Structural controlled pure metallo-triangular assembly through bisterpyridinyl Dibenzo[b,d]thiophene,Dibenzo[b,d]furan and Dibenzo[b,d]carbazole

A novel family of metallocycles was constructed by a one-pot self-assembly of three analogous bis(terpyridine) ligand monomers L1-L3, having different bent angles, with metal ions (Zn²⁺ or Cd²⁺). The dibenzo[b,d]thiophene-containing ligand L3 assembled with the metal ions to form a single trimer, whereas the dibenzo[b,d]furan-containing ligand L2 and dibenzo[b,d]carbazole-containing ligand L1 formed a mixture of trimers and tetramers. Heteroatoms (N, O, S) significantly contributed to the molecular size of the assemblies, owing to the bent angle of the bis-terpyridines ligands.     

Dibenzo[b,e][1,4]diazepin-1-Ones,Synthesis and Derivatization

Several linearly fused tricyclic 6,7,6-systems were prepared. Reaction of 1,2-diamino-4-nitrobenzene with 5,5-dimethylcyclohexan-1,3-dione gave 3-(2-amino-5-nitroaniIino)-5,5-dimethylcyclohex-2-en-1-one (8) . Reaction of 8 and its analogue 6 with various aldehydes gave 2,3,4₎5,10,11-hexahydro-3,3-dimethyl-11-substituted-1H-dibenzo[b,e][1,4]diazepin-1-ones 9 and 10 . Acetylation of 9 and 10 gave the corresponding N-acetyl derivatives. Spectral data of the products are discussed.     

Aktivierte Chinone: regiospezifische Synthesen von substituierten Dibenzo [b,d]pyran-6-onen und Benzo [b]naphtho [d]pyran-6-onen

Activated Quinones: Regiospecific Syntheses of Substituted Dibenzo [b, d]pyran-6-ones and Benzo[b]naphtho [d]pyran-6-ones The reaction of 2-methoxycarbonyl-1, 4-benzoquinone (1) with substituted phenols leads in an acid-catalyzed, regiospecific way to substituted dibenzo [b, d]-pyran-6-ones (compounds 3 and 6 ). The cycloaddition of 1,3-butadiene to the latter yields compounds 7. Tautomerisation of 7 and oxidation gives the benzo[b]-naphtho[d]pyran-6-ones 8 and 10 , respectively.     

Benzo[b]tellurophene, Dibenzo[b,d]tellurophene, and Their Derivatives. (Review)

Data on the synthesis, reactions, crystal structure, and spectral characteristics of benzo[b]tellurophene, dibenzo[b,d]tellurophene, and their derivatives are reviewed and analyzed.     

Diindeno-Fused Dibenzo[a,h]anthracene and Dibenzo[c,l]chrysene: Syntheses,Structural Analyses,and Properties

Diindeno-fused dibenzo[a,h]anthracene 6 and diindeno-fused dibenzo[c,l]chrysene 9 contain the key moieties 1,4-quinodipropene (1,4-QDP) and 2,6-naphthoquinodipropene (2,6-NQDP), respectively, and they both have an open-shell singlet ground state. The latter compound exhibits a strong biradical character and interesting properties, including a low ΔE_T−S (2.44 kcal mol⁻¹), a small HOMO–LUMO gap (1.06 eV), a wide photoabsorption range (250–1172 nm), and a large two-photon absorption cross-section (σ=1342±56 GM). This work verifies that 6 has a slightly larger HOMO–LUMO gap and ΔE_T−S than its helical isomer diindeno[2,1-f:1′,2′-j]picene (DIP), but is a much stronger two-photon absorber, verifying the important effect of geometry on the photophysical properties.     

Preparation of Benz[b]Indeno[1,2-e]Pyran-11(6H)-Ones and Benz[b]Indeno[1,2-e]Thiopyran-11(6H)-One from Dilithiated 2-Indanone and Lithiated Methyl Salicylates or Lithiated Methyl Thiosalicylate

Dilithiated 2-indanone was prepared with excess lithium diisopropylamide, and the resulting intermediate was condensed with several lithiated methyl salicylates or lithiated methyl thiosalicylate, which was followed by acid cyclization to benz[b]indeno[1,2-e]pyran-11(6H)-ones 3--9 or benz[b]indeno[1,2-e]thiopyran-11(6H)-one 10, which are rare fused-ring indeno-chromones and a new indeno-thiochromone, respectively.     

