• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.201-206
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• 2013

The second-order rate constants have been measured spectrophotometrically for the reactions of paraoxon 1 and parathion 2 with a series of alicyclic secondary amines, $OH^-$ and $HOO^-$ ions in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. A linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.40 was obtained for the reactions of 1 with amines and $OH^-$. The reaction has been concluded to proceed through a concerted mechanism. $HOO^-$ deviates positively from the linear Br${\o}$nsted-type plot, implying that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect ($k_{HOO^-}/k_{OH^-}$) was found to be ca. 55 for the reaction of 1 and 290 for that of parathion 2, indicating that $HOO^-$ is highly effective in decomposition of the toxic phosphorus compounds although it is over 4 $pK_a$ units less basic than $OH^-$. Among the theories suggested as origins of the ${\alpha}$-effect (e.g., TS stabilization through an intramolecular Hbonding interaction, solvent effect, and polarizability effect), polarizability effect appears to be the most important factor for the ${\alpha}$-effect in this study, since the polarizable $HOO^-$ exhibits a larger ${\alpha}$-effect for the reaction of the more polarizable substrate 2.

• Journal of the Korean Chemical Society
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• v.23 no.2
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• pp.99-103
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• 1979

The reductive amination of three ${\alpha}$,${\beta}$-unsaturated aldehydes, cinnamaldehyde, crotonaldehyde, and acrolein are carried out successfully by tetracarbonylhydridoferrate in the presence of various primary amines. In a typical reaction, a mixture of potassium tetracarbonylhydridoferrate (22 mmole), an amine (22∼44 mole) and ${\alpha}$,${\beta}$-unsaturated aldehyde (22 mmole), in ethanol (30∼50 ml) was stirred for 9∼60 hours at room temperature under carbon monoxide atmosphere. All the products were characterized as secondary amines by mass, infrared, and nmr spectra as well as gas chromatographic data.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2443-2447
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate (7) and 4-nitrophenyl isonicotinate (8) with a series of cyclic secondary amines in $H_2O$ containing 20 mol % DMSO at $25.0^{\circ}C$. The Br${\o}$nsted-type plots for the reactions of 7 and 8 are linear with ${\beta}_{nuc}=0.90$ and 0.92, respectively, indicating that the reactions proceed through a stepwise mechanism with expulsion of the leaving group occurring in the rate-determining step. Comparison of the reactivity of 7 and 8 with that of 4-nitrophenyl benzoate (2a) and 4-nitrophenyl picolinate (6) has revealed that their reactivity toward the amines increases in the order 2a < 7 < 8 < 6, although the reactions of these substrates proceed through the same mechanism. Factors that control reactivity and reaction mechanism have been discussed in detail (e.g., inductive and field effects, H-bonding interaction, solvent effect, etc.).

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.2909-2912
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• 2009

The amines studied in this study are less reactive toward ethyl propiolate (3) in MeCN than in H$_2$O although they are 7 to 9 pK$_a$ units more basic in the aprotic solvent. The reactivity of morpholine and deuterated morpholine toward 3 is found to be identical, indicating that proton transfer occurs after rate-determining step (RDS). The fact that kinetic isotope effect is absent excludes a stepwise mechanism in which proton transfer occurs in RDS as well as a concerted mechanism in which nucleophilic attack and proton transfer occur concertedly through a 4-membered cyclic transition state (TS). Thus, the reactions have been concluded to proceed through a stepwise mechanism in which proton transfer occurs after RDS. Brønsted-type plots are linear with small ${\beta}_{nuc}$ values, i.e., ${\beta}_{nuc}$ = 0.29 in H$_2$O and ${\beta}_{nuc}$ = 0.51 in MeCN, indicating that bond formation is not advanced significantly in RDS. The small ${\beta}_{nuc}$ value also supports the conclusion drawn from the study of kinetic isotope effect.

• Bulletin of the Korean Chemical Society
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• v.28 no.2
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• pp.220-224
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• 2007

Second-order rate constants (kN) have been determined spectrophotometrically for reactions of 2,4-dintrophenyl 2-furoate (2) with a series of alicyclic secondary amines in 80 mol % H2O/20 mol % dimethyl sulfoxide (DMSO) at 25.0 oC. The furoate 2 is more reactive than 2,4-dintrophenyl benzoate (1) toward all the amines studied. The higher acidity of 2-furoic acid (pKa = 3.16) compared with benzoic acid (pKa = 4.20) has been suggested to be responsible for the reactivity order, at least in part. The Brønsted-type plots for the reactions of 1 and 2 are curved downwardly, indicating that the aminolyses of both 1 and 2 proceed through a zwitterionic tetrahedral intermediate (T±) with a change in the rate-determining step on changing the amine basicity. Dissection of the kN values into their microscopic rate constants has revealed that the pKao and k2/k-1 ratios for the reactions of 1 and 2 are identical, indicating that the nature of the nonleaving group (i.e., benzoyl and 2-furoyl) does not affect the reaction mechanism. The k1 values have been found to be larger for the reactions of 2 than for those of 1, which is fully responsible for the fact that the former is more reactive than the latter.

