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121.
We achieved the total synthesis of the histone deacetylase inhibitor spiruchostatin A, as the prelude to the preparation of a combinatorial library of its analogues. Two key reactions were an asymmetric acetate aldol reaction using a Zr-enolate and macrolactonization using the Shiina method. 相似文献
122.
S. V. Koroteev D. S. Ermekov Z. V. Todres A. D. Malievskii 《Russian Chemical Bulletin》1992,41(1):60-64
Reaction of cis-,-dinitrostilbene (substrate) with morpholine (reagent) in n-hexane leads to cis--nitro--morpholinostilbene (end product). The process is of first order with respect to the substrate and second order with respect to the reagent. Possible reaction mechanisms are analyzed, and it is established that the following are most probable on the basis of kinetic patterns and stereochemistry: development of a charge transfer complex having a hydrogen bond between the substrate nitro group and reagent amino group; reaction of the complex with a second reagent molecule and formation of a carbanion (this stage determines the overall reaction rate); and detachment of a nitrite ion from the nitrocarbanion and its protonation to form the end product.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. A. N. Nesmeyanov Institute of Heteroorganic Compound, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 78–83, January, 1992. 相似文献
123.
The ion product of water and the dissociation constants of carbonic acid have been determined in 0.1, 1.0, 3.0, and 5.0M NaClO4 at 25°C. The ion product of water K
w
'
has been evaluated by emf measurements with a combined glass electrode in NaClO4 solutions containing 0.001–0.1M HCLO4 or NaOH. The product K
H
'
K
l
'
K
2
'
of the Henry constant for CO2 and the dissociation constants for H2CO3 have been determined by titration of carbonate solutions equilibrated with pCO2 =10–3.52 atm, and K
2
'
has been evaluated by potentiometric titration and by measuring the H+ concentration at fixed HCO
3
–
and CO
3
2-
concentrations. The ion interaction (Pitzer) equations are applied to describe the constants K
w
'
, K
2
'
and K
H
'
H
1
'
K
2
'
as a function of the NaClO4 concentration. The experimental data are used to evaluate the mixing parameters
i/ClO
4 and
i/ClO
4
-/Na+ fori = OH
-,HCO
3
-
andCO
3
2- 相似文献
124.
3,4-Dihydro-5(1H)-pyrromethenones are easier attacked at themeso-position by electrophiles than 5(1H)-pyrromethenones. This is demonstrated both by aMannich-type-substitution or deuterium-exchange-experiments and by the addition of O-, S-, and N-Nucleophiles to the exocyclic double bond of the model-dihydropyrromethenone (Z)-1 under very mild reaction conditions. Applying these results to the chemistry of 2,3-dihydro-bilatrienes-abc, their chemical characteristics—especially their tautomeric behavior and their dominant C-5-selectivity towards electrophiles—become better understandable. 相似文献
125.
Laurel A. Goj 《Journal of organometallic chemistry》2003,687(2):498-507
Cycloisomerization of 4,4-bis(acetoxymethyl)-1,6-heptadiene (5) catalyzed by [(phen)Pd(Me)CNCH3]+ [BAr4]− [Ar=3,5-C6H3(CF3)2] (2) to form predominantly 3,3-bis(acetoxymethyl)-1,5-dimethylcyclopentene (6) was ∼400 times faster than was the cycloisomerization of dimethyl diallylmalonate (1) under identical conditions. Mechanistic studies performed in conjunction with density functional theory calculations attribute the large rate acceleration of the cycloisomerization of 5 relative to the cycloisomerization of 1 to the formation of a stable oxo chelate complex as an intermediate in the cycloisomerization of 1, but not in the cycloisomerization of 5. 相似文献
126.