Dibenzo[d,h][1,3,6,7,2]dioxadithiasilonin: Synthesis and characterization

The reaction of 2,4-di-t-butylphenol, 4 , with sulfur monochloride gave the trithiobisphenol 5 rather than the expected dithiobisphenol 7 . The thiol 6 was obtained by the reduction of 5 with zinc under acidic conditions. The dithiobisphenol 7 was prepared by the oxidative coupling of 6 with iodine under alkaline conditions. The dibenzo[d,h][1,3,6,7,2]dioxadithiasilonin 8 was prepared by the reaction of 7 with dichlorodimethylsilane using triethylamine as an acid acceptor. No change was observed in the ¹H nmr spectrum of 8 upon cooling to ?55°, which suggests that the ΔG* for ring inversion is less than the corresponding eight-membered dibenzo[d,g][1,3,2]dioxasilocin and dibenzo[d,g][1,3,6,2]dioxathiasilocin 1 and 2 , respectively. The spectral data and elemental analysis are fully in accord with the nine-membered silonin structure.     

Photolysis of Dibenzo[a,d]cycloheptene Dimer

Photolysis reaction of dibenzo[a,d]cycloheptene dimer 3 provides three dibenzo[a,d]cycloheptyl dimers 4 , 5 and 6 under different irradiation conditions via the intramolecular degradative cyclodimerization. A tetracyclic benzo[4,5]cyclohepta[1,2,3‐de]naphthalene core is also synthesized.     

二苯并[b,f][1,5]二氮杂芳辛四烯衍生物的合成及拆分

以邻氨基二苯甲酮为原料,经自身缩合环化合成了3种二苯并[1,5]二氮杂芳辛四烯衍生物(1a~1c);以邻苯二甲酸酐和溴苯为原料经傅-克反应制得中间体2-(4-溴苯甲酰溴)苯甲酸(M1);M1经叠氮化后自缩合制得6,12-二(4-溴苯基)二苯并[b,f][1,5]二氮杂环辛四烯(1d);以邻氨基苯甲酸甲酯为原料,经自身缩合环化制得中间体二苯并[b,f][1,5]二氮杂环辛四烯-6,12(5H,11H)-二酮(M2);M2经氯化合成6,12-二氯二苯并[b,f][1,5]二氮杂环辛四烯(1e),化合物1a~1e的结构经~1H NMR,~(13)C NMR和ESI-MS表征,其中化合物1c为新化合物。利用超临界色谱(SFC)技术对化合物1a~1e实现了手性拆分,获得5对具有高旋光度的光学活性异构体(ee99%)。     

Dibenzo[d,f][1,3] dioxepine derivatives: A review

This review presents a survey of synthetic methods and reaction mechanism of the dibenzo[d,f][1,3] dioxepine derivatives. Furthermore, the influence of the substituent groups in 6,6′‐position of dibenzo[d,f][1,3] dioxepine on their conformation is explored. The functional dibenzo[d,f][1,3] dioxepine synthetically versatiles substrate, as they can be used for synthesis of a large variety of π‐conjugated oligomer and polymer containing heterocyclic compounds, such as dibromination dibenzo[d,f][1,3] dioxepine derivative as a raw material of synthesis for organic semiconductor polymers. The synthetic and fluorescent property of π‐conjugated polymers basic on dibenzo[d,f][1,3] dioxepine also is explored. J. Heterocyclic Chem., (2012).     

