The insertion and extrusion of heterosulfur bridges. XII. Selectivity and side reactions in the bridging process

1-Phenylnaphthalene undergoes sulfur bridging at 500° in the presence of hydrogen sulfide and a heterogeneous catalyst to produce benzo[b]naphtho[1,2-d]thiophene (13%). 3-Methylphenanthrene and 9-formylphenanthrene diethyl acetal ( 7b ) give sulfur bridging to produce phenanthro[4,5-bcd]thiophene, i.e. with loss of the ring substituent. Additionally, 7b hydrogenolyzes to 9-methylphenanthrene. With decadeuteriobiphenyl as a substrate, the dibenzothiophene formed, as well as the biphenyl recovered, is largely devoid of deuterium label. Confirmation that benzene and toluene react under sulfur-bridging conditions is presented.     

Synthesis of anthra[b]thiophenes and benzo[b]naphtho[d]thiophenes

All isomers of the parent anthra[b]thiophenes and benzo[b]naphtho[d]thiophenes, namely anthra[2,3-b]thio-phene, anthra[2,1-b]thiophene, anthra[1,2-b]thiophene, benzo[b]naphtho[2,3-d]thiophene, benzo[b]naphtho[2,1-d]thiophene and benzo[b]naphtho[1,2-d]thiophene were synthesized using a new procedure.     

Deep‐blue light‐emitting polyfluorenes with asymmetrical naphthylthio‐fluorene as Chromophores

A novel blue polycyclic aromatic compound 2,8‐dibromo‐14,14‐dioctyl‐14H‐benzo[b]benzo [5,6] fluoreno[1,2‐d]thiophene 9,9‐dioxide (Br₂NFSO) is designed and synthesized through multistep synthesis, and its structure is confirmed by nuclear magnetic resonance. Based on synthesized polycyclic aromatic compound Br₂NFSO, a series of twisted blue light‐emitting polyfluorenes derivatives (PNFSOs) are prepared by one‐pot Suzuki polycondensation. Based on the twisted polymer molecular structure resulted from the asymmetric links of 14,14‐dioctyl‐14H‐benzo[b]benzo[5,6]fluoreno[1,2‐d]thiophene 9,9‐dioxide (NFSO) unit in copolymers and better electron transport ability of NFSO than those of the electron‐deficient dibenzothiophene‐S,S‐dioxide counterpart, the resulting polymers exhibit excellent electroluminescent spectra stability in the current densities from 100 to 800 mA cm^?2, and show blue‐shifted and narrowed electroluminescent spectra with the Commission Internationale de L′Eclairage (CIE) of (0.16, 0.07) for PNFSO5, compared to poly(9,9‐dioctylfluorene) (PFO) with the CIE of (0.18, 0.18). Moreover, the superior device performance is achieved based on PNFSO5 with the maximum luminous efficiency (LE_max) of 1.96 cd A^?1, compared with the LE_max of 0.49 cd A^?1 for PFO. The results indicate that the twisted polycyclic aromatic structure design strategy has a great potential to tuning blue emission spectrum and improving EL efficiency of blue light‐emitting polyfluorenes. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 171–182     

Angular polycyclic thiophenes containing two thiophene rings. I

We describe the synthesis of thieno[2,3-c]dibenzothiophene ( 6 ), thieno[3,2-c]dibenzothiophene ( 10 ), thieno-[3,2-a]dibenzothiophene ( 14 ), thieno[2,3-a]dibenzothiophene ( 16 ), benzo[1,2-b:4,3-b]bisbenzo[b]thiophene ( 18 ), benzo[1,2--6:3,4-b]bisbenzo[b]thiophene ( 20 ), benzo[2,1--6:3,4-b]bisbenzo[b]thiophene ( 22 ), benzo[1,2-b:3,4-g]bisbenzo[b]thiophene ( 27 ), benzo[1,2-b:4,3-e]bisbenzo[b]thiophene ( 29 ), benzo[2,1--6:3,4-g]bisbenzo[b]thiophene ( 36 ), benzo[2,1--6:4,3-e]bisbenzo[b]thiophene ( 38 ), benzo[1,2--6:4,3-g]bisbenzo[b]thiophene ( 41 ), benzo[1,2-b:4,5-g]bisbenzo[b]thiophene ( 42 ), benzo[1,2-b:3,4-e]bisbenzo[b]thiophene ( 44 ) and benzo-[1,2-b:5,4-e]bisbenzo[b]thiophene ( 45 ).     

Synthesis and Characterization of Biphenylene‐Containing Diazaacenes

We describe the efficient synthesis of substituted benzo[3,4]cyclobuta[1,2‐b]phenazine, benzo[3,4]cyclobuta[1,2]benzo[1,2‐i]phenazine, and benzo[3,4]cyclobuta[1,2‐b]naphtho[2,3‐i]phenazine by a condensation reaction of aromatic diamines with the stable biphenylene‐2,3‐dione.     

