• Title/Summary/Keyword: trans isomer

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Preparation, Structure, and Property of Re(Nar)$(PR_3)_2Cl_3$, $(PR_3 = PMe_3, PEt_3, P(Ome)_3;Ar = C_6H_5, 2,6-i-Pr_2-C_6H_3)$

  • 박병규;최남선;이순우
    • Bulletin of the Korean Chemical Society
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    • v.20 no.3
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    • pp.314-320
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    • 1999
  • Several bisphosphine- and bisphosphite-substituted Re-imido complexes have been prepared from Re(NPh)(PPh3)2Cl3, 1, and Re(N-C6H3-i-Pr2)2Cl3(py), 4. Compound 1 reacted with trimethyl phosphate (P(OMe)3) to give a mixture of two isomers,mer,trans-Re(NPh)(P(OMe)3)2Cl3, 2, and fac,cis-Re(NPh)(P(OMe)3)2Cl3, 2a. In this reaction, the mer,trans-isomer is a major product. Complex 1 also reacted with triethylphosphine (PEt3) to exclusively give mertrans-Re(NPh)(PEt3)2Cl3, 3. Compound 4 reacted with trimethylphosphine (PMe3) to give mer,trans-Re(N-C6H3-i-Pr2)(PMe3)2Cl3, 5, which was converted to mer-Re(N-C6H3-i-Pr2)(PMe)(OPMe3)Cl3, 6, on exposure to air. Crystallographic data for 2: monoclinic space group P21/n, a = 8.870(2) Å, b = 14.393(3) Å, c = 17.114(4) Å, β = 101.43(2)°, Z = 4, R(wR2) = 0.0521(0.1293). Crystallographic data for 5: orthorhombic space group P212121, a = 11.307(l) Å, b = 11.802(l) Å, c = 19.193(2) Å, Z = 4, R(wR2) = 0.0250(0.0593). Crystallographic data for 6: orthorhombic space group P212121, a = 14.036(4) Å, b = 16.486(5) Å, c = 11.397(3) Å, Z = 4, R(wR2) = 0.0261(0.0630).

프탈로시아닌 유도체 합성 및 광학응답특성 연구

  • Lee, Jun-Hui;Wang, Sheng;Son, Yeong-A
    • Proceedings of the Korean Society of Dyers and Finishers Conference
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    • 2011.03a
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    • pp.67-67
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    • 2011
  • Recently, Phthalocyanine dye has attentions due to their excellent photochemical properties and used to optical applications such as chemical sensors. And azo groups can change photochemical properties in the UV irradiation because their molecualr structure reverse cis-trans isomer and changes cooperative motion, aggregation and so on. In this study, we synthesized the azo compound between amino pyridine and phenol. this azo derivative used the combination with 3-nitro phthalonitrile and makes phthalocyanine structure through the synthesis with 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU), zinc acetate. Finally, we synthesized a new photoswiching dye zinc-phthalocyanine azo compound. This compound was studied by phothoswichiing phenomenon by UV irradiation and analyzed molecular aggregation through the SEM images.

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Dyeing Study on DMF-Modified Polyesters for Morphology Characterization

  • Park, Myung-Ja
    • The International Journal of Costume Culture
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    • v.5 no.2
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    • pp.53-65
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    • 2002
  • Morphology of polyester fiber was physically modified by solvent treatment. PET fiber was treated with N,N-dimethylformamide (DMF) at 100, 120, $140^{circ}C$ for 10 minutes without tension. The structural changes in the morphology of DMF-induced modified PET fiber were FTIR and SEM analysis. Also dyeing behavior of DMF-treated polyester fibers with various disperse dyes was studied to detect changes of amorphous area in fine structure. DMF treatment resulted in increases in total void content, degree of crystallinity, trans isomer content, chain folding, segmental mobility and molecular packing, but it resulted in decreases in amorphous orientation, intermolecular forces and individual void size through longitudinal shrinkage, lateral welling and removal of oligomers. Void-size distribution could be estimated from the dye uptake with various sizes of disperse dyes. In contrast to the large increases in dye uptake with small dye molecules, there is no and little dye uptake with the bulkiest dye, which means that void size is bigger or smaller than the volume of each dye. Diffusion rates of dye molecules showed increases. This dyeing study revealed that the disperse dyeing is very effective method for characterizing the internal morphology of polyester fiber.

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Dehydrogenation of 9,10-Dialkyl-9,10-dihydroanthracene with 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (2,3-디클로로-5,6-디시아노-1,4-벤조퀴논을 利用한 9,10-디알킬-9,10-디히드로안트라센 化合物의 수소이탈 반응)

  • Wu-Lang Kim;Moo-Jin Jun
    • Journal of the Korean Chemical Society
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    • v.19 no.6
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    • pp.443-448
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    • 1975
  • A series of 9,10-dialkyl-9,10-dihydroanthracene has been dehydrogenated by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in good yields. The yield decreased with the larger alkyl groups in this 9,10-dialkyl-9,10-DHA series(DHA=dihydroanthracene). It is conceivable that trans-9,10-diisopropyl-9,10-DHA was dehydrogenated more rapidly than the cis-isomer, and, bassed on this observation, a concerted mechanism was ruled out and an ionic mechanism is proposed.

