Amines method

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. 

A number of 2eohtic materials have been claimed to cataly2e this reaction and reaction temperatures are on the order of 200—350°C with pressures as high as 18000 kPa (2600 psi) reported. This is a low conversion process and recycle of the unconverted starting materials is necessary to provide an economical process. Amination of ethylene to produce ethylamines cataly2ed by ammonium iodide is reported, but not beheved to be practiced commercially (15,16). Alkyl Halide Amination (Method 7). The oldest technology for pioducing amines is the reaction of ammonia with an alkyl hahde. This... 

Hartwig, J. F. In Modern Amination Methods A. Ricci, Ed. Wiley-VCH Weinheim, 2000. 

Santagada and coworkers have disclosed a reductive amination method for the generation of a reduced peptide bond by reaction of a protected amino acid aldehyde with an N-deprotected amino ester using sodium cyanoborohydride as reducing agent [296]. 

Scheelite, 25 349-350 Scheelite sorting, 16 626 Scheibel column, 10 777-778 Scheibler filter, 11 364 Schiff base(s), 21 203, 204, 25 100-101 chelating agents, 5 712t reaction with amino acids, 2 567 reaction with aniline, 2 786 thermochromic materials, 6 622-623 Schiff base chemistry, 24 42 Schiff base (reductive amination) method, for covalent ligand immobilization, 6 396t... 

The established activity of ethereal a-C-H bonds toward carbene and nitrene insertion has evoked new applications for sulfamate oxidation [76-78] In principle, a C-H center to which an alkoxy group is attached should be a preferred site for amination irrespec-hve of the addihonal functionality on the sulfamate ester backbone (Scheme 17.20). Such a group can thus be used to control the regiochemistry of product formation. The N,0-acetal products generated are iminium ion surrogates, which may be coupled to nucleophiles under Lewis acid-promoted conditions [79]. This strategy makes available substituted oxathiazinanes that are otherwise difficult to prepare in acceptable yields through direct C-H amination methods [80]. 

Meth-Cohn, C.W. Rees), Elsevier Science, Oxford, 1995, pp. 297-Modern Amination Methods (Ed. A. Ricci), Wiley-VCH, Weinheim, 2000. 

Cyanogen bromide method A,A -Carbonyl diimidazole method Divinylsulfone method Epoxy (bisoxirane) method Ethyldimethylaminopropyl carbodiimide method Eluoromethylpyridinium toluenesulfonate method A-hydroxysuccinimide ester method Schiff base (reductive amination) method Tresyl chloride/tosyl chloride method Sulfhydryls Azalactone method (for azalactone supports)... 

Schiff base (reductive amination) method Nucleic acids Carbodiimide method... 

The Buchwald-Hartwig aryl amination methodology cited above in this section was engaged by Hartwig and others to synthesize N-arylindoles 377 [469]. Carbazole can be N-arylaied under these same conditions with p-cyanobromobenzene (97% yield). Aryl chlorides also function in this reaction. The power of this amination method is seen by the facile synthesis of tris-carbazole 378 [469c]. 

The main route to rhenium alkoxides is the interaction of halids and oxy-halids with alkali alkoxides or alcohols in presence of amines (method 5). As the important starting reagents can serve also Re2(CO),0 and Re207 (method 3) The preparation ofrhenium (V) and (VI) oxoderivatives by the anodic oxidation of metal in alcohols has also been described (method 2) (see Table 12.22). The bimetallic alkoxides ofrhenium and heavy transition metals can most efficiently be obtained by interaction ofrhenium (VII) oxide with the alkoxides ofthese elements in refluxing toluene ... 

The present chapter on modem allylic amination methods will be restricted mainly to an overview of some of the major developments for the transformation of allylic compounds into allyl amines according to reaction types (a) and (b) in Scheme 1, and an attempt is made to cover the literature up to August 1999. 

Finally, the hydroboration-amination method via azides might be the key step in the synthesis of alkyl aryl ketones involving a free radical mechanism as opposed to the usual ionic pathway [64,65] (Scheme 23). 

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