• Title/Summary/Keyword: allyl alcohol

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First-principles Study of the Structure and Growth Mechanism of Allyl Alcohol Lines on the H-terminated Si(001)

  • Choi, Yun-Ki;Choi, Jin-Ho;Cho, Jun-Hyung
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.184-184
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    • 2011
  • Using first-principles density-functional calculations, we investigate the chain reaction mechanism of allyl alcohol (ALA) molecules on the H-terminated Si(001)-2${\times}$1 surface. Recently, it was reported [1] that allyl mercaptan (ALM) molecules show a self-directed line growth across the dimer rows through a chain reaction involving several reaction processes: (i) The created radical at the C atom is transferred to the S atom, (ii) the resulting S-centered radical easily abstracts an H atom from the neighboring dimer row, and (iii) the generated S-H group further reacts with the neighboring dimer row to produce the Si-S bond on the neighboring dimer row, accompanying the associative desorption of H2. This H2-desorption process creates a new DB on the neighboring dimer row, setting off the chain reaction across the dimer rows. In the present study, we find that although the structure of ALA with -OH functional is analogous to that of ALM with -SH functional, ALA and ALM lines show a difference in their growth direction. We predict that ALA undergoes the chain reaction to show a line growth along the dimer row, contrasting with the ALM line growth across the Si dimer rows. Our analysis shows that the different growth direction of ALA is due to the strong instability of oxygen radical intermediate, which prevents from growing across the dimer rows. Thus, we demonstrate that the stability of the radical intermediate plays a crucial role in determining the direction of molecular line growth.

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Volatile Flavor Compounds of Freeze Dried Garlic and Garlic Roasted with Oils (건조마늘과 기름에 볶은 마늘의 향기성분)

  • Seo, Hye-Min;Joo, Kwang-Jee
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.36 no.3
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    • pp.332-341
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    • 2007
  • The purpose of this study was to investigate the change of flavor compounds of freeze-dried garlic and garlic roasted with soybean oil and sesame oil. Freeze-dried garlic and ground raw garlic roasted with oils was prepared at $180^{\circ}C$ for 5 minutes. Volatile compounds of garlic samples were obtained by Likens-Nickerson distillation/solvent extraction and identified by GC and GC/MS. Sulfur compounds, methyl allyl sulfide, diallyl sulfide, methyl allyl disulfide, dimethyl trisulfide, diallyl disulfide, methyl allyl trisulfide and diallyl trisulfide were the major volatile in garlic flavor which was more than 98% of the total volatile compounds. The total amount of sulfur compounds in freeze-dried garlic roasted with soybean oil was decreased to 20% compare to that of garlic flavor; however, 10 pyrazines such as 2-methyl pyrazine, 2,6-dimethyl pyrazine, 2-ethyl-5-methyl pyrazin and 3-ethyl-2,5-dimethyl pyrazine which were not originated from both freeze-dried garlic and soybean oil were identified. They might be generated from thermal interactions of sugars and nonvolatile flavor precursors of garlic. In freeze-dried garlic roasted with sesame oil, the amount of diallyl sulfide, methyl allyl disulfide, dimethyl trisulfide increased whereas diallyl disulfide completely disappeared. The amount of two cyclic compounds 3,4-dihydro-3-vinyl-1,2-dithiin and 2-vinyl-4H-1,3-dithiin, which were artifacts from allicin, increased in roasted garlic with sesame oil.

Rate and Product Studies on the Solvolyses of Allyl Chloroformate

  • Koh, Han Joong;Kang, Suk Jin
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4117-4121
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    • 2012
  • The solvolysis rate constants of allyl chloroformate ($CH_2=CHCH_2OCOCl$, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with the sensitivity values of $0.93{\pm}0.05$ and $0.41{\pm}0.02$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.5 to 13.4 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -34.4 to -37.3 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.16 was also in accord with the $S_N2$ mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.

