• Title/Summary/Keyword: 1,2-Ketone

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The Synthesis of 2-Furyltriisopropoxytitanium and its Reactivity to Carbonyl Compounds (2-Furytriisopropoxytitanium의 합성 및 카르보닐 화합물에 대한 반응성)

  • Koo, Doo-Hyo;Kyung, Suk-Hun
    • Applied Biological Chemistry
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    • v.39 no.4
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    • pp.309-314
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    • 1996
  • 2-Furyltriisopropoxytitanium was synthesized in situ through transmetallation of 2-furyllithium with chlorotitaniumtriisopropoxide. The compound could be isolated at room temperature and preserved at $-10^{\circ}C$ for several weeks. The reactivity 2-furyltriisopropoxytitanium to carbonyl compounds proved to be high. A complete aldehyde selectivity was observed in competition reactions of 2-furyltriisopropoxytitanium with a 1:1 mixture of aldehyde and ketone. In competition reactions of 2-furyltriisopropoxytitanium with a 1 : 1 mixture of ketone and ketone, the degree of ketone / ketone discrimination was substantial. In the reaction of 2-furyltriisopropoxytitanium to ketone-ester function, the reagent was solely reacted with the ketone function.

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Singlet-Triplet Reactivity of 1-Methyl-2-Cyclohexenyl Aryl Ketones : Racemization vs 1,3-Acyl Shift in the Excited States

  • Woo Ki Chae;Mi Young Chae;Mi Kyung Park;Chung Hee Lee;Eun Hee You
    • Bulletin of the Korean Chemical Society
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    • v.11 no.3
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    • pp.241-244
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    • 1990
  • The photochemistry of 1-Methyl-2-cyclohexenyl aryl ketones (phenyl ketone 7a, p-toluyl ketone 7b, biphenyl ketone 7c and -naphthyl ketone 7d) is reported. The aryl ketone 7a, 7b and 7c undergo photo-racemization with efficiencies of 0.75, 0.79 and 0.76 respectively on direct irradiation. Direct irradiation of the ketone 7d, however, undergoes 1,3-shift with an efficiency of 0.02. Triplet states are responsible for the racemizations and singlet state is responsible for 1,3-shift as in general. The ketone 7a, 7b and 7c are good example of a few ${\beta},{\gamma}$-unsaturated ketones which undergo efficient intersystem crossing on direct irradiation.

C-C Bond Cleavage of 8-Quinolinyl Alkyl Ketone by $\sigma,\eta^{3-}$-Allyl Rhodium(III) Complex

  • 이대윤;임영권;전철호
    • Bulletin of the Korean Chemical Society
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    • v.18 no.8
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    • pp.824-827
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    • 1997
  • Bis(ethylene)rhodium(Ⅰ) chloride dimer reacted with vinylcyclopropane to give σ,η3-allylrhodium(Ⅲ) complex 3. Complex 3 underwent C-C bond cleavage of 8-quinolinyl ethyl ketone 11, to form η3-1,3-dimethylallylrhodium(Ⅲ) complex 8, which was reductively eliminated by trimethyl phosphite to give 8-quinolinyl-1-methylbut-2-enyl ketone (10). More sterically hindered 8-quinolinyl alkyl ketones were allowed to react with complex 3 to afford corresponding alkenes as well as a mixture of complex 8 and η3-1-ethylallyl rhodium(Ⅲ) complex 19, identified as 10 and 8-quinolinyl-pent-2-enyl ketone (20) after reductive elimination. 8-Quinolinyl alkyl ketone bearing a sterically hindered alkyl group showed less reactivity for C-C bond cleavage and higher 20/10 ratio compared with those having a less sterically hindered alkyl group, such as 8-quinolinyl ethyl ketone (11).

Synthesis and Exploratory Photochemistry of ${\beta},\;{\gamma}$-unsaturated Carboxylic Acid, Carboxamide and Nitrile Derivatives (${\beta},\;{\gamma}$-불포화카르복시산, 카르복시아미드와 니트릴 유도체의 합성과 이들의 광화학적 반응에 관한 연구)

  • Givens Richard S.;Woo Ki Chae
    • Journal of the Korean Chemical Society
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    • v.26 no.2
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    • pp.99-106
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    • 1982
  • The ketone chromophore of 1-Acetyl-1-methyl-2-cyclopentene (1) was replaced by nitrile, carboxylic acid and acetamide group, and their photochemical reactions were investigated. While the ${\beta},\;{\gamma}$-unsaturated ketone 1 afforded 1,2 ar 1,3-Acyl shift product, these replaced chromophores did not afford any monomeric rearranged products. 1-Cyano-1-methyl-2-cyclohexene also afforded no product anology of the 1,2-acyl shift reaction. The replacement of the ketone chromophore by nitrile, carboxylic acid and carboxamide has greatly altered the photochemistry of ${\beta},\;{\gamma}$-unsaturated ketones.

