• Title/Summary/Keyword: borohydride

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Selective Reduction with Zinc Borohydride. Reaction of Zinc Borohydride with Selected Organic Compounds Containing Representative Functional Groups (수소화붕소아연에 의한 선택환원. 수소화붕소아연의 대표적 유기화합물과의 반응)

  • Yoon Nung Min;Ho Jun Lee;Hye Kyu Kim;Jahyo Kang
    • Journal of the Korean Chemical Society
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    • v.20 no.1
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    • pp.59-72
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    • 1976
  • The addition of one mole of zinc chloride to 2.33 moles of sodium borohydride in tetrahydrofuran at room temperature gave a clear chloride-free supernatant solution of zinc borohydride after stirring three days and standing at room temperature.The approximate rates and stoichiometry of the reaction of zinc borohydride with 54 selected organic compounds were determined in order to test the utility of the reagent as a selective reducing agent. Aldehydes and ketones were reduced rapidly, aromatic ketones being somewhat slowly, and the double bond of cinnamaldehyde was not attacked. Acyl halides were reduced rapidly within one hour, but acid anhydrides were reduced at a moderate rate. Carboxylic acids, both aliphatic and aromatic, were slowly reduced to alcoholic stage. Esters were inert to this reagent but a cyclic ester, γ-butyrolactone, was slowly attacked. Primary amides were reduced slowly with partial evolution of hydrogen, whereas tertiary amides underwent neither reduction nor hydrogen evolution. Epoxides and nitriles were all inert, as well as nitro, azo, and azoxy compounds. Cyclohexanone oxime and phenyl isocyanate were reduced slowly but pyridine was inert. Disulfide, sulfoxide, sulfone and sulfonic acids were stable to this reagent.

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Development of an Catalyst for Hydrolysis of Aqueous Sodium Borohydride Solution ($NaBH_4$ 수용액 분해 수소 발생용 최적 촉매 개발)

  • Yang Tae-Hyun;Krishnan Palanichamy;Lee Won-Yong;Kim Chang-Soo
    • 한국신재생에너지학회:학술대회논문집
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    • 2005.06a
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    • pp.296-298
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    • 2005
  • Hydrogen generation by the hydrolysis of aqueous sodium borohydride $(NaBH_4)$ solutions was studied using IRA-400 anion resin dispersed Pt. Ru catalysts and Lithium Cobalt oxide $(LiCoO_2)$ supported Pt, Ru and PtRu catalysts. The performance of the $LiCoO_2$ supported catalysts is better than the ion exchange resin dispersed catalysts. There is a marked concentration dependence on the performance of the $LiCoO_2$ supported catalysts and the hydrogen generation rate goes down if the borohydride concentration is increased beyond $10\%$. The efficiency of PtRu- $LiCoO_2$ is almost double that of either Ru-$LiCoO_2$ or Pt-$LiCoO_2$ for $NaBH_4$ concentrations up to $10\%$.

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Retardation of Degradation in Accelerated Aging of Cotton Cellulose Using Borohydride Reduction

  • Kim, Hye-Kyung;Choi, Hyung-Min
    • International Journal of Human Ecology
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    • v.8 no.1
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    • pp.1-8
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    • 2007
  • Degradation of cellulose during prolonged exposure in atmospheric conditions has been recognized as one of main problems in preserving cellulose-made products. The purpose of this research was therefore to study effects of borohydride reduction in improving both the color and strength retention of cotton fabrics artificially aged at temperatures ranging from $100^{\circ}C$ to $150^{\circ}C$. Results indicated that the fabrics treated with either sodium or tetramethylammonium borohydrides (TMA) were degraded at rates about one-half that of water-washed cotton. These results were consistent over the temperature range. Calculation of the activation energy (Ea) by different methods showed $Ea\;=\;25.5{\pm}\;1.5\;Kcal$, in keeping with measurements made by others at lower temperatures. The TMA-treatment was effective in minimizing discoloration of the fabrics with pre-baking, but not of the un-prebaked fabrics.

