• Journal of the Korean Chemical Society
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• v.17 no.4
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• pp.275-285
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• 1973

The addition of one mole of aluminum chloride to three moles of sodium borohydride in tetrahydrofuran gives a turbid solution with enormously more powerful reducing properties than those of sodium borohydride itself. The reducing properties of this reagent were tested with 49 organic compounds which have representative functional groups. Alcohols liberated hydrogen immediately but showed no sign of hydrogenolysis of alkoxy group. Aldehydes and ketones were reduced rapidly within one hr. Acyl derivatives were reduced moderately, however, carboxylic acids were reduced much more slowly. Esters, lactones and epoxides were reduced readily than sodium borohydride or borane. Tertiary amide was reduced slowly, however, primary amide consumed one hydride for hydrogen evolution but reduction was sluggish. Aromatic nitrile was reduced much more readily than aliphatic nitrile. Nitro compounds were inert to this reagent but azo and azoxy groups were slowly attacked. Oxime was reduced slowly but isocyanate was only partially reduced. Disulfide and sulfoxide were attacked slowly but sulfide and sulfone were inert. Olefin was hydroborated rapidly.

• Advances in Energy Research
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• v.8 no.4
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• pp.223-231
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• 2022

An ex-situ gravitational fixed bed pyrolysis reactor was used over Al₂O₃ supported Ni₂P based catalyst with various Ni/P molar ratios (0.5-2.0) and constant nickel loading of 5.37 mmol/g Al₂O₃ to determine the hydrodeoxygenation of rubberwood sawdust (RWS) at atmospheric pressure. The 3D catalysts formed were characterized structurally as well as acidic properties were determined by hydrogen-temperature programmed reduction (TPR). The Ni₂P phase formed completely on Al₂O₃ for 1.5 Ni/P ratio, although lesser crystallite sizes of Ni₂P were seen at Ni/P ratios less than 1.5. Additionally, it was shown that when nickel loading level increased, acidity increased and specific surface area dropped, probably because nickel phosphate is not easily converted to Ni₂P. When Ni/P ratio was 1.5, Ni₂P phase fully formed on Al₂O₃. The catalytic activity was explained in terms of impacts of reaction temperature and Ni/P molar ratio. At relatively high temperature of 450℃, the high-value deoxygenated produce was predominantly composed of n-alkanes. Based on the findings, it was suggested that hydrogenolysis, hydrodeoxygenation, dehydration, decarbonylation, and hydrogenation are all part of mechanism underlying hydrotreatment of RWS. In conclusion, the synthesized Ni₂P/ Al₂O₃ catalyst was capable of deoxygenating RWS with ease at atmospheric pressure, primarily resulting in long chained (C₉-C₂₄) hydrocarbons and acetic acid.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.6 no.2
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• pp.75-91
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• 2020

[^99mTc]Tc-Hexamethylpropylene amine oxime (HMPAO) is currently used as a regional cerebral blood flow imaging agent for single photon emission computed tomography (SPECT). The HMPAO ligand exists in two isomeric forms: d,l and meso showing different properties in vivo. Later studies indicated that brain uptake patterns of ^99mTc-complexes formed from separated enantiomers differed. Separation of enantiomers is difficult by fractional crystallizations method. Usually, the substance is obtained in low chemical yield in a time-consuming procedure. Furthermore, the final product still contains some impurity. So we have developed new efficient route for synthesis of R,R- and S,S-HMPAO enantiomeric compounds in 6-steps. Nucleophilic substitution (S_N2) reactions of 2,2-dimethylpropane-1,3-diamine either with S- (1a) or R-methyl2-chloropropanoate (1b) were performed to produce compounds R,R- (2a) or S,S-isomer (2b) derivatives protected with benzylchloroformate (Cbz), respectively. And then Weinreb amide and methylation reaction using Grignard reagent, oxime formation with ketone group and deprotectiion of Cbz group by hydrogenolysis gave S,S- (7a) or R,R-HMPAO (7b), respectively. Entaniomeric compounds were synthesied with high yield and purity without any undesired product. The 7a or 7b kits containing 10 ㎍ SnCl₂-2H₂O were labeled with ^99mTc with high radiolabeling yield (90%).

