2-氨基-6-氟-9-(4-羟基-3-羟甲基丁基)嘌呤的合成

报道了2-氨基-6-氟-9-(4-羟基-3-羟甲基丁基)嘌呤(1)的合成, 通过对起始原料2-氨基-6-氯-9-(4-乙酰氧基-3-乙酰氧甲基丁基)嘌呤(2)水解脱去乙酰基, 得到2-氨基-6-氯-9-(4-羟基-3-羟甲基丁基)嘌呤(3). 化合物3与三甲胺乙醇溶液在混合溶剂[V(THF)∶V(DMF)＝3∶1]中反应得到相应的氯化铵盐4, 然后与KF在DMF溶剂中反应, 得到化合物1. 产品经UV-vis, IR, ¹H NMR, ¹⁹F NMR和MS表征. 考察了反应温度、氟化试剂等因素对氟化反应的影响, 为6位含氟的嘌呤核苷类化合物的合成提供了一种直接、简易的新方法.     

Controlled synthesis and fluorescent properties of poly(9-(4-vinylbenzyl)-9H-carbazole) via nitroxide-mediated living free-radical polymerization

The functional polymer containing carbazole unit, [(poly(9-(4-vinylbenzyl)-9H-carbazole) (PVBK)], was successfully prepared via nitroxide-mediated living free-radical polymerization of 9-(4-vinylbenzyl)-9H-carbazole (VBK). The controlled features of the polymerization were confirmed by the linear increase in the molecular weight with the monomer conversion while keeping the relative narrow molecular weight distribution (M_w/M_n ? 1.51), and successful chain extension with styrene. The resulting polymer absorbed light in the 305-355 nm range and exhibited fluorescent emission at 350 nm. The fluorescent intensity of the polymer was lower than that of monomer and was affected by the properties of the different solvents, which decreased in the following order: DMF > THF > CHCl₃ at the same concentration of carbazole units. The fluorescence intensity of the polymer was apparently influenced by chromophore concentration, and the maximum value was obtained when the carbazole unit concentration was around 8 × 10⁻⁵ mol/L. Moreover, it was shown that the strong fluorescence of PVBK can be quenched by methyl acrylate (MA).     

Hydrogenation of 9-pyridylmethylene- and 9-benzylidene(aza)fluorenes in the presence of rhenium heptasuifide

Hydrogenation of 9-pyridylmethylene(aza)fluorenes and 9-benzylidene-4-azafluorene at 250 °C andp _{H 2} = 130 atm in the presence of Re₂S₇ as a catalyst occurs preferably at the exoeyclic double bond of the fulvene fragment to yield pyridyl-9-(aza)fluorenylmethanes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 180–182, January, 1996.     

Palladium-Catalysed Amination of Hindered Aryl Halides with 9H-Carbazole

Palladium-catalysed Buchwald–Hartwig amination of ortho-substituted hindered aryl bromides or chlorides with 9H-carbazole has been investigated. In the amination of 1-bromo- or chloronaphthalene with 9H-carbazole, the combined use of Pd₂(dba)₃ as a Pd precursor, Buchwald ligands with two tert-butyl groups and LiOtBu or lithium hexamethyldisilazide as a base led to satisfactory yields. N,N’-Bis[2,6-bis(diphenylmethyl)-4-methoxyphenyl]imidazol-2-ylidene (IPr*^OMe), which is a bulky N-heterocyclic carbene ligand, showed similar activity as Buchwald ligands with two tert-butyl groups. In contrast, only IPr*^OMe provided satisfactory yields in the amination of 2-bromo-1,1′-biphenyl with 9H-carbazole. The amination of 2-bromo- or chlorotoluene and 1-(2-bromo- or chlorophenyl)naphthalene with 9H-carbazole proceeded smoothly when the IPr*^OMe ligand was used.     

具有空穴传输性能高效蓝光咔唑芘

A novel bifunctional blue-light material, 9-(pyren-1-yl)-9H-carbazole (CzPy), has been syn-thesized and its structure is identified by electron ionization mass spectrometry, ¹H NMR, and element analysis. The absorption, photoluminescence spectra and thermal properties were studied, results showedthat CzPy was stable under ambient conditions with a blue-light emission (461 nm).Additionally, its electroluminescence properties were characterized with four different devices. Results indicated a maximum luminous efficiency reached 1.56 cd/A and maximum luminance up to 3526 cd/m² at 10 V with commission international De L'Eclairage coordinates of (0.20, 0.24) when it was used as emitter. Furthermore, CzPy also indicated hole-transporting ability.     

