• YAKHAK HOEJI
• /
• v.35 no.3
• /
• pp.182-189
• /
• 1991

Systematic study on the extraction of ion pair by the use of picric acid (PCA) as an ion pair forming reagent to the aliphatic amines has not be done by spectrophotometric method. The extraction of ion pair by the use of PCA and 23 kinds of the aliphatic amines was examined. The procedure is as follows; Elving's buffer solution (pH 1.3~10, ionic strength 0.5) each amine solution, and PCA solution were taken into a test tube. The mixture was shaken mechanically with chlorform. The organic phase was filtered through a filter paper to remove water droplets. The absorbance was examined at $\lambda_{max}$ against a reagent blank. Primary and secondary whose carbon number were more than 7 or 6, respectively, are extractable as ion pairs with PCA, while tertiary amines and quaternary ammonium salts are also extractable without the correlation of carbon number. It was considered that the ion pair extraction of primary and secondary amines was affected by the number of carbon of amines, but its extraction of tertiary amines or quaternary ammonium salts was affected by kind of aliphatic amines rather than pKa values or carbon number of amines.

• Journal of Integrative Natural Science
• /
• v.10 no.4
• /
• pp.175-191
• /
• 2017

In organic chemistry amide synthesis is performed through condensation of a carboxylic acid and an amine with releasing one equivalent of water via the corresponding ammonium carboxylate salt. This method is suffering from tedious processes and poor atom-economy due to the adverse thermodynamics of the equilibrium and the high activation barrier for direct coupling of a carboxylic acid and an amine. Most of the chemical approaches to amides formations have been therefore being developed, they are mainly focused on secondary amides. Direct carbonylations of tertiary amines to amides have been an exotic field unresolved, in particular direct carbonylation of trimethylamine in lack of commercial need has been attracted much interests due to the versatile product of N,N-dimethylacetamide in chemical industries and the activation of robust N-C($sp^3$) bond in tertiary amine academically. This review is focused mainly on carbonylation of trimethylamine as one of the typical tertiary amines by transition metals of cobalt, rhodium, platinum, and palladium including the role of methyl iodide as a promoter, the intermediate formation of acyl iodide, the coordination ability of trimethylamine to transition metal catalysts, and any possibility of CO insertion into the bond of Me-N in trimethylamine. In addition reactions of acyl halides as an activated form of acetic acid with amines are reviewed in brief since acyl iodide is suggested as a critical intermediate in those carbonylations of trimethylamine.

• Bulletin of the Korean Chemical Society
• /
• v.11 no.6
• /
• pp.494-496
• /
• 1990

Catalytic effects of tertiary amines on N-sulfinylation of p-toluenesulfonamide, p-toluidine, and p-toluamide have been investigated by proton NMR studies. Though the catalytic effects were dependent on the substrates, 4-dimethylaminopyridine, pyridine and triethylamine exerted stronger catalytic effects than imidazole and N,N-dimethylaniline. Among the substrates employed, p-toluenesulfonamide turned out to be catalyzed greater than p-toluidine and p-toluamide.

• Journal of the Korean Chemical Society
• /
• v.6 no.2
• /
• pp.148-154
• /
• 1962

The reactions between organic halides$(CCl_4,\;C_6H_5Br,\;C_6H_5Cl,\;C_6H_5I)$ and amines $(C_6H_5NH_2,\;R_2NH,\;R_3N,\;(CH_2)_5NH,\;pyridine)$ were studied under mixed u.v. irradiation. The modes of reactions were examined by means of gas chromatography and product-reactant ratio determination. The reaction of $CCl_4$ with amines give chloroform and hexachloroethanes, and the reaction of aromatic halides with amines gave biphenyl and benzene. In each series of reaction there obtained mainly corresponding amine hydrohalides, but no amination products. The reactivity was in the order of the basicity of amines and of the reactivity of organic hahides, except in the case of cyclic tertiary amine. The result was interpreted as a non-chain photodecomposition process. A competitive proton abstraction reaction path via the formation of a change transfer complex was proposed as the reaction mechanism.

