• Title/Summary/Keyword: Aryl ketone

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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.

A Facial Protocol for the Synthesis of Benzofuran Derivatives by the Reaction of o-Hydroxy Aryl Ketone, Amine and Chloroacetyl Chloride

  • Xia, Shuai;Wang, Xiu-Hua;Liu, Ji-Qiang;Liu, Chang;Chen, Jian-Bin;Zuo, Hua;Xie, Yong-Sheng;Dong, Wen-Liang;Shin, Dong-Soo
    • Bulletin of the Korean Chemical Society
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    • v.35 no.6
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    • pp.1743-1748
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    • 2014
  • A facile and effective method has been developed for the synthesis of a novel series of benzofuran derivatives via N-acylation, O-alkylation and intramolecular condensation reactions, starting from readily available substituted o-hydroxy aryl ketone, and chloroacetyl arylamides. This metal-free transition process is characterized by mild reaction conditions, atom economy, short reaction time and a high yield with a decreased amount of by-products.

Silica Supported Tungstosilicic Acid as an Efficient and Reusable Catalyst for the One-Pot Synthesis of β-Acetamido Ketones via a Four-Component Condensation Reaction

  • Nasr-Esfahani, Masoud;Montazerozohori, Morteza;Gholampour, Tahere
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3653-3657
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    • 2010
  • Silica supported tungstosilicic acid has been used as an effective catalyst for a modified Dakin-West one-pot, four-component condensation of an aryl aldehyde, an aryl ketone, acetyl chloride and acetonitrile for the synthesis of $\beta$-acetamido ketones. This catalytic system can act as an active, inexpensive, recoverable and recyclable catalyst. Some advantages of this system are short reaction times, good to excellent yields, easy work up and the ability to be carried out at the large scale reactions.

Ammonium Acetate: An Efficient Reagent for the One-pot Synthesis of 5-Aryl-7,8,13,14-tetrahydrodibenzo[a,i] phenanthridines, 2,4-Diaryl-6,7-benzo-3-azabicyclo[3.3.1]nonan-9-ones and α,α'-Bis(substituted benzylidene)cycloalkanones

  • Karthikeyan, Natesan Sundaramurthy;Sathiyanarayanan, Kulathu Iyer;Aravindan, Paduthapillai Gopal
    • Bulletin of the Korean Chemical Society
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    • v.30 no.11
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    • pp.2555-2558
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    • 2009
  • The condensation of cyclic ketone with aromatic aldehydes in the presence of ammonium acetate under ethanol media affords the corresponding 5-aryl-7,8,13,14-tetrahydrodibenzo[a,i]phenanthridine with excellent yield. This mild and efficient procedure with high yield is also applied to the synthesis of 2,4-diaryl-6,7-benzo-3-azabicyclo- [3.3.1]nonan-9-ones and ${\alpha},{\alpha}{$’-bis(substituted benzylidene)cycloalkanones.

X-ray Diffraction Studies of Poly(aryl ether ether ketone) Fibers with Different Degrees of Crystallinity and Orientation

  • Karacan Ismail
    • Fibers and Polymers
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    • v.6 no.3
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    • pp.206-218
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    • 2005
  • Structural studies of series of 'as spun' and drawn PEEK fibers have been carried out using X-ray diffraction and optical microscopy techniques. The analysis of results suggest that fibers produced at a constant draw ratio with increasing draw temperatures show enhanced orientation and crystalline behaviour. The resolved equatorial and meridional traces provide additional structural parameters in terms of crystallinity, crystallite size, and crystallite thickness. It is concluded that drawing at a temperature below $T_g(i.e.,\;144^{\circ}C)$ results in poorly oriented non-crystalline materials, whereas drawing above $T_g$ results in highly oriented semi crystalline materials. Additional drawing proved to increase the overall orientation with slight improvements in lateral order of the chain molecules. Quantitative analysis revealed that the crystallite size increases with increasing drawing temperature. The results also revealed the increased crystallite size upon additional drawing. Crystalline orientation parameter, $_c$, suggests almost perfect orientation. In all cases, the amorphous orientation is found to be lower than the overall orientation parameter obtained from the optical birefringence. As a result of additional drawing, crystalline orientation was found to increase slightly but the increase in the orientation of non-crystalline material was found to be substantial. An average crystalline density was determined from the orthorhombic unit cell dimensions. It was found to vary as a result of processing conditions. It was also found that the value of the maximum birefringence shows heavy dependence on the chain conformation.

