相間移動觸媒에 의한 鹽化 벤질과 알콜올類와의 反應

呂壽東,韓仁淑,沈光澤,張萬植 경북대학교 교육대학원 1985 논문집 Vol.17 No.-

Recently, Phase Transfer Catalyzed Organic Synthesis is studied intensely. The Reactions of benzyl chloride with various alcohols (Et, n-Pr, iso-Pr, n-Bu, iso-Bu, sec-Bu, tet-Bu, Ph, Bz-OH) were investigated under Phase Trasfer Catalysis in this research. Benzyltrietylammonium chloride(B.T.E.A.C), dodecyltrietylammonium bromide(L.T.E.A.B) and tetrabutylammonium chloride(T.B.A.C) were used as Phase Transfer Catalyst. The Optimum Conditions between benzyl chloride and varios alcohols were studied in the presence of T.B.A.C which proved to be most effective among catalysts tested. Optimized conditions were as following. The molar ratio between benzyl chloride and tertiary butanol was 1:3. The amount of catalyst was 1.08mmol. And the amount of 50% NaOH aqueous solution was 7g. Under optimized conditions, it has been observed that benzyltet-alkyl ether, benzylphenyl ether and dibenzyl ether can be obtained in good yield over 80%, benzyliso-alkyl ether in about 50%, benzyln-alkyl ether only in less than 20%. The tendency of yield in various alcohols was increased Et<Pr<Bu<Bz<Ph-OH. And the tendency of yield in isomeric alcohols was increased primary<secondary<tertiary alcohol.

Methanol과 DMF용매에서의 Phenacyl bromide와 치환피리딘類의 置換基效果에 關한 硏究

呂壽東,趙舜煥,沈光澤 경북대학교 과학교육연구소 1979 科學敎育硏究誌 Vol.3 No.-

The rates of the reaction of phenacyl bromide with substituted pyridines in MeOH and DMF were measured by electric conductivity method. The rates of reaction were increased with the electron donation power of substituents of pyridiness and the results were more increased in DMF than MeOH The isokintic relationship was seen between Ea and ΔS^≠, it's temperature was 401˚K in MeOH and 202˚K in DMF. Bro¨nsted linear relationship was shown as log k=0.28pka -2.47 (r=0.988) in MeOH at 45℃ log k=0.37pka -1.79 (r=0.981) in DMF at 45℃ The Hammett polt showed a linearity about substituent except for 4-NH_2, 4-CN. This deviations of above 2 groups were considered to be attributed to the localization of π-electrone on pyridine ring induced by the nuclear nitrogen atom, resonauce effects and solvent effects.

Phenyl Chloroformate와 置換아닐린의 아미드化 反應

呂壽東,文泰守,沈光澤 慶北大學校 1985 論文集 Vol.39 No.-

The second-order rate constants of carbamate formation from phenyl chloroformate and substituted anilines were determined conductometrically in acetone. The effect of substituent of substituted anilines were discussed. The amidation of phenyl chloroformate with several anilines of electron-donating groups are faster than that of anilines of electron-withdrawing groups. 〔For example, k_2 values: 1.91(p-Me, at 0℃), 1.22×10 exp (-2)(p-NO_2, at 0℃)〕. Hammett-type plots of the rate data with σ(σ^-) gave two straight lines 〔for anilines with electron-donating groups: log k_2=-4.61σ(σ^-)+1.77(r=0.98) in acetone at 10℃, for anilines with electron-withdrawing groups: logk_2=-0.73σ(σ^-)+1.12(r=0.98) in acetone at 10℃ Based on the Hammett plots, Bronsted plots and activation entropy, we assume an addition-elimination mechanism for the amidation of phenyl chloroformate with substituted anilines. In the case of anilines with electron-donating substituents, the rate of C-N bond formation increase and also assist the rate of Cl^- elimination. Therefore, the rate determining step seems to be Cl^- elimination. On the other hand, in the case of anilines with electron-withdrawing groups, they decrease not only the rate of C-N bond formation but the rate of Cl^- elimination. Thus C-N bond formation become rate-determining step.

