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以焦脱镁叶绿酸-a甲酯(MPP-a)(1)为起始原料,在二氯甲烷中与醋酸锌共回流得锌配合物2,在四氯钯锂催化下,通过与苯基氯化汞的偶联反应生成3b-苯基焦脱镁叶绿酸-a甲酯(3).分别选用四氧化锇、高钌酸四丙基铵(TPAP)和N-甲基吗啉N-氧化物将环外烯键氧化成邻二酮(4).在酸性条件下,4与邻苯二胺的缩合形成了3-位喹喔啉取代的焦脱镁叶绿酸-a甲酯(5).用四氧化锇和高碘酸钠将1的3-位碳碳双键氧化,则生成焦脱镁叶绿酸-d甲酯(6).所得卟吩醛与环己二酮和萘胺进行一锅法反应,得到3-位苯并吖啶取代的焦脱镁叶绿酸-a甲酯(7).所合成的新卟吩化合物均经UV,IR,^1H NMR及元素分析证明其结构. 相似文献
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以焦脱镁叶绿酸-a甲酯为起始原料,利用加成和氧化反应将其转化成3-甲酰基或者3-乙酰基取代和E-环保护的反应前体,通过Grignard反应在3-位上引进炔基并构建了叔醇或者仲醇结构,再经脱水和氧化反应生成端位烯炔和炔酮取代的二氢卟吩衍生物.3-甲酰基焦脱镁叶绿酸-a甲酯与癸基溴化镁的Grignard反应、E-保护和C(3)-羟基的氧化反应得到C(3)-长链烷酰基取代的焦脱镁叶绿酸-a甲酯,再经酸催化脱水则得到含有链间烯炔结构的二氢卟吩.首次报道的叶绿素类二氢卟吩衍生物均经UV,IR,1H NMR及元素分析确定其化学结构,对相应的化学反应也提出了可能的反应机理. 相似文献
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叶绿素降解产物是合成光动力治疗药物的理想合成前体.为了获得新型叶绿素类光敏剂,以焦脱镁叶绿酸-d甲酯为起始原料,通过空气氧化反应、Knoevenagel反应、Hener反应、Tiffeneau-Demjanov重排、Friedlaender缩合和还原等经典化学反应对其甲酰基和外接环羰基实施化学修饰,在C(3)-位和外接E-上建立了不同的化学结构,合成出一系列具有叶绿素基本碳架结构的二氢卟吩衍生物,讨论了分子结构与其紫外-可见光谱之间的联系,并对相应的化学反应提出了可能的反应机理.新报道的叶绿素衍生物的化学结构均经UV,IR,1H NMR及元素分析得以证实. 相似文献
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氢氧化锂存在下(焦)脱镁叶绿酸-a甲酯的空气重排反应 总被引:1,自引:0,他引:1
在氢氧化锂存在下, 脱镁叶绿酸-a甲酯(1a)发生空气氧化和重排反应, 经盐酸酸化和重氮甲烷甲基化, 得到由紫红素-7三甲酯(2)、紫红素-18甲酯(3)、卟吩-p6三甲酯(4)、地质卟啉衍生物(5)和3-环氧乙基-3-去乙烯基紫红素-18甲酯(6)所组成的混合物. 用相同的方法处理焦脱镁叶绿酸-a甲酯(1b), 则分离出132-氧代焦脱镁叶绿酸-a甲酯(7)、15-甲酰基紫红素-5二甲酯(8)、紫红素-18甲酯(3)和3-环氧乙基-3-去乙烯基紫红素-18甲酯(6). 所得新叶绿素衍生物5, 6和8的化学结构均经UV, IR, 1H NMR及元素分析得以证实, 并对相应的反应提出可能的反应机理. 相似文献
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以meso-焦脱镁叶绿酸-a甲酯为起始原料,利用其二氢卟吩大环上的活性反应区域,选用不同的亲电试剂进行卤化和硝化反应,分别在20-meso-位上选择性地引进了氯、溴、碘和硝基;通过空气氧化和胺解等反应,对其五元E-环实施了结构改造,并在外接环上稠并了不同的含氮杂环,完成了13个未见报道的叶绿素类二氢卟吩衍生物的合成,其化学结构均经UV-Vis,IR,1H NMR及元素分析予以证实,同时讨论了meso-焦脱镁叶绿酸-a的化学反应机理和相应的光谱性质. 相似文献
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以焦脱镁叶绿酸-a甲酯(MPP-a)(1)为起始原料,在二氯甲烷中与醋酸锌共回流得锌配合物2,在四氯钯锂催化下,通过与苯基氯化汞的偶联反应生成3b-苯基焦脱镁叶绿酸-a甲酯(3).分别选用四氧化锇、高钌酸四丙基铵(TPAP)和N-甲基吗啉N-氧化物将环外烯键氧化成邻二酮(4).在酸性条件下,4与邻苯二胺的缩合形成了3-位喹喔啉取代的焦脱镁叶绿酸-a甲酯(5).用四氧化锇和高碘酸钠将l的3-位碳碳双键氧化,则生成焦脱镁叶绿酸-d甲酯(6).所得卟吩醛与环己二酮和萘胺进行一锅法反应,得到3-位苯并吖啶取代的焦脱镁叶绿酸-a甲酯(7).所合成的新卟吩化合物均经UV,IR,1H NMB及元素分析证明其结构. 相似文献
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From methyl pyropheophorbide‐a (MPPa, 1 ), the vinyl group was converted into other functional groups including 2‐dimethoxylethyl, 1‐hydroxylalkyl, and alkylcarbonyl groups by addition and oxidization to form chlorin ( 2?5b ). The nickel complexes ( 6a?e ) were prepared by treatment with excess nickel acetate in MeOH by refluxing and were used directly for the next reaction without further separation. The Vilsmeier reactions of nickel chlorins with 3‐(dimethylamino)acrolein/phosphoryl chloride (3‐DMA/POCl3) are carried out to give meso‐20‐fotmyl‐vinylpyropheophorbide‐a ( 7a?9b ). 相似文献
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The Wittig reaction of methyl pyropheophorbide-d 2,obtained from methyl pyropheophorbide-a 1,with ben-zyltriphenylphosphonium bromide was performed to yield isomers 3a and 3b.The Vilsmeier reaction of nickelcomplex 4 or 7 with 3-dimethylaminoacrolein in the presence of phosphoryl chloride was carried out to form20-meso-2'-formylvinylpyropheophorbide-a 5 or 8,which was reacted with Wittig reagent to afford nickel complexisomers 6a and 6b or 9a and 9b,10a and 10b. 相似文献
