• Bulletin of the Korean Chemical Society
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• 제19권7호
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• pp.776-779
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• 1998

Second-order rate constants have been measured spectrophotometrically for the addition reaction of a series of alicyclic amines to 3-butyn-2-one to yield their respective enamines at 25.0 'C. The reactivity of the amines increases with increasing the basicity of the amines. However, the Bronsted-type plot obtained exhibits a downward curvature as the basicity of the amines increases, i.e. βnuc decreases from 0.3 for low basic amines (pKa < 9) and to 0.1 for highly basic amines (pKa > 9). Such a curvature in the Bronsted-type plot is clearly indicative of a change in the reaction mechanism or transition state structure. From the corresponding reactions run in D2O, the magnitude of kinetic isotope effect (KIE) has been calculated to be about 0.8 for highly basic amines and 1.21 for weakly basic amines. The difference in the magnitude of KIE also supports a change in the reaction mechanism or transition state structure upon changing the basicity of the amines. Furthermore, the small KIE clearly suggests that H+ transfer is not involved in the rate-determining step, i.e. the addition reaction is considered to proceed via a stepwise mechanism in which the attack of the amines to the acetylene is the rate-determining step. The curvature in the Bronsted-type plot has been attributed to a change in the degree of bond formation between the amine and the acetylene.

• 공업화학
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• 제9권5호
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• pp.661-666
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• 1998

고시리카제올라이트 (HSZ), 거대망상수지입자(MR) 및 입상활성탄(GAC)에 의한 수용액중의 12가지 아민유도체의 평형흡착 실험 데이터와 Freundlich, Langmuir, Toth, Redlich-Peterson 식의 인자들을 각각 구하였다. 아민류의 흡착특징에 있어서는 고시리카제올라이트는 unfavourable, 입상활성탄은 favourable로 비선형이나, 거대망상수지흡착제는 선형관계의 특성을 나타내며, 변수가 2개인 Freundlich 식과 3개인 Redlich-Peterson 흡착등온식에 잘 일치하였다. HSZ, MR, GAC에 의한 아민류의 흡착능은 방향족>1급아민>2급아민 순이었으며, Freundlich상수 k와 n의 곱인 (k n)값은 HSZ와 MR 및 GAC에서 아민류의 끓는 점 $T_B$, 몰부피 $V_m$, 그리고 해리상수 $pK_a$에 비례하여 증가하였다.

• 약학회지
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• 제35권3호
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• pp.182-189
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• 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.

• 대한화학회지
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• 제6권2호
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• pp.148-154
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• 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.

• 미생물학회지
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• 제48권3호
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• pp.220-224
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• 2012

전통 장류 제품 내 유해한 biogenic amines 양을 감소하기 위해, 83종의 전통 장류에서 biogenic amines을 분해할 수 있는 5종의 균주들을 분리하였다. 이들 균주들을 histamine, tyramine, putrescine, cadaverine이 각각 5.3% 함유된 삶은 콩에 접종하여 10일 간 발효시킨 결과 biogenic amines 함량을 27-92% 수준으로 감소시켰다. 선발한 균주들의 형태 및 생화학적 특성, 16S rRNA 유전자 서열 해독 결과 5종의 균주들은 Bacillus subtilis 또는 B. amyloliquefaciens에 속했다. 이 선발 균주들을 사용함으로서 biogenic amines 수준을 제어하기 힘든 전통 장류의 제조에 이 선발 균주들의 사용은 이들 함량을 줄일 수 있는 효과적 방안이 될 수 있다.

• Bulletin of the Korean Chemical Society
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• 제7권1호
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• pp.70-73
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• 1986

New amino protective reagents, t-butyl benzotriazol-1-yl carbonate and benzyl benzotriazol-1-yl carbonate, for t-butoxycarbonylation and benzyloxycarbonylation of amines and amino acids have been developed. t-Butyl benzotriazol-1-yl carbonate reacts rapidly and cleanly with various amines and amino acids to afford N-Boc amines and N-Boc amino acids in high yields and benzyl benzotriazol-1-yl carbonate is also found to be very effective in the benzyloxycarbonylation of amino acids.