Shigeru Matsuo Tomoyoshi Murakami Ryuichi Takasawa 《Journal of polymer science. Part A, Polymer chemistry》1993,31(13):3439-3446
Crystalline poly(arylene ether nitrile) could be prepared by the polycondensation of 2,6-dihalobenzonitrile with resorcinol at 200°C in N-methylpyrrolidone in the presence of sodium carbonate. A reaction temperature of at least 200°C was necessary to attain high molecular weight polymer. Spectral data indicated that the polymer had the structure of a poly(meta-phenylene ether) with pendent nitrile groups on every other phenylene unit. Despite this structure, the crystallinity and the crystallization rate of the polymer were greater than those of the corresponding polymer with a para-linked structure. The glass transition temperature and the melting temperature of the polymer were almost the same as those of poly(etheretherketone) (PEEKTM). A series of other new poly(arylene ether nitriles) were also examined. The polymers derived from 4,4′-biphenol, dihydroxytetra-phenylmethane, dihydroxydiphenylsulfone, and 1,5-isoquinolinediol had high glass transition temperatures. The poly(arylene ether nitriles) exhibited excellent tensile strength compared with the corresponding ketone- or sulfone-containing polymers. Comparing the three different kinds of polymers containing the same bisphenol units, the order of glass transition temperature was found to be sulfone- > nitrile- > ketone-containing polymers, while the order of tensile strength was nitrile- > ketone- > sulfone-containing polymers. The excellent mechanical properties are attributable to dipole-dipole interactions of nitrile groups. © 1993 John Wiley & Sons, Inc. 相似文献
127.
Laurence E. Strong Thomas G. Copeland Margaret Darragh Carter Van Waes 《Journal of solution chemistry》1980,9(2):109-128
Conductivities of aqueous solutions ofortho-, meta-, andpara-toluic acids have been measured for the concentration range 0.1–2 millimolar and at 5° intervals from 5 to 100°C. At each temperature pK
a(m) andA
0 have been calculated using the paired ion model recently described by Fuoss. Thermodynamic parameters have been calculated for the ionization of each acid, and Walden products for the anions. Results are discussed in terms of contributions to acidity by enthalpy and entropy changes as well as by hydration of the various solute species. 相似文献
128.
A practical and efficient stereoselective synthesis of the side chain of neomarinone is reported. The synthesis was achieved in six steps (41% overall yield) from 2-methyl-2-cyclohexenone. The key step is a novel stereoselective 1,4-conjugate addition/enolate alkylation by an epoxide-opening reaction. 相似文献
129.
Marc Wende 《Journal of fluorine chemistry》2003,124(1):45-54
Most compounds designed for immobilization in fluorous media feature linear pony tails of the formula (CH2)m(CF2)n−1CF3 [(CH2)mRfn]. This paper presents a first-generation approach to compounds with branched or “split” pony tails of the formula (CH2)lCH[(CH2)mRfn]2. Allyl tri(n-butyl)tin is reacted twice with perfluorooctyl iodide (Rf8I; first, photochemical, 78-81%; second, thermal with radical initiator, 71%; 13-18 g scales) to give the secondary alkyl iodide ICH(CH2Rf8)2 (3). A subsequent Ni(Cl)2(PPh3)2-catalyzed reaction with allyl tri(n-butyl)tin yields the branched alkene H2CCHCH2CH(CH2Rf8)2 (74%). A palladium-catalyzed Heck coupling with OP(p-C6H4Br)3 gives the fluorous phosphine oxide OP(p-C6H4CHCHCH2CH(CH2Rf8)2)3 (84%), and Pd/C-catalyzed hydrogenation affords OP(p-C6H4(CH2)3CH(CH2Rf8)2)3 (>99%). Reduction with SiHCl3 gives P(p-C6H4(CH2)3CH(CH2Rf8)2)3, which is protected as the air-stable borane adduct H3B·P(p-C6H4(CH2)3CH(CH2Rf8)2)3 (9, 64%). The CF3C6F11/toluene partition coefficient of 9 is much higher than that of the analog with p-(CH2)3Rf8 groups (96.6:3.4 versus 37.3:62.7). The iodide 3 is unreactive towards PAr3 at 175-250 °C. However, a CuBr-catalyzed reaction with C6H5MgBr gives C6H5CH(CH2Rf8)2, which also exhibits a high partition coefficient (97.9:2.1). 相似文献
130.