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STEREOCHEMISTRY IN LONG-CHAIN BIRADICAL CYCLIZATION

  • Hasegawa, Tadashi;Yamazaki, Yuko;Yoshioka, Michikazu
    • Journal of Photoscience
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    • v.4 no.1
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    • pp.7-10
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    • 1997
  • The structures of 8-membered azalactone isomers produced from photocyclization of 2-(N,N-dibenzylamino)ethyl benzoylacetate were determined by the X-ray structure analysis to clarify the stereochemical behavior of a 1,8-biradical. The remarkable stereoselectivity in cyclization of the 1,8-biradical to form cis- and trans-isomers of the azalactone was not observed. The ring conformations were boat-chair like and dihedral angles between C$_5$- and C$_6$- phenyl groups were ca 45$\circ$ in the both isomers. The 1,8-biradicals in the transition state for the cyclization would have nearly same boat-chair like conformation and twisted configuration with the dihedral angle of ca 45$\circ$ as the corresponding isomer, and this is responsible for luck of stereoselectivity in long-chain biradical cyclization.

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A Study on the Dynamics Behavior of Mixed Organic Monolayers (혼합 유기단분자의 동적 거동에 관한 연구)

  • Kim, Sung-Jin;Lee, Kyung-Sup
    • Proceedings of the KIEE Conference
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    • 2000.11c
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    • pp.470-472
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    • 2000
  • In this paper generation from of displacement current was compared and measured with light stimulus induce monolayers which 8A5H with azobenzene and arac.acid mixed. Light response of two monolayers which dynamics behavior are different was compared and measured though they are the same isomer The experimental results are as following; In the case of light stimulus mixed monolayers reacted less than 845H about 5[fA]. This is the mason molecule dynamic behaviour and trans was not activated due to its very chain length.

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The Effect According to Chain Length of Light Response Displacement Current (광반응 변위전류의 체인길이에 따른 영향)

  • 김성진;강용철;정헌상;구할본;최영일;백순기;이경섭
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2000.07a
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    • pp.495-498
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    • 2000
  • In this paper, generation form of displacement current was compared and measured with air-water interfacing induce monolayers which 8A5H with azobenzene and arac.acid mixed. Light response of two monolayers which chain length are different was compared and measured though they are the same isomer. The experimental results are as following; In the displacement current form of mixed monolayers and 8A5H, mixed monolayers which chain length is longer than that of 8A5H caused the displacement current about 40[fA] mole. This is the reason chain length of hydrophobicity in mixed monolayers is longer than that of 8A5H In the case of light stimulus mixed monolayers reacted less than 8A5H about 9[fA]. This is the reason molecule dynamic behaviour in cia and trans was net activated due to its very long chain length.

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A Study on the Light Stimulus of Organic Thin Films (유기박막의 광 자격에 관한 연구)

  • 김성진;이경섭
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2000.11a
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    • pp.283-286
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    • 2000
  • In this paper, generation form of displacement current was compared and measured induce monolayers which 8A5H with Pure azobenzene. Light response of two monolayers which compared and measured though they are the same isomer. The experimental results are as following; In case of ultraviolet($\lambda_1$) and visible($\lambda_2$) irradiation on 8A5H induce monolayers depositioned on board the peak of current was detected about 10[fA]. but light irradiation on pure azobenzene any particular reaction for detailed. This is the reason of hydrophobicity construct in molecule structures its molecule dynamic behaviour in cis and trans was not due to activated.

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Asymmetric Intramolecular Diels-Alder Cycloadditions of 2-Pyrone-3-Carboxylates and Synthesis of Vitamin $D_3$ A Ring Phosphine Oxide

  • 조천규;Gary H. Posner
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.957-961
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    • 1998
  • Intramolecular Diels-Alder cycloadditions of 2-pyrone-3-carboxylates with trans-vinyl silaketal groups tethered via a chiral, non-racemic 1,3-butanediol auxiliary proceeded in unexpected stepwise cycloadditions through ionic intermediates to provide cis-disubstituted bicylolactones. The ratio of two isomers, exo and endo, was 5 to 1, and each isomer was found to be diastereomerically pure (>99% de). Their relative and absolute stereochemistries were determined by $^1H$ NMR spectroscopy and confirmed by X-ray crystallography of minor, endo-adduct 9. The major exo-adduct was successfully transformed to (-)-2-butyl substituted A-ring phophine oxide 16, a key element for the synthesis of 2-butyl vitamin D3.

Theoretical Study on Antitumor Activity of Palladium(II) and Platinum(II) Complexes with Isoxazole and Its Derivatives (이소옥사졸과 그의 유도체들이 배위된 팔라듐(Ⅱ)과 백금(Ⅱ) 착물의 항암활성에 관한 이론적 연구)

  • Kim, Jung-Sung;Song, Young-Dae
    • Journal of the Korean Chemical Society
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    • v.42 no.4
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    • pp.369-377
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    • 1998
  • The palladium(II) and platinum(II) complexes(where, $([M(L)_2X_2]$, M=Pd(II), Pt(II); L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Ph-isox), and 4-amino-3,5-dimethylisoxazole (4-ADI); X=Cl, Br) with isoxazole and its derivatives were investigated on antitumor activity by MM2 and EHMO calculation. Because for all the complexes the ${\sigma}MO$ energy level $(E_{{\sigma}(M-X)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of halogen atom is less than ${\sigma}MO$ energy level $(E_{{\sigma}(M-N)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of N atom, without exception. And judging, from the lower $(E_{\'{o}(m-x)})$ value in trans, the bonding strength was found to be weaker in trans isomer than in cis. For the Pd(II) and Pt(II) complexes which have planar ligands, it was shown that for all the complexes dissociation of X-atom in the Pd(II) complexes is easier than that of X-atom in the Pt(II) complexes in both cis- and trans-complexes. Therefore it suggests that the easier dissociation of $X^-$ ion has some relations with antitumor activity, and a linear equation with correlation coefficient of 0.96 was found between ${\Delta}E_{{\sigma}(N-X)}(E_{{\sigma}(M-N)}-E_{{\sigma}(M-X)})$ and inhibitory activity coefficient, logIA.

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