• Toxicological Research
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• 제31권3호
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• pp.299-305
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• 2015

An HPLC analytical method was validated for the quantitative determination of biogenic amines in agricultural products. Four agricultural foods, including apple juice, Juk, corn oil and peanut butter, were selected as food matrices based on their water and fat contents (i.e., non-fatty liquid, non-fatty solid, fatty liquid and fatty solid, respectively). The precision, accuracy, recovery, limit of detection (LOD) and quantification (LOQ) were determined to test the validity of an HPLC procedure for the determination of biogenic amines, including tryptamine, ${\beta}$-phenylethylamine, putrescine, cadaverine, histamine, tyramine, spermidine and spermine, in each matrix. The LODs and LOQs for the biogenic amines were within the range of 0.01~0.10 mg/kg and 0.02~0.31 mg/kg, respectively. The relative standard deviation (RSD) of intraday for biogenic amine concentrations ranged from 1.86 to 5.95%, whereas the RSD of interday ranged from 2.08 to 5.96%. Of the matrices spiked with biogenic amines, corn oil with tyramine and Juk with putrescine exhibited the least accuracy of 84.85% and recovery rate of 89.63%, respectively, at the lowest concentration (10 mg/kg). Therefore, the validation results fulfilled AOAC criteria and recommendations. Subsequently, the method was applied to the analysis of biogenic amines in fermented agricultural products for a total dietary survey in Korea. Although the results revealed that Korean traditional soy sauce and Doenjang contained relatively high levels of histamine, the amounts are of no concern if these fermented agricultural products serve as condiments.

• 대한화학회지
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• 제15권3호
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• pp.147-152
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• 1971

On the baisis of the calculations by the two centre Huckel method for sigma electron system, the electronic structure of the various aliphatic amines including ammonia, and the relationship between the observed $pK_b$ and the change in the sigma electronic energy, ${\Delta}E{\sigma}$ in the course of protonation are discussed. A parallelism is observed between the $pK_b$ and the calculated ${\Delta}E{\sigma}$ of the amines. Also, it is observed that the electron densities of hydrogen atom directly bonded to nitrogen of the amines, likewise have a linear relationship with the $pK_b$. Therefore, the basicity of the aliphatic amines may be estimated qualitatively by means of the two center Huckel method.

• Bulletin of the Korean Chemical Society
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• 제33권7호
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• pp.2251-2254
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• 2012

A rapid and practical green route for N-formylation of primary and secondary amines with formic acid at room temperature under the solvent-free conditions using HEU zeolite as a heterogeneous, reusable and highly efficient catalyst is described. The process is remarkably simple and environmentally benign. Excellent chemoselectivity was observed for the conversion of primary amines in the presence of secondary amines.

• Archives of Pharmacal Research
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• 제24권6호
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• pp.503-507
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• 2001

trans-Metanicotine, a subtype (${\alpha}_4{\beta}_2$)-selective ligand for neuronal nicotinic acetylcholine receptor, is under clinical phase for Alzheimer's disease. An efficient synthetic route for ($\pm$)-methyl-(1-aryl-4-pyridin-3-yl-but-3-enyl)-am ices, derivatives of tracts-metanicotine, was explored. Allylation reaction of aryl aldimines with allylmagnesium bromide in THF gave ($\pm$)-methyl-(1-aryl-but-3-enyl)-amines. Protection of the amines with the Boc group and following Heck reaction of the N-Boc amines with 3-bromopyridine gave ($\pm$)-methyl-(1-aryl-4-pyridin-3-yl-but-3-enyl)-carbamic acid tert-butyl esters. Deprotection of the N-Boc group in aqueous 1 N-HCI solution gave the titled amines in good yields. Thus, trans-metanicotine analogues modified at the ${\alpha}-position$ of the methylamino group with amyl groups were obtained in 5 steps.