Cathode Catalyst of Direct Borohydride/Hydrogen Peroxide Fuel Cell for Space Exploration (우주탐사용 직접 수소화붕소나트륨/과산화수소 연료전지의 환원극 촉매)

  • YU, SU SANG;OH, TAEK HYUN
    • Journal of Hydrogen and New Energy
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    • v.31 no.5
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    • pp.444-452
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    • 2020
  • This study investigated the cathode catalyst of direct borohydride/hydrogen peroxide fuel cells for space exploration. Various catalysts such as Au, Ag, and Ni were supported on multiwalled carbon nanotubes (MWCNTs). Various techniques, such as transmission electron microscopy, Brunauer-Emmett-Teller method, scanning electron microscopy, and X-ray diffraction were conducted to investigate the characteristics of the catalysts. Fuel cell tests were performed to evaluate the performance of the catalysts. Ag/MWCNTs exhibited better catalytic activity than the Ni/MWCNTs and better catalytic selectivity of the Au/MWCNTs. Ag/MWCNTs presented good catalytic activity and selectivity even at an elevated operating temperature. The performance of Ag/MWCNTs was also stable for up to 60 minutes.

Effect of Trialkylborane on the Stereochemistry of Ketone Reduction with Lithium Borohydride

  • Nung-Min Yoon;Jin-Soon Cha;Won-Suh Park
    • Bulletin of the Korean Chemical Society
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    • v.4 no.1
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    • pp.14-17
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    • 1983
  • The effects of trialkylborane on the stereochemistry of ketone reduction with lithium borohydride were studied for the four representative ketones, namely 4-t-butylcyclohexanone, 2-methylcyclohexanone, norcamphor, and camphor. The presence of trialkylborane increased the yields of the less stable alcohols. For example, in the presence of tri-s-butylborane, 42 % yield of cis-4-t-butylcyclohexanol was observed whereas only 8 % yield with lithium borohydride alone in the reduction of 4-t-butylcyclohexanone. The in situ formation of lithium trialkylborohydride, by the hydride transfer from lithium trialkoxyborohydride to trialkylborane, was demonstrated as a possible mechanism for the catalytic effect of trialkylborane.

Kinetic Studies on the Reduction of 1-Benzyl-3-cyanoquinolinium Cations by Sodium Borohydride and the Applicability Marcus Theory

  • Han, In-Sook;Lee, Chang-Kiu;Han, In-Sup
    • Bulletin of the Korean Chemical Society
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    • v.8 no.2
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    • pp.79-83
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    • 1987
  • The reduction of a series of 1-substituted benzyl-3-cyanoquinolinium ions (p-$cH_3$, H, p-Br, m-F, p-CN) by sodium borohydride has been investigated. In all cases the products from these reactions were found to be 1, 2-dihydroquinolines over 82% yields. Rates of reduction were measured in basic condition and in solvent system consisting of 4 parts of isopropyl alcohol and 1 part of water by volume. Second order rate constants were obtained for these reactions. When the ratio of [$OH^-$] to [$BH_4^-$] becomes large the observed rate constants ($K_{obs}$) decrease by a small factor. Reaction scheme and rate law are discussed. Bronsted ${\alpha}(=\frac{d\;In\;k}{d\;In\;K})$ obtained by using the value of equilibrium constant K, which was obtained previously, was not 0. Instead, a value of 0.36 was obtained which indicated that the reduction by borohydride was structure-dependent according to the Marcus formalism even though the reaction rate was close to the diffusion limit.