• Korean Journal of Food Science and Technology
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• v.5 no.3
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• pp.169-173
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• 1973

Secondary amines and nitrites in various daily foods have been known as the precursors of potent carcinogenic nitroso compound produced in the human stomach when they were ingested simultaneouly in high concentration. In this report, the amounts and distribution of secondary amines and nitrites in Korean daily foods, kim-chi, fishes, fish eggs, sausages, canned fish foods and fish sauces (salted fish) were studied.Nitrite contents were low in most subjected foods except in sausages. Secondary amines showed low contents in kim-chi, fishes, but high in fish sauces, fish eggs and canned fish foods. The result of this study suggested that the possible formation of carcinogenic nitrosamines during manufacturing, storage and cooking of all Korean foods should be studied.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.14 no.1
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• pp.7-14
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• 1981

Secondary amines are known as one of the precursors of nitrosamines which are potent carcinogenic compounds for human being and animals. In this study, trimethylamine and dimethylamine contents of salted, hot-air dried and sun dried samples of two commercial fishes, mackerel pike and seerfish were analyzed and quantitatively compared at three different temperature conditions. The formation of both secondary amines was more rapid at$10^{\circ}C\;and\;15^{\circ}C\;than\;at\;2^{\circ}C$. Residual amounts of trimethylamine oxide of salted samples were relatively higher than those of the other samples. Trimethylamine contents of hot-air dried mackerel pike and sun dried seerfish were relatively higher than those in the other samples, while those of salted samples were comparatively lower than those of others. Dimethylamine contents of hot-air dried samples were higher than those of the other samples, whereas those of salted samples were comparatively lower than those of the other samples.

• Korean Chemical Engineering Research
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• v.50 no.1
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• pp.135-140
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• 2012

In this study, the heats of absorption of $CO_2$ with aqueous solutions of primary, secondary and tertiary amine aqueous solutions were measured in the commercial reaction calorimeter SIMULAR (HEL, UK). The heats of absorption of 30 wt% amine aqueous solutions of MEA (monoethanolamine, primary amine), EAE(2-(ethylamino)ethanol, secondary amine), and MDEA (methyldiethanolamine, tertiary amine) were measured as function of the $CO_2$ loading ratio at $40^{\circ}C$, in each case. In addition, the heats of absorption of sterically-hindered amine aqueous solutions of AMP(2-amino-2-methyl-1-propanol, primary amine), DEA(diethanolamine, secondary amine) and TEA(triethanolamine, tertiary amine) were measured to observe the steric hindrance effect. The heat of absorption is high in the following order regardless of the steric hindrance: primary amine > secondary amine > tertiary amine. The heats of absorption of amines having sterically-hindered substituents surrounding nitrogen atoms are relatively low compare to that of sterically-free amines, although the difference is very small.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.11 no.7
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• pp.2708-2712
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• 2010

Amines, ammonia or 3-methoxypropylamine (MPA), are used to maintain the optimized pH for the prevention of corrosion in the secondary side of Pressurized Water Reactors (PWRs). They are differently dissociated as a function of temperature which is not same in each location of the water-steam cycle. pH at the operation temperature depends on temperature of fluid and equilibrium constants of water and amines. Thus, every amine provides the different pH in the entire secondary side so that pH is not only the sufficient parameter in corrosion control. The secondary parameter, i.e., buffer intensity, is the ability to maintain a stable pH when $H^+$ are added or removed due to the ingress of impurities or the reaction of corrosion. The buffer intensity is necessary to provide the selection criteria for the best pH control agent for secondary side and the basic understanding of the reason why the flow-accelerated corrosion(FAC) rate may demonstrate the bell-shape curve over temperature. The buffer intensities of ammonia and MPA were reviewed over the entire operation temperature of PWRs. The sufficient buffer intensity is provided for the inhibition of corrosion by ammonia in low temperature $(25{\sim}100^{\circ}C)$ and by DMA in high temperature $(150{\sim}250^{\circ}C)$. In terms of buffer intensity, i) the best pH control agent is an amine with $pK_a(T)$ range of pH(T)- $1{\leq}pK_a(T){\leq}pH(T)$ + 0.5 and ii) the amine solution should have sufficient buffer intensity, ${\beta}$ to inhibit corrosion, and iii) FAC rate may be maximum at the temperature, where ${\beta}_B/{\beta}$ ratio is lowest.

• Korean Chemical Engineering Research
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• v.61 no.4
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• pp.619-626
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• 2023

Primary and secondary amine-based sorbents were synthesized to investigate the operation capacity for the carbon dioxide separation TSA process. (3-Aminopropyl) triethoxysilane was used as a primary amine precursor as a crosslinking agent to synthesize a secondary amine precursor in which amine groups were crosslinked with a crosslinking agent. Carbon dioxide absorbed by primary amines is completely separated above 170 ℃. The working capacity of the primary amine absorbent was less than 2% when regenerated at 130℃. The secondary amine absorbent has a higher carbon dioxide separation capacity at a lower regeneration temperature than the primary amine absorbent. The secondary amine absorbent could predict process operation performance of about 6.5% with 2% carbon dioxide absorption and 100% carbon dioxide regeneration conditions. Therefore, it was found that the working capacity of the secondary amine absorbent was higher than that of the primary amine.