• Applied Biological Chemistry
• /
• v.17 no.3
• /
• pp.149-176
• /
• 1974

Eight substituted diphenyl ether herbicides and some of their photoproducts were studied in terms of solution phase photolysis under simulated environmental conditions by using a Rayonet photochemical reactor. The test compounds absorbed sufficient light energy at the wavelength of 300 nm to undergo various photoreactions. All the photoproducts were confirmed by means of tlc, glc, ir, ms, and/or nmr spectrometry. The results obtained are summarized as follows: Solution phase photolysis of C-6989: An exceedingly large amount of p-nitrophenol formed strongly indicates the readiness of the ether linkage cleavage of this compound as the main reaction in all solvents used. Photoreduction of nitro to amino group(s) and photooxidation of trifluoromethyl to carboxyl group were recognized as minor reactions. Aqueous photolysis of p-nitrophenol: Quinone(0.28%), hydroquinone (0.66%), and p-aminophenol (0.42%) were confirmed as photoproducts, in addition to a relatively small amount of an unknown compound. The mechanisms of formation of these products were proposed to be the nitro-nitrite rearrangement via $n{\rightarrow}{\pi}^*$ excitation and the photoreduction through hydrogen abstractions by radicals, respectively. Solution phase photolysis of Nitrofen: Photochemical reduction leading to the p-amino derivative was the main reaction in n-hexane. In aqueous solution, the photoreduction of nitro to amino group and hydroxylation predominated over the ether linkage cleavage. Nucleophilic displacement of the nitro group by hydroxide ion and replacement of chlorine substituents by hydroxyl group or, to a lesser extent, hydrogen were also observed as minor reactoins. Solution phase photolysis of MO-338: Photoreduction of the nitro to amino group was marked in the n-hexane solution photolysis. In the aqueous solution, photoreduction of the nitro substituent and hydroxylation were the main reactions with replacement of chlorine substituents by the hydroxyl group and hydrogen, and cleavage of the ether linkage as minor reactions. Photolyses of MC-4379, MC-3761, MC-5127, MC-6063, and MC-7181 in n-hexane and cyclohexane: Photoreduction of the nitro group leading to the corresponding amino derivative and replacement of one of the halogen substituents by hydrogen from the solvent used were the key reactions in each compound. Aqueous photolysis of MC-4379: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, hydroxylation, and replacement of the nitro by hydroxy group were prominent with photoreduction and dechlorination as minor reactions. Aqueous photolysis of MC-3761: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, and photoreduction followed by hydroxylation were the main reactions. Aqueous photolysis of MC-5127: Replacement of carboxyethyl by hydrogen was predominant with ether linkage cleavage, photoreduction, and dechlorination as minor reactions. It was obvious that the decarboxyethylation proceeded more readily than decarboxymethylation occurring in the other compounds. Aqueous photolysis of MC-6063: Cleavage of the ether linkage and photodechlorination were the main reactions. Aqueous photolysis of MC-7181: Replacement of the carboxymethyl group by hydrogen and monodechlorination were the remarkable reactions. Cleavage of the ether linkage and hydroxylation were thought to be the minor reactions. Aqueous photolysis of 3-carboxymethyl-4-nitrophenol: The photo-induced Fries rearrangement common to aromatic esters did not appear to occur in the carboxymethyl group of this type of compound. Conversion of nitro to nitroso group was the main reaction.

• 한국정보디스플레이학회:학술대회논문집
• /
• 2003.07a
• /
• pp.937-939
• /
• 2003

We synthesized and characterized new fluorene-based polyquinoxalines with ether-linkage in the main chain, which have luminescent properties. Cyclic voltammetry reveals that these polymers have a low-lying LUMO and HOMO energy levels. Therefore, the polymers would be attractive candidates for electron-tansporting or hole-blocking materials in LEDs.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2003.08a
• /
• pp.110-113
• /
• 2003