Novel Sulfonated Poly(arylene ether ketone) Containing Benzoxazole Membranes for Proton Exchange Membrane Fuel Cell

  • Li Jin-Huan;Lee Chang-Hyun;Park Ho-Bum;Lee Young-Moo
    • Macromolecular Research
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    • v.14 no.4
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    • pp.438-442
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    • 2006
  • Novel sulfonated poly(aryl ether ketones) containing benzoxazole were directly synthesized by aromatic nucleophilic polycondensation using various ratios of 2,2'-bi[2-( 4-flurophenyl)benzoxazol-6-yl]hexafluoropropane to sodium 5,5'-carbonylbis(2-fluorobenzenesulfonate). The copolymers were soluble in polar aprotic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide at a relatively high solid composition (>15 wt%) and formed tough, flexible and transparent membranes. The membranes exhibited a degradation temperature of above $290^{\circ}C$. The exact dissolution times of these membranes at $80^{\circ}C$ in Fenton's reagent (3 wt% $H_2O_2$ containing 2 ppm $FeSO_4$) were undetectable, confirming their excellent chemical stability in fuel cell application. The membranes showed a moderate increase in water uptake with respect to increasing temperature. The proton conductivities of the membranes were dependent on the composition and ranged from $1.10{\times}10^{-2}$ to $5.50{\times}10^{-2}Scm^{-1}$ at $80^{\circ}C$ and 95% relative humidity (RH). At $120^{\circ}C$ without externally humidified conditions, the conductivities increased above $10^{-2}Scm^{-1}$ with respect to increasing benzoxazole content, which suggested that the benzoxazole moieties contributed to the proton conduction.

Resolution of Aryl α-Aminoalkyl Ketones on a Doubly Tethered Liquid Chromatographic Chiral Stationary Phase Based on (+)-(18-Crown-6)-2,3,11,12-tetracarboxylic Acid

  • Jin, Kab-Bong;Kim, Hee-Jin;Hyun, Myung-Ho
    • Journal of the Korean Chemical Society
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    • v.55 no.5
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    • pp.751-755
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    • 2011
  • A doubly tethered chiral stationary phase (CSP) based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid was applied to the resolution of various aryl ${\alpha}$-aminoalkyl ketones with the use of 80% ethanol in water containing 10 mM sulfuric acid as a mobile phase. The chiral resolution was quite successful, the separation factors (${\alpha}$) and the resolutions ($R_S$) being in the range of 1.39-2.05 and 3.18-5.22, respectively. The separation factors (${\alpha}$) on the doubly tethered CSP were slightly worse than those on the corresponding singly tethered CSP. However, the resolutions ($R_S$) on the doubly tethered CSP were generally greater than those on the corresponding singly tethered CSP. The chromatographic behaviors for the resolution of aryl ${\alpha}$-aminoalkyl ketones on the doubly tethered CSP were demonstrated to be dependent on the type and the content of the organic and acidic modifiers in aqueous mobile phase and the column temperature.

Synthesis of 1-(Benzotriazol-1-yl)alkyl Aryl Sulfones (1-(Benzotriazol-1-yl)alkyl Aryl Sulfone의 합성)

  • Hong, Young Seuk;Kim, Hyun Muk;Lee, Jeong Geun;Park, Yong Tae;Kim, Ho Sik
    • Journal of the Korean Chemical Society
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    • v.40 no.9
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    • pp.615-622
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    • 1996
  • (Benzotriazol-1-yl)arenesulfonylalkanes, 2a, 2b, 3a and 3b, were prepared by lithiation of 1-(benzotriazol-1-yl)arenesulfonylmethanes followed by reaction with alkyl iodides. Very bulky molecules such as 1,1-di(benzotriazol-1-yl)-1-aryl-1-thiophenoxymethanes 5, 1,1-di(benzotriazol-1-yl)-1-thiophenoxymethane 9a and 1,1-di(benzotriazol-1-yl)-1,1-dithiophenoxymethane 9b were synthesized. 1,1-Di(benzotriazol-1-yl)-1-benzenesulfoxymethane 10a and 1,1-di(benzotriazol-1-yl)-1-benzenesulfonylmethane 10b were also synthesized by the oxidation of compound 9a, while oxidation of sulfide group on compound 5 and 9b by m-CPBA were not successful. On the other hand, pyrolysis and hydrolysis of 3-(benzotriazol-1-yl)-3-toluenesulfonylpentane 3b gave 3-toluenesulfonyl-2-pentene 11 and diethyl ketone 13a, respectively, which means there are both C-N and C-S bond cleavages.

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