질산 팔라듐-포스핀 촉매에 의한 방향족 C-H 결합의 활성화반응

黃英愛 상명대학교 기초과학연구소 1999 기초과학연구 Vol.12 No.-

스티렌과 벤젠을 사용하여, 질산 팔라듐과 포스핀 (PR₃, R=C_(6)H_(5) , C_(6)H_(11), C_(6)H₄CH₃, C_(6)H₄F)을 촉매로 하여 일정한 조건 (55 ℃, 20 psi O₂ , 20 h) 하에서 진행된 C- H 결합의 활성화 반응에 대하여 이미 발표된 아세트산팔라듐의 경우와 비교하였다. 아릴화 스티렌의 수득률은 벤젠유도체의 치환기의 전자주게 능력이 증가함에 따라 증가하였다. 일반적으로, 수득률은 질산염의 경우가 아세트산염의 경우보다 낮았는데, 이는 반응 중간과정에서 안정한 중간체인 cis- Pd(NO₃)₂ (PR₃)₂를 형성하여 더 이상 반응이 진행되려 하지 않은 것으로 본다. The aromatic C-H activation reactions using styrene and benzene have been carried out in the presence of Pd(NO₃)₂ and phosphines (PR₃, R=C_(6)H_(5), C_(6)H_(11), C_(6)H₄CH₃, C_(6)H₄F) under the constant condition (55 ℃, 20 psi O₂ , 20 h) to compare the effect of the nitrate anion with the previously reported acetate anion. The yield of arylated styrene increases as the electron donating ability of the substituents of phospnie increases. The yield of the product is generally lower for the nitrate catalyst than for the acetate case, probably due to the formation of stable intermediate, cis- Pd(NO₃)₂ (PR₃)₂, so that the reaction doesn't want to go any further.

Arylation of Styrene Catalyzed by Palladium Nitrate - Phosphine Complexes

Park, Young Ae Whang,Woo, Je Wan,Park, Yong Sung,Shin, Jung Ae 한국공업화학회 2001 Journal of Industrial and Engineering Chemistry Vol.7 No.5

The reactions of styrene with benzene to activate the aromatic C-H bond have been carried out using Pd(NO₃)₂ and phosphines (PR₃, R=C_6H_5, p-C_6H₄CH₃, p-C_6H₄F, C_6H_(11)) as the catalytic system. The reaction conditions in this work (55 ℃, 20 psi O₂, 20 h) has been kept identical to those in the previously reported work using Pd(OAc)₂ and phosphines to compare the effect of nitrate with acetate. The yield of the product, trans-stilbene, increases as the electron donating ability of the substituents on the phosphine increases and decreases as the steric hindrance increases; P(C_6H_5)₃ > P(C_6H_(11))₃ > P(p-C_6H₄CH₃)₃ >> P(p-C_6H₄F)₃. On the other hand, the migratory aptitude of the substituent in phosphine to the palladium metal is reinforced as the electronegativity of the substituent increases. Generally, the yield of the product is lower for the less basic nitrate system than for the acetate one, which shows a parallel result with the above substituent effect.

Organocobalt(III) Complexes of the Tetraazamacrocyclic Ligand, $C_{32}H_{26}N_4^{2-}(I)$

Young-ae Whang Park Korean Chemical Society 1990 Bulletin of the Korean Chemical Society Vol.11 No.3

Dehydrogenation Reaction of Cycloalkanones Catalyzed by Palladium Nitrafe-Phosphine and -Sulfide Systems

Park, Young Ae Whang,Hwang, Seong Won 한국공업화학회 2000 Journal of Industrial and Engineering Chemistry Vol.6 No.2

