• Title/Summary/Keyword: carbonyl group

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Substituent Effect in Photochemistry of Carbonyl Compounds: α-Halovalerophenones

  • Cho, Sung-Su;Park, Bong-Ser
    • Bulletin of the Korean Chemical Society
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    • v.25 no.1
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    • pp.42-44
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    • 2004
  • Valerophenones containing a substituent at alpha position to the carbonyl group show the remarkable substituent effects on their photochemical reactions. ${\alpha}$-Bromovalerophenone gives only the C-Br bond cleavage products, but the ${\alpha}$-chlorovalerophenone follows the classical Norrish/Yang reaction pathway predominantly.

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.

Durable Press Finishing of Silk/Cotton Fabrics with BTCA (3) - The Study of Ester Crosslinkages of Silk/Cotton Fabrics Treated with BTCA by FT-IR Spectroscopy - (BTCA에 의한 실크/면 교직물의 DP 가공 (3) - FT-IR 분광법에 의한 BTCA 처리 실크/면 교직물의 에스테르 가교 평가 -)

  • Cho, Seok-Hyun;Kim, Yong;Park, Jong-Jun;Lee, Moon-Chul
    • Textile Coloration and Finishing
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    • v.15 no.4
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    • pp.17-23
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    • 2003
  • Fourier transform infrared spectroscopy(FT-IR) was used to characterize the intermolecular ester crosslinkages in cotton cellulose. The FT-IR data show that the band of the ester carbonyl group can be separated from overlapping carboxyl/carbonyl band by converting carboxyl group to carboxylate. When esterification occurs between a polycarboxylic acid and cotton cellulose, the carbonyl groups retained in the cotton exist in three forms; ester, carboxyl, and carboxylate anion. The FT-IR data were also correlated to the durable press rating result obtained. The appearance of BTCA-finished durable press silk/cotton fabrics were improved.

Nucleophilic Substitution at a Carbonyl Carbon Atom - Part I. MO-Theoretical Studies on Methyl Chloro-and fluoro-formates

  • Lee, Ikchoon
    • Nuclear Engineering and Technology
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    • v.4 no.4
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    • pp.294-300
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    • 1972
  • CNDO/2 and INDO calculations have been carried out on varying geometries of methyl chloro-and fluoro-formates. Results show that the configuration in which halogen atom is trans to methyl group is the most stable. Atomic charges and overlap population show that the trans form is stabilized by conjugation of carbonyl double bend with the unshared pairs of the ether oxygen and by electrostatic attraction of carbonyl oxygen to methyl group. Dipole moments of the trans forms agree reasonably well with the experimental values but showed that any generalizations made with dipole moments from bond moments should be accepted with considerable reservations.

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Selective Reduction of Carbonyl Group with Borohydride Exchang Resin (BER)-LiCl System

  • Gyoung, Young-Soo;Yoon, Nung-Min;Jeon, Dae-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.8 no.3
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    • pp.162-165
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    • 1987
  • The reduction rate of borohydride exchange resin (BER) was greatly enhanced in the presence of lithium salts. Thus 2-heptanone was reduced completely with BER-LiCl in 1 h at room temperature. However, no reduction was observed with BER alone under the same conditions. With this system, organic compounds containing various fuctional groups were examined in ethanol at room temperature. This study revealed that BER-LiCl system exhibits an excellent chemoselectivity for carbonyl group in the presence of other functional groups. Keto esters and epoxy ketones were reduced with BER-LiCl to give the corresponding hydroxy esters and epoxy alcohols with excellent yields. Selective reductions of carbonyl groups were also possible in the presence of other organic compounds containing functional groups such as 1-idooctane, 1-bromooctane, caproamide, hexanenitrile, nitrobenzene, n-butyl disulfide, dimethyl sulfoxide and 1-dodecene.

Photocyclization Reactions of N-(Trimethylsilylmethoxyalkyl)Phthalimides. Efficient and Regioselective Route to Heterocycles

  • Yoon Ung Chan;Oh Ju Hee;Lee, Sang Jin;Kim, Dong Uk;Lee, Jong Gun;Kang Kyung-Tae;Mariano Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.13 no.2
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    • pp.166-172
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    • 1992
  • Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethoxyalkyl)phthalimides(alkyl=E thyl, n-propyl, n-butyl, n-pentyl, and n-octyl). Photocyclizations occur in methanol in high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from oxygen in the $\alpha-silylmethoxy$ groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate $\alpha-silylmethoxy$ cation radicals and cyclization by radical coupling are proposed. In contrast, photoreaction of N-(trimethylsilylmethoxyethyl) phthalimide in acetone follows different reaction routes to produce two cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon $\alpha$ to silicon and oxygen atoms via triplet carbonyl hydrogen abstraction triplet carbonyl silyl group abstraction pathways. The normal singlet SET pathway dominates these triplet processes for photoreaction of this substance in methanol. The efficient and regioselective cyclization reactions observed for photolysis in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

Insecticidal Activation Mechanism of m-Methylphenyl N-methylcarbamate Derivatives (m-Methylphenyl N-methylcarbamate 유도체들의 살충활성 메카니즘)

  • Park, Seung-Heui;Nam, Sang-Kil;Sung, Nack-Do
    • Korean Journal of Agricultural Science
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    • v.22 no.2
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    • pp.127-133
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    • 1995
  • A Series of meta and para-substituted phenyl N-methylcarbamate derivatives were synthesized and influence of substituents(X) on the molecular orbital(MO) quantities of carbonyl group, carbamylation reaction center, and insecticidal activities($pI_50$) were discussed quantitatively. From these findings, the most stable streo conformer(Z) shows that the planer phenyl group occupies vertical(${\theta}=90^{\circ}$) position on the plane of the N-methylcarbamyl group. The carbamylation mechanism was proposed that the carbamylation process of acetylcholinesterase(ACh.E) by m-methyl substituted phenyl N-methylcarbamate derivatives proceeds via hyperconjugation of m-methyl group and carbonyl oxygene protonation, theromodynamically control reaction with acidic site of ACh.E.

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Aldehydes in $\gamma$-irradiated Solid Starch

  • Kim, Chul;Ohm, Young-Ran
    • Nuclear Engineering and Technology
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    • v.4 no.1
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    • pp.35-38
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    • 1972
  • A study of the radiation-induced formation of carbonyl compounds in solid starch by means of precipitation with 2, 4-dinitrophenylhydrazine and subsequent analysis of the hydrazones by gas chromatograph has been performed. formation of carbonyl groups was found to increase linearly with increasing doses up to about 2$\times$10$^{21}$ eV/g. Generally, at least 5 different peaks can be detected including formaldehyde and acetaldehyde.

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