芳氧基取代酞菁锌的合成及光物理化学性质

合成得到3-(5-氨基-萘氧基)邻苯二甲腈(C18H11N3O)、4-(5-氨基-萘氧基)邻苯二甲腈(C18H11N3O)、3-联苯氧基邻苯二甲腈(C20H12N2O)及4-联苯氧基邻苯二甲腈(C20H12N2O)4种未见报导的取代邻苯二甲腈,以此为前躯体合成了四[α-(5-氨基-萘氧基)]酞菁锌(C72H44N12O4Zn)、四[β-(5-氨基-萘氧基)]酞菁锌(C72H44N12O4Zn)、四[α-(联苯氧基)]酞菁锌(C80H48N8O4Zn)和四[β-(联苯氧基)]酞菁锌(C80H48N8O4Zn)4种未见报导的芳氧基取代酞菁锌配合物。通过测定它们的紫外-可见吸收光谱、荧光发射光谱,获得其最大吸收波长及其摩尔消光系数、最大发射波长、荧光量子产率(ΦF)、单线态氧量子产率(ΦΔ)及光降解速率常数并与其类似物进行了比较,探讨了它们的光物理光化学性质的构效关系。研究结果表明四[α-(联苯氧基)]酞菁锌在红光区具有大的摩尔消光系数,且具有较高的ΦΔ,有望开发成为光动力治疗用光敏剂。     

四-α(β)-(4-吡啶氧基)酞菁锌的光物理性质研究

测定了新合成的α位取代和β位取代的四-(4-吡啶氧基)酞菁锌配合物的UV-Vis吸收光谱、荧光光谱及激发单重态寿命、纳秒瞬态吸收光谱与激发三重态寿命.在此基础上,与相关配合物进行了比较,探讨了取代基及其取代位置对酞菁锌配合物的吸收光谱、激发单重态寿命及激发三重态寿命的影响.     

喹啉氧基酞菁金属配合物光敏化氧化色氨酸能力的研究

酞菁金属配合物是光动力治疗的新一代光敏剂,其治疗作用的机理以及引起的生物效应一直是人们研究的热点.本文选用色氨酸作为与喹啉氧基酞菁金属配合物作用的靶分子,讨论了配合物的组成结构与其光敏化氧化色氨酸能力的相关性.结果表明,酞菁环内中心金属离子和环周边取代基的组成结构以及取代位置与数目都影响其光敏化氧化色氨酸能力,中心金属离子为闭壳层电子结构、取代基位于α位以及提高取代基数目均有利于提高光敏化氧化活性,同时显示,取代基的组成结构对靶分子有一定选择性,研究结果可为研发该类光敏剂提供依据.     

具有Frétchet树枝结构的新型酞菁锌(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

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.     

磺化2,3-萘酞菁锌(Ⅱ)、钴(Ⅱ)的电子吸收光谱和荧光光谱的研究

研究了磺化2，3-萘酞菁锌(Ⅱ)、钴(Ⅱ)在DMF(N，N-二甲基甲酰胺)、DMSO(二甲基亚砜)、乙醇、水等溶剂中的电子吸收光谱和荧光光谱．萘酞菁配合物的Q带与相应的酞菁配合物Q带相比，电子吸收光谱红移80～90nm，荧光光谱红移约100nm，荧光强度也显增加．在金属萘酞菁中引入磺酸基，配合物的电子吸收光谱Q带发生红移，但是影响不大、对于相同中心金属的配合物，改变溶剂的种类对配合物的电子吸收光谱的Q带影响较大．在金属萘酞菁环上引入一个磺酸基时，在相同溶剂中与无取代萘酞菁相比发生荧光光谱Q带红移，荧光强度增大．但在萘酞菁环上继续引入磺酸基时，荧光强度反而减少．磺化萘酞菁钴比磺化萘酞菁锌有较大的荧光强度．不同浓度下的电子吸收光谱和荧光光谱说明金属萘酞菁有集聚倾向、能形成基激缔合物．     

