• Bulletin of the Korean Chemical Society
• /
• 제14권5호
• /
• pp.549-554
• /
• 1993

The CO substitution reactions in the complex, $Cp^*(C_5H_7)$CrCO with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. For the reaction rates, it was suggested that the CO substitution reaction took place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}= 21.99{\pm}2.4$ kcal/mol, ${\Delta}S^{\neq}= 8.9{\pm}7.1$ cal/mol·k. Unusually low value of ${\Delta}S^{\neq}$, suggested an ${\eta}^5-S{\to}\;{\eta}^5$-U conversion of the pentadienyl ligand. At various temperature, the rates of reaction for the Cp(pdl)CrCO complexes increase in the order $Cp^*(C_5H_7)$-CrCO < Cp$(C_5H_7)$CrCO < Cp(2,4-$C_5H_{11}$)CrCO, which can be attributed to the usual steric acceration or electronic influence for the ligand substitution of metal complexes. This suggestion was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the energy of $[Cp^*(U-C_5H_7)Cr]^{\neq}$ transition state is about 4.93 kcal/mol lower than that of [Cp(S-$C_5H_7)Cr]^{\neq}$ transition state, and the arrangement of the overlap populations between Cr and the carbon of CO is $Cp^*(C_5H_7)$CrCO > Cp($C_5H_7$)CrCO > Cp(2,4-$C_7H_{11}$)CrCO.

• 약학회지
• /
• 제29권2호
• /
• pp.62-69
• /
• 1985

The isomeric intermediates, $3{\alpha}$and $3{\beta}-amino-5{\alpha}-cholestane required for the synthesis of N-nitrosoureas, N-(2-chloroethyl)-N-nitrosocarbamoyl-$3{\alpha}-amino-5{\alpha}$-cholestane (9), N-methyl-N-nitrosocarbamoyl-3${\alpha}-amino-5{\alpha}-cholestane$ (10), N-(2-chloroethyl)-N-nitrosocarbamoyl-$3{\beta}-amino-5{\alpha}-cholestane$: (7), and N-methyl-N-nitrosocarbamoyl-$3{\beta}-amino-5{\alpha}-cholestane$ (8) were obtained through the $LiAlH_{4}$ reduction of $5{\alpha}$-cholestan-3-one oxime, followed by the chromatographic separation: the assignment of the stereochemistry of both isomers were based on the shape and chemical shift of $C_{3}$-proton resonances on their NMR spectra and on the elution mobility on the TLC. The urea intermediates, N-(2-chloroethyl) carbamoyl-3.alpha.-amino-5.alpha.-cholestane (13), N-methylcarbamoyl-$3{\alpha}-amino-5{\alpha}-cholestane$ (14), N-(2-chloroethyl) carbamoyl-$3{\beta}-amino-5{\alpha}-cholestane (11) and N-methyl-$3{\beta}-amino-5{\alpha}$-cholestane (12) were prepared by the treatment of each isomers ($3{\alpha}$-amino-and $3{\beta}-amino-5{\alpha}$-cholestane) with alkyl isocyanates in anhydrous $CHCl_{3}$, and the corresponding nitrosoureas, 7-10 were obtained by the nitrosation of the ureas, 11-14, with AcOH (or HCOOH)/$NaNO_{2}$ in ice-cold condition. The inhibitory activity of the nitrosoureas, 7-10, and their intermediates, 12-14 towards the growth of L1210 murine leukemia cells, were examined. Among them, the compounds 9 and 10 exhibited high activity having $ED_{50}$ to be 5.5g/ml and 6.1g/ml, respectively.

• 분석과학
• /
• 제6권5호
• /
• pp.417-424
• /
• 1993

5,7-디클로로-8-히드록시퀴놀리놀(Hdcq)과 2-메르캅토피리미딘(Hmpd)를 포함하는 8-배위 테트라키스 몰리브데늄(IV) 착물을 합성하였다. $Mo(mpd)_4$, $Mo(dcq)(mpd)_3$, $Mo(dcq)_2(mpd)_2$, $Mo(dcq)_3(mpd)$와 $Mo(dcq)_4$ 착물들을 TLC plate에서 분리하였다. 이 착물들의 특성을 $^1H-nmr$ 스펙트럼과 자외선-가시광선 스펙트럼으로 조사하였다. 리간드의 질소원자에 대한 ${\alpha}$위치 양성자의 화학적 이동값은 낮은 장으로 이동되었으며, $Mo(dcq)(mpd)_3$와 $Mo(dcq)_3(mpd)$는 같은 위치의 양성자가 2:1의 상대적 세기로 나타났고 $Mo(dcq)_2(mpd)_2$는 거의 같은 세기였다. 이들 착물의 입체화학을 nmr 스펙트럼과 Orgel 규칙으로 고찰했다. 이 착물들의 전자전이 스펙트럼은 세기(${\varepsilon}$>10,000~25,000)와 낮은 에너지($16,600{\sim}19,800cm^{-1}$) 흡수띠를 관찰하여 이를 전하이동 흡수띠로 해석하였다.