Amines alkylation with olefins

All lation of Aromatic Amines and Pyridines. Commercially important aromatic amines are aniline [62-53-3] toluidine [26915-12-8], phenylenediamines [25265-76-3], and toluenediamines [25376-45-8] (see Amines, aromatic). The ortho alkylation of these aromatic amines with olefins, alcohols, and dienes to produce more valuable derivatives can be achieved with soHd acid catalysts. For instance, 5-/ f2 butyl-2,4-toluenediamine (C H gN2), which is used for performance polymer appHcations, is produced at 85% selectivity and 84% 2,4-toluenediamine [95-80-7] (2,4-4L)A)... 

Linear alpha-olefins are the source of the largest volume of ahphatic amine oxides. The olefin reacts with hydrogen bromide in the presence of peroxide catalyst, to yield primary alkyl bromide, which then reacts with dimethylamine to yield the corresponding alkyl dimethyl amine. Fatty alcohols and fatty acids are also used to produce amine oxides (Fig. 1). 

In 1974, Hegedus and coworkers reported the pa]ladium(II)-promoted addition of secondary amines to a-olefins by analogy to the Wacker oxidation of terminal olefins and the platinum(II) promoted variant described earlier. This transformation provided an early example of (formally) alkene hydroamination and a remarkably direct route to tertiary amines without the usual problems associated with the use of alkyl halide electrophiles. 

A general synthesis of the secondary amines RNHMe and RNHEt has been developed starting from the iminophosphoranes (181). Alkylation with methyl or ethyl iodides (all other halides gave olefins) gave the salts (182) from which secondary amines were obtained on alkaline hydrolysis. 

For some organic compounds, such as phenols, aromatic amines, electron-rich olefins and dienes, alkyl sulfides, and eneamines, chemical oxidation is an important degradation process under environmental conditions. Most of these reactions depend on reactions with free-radicals already in solution and are usually modeled by pseudo-first-order kinetics ... 

Triazoline-3,5-dione 184 underwent an ene reaction with olefins 183 to yield trialkylated allylic urazoles 185, which were further elaborated into allylic amines 186 . DBU has been found to be a mild and convenient base for the alkylation of 1,2,4-triazole with various alkyl halides in the high yielding syntheses of 1-substituted-1,2,4-triazoles <00TL1297>. 

U.S. 4,259,216 (1981) Miyajima et al. (Lion) a-Olefin sulfonate, alkylethoxy sulfate, and alkyl amine oxide with aryl sulfonate No hand roughening and good for vegetables... 

The direct alkylation of ammonia and amines with olefins in the presence of alkali metals as catalysts was reported by Howk and coworkers (17), The general procedure is shown in the following reaction, where R can be a hydrogen atom or an alkyl or aryl group ... 

With 41 in hand, a two-step nitro reduction and protection, followed by partial reduction of the lactam and resulting cyclization furnished aminal 42. Further treatment with cyanogen azide generated Wcyanoamidine 43. Hydrolysis and amide protection followed by alkylation with allyl iodide yielded olefin 44 as a single diastereomer. Conversion of 44 to aldehyde 45 was the followed reaction of the mesylate with azide, a cross-aldol reaction with acetone, lactam reprotection with Boc, and trimethylphosphine-mediated reductive rearrangement to provide spiro-y-lactam 46. Methyllithium addition to lactam 46 and similar chemistry as reported by Qin et al. gave communesin F (17) (Scheme 6). 

The Hegedus indole synthesis is not only compatible with a wide range of functional groups on the aromatic ring but is also tolerable for the alkyl groups at the 2 or 3 position of the allyl side chain." Other features of this reaction include (a) general accessibility for the intramolecular amination of mono-olefin from primary amines and weakly basic... 

Elimination reaction of alkyl trimethyl amines proceeds with anh-stereochemistry, furmshing the least highly substituted olefins. 

Ritter Reaction (Method 4). A small but important class of amines are manufactured by the Ritter reaction. These are the amines in which the nitrogen atom is adjacent to a tertiary alkyl group. In the Ritter reaction a substituted olefin such as isobutylene reacts with hydrogen cyanide under acidic conditions (12). The resulting formamide is then hydroly2ed to the parent primary amine. Typically sulfuric acid is used in this transformation of an olefin to an amine. Stoichiometric quantities of sulfate salts are produced along with the desired amine. 

In addition to the nitrile and alcohol routes for fatty amine preparation, processes have been described by Unocal and Pennwalt Corporation, using an olefin and secondary amine (14—16) by Texaco Inc., hydrogenation of nitroparaffins (17—20) by Onyx Corporation, reaction of an alkyl haUde with secondary amines (21,22) by Henkel Cie, GmbH, reduction of an ester in the presence of a secondary amine (23) by catalytic hydroammonolysis of carboxyhc acids (24) and by the Hofmann rearrangement (25). 

The kinetics of formation and hydrolysis of /-C H OCl have been investigated (262). The chemistry of alkyl hypochlorites, /-C H OCl in particular, has been extensively explored (247). /-Butyl hypochlorite reacts with a variety of olefins via a photoinduced radical chain process to give good yields of aUyflc chlorides (263). Steroid alcohols can be oxidized and chlorinated with /-C H OCl to give good yields of ketosteroids and chlorosteroids (264) (see Steroids). /-Butyl hypochlorite is a more satisfactory reagent than HOCl for /V-chlorination of amines (265). Sulfides are oxidized in excellent yields to sulfoxides without concomitant formation of sulfones (266). 2-Amino-1, 4-quinones are rapidly chlorinated at room temperature chlorination occurs specifically at the position adjacent to the amino group (267). Anhydropenicillin is converted almost quantitatively to its 6-methoxy derivative by /-C H OCl in methanol (268). Reaction of unsaturated hydroperoxides with /-C H OCl provides monocyclic and bicycHc chloroalkyl 1,2-dioxolanes. 

---