• Clean Technology
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• v.16 no.1
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• pp.19-25
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• 2010

In this work, the conversion of crystalline cellulose into polyols in the presence of hydrogen was examined over noble metal (Pt, Ru, Ir, Rh, and Pd) catalysts supported on activated carbon. For comparison, Pt/${\gamma}-Al_2O_3$ and Pt/H-mordenite were also investigated. Several techniques: $N_2$ physisorption, X-ray diffraction(XRD), inductively-coupled plasma-atomic emission spectroscopy (ICP-AES), temperature-programmed reduction with $H_2$ ($H_2$-TPR) and CO chemisorption were employed to characterize the catalysts. The cellulose conversion was not strongly dependent on the types of the catalyst used. Pt/AC showed the highest yields to polyols among activated carbon-supported noble metal catalysts, viz. Pt/AC, Ru/AC, Ir/AC, Rh/AC and Pd/AC.

• Korean Chemical Engineering Research
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• v.50 no.3
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• pp.435-441
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• 2012

The direct conversion of cellulose into polyols in $H_2$ was examined over Pt catalysts supported on various zeolites, viz., mordenite, Y, ferrierite, and ${\beta}$. For comparison, Pt catalysts supported on ${\gamma}-Al_2O_3$, $SiO_2-Al_2O_3$, and $SiO_2$ were also tested. The physical properties of the catalysts were probed with $N_2$ physisorption. The surface acidity was measured with temperature programmed desorption of ammonia ($NH_3$-TPD). The Pt content was quantified with inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The Pt dispersion was determined with CO chemisorptions and transmission electron microscopy (TEM). The conversion of cellulose appeared to be mainly dependent on the reaction temperature and reaction time because it depends on the concentration of $H^+$ ions reversibly formed in hot water. Pt/H-mordenite (20) showed the highest yield to polyols among the tested catalysts. Pt/H-zeolite was superior to Pt/Na-zeolite for this reaction. The polyol yield was dependent on the surface acid density and the external surface area.

• Journal of the Korean Chemical Society
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• v.5 no.1
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• pp.33-37
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• 1961

We have shown that carboxy-peptidase destroys the biological activity of angiotensin octa-and deca-peptides. Since Proline occurs as the seventh amino acid from the amino end of the chain and since carboxypeptidase does not cleave proline from a peptid chain, it is evident that the heptapeptid H.asp-arg-val-tyr-ileu-his-pro.OH is formed by this hydrolysis. This peptide must then be biologically inactive. In order to determine whether the phenyl group of the C-terminal amino acid was the necessary requirement for biological activity of the octapeptide, $ala^8$ angiotensin octapeptide(amino acids of peptides numbered from amino end) was synthesized. For this synthesis the four dipeptides were prepared: carbobenzoxy-L-prolyl-L-alanine-P-nitrobenzyl-ester, m.p. $134-135^{\circ}C,$ carbobenzoxy-L-isoleucyl-imidazole benzyl-L-histidine methyl ester, m.p. $114-116^{\circ}C,$ carbobenzoxy-L-valyl-L-tyrosine hydrazide and carbobenzoxy B-benzyl-L-aspartyl-nitro-L-arginine. The first three dipeptides were obtained as crystalline compounds. Imidazole-benzyl-L-histidine was used in the hope that it would block the histidine imidazole against side reactions in steps subsequent to the formation of the C-terminal tetrapeptide. Also, it was through that the imidazole benzylated peptides would be easier to crystallize. This, however, was not the case. The tetrapeptide, carbobenzoxy-L-isoleucyl-L-im, benzyl-histidyl, L-prolyl-L-alanine-nitrobenzyl ester was not obtained in a crystalline form. Neither could the mono-or dihydrobromide of the tetrapeptide free base be induced to crystallize. Carbobenzoxy-L-valyl-L-tyrosine azide was condensed with the tetrapeptide free base to yield the protected hexapeptide; carbobenzoxy-L-valyl-L-tyrosyl-L-isoleucyl-L-im, benzyl, histidyl-L-Prolyl-L-alanine-nitrobenzyl ester. Upon removal of the carbobenzoxy group with hydrogen bromide in acetic acid an amorphous free base hexapeptide ester was obtained. This compound gave the correct C, H, N analysis and contained the six amino acids in the correct ratio. The octapeptide was obtained by condensing this hexapeptide with carbobenzoxy-B-benzyl-L-aspartyl-nitro, L-arginine using the mixed anhydride method of condensation. This amorphous product was proven to be homogenous by chromatography in two solvent systems and upon hydrolysis yielded the eight amino acids in correct ratio. The five protecting groups were removed from the octapeptide by hydrogenolysis over palladium black catalyst. Biological assay of the free peptide indicated that it possessed less than 0.1 per cent of both pressor and oxytocic activity of the phenylalanine8 angiotensin. This suggests that the phenyl group is a point of attachment between angiotensin and its biological receptor site.

