• Title/Summary/Keyword: Carbonyls

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Oxidative Rearrangement of Tertiary Allylic Alcohols (3차 알릴알코올의 산화전위반응)

  • In Kyu Kim;Chang Sok Oh;Young Tech Hong
    • Journal of the Korean Chemical Society
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    • v.29 no.4
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    • pp.414-418
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    • 1985
  • A general synthesis of ${\alpha},\{\beta}$-unsaturated carbonyl compounds has been developed by oxidation of t-allylic alcohols. In simpler system, pyridinium chlorochromate oxidation affords the functionality transposed carbonyls in excellent yields, making the reaction a useful and versatile synthetic method.

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MPV-Reduction of C=O bond with Al-substituted-dialkylalan; A Theoretical Study on Relative Reactivity of Various Carbonyl Substrates

  • Nahm, Keepyung
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.546-550
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    • 2014
  • Relative reactivity of various carbonyl and acid derivatives in MPV-type (Meerwein-Ponndorf-Verley) reduction with an DIBAL(F) model has been studied via DFT and MP2 methods. Free energies of initial adduct formation (-Gadd) of DIBAL(F) model and carbonyls are in the order of amide < ester < aldehyde < ketone < acid chloride; in the alan-amide adduct, the developed positive charge at carbonyl carbon is expected to be stabilized by amide resonance, but in the acid chloride adduct it is destabilized by inductive effect of chloride. However the TS barrier energies (${\Delta}G_{TS}$) for the MPV-type hydride reduction of the carbonyl adducts are in the order of aldehyde < ketone < acid chloride << ester < amide; presumably decreasing order of electrophilicity of carbonyl carbon at adducts, which is well correlated with experimental data. It is noted that the relative reactivity of carbonyl derivatives in MPV-type reduction with DIBAL(X) is not governed by the alan-adduct formation energies, but follows the order of electrophilicity of carbonyl carbon of transition states.

Nickel Catalyzed Silylation Reaction of Carbonyl Compounds with 1,1'-Bis(dimethylsilyl)ferrocene (니켈 촉매를 이용한 1,1'-Bis(dimethylsilyl)ferrocene과 Carbonyl 화합물의 Silylation 반응)

  • Gong, Yeong-Geon;Lee, Jeong-Hyeon
    • Journal of the Korean Chemical Society
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    • v.46 no.2
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    • pp.139-144
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    • 2002
  • The nickel-catalyzed reation of 1,1'-bis(dimethysilyl)ferrocene[1] with carbonyls such as benzaldehyde, 4-cyaonbezaldehyde, trimethylacetaldehyde, acethon, and benzophenone afforded 3-oxa-2,5-disilacyclo-1,1'-ferrocene. In contrast, the reation of [1] with isobutyraldehyde under the same reation condition yielded the diinsertion products formed via the insertion of two aldehyde ligands into the Si-H bond of 1,1'-bis(dimethy)ferrocene.

Volatile Flavor Constituents in the Rhizoma of Gastrodia elata (천마의 휘발성 향기성분)

  • Kim, Young-Kyoo;Lee, Jong-Won
    • Applied Biological Chemistry
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    • v.40 no.5
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    • pp.455-458
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    • 1997
  • Crude oils in the rhizoma of fresh and dried Gastrodia elata were obtained by a simultaneous steam distillation and extraction(SDE) method using n-pentane/diethyl ether (1 : 1) as solvent, and their volatile constituents were analyzed by gas chromatography-mass spectrometry(GC/MS) A total of 39 volatile flavor constituents (11 acids, 13 alcohols,6 hydrocarbons,7 carbonyls,2 esters) and 25 constituents (6 alcohols, 13 acids, 4 hydrocarbons, 1 carbonyl, ester) were identified in the fresh and dried Gastrodia elate respectively. The major volatile components of the fresh and dried sample were hexadecanoic acid(66.78%, 50.72%), 9-hexadecenoic acid(8.07%, 9.58%), heptadecanoic acid(2.01%, 0.13%), pentadecanoic acid(6.41%, 4.94%), p-cresol(1.43%,0.52%) and cyclododecene(1.83%, 6.00%).

