• Archives of Pharmacal Research
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• v.29 no.10
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• pp.840-844
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• 2006

For the exploration of pharmacophoric moiety of malloapelta B (1) possessing the inhibitory activity of $NF-{\kappa}B$ activation, structural variation of ${\alpha},{\beta}-unsaturated$ carbonyl motif was attempted. 1 was reduced by catalytic hydrogenation, sodium borohydride, and lithium aluminumhydride. Catalytic hydrogenation with 30 psi or 15 psi of $H_2$ gas of 1 generated 8-butyl-5,7-dimethoxy-2,2-dimethylchroman (2) and 1-(5,7-dimethoxy-2,2-dimethylchroman-8-yl)butan-1-one (3), respectively. Reduction with sodium borohydride occurred at the double bond of ${\alpha},{\beta}-unsaturated$ ketone of 1 to give 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)butan-1-one (4). Reduction of 1 with lithium aluminumhydride and then quenched with methanol and water produced unexpected products, 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)-3-methoxy-1-butene (5) and 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)-3-hydroxy-1-butene (6). These are formed from the isomerization of initial product 9 through the continuous conjugate carbocation intermediate 11. Addition of ethylmagnesium bromide and dimethyl malonate anion to 1 gave the conjugate adducts 7 and 8. Ethylmagesium bromide and sodium borohydride reduction unusually gave the conjugate addition due to steric congestion around carbonyl group of 1. Compound 2 exhibits the reduced inhibitory activity against $NF-{\kappa}B$ activation and the others do not show the activity. Therefore ${\alpha},{\beta}-unsaturated$ carbonyl group of 1 should be important for its inhibitory activity.

• Proceedings of the Korea Technical Association of the Pulp and Paper Industry Conference
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• 2006.06b
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• pp.337-347
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• 2006

Papers made from unbleached and bleached bagasse chemimechanical pulp were chemically modified by acetylation. The effects of irradiation on unbleached and bleached also reduced papers of bagasse chemimechanical pulp before and after acetylation were investigated in this study. Chemimechanical pulp was prepared from bagasse and then bleached with hydrogen peroxide. Unbleached and hydrogen bleached pulps were reduced by Sodium borohydride in different procedures. Paper sheets were prepared from pulps and then acetylated using a technical grade of acetic anhydride. Accelerated photo-aging was run on the samples using fluorescent lamps to verify photo-stability of paper sheets before and after pretreatments. Brightness reversion (as Post-color number) and other optical properties of the paper sheets were measured. Efficient inhibition of photo-yellowing of papers made from bagasse CMP was achieved by acetylation. The acetylated unbleached CMP was noticeably photo-bleached during irradiation. Sodium borohydride reduction followed by acetylation had the same effect as acetylation alone at the same degree of reaction time and reductive treatment did not affect the yellowing rate to any great extent. The pre-reduced, acetylated unbleached papers were, however, not brightened during irradiation. Calculation done by Kubelka-Munk equation showed that reductive treatment had little effect in reducing the photo-yellowing of paper made from CMP pulp; a small stabilization effect was observed in the case of bleached CMP, while unbleached CMP was slightly more prone to discolor in the later phase of photo-reversion. The improved stability towards light may was closely related to the decrease in the phenolic hydroxyl content as a result of blocking by acetyl groups during treatment with acetic anhydride. The results support the hypothesis that phenolic hydroxyl has an important role in the process of photo-reversion of high-yield pulps. The results obtained in this study demonstrate that the acetylation of paper manufactured from peroxide bleached Bagasse CMP significantly retards light-induced discoloration. The inhibition of yellowing is connected with a decrease in the phenolic hydroxyl content of both unbleached and peroxide bleached papers.

• Journal of the Korean Chemical Society
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• v.37 no.7
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• pp.648-654
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• 1993

$[M(cyclam)X_2]Y(M=Co^{3+},\;Fe^{3+},\;Mn^{3+}\;:\;X=Cl-^,\;Br^-,\;NCS^-\;:\;Y=Cl^-,\;Br^-,\;NCS^-),\;[Co(trans-14-diene)X_2]Y(X=Cl^-,\;Br^-\;:\;Y=ClO_4^-)\;and\;[Co(trans-14-diene)](ClO_4)_2$ were able to activate an molecular oxygen under sodium borohydride. 2,4-di-tert-butylphenol and 2,6-di-tert-butylphenol reacted with activated molecular oxygen to give 2,4-tert-butyl-1,6-benzoquinone(BQ) and 3,5,3',5'-tetra-tert-butyldiphenoquinone(DPQ). The saturated tetraazamacrocyclic complexes, $[Co(cyclam)X_2]Y$, were more an effective catalyst than $[Co(trans-14-diene)X_2]Y$ the unsaturated complexes in the formation of BQ and DPQ. The mole ratio of $O_2$ vs. catalyst $(O_2/M)$ for $[Co(cyclam)X_2]Y$ and [Co(trans-14-diene)X_2]Y$ was 1/1, while it was 1/2 for $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$. The results suggested that Co(III)-macrocyclic complexes activated molecular oxygen as superoxolike ${O_2}^-$ and $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$ activated that as peroxolike $O_2^{2-}$.

• 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.

• 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.

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.765-768
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• 2006

• Proceedings of the Korean Society of Precision Engineering Conference
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• 2007.06a
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• pp.727-728
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• 2007

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.305-308
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• 2014

• Bulletin of the Korean Chemical Society
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• v.24 no.1
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• pp.141-143
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• 2003

• Bulletin of the Korean Chemical Society
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• v.15 no.4
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• pp.273-273
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• 1994