Activation of the aliphatic carbon-hydrogen bond was investigated in the dehydrogenation reaction of cycloalkanone (1-cyclopentanone, 1-cyclohexanone) using Pd(NO₃)₂-PR₃ (PR₃= PPh₃, P(p-C_6H₄CH₃)₃, P(p-C_6H₄-OCH₃)₃, P(p-C_6H₄F)₃) and Pd(NO₃)₂-SR₂ catalytic systems (SR₂=SPh₂, S(CH₂Ph)₂, S(CH₂CH₂CH₃)₃, S[C(CH₃)₃]₂, S[CH(CH₃)₂]₂, S[(CH₃)CH(C₂H_5)]₂). The reaction of cyclic ketones was carried out for 1.5 h in the presence of Pd(NO₃)₂ with phosphine or sulfide at 75℃. The molar ratio of Pd(N0₃)₂ to PPh₃ providing the highest yield was 1:3 and this ratio was maintained for the other phosphines and sulfides used in this work. The yield of 2-cyclohexen-1-one decreased as the basicity of the substituent on the phosphorus decreased; P(p-C_6H₄CH₃)₃> P(p-C_6H₄OCH₃)₃ > P(C_6H_5)₃ > P(p-C_6H₄F)₃> none. For sulfides, a similar trend was observed except for the lower yield than for phosphines with the same substituent; S[CH(CH₃)₂]₂>S[(CH₃)CH(C₂H_5)]₂>S(CH₂CH₂CH₃)₂>S(C_6H_5)₂>S(CH₂C_6H_5)₂∼S[C(CH₃)₃]₂. In the case of 2-cyclopenten-1-one, the order of the yield for the phoshine ligand indicated that the reaction proceeded in the same manner as in the case of 2-cyclohexen-l-one; P(p-C_6H₄CH₃)₃ > P(C_6H_5)₃ >none > P(p-C-6H₄F)₃. However, the reaction seemed to proceed with a different mechanism for the sulfide ligand considering the different order of the yield; S(C_6H_5)₂ > S(CH₂C_6H_5)₂ = S[(CH₃)CH(C₂H_5)₂ > S[CH(CH₃)₂]₂ > S(CH₂CH₂CH₃)₂.

The Solvent Effect on the Electronic Spectra of Organnocobalt(Ⅲ) Complexes

Park, Young-ae Whang,Seo, Hye Kyung 상명대학교 기초과학연구소 1991 기초과학연구 Vol.5 No.-

5-배위인 유기 코발트(Ⅲ) 착물인 CH3CoL과 C6H5CoL의 전자스펙트럼에서 600nm에서 나타나는 흡수띠는 용매의 극성이 변화함에 따라 그 위치가 크게 이동하였다. CH3CoL은 메탄올에서 568nm이고 벤젠에서는 610nm에서 나타났고, C6H5CoL의 경우는 메탄올에서 572nm이고 벤젠에서는 624nm에서 이동하였다. 이와 같이 600nm부근의 흡수띠는 코발트-유기그룹의 결합과 관계되는 전하이동의 전이에 의한 것으로 지정될 수 있다. 일곱 개의 극성이 다른 용매에서 흡수띠의 이동을 측정한 바, 전이 에너지 (Er)는 용매극성도 변수(Z)에 대해 일차함수로 표시할 수 있었고, 그 방정식은 각각 Er=0.130Z+39.6(CH3CoL)와 Er=0.151Z+37.4(C6H5CoL)이다. The absorption band in 600nm region in the electronic spectra of both 5-coordinate CH₃CoL and C_{6}H_{5}CoL complexes is very sensitive to the solvent polarty ; λ_{max} being varied from 568nm in methanol to 610nm in benzene for CH₃CoL and 572nm in methanol to 624nm in benzene for C_{6}H_{5}CoL. Thus the band mentioned above can be reasonably assigned to the charge- transfer transition for the cobalt -carbon (organic group) bond. The transition energies (E_{T}) have linear relationship with solvent polarity parameter (Z) by the equations of E_{T}=0.130Z+39.6 for CH₃CoL and E_{T}=0.151Z+37.4

Oxidation of Dibenzyl Sulfide via an Oxygen Transfer from Palladium Nitrate

Young-ae Whang Park,Yongho Na,Du-Jong Baek* 대한화학회 2006 Bulletin of the Korean Chemical Society Vol.27 No.12

