Olefin amination process

Tertiary butylamine had a world wide production of 1.4 million tons in 1988 [108]. Over 57% was produced using the Ritter reaction. Sterling Chemicals, Nitto Chemical Industry, and Sumitomo Chemicals use the Ritter process [109]. BASF is the only company producing tertiary butylamine with the olefins amination process. 

Hegedus developed an olefin amination process that generates indoles by intramolecular nucleophilic attack of substituted amines on allylarenes (Equation 11.27). In this process, an N-tosyl arylamine attacks the coordinated olefin of an allyl group in the ortho position of the aniline, and p-hydrogen elimination generates a tautomer of indole and a reduced palladium complex. This reduced complex is then re-oxidized by quinone to regenerate the starting palladium(II), and the product tautomerizes to the final indole product. This cycle was one of the earliest catalytic olefin aminations. 

Cu-promoted reaction and Cu-catalyzed C-H amination merit some analysis of the former process. From the standpoint of reaction utility, the work of Dauban and Dodd [31, 32] and, more recently, Lebel [33] has advanced Cu-catalyzed alkene aziridination to a state-of-the-art synthetic method. In particular, Dauban and Dodd have shown that pre-formation of sulfonyliodoimines is not required and that such species can be generated in situ from the corresponding sulfonamide and Phl=0. These conditions greatly expand the number and type of sulfonamide derivatives that will engage in olefin aziridination processes. 

The only other successful process to produce tertiary butylamine is olefin amination. Isobutylene is reacted with ammonia using a zeolite catalyst at temperatures of 200-350°C and pressures as high as 18 MPa [106]. This process has a low conversion which makes recycling unconverted feed economical [107]. 

Moreover, there are already two other oxidative amination processes on the horizon, namely allylic amination of olefins and 1,2-diamination of 1,3-dienes [14]. Could these useful, but stochiometric transformations be rendered catalytic and perhaps also asymmetric some day ... 

Aminated olefin pol mers Ethylene/a-olefin copol mer composition, graft modified, ethylene/a-olefin copolymer composition, ethylene copol mer composition, and multi-stage olefin polymerization process Polypropylene resin expanded particles... 

Apparently the alkoxy radical, R O , abstracts a hydrogen from the substrate, H, and the resulting radical, R" , is oxidized by Cu " (one-electron transfer) to form a carbonium ion that reacts with the carboxylate ion, RCO - The overall process is a chain reaction in which copper ion cycles between + 1 and +2 oxidation states. Suitable substrates include olefins, alcohols, mercaptans, ethers, dienes, sulfides, amines, amides, and various active methylene compounds (44). This reaction can also be used with tert-huty peroxycarbamates to introduce carbamoyloxy groups to these substrates (243). 

However, when the temperature is increased to 120°C, the principal reaction is the elimination to olefin. The thermal decomposition of dimethyl dodecyl amine oxide at 125°C in a sealed system, as opposed to a vacuum used by Cope and others, produces 2-methyl-5-decyhsoxa2ohdine, dimethyl dodecyl amine, and olefin (23). The amine oxide oxidi2es XW-diaLkylhydroxylainine to the nitrone during the pyrolysis and is reduced to a tertiary amine in the process. 

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. 

Selenium diimides react in a manner similar to SeOa with unsaturated organic compounds. The first report of BuN=Sc=N Bu described its use as an in situ reagent for allylic amination of olefins and acetylenes. Improved procedures for this process (Eq. 10.5) and for the diamination of 1,3-dienes (Eq. 10.6) have been developed using the reagents RN=Se=NR [R = para-toluenesulfonyl (Ts), ort/io-nitrobenzenesulfonyl (Ns)]. ... 

FD-MS is also an effective analytical method for direct analysis of many rubber and plastic additives. Lattimer and Welch [113,114] showed that FD-MS gives excellent molecular ion spectra for a variety of polymer additives, including rubber accelerators (dithiocar-bamates, guanidines, benzothiazyl, and thiuram derivatives), antioxidants (hindered phenols, aromatic amines), p-phcnylenediamine-based antiozonants, processing oils and phthalate plasticisers. Alkylphenol ethoxylate surfactants have been characterised by FD-MS [115]. Jack-son et al. [116] analysed some plastic additives (hindered phenol AOs and benzotriazole UVA) by FD-MS. Reaction products of a p-phenylenediaminc antiozonant and d.v-9-lricoscnc (a model olefin) were assessed by FD-MS [117],... 

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 ... 

The same group recently disclosed a related free radical process, namely an efficient one-pot sequence comprising a homolytic aromatic substitution followed by an ionic Homer-Wadsworth-Emmons olefination, for the production of a small library of a,/3-unsaturated oxindoles (Scheme 6.164) [311]. Suitable TEMPO-derived alkoxy-amine precursors were exposed to microwave irradiation in N,N-dimethylformam-ide for 2 min to generate an oxindole intermediate via a radical reaction pathway (intramolecular homolytic aromatic substitution). After the addition of potassium tert-butoxide base (1.2 equivalents) and a suitable aromatic aldehyde (10-20 equivalents), the mixture was further exposed to microwave irradiation at 180 °C for 6 min to provide the a,jS-unsaturated oxindoles in moderate to high overall yields. A number of related oxindoles were also prepared via the same one-pot radical/ionic pathway (Scheme 6.164). 

Scheme 28 Examples of two aspirational processes byproduct-free couplings of a-olefins to (renewable) alcohols and amines with linear or branch regiocontrol...

A wide variety of cyclic monomers have been successfully polymerized by the ring-opening process [Frisch and Reegan, 1969 Ivin and Saegusa, 1984 Saegusa and Goethals, 1977]. This includes cyclic amines, sulfides, olefins, cyclotriphosphazenes, and IV-carboxy-oc-amino acid anhydrides, in addition to those classes of monomers mentioned above. The ease of polymerization of a cyclic monomer depends on both thermodynamic and kinetic factors as previously discussed in Sec. 2-5. 

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