Synthesis of Amides and Amines via Catalytic Activation of Alcohols Using Ruthenium and Iridium Complexes

학위논문 (박사)-- 서울대학교 대학원 자연과학대학 화학부, 2017. 8. Soon Hyeok Hong.The research described in this thesis covers the development of new eco-friendly and atom-economic synthetic methods for C–N bond formation based on the transition-metal-catalyzed activation of alcohol. This study focused on the synthesis of synthetically and industrially valuable molecules such as amides and amines. Along with the great importance of the alcohol activation strategy, the basic concepts and the corresponding state-of-the-art reactions are explained in Chapter 1. Efficient synthesis of amides from alcohols and azides, a new alternative nitrogen source, using the alcohol activation strategy is described in Chapter 2. The amide synthetic method utilizing stable, easy-to-handle, and readily available starting materials is highly desirable. Our developed method presents the first example of amide synthesis starting from alcohols and azides via the Ru-catalyzed dehydrogenation of alcohol-in situ reduction of azides. Amides and secondary amines were synthesized from esters and primary amines for the first time using a commercially available Ir catalytic system as described in Chapter 3. Two important C–N bonds were obtained in one-pot sequential reactions via amidation and borrowing-hydrogen method. This method provides an efficient way to utilize an ester group using the removed alcohol as the next carbon source after the amidation. These synthetic protocols generate hydrogen or water as the non-harmful by-products, satisfying the concept of sustainable chemistry. The developed methods expand the synthetic versatility and efficiency of amide and amine bond formation. In the final part of this study, as a parallel concept to sustainable chemistry, a series of immobilized olefin metathesis catalysts were prepared (Chapter 4). Vinyl sulfonamide-based ligands were synthesized, and the ligands and silane groups were successfully linked via carbamate to immobilize the ligands on silica. The catalytic activities of these heterogeneous Ru catalysts for ring-closing metathesis were evaluated. The catalysts could be effectively removed from the reaction mixture.Chapter 1. Dehydrogenative Alcohol Activation 1 1.1 Introduction 1 1.2 Conventional and potential reactivity of alcohols 2 1.3 Amide bond synthesis 5 1.3.1 Introduction 5 1.3.2 Conventional amide bond formation method 6 1.3.3 Metal catalyzed dehydrogenative synthesis of amide 7 1.3.4 Other dehydrogenative amide synthesis 10 1.4 Borrowing hydrogen method 15 1.4.1 Introduction 15 1.4.2 Transition metal catalyzed N-alkylation of amines with alcohols 16 1.5 References 21 Chapter 2. Dehydrogenative Amide Synthesis: Azide as a Nitrogen Source 25 2.1 Introduction 25 2.2 Results and discussion 28 2.2.1 Optimization for amide synthesis from azides and alcohols 28 2.2.2 Substrate scope 30 2.2.3 Isotope labeled amide synthesis 34 2.2.4 Mechanism study 35 2.3 Conclusion 38 2.4 Experimental section 39 2.4.1 General information 39 2.4.2 General procedure for amide synthesis 40 2.4.3 Characterization of amides 40 2.4.4 References in supporting information 43 2.5 Reference 44 Chapter 3. Tandem Synthesis of Amides and Secondary Amines from Esters with Primary Amines under Solvent-Free Conditions 48 3.1 Introduction 48 3.2 Results and discussion 51 3.2.1 Optimization of the reaction 51 3.2.2 Substrate scope 53 3.2.3 Mechanism study 58 3.2.4 Applications 62 3.3 Conclusion 65 3.4 Experimental section 65 3.4.1 General information 66 3.4.2 GC analysis for the reaction profile 66 3.4.3 General procedure for amide synthesis 66 3.4.4 Synthesis of amides and secondary amines with different primary amines 69 3.4.5 Synthesis of amides and secondary amines with different esters 75 3.4.6 Complementary reaction optimization table 78 3.5 Reference 80Docto

Comparative Study on the Structure of Underlying Causes of Death among Korean in Autopsy Cases between 1930s and 1960s