Photochemical synthesis of heteroatom-containing polycyclic aromatic compounds

Anthra[2,1-b]furan, anthra[2,1-b]benzo[d]furan, anthra[2,1-b]thiophene, anthra[1,2-b]thiophene, anthra[2,1-b]benzo[d]thiophene, anthra[2,1-b]pyrrole and naphtho[2,3-c]carbazole derivatives were synthesized in fairly good yields by a one-pot photocycloaddition reaction of 2,3-disubstituted 1,4-naphthoquinone with 1,1-diarylethylene. This is the first reported synthesis of these aromatic compounds.     

On the π‐Electron Distribution in Biphenylene Analogues

The bonding situation in a series of biphenylene analogues – benzo[b]biphenylene and its dication, 4,10‐dibromobenzo[b]biphenylene, naphtho[2,3‐b]biphenylene and its dianion, benzo[a]biphenylene, (biphenylene)tricarbonylchromium, benzo[3,4]cyclobuta[1,2‐c]thiophene, benzo[3,4]cyclobuta[1,2‐c]thiophene 2‐oxide, benzo[3,4]cyclobuta[1,2‐c]thiophene 2,2‐dioxide, 4,10‐diazabenzo[b]biphenylene, biphenylene‐2,3‐dione, benzo[3,4]cyclobuta[1,2‐b]anthracene‐6,11‐dione, and 3,4‐dihydro‐2H‐benzo[3,4]cyclobuta[1,2]cycloheptene – where one of the two benzo rings of biphenylene is replaced by a different π‐system (B) was investigated on the basis of the NMR parameters of these systems. From the vicinal ¹H,¹H spin‐spin coupling constants, the electronic structure of the remaining benzo ring (A) is derived via the Q‐value method. It is found that increasing tendency of B to tolerate exocyclic double bonds at the central four‐membered ring of these systems favors increased π‐electron delocalization in the A ring. The analysis of the chemical shifts supports this conclusion. NICS (nucleus‐independent chemical shift) values as well as C,C bond lengths derived from ab initio calculations are in excellent agreement with the experimental data. The charged systems benzo[b]biphenylene dication and naphtho[2,3‐b]biphenylene dianion ( 7 ²⁻) are also studied by ¹³C NMR measurements. The charge distribution found closely resembles the predictions of the simple HMO model and reveals that 7 ²⁻ can be regarded as a benzo[3,4]cyclobuta[1,2‐b]‐substituted anthracene dianion. It is shown that the orientation of the tricarbonylchromium group in complexes of benzenoid aromatics can be derived from the vicinal ¹H,¹H coupling constants.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 22 Dibenzo[f,h]benzothieno[2,3‐c]quinoline,dibenzo[f,h]benzothieno[2,3‐c][1,2,4]triazolo[4,3‐a]quinoline and dibenzo[f,h]naphtho[2′,1′:4,5]thieno[2,3‐c]quinoline

Photocyclization of 3‐chloro‐N‐(9‐phenanthryl)benzo[b]‐thiophene‐2‐carboxamide ( 3 ) and 3‐chloro‐N‐(9‐phenanthryl)‐naphtho[1,2‐b]thiophene‐2‐carboxamide ( 10 ) yielded dibenzo[f,h]benzothieno[2,3‐c]‐quinolin‐10(9H)‐one ( 4 ) and dibenzo[f,h]naphtho[2′,1′:4,5]thieno[2,3‐c]quinolin‐10(9H)‐one ( 11 ), respectively. Further elaboration of the lactams provided three novel unsubstituted new ring systems.     

原油中芳香硫化合物形态分布的研究

建立了原油中多环芳香硫化合物形态分布的研究方法。采用氯化钯/硅胶配位交换色谱分离原油中的芳香硫化合物,并用气相色谱/质谱分析、气相色谱-硫化学发光检测法结合色谱保留指数,鉴定出原油中的100多个多环芳香硫化物,包括含烷基取代基的苯并噻吩和二苯并噻吩类硫化物。定量分析表明,二苯并噻吩类化合物的含量占芳香硫化合物总量的91%左右。该方法可用于不同来源的原油中芳香硫化合物的形态分布研究。     

Angular polycyclic thiophenes containing two thiophene rings. Part II

The syntheses of naphtho[1,2–6:7,6-b′]bisbenzo[b]thiophene ( 4 ), naphtho[1,2–6:7,8-b′]bisbenzo[b]thiophene ( 5 ), naphtho[2,1-b:7,6-b′]bisbenzo[b]thiophene ( 8 ), naphtho[2,1-b:7,8-b′]bisbenzo[b]thiophene ( 9 ), naphtho-[1,2–6:5,6-b′]bisbenzo[b]thiophene ( 14 ), naphtho[1,2–6:6,5-b]bisbenzo[b]thiophene ( 17 ) and naphtho[2,1–6:-6,5-b′]bisbenzo[b]thiophene ( 23 ) are reported.     