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以N-甲基,N-取代苯胺为原料,用环己烷作溶剂,以DMF和SOCl2替代经典的DMF和POCl3组成的Vilsmeier试剂,合成了5个4-(N-甲基,N-取代)氨基苯甲醛,确立了较优反应条件,一次收率达85~91%,溶剂可循环利用。对合成目标化合物进行了IR,1HNMR结构表征。 相似文献
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Methyl 9-ethylenedioxpyropheophorbide-d was prepared from methyl pyropheophorbide-a by protection of cyclic ketone with ethylene glycol,and oxidation with OsO4 in vinyl group at 2-position.The terminal alkyne was introduced into chlorin chromophore by Grignard reaction,and the enediyne moiety was constructed by a palladium-catalyzed coupling reaction with (Z)-chloroenynes. 相似文献
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As part of a program aimed at introducing functionality onto the Tröger’s base framework post-synthesis, we investigated the formylation reaction of Tröger’s base analogues with Vilsmeier reagents. We found that rather than the anticipated reaction at the aryl rings, these compounds react with Vilsmeier reagents to afford compounds with a modified strap, whereby the apical methylene group is replaced by a methylene strap bearing an N,N-disubstituted amine. 相似文献
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Hemanta Kalita Dhrubajyoti Kalita Prof. Way‐Zen Lee Prof. Jayesh Bellare Prof. Mangalampalli Ravikanth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10404-10413
Unsymmetrical 22‐oxacorrole containing two aryl groups and one pyrrole group at the meso position was synthesized by condensing one equivalent of 16‐oxatripyrrane with one equivalent of meso aryl dipyromethane under mild acid‐catalyzed conditions followed by oxidation with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ). This [3+2] condensation approach was expected to yield meso‐free 25‐oxasmaragdyrin but unexpectedly afforded unsymmetrical meso‐pyrrole‐substituted 22‐oxacorrole. We demonstrated the versatility of the reaction by synthesizing four new meso‐pyrrole‐substituted 22‐oxacorroles. The reactivity of α‐position of meso‐pyrrole was tested by carrying out various functionalization reactions such as bromination, formylation, and nitration and obtained the functionalized meso‐pyrrole‐substituted 22‐oxacorroles in decent yields. The X‐ray structure obtained for one of the functionalized meso‐pyrrole substituted 22‐oxacorrole revealed that the macrocycle was nearly planar and the meso‐pyrrole was in the perpendicular orientation with respect to the macrocyclic plane. The meso‐pyrrole‐substituted 22‐oxacorroles absorb strongly in 400–700 nm region with one strong Soret band and four weak Q bands. The 22‐oxacorroles are strongly fluorescent and showed emission maxima at ≈650 nm with decent quantum yields and singlet‐state lifetimes. The 22‐oxacorroles are redox‐active and exhibited three irreversible oxidations and one or two reversible reduction(s). A preliminary biological study indicated that meso‐pyrrole corroles are biocompatible. 相似文献