Kinetic Study on the Oxidation Reaction of Alcohols by Cr(VI)-Quinoline Compound (크롬(VI)-퀴놀린 화합물에 의한 알코올류의 산화반응에 대한 반응속도론적 연구)

  • Park, Young-Cho;Kim, Soo-Jong
    • Journal of Convergence for Information Technology
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    • v.11 no.9
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    • pp.109-114
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    • 2021
  • Cr(VI)-quinoline compound[(C9H7NH)2Cr2O7] was synthesized by the reaction between of quinoline and chromium(VI) trioxide, and structure was FT-IR, elemental analysis. The oxidation ability of benzyl alcohol greatly depends upon the dielectric constant of the used organic solvent, where carbon tetrachloride was worst and N,N'-dimethylformamide was best solvent. Noticeably, in N,N'-dimethylformamide solvent, Cr(VI)-quinoline compound oxidized substituted benzyl alcohols. The Hammett reaction constant(ρ)=-0.69(303K). As a resuit, Cr(VI)-quinoline compound was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones. Cr(VI)-quinoline compound was selective oxidizing agent of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary alcohol ones.

Fluorine Labeling in Biosynthetic Studies (I) : Synthesis of Fluorfarnesols

  • Park, O-Sook
    • Archives of Pharmacal Research
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    • v.9 no.4
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    • pp.237-242
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    • 1986
  • The Synthesis of E, E, E-12-fluorofarnesol and E, Z-6-fluorofarnesol which are key intermediates for the study of biosynthesis of some sesquiterpenes, is described. E, E-Farnesyl acetate is treated with selenium dioxide to give E, E, E-12-hydroxy farnesyl acetate, whih is transformed by DAST into E, E, E-12-hydroxy farnesyl acetate, which is transformed by DAST into E, E, E,-12-fluorofarnesylacetate. The latter compound is hydrolyzed to E, E, E,-12-fluorofarnesol. The reformatsky reaction of 6-methyl-5-hepten-2-one with ethyl bromofluoroacetate affords ethyl 2-fluoro-3-hydroxy-3, 7 dimethyl-6-octanoate. This ester is acetylated and eliminated to give ethyl (Z)-2-fluoro-3, 7-dimethylocta-2, 6-dienoate, which is transformed to allyl bromide via allylic alcohol. The allyl bromide is treated with dianion of methyl acetate to give-keto ester. The $\beta$-keto ester is converted to diethyl phosphoryloxy compound. The conjugate addition of lithium dimethylcuprate to the latter compound gives fluoro ester, which is treated with DIBAL to afford E, Z-6-fluorofarnesol.

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Study of Heat of Reaction Between Plasma Polymer Coated Silica Fillers and Biphenyl Epoxy Resin (플라즈마 코팅된 실리카와 에폭시 수지간의 반응성 연구)

  • Kim N. I.;Kang H. M.;Yoon T. H.
    • Proceedings of the Korean Society For Composite Materials Conference
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    • 2004.10a
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    • pp.96-99
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    • 2004
  • Silica fillers were coated by plasma polymer coatings of 1,3-diaminopropane, allylamine, pyrrole, 1,2-epoxy-5-hexene, allyl mercaptan and allyl alcohol using RF plasma (13.56 MHz). The coated fillers were then mixed with biphenyl epoxy, phenol novolac (curing agent) and/or triphenylphosphine (catalyst), and subjected to DSC analyses in order to elucidate the chemical reaction between functional moieties in the plasma polymer coatings and the epoxy resin. Only the samples with 1,3-diaminopropane and allylamine plasma polymer coated silica fillers showed heat of reaction peaks when they were mixed with biphenyl epoxy resin only, while these samples as well as the samples with 1,3-diaminopropane, allylamine and pyrrole plasma polymer coated silica fillers exhibited heat of reaction peaks when mixed with both biphenyl epoxy and phenol novolac (curing agent).

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Protective efficacies of Aronia melanocarpa (Blackberry) on the Allyl Alcohol-damaged Hepatocyte of Mice (쥐의 알코올성 간세포 손상에 대한 Aronia melanocapa(Blackberry)의 보호효과)

  • Han, Sang-Zin
    • Korean Journal of Pharmacognosy
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    • v.44 no.1
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    • pp.91-96
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    • 2013
  • The results of the alcohol decomposition ability of Aronia melanocarpa are as follows. Plasma alcohol concentration of the Aronia group was ca. 48.9% lower than the control group, but half an hour faster in that of Aronia before alcohol group, ca. 54.9% higher and half an hour later than that of the control group. ALDH(acetaldehyde dehydrogenase) of the Aronia group was ca. 243% higher than that of the control group. But maximal ALDH of the group taking Aronia before alcohol administration showed 0.5h faster and ca. 267% higher than that of the control group. This result shows that the activity of ALDH was increased by the Aronia. Aronia group's AST and ALT are increasing with similar patterns and their levels continually under the control's, but ca. 12.6% lower at AST and ca. 19.0% lower at ALT than those of control group. Ca. 21.7% lower at AST and ca. 40.5% lower at ALT in the Aronia group before alcohol administration than those of the control group. This result shows that Aronia has a role of suppressor against the liver damage. Therefore, this study proved lucidly the protective effects of Aronia on the hepatocyte.

