Synthesis and Characterization of a Novel Frétchet Dendritic Phthalocyanine Zinc(II): Tetra-{3,5-di-[3,5-di-(4-carboxylic benzyloxy)benzyloxy]benzyloxy} Phthalocyanine Zinc(Ⅱ)

报道了一种新型fréTCHET树枝配体取代酞菁锌(II)配合物:四-{3,5-二-[3,5-二-(4-羧基苯甲氧基)苯甲氧基]-苯甲氧基}酞菁锌(II)的合成与表征.首先将对氰基苄溴与3,5-二羟基苯甲醇通过fréTCHET反应合成3,5-[二-(4-氰基苯甲氧基)]苯甲醇(1),1与四溴化碳和三苯基膦在四氢呋喃中反应合成3,5-二-(4-氰基苯甲氧基)苄溴(2),2与3,5-二羟基苯甲醇反应合成3,5-二-[3,5-二-(4-氰基苯甲氧基)苯甲氧基]苯甲醇(3),接着,3与4-硝基邻苯二甲腈合成“前驱物“四-{3,5-[二-(4-氰基苯甲氧基)]}苯甲氧基邻苯二甲腈(4),然后以1,8-二氮杂双环[5.4.0]十一碳-7-烯(dbu)为催化剂,醋酸锌为模板剂,4通过缩聚反应合成氰基端基的fréTCHET树枝配体取代酞菁锌四-{3,5-二-[3,5-二-(4-氰基苯甲氧基)苯甲氧基]-苯甲氧基}锌酞菁配合物5,最后,5的氰基端基在nAOH溶液中水解为相应的以羧基端基fréTCHET树枝配体取代酞菁锌:四-{3,5-二-[3,5-二-(4-羧基苯甲氧基)苯甲氧基]-苯甲氧基}酞菁锌(II)(6).采用元素分析,Ir,1H nMr,ESI-MS和MAldI-TOf-MS表征所有化合物的结构,通过uV/VIS,稳态和瞬态荧光光谱法研究了5和6的光物理性质.5和6是一类性能较好的树枝状酞菁光敏剂.A novel Frétchet structural dendritic substituted photosensitizer,tetra-{3,5-di-[3,5-di-(4-carboxylic benzyloxy)benzyloxy]benzyloxy} phthalocyanine zinc(II)(6),was synthesized by the following steps.Firstly,3,5-di-(4-cyanobenzyloxy) benzyl alcohol(1) was obtained by reaction of 3,5-di-hydroxybenzyl alcohol with p-cyanobenzylbromide.Then,3,5-di-(4-cyanobenzyloxy) benzyl bromide(2) was synthesized by the reaction of 1 with carbon tetrabromide in the presence of triphenylphosphine and tetrahydrofuran.Following,2 reacted with 3,5-di-hydroxybenzyl alcohol to afford 3,5-di-[3,5-di-(4Chinese Journal of Organic Chemistry NOTE Chin.J.Org.Chem.2012,32,1320～1326 2012 Chinese Chemical Society & SIOC,CAS http://sioc-journal.cn/ cyanobenzyloxy)benzyloxy] benzyl alcohol(3).The fragment 4-{3,5-di-[3,5-di-(4-cyanobenzyloxy)benzyloxy]} phthalonitrile(4) was obtained by reaction of 3 with 4-nitrophthalonitrile.Tetra-{3,5-di-[3,5-di-(4-cyanobenzyloxy)benzyloxy]benzyloxy} phthalocyanine zinc(II)(5) was obtained by condensation of 4 with acetate zinc and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU) in n-pentanol.The tetra-{3,5-di-[3,5-di-(4-carboxylic benzyloxy)benzyloxy]benzyloxy} phthalocyanine zinc(II)(6) was obtained by hydrolyzed 5 in NaOH.The structures of above compounds were characterized by a combination of methods including elemental analysis,1H NMR,IR,ESI-MS and MALDI-Tof-MS.The photophysical properties of 5 and 6 were studied by UV/Vis,steady state and transient fluorescence spectrometry.The compound 6 is a kind of good performance of dendritic photosensitizer.国家自然科学基金(Nos.60978071;20604007);福建省自然科学基金(Nos.2011J01029;2010J01322);卫生部科学研究基金(No.WKJ2008-2-61)资助项目---

Oxidative Carbonylation of Aniline by Pd/C Catalyst

研究了催化剂制备条件、助催化剂对负载型Pd/C催化剂性能的影响及氧分压、原料苯胺中硝基苯的加入对苯胺氧化羰基化反应的影响；用X光电子能谱（XPS）、程序升温还原（TPr）和现场红外（Ir）表征钯催化剂；根据实验结果提出在Pd/C-nAI催化剂体系、醇介质中，苯胺氧化羰基化可能的反应机理.The eFFects of the preparation conditions of Pd/C catalyst and the promoters on the catalytic property have been investigated.The inFluences of partial oxygen pressure and addition of nitrobenzene on the oxidative carbonylation of aniline to ethyl Nphenyl carbamate also have been tested.The Pd/C catalyst was characterized by XPS, TPR and insitu IR techniques.A possible mechanism of the oxidative carbonylation of aniline catalyzed by Pd/CNaI system in alcohol medium has been proposed