置換 Phenacylbromide와 Pyridine類와의 反應에 관한 溶媒와 置換基效果에 대한 硏究

沈光澤 울산과학대학 1981 연구논문집 Vol.6 No.1

DMF와 MeOH 두 溶媒中에서 置換 Phenacylbromide와 Pyridine 類와의 反應速度를 電氣傳導度法으로 測定하였다. 反應速度는 Pyridine의 置換基에 對해서는 Electron-releasing 能力이 클수록 빨랐으며 Phenacylbromide 類에 對해서는 그 反對였다. 또 MeOH 中에서 反應速度가 빨랐으며 等速關係와 Bro¨nsted plot에서는 좋은 直線關係를 보였고 Hammett plot에서도 4-NH_2, 4-CN 基를 除外하고는 S_N-2 反應 특징인 좋은 相關性을 얻었다. 實驗結果를 分析해 보고 反應 Mechanism을 檢討해 보았다. The rates of the reaction of substituted phenacylbromides with pyridines in MeOH and DMF were measured by electric conductivity method. The effect of substituents and solvents o the reaction were discussed. The rates of reaction were increased with the electron releasing power of substituents of pyridine and the results were more increased in DMF than MeOH. The isokinetic relationship was seen between E_a^‡ and ΔS^‡, it's temperature was 401°K in MeOH and 202°K in DMF. Br nsted linearelationship was shown as logK=0.31 PKa-2.65 in MeOH at 45℃ logK=0.36 PKa-1.79 in DMF at 45℃ The Hammett plot showed a linearity about substituents except 4-NH_2, 4-CN. This deviation of above 2 groups were considered to be attributed to the localization of π-electron on pyridine ring induced by the nitrogen atom, resonance effect, and solvent effect. From above results and the reports of Baker, Hughes, and Peason, It was considered that this reaction was S_N-2 mechanism in which nucleophile simultaneously attacks between the carbonyl group and α-carbon to form π-complex.

Evaluation of adrenal suppression after dexamethasone therapy as an antiemetic in cancer patients (초)

( Young Kwang Shim ),( Hye Suk Han ),( Sung Nam Lim ),( Tae Keun Oh ),( Hyun Jung Jeon ),( Ki Hyeong Lee ),( Seung Taik Kim ) 대한내과학회 2010 대한내과학회 추계학술발표논문집 Vol.2010 No.-

反應速度에 關한 硏究 및 分子軌道法의 應用 : 第三次 Amine의 四次化 反應 Studies on the Quaternization of Tertiary Amines

李甲龍,沈光澤 울산과학대학 1982 연구논문집 Vol.7 No.1

單純 Hu¨ckel 法으로 Phenacylhalide (X=Cl; PNC, Br; PNB, I; PNI)와 β-Phenethyl halide (X=Cl; PEC, Br; PEB, I; PEI) 그리고 親核試藥으로 Pyridine를 통하여 이들의 π-電子密度 및 Frontier 電子密度를 구하여서 親核試藥이 어느 位置에 공격될 것인지를 고찰한다. 용매 MeOH 中에서 이들의 Substrate와 親核試藥이 反應함에 따라 生成되는 鹽을 電氣傳導度法으로 測定해서 反應速度常數를 구하였으며 反應速度는 PNX보다는 PEX가 느렸다. E^≠_a 및 ΔS^≠ 값을 구하여서 Menshutkin 反應과 비교하여 反應 Mechanism을 檢討해 보았다. The molecular orbital theory was applied to the quaternization of tertiary amines of phenacyl halides, β-phenethyl halides, with pyridine. The π-election density and frontier election density were calculated by simple Hu¨ckel method. The expected position of substrate were in agreement with expriment. The rate of reaction was measured by means of electric conductivity because the reaction is a kind of salt-formation. The rate constant for the reaction of phenacylhalide with pyridine is larger than that for the reaction of phenethylhalide with pyridine. The values of entropy (ΔS^≠) and activation energy (E^≠_a) were similar to those of the Menshutkin reaction-typical S_N2)-type. This reaction showed that the cleavage of the c-x bond in S_N2 transition state was prior to the role of necleophile.