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Nicorandil alleviated cardiac hypoxia/reoxygenation-induced cytotoxicity via upregulating ketone body metabolism and ACAT1 activity

  • Bai, Yan Ping;Han, Lei Sen
    • The Korean Journal of Physiology and Pharmacology
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    • v.23 no.1
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    • pp.37-45
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    • 2019
  • To study the effect of nicorandil pretreatment on ketone body metabolism and Acetyl-CoA acetyltransferase (ACAT1) activity in hypoxia/reoxygenation (H/R)-induced cardiomyocytes. In our study, we applied H9c2 cardiomyocytes cell line to evaluate the cardioprotective effects of nicorandil. We detected mitochondrial viability, cellular apoptosis, reactive oxygen species (ROS) production and calcium overloading in H9c2 cells that exposed to H/R-induced cytotoxicity. Then we evaluated whether nicorandil possibly regulated ketone body, mainly ${\beta}$-hydroxybutyrate (BHB) and acetoacetate (ACAC), metabolism by regulating ACAT1 and Succinyl-CoA:3-ketoacid coenzyme A transferase 1 (OXCT1) protein and gene expressions. Nicorandil protected H9c2 cardiomyocytes against H/R-induced cytotoxicity dose-dependently by mitochondria-mediated anti-apoptosis pathway. Nicorandil significantly decreased cellular apoptotic rate and enhanced the ratio of Bcl-2/Bax expressions. Further, nicorandil decreased the production of ROS and alleviated calcium overloading in H/R-induced H9c2 cells. In crucial, nicorandil upregulated ACAT1 and OXCT1 protein expressions and either of their gene expressions, contributing to increased production of cellular BHB and ACAC. Nicorandil alleviated cardiomyocytes H/R-induced cytotoxicity through upregulating ACAT1/OXCT1 activity and ketone body metabolism, which might be a potential mechanism for emerging study of nicorandil and other $K_{ATP}$ channel openers.

Hydroacylation of 1,5-Hexadiene through C-H Bond Activation (탄소-수소 결합 활성을 이용한 1,5-헥사디엔의 하이드로아실화반응 연구)

  • Jeon, Cheol Ho;Han, Jong Su;Kim, Seon Il
    • Journal of the Korean Chemical Society
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    • v.38 no.11
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    • pp.833-840
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    • 1994
  • 8-Quinolinecarboxaldehyde (1) reacted with 1,5-hexadiene (2) in THF under Wilkinson's catalyst(3) and $AgBF_4(8)$ to give a mixture of 8-quinolinyl 5-hexenyl ketone (4) and 8-quinolinyl 5-hexen-2-yl ketone (9) at initial reaction stage. The reason for the formation of the branched alkenyl ketone 9 is supposed to be that the vacant coordination site, generated from Wilkinson's catalyst and $AgBF_4(8)$, makes it possible to form the 5.5 membered ring metallacycle intermediate. The higher the concentration of $AgBF_4(8)$ was used, the greater the ratio of 9 to 4 was observed. Longer reaction time and high temperature induced isomerization of 9 and 4 to 10 and 5. Especially the high reaction temperature increased the possibility of cyclization of the 5-hexenyl metal intermediate to give 8-quinolinyl cyclopentylmethyl ketone (11).

