corn husk, which is a biomass from agro-industry, as an alternative source of energy through its pyrolysis. Green corn husk characterization was done through immediate and elemental analysis of its components: cellulose, hemicelluloses, and lignin. It was also measured its higher calorific value. The pyrolysis study of green corn husk was done by the isoconversion and the Master plots method. Thermogravimetric plots were obtained at heating rates of 5, 10, 15, and 20 °C min^?1. The pyrolysis kinetics parameters were studied through the Flynn–Wall–Ozawa (FWO), Kissinger, and Friedman models. The Master plots method was used to determine the pyrolysis reaction order. The results of the reaction energy activation were found to be in the range 105.21–157.46 kJ mol^?1 by the FWO method, 150.50 kJ mol^?1 by the Kissinger method, and ranged 120.66–163.81 kJ mol^?1 by the Friedman method. The Master plots method showed a three-way-transport diffusional kinetics for the biomass de-volatilization process. The higher calorific value found for green corn husk was 16.14 MJ kg^?1. The simulation showed correlation between the experimental data and the proposed model for conversion values up to 0.8.

     

Katalytische reaktionen von aminen mit olefinen

Tetramethylethylenediamine (TMED) reacts with ethylene (propene) under the influence of catalytic amounts of alkyllithium to give dimethylvinylamine and dimethylethylamine (dimethylisopropylamine). In competitive reactions alkyl-lithium and the amides formed by this with primary or secondary amines in presence of tetramethylethylenediamine enhance the addition of primary or secondary amines to ethylene more strongly than in the absence of the diamine. The pressures are $\text{1}\text{5}$ to $\text{1}\text{10}$ of those needed when sodium catalysts are used and the temperatures required are 50–100° lower. Dimethylamine but not diethylamine, which however reacts with cycloolefins containing strained double bonds, adds to propene.     

Zur Kenntnis der nickel-katalysierten Mischoligomerisation von Butadien mit Hydrazonen. Vorläufige Mitteilung

Studies on the nickel-catalysed reaction of butadiene with hydrazones The nickel-catalysed reaction of butadiene with methyl-hydrazones yields a series of isomeric azo-compounds identified as 2:1 adducts. The products are compared with those of the analogous reaction of butadiene with imines (cf. Scheme 1–3).     

Nickel-katalysierte Isomerisierung von Butadien-Hydrazon-Misch-Oligomeren. Vorläufige Mitteilung

Nickel-catalysed Isomerization of Unsaturated Azocompounds Unsaturated azocompounds, produced by the nickel-catalysed reaction of butadiene with hydrazones, can be isomerized in presence of the same nickel catalyst. The influence of nickel concentration, temperature and structure of the azocompound on this rearrangement is described.     

Addition von organomagnesium-verbindungen an nicht aktivierte CC-doppelbindungen: III. 2-alkenylmagnesiumhalogenide und bicyclo[2.2.1]hept-2-en

2-Methyl-2-propenyl- (I) and 2-Butenylmagnesium halide (II) react with bicyclo[2.2.1]hept-2-en (III) erhaltenen $\text{1}\text{1}$-Addukte (IV) und (V) lagern sich converted by heating under opening of one 5-ring. On the basis of the products of hydrolysis, the dialkenylcyclopentanes (X) and (XI), formed by conversion of (V), the mechanism of this reaction hitherto unknown for a saturated 5-cyclic compound is discussed.