• Elastomers and Composites
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• v.55 no.1
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• pp.51-58
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• 2020

In this study, the thermal oxidation of raw natural rubber (NR) was investigated under controlled conditions by optical image and fourier transform infrared (FT-IR) analysis. The thermal oxidation was performed on a transparent thin film of raw NR coated on a KBr window in a dark chamber at 80℃ under low humidity conditions to completely exclude moisture and restrict light oxidation. Images of the thin film of raw NR were obtained before and after thermal oxidation. FT-IR absorption spectra were measured in the transmission mode at different thermal exposure times. The thermal oxidation of NR was examined by the changes in the absorption peaks at 3449, 1736, 1447, 1377, 1242, 1072, and 833 cm^-1, which corresponded to a hydroxyl group (-OH), a carbonyl group (-C=O) from an aldehyde and a ketone, a methylene group (-CH₂-), a methyl group (-CH₃), a carbon-oxygen single bond (-C-O) from an epoxide, a carbon-oxygen bond (-C-O) from an ether, an alcohol, a peroxide, or a cyclic peroxide, and a cis-methine group (cis-CCH₃=CH-), respectively. In the initial stage of thermal oxidation, two different types of free radicals were produced quickly and randomly by the homolytic cleavage of a double bond and allylic hydrogen abstraction. Aldehydes and ketones were formed from chain scissions of the double bonds and alcohols were produced from allylic hydrogen abstraction at the methylene or methyl groups. Two reactions seemed to proceed competitively with each other. At a later stage, oxidative crosslinks seemed to dominate through the combination of free radicals such as an allyl radical (CH=CHCH₂·), alkoxy radical (RO·), and peroxy radical (ROO·) and the reaction of a hydroperoxide (-ROOH) with a double bond. The image obtained after thermal oxidation showed hardening without cracks. Based on these observations, a plausible two-step mechanism was suggested for chain hardening caused by the thermal oxidation.

• Bulletin of the Korean Chemical Society
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• v.13 no.5
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• pp.531-537
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• 1992

The approximate rates and stoichiometry of the reaction of excess potassium 2-thexyl-1,3,2-dioxaborinane hydride(KTDBNH) with 55 selected compounds containing representative functional groups under standardized conditions (tetrahydrofuran, TEX>$0^{\circ}C$, reagent : compound=4 : 1) was examined in order to define the characteristics of the reagent for selective reductions. Benzyl alcohol and phenol evolve hydrogen immediately. However, primary, secondary and tertiary alcohols evolve hydrogen slowly, and the rate of hydrogen evolution is in order of $1^{\circ}$> $2^{\circ}$> $3^{\circ}$. n-Hexylamine is inert toward the reagent, whereas the thiols examined evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to give the corresponding alcohols. Cinnamaldehyde is rapidly reduced to cinnamyl alcohol, and further reduction is slow under these conditions. The reaction with p-benzoquinone dose not show a clean reduction, but anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol. Carboxylic acids liberate hydrogen immediately, further reduction is very slow. Cyclic anhydrides slowly consume 2 equiv of hydride, corresponding to reduction to the caboxylic acid and alcohol stages. Acid chlorides, esters, and lactones are rapidly and quantitatively reduced to the corresponding carbinols. Epoxides consume 1 equiv hydride slowly. Primary amides evolve 1 equiv of hydrogen readily, but further reduction is slow. Tertiary amides are also reduced slowly. Both aliphatic and aromatic nitriles consume 1 equiv of hydride rapidly, but further hydride uptake is slow. Analysis of the reaction mixture with 2,4-dinitrophenylhydrazine yields 64% of caproaldehyde and 87% of benzaldehyde, respectively. 1-Nitropropane utilizes 2 equiv of hydride, one for hydrogen evolution and the other for reduction. Other nitrogen compounds examined are also reduced slowly. Cyclohexanone oxime undergoes slow reduction to N-cyclohexylhydroxyamine. Pyridine ring is slowly attacked. Disulfides examined are reduced readily to the correponding thiols with rapid evolution of 1 equiv hydrogen. Dimethyl sulfoxide is reduced slowly to dimethyl sulfide, whereas the reduction of diphenyl sulfone is very slow. Sulfonic acids only liberate hydrogen quantitatively without any reduction. Finally, cyclohexyl tosylate is inert to this reagent. Consequently, potassium 2-thexyl-1,3,2-dioxaborinane hydride, a monoalkyldialkoxyborohydride, shows a unique reducing characteristics. The reducing power of this reagent exists somewhere between trialkylborohydrides and trialkoxyborohydride. Therefore, the reagent should find a useful application in organic synthesis, especially in the field of selective reduction.

