Primary amines determination

Method 1. Treat 2 0 g. of the mixture of amines with 40 ml. of 10 per cent, sodium hydroxide solution and add 4 g. (3 ml.) of benzenesulphonyl chloi de (or 4 g. of p-toluenesulphonyl chloride) in small portions. Warm on a water bath to complete the reaction. Acidify the alkaline solution with dilute hydrochloric acid when the sulphonamides of the primary and secondary amines are precipitated. Filter off the solid and wash it with a little cold water the tertiary amine will be present in the filtrate. To convert any disulphOnamide that may have been formed from the primary amine into the sulphonamide, boil the solid under reflux with 2 0 g. of sodium dissolved in 40 ml. of absolute ethyl alcohol for 30 minutes. Dilute with a little water and distil off the alcohol filter off the precipitate of the sulphonamide of the secondary amine. Acidify the filtrate with dilute hydrochloric acid to precipitate the derivative of the primary amine. Recrystallise the respective derivatives from alcohol or from dilute alcohol, and identify them inter alia by a determination of the m.p. 

The results obtained have allowed us to develop the analytical procedures for the preconcentration and determination of microquantities of the monatomic phenols, aromatic amines and total volatile primary amines by HPLC and photometric methods. 

The kinetics of the hydrolysis of some imines derived from benzophenone anc primary amines revealed the normal dependence of mechanism on pH with ratedetermining nucleophilic attack at high pH and rate-determining decomposition of the tetrahedral intermediate at low pH. The simple primary amines show a linear correlation between the rate of nucleophilic addition and the basicity of the amine Several diamines which were included in the study, in particular A, B, and C, al showed a positive (more reactive) deviation from the correlation line for the simple amines. Why might these amines be more reactive than predicted on the basis of thei ... 

The determination of primary amines on the macro scale is most conveniently carried out by titration in non-aqueous solution (Section 10.41), but for small quantities of amines spectroscopic methods of determination are very valuable. In some cases the procedure is applicable to aromatic amines only, and the diazotisation method described for determination of nitrite (Section 17.38) can be adapted as a method for the determination of aromatic primary amines. On the other hand, the naphthaquinone method can be applied to both aliphatic and aromatic primary amines. 

The method can be applied to most phenols substituted in the ortho or meta position and to phenols substituted in the para position by OH or OCH3 groups most other substituents in the para position inhibit the reaction. Aromatic primary amines unsubstituted in the para position interfere and must be removed if possible before commencing the determination by extraction with acid. 

As discussed in the three preceding sections, the key intermediate in diazotizations is the A-nitroso derivative of the primary amine, the formation of which is usually the rate-determining step of diazotization. The subsequent steps are faster and therefore not easily accessible to study. The sequence of protonation, deprotonation, protonation, and dehydration in Scheme 3-36 seems to be the most reasonable mechanism. 

Fe/MgO catalysts with 5 to 30 mol % Fe have been prepared by impregnation and coprecipitation. Their reducibility has been measured and a comparison made of their Fe° surface areas. Catalysts prepared via coprecipitation yielded larger iron areas than those via impregnation. The activity and selectivity of the reduced catalysts for the hydrogenation of propanenitrile at 20-30 bar and 473 K and of ethanenitrile at 1 bar and 508 K have been determined. The most active catalysts are those prepared by coprecipitation and they show high selectivity for primary amines. The activity for ethanenitrile hydrogenation correlates with the iron surface area. 

Since the hydrogenation is a metal-catalyzed reaction, it is appropriate to use an oxide support to enhance the dispersion. However, the support, like the metal, needs to be chosen with the desired selectivity in mind. The early view [5] that the selectivity in nitrile hydrogenation is determined largely by the behaviour of the partially-hydrogenated intermediate, the imine R-CH = NH, which can either accept two further hydrogens to form the primary amine or can react with an already-formed amine to start a sequence which... 

