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61.
Hassan Rabaâ Bernd Engels Thomas Hupp A. Stephen K. Hashmi 《International journal of quantum chemistry》2007,107(2):359-365
A general scheme for the endo‐ and exo‐cyclization of furan reactivity with [L ‐AuIII, IClx] with (x = 3, 1 and L ‐acetylene and vinylidene) complexes is investigated using density functional theory (DFT) code. Two conceivable mechanisms via a [4 + 2] Diels–Alder process or carbene complex are analyzed. According to the activation energy values of the gold (III and I) catalyst, the first mechanism, which implies the Diels–Alder reaction of AuIII, is thermodynamically favored and gives more evidence of the intramolecular addition of the furan with the alkynes. The second mechanism, presumably assisted by the spontaneous formation of the exo‐vinylidene complexes and intermediates of gold (III, I) by forming the carbene complex, is kinetically favored. Additionally, we compare our results with other structures with intramolecular additions that exhibit the quasi‐similarity of gold analogue structures. Differences in activation energies are observed, according to the functional used. Finally, we probe the solvent effects, which decrease the energy barrier in the path. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
62.
用甲基叔丁基甲醚对苯酚叔丁基化的反应研究 总被引:1,自引:0,他引:1
目前我国生产对叔丁基苯酚的方法通常以酚类为原料,烯烃或醚类为烷基化试 剂,其中异丁烯是主要烷基化试剂,但异丁烯在储存、运输等方面存在着一定的弊 端.采用直接以甲基叔丁基甲醚为烷基化试剂,研究了苯酚与甲基叔丁基甲醚的烷 基化反应.并对各影响因素进行了讨论,其中催化剂用量和原料比对反应影响最大 ,温度次之,反应时间影响最小.实验中得出了制备反应的最佳条件;苯酚转化率 大于85%,对叔丁基苯酚产率为78%,得到较理想产率.并与以异丁烯为烷基化试 剂进行了比较,具有成本低、流程短、操作简便、安全等特点,应用前景非常好. 相似文献
63.
双臂套索冠醚PVC膜碘离子选择电极 总被引:2,自引:2,他引:2
研究了两种新型双臂套索冠醚1,10-二(5-氯-8-羟基喹啉-7-亚甲基)-1,10-二氮杂-4,7,16-三氧杂-13,19-二硫杂环二十一烷(Ⅰ)和1,13-二(5-甲基-8-羟基喹啉-7-亚甲基)-1,13-二氮杂-4,7,10-三氧杂-16,19-二硫杂环二十一烷(Ⅱ)为载体的PVC膜电极的响应行为;实验结果表明,两电极均显示阴离子响 应,其中对碘离子具有优良的能斯特电位响应性能,线性范围为10^-5-10^-1mol/L,斜率分别为-59.1mV/pcI-和-57.6mV/pcI-;电极具有读数稳定,重复性好,PH值范围宽等优点;将该电极用于药品中碘含量的测定,其结果与药典法一致。 相似文献
64.
Methyl trifluoropiruvate in trifluoroacetic acid at 20 °C rapidly C-hydroxyalkylates various phenols at thepara-positions to afford the corresponding esters ofpara-hydroxy substituted -trifluoromethylmandelic acids.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 528–530, March, 1995.The present study was carried out with the financial support of the Russian Foundation for Basic Research (Project code 93-03-22696). 相似文献
65.
A four-step synthesis of 1-(-ydroxyalkyl)- and 1-(4-hydroxyphenyl)silacyclobutanes was carried out. The influence of the structure of the initial compounds and the reaction conditions on the ratio of the reaction products formed was studied. The stability of the silacyclobutane alcohols and the hydrolysis of their trimethylsilyl ethers were investigated.For preliminary communication, see Ref. 6.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 946–954, April, 1996. 相似文献
66.
G. A. Tolstikov I. V. Kresteleva A. Yu. Spivak A. A. Fatykhov V. R. Sultanmuratova 《Russian Chemical Bulletin》1993,42(3):557-563
Aluminum and manganese derivatives of lithiated bis-lactim ethers of cyclo-(L-Ala-L-Ala) were used for the enantioselective synthesis of -hydroxy and polyhydroxy -amino acids of the 2-methyIserine series. A new variant of the synthesis of these acids via 3-acyl-2, 5-dialkoxy-3, 6-dimethyl-3, 6-dihydropyrazines is proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 590–595, March, 1993. 相似文献
67.
68.
Zauresh S. Nurkeeva Al-Sayed Abdel Aal Vitaliy V. Khutoryanskiy Grigoriy A. Mun Aida G. Beksyrgaeva 《Radiation Physics and Chemistry》2003,67(6):717-722
Gamma-radiation grafting of vinyl ether of monoethanolamine and vinyl ether of ethyleneglycol (VEEG) on polyethylene films has been studied from binary monomer mixtures. The effect of co-monomer composition and total exposure radiation dose on the grafting process is investigated. A combination of potentiometric and gravimetric techniques is applied to determine the grafting degree of each monomer in the final graft copolymer. The presence of more active monomer VEEG in the mixture was found to enhance the grafting of both monomers because the increasing of copolymerization rate which in turn increases the total grafting degree. The modification of the hydrophilic properties of the graft copolymer is studied by examining the grafted films for water- and copper (II) ions uptake. 相似文献
69.
Macrocycle opening in derivatives of benzocrown ethers under the action of amines is affected by the nature of the heteroatoms in the macrocycle, the nature of the functional group in the benzene ring of the crown ether, and the length, branching, and number of hydrocarbon radicals at the amine nitrogen atom. A distinguishing feature of this reaction is the template effect of MeNH3
+, Me2NH2
+, Na+, and K+ ions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 687–692, March, 1996.For Part I see Ref. 1. 相似文献
70.
A new method for synthesizing nitrogen-containing podands by nucleophilic regioselective cleavage of the macrocycle in formyl derivatives of benzocrown ethers by heating with methylamine and methylammonium chloride has been developed. This reaction is the first example of crown ether opening by a nitrogen-containing nucleophile.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 950–953, May, 1995. 相似文献