Synthesis of 9-arylamino- and (Z)-9-arylimino-9H-pyrrolo[1,2-a]indoles by reactions of 2-(pyrrol-1-yl)benzaldehydes with aryl amines

Heating mixtures of 2-(pyrrol-1-yl)benzaldehydes and aryl amines under argon afforded 9-arylamino-9H-pyrrolo[1,2-a]indoles, via cyclization of the resulting 2-(pyrrol-1-yl)benzaldimine intermediates. Heating in the presence of oxygen afforded (Z)-9-arylimino-9H-pyrrolo[1,2-a]indoles, which were successfully hydrolyzed with hydrochloric acid to give pyrrolo[1,2-a]indol-9-ones.     

On the chemistry of pyrrole pigments,XCIV: 1-(Dipyrrinon-9-yl)-3-(dipyrrinon-9-ylidene)-1-propene — a novelb-vinylogous verdin chromophore

Summary 1-(Dipyrrinon-9-yl)-3-(dipyrrinon-9-ylidene)-propene, ab-vinylogous verdin, was synthesized by condensation of 3-(dipyrrinon-9-yl)-propenal with a dipyrrinone unsubstituted in position 9. By condensing the latter with dimedone or squaric acid,b-vinylogous verdin pigments with restricted configurational and conformational degrees of freedom were obtained. The chemical and spectroscopic properties of these novel systems are discussed.

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Zur Chemie von Pyrrolpigmenten, 94. Mitt.: 1-(Dipyrrinon-9-yl)-3-(dipyrrinon-9-yliden)-1-propen — Ein neuerb-vinyloger Verdinchromophor

Zusammenfassung 1-(Dipyrrinon-9-yl)-3-(dipyrrinon-9-yliden)-propen, einb-vinyloges Verdin, wurde durch Kondensation von 3-(Dipyrrinon-9-yl)-propenal mit einem in Position 9 unsubstituierten Dipyrrinon dargestellt. Kondensation des Letzteren mit Dimedon oder Quadratsäure lieferte vinyloge Pigmente, welche in ihren konfigurationellen und konformationellen Freiheiten eingeschränkt sind. Die chemischen und spektroskopischen Eigenschaften dieser neuen Systeme werden diskutiert.

     

(E)-N-芳基-3-[2-(8-羟基喹啉基)-乙烯基]咔唑的合成、抗氧化活性及促进鼠骨髓间质干细胞增殖的研究

设计合成了3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲苯基咔唑(8)和3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲氧苯基咔唑(9)两个新的化合物, 用IR, MS, 1H NMR和元素分析确认其结构. 并利用DPPH•方法, 超氧阴离子自由基( )法, 羟基自由基HO•法和噻唑蓝比色法(MTT法)分别测定了目标产物的抗氧化活性和调控鼠骨髓间质干细胞(MSCs)的作用. 结果表明, 这两种化合物对DPPH•自由基、超氧阴离子自由基和羟基自由基具有较强的抗氧化活性, 化合物9在低浓度时对鼠骨髓间质干细胞增殖有很好的促进作用.     

Synthesis of conjugated 2,7-bis(trimethylsilylethynyl)-(phenylethynyl)nfluoren-9-one and 9-(p-methoxyphenyl)-9-methyl derivatives: optical properties

2,7-Substituted 9-fluorenones and 9,9-disubstituted fluorene have been synthesized and their fluorescence properties analyzed. The synthesis of conjugated 2,7-bis(trimethylsilylethynyl)-(phenylethynyl)_nfluoren-9-one (or the 9-(p-methoxyphenyl)-9-methyl) structures was carried out by the heterocoupling reaction between the 2,7-di(halo)fluoren-9-one (or 2,7-dibromo-9-(p-methoxyphenyl)-9-methylfluorene) and p-trimethylsilylethynyl(phenylethynyl)_n (n=1,2), catalyzed by the dichloro bis(triphenylphosphine)palladium and cuprous iodide system, in a divergent synthesis.The π-extended conjugated compounds exhibit fluorescence radiation emission (blue light-emitting), with important quantum yield for the 9-(p-methoxyphenyl)-9-methyl-2,7-bis(trimethylsilylethynyl)-(phenylethynyl)_nfluorenes which increases with the conjugation.     