An analysis of autopsy cases provides the most accurate statistical information on the structure of the cause of death. A total of 862 Korean cases which were autopsied in the Department of Pathology, Keijo Imperial Univetrsity Faculty of Medicine during 1929 to 1941, and a total of 1,540 Korean autopsy cases admitted to the National Medical Center at the period of 1958~1967 were statistically analysed according to the Korean Standard Classification of Causes of Death" provided by the Economic Planning Board of the Republic of Korea. The main objectives of this study is to examine the structure of the major causes of Korean deaths in 1930 sand 1960 s, and changing patterns of the main causes during those periods. Thus, the following results were obtained

Modeling of the performance characteristics of electrical energy storage devices

학위논문(박사)--아주대학교 일반대학원 :에너지시스템학과,2015. 8Chapter 1. Introduction 1 1.1 Background and motivation 1 1.2 Lithium Ion Batteries 2 1.3 Absorbent Glass Mat (AGM) Batteries 4 1.4 Ultracapacitors 6 1.5 Dissertation Outline 7 Chapter 2. Modeling the Effects of the Cathode Composition of a Lithium Iron Phosphate Battery on the Discharge Behavior 10 2.1 Introduction 10 2.2 Mathematical Model 12 2.2.1 Electrode Synthesis 12 2.3 Experimental Section 20 2.4 Results and Discussion 23 2.5 Conclusions 34 Chapter 3. Mathematical Model of the Cycle Life of an AGM Battery 36 3.1 Introduction 36 3.2 Mathematical Model 40 3.2.1 Chemical Reactions for the AGM Battery 40 3.2.2 Deterioration Factors of the AGM Battery 40 3.2.3 Aging Mechanisms of the AGM Battery 44 3.2.3.1 Corrosion at Cathode 44 3.2.3.2 Degradation of Active Materials 44 3.2.4 ChargeDischarge Behavior Governing Equations for the AGM Battery 45 3.2.5 Governing Equations of ageing model for the AGM Battery 52 3.3 Results and Discussion 55 3.3.1 The AGM Battery ChargeDischarge Modeling 55 3.3.2 Experimental section 60 3.3.3 Results of SOH and SOF Modeling for the AGM Battery 63 3.4 Conclusions 70 Chapter 4. Modeling of the Electrical and Thermal Behaviors of an Ultracapacitor 72 4.1 Introduction 72 4.2 Mathematical Model 76 4.3 Results and discussion 93 4.4 Conclusions 106 Chapter 5. Conclusions 107 Bibliography 110 국문요약 119 Appendix. Nomenclature 122DoctoralAmong various energies, electric energy is one that we cannot live without for a moment in this automated and computerized society. There are electric energy devices to allow people to store and use electric energy as needed. It is important to understand characteristics of electric energy devices for efficiently using these devices. This thesis is performed to predict characteristics of electric energy devices as a lithium ion battery, an absorbent glass mat (AGM) battery and an ultracapacitor. Chapter 1 described the fundamentals and application field for a lithium ion battery, an AGM battery and an ultracapacitor as typical electrical energy storage device. In chapter 2, this thesis reported a modeling methodology to predict the effects on the discharge behavior of the cathode composition of a lithium iron phosphate (LFP) battery cell comprising a LFP cathode, a lithium metal anode, and an organic electrolyte. A one-dimensional model based on a finite element method is presented to calculate the cell voltage change of a LFP battery cell during galvanostatic discharge. To test the validity of the modeling approach, the modeling results for the variations of the cell voltage of the LFP battery as a function of time are compared with the experimental measurements during galvanostatic discharge at various discharge rates of 0.1C, 0.5C, 1.0C, and 2.0C for three different compositions of the LFP cathode. The discharge curves obtained from the model are in good agreement with the experimental measurements. On the basis of the validated modeling approach, the effects of the cathode composition on the discharge behavior of a LFP battery cell are estimated. In chapter 3, for optimal design and operation of vehicle electrical systems, we conducted modeling to predict the AGM battery cycle life and performance. The AGM battery model was formulated considering various phenomena occurring inside an AGM battery, including electrochemical reaction, transfer of ions, and porosity of electrode. In addition, to predict AGM battery cycle life, we considered the additional factors of corrosion of electrode plate and loss of active materials as a function of charge?discharge cycles. Using electrochemical modeling of the AGM battery, we incorporated nonlinearity of AGM battery aging, which was impossible with electrical equivalent circuit modeling. The model was validated by comparison of results of the modeling and actual experimental data. Using the development modeling, SOH and SOF were calculated. In chapter 4, this thesis reported a modeling methodology to predict the electrical and thermal behaviors of a 2.7 V/650 F ultracapacitor (UC) cell from LS Mtron Ltd. (Anyang, Korea). The UC cell is subject to the charge/discharge cycling with constant-current between 1.35 V and 2.7 V. The charge/discharge current values examined are 50, 100, 150, and 200 A. A three resistor-capacitor (RC) parallel branch model is employed to calculate the electrical behavior of the UC. The modeling results for the variations of the UC cell voltage as a function of time for various charge/discharge currents are in good agreement with the experimental measurements. A three-dimensional thermal model is presented to predict the thermal behavior of the UC. Both of the irreversible and reversible heat generations inside the UC cell are considered. The validation of the three-dimensional thermal model is provided through the comparison of the modeling results with the experimental infrared (IR) image at various charge/discharge currents. A zero-dimensional thermal model is proposed to reduce the significant computational burden required for the three-dimensional thermal model