스테인레스강의 도장 전처리에 관한 연구

김석현,심광택 울산과학대학 1991 연구논문집 Vol.16 No.-

본 연구는 스테인레스강에 대한 화성피막의 구조확인과 전처리액의 조제에 목적이 있다. 세척하지 않는 Chromium chromate 전처리법이 대체로 적당하며 Chromium chromate 화성피막은 분자응집의 비결정질의 겔형으로 생각된다. [Cr^(3+)]/[Cr^(6+)]의 값이 0.3 정도일 때 도막의 부착력이 우수하다. 인산, 실리카 및 수화된 산화크롬 등이 도막의 부착력에 기여한다. This Study is aimed to confirm the structure of paint base coating and prepare the pre-treatment solution for stainless steel. The chromium chromate method of no-rinse is desirable and the structure of chromium chromate coating is inferred as amorphous gel type of molecular aggregation. In case that the value of [Cr^(3+)] to [Cr^(6+)] is about 0.3, the adhesion of paint is excellent. Phosphoric acid, Silica and hydrated Chromiun oxides contribute to the adhesion of paint.

대퇴골 간부 골절 후 불유합의 수술적 치료

심재익 ( Jae Ik Shim ),김택선 ( Taik Seon Kim ),이성종 ( Sung Jong Lee ),이석하 ( Suk Ha Lee ),김영배 ( Young Bae Kim ),윤정로 ( Jong Ro Yoon ),설의상 ( Eui Sang Seol ),박광열 ( Kwang Yeol Park ),강대웅 ( Dae Woong Kang ) 대한골절학회 2001 대한골절학회지 Vol.14 No.3

목적: 대퇴골 간부 골절치료 후 발생한 불유합의 수술적 치료 결과를 임상적 및 방사선학적으로 분석하고자 하였다. 대상 및 방법: 1993년 1월부터 1999년 12월까지 대퇴골 간부 불유합으로 수술한 환자 21예를 대상으로 하였으며 추시 기간은 평균 15개월이었다. 초기 골절의 원인, 형태와 분류 및 불유합의 원인을 임상적 및 방사선학적으로 분석하였다. 불유합의 수술 방법으로 자가골 이식술과 교합성 골수강내 금속정을 이용한 견고한 내고정술을 시행하였으며 골유합의 기간과 결과를 분석하였다. 결과: 평균 골유합 기간은 22주이었으며 21예중 18예(85.7%)에서 골유합 소견을 보였고 합병증으로는 하지 단축과 파행이 2예, 관절 부분 강직이 2예, 천부 감염이 2예이었다. 결론: 대퇴골 간부 불유합의 치료시 그 원인과 형태에 따라 자가골 이식술과 교합성 골수강내 금속정을 이용한 견고한 내고정술로 양호한 결과를 얻을 수 있을 것으로 생각되었다. Purpose: The purpose of this study is to analyze the clinical and radiological result of surgical treatment for femoral shaft nonunion. Materials and methods: From January 1993 to December 1999, 21 cases of femoral shaft nonunion were treated surgically and followed for an average of 15 months. We analyzed initial cause of injuries, classification of fractures, and cause of nonunion in clinically and radiologically. The authors analyzed the average time to union and results after surgical treatment by rigid internal fixation with interlocking intramedullary nail and autogenous bone graft. Results: The mean duration of bony union was 22 weeks and bony union achieved in 18 cases(85.7%) of 21 cases. The complications were shortening of leg length and limping gait in 2 cases, partial limitation of knee joint in 2 cases, superficial infection in 2 cases. Conclusion: Rigid internal fixation with interlocking intrameduallary nail and bone graft is useful method of treatment for femoral shaft nonunion according to cause and type of nonunion.

치환(置換) Phenacyl bromide와 Pyridine류(類)와의 반응(反應)에 관(關)한 반응속도론적(反應速度論的) 연구(硏究)

려수동 ( Soo Dong Yoh ),침광택 ( Kwang Taik Shim ),황규탁 ( Kyu Tag Howang ) 경북대학교 과학교육연구소 1978 科學敎育硏究誌 Vol.2 No.-

The rates and the acyivation parameters for the reaction of substituted phenacyl bromides with pyridines in methanol were measured. The effects of substituents on the reaction of substiuted phenacyl bromides with pyridines were discussed. The rates of reaction were increased with the electron attraction power of substituents of phencyl bromides. The isokinetic relationship was seen between Ea and ΔS≠. The exellent linear relationships, given by following equation, were observed between log kand pka of pyridines except for 4-cyanopyridine. log k=0.31 pka -2.65 in MeOH at 45℃ The Hammett o plot showed a linearity about substituents of phenacyl bromi-des and pyridines except for p-methoxy, 4-cyano groups. This deviation of 4-cyanopyrdine was considered to be attributed to the localization of π-electron on pyridine ring induced by the nuclear nitrogen atom and crano group. From the above results and the reports of Baker, Hughes, and Pearson, it was considered that this reaction was a SN2 mechanism in which nucleophile simultaneously attachks between the carbonyl group and a-carbon to form π-complex.