We report herein synthetic results obtained six new types of bis-benzocrown ethers containing imine group. Bis crown ethers l~3 are aminobenzo-15-crown-5-ether linked with terephthalaldehyde, isophthalaldehyde, phthaldehyde respectively by imine reaction. Bis crown ethers l~3 are different distances in each crown ether rings. Bis crown ether 4 has large cavity in crown ethers. Functionalized crown ether 5 is synthesized amonobenzo-l5-crown-5-ether and terephthaladehyde same ratio at one to one. Bis crown ether 6 has phothosensitive linkage between crown ethers. Bis crown ether 7 is prepared by amonobenzo-l5-crown-5-ether and triethyl ortho formate. 4'-Nitrobenzo-crown ethers and 3',4'-dinitrobenzo-crown ethers were prepared by nitration of benzo crown ethers, obtained from the reaction of catechol and oligoethylene glycol ditosylate. Crown ethers containing aldehyde group were synthesized from the reaction of 3,4-dihydroxybenzaldehyde and corresponding ditosylate respectively. The synthesized crown ethers were characterized respectively by IR, NMR. GC-Mass.

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.11 no.4
• /
• pp.1367-1372
• /
• 2010

Copoly(ether-ether-ester)s having flexible side chain were synthesized by polycondensation. Intrinsic viscosities of polymers were between 0.42 and 0.78dl/g in tetrachloroethane. The polymer structures were investigated by $^1H$-NMR and FT-IR, and thermal and liquid crystalline properties of polymers were measured by DSC, TGA, POM and XRD. As results of investigations, synthetic copolymers exhibited lower melting temperature than homopolymers. When the biphenylene units contents in copolymer were more than 60 mol %, nematic mesophase was observed, and the mesophase of synthetic polymers was dependent upon biphenylene content.

• Journal of the Korean Society of Industry Convergence
• /
• v.6 no.1
• /
• pp.73-80
• /
• 2003

We report herein synthetic results obtained six new types of bis-benzocrown ethers containing imine group. Bis crown ethers1~3 are aminobenzo-15-crown-5-ether linked with terephthalaldehyde, isophthalaldehyde, phthaldehyde respectively by imine reaction. Bis crown ethers1~3 are different distances in each crown ether rings. Bis crown ether 4 has large cavity in crown ethers. Functionalized crown ether 5 is synthesized amonobenzo-15-crown-5-ether and terephthaladehyde same ratio at one to one. Bis crown ether 6 has photosensitive linkage between crown ethers. Bis crown ether 7 is prepared by amonobenzo-15-crown-5-ether and triethyl ortho formate. 4'-Nitrobenzo-crown ethers and 3',4'-dinitrobenzo-crown ethers were prepared by nitration of benzo crown ethers, obtained from the reaction of catechol and oligoethylene glycol ditosylate. Crown ethers containing aldehyde group were synthesized from the reaction of 3,4-dihydroxybenzaldehyde and corresponding ditosylate respectively. The synthesized crown ethers were characterized respectively by IR, NMR, GC-Mass.

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.10 no.11
• /
• pp.3060-3065
• /
• 2009

A series of wholly aromatic Poly(ether-ether-ester)s with flexible side chain was synthesized by direct polycondensation from ether linkaged triad diol and 2,5-dialkoxyterephthalic acid. The chemical structures and physical properties of these polymers were investigated by using $^1H$-NMR, FT-IR, DSC and TGA. As results of investigations, the inherent viscosities($\eta$inh) measured at $40^{\circ}C$ in 1,1,2,2-tetrachloroethane(TCE) were 0.45~0.86 dl/g and initial decomposition(Td) in TGA occurred at 378~418 $^{\circ}C$ in N2 gas. The majority of these polymers were soluble in organic solvents used in this experiments at elevated temperatures. Melting temperatures(Tm) decreased with increasing the length of the side chain and showed odd-even effects.

