FRIEDEL-CRAFTS CHEMISTRY .11. BORON, ALUMINUM, AND GALLIUM TRIS(TRIFLUOROMETHANESULFONATE) (TRIFLATE) - EFFECTIVE NEW FRIEDEL-CRAFTS CATALYSTS
FRIEDEL-CRAFTS CHEMISTRY .11. BORON, ALUMINUM, AND GALLIUM TRIS(TRIFLUOROMETHANESULFONATE) (TRIFLATE) - EFFECTIVE NEW FRIEDEL-CRAFTS CATALYSTS
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DOI：
10.1021/ja00216a032
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发表时间：
1988-04-13
影响因子：
15
通讯作者：
OLAH, JA
中科院分区：
文献类型：
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作者：
OLAH, GA;FAROOQ, O;OLAH, JA
硼、铝和镓三（三氟甲磺酸盐）由相应的氯化物（溴化物）和三氟甲磺酸制备。IIIA族三氟甲磺酸酯以纯的形式分离并充分表征（元素分析、分子量、NMR和IR光谱）。三（三氟甲磺酸）硼是单体的、相对挥发性的化合物[熔点43-45 ℃，沸点68-73 ℃（0.5托）]，而铝和三氟甲磺酸镓是缔合的、高熔点的缔合固体。硼、铝和三氟甲磺酸镓是有效的新型Friedel-Crafts催化剂，如在烷基化、异构化和酰化反应中所示。苯和甲苯与甲基、乙基、异丙基和叔丁基卤化物（氟化物、氯化物和溴化物）的烷基化在室温下用三（三氟甲磺酸）硼、铝和镓作为催化剂在CH 2Cl 2和CH 3 NO2溶剂中进行。通过GLC测定底物（kT/kB）和位置选择性（异构体分布）。三氟甲磺酸硼的催化活性最高，其次是三氟甲磺酸镓和三氟甲磺酸铝，这反映在烷基化反应的总产率和伴随的异构化倾向，导致Meta取代和异构化的显著增加。
Boron, aluminum, and gallium tris (trifluoromethanesulfonate)(triflate) were prepared from the corresponding chlorides (bromides) and triflic acid. The group IIIA triflates were isolated in pure form and fully characterized (elemental analysis, molecular weight, and NMR and IR spectroscopy). Boron tris (triflate) is a monomeric, relatively volatile compound [mp 43-45 C, bp 68-73 C (0.5 Torr)], whereas aluminum and gallium triflate are associated, high-melting associated solids. Boron, aluminum, and gallium tris (triflate) are efficient new Friedel-Crafts catalysts as shown in alkylation, isomerization, and acylation reactions. Alkylation of benzene and toluene with methyl, ethyl, isopropyl, and rerf-butyl halides (fluoride, chloride, and bromide) were carried out with boron, aluminum, and gallium tris (triflate) as catalyst in CH2C12 and CH3N02 solvent at room temperature. Substrate {kT/kB) and positional selectivity (isomer distribution) were determined by GLC. Boron triflate shows the highestcatalytic activity followed by gallium and aluminum triflate as reflected by overall yields in the alkylation reactions and tendency of accompanying isomerization, causing substantially increased meta substitution and disproportionation.