STRATI-BISPORPHYRINS - NOVEL CYCLOPHANE SYSTEM
STRATI-BISPORPHYRINS - NOVEL CYCLOPHANE SYSTEM
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DOI：
10.1021/ja00458a045
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发表时间：
1977-01-01
影响因子：
15
通讯作者：
MERRIFIELD, RB
中科院分区：
文献类型：
--
作者：
KAGAN, NE;MAUZERALL, D;MERRIFIELD, RB
细菌光合作用中的主要电子供体是细菌叶绿素分子的二聚体。这一论断的证据来自ESR和ENDOR测量的阳离子产生的初始光作用。[1]在环番、三蝶烯和其他紧密环系统的自由基离子种类中，也发生了类似的电子离域。[2]这种离域作用强烈依赖于这些多环化合物的几何结构。已经合成了卟啉的线性和松散堆叠的二聚体，3-4但环-环相互作用似乎是最小的。在叶绿素二聚体的情况下举行的氢键亲核试剂和尿素连接的二元叶绿素，大量的光谱变化已被观察到。5-6为了评估距离和取向参数对电子转移现象的影响，我们已经开始合成定义明确的二聚体系统，其中可以观察到跨环相互作用。本文报道了一类新的大环环番化合物--四-meso-[f），p ′-（2-苯氧乙氧基羰基苯基）]-sf Y f f-双卟啉。7-8现在我们给出这个化合物的结构证明和一些有趣的光谱性质。通过应用Adler-Longo卟啉缩合过程的四醛修饰9合成了s/ra/z-双卟啉III。合适的卟啉四醛II是通过用对氯羰基苯甲醛酰化卟啉四氢氧化物I而衍生的（图1）。四甲基-[对-（2-羟乙氧基）苯基]卟啉，I是由吡咯和对-（2-羟乙氧基）苯甲酰基卟啉在酸化二甲苯（8 mM三氟乙酸）中反应制得。二甲苯沉淀物从二甲基甲酰胺中重结晶，得到14%I：mp> 330 ℃; pmax（KBr）1240，1605 cm-1; Amax（吡啶）426 nm（f 471000，14-nm半宽），521（16500），558（13000），595（5090），653（7500）. 13肛门。C52 H46 N4 〇 8（摩尔重量854.9）的计算值：C，73.05; H，5.42; N，6.55;实测值：C，72.80; H，5.36; N，6.54。1与亚硫酰氯反应生成的对羧基苯甲醛酰氯在二氯甲烷-吡啶-二异丙基乙胺（DIEA）（50：25：2）中反应。完成后，将溶液用碱水溶液中和，并将产物萃取到氯仿中，浓缩，并用甲醇沉淀。沉淀物用氯仿在失活的氧化铝14上层析，收集第一个条带。从CHCl-MeOH中结晶，产率为40%，熔点225-228 ℃，最大吸收峰（KBr）1240，1275，1605，1705，1725 cm-1; Amax（吡啶）425 nm（e 464 000，14 nm半宽），519（17 400），556（12 700），593（5330），651（7170）; 13 FT NMR（220 MHz，1 mM，在CDCl3中）15 5 NH at-2.77（2 H，s），CH2O at 4.61（8H，t，J= 4Hz），CO2CH2在4.89（8 H，t，J= 4 Hz），C6H40在7.31（8H，d，J= 8Hz），8.12（8H，d，J = 8Hz），C6H4CO2在7.99（8H，d，J= 8Hz），8.32（8H，d，J= 8Hz），3-吡咯H在8.83（8H，s），CHO在10.11ppm（4H，s）。Anal. C84 H62 N4 O 16（摩尔/重量1383.4）的计算值：C，72.93; H，4.52; N，4.05。实测值：C，71.72; H，4.36; N，4.05。16 a层状双卟啉III是通过将II和吡咯（4当量）加入到丙酸-β-D-（1：1）（0.4mM在II中）中制得的。1.5小时后，通过蒸发除去溶剂，收集吡啶可溶性产物并在Bio-Beads S-Xl排阻凝胶上分级。17在聚合卟啉（R 0.5-1.0）的一条长的、逐渐减弱的带之后，III洗脱为一条狭窄的、孤立的紫色带（R 0.45），
The primary electron donor in bacterial photosynthesis is a dimer of bacteriochlorophyll molecules. Theevidence for this assertion comes from ESR and ENDOR measurements on the cation resulting from the initial photoact. 1 Similar electron delocalization is known to occur in the radical-ion species of cyclophanes, triptycenes, and other intimate ring systems. 2 This delocalization is strongly dependent on the geometry of these multiring compounds. Linear and loosely stacked dimers of porphyrins have been synthesized, 3-4 but the ring-ring interactions appear to be minimal. In the cases of chlorophyll dimers held together by hydrogen-bonding nucleophiles and urea-linked binary prophyrins, substantial spectral alterations have been observed. 