Preparation of α-Linked 6-Deoxy-D-altro-heptopyranosidic Residues

  • 신영숙;천근호;Shin, E. Nam;Gerald O. Aspinall
    • Bulletin of the Korean Chemical Society
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    • v.16 no.7
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    • pp.625-630
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    • 1995
  • α-Linked D-altropyranosidic derivatives were obtained by configurational change at C-3 of α-D-mannopyranosides as the key step in preparation of allyl and methyl α-D-glycopyranosides of 6-deoxy-D-altro-heptose. The manno-altro conversion was effected by sequential reactions of Swern oxidation and stereoselective borohydride reduction. Allyl 4,6-O-benzylidene-2-O-p-methoxybenzyl-α-D-mannopyranoside was transformed to the corresponding altropyranoside via 3-oxo-arabino-hexopyranoside. Allyl 7-O-benzyl-6-deoxy-3,4-O-isopropylidene-α-D-altro-heptopyranoside has been prepared as a glycosyl acceptor to be coupled with β-D-GlcpNAc-(1→3)-α-D-Galp glycosyl donor for the synthesis of an O-antigen repeating unit of Campylobacter jejuni serotypes O:23 and O:36. Stereoselective borohydride reduction also succeeded in yielding methyl 2,4,7-tri-O-benzyl-6-deoxy-α-D-altro-heptopyranoside from the corresponding 3-oxo-α-D-arabino-heptopyranoside. C-6 Homologation was achieved by sequential reactions of cyanide displacement of 6-sulphonates, reduction of the resulting heptopyranosidurononitrile with diisobutylaluminum hydride, hydrolysis of the imine, and further reduction with sodium borohydride.

Study on the Stability of NaBH4 Solution during Storage Process (NaBH4수용액 저장과정 중 안정성에 관한 연구)

  • Sim, Woojong;Jo, Jaeyoung;Choi, Daeki;Nam, Sukwoo;Park, Kwonpil
    • Korean Chemical Engineering Research
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    • v.48 no.3
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    • pp.322-326
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    • 2010
  • Stability of sodium borohydride solution during storage was studied. In order to enhance the $NaBH_4$ stability, NaOH and KOH were added to the $NaBH_4$ solution. The effect of concentration of the borohydride and alkaline solution, temperature and materials of storage vessels on the rate of borohydride hydrolysis was investigated. The rate of hydrogen evolution decreased as the concentration of alkaline increased due to increase of $NaBH_4$ stability in the solution. The stability of $NaBH_4$ solution decreased when the borohydride concentration raised from 10 to 15 wt% and then increased when the $NaBH_4$ concentration increased above 15 wt% due to increase in the pH of the concentrated solution. The activity coefficient of hydrolysis of $NaBH_4$ solution(NaOH 3.0 wt%, $NaBH_4$ 25 wt%) was 115.1 kJ/mol and this value was 1.5~4.0 times higher than that of hydrolysis of $NaBH_4$ solution with catalyst. The borohydride solutions in glass and stainless-steel vessel were more stable than the solution in plastic(PE) vessel.

Two Phase Reduction of Carbonyl Compounds with Sodium Borohydride

  • Jin Soon Chong;Nung Min Yoon
    • Journal of the Korean Chemical Society
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    • v.15 no.3
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    • pp.117-120
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    • 1971
  • Possibility of two phase reduction of carbonyl compounds to the corresponding alcohols was studied. Thus the 0.5 M ether solutions of the representative carbonyl compounds were treated with alkaline stabilized sodium borohydride aqueous solution at room temperature. Butyraldehyde was reduced rapidly within one hr., whereas other aldehydes tested; heptaldehyde, benzaldehyde, and 1-naphthaldehyde were reduced in 6-12 hr. 2-Heptanone was reduced much slowly; 87% in 48 hr., however, acetophenone was reduced moderately; 92% in 12 hr. and cycloalkanones were reduced rapidly (cyclohexanone in 0.5 hr., and cyclopentanone in 3-6 hr.).

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One-Pot Reductive Amination of Carbonyl Compounds Using Sodium Borohydride-Cellulose Sulfuric Acid

  • Alinezhad, Heshmatollah;Tollabian, Zakieh
    • Bulletin of the Korean Chemical Society
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    • v.31 no.7
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    • pp.1927-1930
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    • 2010
  • A fast, efficient, and high yielding method for the preparation of amines by reductive amination of aldehydes and ketones using sodium borohydride in the presence of cellulose sulfuric acid in EtOH and under solvent-free conditions at room temperature is described.