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Development of the method of alkylation of C_<60> by way of alkylfullerenyl cation

Development of the method of alkylation of C_<60> by way of alkylfullerenyl cation
烷基富勒烯基阳离子烷基化C_<60>方法的开发
批准号:
12650810
负责人:
KITAGAWA Toshikazu
金额:
$2.18万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (C)
财政年份:
2000
资助国家:
日本
项目状态:
已结题
起止时间:
2000 至 2001

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中文摘要
翻译
我们发现富勒烯C&lt;60&gt;在氯代烷(RCL)中与大量过量的AlCl3发生亲电加成反应,以较高的产率得到加合物RC&lt;60&gt;-Cl。中间体烷基富勒烯基阳离子(RC_&lt;60&gt;^)可通过富勒烯醇(RC_&lt;60&gt;OH)在CF_3SO_3H和H_2SO_4等强酸中溶解而生成类长离子。核磁共振谱表明正电荷主要位于C-2上,结构具有C_S对称性。阳离子中心的化学位移(175-180ppm)表明R基氯原子(S)与阳离子中心的配位较弱。阳离子RC_&lt;60&gt;也可通过与AlCl3从氯化物RC_&lt;60-&gt;Cl中提取氯离子而原位生成。当反应在苯甲醚中进行时,溶剂分子与RC_&lt;60&gt;^发生亲核加成反应,得到相应的加合物RC_&lt;60&gt;-C_6H_4OCH_3-p。氯离子也能被AgBF_4萃取。在醇(R‘OH)中,反应可以进行,生成相应的醚类化合物RC_&lt;60&gt;-OR’。氯化物RC_&lt;60&gt;-Cl(R=氯烷基)在苯甲醚-三氟乙醇混合溶剂(1:9v/v)中发生溶剂分解,生成S_N1反应产物RC_&lt;60&gt;-Y(Y=对-苯甲酰基和三氟乙氧基)。其活化能仅略低于叔丁基氯的活化能(25℃时为24-25千卡/摩尔),表明阳离子RC_(60)与叔丁基阳离子的稳定性接近,并根据相应富勒烯醇电离平衡常数确定了阳离子RC_(60)的pKR^值。所得结果与叔丁基阳离子的pK_R值相当。这一结果也支持RC_&lt;60和叔丁基阳离子在稳定性上的相似性。
英文摘要
We found that fullerene C_<60> undergoes electrophilic addition when treated with a large excess of AlCl_3 in chloroalkanes (RCl), giving adducts RC_<60>-Cl in good yields. The intermediate, alkylfullerenyl cations (RC_<60>^+), could be generated as long-likved ions by dissolving fullerenols (RC_<60>OH) in strong acids such as CF_3SO_3H and H_2SO_4. These cations were observed by NMR and vis/NIR spectra as long-lived species. The ^<13>C NMR spectra indicated that the positive charge is located mainly on C-2, and the structure has C_s symmetry. The chemical shift of the cationic center (175-180 ppm) suggested a weak coordination of chlorine atom(s) in the group R to the cationic center.Cations RC_<60>^+ could be also generated in situ by the abstraction of a chloride ion from chlorides RC_<60-> Cl with AlCl_3. When the reactions were carried out in anisole, nucleophilic addition of a solvent molecule to RC_<60>^+ occurred, giving the corresponding adducts RC_<60>-C_6H_4OCH_3-p. The chloride ion can be also abstracted by AgBF_4. With this reagent the reaction could be carried out in alcohols (R'OH), giving the corresponding ethers RC_<60>-OR' in good yiels.Chlorides RC_<60>-Cl (R=chloroalkyl) were found to undergo solvolysis in anisole-trifluoroethanol mixed solvent (1:9 v/v) to give S_N1 reaction products, RC_<60>-Y(Y=p-anisyl and trifluoroethoxy). The free energies of activation (24-25 kcal/mol at 25℃) were only slightly lower than that for the tert-butyl chloride, indicating that cations RC_<60>^+ have stabilities close to that of the tert-butyl cation.The pK_R^+ values of cations RC_<60>^+ were also determined from the equilibrium constants for the ionization of the corresponding fullerenols. The obtained values are comparable to the pK_R+ of the tert-butyl cation. Thsi result also support the similarity in stability between RC_<60>^+ and the tert-butyl cation.
期刊论文(8)
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会议论文
北川敏一, 李 洋洙, 花村政暁, 坂本晴美, 紺野博文, 竹内賢一, 小松紘一: "Nucleophilic Substitution of Alkylchlorodihydro [60] fullerenes : Thermodynamic Stabilities of Alkylated C_<60> Cation Intermediates"Chemical Communications. 3062-3063 (2002)
Toshikazu Kitakawa、Yosu Lee、Masaaki Hanamura、Harumi Sakamoto、Hirofumi Konno、Kenichi Takeuchi、Koichi Komatsu:“烷基氯二氢[60]富勒烯的亲核取代:烷基化 C_<60> 阳离子中间体的热力学稳定性”化学通讯 3062-3063(2002 年)。 )
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通讯作者:
北川敏一, 田中 徹, 村北英之, 西川敦准, 竹内賢一: "Reaction of Cyclopropenylium Ion with the tert-Butyl-C_<60>-anion : Carbocation-Carbanion Coordination vs Salt Formation"Tetrahedron. Vol.57. 3537-3547 (2001)
Toshikazu Kitakawa、Toru Tanaka、Hideyuki Murakita、Atsushi Nishikawa、Kenichi Takeuchi:“环丙烯离子与叔丁基-C_<60>-阴离子的反应:碳正离子-碳负离子配位与盐形成”四面体第 3537-3547 卷。 (2001)
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北川敏一, 竹内賢一: "Monofunctionalized C_<60> Ions : Thier Generation, Stability, and Reactions"Bulletin of the Chemical Society of Japan. Vol.74. 785-800 (2001)
Toshikazu Kitakawa、Kenichi Takeuchi:“单官能化 C_<60> 离子:其生成、稳定性和反应”日本化学会通报第 74 卷(2001 年)。
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通讯作者:
Toshikazu Kitagawa, Yangsoo Lee, Masaaki Hanamura, Harumi Sakamoto, Hirofumi Konno, Ken'ichi Takeuchi and Koichi Komatsu: "Nucleophilic Substitution of Alkylchlorodihydro [60] fullerenes : Thermodynamic Stabilities of Alkylated C_<60> Cation Intermediates
Toshikazu Kitakawa、Yangsoo Lee、Masaaki Hanamura、Harumi Sakamoto、Hirofumi Konno、Kenichi Takeuchi 和 Koichi Komatsu:“烷基氯二氢 [60] 富勒烯的亲核取代:烷基化 C_<60> 阳离子中间体的热力学稳定性
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8
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