Amines as reagents

Kuck, M., Balle, G., and Slawyk, W., Sampling of diisocyanates (HDI, TDI) in air by derivatisation with secondary amines as reagents - Part 1 Partial rate factors (PRF) of reagents. Analyst, 124, 933-939, 1999. 

Kappelmeier [35] has suggested the use of aniline, benzylamine, and phenyl-ethyl-amine as reagents for the identification and analysis of urea in UF resins. He has provided evidence that the methylene-ether groups form a bridge between urea residues in UF resins. The use of benzylamine in particular (which yields dibenzylurea from urea derivatives), has been developed as a method of analysis. In determining the ratio of urea to formaldehyde in UF resins, the benzylamine method has been coupled with a process of formaldehyde estimation which involves depolymerization with phosphoric acid, followed by distillation into alkaline potassium cyanide solution [36]. 

Throughout this chapter, we will focus on base metal-catalyzed reactions that create C-N bonds via C-H activation using amines as reagents and oxygen as the oxidant. This work does not aim to be comprehensive, but merely highlights some selected examples that illustrate the current state-of-the-art in this field. 

Chlorothioethers s. a,o-Di-chloromethyl sulfide (2-Chloro-l,l,2-trifluoroethyl)-diethylamine s. 2-Chloro-1,1,2-trifluoro-triethylamine 2-Chloro-l,l,2-trifluorotriethyl-amine as reagent 17, 549 suppl. 23 22, 571 Chlorotris(triphenylphosphine)-rhodium... 

To 5 ml. of water add 1-2 drops of the amine if the amine does not dissolve, add a drop or two of concentrated hydrochloric acid. Add 0-5-1 ml. of this amine solution to 2-3 ml. of the reagent an almost immediate precipitate indicates the presence of a primary amine. A slight turbidity indicates the presence of a primary amine as an impurity. (Primary aromatic amines generally require 2-3 minutes for the test. Urea and other amides, as well as amino acids, do not react.)... 

A method that achieves the same end result as that desired by alkylation of ammonia but which avoids the formation of secondary and tertiary amines as byproducts is the Gabriel synthesis Alkyl halides are converted to primary alkylamines without contam mation by secondary or tertiary amines The key reagent is the potassium salt of phthal imide prepared by the reaction... 

Collectors Fitting into Fattice Cavities. Lattice site fitting of collectors at sohd walls has been invoked as a means of explaining the selective behavior of amines (cationic coUectors) as reagents in the flotation-separation of soluble salt minerals such as KCl and NaCl (22). 

Both dimethyl carbonate [616-38-6] and diphenyl carbonate [102-09-0] have been used, in place of carbon monoxide, as reagents for the conversion of amines into isocyanates via this route (28,29). Alternatively, aniline [62-53-3] toluene diamines (I JJA), and methylene dianilines (MDA) have also been used as starting materials in the carbonylations to provide a wide variety of isocyanate monomers. 

Phosphorus(V) sulfide reacts with olefins, amines, Grignard reagents, and terpenes (6,26) as follows ... 

The use of silver (II) salts, particularly argentic picolinate, as reagents for hydroxyl oxidation has also been disclosed recently. The reaction may be run in acid, neutral or basic media in aqueous or polar organic solvents at room or slightly elevated temperatures. Primary alcohols may be oxidized to aldehydes or acids depending on the conditions used. Amines and trivalent phosphorous compounds are more sensitive to oxidation with this reagent than are hydroxyl groups. 

Carbonates, like esters, can be cleaved by basic hydrolysis, but generally are much less susceptible to hydrolysis because of the resonance effect of the second oxygen. In general, carbonates are cleaved by taking advantage of the properties of the second alkyl substituent (e.g., zinc reduction of the 2,2,2-trichloroethyl carbonate). The reagents used to introduce the carbonate onto alcohols react readily with amines as well. As expected, basic hydrolysis of the resulting carbamate is considerably more difficult than basic hydrolysis of a carbonate. 

Relative rates of alkylation of toluene and benzene using a mixture of nitro-sonium hexafluorophosphate, nitromethane (or acetonitrile) and aliphatic amine as the alkylations agent have been determined at 25 °C as follows360 1.5 (ethyl-amine), 2.5 (i-propylamine) and 3.5 (benzylamine) nothing more as yet is known about the kinetics of alkylation with these new alkylating reagents. 

This procedure also incorporates the use of bis(3-dimethylamino-propyl)phenylphosphine as a combined amine-phosphine reagent. The merits of using this basic phosphine as opposed to a tertiary amine and a phosphine lies in the ease of workup. Excess phosphine and phosphine sulfide can be removed by extraction with aqueous dilute acid. 

Although there are several reports in the literature on boron-mediated amide formations, the boron reagents had to be used in stoichiometric amounts.1-4-5-6-7-8-9 Recently, Yamamoto et al. presented the first truly catalytic method allowing for a direct amide formation from free carboxylic acids and amines as the reaction partners.10-1112 Best results were obtained by using phenylboronic acids bearing electron withdrawing substituents in the meta- and/or para-positions such as 3,4,5-trifluorophenylboronic acid or 3,5-bis(trifluoromethyl)boronic acid as the catalysts. 

Figure 17.10 Propargylamine can be used to add an alkyne group to amine-reactive reagents, such as the NHS ester group on the biotin-PEGj compound.

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