Glomerulopathies associated with Chronic Hepatitis ---Histological Reapprasal of Glomerular Lesions

In order to verify the immunologic mechanism in glornerulopathies following viral hepatitis in Korea. a light microscopic examination was carried out on 9 cases of glomerulopathy associated with histologically or clinically proven chronic and subsiding viral [tepatitis. Among the nine glomerular alterations were 6 cases of membrana-proliferative glomerulonephritis. 2 cases of membraneous glomerulopathy and 1 case of sclerosing glomerulonephritis probably resulting from mernbraneous glomerulopathy. Of the five liver needle biopsies 3 were chronic aggressive hepatitis, 1 subsiding acute viral hepatitis with residual fibrosis and micronodular cirrhosis of the liver. With relatively high incidence of membrano-proliferative glomerulonephritis among Koreans, seemingly reflected in part by the influence of serum hepatitis, especially with deposit of HBAg-Ab complexes, it is assumed that viral hepatitis is supposed to play an important role in the pathogenesis of glomerulonephritis in Korea. Also a discussion is made on that possibility of similar immune injury to the glomerular structures as shown in this investigation may replace the original concept of cirrhotic glomerulosclerosis

Pilot scale reactor에서 비촉매 환원공정을 이용한 NOxNO_x 제거 연구

학위논문(박사) - 한국과학기술원 : 화학공학과, 1997.2, [ xiii, 194 p. ]The present study entails a systematic experimental investigation and a kinetic model development of selective non- catalytic reduction of $NO_x$ by ammonia, urea, and hydrazine which is thought to be a successful replacement of ammonia or urea. The effects of urea molar ratio to NO, reaction temperature and additives (polyethylene oxide (PEO), CO, $C_3H_8$, MeOH and EtOH) on NO reduction in flue gas have been determined in a pilot-scale flow reactor (0.2 m-ID × 6.0 m-high). The flow rate of the flue gas was varied from 50 to 100 N㎥/hr. The inlet concentration of NO in the reactor was varied between 250 and 350 ppm and the outlet concentration of NO was measured at the injection temperature range of 700K-1373K at 50K intervals. During the experiments, the molar ratio of urea solution (5% w/w) to NO was varied from 1.0 to 2.5 and that of oxygen was varied in the range of 3 to 5%. Significant NO reduction begins to occur at a reaction temperature of approximately 1223K, and ammonia emission rapidly decreases with increasing the reaction temperature. As the temperature increases to approximately 1273K, the maximum NO reduction can be attained. At temperatures above 1273K, NO reduction decreases with increasing temperature and ammonia emission is negligible. The temperature range in which the effective NO reduction occurs is called ``temperature window``. The molar ratios of urea to NO does not affect the temperature window but the degree of NO reduction increases to 80% with increasing the molar ratio of urea to NO up to 2.0. Among the tested additives, CO additive has the greatest effect with respect to the shift of effective temperature window and alcohol additives have the least effect. The effect of reaction temperature and CO additive on the $N_2H_4 - NO_x$ reaction is determined with 12 % w/w $O_2$. The experimental procedure was basically the same as those of the urea process. The outlet concentration of NO was measured at the injection temperature ra...한국과학기술원 : 화학공학과

