Ultraviolet spectrophotometric determination of primary and secondary aliphatic amines by formation of dithiocarbamates

Primary and secondary aliphatic amines (ca. 0.2–6 μg ml^?1) determined at 250 and 280 nm, respectively, after in situ derivatization to dithiocarbamates in a carbon disulphide/ aqueous sodium hydroxide two-phase system. Alcohols, aromatic and tertiary amines do not interfere.     

Indirect determination of some aliphatic secondary amines by catalytic thermometric titration

The determination of some secondary aliphatic amines by catalytic titration is described. The amines can be determined in the range 0.1-5 mumole with relative errors of about 3%.     

Spectrophotometric determination of aliphatic primary and secondary amines by reaction with p-benzoquinone

A simple, sensitive and selective spectrophotometric method has been developed for determination of aliphatic primary and secondary amines. It is based on a reaction with excess of p-benzoquinone in ethanol whereby 1:1 (amine:quinone) coloured products are obtained, which have maximum absorption at 510 nm and E(1cm)(1%) in the range 400-650. The effect of solvent, temperature, concentration of quinone and the presence of water have been kinetically investigated by the initial rate method. The conditions for monitoring amine concentrations as low as 0.1 microg/ml are optimized in the light of the kinetic data. Results with an average recovery of 98.5% and mean standard deviation of 1.9% are obtained with 9 different amines without interference from tertiary amines, ammonia, amides, imides, anilides, hydrazines and alpha-amino-acids.     

Anion-exchange initiation of reactions: Detection and spectrophotometric determination of aliphatic amines with 2,4-dinitrophenylhydrazine

The role of anion-exchange resin beads in the initiation of reactions of tertiary amines with 2,4-dinitrophenylhydrazine has been explored. This reagent has been used for the selective detection and determination of aliphatic amines. Radiochemical studies have been performed to show that the coloured species is adsorbed but not exchanged on ion-exchange beads. A model for the interaction is proposed.     

The spectrophotometric determination of aliphatic hydroxyl in esters with vanadium oxinate

A method is described for the precise determination of small amount of aliphatic alcohols in esters. The procedure is based on the formation of a red-coloured complex between the alcohol and a solution of vanadium oxinate in nitrobenzene. Studies have been made on the effect of solvent, reaction time and the stability of the complex on the accuracy of the determination.     

Application of silver/sulfide ion-selective electrode for the determination of aliphatic primary and secondary amines

Aliphatic primary and secondary amines were determined utilizing their reaction with carbon disulfide. A potentiometric titration of the formed dithiocarbamates (I) with silver nitrate using a silver/sulfide ion-selective electrode was carried out. The effects of solvent, base, temperature and reaction time were investigated. The optimum conditions for a quantitative formation of (I) requires a minimal amount of 1,4-dioxane, 2 drops of 0.2% sodium hydroxide solution, excess carbon disulfide to stand at room temperature for 15 min. The titration requires prior evaporation of the unreacted carbon disulfide at 46 ° C. An average recovery of 98.5% with a standard deviation of 0.69 was obtained for the analyzed amines.     

N-arylation of primary and secondary aliphatic amines on solid supports

A general and mild method for the N-arylation of primary and secondary aliphatic amines is reported. Copper acetate, triethylamine mediated C/N cross-coupling reaction of arylboronic acids at room temperature to solid-supported primary and secondary amines gave good to excellent yields of the desired N-arylated products.     

Microdetermination of secondary aliphatic amines using a copper ion-selective electrode

A simple, accurate, and selective method is described for the microdetermination of aliphatic secondary amines. The method is based on their reaction with carbon disulfide and ammoniacal copper sulfate at 40 °C for 30 min to yield copper dialkyldithiocarbamate. The excess copper is then measured by titration with EDTA or NaDDC using a copper ion-selective electrode. A mean recovery of 98.2% with a standard deviation of 0.8% is obtained for aliphatic secondary amines and their salts having a wide range of pK_a.     

Some new acridinium trifluoromethanesulfonates as spectrophotometric derivatization reagents for aromatic and aliphatic primary amines

Some new 9-substituted 10-methylacridinium trifluoromethanesuifonate (triflate) salts have been synthesized and shown to react in methanol with the model aromatic and aliphatic amines, aniline and n-butylamine, to form derivatives which absorb strongly at 445 and 439 nm, respectively. The color development is affected by heat and heating time and by the quantity of acridinium triflate used. A 10-50-fold molar excess of the triflate should be used and the solution heated at 60 degrees for 30 min. The linearity and reproducibility of the assay are improved by the presence of pyridine (for aniline) and triethylamine (for n-butylamine) in the reaction mixture. Beer's law is obeyed over the range 0-1860 ng/ml for aniline and 0-1440 ng/ml for n-butylamine, with each of the new reagents. The relative error and the precision of determination depends on the acridinium triflate used.     

Automatic determination of total aliphatic amines by on-line photometric liquid-liquid microextraction

An automatic flow method for the determination of total aliphatic amines has been developed. Using an integrated micro extraction unit at the detection point that allows continuous on-line monitoring of small organic plug from which amines are extracted. It is based on the formation of ion-pairs between aliphatic amines and sodium 1,2-naphthoquinone-5-sulphonate that are subsequently extracted into chloroform. The gradual enrichment of the organic phase with the ion-pair is continuously monitored at 460 nm. Absorbance readings at a fixed time and the slopes of absorbance-time recordings are the measured parameters used for determination purposes. The proposed method has been applied to the determination of total aliphatic amines in both synthetic and real (food) samples.     

