Amine and diamine

Salt Formation. Salt-forming reactions of adipic acid are those typical of carboxylic acids. Alkali metal salts and ammonium salts are water soluble alkaline earth metal salts have limited solubiUty (see Table 5). Salt formation with amines and diamines is discussed in the next section. 

Cycloaliphatic amines are comprised of a cyclic hydrocarbon stmctural component and an amine functional group external to that ring. Included in an extended cycloaUphatic amine definition ate aminomethyl cycloaUphatics. Although some cycloaUphatic amine and diamine products have direct end use apphcations, their major function is as low cost organic intermediates sold as moderate volume specification products. 

Larger volume cycloaUphatic amines and diamines, their worldwide major manufacturers and approximate January 1990 prices are shown in Table 4. Shipment of these Hquid products is by nitrogen-blanketed tank tmck or tank car. Dmm shipments are usually in carbon steel, DOT-17E. 

Liquid cycloahphatic amines and diamines have exacting purity and color standards. Almost all are sold to specification, not performance standards. Use as isocyanate precursors requites low water content criteria for these hygroscopic fluids, hence nitrogen blanketing is often specified for product sampling as well as storage and transport. 

Skin and Eye Irritation. Fatty alkylamines are generally considered to be irritating to both the skin and eyes (83). The severity or degree of irritation is usually dependent on the type of alkylamine, concentration of the chemical, time of exposure to the chemical, and sensitivity to the chemical. A small percentage of the population who come into contact with fatty amines may develop a skin hypersensitivity to certain amines and diamines. 

Table 1. Primary Monofluorides and a,oi-Difluorides from 2,4,6-Triphenylpyridinium Fluoride and Primary Amines and Diamines [1,2]...

The reactions of 4-alkoxybut-3-en-2-ones with primary aromatic amines and diamines of the aromatic and heteroaromatic series follow analogous schemes. 

Diaminoethane, diaminopropane, 1-amino-2-propanol, diami-nobutane, diaminopentane. u-decylamine 25 m CPWAX column for amines and diamines at 135°. 

Apart from metals, ammonium chloride, amine, and diamine salts, and various organic polymeric dispersants and surfactants are employed in fuel treatment additive formulations. 

Bidentate binding of two Lewis acidic boron centers to one methoxide anion was first reported in 1967 [241]. Further examples did not appear until 1985 [242]. Today, other bis(boronates) like 152 and 154-158 (Fig. 41) are known that can be applied to the selective complexation of amines and diamines [243-247]. 

Chiral amines and diamines are readily available substrates for the synthesis of ligands for transition metal-catalysed reactions since they can easily be transformed into chiral ureas and thioureas. Therefore, several groups have prepared chiral symmetrical ureas and thioureas, dissymmetrical ureas and thioureas, amino-urea and thiourea derivatives. Finally polyureas and non-soluble polythioureas were also prepared and tested as ligands for asymmetric catalysis. 

Catalytic Reductive Alkylation of Aromatic and Alkyl Amines and Diamines over Sulfided and Unsulfided Platinum Group Metals... 

Figure 17.1. General schematic for the reductive alkylation of primary amines and diamines...

In this study we examine the generalities in reductive alkylation however, since the subject is vast, we limited ourselves to the interaction of aromatic and aliphatic primary amines and diamines with ketones. The ketones examined include the cyclic ketone, cyclohexanone, and aliphatic ketones such as acetone, and methyl isobutyl ketone (MIBK). We limited our study to sulfided and unsulfided Pt and Pd catalysts supported on activated carbon that were commercially available from Evonik Degussa Corporation. 

Oxidation of ascorbate (reduction of 02 to H20) Oxidation of primary alcohols to aldehydes in sugars (reduction of 02 to 11202) Removal of amines and diamines Electron-transfer... 

In a similar manner, polymers with unsaturated chains or side chains can be converted to polyamines [66-69]. Conjugated diolefins usually undergo hydroformylation with low selectivities [70]. Mostly hydrogenation of at least one double bond occurs and mixtures of various saturated and unsaturated amines and diamines are obtained [71]. Similar to alkenes also alkynes may serve as unsaturated compounds in hydro aminomethylation reaction sequences. Although synthetically attractive, only a few investigations towards hydroformylation and hydroaminomethylation of alkynes in the presence of N-nuclcophilcs are known. Usually a preferred transformation to furanonic derivatives is observed under hydroformylation conditions [27]. 

The new method of Yoneda s group132 is also a one-pot diazotization-fluoro-de-diazoniation in a liquid-liquid two-phase mixture of pyridine and hydrogen fluoride. Yields for 25 aromatic amines and diamines are 50-100%, except for 2-and 3-fluorobenzoic acid, the three nitroanilines, 3- and 4-diaminobenzene and 4,4 -diaminodiphenyl-oxide (10-50%). In their 1994 paper the authors demonstrate that, in the same system, the photochemical decomposition gives in many cases significantly higher yields than the thermal reaction. The most spectacular increase in yield was found for the fluorination of 2-fluoroaniline where o-difluorobenzene was obtained photochemically in 80.2% yield, but thermally only in 0.6% ... 

Frankel and Klager have reported using the Mannich reaction for the condensation of 2,2-dinitroalkanols with ammonia and hydrazine. This method was used to synthesize 2,2,6,6-tetranitro-4-azaheptane (100%) and bis(2,2-dinitropropyl)hydrazine (162) (73%) from the reaction of 2,2-dinitropropanol (25) with ammonia and hydrazine hydrate respectively. This work was later extended to using polynitroaliphatic amines and diamines. " ... 

The approach to polyketide synthesis described in Scheme 5.2 requires the relatively nontrivial synthesis of acid-sensitive enol acetals 1. An alternative can be envisioned wherein hemiacetals derived from homoallylic alcohols and aldehydes undergo dia-stereoselective oxymercuration. Transmetallation to rhodium could then intercept the hydroformylation pathway and lead to formylation to produce aldehydes 2. This proposal has been reduced to practice as shown in Scheme 5.6. For example, Yb(OTf)3-cata-lyzed oxymercuration of the illustrated homoallyhc alcohol provided organomercurial 14 [6]. Rhodium(l)-catalyzed hydroformylation of 14 proved successful, giving aldehyde 15, but was highly dependent on the use of exactly 0.5 equiv of DABCO as an additive [7]. Several other amines and diamines were examined with variation of the stoichiometry and none proved nearly as effective in promoting the reaction. This remarkable effect has been ascribed to the facilitation of transmetallation by formation of a 2 1 R-HgCl DABCO complex and the unique properties of DABCO when both amines are complexed/protonated. 

Normal acylation of carbazole amines and diamines, without reaction at the ring nitrogen, has been reported. Such amides can be easily... 

Primary Aliphatic Amines and Diamines Hexylamine Monomethylamine Primary Aliphatic Amines Pyridine and Substituted Pyridines Paraquat... 

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