[Z]-2-(芳基锡基)-1-(9-芴醇)乙烯的合成、结构与性质

用三苯基氢化锡,三对甲苯基氢化锡作为锡氢化试剂与9-乙炔基-9-芴醇进行反应,合成了2个有机锡化合物:[Z]-2-(三苯基锡基)-1-(9-芴醇)乙烯(1)和[Z]-2-(三对甲苯基锡基)-1-(9-芴醇)乙烯(2)。化合物1和2分别与ICl,Br~2,I~2反应,得到6个有机锡一卤化物,6个有机锡二卤化物和2个有机锡混合卤化物(3-16)。有机锡一碘化物7,13和有机锡二碘化物8,14与KOH乙醇溶液反应,分别得到相应的有机锡氢氧化物17,18和有机锡氧化物19,20。有机锡二碘化物8,14分别与含氮双齿配体1,10-邻菲罗啉(Phen),2,2'-联吡啶(Bipy),8-羟基喹啉(Oxin)反应,得到6个相应的配合物21-26。26个新化合物通过元素分析,锡含量测定,IR,^1HNMR测定对其结构进行了表征。同时测定了化合物2的晶体结构,晶体属单斜晶系,空间群P2~1/c。化合物2是以Sn原子为中心扭曲的四面体构型。     

基于N-乙基咔唑-2-乙烯基-8-羟基喹啉锌的黄绿色有机电致发光器件的性能

通过用一种既具有空穴传输特性又具有发光特性的新型荧光染料N-乙基咔唑-2-乙烯基-8-羟基喹啉锌((E)-2-(2-(9-ethyl-9H-carbazol-3-yl)vinyl) quinolato-zinc, CzHQZn)作为受主, 制备了结构为ITO/2T-NATA (30 nm)/CBP: 6%Ir(ppy)3:wCzHQZn(20 nm)/Alq3(50 nm)/LiF/Al(ITO: indium-tin oxide, 2T-NATA: 4,4',4'-{N,N-(2-naphthyl)-N-phenylamino}-triphenylamine, CBP: 4,4-N,N'-dicarbazole-biphenyl, Ir(ppy)3: factris (2-phenylpyridine) iridium, Alq3: tris(8-quinolinolato) aluminum; w 是CzHQZn 的质量分数)的黄绿色有机电致发光器件(OLEDs). 研究了掺杂体系在不同掺杂浓度(w=5%、10%、12%、15%)时的电致发光(EL)特性. 结果表明, CzHQZn 掺杂浓度为10%的器件在11 V 电压下实现了黄绿光发射, 色坐标为(0.4045, 0.5113), 最大发光亮度为16110 cd·m-2; 而在7 V电压下的最大发光效率为2.19 cd·A-1, 最大外量子效率为0.775%.     

Regioselective Sonogashira cross-coupling reactions of 6-chloro-2,8-diiodo-9-THP-9H-purine with alkyne derivatives

Lithiation of 6-chloro-9-(tetrahydro-2H-pyran-2-yl)-9H-purine with LiTMP, gave access to 6-chloro-2,8-dihalogenated purine derivatives. In particular, the 6-chloro-2,8-diiodopurine derivative is an interesting new intermediate which gave regioselectively various 2-alkynylated compounds or 2,8-dialkynylated purines by using an excess of alkyne.     

On the chemistry of pyrrole pigments,XCVII: Synthesis,stereochemistry, and solvatochromic effects of a 1-(dipyrrinon-9-yl)-3-(dipyrrinon-9-ylidene)-1-propene

Summary By condensing a dipyrrinon-9-yl-acrolein with a dipyrrinone unsubstituted in position 9, an unsymmetricb-vinylogous verdinoid pigment was prepared. The configuration of this molecule was elucidated by means of 2D¹H NMR experiments to be (4Z,10E,12Z,17Z) in solutions of chloroform and dimethylsulfoxide, and its conformation was derived to be 5syn,9syn,11anti,16syn. The pronounced solvatochromic effect of this molecule with a cyclic helical geometry could be explained by solvent induced conformational changes.

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Zur Chemie von Pyrrolpigmenten, 97. Mitt.: Synthese, Stereochemie und Solvatochromer Effekt eines 1-(Dipyrrinon-9-yl)-3-(dipyrrinon-9-yliden)-1-propens

Zusammenfassung Durch Kondensation eines Dipyrrinon-9-yl-acroleins mit einem in Position 9 unsubstituierten Dipyrrinon wurde ein unsymmetrischesb-vinyloges verdinoides Pigment dargestellt. Die Konfiguration dieses Moleküls wurde mit Hilfe von 2D-¹H-NMR-Experimenten in Lösungen von und Dimethylsulfoxid als (4Z,10E,12Z,17Z) abgeleitet; seine Konformation konnte zu 5syn,9syn,11anti,16syn festgelegt werden. Die ausgeprägte Solvatochromie dieses Moleküls mit cyclisch helikaler Geometrie konnte auf solvensinduzierte konformative Veränderungen zurückgeführt werden.

