Tripledecker 착물, (CpCo)_2(C_4R_4)과 Alkyne과의 반응

嚴在國,李元植,金碩峯,車震淳,李炯秀,李東鎬,金洪碩,沈相喆 대구효성가톨릭대학교 자연과학연구소 1993 基礎科學硏究論集 Vol.1993 No.1

트리플데카 착물류, bis-(η^5-cyclopentadienyl)-μ-(η^4-1,2,3,4-tetraalkylcyclobutadiene)dicobalt들은 Jonas시약과 2-hexyne 또는 3-hexyne을 실온에서 동량으로 반응시킬때, 50% 이상의 최대 수율이 얻어졌다. 한 종류의 트리플데카 착물인 bis-(η^5-cyclopentadienyl)-μ-(η^4-1,2,3,4-tetraalkylcyclobutadiene)dicobalt(13)는 실온에서 3-hexyne과 반응시키면, 착물 (η^5-cyclopentadienyl)cobalt-acyclopentadiene-μ-(η^4-2,4-cobaltacyclope-ntadiene)(η^5-cyclopentadienyl)cobalt(15)로 이성화되었다. 다른 한 종류의 트리플데카 착물, bis-(η^5-cyclopentadienyl)-μ-(η^4-1,3-dimethyl-2,4-dipropyl-cyclobutadiene)dicobalt(14)를 2-hexyne 과 반응시켰더니 1,3,5-tri-methyl-2,4,6-tripropyl benzene화합물이 생성되었다. The tripledecker complexes, bis-(η^5-cyclopentadienyl)-μ-(η^4-1,2,3,4-tetraalkylcyclobutadiene)dicobalt were produced by the reaction of Jonas reagent with 2-hexyne and 3-hexyne in the maxi-mum yield(above 50%) when they were reacted in eq-molar amounts at room temperature. A tripledecker complexes,bis-(η^2-cyclopentadienyl)-μ-(η^4-1,2,3,4-tetraalkylcyclobutadiene)dicobalt(13) was isomerized to (η^5-cyclopentadienyl)cobalt-acyclopentadiene-μ-(η^4-2,4-cobaltacyclope-ntadiene)(η^5-cyclopentadienyl)cobalt(15) on reacting with 3-hexyne at room temperature. Another tripledecker complex, bis-(η^5-cyclopentadienyl)-μ-(η^4-1,3-dimethyl-2,4-dipropyl-cyclobutadiene)dicobalt(14) was decomposed to give 1,3,5-trimethyl-2,4,6-trip-ropylbenzene through an intermediate complex by the reaction of 2-hexyne.

Para 置換 芳香族 Oxime 類의 Chemical shift에 미치는 置換基의 效果

嚴在國,洪永錫,崔潤壽 啓明大學校 生活科學硏究所 1981 科學論集 Vol.7 No.-

Para-substituted benzaldehyde-anti-oximes were synthesized from parasubstituted benzaldehydes and their NMR spectra were checked in various solvents. The chemical shift differences and coupling constants between ?? and ?? were calculated from NMR spectra which were shown the spin system of Α₂Β₂ in ??, ?? protons. ?? -Χ=-(CH₃)₂N, -OH, -OCH₃, -OCH₂CH₃, -H, -NO₂, -CI, In order to examine the effect of substituents attached on the para-position, we used the substituents in order of -N(CH₃)₂>-OH>-OCH₂CH₃>-OCH₃ as the electron-donating groups and those of -NO₂, CI, as the electron-withdrawing groups. The chemical shift differences in the case of electron-donation groups were increasing according to the intensity of the corresponding substituents but the chemical shifts of ?? proton in compounds with the electron-withdrawing groups were resonated at the lower fields than those of ??. The substituent-effect of formaldoxime group was assigned as an electron-withdrawing form the chemical shift differences of ?? and its intensity might be larger than that of -CL but be smaller than that of aldehydic group. We also examined the chemical shifts of aldehydic protons and hydroxyl protons in formaldoxime group to assign the long-range shielding effect of various substituents. The chemical shifts of aldehydic protons and hydroxyl protons of Ρ-substituted benzaldehyde-anti-oximes with the electron-donating groups were resonated at the lower fields. We found that the plots of chemical shift differences vs Hammett's σ-function have the good linearities between substituents and aldehydic protons and hydroxy1 protons.