• Journal of Soil and Groundwater Environment
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• v.11 no.5
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• pp.35-42
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• 2006

The following results were obtained in the reductive degradation of hexachloroethane (HCA), and surface characteristics by using iron sulfide ($FeS,\;FeS_{2}$) mediators. HCA was degraded to pentachloroethane (PCA), tetrachloroethylene(PCE), trichloroethylene(TCE) and cis-l,2-dichloroethylene (cis-1,2-DCE) by complicated pathways such as hydrogenolysis, dehaloelimination and dehydrohalogenation. FeS had more rapid degradation rates of organic solvent than $FeS_{2}$. In liquidsolid reaction, the reaction rates of organic solvents were investigated to explain surface characteristics of FeS and $FeS_{2}$.. To determine surface characteristics of FeS and $FeS_{2}$, the specific surface area and surface potential of each mineral was determined and the hydrophilic site ($N_{s}$) was calculated. The specific surface area ($107.0470m^{2}/g\;and\;92.6374m^{2}/g$) and the $pH_{ZPC}$ of minerals ($FeS\;PH_{ZPC}=7.42,\;FeS_{2},\;PH_{ZPC}=7.80$) were measured. The results showed that the Ns of FeS and $FeS_{2}$ were $0.053\;site/mm^{2}\;and\;0.205\;site/mm^{2}$, respectively. $FeS_{2}$ had more hydrophilic surface than FeS. In other words, FeS have more hydrophobic surface site than $FeS_{2}$.

• Clean Technology
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• v.28 no.3
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• pp.232-237
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• 2022

Biorefineries, in which renewable resources are utilized, are an eco-friendly alternative based on biomass feedstocks. Alginic acid, a major component of brown algae, which is a type of marine biomass, is widely used in various industries and can be converted into value-added chemicals such as sugars, sugar alcohols, furans, and organic acids via catalytic hydrothermal decomposition under certain conditions. In this study, ruthenium-supported activated carbon and magnesium oxide were mixed and applied to the depolymerization of alginic acid in a batch reactor. The addition of magnesium oxide as a basic promoter had a strong influence on product distribution. In this heterogeneous catalytic system, the separation and purification processes are also simplified. After the reaction, low molecular weight alcohols and organic acids with 5 or fewer carbons were produced. Specifically, under the optimal reaction conditions of 30 mL of 1 wt% alginic acid aqueous solution, 100 mg of ruthenium-supported activated carbon, 100 mg of magnesium oxide, 210 ℃ of reaction temperature, and 1 h of reaction time, total carbon yields of 29.8% for alcohols and 43.8% for a liquid product were obtained. Hence, it is suggested that this catalytic system results in the enhanced hydrogenolysis of alginic acid to value-added chemicals.

• Journal of Soil and Groundwater Environment
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• v.9 no.2
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• pp.11-19
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• 2004

Chlorinated and nitroaromatic compounds are non-degradable substances that are extremely toxic and are known to be carcinogens and mutation causing agents. Moreover, the half-lives of substances such as carbon tetrachloride, hexachloroethane and nitroaromatic compounds are several decades. In this study, the optimal conditions to detoxify chlorinated compounds by the reductive degradation were investigated. The following results were obtained in the reductive degradation of CCl$_4$, C$_2$Cl$\_$6/, C$_2$HCl$\_$5/, C$_2$Cl$_4$, and C$_2$HCl$\_$5/ by using Fe, FeS and FeS$_2$ as mediators. CCl$_4$ was reduced to CH$_2$Cl$_3$ and CH$_2$Cl$_2$in anaerobic conditions when FeS was used as a mediator. While the reduction of CCl$_4$ to CHCl$_3$ was rapidly proceeded, the reduction of CHCl$_3$ to CH$_2$Cl$_2$ was occurred slowly. Further reduction to CH$_3$Cl was not observed. Unlike CCl$_4$, C$_2$Cl$\_$6/ was degraded to C$_2$HCl$\_$5/, C$_2$Cl$_4$. C$_2$HCl$_3$ and cis-1,2-C$_2$H$_2$Cl$_2$ by complicated pathways such as hydrogenolysis, dehalo-elimination and dehydrohalogenation. A small amount of C$_2$HCl$\_$5/ was detected only in the early stages of the reduction. However, majority of the C$_2$Cl$\_$6/ was reduced to C$_2$Cl$_4$. cis-1,2-C$_2$H$_2$C1$_2$ was the only product among other possible isomers.