Static and dynamic stereochemistry of 1,1′-bi(9,10-dihydro-9,10-ethano-anthryl)

Summary The title compound2 was prepared either by highpressure reaction of 1,1-bianthryl with ethylene or by coupling of 1-bromo-9,10-dihydro-9,10-ethanoanthracene (4). Both syntheses afforded a mixture of diastereoisomers (meso2a and racemate2b) in a ratio of 1.5:1 and 2.3:1, respectively. Configurational assignment was possible both from the¹H- and¹³C-NMR spectra and by coupling of laevorotatory4 (accessibly by enantioselective chromatography on triacetyl cellulose in ethanol) to laevorotatory2b. (+)-4 was tranformed into the dextrorotatory carboxylic acid (+)-5 of known configuration (9R) thus establishing the configuration of (+)-4 as (9R) too and hence the centrochirality in (–)-2b as (9S)(9S). The racemic form2b is a conformational (appr. 1.8:1) mixture of two rotamers.The rotational barrier was established as G ^#=92–95 kJ mol^–1 (depending on the temperature) both by¹H-NMR and CD kinetics (based on equilibration of the separated optically active rotamers ofracem.2). For the latter preferred conformations were assumed allowing the assignment of the axial chirality: e.g. (–)-(9S)(R)_a(9S) for the main rotamer of (–)-2 b [and (–)(9S)(S)_a(9S) for the underpopulated one].All assumptions were confirmed by X-ray crystal structure analyses of2 a and the main rotamer of2b with torsional angles around the 1,1-bonds of –111.1 and –121.2°, respectively.Dedicated to Prof. K. L. Komarek (Vienna) with cordial wishes on the occasion of the 65th anniversary of his birthday     

Gauche and staggered forms of diethylamine in solvates of 1,5-dichloro-cis-9,10-diethynyl-9,10-dihydroanthracene-9,10-diol. A case of conformational pseudopolymorphism?

Diethylamine has been trapped in its less stable gauche conformation in a solvate of the title diol; the staggered conformation, which is ca. 4 kJ mol(-1) more stable, is found in another solvate of the same host.     

Two New Organic Supramolecular Complexes Based on 2,3,6,7-Tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene and 4,4′-Bipyridine or 4,4′-Bipyridinylethane

Two new organic supramolecular cocrystal complexes C18H18O4·C10H8N2(I) and C18H18O4·C12H10N2(II)(C18H18O4 = 2,3,6,7-tetrahydroxyl-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene(LH4), C10H8N2 = 4,4'-bipyridine(bpy) and C12H10N2 = 4,4'-bipyridinylethane(bpe)) have been obtained by mixing LH4 with corresponding bpy or bpe ligand. The two complexes have been determined by X-ray crystal structure analysis, elemental analysis and IR analysis. Compound I crystallizes in the orthorhombic Pnma with a = 9.7078(4), b = 22.4974(10), c = 20.6272(9) V = 4505.0(3)3, Mr = 454.51, Dc. = 1.340 g·cm-3, μ = 0.09 mm-1, F(000) = 1920, Z = 8, R = 0.0503 and wR = 0.1360. Compound II crystallizes in monoclinic C2/c with a = 29.944(6), b = 9.820(2), c = 22.643(5) , V = 5048.4(18)3, Mr = 480.54, Dc. = 1.265 g cm–3, μ = 0.084 mm–1, F(000) = 2032, Z = 8, R = 0.0548 and wR = 0.1600. X-ray single-crystal structure analysis shows that two-dimensional(2D) layer supramolecular structures are formed through hydrogen bonds and π-π interactions in the two complexes. IR analysis also indicates that there are only associated hydroxyl groups in the two complexes.     