C_4型 Oxime化合物의 立體構造와 Chemical Shift에 關한 硏究

민경은,嚴在國,朴英培 경북대학교 공과대학 1980 工大硏究誌 Vol.9 No.-

Some C_4-type oximino compounds 2-butene oxime, 2, 3-butanedione mono and dioxime, a-benzil monooxime,, r-benzil dioxime, and B-benzoin oxime were synthesized and studied. Their structures were compared with another C_4-type oximino compounds investigated already. The structure of 2-butanone oxime is in syn and anti form, 2, 3-butanedione mooooxime is in syn, and 2, 3-butanedione dioxime is in syn-syn form respectively. As the results of chemical shift changes of these compounds in various solvents, following conclusion was made, i. e., 1. Among thoes conformers, a-methyl protons are more deshielded 0.7~1.3ppm than other methyl protons which were not affected vicinal functional groups. 2. While the oximino hydroxyl proton hydrogen bonded to solvent molecule, the vicinal functional groups of aliphatic oxime were deshielded ca 0.2ppm in chemical shift, and that of B-benzoin oxime was ca. 0.3~0.4ppm. 3. The anisotropy effect of adjacent functional group to the oximino hydroxyl proton was ca 0.8ppm in case of carbonyl group, and that of phenyl ring was ca. 0.7ppm.

KHFe(CO)_4-HCHO系를 利用한 Nitro 및 Nitroso化合物의 환원 N-메칠화 반응

沈相喆,閔庚隱,嚴在國,洪錫 경북대학교 1978 논문집 Vol.10 No.-

The reduction of nitro and nitroso compounds using tetracarbonylhydridoferrate-formaldehyde under mild conditions (at room temperature and then 60℃ under CO) gives the corresponding N, N-dimethylation via N-methylation in good to excellent yields. The reaction mechanism via immonium salt is assumed.

NMR에 依한 trans-2-Butene-dial dioxime의 立體構造에 關한 硏究

李學沂,沈相喆,嚴在國 慶北大學校 1976 論文集 Vol.21 No.-

The structure of trans-2-butene-dial dioxime was investigated by means of NMR spectroscopy. Its conformer was found to have the planar structure conjugated with the double-bonds from the vicinal spin-spin coupling constants. The configurations of two oxime group were investigated from the solvent effects and assigned as the perfect symmetric structures, mixture of "syn-syn" and "anti-anti" forms.

Reaction of CpCo$(C_2H_4)_2$ with Diphenylacetylene

Uhm Jae-Kook,An Hee-Won,Chung Chinkap,Kim Hon-Rak Korean Chemical Society 1994 Bulletin of the Korean Chemical Society Vol.15 No.12

Synthesis of Tetradecker Sandwich Complex with 1,4-Dialkyl-1,4-dibora-2,5-cyclohexadiene

Jae Kook Uhm,Walter Siebert Korean Chemical Society 1992 Bulletin of the Korean Chemical Society Vol.13 No.5

A tetradecker sandwich compiex (7a) was synthesized in low yield by the reaction of a tripledecker, bis(${\eta}^5$-cyclopentadienyl)-${\mu}$-(${\eta}^6$-1,2,3,4-tetramethyl 1,4-dibora-2,5-cyclohexadiene) dinickel (5a) with potassium and Fe$Cl_2$${\cdot}$2THF. The reaction of another tripledecker, bis(${\eta}^5$-cyclopentadienyl)-${\mu}$-(${\eta}^6$-2,3-diethyl-1,4-dimethyl-1,4-dibora-2,5-cyclohex adiene) dicobalt (4a) with potassium and Fe$Cl_2$${\cdot}$2THF at room temperature produced a doubledecker complex (2b) via the decomposition of the dark green crystal.

