Olefinic amines

PMMA is not affected by most inorganic solutions, mineral oils, animal oils, low concentrations of alcohols paraffins, olefins, amines, alkyl monohahdes and ahphatic hydrocarbons and higher esters, ie, >10 carbon atoms. However, PMMA is attacked by lower esters, eg, ethyl acetate, isopropyl acetate aromatic hydrocarbons, eg, benzene, toluene, xylene phenols, eg, cresol, carboHc acid aryl hahdes, eg, chlorobenzene, bromobenzene ahphatic acids, eg, butyric acid, acetic acid alkyl polyhaHdes, eg, ethylene dichloride, methylene chloride high concentrations of alcohols, eg, methanol, ethanol 2-propanol and high concentrations of alkahes and oxidizing agents. 

Phosphorus(V) sulfide reacts with olefins, amines, Grignard reagents, and terpenes (6,26) as follows ... 

Method 6. Olefin amination reaction of an olefin with ammonia. 

Olefin Amination (Method 6). The most recent technology for the production of lower alkylamines is olefin amination (14). This is 2eohte-cataly2ed reaction of ammonia with an olefin, eg, isobutylene, and is practiced in a packed-bed reactor system in the vapor phase. 

Dinitrobenzenesulfenyl chloride is a versatile analytical reagent for the characterization of a wide variety of organic compounds, including alcohols, mercaptans, ketones, olefins, amines, aromatic compounds, olefin oxides, and hydroxysteroids. Review articles summarize these applications.9 10... 

Optical yields up to 17% and 25%, respectively, have been reached in the styrene hydroformylation in the presence of cobalt or rhodium catalysts using N-alkylsalicylaldimine or phosphines as asymmetric ligands. Furthermore the hydroformylation of aliphatic and internal olefins have been achieved using rhodium catalysts in the presence of optically active phosphines. With the same catalysts, cis-butene surprisingly undergoes asymmetric hydroformulation with optical yields up to 27%. On the basis of the results obtained for cis-butene and the asymmetric induction phenomena in dichlor(olefin)(amine)platinum( 11) com-... 

The major value of the vinylic halide-olefin-amine reaction is for synthesizing polyfunctional aliphatic compounds. The compounds are constructed from the vinylic halide, the olefinic reactant with the necessary substituents, and a secondary amine (or tertiary amine if activating groups are present in the appropriate positions). It is possible to have various functional groups present in either the halide or the olefinic compound and there is a choice of which part of the molecule is the olefinic reactant and which part is the vinylic halide. 

An ab initio method has been employed to study the mechanism of the thermal isomerization of buta-1,2-diene to buta-1,3-diene. The results of the study have indicated619 that the transformation proceeds in a stepwise manner via a radical intermediate. Experimental free energies of activation for the bond shift in halocyclooctatetraenes have been reported and analyzed by using ab initio MO calculations.620 The isomerization of hexene using a dihydridorhodium complex in dimethyl sulfoxide has been reported,621 and it has been suggested622 that the Pd(II)-catalysed homogeneous isomerization of hexenes proceeds by way of zr-allylic intermediates. A study has been made623 of alkene isomerization catalysed by the rhodium /-phosphine-tin dichloride dimeric complex, and the double-bond isomerization of olefinic amines over potassium amide loaded on alumina has been described.624... 

Cyclopropane compounds containing the olefin isostere replacement for the amide bond were prepared using Julia olefination chemistry. Aldehydes 39 and 40 were obtained by LAAIH4 reduction of the chiral w-butyl esters of 32 and 33, respectively, followed by swera oxidation of the corresponding alcohols (Figure 22). Condensation of the (S)-N-BOC-cyclohexylalanine sulfone 41 with aldehyde 39 gave after treatment with 2% Na(Hg) and deprotection, the trans and cis olefin-amines... 

Figure 22. Intermediates for synthesis of cyclopropyl-olefin-amine H3 antagonists...

In this reaction, carbamate esters were obtained after long reaction times (70 h), in 0.06-11% yield, depending on the olefin/amine molar ratio (l-10mol/mol) and temperature (308-353 K). Since 1-ethoxyethyl carbamate was formed as the sole regio-isomer product, but there was no formation of the 2-ethoxyethyl ester, the reaction was believed to proceed by an electrophilic addition to the vinyl ether of carbamic acid, formed by reversible reaction of C02 with amine (see Equation 6.1). 

Some materials are of natural origin, others are purely synthetic and some are available from both sources, natural and synthetic. Almost all kinds of organic functionalities are represented in the broad palette of the flavorist and perfumer - alcohols, aldehydes, ketones, esters, hydrocarbons, olefins, amines, phenols, heterocy-clics, etc. Alcohols are particularly important because they are prominent among the relatively inexpensive and readily available materials which make up the bulk of flavors and especially fragrances. 

V-trimethylsilyl protected olefinic amines and terminal diolefins have been successfully hydroborated with dimethylborane. The resulting organoborane was treated with in situ-generated chloramine or chloralkylamine to produce isomerically pure diamines or N-substituted unsymmetrical diamines in good yields [26] (Scheme 9). 

In the presence of allylzinc bromide, a branched olefinic amine... 

Studies have been made on the influence of various groups on the rate of hydrogenation of the double bond. Reductions of olefinic alcohols (method 85), olefinic aldehydes (method 161), olefinic ketones (method 196), olefinic acids (method 267), olefinic esters (method 303), olefinic Cyanides (method 394), and olefinic amines (method 460) are treated separately. 

CHCI3. Photolysis of trans-PtClj(olefin)(amine) complexes leads to olefin loss and the dimerization ... 

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