Supported iron catalysts are notoriously difficult to reduce [6-8] and thus a substantial fraction of the iron can be expected to remain inactive for the catalysis of hydrogenation. Particular attention has therefore been paid to the preparation of Fe/MgO catalysts by several different methods and examination of their effectiveness in producing metallic iron of adequate specific surface area after reduction in hydrogen. The activity and selectivity for primary amine formation have been determined for the hydrogenation of ethanenitrile (acetonitrile) and propanenitrile. 

The current work indicates that sulfided platinum catalysts are, in general, more active and selective than Pt, Pd, or sulfided Pd catalysts for reductive alkylation of primary amines with ketones. The choice of the catalyst preparation parameters, especially the support, plays a major role in determining the performance of the catalyst. Diamines, especially of lower molecular weight, tend to react with ketones even at room temperature to form heterocycles such as imidazolidine, diazepanes, and pyrimidines. Hence, a continuous reactor configuration that minimizes the contact between the amine and the ketone, along with a highly active catalyst is desired to obtain the dialkylated product. In general, sulfided Pt appears to be more suited for the reductive alkylation of ethylenediamine while unsulfided Pd or Pt may also be used if 1,3-diaminopropane is the amine. 

For fast reactions (i.e., < 1 min.), open tubular reactors are commonly used. They simply consist of a mixing device and a coiled stainless steel or Teflon capillary tube of narrow bore enclosed in a thermostat. The length of the capillary tube and the flow rate through it control the reaction time. Reagents such as fluorescamine and o-phthalaldehyde are frequently used in this type of system to determine primary amines, amino acids, indoles, hydrazines, etc., in biological and environmental samples. 

Liu, J., Hsieh, Y.-Z., Wiesler, D., Novotny, M., Design of 3-(4-carboxybenzoyl)-2-quinolinecarboxaldehyde as a reagent for ultrasensitive determination of primary amines by capillary electrophoresis using laser fluorescence detection, Anal. Chem., 63, 408, 1991. 

Citron IM, Allan M (1964) Spectrophotometric determination of primary amines in aqueous solution with copper-(ethylenedinitrilo) tetraacetic acid. Anal Chem 36(1) 208-210... 

In determination of the enantiomeric purity of aliphatic primary amines, the use of (S-aminoalcohols and ot-amino acids 1R(—)-myrtenal as a derivatising agent has been tested.1... 

Derivatization of the optically active aldehydes to imines has been used for determination of their enantiomeric excess. Chi et al.3 have examined a series of chiral primary amines as a derivatizing agent in determination of the enantiomeric purity of the a-substituted 8-keto-aldehydes obtained from catalysed Michael additions. The imine proton signals were well resolved even if the reaction was not completed. The best results were obtained when chiral amines with —OMe or —COOMe groups were used [2], The differences in chemical shifts of diastereo-meric imine proton were ca. 0.02-0.08 ppm depending on amine. This method has been also used for identification of isomers of self-aldol condensation of hydrocinnamaldehyde. 

In determination of the absolute configuration of a-chiral primary amines, BINOL derivatives were used as chiral derivatizing agent.10 In this procedure, the chiral substrate was derivatized with R and S enantiomers of the 2,-methoxy-l,l -binaphthalene-8-carbaldehyde and the XH spectra of both diastereomers were compared. Comparison of the chemical shift differences of the diastereomers has allowed determination of the absolute configuration of the chiral substrate [5]. 

There are several methods available for the detection or measurement of amine groups in proteins and other molecules. Accurate determination of target amine groups in molecules before or after modification may be important for assessing reaction yield or suitability for subsequent crosslinking procedures. The following methods use commercially available reagents and are easily employed to detect primary amines with simple spectrophotometric measurement. 

Petty et al. [293] used flow injection sample processing with fluorescence detection for the determination of total primary amines in sea water. The effects of carrier stream flow rate and dispersion tube length on sensitivity and sampling rates were studied. Relative selective responses of several amino acids and other primary amines were determined using two dispersion tube lengths. Linear calibration curves were obtained over the ranges 0-10 6 M and... 

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