四-β -(8-喹啉氧基)取代酞菁金属配合物的合成、表征及其荧光性质研究

本文利用DBU催化法合成得到4种四-β-(8-喹啉氧基)取代酞菁金属配合物(金属分别为钴、镍、铜、锌)，同时分别进行了元素分析、UV-Vis、IR光谱、质谱表征。还对四-β-(8-喹啉氧基)取代酞菁金属配合物进行了荧光性质研究，为其进一步应用提供依据。     

四-α-(2-甲基-8-喹啉氧基)酞菁金属配合物的合成、表征及光敏活性研究

利用DBU催化法合成得到4种两亲性的四-α-(2-甲基-8-喹啉氧基)酞菁金属配合物[金属＝Co(II), Ni(II), Cu(II), Zn(II)], 同时分别进行了元素分析、质谱、UV-Vis、IR光谱表征. 测定了它们在670 nm光激发下产生单线态氧的速率及光动力氧化氨基酸底物的速率常数, 探讨了它们光敏活性的构效关系.     

以二苯甲酮为端基的第一代树状取代酞菁锌的合成

4-甲基二苯甲酮经N-溴代丁二酰亚胺溴代制得4-溴甲基二苯甲酮(1);1与3,5-二羟基苯甲醇反应合成了外围带有二苯甲酮取代基的第一代树枝状分子3,5-二(二苯甲酮-4-甲氧基)苯甲醇(2);2与4-硝基邻苯二甲腈缩合制得外围带有二苯甲酮取代基的第一代树枝状分子4-[3,5-二(二苯甲酮-4-甲氧基)苯甲氧基]邻苯二甲腈(3);3经"液相法"环合生成外围带有二苯甲酮取代基的第一代树枝状分子取代的酞菁锌配合物——四[3,5-二(二苯甲酮-4-甲氧基)苯甲氧基]锌酞菁[ZnPc(C35H27O5)4],其结构经UV,1HNMR,IR和MS表征。     

具有不同芳氧基取代酞菁钯聚集行为研究

为了研究具有不同芳氧基取代酞菁的聚集行为，合成了5种酞菁如 1,8,15,22- 四(2,4-二氯芳氧基)酞菁钯(Pel);1,8,15,22-四芳氧基酞菁钯(Pc2);1,8,15,22-四 (2,4-二特丁基芳氧基)酞菁钯(Pc3);1,8,15,22-四(2.5-二特丁基芳氧基)酞菁钯 (Pc4)和1,8,15,22-四(2,6-二溴-4-甲基芳氧基)酞菁钯(Pc5).酞菁的聚集行为由芳 氧基的性质不同决定。在四氢呋喃(THF)溶液中浓度在10~(-6)-10~(-5)mol·dm~(- 3)范围内，计算 得到5种酞菁的聚集常数分别为1.61*10~(-5)mol~(-1)·dm~3, 3. 87*10~(-5)mol~(-1)·dm~3, 2.60*10~(-5)mol~(-1)·dm~3, 1.21*10~(-5)mol~(- 1)·dm~3, 2.57*10~(-5)mol~(-1)·dm~3. 除了Pc1外，其余酞菁的单体和二聚体 吸收行为类似。在薄膜状态下，不同取代基对酞菁的吸收性质影响较大。成膜后5 种酞菁的吸收光谱都发生了改变，其中Pc1的吸收开关改变量大，而Pc5的吸收位置 改变最大。     

2,7,12,17-四(甲硫基)-3,8,13,18-四(苯甲酰硫基)四氮杂卟啉及其Mg(Ⅱ)、Cu(Ⅱ)、Ni(Ⅱ)配合物的合成与表征

硫杂酞菁、含硫取代基的四氮杂卟啉及其金属配合物由于具有优异的光、电及催化性能而日益受到重视.据此,我们以自制的1-甲硫基-2-苯甲酰硫基马来二腈(MBM)为原料,合成了2,7,12,17-四(甲硫基)-3,8,13,18-四(苯甲酸硫基)四氮杂卟啉H_2T(mbm)TAP及其Mg(Ⅱ)、Cu(Ⅱ)、Ni(Ⅱ)配合物MT(mbm)TAP,经IR、UV-Vis和DTA等进行了表征.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.