A Search for Korean Origins through Genetic and Comparative Linguistic Methods

In exploring the origins of the Korean language, there are three windows through which we may penetrate the mysteries of this difficult question: archaeological, genetic/ genomic, and linguistic. In this paper I will try to answer this question by looking mainly through the latter two windows. As many linguists have attempted to place the Korean language into the proper language family according to linguistic affinity, I also want to classify the Korean language with linguistically related languages, mainly the Altaic languages. The so-called Altaic linguistics is very unstable compared with the more rigorously documented Indo-European linguistics. The lack of sufficient evidence, such as a common indigenous lexicon, has made it difficult to ascertain the genetic relationships and origins of languages such as Korean, Japanese, Manchu-Tungusic (Man, Gold(i), Oroqen, Ewenke, Lamut, Nanay, etc.), Mongolian (Khalkha, Chakhar, Urat, Khorchin, Ordos, Buriat, Oirat, Kalmyk, Da(g)ur, Monguor, Yellow Uighur. etc.) and Turkish (Turkish, Turkmen(ian), Azerbaidjani, Uighur, Uzbek, Kumyk, Tatar, Kazakh, Kirg(h)iz, Yakut, Altai, and Chuvash, etc.), which are typically classified as Altaic. Recently Starostin (1991) claimed that Proto-Altaic had disappeared around the sixth century B.c. Other measures are needed to evaluate this hypothesis, though, since the intra-linguistic debate has not provided any clear evidence or breakthroughs. That is why we turn to genetics as an approach and incorporate the results to shed new light on the origins of the Korean language. It has been shown that analysis of mitochondrial DNA, transmitted through maternal lineage, can be used to test this kind of hypothesis. After collecting data from such ethnic groups as Korean, Japanese, Ewenke, Nanay, Khalkha, Buriat, and Turkish, we have investigated information on mtDNA (mitochondrial DNA). While we do not use the popular STR markers on Y chromosomes (namely, DYS19, DYS389I, etc.) in this study, we will type a number of Korean, Tungusic and Mongolian populations on Y chromosomes, and other nuclear markers such as the gene encoding cytochrome B will be isolated by the polymerase chain reaction, as in the next study,. In reality, it was rather difficult to extract genes from hair-roots and saliva, especially when there were not many samples available for serious study. Yet, we could fill the void for Koreans in the map that shows the mitochondrial DNA types in Africans, Australian Aborigines, Caucasians, East Asians, Native Americans, and New Guineans. The nucleotide sequences were determined through phylogenetic analysis. If we can position the sequences from Koreans in the currently available genealogical tree based on mitochondrial DNA, we may be able to reassess the existing hypotheses on linguistic genealogy. However, because primordial remains or ancient fragments of linguistic evidence are not readily available in Korea due to special geo-political situations, the position of the Korean language has been left unattested in the genealogical tree based on languages. Nonetheless, there are some examples similar to the Altaic languages that are estimated to have been used in Korea, and using these we may draw the linguistic tree shown below

Inflammatory Fibroid Polyps of the Stomach -Report of 2 Cases with Unusual Histological Characteristics-

Two cases of inflammatory fibroid polyps of the stomach in Korean men were presented. and their histological characteristics and pathogenesis were briefly discussed along the line of inflammatory basis Both lesions occurred in the antral portions of the stomach, and each was confined to the submucosa: One accompanied marked myxoid degeneration of stromal tissue as its earlier manifestation. Fundamental proliferative cells were of fibroblastic series , being separated by edematous or even myxoid collagenous fibers. Dispatched small arteries within the lesions were assumed to be original vascular structure of underlying tissue rather than the component of the lesion. It is of authors opinion that the lesion represents an over-response to certain specific inflammatory stimuli and eosinophilic infiltration reflects an organ• specific reparative process