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Adsorption Mechanism of Alkyl Ketones on Cation Supported by Layer Silicate. Link Formation of Hydroxyl Group (Layer Silicate에 지지된 양이온상에서 일어나는 Alkyl Ketones의 흡착기구. 水酸基의 Link 形成理論)

  • Jong Taik Kim;Jong Rack Sohn
    • Journal of the Korean Chemical Society
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    • v.17 no.4
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    • pp.247-255
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    • 1973
  • The self supported film specimen of Wyoming montmorillonite as a layer silicate saturated by cations,$Li^{+},\;Na^{+},\;K^{+},\;Ca^{2+},\;Ni^{2+},\;Al^{3+}$and$F^{3+}$ were allowed to contact acetone, methyl-ethyl ketone and diethyl ketone within the heatable gas cell. The i.r. spectra between $4000{\sim}1200cm^{-1}$ at different pressures of adsorbates indicated bond formation through carbonyl oxygen. Two types of carbonyl bond shift with maxima at $1713cm^{-1}$ and $1690cm^{-1}$ are attributed as coordinate bond formation of carbonyl with either surface hydroxyl or cationic hydroxyl group. The intensity of the vOH was analyzed and resonance form of cationic hydroxyl was proposed as an adsorption site. The tendency to form coordinate bond was in good agreement with calculated formal charge of carbonyl oxygen in an increasing order, acetone < methyl-ethyl ketone < diethyl ketone. As an additional mechanism of adsorption, weak hydrogen bonding of methyl hydrogen with surface oxygen was observed.

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A Study for the Standardization of Elsholtzia ciliata (Thunb.) Hylander and Elsholtzia splendens Nakai ex F. Maekawa

  • Yun, Jong-Seong;Lee, Sang-In;Rhee, Jae-Seong;Park, Ho-Koon
    • The Journal of Korean Medicine
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    • v.19 no.1
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    • pp.19-26
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    • 1998
  • The purpose of present study is to clarify the differences between EIslwitzia Ciliata (Thunb.) Hylander(향유) and Elsholtzia splendens Nakai ex F. Maekawa (꽃향유) for standardization and the proper usage as medicinal herbs. The major ingredients of both species were isolated by distillation and extraction. The qualitative and quantitative analyses of major distillates were carried out by the use of GC/MS. There was a significant difference between the components of Elsholtzia ciliata and Elsholtzia splendens in the aspects of major components. Several common ingredients were identified as linalool, cumene, elsholtzia ketone, naginata ketone isomer, naginata ketone, myristicin, and sesquiterpene alcohol. Comparison between Elsholtzia. ciliata and Elsholtzia splendens was done in the aspect of major compounds. Myristicin (33.7%) has been shown to be the major component in Elsholtzia ciliata whereas naginata ketone isomer (26.1%) was believed to be a major ingredient in Elsholtzia splendens. The elsholtzia ketone was also one of the major differentiating factors between Elsholtzia splendens and Elsholtzia ciliata, and the quantity is 15.1% in Elslwltzia splendens compared to 2.87% in Elsholtzia ciliata. Moreover, in the Elsholtzia splendens, 4- vinylguaiacol and isoosmorhizole were absent, but both compounds were present in the EIsholtzia ciliata.

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A Study on the Explosion Pressure Behavior of Methyl Ethyl Ketone Peroxide with Addition of Sulfuric Acid (황산의 첨가에 따른 Methyl Ethyl Ketone Peroxide의 폭발압력거동에 관한 연구)

  • Choi Jae-Wook;Jung Doo-Kyun;Choi Il-Gon
    • Journal of the Korean Institute of Gas
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    • v.8 no.4 s.25
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    • pp.50-54
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    • 2004
  • To examine the danger of explosion caused by decomposition explosion of Methyl Ethyl Ketone Peroxide, the mini cup pressure vessel tester (MCPVT) was used in the experiment. The maximum explosion pressure increased as the amount of $98\%H_2SO_4$ added to MEKPO increased from $0\%$ to $1\%,\;3\%$, and $5\%$, and the maximum pressure rising velocity increased as well. In addition, the temperature under the pressure at which decomposition starts decreased from $168.16^{\circ}C$ to $126.76^{\circ}C,\;91.21^{\circ}C$, and $81.25^{\circ}C$ as the amount of $H_2SO_4$ added increased.

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Synthesis of 6'-Substituted Dobutamine Analogues

  • Yoon, Sung-Hwa
    • Archives of Pharmacal Research
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    • v.15 no.3
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    • pp.191-195
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    • 1992
  • Two 6'-substituted dobutamine analogues (1, 2) were synthesized from the coupling reaction of dopamine with the corresponding ketones. The ketone (8) was obtained from 4-nitrosalicyladehyde via 6 synthetic steps while the ketone (12) was prepared from 2-methyl-5-nitrobenzoic acid via 7 synthetic steps. Another synthetic attempts were also reported.

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