新型非对称二苯并[b,f][1,5]二氮杂环辛四烯的合成

以两种不同取代的2-氨基二苯甲酮为原料,氯苯为溶剂,BF3-Et2O为脱水剂,通过分子间脱水一步环化缩合制备非对称二苯并[b,f][1,5]二氮杂环辛四烯衍生物。运用HPLC监控反应过程,优化合成工艺,得到最佳反应条件为:等物质的量的两种不同取代2-氨基二苯甲酮和BF3-Et2O,在氯苯中回流反应12 h。化合物4a^4c为新化合物,其结构经1H NMR,13C NMR和MS(ESI)表征。     

Microwave‐Assisted Synthesis of Substituted Dibenzo[b,f][1,4]thiazepines,Dibenzo[b,f][1,4]oxazepines,Benzothiazoles, and Benzimidazoles

A highly efficient synthesis for possessing 7‐membered rings with two heteroatoms is described, using efficient microwave‐assisted one‐pot method to synthesize (substituted) dibenzo[b,f][1,4]thiazepines [1] and dibenzo[b,f][1,4]oxazepines [2] in high yields (up to 99%) by cyclocondensations of o‐aminothiophenol or o‐aminophenol with o‐halobenzaldehydes, o‐fluoroacetophenone, and o‐fluorobenzophenone. In the absence of base, o‐aminothiophenol reacted with o‐halobenzaldehydes to afford benzothiazoles.     

区域选择性合成二苯并[d,f][1,3]二噁烷

针对二苯并[d,f][1,3]二噁烷传统制备方法中易产生二羟基联苯乙烯副产物的缺点,本文以路易斯酸性胍盐离子液体为催化剂,2,2'-二羟基联苯和端基炔为原料,高区域选择性的合成了二苯并[d,f][1,3]二噁烷,收率39%~84%。 本方法适用于各种端基炔。路易斯酸性胍盐离子液体循环利用5次,活性不变。     

Synthesis of substituted 6h-dibenzo[b,d]pyran-6-one

Chemistry of Heterocyclic Compounds -     

Synthese und NMR-spektroskopische Untersuchungen von Dibenzo[d,g]-1,3-dioxa-2-element-6-silocinen

Synthesis and NMR Spectroscopic Investigations of Dibenzo [d,g]-1,3-dioxa-2-element-6-silocine Bis-(o-halogenoaroxy)silanes react with sodium via metallation and a fast two-step [1.3]-rearrangement to the sodium salts of bis(o-hydroxyaryl)silanes. These are cyclized in a one-pot-reaction with element halides of silicon, phosphorus and arsenic to the title compounds of the general formula R¹R²Si(C₆H₄O)₂E (E = SiR₂, P(Y)R, As(Y)R). One conformer is prefered according to N.M.R. spectroscopical investigations.     

Synthesis of nitro-substituted dioxotetrahydrodioxapyrenes and 6H-dibenzo[b,d]pyran-6-one

Methods for the synthesis of tri- and tetranitro-substituted 5,9-dioxo-4,5,9,10-tetrahydro-4,10-dioxapyrenes, 5,10-dioxo-4,5,9,10-tetrahydro-4,9-dioxapyrenes, and 6H-dibenzo[b,d]pyran-6-one were developed in a search for effective sensitizers for electrophotographic layers based on carbazole-containing polymers. The possibility of the production of nitro compounds that contain three vicinal nitro groups was demonstrated. Under severe nitration conditions 2,4,8-trinitro-6H-dibenzo[b,d]pyran-6-one is cleaved to give 2-hydroxy-2-carboxy-3,5,4-trinitro-biphenyl, which is resistant to cyclization to give the starting compound, evidently because of the existence of an intramolecular hydrogen bond between the hydroxy group and the nitro group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 463–467, April, 1985.     

The synthesis of benzo[b]phenanthro[d]thiophenes and anthra[b]benzo[d]thiophenes

The synthesis of benzo[b]phenanthro[2, 3-d]thiophene ( 5 ), benzo[b]phenanthro[4, 3-d]thiophene ( 6 ), benzo-[b]phenanthro[2, 1-d]thiophene ( 9 ), benzo[b]phenanthro[3, 2-d]thiophene ( 14a ), anthra[1, 2-b]benzo[d]thiophene ( 24 ), anthra[2, 3-b]benzo[d]thiophene ( 29 ) and anthra[2, 1-b]benzo[d]thiophene ( 30 ) is described as well as the preparation of 13-methylbenzo[b]phenanthro[3, 2-d]thiophene ( 14b ).