• Bulletin of the Korean Chemical Society
• /
• v.23 no.1
• /
• pp.23-24
• /
• 2002

• Journal of the Society of Cosmetic Scientists of Korea
• /
• v.14 no.1
• /
• pp.1-15
• /
• 1988

A new method for liquid chromatography with post column reaction is suggested for the separation and quantification of tertiary amines. A mixture of triethanolamine and N-ethyl diethanolamine was separated by a strong cation exchange column, followed by spectrophtometric detection of the blue colors generated from the reaction of each amine with the Folin-Ciocalteau reagent. The tertiary amines were properly separated when an eluent of pH 9.5 containing 0.5M sodium nitrate was used. Under this condition, calibration curve of triethanolamine in 2-10mg/100ml concentration range was attained. Good results were obtained when cream and shampoo preparations containing known amount of triethanolamine were analysed according to this method. In case the sample did not contain any other interfering reducing substances, the amine was quantitatively determined by the simple reaction of the samples with Folin-Ciocalteau reagent, and the subsequent spectrophotometric measurement.

• Bulletin of the Korean Chemical Society
• /
• v.10 no.1
• /
• pp.12-15
• /
• 1989

Various tertiary amides have been subjected to the reduction by borane-THF in the presence of trimethyl borate at $0^{\circ}C$ and the product ratio of alcohol and amine have been analyzed in order to find out the possible way to obtain one product exclusively on the basis of the structure of amides. In the case of N,N-dimethyl derivatives of both linear aliphatic and aromatic amides the corresponding alcohols were produced predominantly. However, the bulkier tertiary amides such as N,N-diethyl and hindered acid derivatives afforded amines rather than alcohols. The mechanism of borane reduction of tertiary amides is also discussed.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.3
• /
• pp.746-748
• /
• 2010

• Bulletin of the Korean Chemical Society
• /
• v.16 no.3
• /
• pp.217-221
• /
• 1995

Axial coordination of anions or water to the square-planar nickel(Ⅱ) complexes of the hexaaza macrocyclic ligands 1, 2, and 3, which contain two extra uncoordinated tertiary nitrogens, have been investigated in aqueous solutions containing HX (X=Cl-, Br-, NO3-, or ClO4-) and/or NaX. The nickel(Ⅱ) complexes exist in the acidic solutions as equilibrium mixtures of the square-planar [Ni(L)]2+ (L=1, 2, and 3) and octahedral species [Ni(H2L)X2]2+ (H2L=diprotonated form of L). Some octahedral complexes have been isolated and characterized. The solution behaviors of the complexes indicate that the formation of the octahedral complexes are significantly promoted by the protonation of the uncoordinated tertiary amines. The proportion of the octahedral complexes depends on the type of acid, and increases in the order of HBr < HNO3 < HCl.

• Analytical Science and Technology
• /
• v.10 no.4
• /
• pp.231-239
• /
• 1997

We developed a procedure that can effectively separate and determine tertiary amines and quaternary ammonium salts in some samples with reverse phase ion-pair high performance chromatography, employing indirect spectrophotometric detection method. Detection and ion-pairing reagents used in this study were benzyl trimethylammonium chloride (BTMACl) and sodium dodecyl sulfate(DDSANa), respectively. Eluting the electrolyte solutions of some commercial electrolytic capacitors with a MeOH(40):water(60) eluent (pH 8.5 adjusted with NH4Cl-NH3 buffer) containing 0.010M DDSANa and 0.004 M BTMACl through Supelco LC-18 or ${\mu}$-Bondapak phenyl column, amines and ammonium salts contained in the sample were successfully separated and determined. Varying the composition, especially the content of quaternary ammonium salts, of electrolyte solutions based on this analysis. we could prepare the low impedance(0.08~0.13) electrolytic capacitors with excellent electrical properties and it was a confirmation that the analysis is favorable.