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A Study on CO Substitution of Group 6 Metal Carbonyls by Using Phase Transfer Catalyst(2) (상이동촉매에 의한 GROUP 6 금속카르보닐의 CO 치환에 관한 연구(2) : 반응시간과 촉매량에 의한 영향)

  • Yang, Hyun-Soo;Park, Ha-Seon
    • Applied Chemistry for Engineering
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    • v.3 no.3
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    • pp.407-411
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    • 1992
  • The effects of phase transfer catalyst was studied on the substitution of CO ligand of $Mo(CO)_6$ [M=Cr, Mo, W] with two electron-pairs donating ligands, 2, 2'-bipyridine and 2, 2'-biquinoline. The change of product yield, $M(CO)_4(L)_2$, was discussed according to reaction time, mole composition of $M(CO)_6$, and type of ligand.

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Modification of Poly(methylsilene) Catalyzed by Group 4 and 6 Transition Metal Complexes and Its Pyrolysis

  • 양수연;박종목;우희권;김환기;김동표;황택성
    • Bulletin of the Korean Chemical Society
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    • v.18 no.12
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    • pp.1264-1268
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    • 1997
  • The poly(methylsilene) (1) was modified with the group 4 metallocene Cp2MCl2/Red-Al (M = Ti, Zr, Hf) combination catalyst and with the group 6 metal carbonyl M(CO)6 (M = Cr, Mo, W) catalyst, producing the highly cross-linked isoluble polymer and the lowly cross-linked soluble polymer, respectively. An interrelationship between molecular weight and percent ceramic residue yield with metal within the respective group was not found. The polymers modified with the group 4 metallocene combination catalysts have higher molecular weight and lower percent ceramic residue yield than the polymers modified with the group 6 metal carbonyl catalysts do. The catalytic activity of group 4 metallocene combinations appears to be higher at ∼100 ℃, but to be lower at very high temperature than those of group 6 metal carbonyls. The pyrolysis of the modified 1 yielded SiC ceramic.

Modification of Thermal Degradation of Oligo(methylsilene) Catalyzed by Group 4 and 6 Transition Metal Complexes

  • 우희권;양수연;황택성;김동표
    • Bulletin of the Korean Chemical Society
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    • v.19 no.12
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    • pp.1310-1314
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    • 1998
  • The oligo(methylsilene) (1) was treated with the group 4 metallocene Cp2MCl2/Red-Al (M = Ti, Zr, Hf) combination catalysts and with the group 6 metal carbonyl M(CO)6 (M = Cr, W) catalysts, producing the modified, cross-linked polymers. The average molecular weights and percent ceramic residue yields of modified polymers increase as the catalyst goes down from Ti to Hf and similarly as the catalyst goes down from Cr to W. An interrelationship between average molecular weights and percent ceramic residue yield is found within the respective group of catalysts, but is not observed as the catalyst goes down from Ti to W. The polymers modified with the group 4 metallocene combination catalysts have higher molecular weights and similar percent ceramic residue yields as compared to the polymers modified with the group 6 metal carbonyl catalysts. The catalytic activities of group 4 metallocene combinations appear to be higher -100 ℃, but to be lower at very high temperature than those of group 6 metal carbonyls.

Effect of fermented blueberry on the oxidative stability and volatile molecule profiles of emulsion-type sausage during refrigerated storage

