• 대한화학회지
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• 제48권5호
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• pp.473-482
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• 2004

동종이핵착물인 $M^+({\eta}^5-MeCp)Mn(CO)_2Mn(CO)_5^-(M^+=Na^+,\;PPN^+)$과 염화알릴과의 반응을 고순도 질소속에서 염화알릴을 다량 넣어서 유사1차 반응조건에서 다양한 온도($20^{\circ}C{\sim}50^{\circ}C$)에서 반응시켰다. 이 동종이핵착물을 네 개의 원자를 있는 전이 상태를 거치는 단일 단계 반응과 관련되는 것으로 보인다. 이러한 전이 상태 후 CO와 만나서 $({\eta}^5-MeCp)Mn(CO)_3와\;({\eta}^1-allyl)Mn(CO)_5$로 이어지는 것 같다. 그러나 양이온이 $Na^+$인 경우, 이 양이온은 이 반응에서 동종이핵착물의 $Mn(CO)_5$ 부분에서 CO하나를 $({\eta}^5-MeCp)Mn(CO)_2$쪽으로 이동시켜 결국 $({\eta}^5-MeCp)Mn(CO)_3$로 만들거나 혹은 양이온($Na^+$)과 이탈기인 Cl을 끌어당겨서 반응을 가속화 시키는 역할을 하는 것으로 생각되었다. 이 반응은 각각의 반응물질에 관해서 1차, 따라서 전체적으로 2차 반응이며 이 반응에 관련된 활성화 에너지 관련 매개변수들은 다음과 같다(양이온이 $Na^+$인 경우 ${\Delta}H^{\neq}=17.15{\pm} 0.17 kcal/mol,\;{\Delta}S^{\neq}=-9.63{\pm}0.10$ e.u.; 양이온이 인 경우 ${\Delta}H^{\neq}=22.13{\pm}0.21 kcal/mol,\;;{\Delta}S^{\neq}=9.74{\pm}0.19$ e.u.).

• Bulletin of the Korean Chemical Society
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• 제34권12호
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• pp.3771-3776
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• 2013

1-Alkyl-3-methylimidazolium chloride-LiCl melts were prepared from the reaction of 1-alkyl-3-methylimidazolium chloride ([RMIm]Cl; R=allyl or n-butyl) and lithium chloride, and their ability to dissolve cellulose was evaluated. The solubility of cellulose was greatly increased to 320% when [RMIm]Cl was replaced by [RMIm][$LiCl_2$]. Dissolved cellulose in LiCl/[RMIm]Cl melts was successfully regenerated by adding water and LiCl/[RMIm]Cl melts were easily recovered by removing water. As supported by the computational results, the higher solubility of cellulose in [RMIm][$LiCl_2$] can be ascribed to the increased bond distance between anion and C(2)-H of the imidazolium ring compared with that in [RMIm]Cl, thereby resulting in the increased interaction between $[LiCl_2]^-$ and the hydroxyl groups of cellulose.

• 약학회지
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• 제58권1호
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• pp.28-32
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• 2014

A new series of 3-allylthio-6-alkylthiopyridazines (3)~(12) was synthesized from dichloropyridazine (1) for development of candidates to retain anticancer activity of human breast cancer. The process involves allythiolation and alkylthiolation from 3,6-dichloropyridazine. 6-Substituted allylthiopyridazines (3)~(12) were prepared from 3-allylthiopyridazinyl chloride (2) via nucleophilic substitution with alkylthiol anion as nucleophile. 3-Allylthiopyridazinyl chloride (2) could be converted to pyridazines (3)~(11) using 1 equivalent of alkyl mercaptan at reflux temperature in methanol. 3,6-Diallylthiopyridazine (12) was synthesized from 3,6-dichloropyridazine (1) using allyl mercaptan (4 equivalent) and sodium hydroxide in methanol. Synthetic compounds were fully identified using NMR, IR, GC-MS data.

• Bulletin of the Korean Chemical Society
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• 제10권3호
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• pp.262-269
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• 1989

The gas phase thermal decomposition of 1-bromo-3-chloropropane in the presence of radical inhibitor was studied by using the conventional static system. The mechanism of unimolecular elimination channel is shown below. [...] In this scheme, the total molecular dissociation rate constant, ($k_1\;+\;k_2$), for the decomposition of $BrCH_2CH_2CH_2Cl$ was determined by pyrolyzing the $BrCH_2CH_2CH_2Cl$ in the temperature range of $380-420^{\circ}C$ and in the pressure range of 10∼100 torr. To obtain $k_3\;and\;k_4,\;and\;to\;obtain\;k_1\;and\;k_2$ independently, the thermal decompositions of allyl chloride and allyl bromide were also studied. The Arrhenius parameters for each step are as follows; $log\;A_{\infty}\;=\;14.20(sec^{-1}),\;E_a$ = 56.10(kcal/mol) for reaction path 1; $log\;A_{\infty}\;=\;12.54(sec^{-1}),\;E_a$ = 49.75(kcal/mol) for reaction path 2; $log\;A_{\infty}\;=\;13.41(sec^{-1}),\;E_a$ = 50.04(kcal/mol) for reaction path 3; $log\;A_{\infty}\;=\;12.43(sec^{-1}),\;E_a$ = 52.78(kcal/mol) for reaction path 4; Finally, the experimentally observed pressure dependence of the rate constants in each step is compared with the theoretically predicted values that are obtained by the RRKM calculations.