• Bulletin of the Korean Chemical Society
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• v.13 no.2
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• pp.199-207
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• 1992

The approximate rates and stoichiometry of the reaction of excess sodium diethyldihydroaluminate (SDDA) with 68 selected organic compounds containing representative functional groups were examined under standard conditions (THF-toluene, $0^{\circ}C$ in order to compare its reducing characteristics with lithium aluminum hydride (LAH), aluminum hydride, and diisobutylaluminum hydride (DIBAH) previously examined, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, thiols and amines evolve hydrogen rapidly and quantitatively. Aldehydes and ketones of diverse structure are reduced rapidly to the corresponding alcohols. Reduction of norcamphor gives 11% exo-and 89% endo-norborneol. Conjugated aldehydes such as cinnamaldehyde are rapidly and cleanly reduced to the corresponding allylic alcohols. p-Benzoquinone is mainly reduced to hydroquinone. Hexanoic acid and benzoic acid liberate hydrogen rapidly and quantitatively, however reduction proceeds very slowly. Acid chlorides and esters tested are all reduced rapidly to the corresponding alcohols. However cyclic acid anhydrides such as succinic anhydride are reduced to the lactone stage rapidly, but very slowly thereafter. Although alkyl chlorides are reduced very slowly alkyl bromides, alkyl iodides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced very slowly; however, tertiary amides take up 1 equiv of hydride rapidly. Tertiary amides could be reduced to the corresponding aldehydes in very good yield ( > 90%) by reacting with equimolar SDDA at room temperature. Hexanenitrile is reduced moderately accompanying 0.6 equiv of hydrogen evolution, however the reduction of benzonitrile proceeds rapidly to the imine stage and very slowly thereafter. Benzonitrile was reduced to give 90% yield of benzaldehyde by reaction with 1.1 equiv of hydride. Nitro compounds, azobenzene and azoxybenzene are reduced moderately at $0^{\circ}C$, but nitrobenzene is rapidly reduced to hydrazobenzene stage at room temperature. Cyclohexanone oxime is reduced to the hydroxylamine stage in 12 h and no further reaction is apparent. Pyridine is reduced sluggishly at $0^{\circ}C$, but moderately at room temperature to 1,2-dihydropyridine stage in 6 h; however further reaction is very slow. Disulfides and sulfoxides are reduced rapidly, whereas sulfide, sulfone, sulfonic acid and sulfonate are inert under these reaction conditions.

• Korean Journal of Food Science and Technology
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• v.20 no.2
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• pp.176-187
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• 1988

Volatile flavor components in the Chinese quince fruits were trapped by simultaneous steam distillation-extraction method, and these were fractionated into the neutral, the basic, the phenolic and the acidic fraction. In the identification of carboxylic acids, the acidic fraction was methylated with diazomethane. Volatile flavor components in these fractions were analyzed by the high-resolution GC and GC-MS equipped with a fused silica capillary column. The total of one hundred and forty-five compounds from the steam volatile concentrate of the Chinese quince fruits were identified: they were 3 aliphatic hydrocarbons, 1 cyclic hydrocarbon, 4 aromatic hydrocarbons, 9 terpene hydrocarbons, 17 alcohols, 3 terpene alcohols, 6 phenols, 21 aldehydes, 7 ketones, 28 esters, 27 acids, 3 furans, 2 thiazoles, 2 acetals, 3 lactones and 9 miscellaneous ones. The greater part of the components except for carboxylic acids were identified from the neutral fraction. The neutral fraction gave a much higher yield than others and was assumed to be indispensable for the reproduction of the aroma of the Chinese quince fruits in a sensory evaluation. According to the results of the GC-sniff evaluation, 1-hexanal, cis-3-hexenal, trans-2-hexenal, 2-methyl-2-hepten-6-one, 1-hexanol, cis-3-hexenol, trans, trans-2, 4-hexadienal and trans-2-hexenol were considered to be the key compounds of grassy odor. On the other hand, esters seemed to be the main constituents of a fruity aroma in the Chinese quince fruits.