• Bulletin of the Korean Chemical Society
• /
• v.25 no.11
• /
• pp.1641-1644
• /
• 2004

Several [2]- and [3]rotaxanes bearing some functional groups on their wheel components and spacers with different lengths between two ammonium centers on their dumbbell components were prepared in good yields from dibenzo-24-crown-8-ether derivatives and dumbbell-shaped bis(sec-ammonium salt)s having a centrally located disulfide linkage, by utilizing the reversible thiol-disulfide interchange reaction. The shuttling behaviors of the [2]rotaxanes were investigated by $^1H$ NMR by use of the spin polarization transfer-selective inversion recovery technique. It was found that the change in spacer length in the axle resulted in a drastic change in shuttling rate of the [2]rotaxanes, although the introduction of the functional groups to the wheels did not affect the shuttling behavior at all.

• Korean Journal of Food Science and Technology
• /
• v.31 no.3
• /
• pp.600-605
• /
• 1999

Methyl linoleate was oxidized at 60, 90, 120 and $150^{\circ}C$, respectively, with sparging oxygen for different periods of time. On the basis of the peroxide values determined at four temperatures, four heating times were chosen for the analysis of physicochemical parameters, such as peroxide value, total oxidation products, polymer content, viscosity, refractive index and characteristics of thermal degradation by DSC (Differential Scanning Calorimeter). The content of peroxide linkage (C-O-O-C) polymer and ether or carbon to carbon linkage (C-O-C/C-C) polymer were analyzed by High Performance Size Exclusion Chromatography (HPSEC). The polymer formed at four temperatures was qualitatively identified as dimer. The polymer with peroxide linkage (C-O-O-C) were detected from methyl linoleate oxidized at $60^{\circ}C\;and\;90^{\circ}C$, but they were not detected from methyl linoleate oxidized at $120^{\circ}C\;and\;150^{\circ}C$. The enthalpy changes increased as peroxide value increased whereas maximum degradation temperature decreased. The highest correlation coefficients were obtained between maximum degradation temperature $(T_m)$, exothermic enthalpy changes and peroxide value, peroxide linkage (C-O-O-C) polymer content.

• Journal of Forest and Environmental Science
• /
• v.12 no.1
• /
• pp.37-44
• /
• 1996

Two dilignols composed of ${\beta}$-O-4 structure, a important substructure compound in lignin, was synthesized in high yield in a series of the synthetic studies of lignin model compounds. The dimers were identified with $^1H$ and $^{13}C$-NMR and Mass spectroscopy. The important compound of among them, the final synthetic compound [IV].is called 1-(3,4-dimethoxyphenyl)-2-(2'-methoxy-4'-hydroxymethylphenoxy)-propanediol-l,3. This dimeric lignin model compounds should be usefull for the studies of lignin reactions such as pulping, bleaching, pyrolysis, hydrogenolysis, oxidation, reduction, biodegradation, and chemical utilization.

• Korean Journal of Food Science and Technology
• /
• v.28 no.3
• /
• pp.446-450
• /
• 1996

To investigate the effect of heating conditions on the polymerization of methyl linoleate, the esters were heated at $60^{\circ}C,\;90^{\circ}C,\;120^{\circ}C$ and $150^{\circ}C$, respectively, with sparging oxygen for different periods of time. On the basis of the peroxide curve obtained at each of the four temperatures, four heating times were chosen for the analysis of the polymers and total oxidation products. Significant linear relationships were found between polymer contents and total oxidation product contents. The contents of polymers and their linkage types were analyzed by High Performance Size Exclusion Chromatography. The polymers formed at four temperatures were qualitatively identified as dimers. The dimers with peroxide linkages were detected from methyl linoleate oxidized at $60^{\circ}C\;and\;90^{\circ}C$ but they were not detected from methyl linoleate oxidized at $120^{\circ}C\;and\;150^{\circ}C$. Therefore, all dimers formed at $120^{\circ}C\;and\;150^{\circ}C$ seemed to be the ones with ether linkage or carbon to carbon linkage. The degradation rate of the dimers with peroxide linkages at $90^{\circ}C$ was faster than at $60^{\circ}C$.