5-6 To evaluate the influence of distance and orientation parameters on the electron-transfer phenomena, we have begun the synthesis of well-defined dimeric sys-tems in whichtransannular interactions can be observed. Re-cently, we reported the first member of a new class of macro-cyclic cyclophanes, tetra-meso-[/), p'-(2-phenoxyethoxycarbonylphenyl)]-s//Y/f/-bisporphyrin, III. 7-8 Now we present the proof of structure and some interesting spectral properties of this compound. s/ra/z-Bisporphyrin III was synthesized by application of the tetraaldehyde modification9 of the Adler-Longo porphyrin condensation procedure. 10 A suitable porphyrin tetraaldehyde, II, was derived from a porphyrin tetrahydroxide, I, by acylation with p-chlorocarbonylbenzaldehyde (Figure 1). Tetra-meio-[p-(2-hydroxyethoxy) phenyl] porphyrin, I, was made by the reaction of pyrrole with p-2-hydroxyethoxyben-zaldehyde11 in refluxing acidified xylene (8 mM in trifluo-roacetic acid). 12 The xylene precipitate was recrystallized from dimethylformamide yielding 14% I: mp> 330 C; pmax (KBr) 1240, 1605 cm~ 1; Amax (pyridine) 426 nm (f 471 000, 14-nm half-width), 521 (16 500), 558 (13 000), 595 (5090), 653 (7500). 13 Anal. Calcd for C52H46N4O8 (mol wt 854.9): C, 73.05; H, 5.42; N, 6.55; Found: C, 72.80; H, 5.36; N, 6.54. 1 was reacted with the thionyl chloride generated acid chloride of p-carboxybenzaldehyde in methylene chloride-pyridine-diisopropylethylamine (DIEA)(50: 25: 2). At completion, the solution was neutralized with aqueous base and the products were extracted into chloroform, concentrated, and precipitated with methanol. The precipitate was chromatographed with chloroform on deactivated alumina14 and the first band was collected. Crystallizationfrom CHCL-MeOH resulted in 40% yield of tetraaldehyde II: mp 225-228 C; pmax (KBr) 1240, 1275, 1605, 1705, 1725 cm-1; Amax (pyridine) 425 nm (e 464 000, 14-nm half-width), 519 (17 400), 556 (12 700), 593 (5330), 651 (7170); 13 FT NMR (220 MHz, 1 mM inCDCI3) 15 5 NH at-2.77 (2 H, s), CH20 at 4.61 (8 H, t, J= 4 Hz), C02CH2 at 4.89 (8 H, t, J= 4 Hz), C6H40 at 7.31 (8 H, d, J= 8 Hz), 8.12 (8 H, d,/= 8 Hz), C6H4C02 at 7.99 (8 H, d, J= 8 Hz), 8.32 (8 H, d,/= 8 Hz),/3-pyrrole H at 8.83 (8 H, s), CHO at 10.11 ppm (4 H, s). Anal. Calcd for C84H62N4O16 (mol wt 1383.4): C, 72.93; H, 4.52; N, 4.05. Found: C, 71.72; H, 4.36; N, 4.05. 16a strati-Bisporphyrin III was made by theaddition of II and pyrrole (4 equiv) to refluxing propionic acid-ethylbenzene (1: 1)(0.4 mM in II). After 1.5 h, the solvent was removed by evaporation and the pyridine-soluble products were collected and fractionated on a Bio-Beads S-Xl exclusion gel. 17 After a long, diminishing band of polymericporphyrins (R 0.5-1.0), III eluted as a narrow, isolated purple band (R 0.45) followed