Primary amines, derivatives

Potassium chloride coUectors are primary amines derived from beef taUow. Commercially available amine is a homogeneous mixture of palmityl-. 

The first step in the formation of a cap involves nucleophilic attack of a deprotonated primary amine (derived from a coordinated ethylene-diamine) on the carbonyl carbon of formaldehyde to yield a bound imine... 

The classical post-column derivatization, as developed by Moore and Stein, 3 uses ninhydrin and detection is achieved at 570 nm for primary amine derivatives and at 440 nm for secondary amine derivatives with detection limits that strongly depend upon the instrumentation used. 

More examples of phosphazene synthesis by the reaction of carbon tetrachloride with primary amine derivatives of phosphines have appeared ... 

Long-Chain Amines and Their Salts, RNH3 X Primary amines derived from... 

Xu, G., Liu Y, and Sayre L. M. Independent synthesis, solution behavior, and studies on the mechanism of formation of a primary amine-derived fluorophore representing cross-hnking of proteins by (E)-4-hydroxy-2-nonenal. Chem. Res. Toxicol. 64 1999 5732-5745. 

The most important reagents used in flotation are collectors. In the case of flotation to treat sylvinite ores, a cationic collector is added to the closely sized and deslimed ore slurry. These collectors are mostly straight-chain aliphatic primary amines derived from natural fats... 

Moving to the use of 9-deo3gr-9-amino-epi Cinchona-, in 2007, shortly after the disclosure of their usefulness in conjugate additions, summarised in Section 14.2, Liu and coworkers demonstrated that these primaiy amines are also efficient in catalytic asymmetric 1,2-additions proceeding through enamine intermediates. The authors reported a highly enantioselective aldol addition of cyclic ketones to aromatic aldehydes catalysed by a primary amine derived from cinchonine (CNA) and proceeding in the absence of... 

An important contribution elucidating the potential of primary amines derived from Cinchona alkaloids has been the aldol cyclodehydration of achiral 4-substituted-2,6-heptanediones to enantiomerically enriched 5-substituted-3-methyl-2-cyclohexene-l-ones, presented by List and coworkers in 2008 (Scheme 14.26). Both 9-deo>y-9-amino-epr-quinine (QNA) and its pseudoenantiomeric, quinidine-derived amine QDA, in combination with acetic acid as cocatalyst, proved to be efficient and highly enantio-selective catalysts for this transformation, giving both enantiomers of 5-substituted-3-methyl-2-cyclohexene-l-ones with very good results. The authors observed that proline and the catalytic antibody 38C2 delivered poor enantioselectivity in this reaction. Furthermore, the synthetic utility of the reaction was exemplified by the first asymmetric synthesis of both... 

In 2007, Chen, Deng, and co-workers [42] reported the first asymmetric domino reaction catalysed by primary amines. A primary amine derived from quinine catalyzed a Michael-Michael-retro-Michael cascade, where the two reagents (64 and 65) act alternatively and selectively as the Michael donor and acceptor under readily controllable conditions. The corresponding cyclohexenones 66 were obtained in good yields and excellent stereoselectivities (Scheme 10.20). However, an extra step was sometimes necessary in order to push the reaction and thus to obtain the cyclic products. In this case, the initial Michael adduct was treated with benzylamine and TEA to render the cycloadduct. 

In the second case, Melchiorre and co-workers [59] used a Michael—Michael cascade reaction between an unsaturated spirocycle and an enone. This reaction is efficiently catalyzed by a primary amine derived (XIII) in a single step from the cinchona alkaloid hydroquinine. The reaction afforded the final spirooxindoles in... 

The efficiency of secondary amine catalysts is often eroded when moving from aldehydes to ketones as the donor carbonyl substrates, a trend that can be explained in terms of either the greater difficulty in the generation of the intermediate enamine species or their attenuated reactivity. To alleviate this situation, primary amines have emerged as a complementary family of amine catalysts. For instance, proline and related chiral secondary amines are not useful catalysts for the a-amination of aromatic enolizable ketones. As in other similar situations involving ketones as substrates, primary amines proved to be superior catalysts, although in these cases the presence of an acid co-catalyst seems to be crucial for reactivity. For instance (Scheme 11.4), primary amines derived from cinchona alkaloids can efficiently... 

More recently, it has been reported that primary amines derived from cinchona alkaloids [75] as well as proline derivatives [76], combined with achiral Brpnsted or Lewis acids, may also efficiently catalyze the enantioselective Biginelli reaction. Alternatively, a carbohydrate-based bifnnctional primary amine-thiourea catalyst was developed for this transformation, with similar enantiocontrol [77]. 

In their recent work, Liang s group disclosed a convenient protocol for accessing complex pyrrole structures based on a transition metal-catalyzed SnI or SN2 -like substitution reaction of allylpropargylic alcohols with primary amine derivatives (Scheme 8.99) [294]. Thus, easily accessible l-en-4-yn-3-ols 272, upon Au(III)-... 

A number of 4-1-1 protocols for the synthesis of pyrrole cores featuring the Cu (I)carbon-heteroatom bond forming reaction have been reported recently. Thus, Buchwald described an efficient Cu(I)-catalyzed synthesis of tri-, tetra-, and penta-substituted pyrroles 302 from 1,4-dihalo-l,3-dienes 300 and carbamates 281 (Scheme 8.107) [305]. This methodology displayed excellent functional group compatibility, providing good to... 

Deprotection can be achieved in a number of ways, with lithium aluminium hydride seemingly being the reagent of choice to selectively remove the triflate group (eq 3). Yields are excellent, at least with simple substrates. This is in contrast to the removal of triflates from primary amine derivatives, when Red-A1 is the preferred reagent, as LiAlH4 forms stable salts with such reactants. 

Xu G, Singh MP, Gopal D, Sayre LM (2001) Novel 2,5-hexanedione analogues. Substituent-induced control of the protein cross-linking potential and oxidation susceptibility of the resulting primary amine-derived pyrroles. Chem Res Toxicol 14 264—274... 

The EMA anhydride resins may be treated with iV,7V-dialkylaminoal-cohols to produce polyampholytes, ammonia, and primary or secondary amines to produce amides and a host of other mono and polyfunctional active hydrogen compounds to produce a wide variety of derivatives. The primary amine derivatives, i.e., amide-ammonium salts, may be transformed with heat to imide copolymers.Surface tension studies have been explored on EMA resins and octadecylamine derivatives of the copolymer.The effect of steric hindrance on accessibility, inhomogeneous consideration, electrostatic effects, etc., on the reaction of typical aliphatic amines and polymeric amines (polyethylene imine) with propylene-MA copolymer have been recently examined in great detail.The complexity of the reaction did not allow complete separation of the many variables. 

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