RESEARCH ON THERMOREACTIONS BETWEEN INDOLE AND 9,10-PHENANTHRAQUINONE

Solventless reactions between indole and 9,10-phenanthraquinone(PQ)have beencarried out in the presence/absence of zinc chloride.The 1,2-photoadduct between indole and PQ wasidentified as a possible intermediate in thermoreactions.An electrophilic substitution mechanisminvolving formation ofn-EPD/v-EPA complex was proposed.     

An expeditious,highly efficient,catalyst and solvent-free synthesis of 9,10-dihydro-anthracene-9,10-α,β-succiniimide derivatives

Abstract

A simple, fast, and highly efficient protocol has been developed for the synthesis of 9,10-dihydro-anthracene-9,10-α,β-succinic imide derivatives by simple mixing and grinding of 9,10-dihydro-anthracene-9,10-α,β-succinic anhydride with various aliphatic, aromatic amines, and hydrazines. This catalyst and solvent-free green approach provided the condensation products within few minutes at room temperature in quantitative yield.     

9,10-二氢菲-9,10-二醇衍生的新型手性配体的设计、制备和应用

报道了一系列衍生自9，10－二氢菲－9，10－二醇的新型手性配体设计，合成及在不对称催化反应中的应用。     

The Cis and Trans Δ 9,10-Octalin-1,5-Diols

An efficient preparation of the title diols has been achieved by hydride reduction of diketone 2, for which a new, convenient synthesis is described. The diols were separated by chromatography, and their configurations were assigned by NMR analysis of derivatives and confirmed by X-ray analysis of the trans diol.     

9,10-二氢蒽-9,10-桥-α,β-琥珀酰亚胺的N-曼尼希碱的制备

9,10-二氢蒽-9,10-桥-α,β-琥珀酰亚胺在碱性条件下,易与甲醛缩合成N-羟甲基化合物,此N-羟甲基-9,10-二氢蒽-9,10-桥-α,β-琥珀酰亚胺与各种胺反应制得一系列新的化合物——18种9,10-二氢蒽-9,10-桥-α,β-琥珀酰亚胺的N-曼尼希碱。     

Coordination ability of N,N’-disubstituted 9,10-phenanthrenediimines

The ability of N,N’-disubstituted 9,10-phenanthrenediimines in neutral, monoand direduced states to act as bidentate ligands in main-group-metal and transition-metal complexes has been demonstrated for the first time. The formation of metal complexes with the radical anion form of phenanthrenediimines stabilized through the formation of contact pairs (for Li) or chelate complexes (for Rh) has been detected.     

9,10-二羟甲基蒽的单醚化反应

对9,10-二羟甲基蒽(1)的单醚化反应进行了系统研究. 以蒽为起始原料通过氯甲基化、乙酸酯化和水解三步反应制备1, 它通过Williamson单醚化反应, 合成了制备蒽基衍生物的重要反应中间体 9-(3,5-二苄氧基苄氧甲基)-10-羟甲基蒽(5). 1通过以氧化银为中介的单醚化反应也成功地合成了5, 产率达到57%.     

9,10-二氰基蒽光敏化香豆素加成反应的研究

光化学中的电子转移反应近年来引起了人们广泛的重视。9,10-二氰基蒽(DCA)作为贫电子敏化剂敏化的各类烯烃的光氧化反应,光重排反应,光加成反应等均有报道。我们在研究DCA光敏化香豆素反应时发现,香豆素与DCA能够发生电子转移的给体—受体加成反应,联苯(BP)可以充当二次电子转移体加速反应。     

水介质中9,10-二芳基吖啶的洁净合成

水介质中在十二烷基磺酸钠(SDS)催化下, 席夫碱与双甲酮反应合成了一系列9,10-二芳基吖啶衍生物, 同时分离得到一种中间产物. 所有产物的结构通过红外光谱和1H NMR光谱确定, 产物10-(4-氯苯基)-9-(4-甲氧基苯基)-3,3,6,6-四甲基-3,4,6,7,9,10-六氢化吖啶-1,8(2H,5H)-二酮(3i)和中间产物2-{4-氯苯基-[2-(4-甲氧基苯基氨基)-4,4-二甲基-6-氧代环已-1-烯基]甲基}-3-羟基-5,5-二甲基环已-2-烯酮(4h)的结构还通过单晶X射线衍射分析确证.     