     

一步法合成9-去氧-8a-氮杂-8a-同型红霉素A

以(9Z)-9-去氧-9-羟基亚胺基红霉素A为原料,甲醇/水为反应体系,对甲苯磺酰氯为催化剂,硼氢化钠为还原剂,首次用一步法合成了9-去氧-8a-氮杂-8a-同型红霉素A,其结构经1H NMR和FAB-MS表征。在pH8~9,于-3℃反应9 h的较佳反应条件下,收率94.1%,纯度93.0%。     

Self-organization of Gold Nanoparticles Protected by 9-(5-Thiopentyl)-carbazole

Introduction During the past decade, nanometer-sized metal clusters, special the gold clusters, possessing unusual physical and chemical properties have been extensively investigated1-5. In recent years, a new effort has been focused on fabricating ordered metal nanoparticles with well-defined two or three dimensions using nanometer-sized metal clusters as building blocks6-9. This will provide a new horizon to develop novel optical and nanoelectronic devices. Ordered nanoparticle assemblie…     

Doubly hydrogen-bridged 1,2-diphenylenediboranes derived from 9-chloro-9-borafluorene and ligand exchange reactions

Cyclic 1,2-diphenylenediboranes containing a doubly hydrogen-bridged structure, including 1,2-(2,2^′biphenylylene)diborane(I) and 1,2-(2,2^′biphenylylene)-1,2-diethyldiborane (II), are conveniently prepared by treating 9-chloro-9-borafluorene with NaBH₄ and Na(Et)₃BH, respectively. The reaction mechanism involves an initial Cl-H exchange to form 9-borafluorene containing a reactive 5-member ring diarylborane moiety, which subsequently engages in a facile ring expansion with the in situ formed B-H containing residue (BH₃ or HBEt₂) to result in cyclic 1,2-diphenylenediboranes compounds. The doubly hydrogen-bridged structure shows good thermal stability up to 50 °C. Upon thermal cleavage at higher temperature, all free B-H groups become very reactive involving hydroboration with α-olefin. The complexization study also reveals that this intradiborane moiety forms a 1:2 complex with a strong base, such as pyridine.     

Synthesis of Derivatives of 1-(9-Alkyl-9H-carbazol-3-yl)-4-carboxy-2-pyrrolidinones

Derivatives of 1-(9-alkyl-9H-carbazol-3-yl)-4-carboxy-2-pyrrolidinones (methyl esters, hydrazides) were synthesized. The condensation of the synthesized hydrazides with aromatic aldehydes, acetylacetone, and acetoacetic ester was studied. Structure of the obtained compounds was confirmed by IR and NMR spectroscopy. The specific characteristics of the substituents are discussed.     

Metal-Free,Light-Mediated,Site-Specific,Radical C6−H Alkylation of Purines with Alcohols Intervened by Oxalates without Catalysts

Herein, we report the development of a radical deoxy-functionalization strategy for the direct C−H alkylation of purines and purine nucleosides with alcohols (1°, 2°, 3°) intervened by oxalates under 12 W blue LED irradiation. The reaction shows high regioselectivity at C6−H position of purine and is suitable for N9-, N7-substitued purines. The process accommodates purines and alcohols to deliver a wide range of products (31 examples) in 41–91 % yields, which avoids transition metal catalysts and organometallic reagents, and is not sensitive to moisture and air. Besides, the mild protocol displays broad functional groups tolerance and is easily up scalable to gram scale and can be used for late-stage C−H alkylation of purine to synthesize pharmaceutical 6-cyclopentyl nebularine with anti-CEM activity or natural d -menthol modification.     

Simple and Efficient Purification Protocol of 9-(Trifluoroacetyl)anthracene from Anthracene

A protocol has been developed to purify 9-(trifluoroacetyl)anthracene from anthracene, the major impurity associated in its synthesis. The protocol utilizes a chemoselective thermal Diels–Alder reaction, employing maleic anhydride as the dienophile. The resulting Diels–Alder adduct can then be removed by extractive workup followed by recrystallization to give 9-(trifluoroacetyl)anthracene with ≥99% chemical purity.     

取代基对3(5)-(9-蒽基)吡唑光学性质的影响

使用密度泛函理论(DFT)B3LYP/6-31G(d)方法优化得到了3(5)-(9-蒽基)吡唑及其衍生物的基态(S₀)分子结构, 使用单激发组态相互作用(CIS)/6-31G(d)方法优化得到这些分子的第一单重激发态(S₁)的几何结构, 并使用含时密度泛函理论(TD-DFT)B3LYP/6-311++G(d,p)方法计算了它们的吸收和发射光谱. 计算结果表明, 与3(5)-(9-蒽基)吡唑相比, 无论取代基是吸电子基团还是供电子基团, 衍生物的吸收和发射峰均发生红移, 并且当取代基―R=―BH₂, ―CCl₃, ―CHO, ―NH₂时衍生物有较长的吸收波长和发射波长.