• 대한화학회지
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• 제37권1호
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• pp.136-140
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• 1993

새로운 methotrexate 중간체인 diethyl N-[4-{[(2,4-diamino-6-yl)methyl]-amino}benzoyl]-L-glutamate(10)를 합성하기 위하여 p-nitrobenzoic acid를 chlorination한 다음 L-glutamic acid와 coupling하고 이를 esterification한 후, 환원과 methylation시켜 diethyl N-(4-methylaminobenzoyl)-L-glutamate(7)를 합성하였다. 이 화합물(7)을 DMF 존재하에서 NaH와 allyl chloride를 가하여 allylation한 다음 여기에 $IN_3$ addition 반응으로 diethyl-p-[N-(2-azido-3-iodopropyl)-N-methyl]aminobenzoyl-L-glutamate(9)를 합성하였다. 이 화합물(9)을 2,4,5,6-tetraaminopyrimidine hydrochloride와 cyclization시켜 methotrexate diethylester를 얻었다.

• Bulletin of the Korean Chemical Society
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• 제18권8호
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• pp.824-827
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• 1997

Bis(ethylene)rhodium(Ⅰ) chloride dimer reacted with vinylcyclopropane to give σ,η3-allylrhodium(Ⅲ) complex 3. Complex 3 underwent C-C bond cleavage of 8-quinolinyl ethyl ketone 11, to form η3-1,3-dimethylallylrhodium(Ⅲ) complex 8, which was reductively eliminated by trimethyl phosphite to give 8-quinolinyl-1-methylbut-2-enyl ketone (10). More sterically hindered 8-quinolinyl alkyl ketones were allowed to react with complex 3 to afford corresponding alkenes as well as a mixture of complex 8 and η3-1-ethylallyl rhodium(Ⅲ) complex 19, identified as 10 and 8-quinolinyl-pent-2-enyl ketone (20) after reductive elimination. 8-Quinolinyl alkyl ketone bearing a sterically hindered alkyl group showed less reactivity for C-C bond cleavage and higher 20/10 ratio compared with those having a less sterically hindered alkyl group, such as 8-quinolinyl ethyl ketone (11).

• 펄프종이기술
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• 제45권2호
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• pp.56-65
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• 2013

Electron beam treatment was applied for improving dissolution of cellulose with ionic liquids. Two ionic liquids, 1-allyl-3-methylimidazolium chloride ([Amim]Cl]: AC) and 1,3-dimethylimidazolium methylphosphite ([Dmim][$(MeO)(H)PO_2$]: Me) were used for this experiment. Treatment with electron beams up to dose of 400 kGy resulted in the increase of hot water extract and alkali extract of cotton pulp and the great reduction in the molecular weight of cellulose. For the dissolution of cotton pulp with two ionic liquids, the electron beam treated samples showed faster dissolution. The dissolved cellulose with Me ionic liquid were regenerated with acetonitrile and the structure of regenerated cellulose showed distinct difference depending on the electron beam treatment. Those results provide the electron beam pre-treatment could be applied as an energy efficient and environmentally benign method to increase the dissolution of cellulose with ionic liquids.

• 한국펄프종이공학회:학술대회논문집
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• 한국펄프종이공학회 1999년도 Proceedings of Pre-symposium of the 10th ISWPC
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• pp.34-42
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• 1999

The present investigation has focused up on the study of the adsorption of three different molecular mass fractions of a polyDiMethylDiAllylAmmoniumChloride (DMDAAC) (8750(LM\ulcorner), 48000(MM\ulcorner) and 1200000(HM\ulcorner)) on bleached chemical fibres. Both kinetics of adsorption and equilibrium adsorption measurements have been conducted and each adsorption has been measured by polyelectrolyte titration. The results show that the LM\ulcorner polymer can reach all of the charges in the fibre wall whereas the MM\ulcorner and HM\ulcorner can only reach the external surfaces of the fibres. It is also shown that the kinetics of adsorption of the LMw polymer is not at all affected by the presence of a saturated layer of HMw polymer on the surface of the fibres. Finally, the results from the investigation show that it is possible to have full coverage of the external surface of the fibres by a high molecular mass polymer and a full coverage of the internal surface of the fibres with a low molecular mass polymer. This is true if the high molecular masspolymer is added first followed by addition of the low molecular masspolymer.

• 대한화학회지
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• 제34권6호
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• pp.534-538
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• 1990

H$_2$O을 용매로 하여 헤테로고리 염기인 이소퀴놀린과 CrO$_3$를 반응시켜 Cr(Ⅵ)화합물인 [$C_9H_7$NH]$_2Cr_2O_7$을 얻었다. 이 화합물은 비흡수성이면서 물에 잘 녹았다. 그리고 원소분석, 적외선 분광법으로 이 화합물의 구조가 [$C_9H_7$NH]$_2Cr_2O_7$임을 확인하였다. 또한, 이 화합물이 여러 가지 알코올을 알데히드나 케톤으로 전환시킬 수 있는 산화제로 작용하는가를 알아보기 위하여 알릴, 일차, 이차 알코올을 각각 산화반응에 이용한 결과 알코올들에 대해 효율적인 산화제로 작용하였다.

• Bulletin of the Korean Chemical Society
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• 제33권12호
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• pp.4122-4126
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• 2012

Cellulose-graft-poly (L-lactide) (cellulose-g-PLLA) was successfully prepared via ring-opening polymerization (ROP) by using 4-dimethylaminopyridine (DMAP) as an organic catalyst in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl). The structure and morphology of the polymer was characterized by nuclear magnetic resonance (NMR) and transmission electron microscope (TEM). From wide-angle X-ray powder diffraction (WAXD) and degradation test (by acid, alkaline, PBS and enzyme solution), changes in the crystalline structure as a result of degradation was also investigated. The results indicated that materials which have low degree of crystallinity showing higher degradability, however, in acid liquor, enzyme solution, alkaline liquor and PBS system, the degradation rate of the polymer decreased by the above sequence. Moreover, with the further increase of graft degree of this material, its degradation degree decreased.