• Title/Summary/Keyword: Chemical cleavage

Search Result 296, Processing Time 0.032 seconds

Halogenated Cleavage of Epoxides into Halohydrins in the Presence of a Series of Diamine Podands as Catalyst with Elemental Idoine and Bromine

  • Sharghi, Hashem;Paziraee, Zahra;Niknam, Khodabakhsh
    • Bulletin of the Korean Chemical Society
    • /
    • v.23 no.11
    • /
    • pp.1611-1615
    • /
    • 2002
  • The ring opening of epoxides with elemental iodine and bromine in the presence of three diamine podands 7-9 as new catalysts affords vicinal iodo alcohols and bromo alcohols in high yields. This new procedure occurs regioselectively under neutral and mild conditions in various aprotic solvents even when sensitive functional groups are presented.

Study on Photochromism for Transition Metal Compounds by Using the Optieal Waveguide (광 도파관을 이용한 전이금속 화합물의 광색성연구)

  • SeeWooLee
    • Journal of the Korean Graphic Arts Communication Society
    • /
    • v.10 no.1
    • /
    • pp.1-13
    • /
    • 1992
  • The recent results concerning the synthesis and application of spiroxazine dyes have been summerized., The absorption bands of usual spiroxazine dyes are changed from colorless to colored from by irradiation of ultraviolet ray. This mechanism is derived from the cleavage of oxazine ring. Such properties are dependent on its chemical structure and surrounded matrix of spiroxazine dyes. the chemical structure of this dye is similar to the well known spriopyran. But spiroxazine dyes have noticed recently, because of excellent high light-sensitivity and superior fatigue-resistant property. This dye are already applied as photochromic lens, cloths and UV light checker.

  • PDF

Oxidations of Cyclohexanols by N-Bromosuccinimide and Sodium Hypochlorite

  • Chung, Kyoo-Hyun;Kim, Seong-Jin
    • Bulletin of the Korean Chemical Society
    • /
    • v.7 no.2
    • /
    • pp.111-113
    • /
    • 1986
  • The axial alcohol in trans-3,3,5-trimethylcyclohexanol was oxidized more readily than the equatorial alcohol in cis-3,3,5-trimethylcyclohexanol by NBS in aqueous dioxane. On the contrary, the equatorial alcohol was preferentially oxidized to the axial one by 10% aqueous sodium hypochlorite in the presence of tetrabutylammonium hydrogen sulfate (TBHS). The specificity indicates the presence of two different mechanism. In acidic medium, the cleavage of C-H bond is rate determining step while the reactivity of the alcohol is important in the presence of TBHS. The mechanism in basic medium without TBHS will be discussed.

Transition-State Variation in the Solvolysis of Benzoyl Chlorides$^*$

  • Lee, Ik-Choon;Koo, In-Sun;Sohn, Se-Chul;Lee, Hai-Hwang
    • Bulletin of the Korean Chemical Society
    • /
    • v.3 no.3
    • /
    • pp.92-98
    • /
    • 1982
  • Solvolysis reactions of some substituted benzoyl chlorides were studied in ethanol-water, ethanol-trifluoroethanol and methanol-acetonitrile mixtures. Results showed that the reaction proceeds via an $S_N2$ process in which bond formation is more advanced than bond cleavage. Comparison of the two models for predicting transition state variation indicated superior nature of the quantum mechanical model relative to the potential energy surface model.

A Short Synthesis of (Z)-13-Eicosen-10-one the Principal Component of the Peach Fruit Moth Pheromone

  • Lee, Eun;Koh, Soo-Young;Song, Byong-Doo;Park, Tae-Kyo
    • Bulletin of the Korean Chemical Society
    • /
    • v.5 no.6
    • /
    • pp.223-226
    • /
    • 1984
  • (Z)-13-Eicosen-10-one (1), one of the active components of the female pheromone of the peach fruit moth, Carposina niponensis Walsingham, was synthesized from 2-nonanone, succinic anhydride, and n-nonyllithium. The key step involves the preparation of 13-eicosyn-10-one from an epoxyketone via Eschenmoser cleavage.

Eliminations from (E)-2,4-Dinitrobenzaldehyde O-Aryloximes Promoted by R3N in MeCN. Effects of β-Aryl Group and Base-Solvent on the Nitrile-Forming Transition-State

  • Cho, Bong-Rae;Ryu, Eun-Mi;Pyun, Sang-Yong
    • Bulletin of the Korean Chemical Society
    • /
    • v.33 no.9
    • /
    • pp.2976-2980
    • /
    • 2012
  • Nitrile-forming eliminations from (E)-2,4-$(NO_2)_2C_6H_2CH=NOC_6H_4-2-X-4-NO_2$ (1a-e) promoted by $R_3N$ in MeCN have been studied kinetically. The reactions are second-order and exhibit Br$\ddot{o}$nsted ${\beta}$ = 0.83-1.0 and ${\mid}{\beta}_{lg}{\mid}$ = 0.41-0.46. The results have been interpreted in terms of highly E1cb-like transition state with extensive $C_{\beta}$-H bond cleavage and limited $N_{\alpha}$-OAr bond cleavage. Comparison with existing data reveals that the structure of the transition state changes from E2-central to highly E1cb-like either by the change of the ${\beta}$-aryl group from Ph to 2,4-dinitrophenyl under the same condition or by the base-solvent system variation from $EtO^-$-EtOH to $Et_3N$-MeCN for a given substrate (1a-e).

Product-Resolved Photodissociations of Iodotoluene Radical Cations

  • Shin, Seung-Koo;Kim, Byung-Joo;Jarek, Russell L.;Han, Seung-Jin
    • Bulletin of the Korean Chemical Society
    • /
    • v.23 no.2
    • /
    • pp.267-270
    • /
    • 2002
  • Photodissociations of o-, m-, and p-iodotoluene radical cations were investigated by using Fourier-transform ion cyclotron resonance (FT-ICR) spectrometry. Iodotoluene radical cations were prepared in an ICR cell by a photoionization charge-transfer method. The time-resolved one-photon dissociation spectra were obtained at 532 nm and the identities of $C_7H_7^+$ products were determined by examining their bimolecular reactivities toward toluene-$d_8$. The two-photon dissociation spectra were also recorded in the wavelength range 615-670 nm. The laser power dependence, the temporal variation, and the identities of $C_7H_7^+$ were examined at 640 nm. The mechanism of unimolecular dissociation of iodotoluene radical cations is elucidated: the lowest barrier rearrangement channel leads exclusively to the formation of the benzyl cation, whereas the direct C-I cleavage channel yields the tolyl cations that rearrange to both benzyl and tropylium cations with dissimilar branching ratios among o-, m-, and p-isomers. With a two-photon energy of 3.87 eV at 640 nm, the direct C-I cleavage channel results in the product branching ratio, [tropylium cation]/[benzyl cation], in descending order, 0.16 for meta >0.09 for ortho >0.05 for para.