Studies on the Quaternization of Tertiary Amines (Ⅱ). Kinetics and Mechanism for the Reaction of Substituted Phenacyl Bromides with Substituted Pyridines

여수동,심광택,이경아,Yoh Soo Dong,Kwang Taik Shim,Lee Kyung A Korean Chemical Society 1981 대한화학회지 Vol.25 No.2

치환 브롬화페나실과 치환 피리딘과의 반응속도를 메탄올과 DMF 용매중, 25∼$45^{\circ}C$의 온도범위에서 전기전도도법으로 측정하였다. 그 결과 두 용매 다 같이 치환 피리딘에서는 전자를 주는 기가 치환되었을 경우 반응속도 상수는 컸으며, 반대로 전자를 끄는 치환기일 경우는 반응속도 상수가 작았다. 기질에서의 치환기 효과는 핵에 전자를 끄는기가 치환되었을 경우 반응속도는 증가하였다. 이 사실들은 탄소원자에 아민이 친핵적으로 공격한다는 것을 알 수 있다. 브롬화페나실과 피리딘의 반응에서 보여준 등속온도는 메탄올과 DMF에서 각각 614와 $202^{\circ}K$였고 $Br{\phi}nsted {\beta}$값은 0.29와 0.36이었다. 치환 브롬화페나실과 피리딘과의 반응의 경우는 등속온도는 전자를 끄는 치환기일 수록 감소하였으며, ${\beta}$값은 그 반대였다. 위의 결과로부터 p-Cl에서 p-MeO 브롬화페니실로 감에 따라 N…C 결합형성이 점차적으로 줄어들고 있으며 결합 형성은 DMF가 메탄올보다 우세하게 진전함을 추측할 수 있다. 치환 피리딘의 경우 Hammett식의 ${\rho}$값은 양 용매에서 모두 부(-)의 값을 가졌다. 핵 치환 브롬화페나실에서의 ${\rho}$값은 0.3의 적은 값이었으며 이는 메틸렌탄소에 피리딘의 질소 원자가 직접적으로 $S_N2$공격을 한다고 생각된다. Kinetics and mechanism for the reaction of substituted phenacyl bromides with substituted pyridines have been determined at 25, 35 and $45^{\circ}C$ in methanol and dimethylformamide by the conductivity method. The rate constants for the reaction of various pyridines with phenacyl bromide shown that electron-donating substituents in the pyridine increase the rate, while electron-attracting one decrease in both solvents. The effect of substituents in substrate, the rate being increased by electron-attracting substituents. This is as expected for nucleophilic attack of amines on the carbon atom. Isokinetic and $Br{\psi}nsted$ linear relationship were shown in the reaction of phenacyl bromide with pyridines in both solvent in which isokinetic temperature were obtained 614, $202^{\circ}K$ and ${\beta}$ values were 0.29, 0.36 in methanol and dimethylformamide respectively. In the case of the reaction of substituted phenacyl bromide with pyridines, isokinetic temperature decreases with increasing electron-attracting ability of the substituents in the phenacyl bromide, while the ${\beta}$ values were reverse. From the above results, it can be inferred that N…C bond formation decreases progressively from p-chloro- to p-methoxyphenacyl bromide and the bond formation predominates in DMF than methanol. The ${\rho}$ values of Hammett equation of the reaction of phenacyl bromide with substituted pyridines are negative in both solvent, but its value was larger negative in DMF than methanol and the ${\rho}$ value of that of substitutted substrates with pyridine was 0.3, the low value is ascribed to direct $S_N2$ attack of the nitrogen atom in pyridine ring at the methylene carbon.