Stereochemistry of the asymmetric alkylation of Δ9,10-octahydroquinolin-4-ones

The asymmetric character of the alkylation of a series of metallated bicyclic enaminoketones has been established and its stereoselectivity has been investigated. The enantiomers of (3S*)-methyl- and (3S*)- and (3R*)-3-methyl-3-butyl-^9,10-octahydroquinolin-4-ones have been obtained. The possibility of inducing chirality at the 3 position of the enaminoketone molecule during methylation in the presence of chiral lithium amides has been established in principle.M. V. Lomonosov Moscow State University, Moscow 119899. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1531–1542, November, 1995. Original article submitted November 10, 1995     

9,10-二氰基蒽敏化光氧化反应的溶剂效应

本文通过α,β-蒎烯及1,4-二苯基-1,3-丁二烯的9,10-二氰基蒽(DCA)敏化光氧化反应在一系列溶剂中产物生成的相对量子效率及单线态氧(¹O₂)产物的含量,对β-蒎烯在乙腈中的反应动力学分析,讨论了反应的溶剂效应,证明了DCA敏化光氧化反应,包括¹O₂产物都是经由电子转移的反应机理。     

9,10-二氰基蒽光敏夺氢反应的研究

本文研究了缺电子敏化剂9,10-二氰基蒽(DCA)对苄醇类化合物(二苯甲醇、苯甲醇)及甲苯类化合物(甲苯、对-二甲苯)的光敏化夺氢反应,证明上述两类反应是经由两种不同机制进行的。     

两种反式-9,10-二氢-9,10-二乙基蒽-11,12-二羧酸为主体的氢键包合物的合成与晶体结构

合成了反式-9,10-二氢-9,10-二乙基蒽-11,12-二羧酸(EADA)及其与硼酸共同构建主体晶格的正四丁基铵阳离子管状包合物(n-C4H9)4N C18H13O-4?B(OH)3(1)和(n-C4H9)4N C18H13O-4(2),并通过单晶X射线衍射法对其进行了晶体结构测定.结果表明,晶体1属单斜晶系,P2(1)/c空间群,晶胞参数a=1.5699(1)nm,b=0.9955(6)nm,c=2.2933(1)nm,β=109.962(3)°,Z=4,R1=0.0434,wR=0.0759;晶体2属单斜晶系,C2/c空间群,晶胞参数a=1.4005(3)nm,b=1.2821(2)nm,c=1.7657(3)nm,β=100.388(1)°,Z=4,R1=0.0584,wR=0.0966.在晶体1中,EADA阴离子和硼酸分子的氢键四聚体链交错平行排列,生成具有矩形截面的管道式主体晶格,每个管道内包含了两列规则排列的正四丁基铵阳离子(n-C4H9)4N .在晶体2中,相互独立的EADA阴离子交错排列形成类蜂巢形截面的管道式主体晶格,正四丁基铵阳离子形成Z形长列被包合在这些管道里,阳离子的烃链穿插在管道壁中.     

9,10-二氰基蒽光敏分解水制氢反应的研究

本文以9、10-二氰基蒽(DCA)为敏化剂,测定了用胺类,单烯类及取代苯类化合物为电子给体时光敏还原甲基紫精(MV²⁺)的量子产率。用三乙醇胺(TEOA)为电子给体,探索了胶体铂存在下DCA光敏分解水制氩的反应条件并研究了用甲苯、对二甲苯为电子给体时DCA光解水制氢的反应。结果表明以DCA为敏化剂时许多化合物(E^ox<2V)均可作为电子给体,在制氢的同时还有可能合成有用化合物等优点。