  • Zhou, Hengyue;Zhuang, Xinbo;Zhou, Changyu;Ding, Daming;Li, Chunbao;Bai, Yun;Zhou, Guanghong
    • Asian-Australasian Journal of Animal Sciences
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    • v.33 no.5
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    • pp.812-824
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    • 2020
  • Objective: The aim of this work was to assess the effect of fermented blueberry (FB; 2%, 4%, and 6%) on the oxidative stability and volatile molecule profiles of emulsion-type sausage stored at 4℃ for 28 days. Methods: The antioxidant activity of FB was determined through radical-scavenging activity against 2, 2-diphenyl-1-picrylhydrazyl (DPPH) and hydroxyl radicals. Four formulations of sausage treatments with different FB levels (0%, 2%, 4%, 6%) were prepared, then peroxide value (POVs), thiobarbituric acid-reactive substances (TBARS) values, protein carbonyls and thiol groups were measured. The aroma profiles of sausages for each treatment was also determined. Results: The half maximal inhibitory concentration indicated that FB had greater scavenging ability than ascorbic acid against DPPH and hydroxyl radicals. Sausages with FB significantly retarded increases in POVs and TBARS, as well as in the content of protein carbonyls during all storage days (p<0.05). Particularly, 4% and 6% FB-treated sausages had better oxidation inhibition effects. However, FB accelerated the reduction in thiol groups (p<0.05). Additionally, FB inhibits the excessive formation of aldehyde compounds; for example, hexanal, which may cause rancid flavors, decreased from 58.25% to 19.41%. FB also created 6 alcohols (i.e., 2-methyl-1-propanol, 3-methyl-1-butanol, and phenylethyl alcohol), 5 ester compounds (i.e., ethyl acetate, ethyl lactate, and ethyl hexanoate) and 3-hydroxy-2-butanone in the sausages that contribute to sausage flavors. The principal component analysis showed that the aroma profiles of sausages with and without FB are easily identified. Conclusion: The addition of FB could significantly reduce the lipid and protein oxidation and improve oxidative stability for storage. Also, adding FB could inhibit rancid flavors and contribute to sausage flavors.

Chemical Compounds and Volatile Flavor of Rubus coreanum (복분자 열매의 화학성분 및 휘발성 향기성분)

  • 이종원;도재호
    • The Korean Journal of Food And Nutrition
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    • v.13 no.5
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    • pp.453-459
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    • 2000
  • In order to promote the utilization of Rubus coreanum as functional food, and its physicochemical properties and volatile flavor were examined. The contents of chemical compounds showed 5.39% of moisture, 17.3% of total sugars, 8.6% of reducing sugars, 4.5% of crude ash, 3.9% of crude fiber, 10.6% of crude protein and 1.7% of crude fat and that of free sugars was 1.52% of sucrose, 3.98% of fructose, 1.24% of glucose. Among organic acid was 10.2% of citric acid, 6.29% of oxalic acid and 1.94% of malic acid. The highest component of free amino acids was 1,260.3mg of aspartic acid, 1,054.3mg of glutamic acid, respectively. And that of minerals was 38,789ppm of K. A total of 52 volatile flavor components (11 alcohols, 13 acids, 20 carbonyls, 5 hydrocabons, 3 esters) were identified in the Rubus coreanum, respectively. The major volatile flavor components of Rubus coreanum were 3.78% of linalool in alcohols, 14.40% of caproic acid in acids, 2.99% of 2-hydroxy-4-methoxyacetophenone in carbonyls, 1.59% of aromadendrene in hydrocabons and 0.43% of methyl palmitate in esters.

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Volatile Components of Pine Needle(Pinus densiflora S.) by Purge and Trap Headspace (Purge and Trap Headspace 법에 의한 솔잎(Pinus densiflora S.)의 휘발성 성분)

  • Lee Jae-Gon;Lee Chang-Gook;Jang Hee-Jin;Kwag Jae-Jin
    • The Korean Journal of Food And Nutrition
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    • v.17 no.3
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    • pp.260-265
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    • 2004
  • Volatile components of pine needle(Pinus densiflora S.) were isolated by purge & trap headspace technique and analyzed by gas chromatography-mass spectrometry(GC-MS). And then volatile components were extracted for 2 hr and 20 hr at the two different temperature settings: room temperature and 60$^{\circ}C$. A total of 61 volatile components were identified by the four different conditions. These compounds are classified into six categories in terms of chemical functionality: 35 hydrocarbons, 16 alcohols, 4 carbonyls, 2 esters, 1 acid and 3 ethers. The major components were ${\alpha}$-pinene(1.5~15.7%), ${\beta}$-myrcene(13.2~15.6%), ${\beta}$-phellandrene(l2.0~16.0%) and cis-3-hexenol(4.0~18.3%). In the comparison of the four extraction conditions, longer extraction can be effective to extract components that have a high boiling point, but proved useless in obtaining low boiling point components. As a result of these experiments under the four different conditions, the 20 hr extraction at room temperature appeared to be the most optimized condition for the analysis of volatile compounds by using the purge & trap headspace technique.