Growth Inhibitory Activity of Sulfur Compounds of Garlic against Pathogenic Microorganisms (마늘 황화합물의 병원성미생물 번식억제작용)

  • Kyung Kyu-Hang
    • Journal of Food Hygiene and Safety
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    • v.21 no.3
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    • pp.145-152
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    • 2006
  • Efforts have been made to explore the possibility of using garlic as an antimicrobial therapeutic agent since garlic extract and its individual sulfur compounds show antimicrobial activities against all kinds of microorganisms including bacteria, molds, yeasts and protozoa. Staphylococcus aureus has been the most studied bacteria along with many other Gram positive and negative pathogenic bacteria, including species of the genera Clostridium, Mycobacterium, Escherichia, Klebsiella, Bacillus, Salmonella and Shigella. Candida albicans has been the most studied among the eukaryotic microorganisms. A pathogenic protozoa, Giardia intestinalis, was also tested. All the microorganisms tested was inhibited by garlic extract or its sulfur components. Garlic has been known to be growth inhibitory only when fresh garlic is crushed, since allicin-generating reaction is enzyme-catalyzed. Allicin is known to be growth inhibitory through a non-specific reaction with sulfhydryl groups of enzyme proteins that are crucial to the metabolism of microorganisms. Another plausible hypothesis is that allicin inhibits specific enzymes in certain biological processes, e.g. acetyl CoA synthetase in fatty acid synthesis in microorganisms. Allicin transforms into other compounds like ajoene and various sulfides which are also inhibitory to microorganisms, but not as potent as their mother compound. It is reported recently that garlic heated at cooking temperatures is growth inhibitory especially against yeasts, and that the growth inhibitory compound is allyl alcohol thermally generated from alliin in garlic.

A Study on the Volatile Flavor Components in Kimchis (김치의 휘발성(揮發性) 향미성분(香味成分)에 관(關)한 연구(硏究))

  • Yoon, Jin-Sook;Rhee, Hei-Soo
    • Korean Journal of Food Science and Technology
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    • v.9 no.2
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    • pp.116-122
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    • 1977
  • The volatile flavor components of Kimchis were identified and the volatiles of fermented Kimchis (1.29% NaCl and 4.89 NaCl) were compared with those of raw Kimchi (1.29% NaCl). After the existence of carbonyls and sulfur compounds were confirmed by precipitation method, vacuum distillation was carried out to collect the volatiles of Kimchis in traps submerged in ice+salt, dryice-acetone and liquid N, respectively. The volatile flavor components were identified by GLC. The results were; 1. 17 volatile flavor components of Kimchis were identified by comparison of retention time with those of known compounds and acetaldehyde, acetone, ethanol, ethyl sulfide were positively identified by m.p., IR, UV, TLC. etc. 2. Ethanol was the most abundant volatiles of Kimchis and the content was much higher in fermented low salt Kimchi than in unfermented low salt Kimchi. 3. On the contrary, acetaldehyde and volatile sulfur compounds were reduced in fermented Kimchis, especially in fermented low salt Kimchi.

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Chiral Synthesis of Costunolide

  • Sumaila Abu;Jeong, Jin-Hyun;Shin, Dong-Hyok
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.363.1-363.1
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    • 2002
  • Costunolide. a sesquiterpene lactone is isolated from Magnolia Sieboldi. It is known to possess antitumour and anti-inflammatory activities. This compound is synthesized from Ihe easily available decalin dione using the ring cleavage approach to construct the ten-membered ring system. The two keys points in this work are the chiral inductionon the allyl alcohol moiety using Sharpless epoxidation reaction and opening of the eopxide with an organocuprate reagent which leads to a $\alpha$-exomethylene lactone. (omitted)

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