Nitrogen compounds alkenes

The key initiation step in cationic polymerization of alkenes is the formation of a carbocationic intermediate, which can then interact with excess monomer to start propagation. We studied in some detail the initiation of cationic polymerization under superacidic, stable ion conditions. Carbocations also play a key role, as I found not only in the acid-catalyzed polymerization of alkenes but also in the polycondensation of arenes as well as in the ring opening polymerization of cyclic ethers, sulfides, and nitrogen compounds. Superacidic oxidative condensation of alkanes can even be achieved, including that of methane, as can the co-condensation of alkanes and alkenes. 

Electrophilic nitrogen compounds, such as arenesulfonyloxyamines, can convert alkenes to aziridines without the intervention of free nitrenes (80CC560). 

Oxidative reactions frequently represent a convenient preparative route to synthetic intermediates and end products This chapter includes oxidations of alkanes and cycloalkanes, alkenes and cycloalkenes, dienes, aromatic fluorocarbons, alcohols, phenols, ethers, aldehydes and ketones, carboxylic acids, nitrogen compounds, and organophosphorus, -sulfur, -selenium, -iodine, and -boron compounds... 

Other nitrogen compounds, among them hydroxylamine, hydrazines, and amides (15-9), also add to alkenes. Even with amines, basic catalysts are sometimes used, so that RNH or R2N is the actual nucleophile. Tertiary amines (except those that are too bulky) add to Michael-type substrates in a reaction that is catalyzed by acids like HCl or HNO3 to give the corresponding quaternary ammonium salts. " ... 

Addition of NOCl and other nitrogen compounds to alkenes... 

The OPLS parameters (charges and Lennard-Jones terms) were obtained primarily via Monte Carlo simulations with particular emphasis on reproducing the experimental densities and heats of vaporization of liquids. Those simulations were performed iteratively as part of the parametrization, so better agreement with experiment is obtained than in previous studies where the simulations were usually carried out after the parametrization. Once the OPLS parametrization was completed, further simulations were also performed in order to test the new set of parameters in the calculation of other thermodynamic and structural properties of the system, besides its density and its heat of vaporization. Parameters have now been generated, among others, for water, alkanes, alkenes, alcohols, amides, alkyl chlorides, amines, carboxylic esters and acids, various sulfur and nitrogen compounds, and nitriles. A protein force field has been established as well. 

Electrophilic nitrogen compounds, such as arenesulfonyloxyamines, can convert alkenes to aziridines without the intervention of free nitrenes (80CC560). The ylide Ph2S+-NH adds stereospecifically to E and Z conjugated alkenes, and chiral sulfimides can transfer chirality to the aziridines formed (80T73). These reactions are often named aziridinations . 

Percarboxylic acids can be used for the epoxidation of alkenes,114 acetylenes,115 the hydroxylation of alkanes,116 and the oxidation of alcohols,117 and of sulfur118 and nitrogen compounds.119... 

A few syntheses of alkenic nitrogen compounds based on the rDA reaction are known. For example, ynamine (19), via rDA decomposition under FVP conditions, gives l-N,N-diethylamino-3-buten-l-yl (20). 2-Vinylimidazoles had previously been obtained by lengthy reaction schemes with low yields however, a practical laboratory synthesis of 2-vinylimidazoles based on a DA-rDA scheme has been developed. The DA adduct of acrolein and cyclopentadiene was converted to 2-(5-norbomen-2-yl)imida-zole (21), which was readily transformed into 2-vinylimidazole (22) as depicted in equation (16). Glyoxal gave the best result, but other a-dicarbonyl compounds could be substituted to obtain various 2-vinylimidazoles. 

There are many examples of transition catalyzed addition of nitrogen compounds to alkenes, alkynes,and so on. Secondary amines can be added to certain nonactivated alkenes if paUadium(II) complexes are used as catalysts. ... 

Table VH. Hydroformylation of Unsaturated Halogen Compounds Table VIH. Hydroformylation of Un.saturated Nitrogen Compounds Table IX. Hydroformylation of Other Functionalized Alkenes. ...

The direct production of organic nitrogen compounds using dinitrogen has received little attention outside the reactions of organic halides with coordinated dinitrogen. Alkenes and alkynes would be viable carbon-atom... 

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