Synthesis and Properties of 1,4-Diboracyclohexene-2 Derivatives

Uhm, Jae-Kook,Hu D.,Zenneek U.,Pritzkow H.,Siebert W. Korean Chemical Society 1990 대한화학회지 Vol.34 No.5

1,4-dibora-2-cyclohexene 고리화합물 8을 합성하기 위한 두 가지 방법이 개발되었다. 방법 i)은 1,2-bis(dichloroaluminyl)ethane을 출발물질로 하는데 이 물질은 AlCl$_2$ 부분을 BCl$_2$로 치환시켜준다. 1,2-bis(dichloroaluminyl)ethane에 결합된 염소를 BI$_3$로 교환시켜 대응되는 요오드 화합물을 얻고 이 화합물을 alkynes와 반응시켜 헤테로고리화합물 8a, b를 많이 얻었다. 방법 ii)는 B$_2$Cl$_4$를 alkynes에 부가시켜 얻어지는 염소화합물에 BI$_3$를 치환시켜 bis(diiodoboryl)ethane유도체를 얻고 이 화합물에 alkynes와 산화환원반응을 하여줌으로 8c, d를 얻는다. 요오드 유도체인 8a는 pyridine 부가물인 9a를 생성하고 또 ether와 반응하여 ethoxy 유도체인 8e를 생성시킨다. 요오드 유도체의 dimethyl amino 치환제가 8f이다. 8a-d와 AlMe$_3$를 반응시켜 대응되는 methyl유도체인 8g-j를 얻고 이들 화합물은 THF속에서 칼륨과 반응시켜 불안정한 라디칼 음이온이 생성되고 여기서 ESR 결과가 측정된다. 8g-j의 전기화학적인 실험이 비가역적인 환원반응으로 나타났다. 8g-j화합물은 (C$_5$H$_5$)CO(C$_2$H$_4$)$_2$와 반응하여 중간체인 16개 VE(valence electron)를 갖는 착물 (C$_5$H$_5$)Co(8)이 얻어지는데 이 화합물은 다시 C-H 활성화에 의해 대응되는 붉은색의 1,4-diboracyclohexene 착물 10을 생성하게 된다. 착물 10h와 10j의 X-ray 구조가 결정되었다. Two synthetic routes for the 1,4-diboracyclohexene-2 ring 8 have been developed. Method i) starts with 1,2-bis(dichloroaluminyl)ethane, in which the AlCl$_2$ group is replaced by BCl$_2$. Exchange of the chlorine with BI$_3$ in 1,2-bis-(dichloroboryl)ethane yields the corresponding iodo compound, which reacts with the alkynes to heterocycles 8a, b in good yield. In method ii) B$_2$Cl$_4$ is added to alkenes, replacement of chlorine with BI$_3$ yields the bis(diiodoboryl)ethane derivatives which undergo redox reactions with alkynes to give 8c, d. The diiodo derivative 8a forms the pyridine adduct 9a, and reacts with ether to give the ethoxy derivative 8f. 8a-d react with AlMe$_3$ to yield the corresponding dimethyl derivatives 8g-j, which give unstable radical anions when treated with potassium in THF. The ESR parameters are reported. In electrochemical experiments irreversible reductions of 8g-j are observed. 8g-j react with (C$_5$H$_5$)Co(C$_2$H$_4$)$_2$ to give the intermediate 16 VE complexes (C$_5$H$_5$)Co(8), in which C-H activation occurs with formation of the corresponding red 1,4-diboracyclohexadiene complexes 10. The X-ray structure analyses of 10h and 10j are reported.

기초과학연구논문집 - 1993 년 연구실적편 - / 화학 : Tripledecker 착물 , (CpCo)2(C4R4) 과 Alkyne 과의 반응

엄재국(Jae Kook Uhm),이원식(Won Sik Lee),김석봉(Seog Bong Kim),차진순(Jin Soon Cha),이형수(Hyung Soo Lee),이동호(Dong Ho Lee),김홍석(Hong Seok Kim),심상철(Sang Chul Sim) 대구가톨릭대학교 자연과학연구소 1993 기초과학연구논문집 -연구실적편- Vol.1993 No.-

(η⁵-Cyclopentadienyl)-μ-(η⁵-1,2,3,4,5-Pentamethyl-1,3-diborole)Cobalt 착물의 고리팽창에 대한 연구

엄재국,Uhm, Jae-Kook 대한화학회 2007 대한화학회지 Vol.51 No.4