Gas-chromatographic determination of aliphatic amines in natural surface water and wastewater

A procedure was developed for the gas-chromatographic determination of aliphatic amines C₇–C₂₀ with prederivatization by N-methyl-bis(trifluoroacetamide), in the concentration range of natural surface water, to 10^?4-1 mg/L, and wastewater, to 10^?3-1 mg/L. The conditions were optimized for the extraction preconcentration of aliphatic amines with toluene from natural surface water and wastewater. The detection limit for aliphatic amines at a signal-to-noise ratio of 3: 1 was 50 ng/L.     

The reaction of pentachloropyridine with aliphatic amines

The reaction of pentachloropyridine with aliphatic amines has given a series of 2-alkylaminotetrachloropyr idines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 7,pp. 959–962, July, 1970.     

A new spectrophotometric method for the determination of primary aromatic amines

A new spectrophotometric method for the assay of primary aromatic amines with metol-chromium(VI) reagent has been developed. The method is simple, reproducible and accurate within +/- 1.0%. It has been extended to the determination of drugs (in pure samples and pharmaceutical preparations) which either contain a free primary aromatic amine or release it through hydrolysis or reduction. The method is also applicable to the assay of p-aminobenzenesulphonamides in rat urine and blood. All the sulphonamide derivatives tested, as well as other aniline derivatives with an electron-withdrawing group in the para-position, afford nearly the same molar absorptivity. Depending on the absorptivity, 0.3-2 mumole of amine will give an absorbance of approximately 0.1.     

Laboratory investigation of annular denuders as sampling system for the determination of aliphatic primary and secondary amines in stack gas

A method for the sampling and analysis of aliphatic amines ranging from C₁ to C₅ and some diamines in exhaust gas is described. Two different annular denuder systems coated with phosphoric acid were used for the laboratory investigation of sampling gaseous amines. The denuder sampling systems were tested under different conditions for their readiness to work in stack gas.The reagent 2,4-dinitrofluorobenzene (DNFB) was used in pre-column derivatization of the amines investigated. The amino derivatives were separated using high performance liquid chromatography (HPLC) in conjunction with UV-detection. This method has been used for the examination of emissions from a landfill waste disposal and from animal husbandry with respect to traces of aliphatic amine emissions.     

Simultaneous kinetic determination of secondary amines and their isomers by a spectrophotometric stopped-flow method based on the formation of dialkyldithiocarbamates

Secondary amines react with carbon disulphide to form stable dialkyldithiocarbamates at high pH in aqueous Triton X-100 solution. The formation rates of dimethyl-, diethyl-, di-n-propyl-, diisopropyl-, di-n-butyl- and diisobutyldithiocarbamates and pyrrolidinedithiocarbamate were measured by a stopped-flow spectrophotometric method. The reaction rates were a function of the pH of the solution and depended on the size and structure of the amines. The rate of isoalkylamines was far slower than that of the n-alkyl analogues. Individual concentrations of amines were determined in a mixture of di-n- and diisopropylamine and in a mixture of diiso- and di-n-butylamine.     

Simultaneous spectrophotometric analysis of aliphatic amines utilizing thermochromism of charge-transfer complexes with tetrabromophenolphthalein ethyl ester.

Aliphatic amines, such as n-hexylamine (primary), di-n-hexylamine (secondary) and tri-n-hexylamine (tertiary amine), react with tetrabromophenolphthalein ethyl ester molecules (TBPEH) to form reddish or red-violet charge-transfer complexes (CT complexes) in 1,2-dichloroethane (DCE). The absorption maxima of the CT complexes with all primary amines occur at around 560 nm, with secondary amines at 570 nm and, with tertiary amines at 580 nm. The CT complex formation constants with TBPEH in DCE increase in the order of the primary, secondary and tertiary amines, but their constants decrease quantitatively with an increase in temperature. This phenomenon (thermochromism) could be applied to the simultaneous spectrophotometric determination of primary amine and secondary amine, or secondary amine and tertiary amine in a mixed solution utilizing the difference of absorbance with temperature changes.     

Rapid, selective and direct spectrophotometeric determination of aliphatic amines with m-dinitrobenzene

Color reaction has been studied for identification and spectrophotometric determination of aliphatic amines at room temperature by m-dinitrobenzene (m-DNB) as reagent. The λ_max value ranges from 458 to 570 nm. This is a simple and rapid method for determination of aliphatic amines in the acidic, water and acetone medium. Beer's law is verified for methylamine, dimethylamine, trimethylamine and n-butylamine in the range of 0.5–8 mg l⁻¹. The effect of pH on the molar absorptivity is investigated for a representative primary amine i.e. methylamine and it was observed that molar absorptivity increases from acidic to basic pH, with a sharp increase at pH 12. The kinetic of reaction was also studied and found that reaction time has marked effect on the molar absorptivity of electron donor–acceptor (EDA) complex. The detection of methyl amine has been reported in three real samples of water.