Dibenzyl sulfide was oxidized at the a-carbon to yield benzaldehyde in the presence of Pd(NO3)2. Oxygen itself could not oxidize the sulfide directly, instead the nitrato ligand of the palladium complex transferred oxygen to dibenzyl sulfide to form benzaldehyde. The X-ray crystal structure of the intermediate complex, cis-[Pd(NO3)2{S(CH2C6H5)2}2], revealed that the nitrato ligand was unidentate. Para-substituted dibenzyl sulfides I, (YC6H4CH2)2S wherein Y = OCH3, CH3, Cl, CN, or NO2, were synthesized and reacted with palladium nitrate, and those with electron-donating substituents (Y = OCH3 and CH3) were good substrates for the oxidation reaction with palladium nitrate. Thus, the reaction mechanism of the oxygen transfer was proposed to include nucleophilic benzylic carbon.

아세트산 팔라듐-포스핀 착화합물의 합성과 촉매 반응

황영애 ( Young Ae Whang Park ) 상명대학교 자연과학연구소 2005 自然科學硏究 Vol.14 No.-

탄화수소에서 탄소-수소 결합의 활성화 반응은 유기 금속화학 분야에서 매우 활발하게 진행되고 있는 과제이다. 아릴화 올레핀은 방향족 탄소-수소 결합의 활성화에 의하여 얻어진다. 포스핀 리간드를 포함하는 팔라듐 착화합물, [Pd3(C6H4C2H5)2(μ-MeCO2)4{P(o-tolyl)3}2]을 합성하였고, 이의 구조를 확인하였다. 이 촉매는 전에 보고된 황화물 촉매보다 더 온화한 조건, 즉 더 낮은 온도와 낮은 압력의 산소 하에서 사중합체 같은 부산물이 생성되지 않아 더 좋은 촉매임이 확인되었다. 아렌과 포스핀의 여러 가지의 치환체에 따른 아릴화 올레핀의 수율에 대한 영향을 연구하였다.

Palladium 을 이용한 Phenylacetylene 의 Hydrosilylation

박용성,우제완,안보영,황영애 한국공업화학회 2000 응용화학 Vol.4 No.2

Silylstyrenes were prepared by the hydrosilylation reaction of acetylene with alkylsilane using palladium(II) nitrate catalyst in the presence of various sulfides as ligands in toluene. The selectivity of product catalyzed by palladium complex was found to be higher than that catalyzed by previously reported Lewis acid. The effect of the ligands on the yield has been investigated. Sulfides containing less basic substituents increase the yield of product.

치환된 Alkyl Group 에 따른 Acrylate 계 화합물의 흡유 특성

박용성,최중소,우제완,정홍주,황영애,차혜영 한국공업화학회 2000 응용화학 Vol.4 No.2

Oil absorbents were prepared by suspension polymerization of methacrylates that were prepared by esterification of methacrylic acid and alcohol in benzene. The properties of absorbents were influenced by reaction parameters, i.e., concentration of crosslinking agents and substituted alkyl groups. The concentration of crosslinking agent providing maxium absorptive power was 0.1%(w/w). As the length of alkyl chain of acrylates increases, acrylates become more absorptive. They tend to absorb more aromatic oils than alphatic ones except chloroform.

황산암모늄 열 분해에 의한 폐 알칼리전지 중의 Mn 성분의 추출

박용성,우제완,신희관,황영애,나재식 한국공업화학회 2000 응용화학 Vol.4 No.2

A reaction between the solid electrolyte in the spent alkaline batteries and (NH₄)₂SO₄ was carried out to find a new process for the extraction of Mn component from the spent alkaline batteries. The maximum extraction, 97.1%, was achieved when the reaction temperature was 400℃, the weight ratio of (NH₄)₂SO₄ to the solid electrolyte in the spent alkaline batteries was 16.0 and the reaction time was 180 minutes.