The insertion and extrusion of heterosulfur bridges. XV. S-bridging of 2,2′-binaphthyl and 1-(2-naphthyl)cyclohexene. Studies on hydrodehalogenation during the reaction

Regioselectivity occurs in the sulfur-bridging reactions of 2,2′-binaphthyl (1) and 1-(2-naphthyl)cyclohexene (7) by means of hydrogen sulfide and a chromia-alumina-magnesia catalyst (designated I) in a flow apparatus at 550°. Thus, 1 gives a higher yield (6.1%) of dinaphtho[1,2–6:2′,l'-d]thiophene from 1,1′-bridging than of dinaphtho[1,2-b:2′,3′-d]thiophene (3.4%) from l,3′-bridging. No product expected from 3,3′-bridging was identified. Substrate 7 undergoes both dehydrogenation and bridging to yield 2-phenylnaphthalene (8%), benzo[b]naphtho[2,1-d]thiophene (9%) from alpha bridging, and benzo[b]naphtho[2,3-d]thiophene (3%) from beta bridging into the naphthalene ring. Exploratory studies showed that either sulfided catalyst I or a sulfided molybdenum( VI ) oxide-alumina-cobalt( II ) oxide catalyst ( II ) effects hydrodehalogenation of various monohalo- and polyhaloarenes (where halo, X, is chloro or bromo) at 450–550°. In the biphenyl, phenanthrene, naphthalene, and pyrene systems, halogen was lost either under sulfur-bridging conditions or under hydrogenolysis conditions, i.e. with methanol as a reactant. For every substrate the parent arene was isolated or identified as a reaction product. In selected experiments, acid HX was also identified in the effluent. Use of hydrogen sulfide as a reactant led to formation of dibenzothiophene and phenanthro[4,5-bcd]thiophene as main products in the biphenyl and phenanthrene systems, respectively; while use of methanol as a reactant gave small amounts of methyl bromide (for X = Br) and methylarenes.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 8 . [1]Benzothieno[2,3-c]naphtho[1,2-h]quinoline and [1]benzothieno[2,3-c]naphtho[1,2-h][1,2,4]triazolo[4,3-a]quinoline

The previously unknown polycyclic heterocyclic ring systems, namely, [1]benzothieno[2,3-c]naphtho[1,2-h]-quinoline and [1]benzothieno[2,3-c]naphtho[1,2-h][1,2,4]triazolo[4,3-a]quinoline were synthesized via photocyclization of 3-chloro-N-(1′-phenanthryl)benzo[b]thiophene-2-carboxamide.     

Synthesis of Fluorescent Naphthoquinolizines via Intramolecular Houben–Hoesch Reaction

The repertoire of synthetic methods leading to aza‐analogues of polycyclic aromatic heterocycles has been enlarged by the discovery of the rearrangement of 10‐substituted benzo[h]quinolines into compounds bearing an azonia‐pyrene moiety. Acid‐mediated intramolecular cyclization of derivatives bearing ‐CH₂CN and ‐CH₂CO₂Et groups led to compounds bearing a 5‐substituted benzo[de]pyrido[3,2,1‐ij]quinolinium core. Advanced photophysical studies including time‐correlated single photon counting (TCSPC) and transient absorption spectroscopy of 5‐aminobenzo[de]pyrido[3,2,1‐ij]quinolin‐4‐ium salt and 5H‐benzo[de]pyrido[3,2,1‐ij]quinolin‐5‐one showed their promising optical properties such as high fluorescence quantum yields (37–59 %), which was almost independent of the solvent, and high tenability of the absorption band position upon changing the solvent. The benzo[de]pyrido[3,2,1‐ij]quinolinium salt selectively stains nucleic acids (in the nucleus and mitochondria) in eukaryotic cells.     

Recent advances in the synthesis of benzo[b]thiophene fused polycyclic derivatives: Strategies and reactions

Benzo[b]thiophene fused compounds with a unique active heterocyclic skeleton have wide applications in the fields of medicinal chemistry, organic synthesis, and organic functional materials, which resulted in rapid development of many efficient methods for the construction of benzo[b]thiophene-fused heterocycles in recent years. Among these methods, the domino reaction of benzo[b]thiophene derivatives is a practical and powerful synthetic route to access benzo[b]thiophene-fused heterocycles by virtue of the particularity of sulfur atom. This review summarizes the latest developments in the construction of benzo[b]thiophene-fused heterocycles by ring formation at the C2-C3-position of benzo[b]thiophene derivatives in the past decade. Additionally, this review is divided into four parts according to the four kinds of benzo[b]thiophene derivatives used, including thioaurone, thioisatin, substituted benzo[b]thiophene, and azadiene.     

An Efficient Synthesis of Pyrrolo[1,2‐a] or Pyrido[1,2‐a]benzo[4,5]imidazo[1,2‐c]quinazoline Derivatives in Ionic Liquids Catalyzed by Iodine

2‐(1H ‐benzo[d ]imidazol‐2‐yl)anilines reacted with haloketones including 5‐chloropentan‐2‐one and 6‐chlorohexan‐2‐one catalyzed by iodine, giving benzo[4,5]imidazo[1,2‐c ]pyrrolo[1,2‐a ]quinazoline and 6H ‐benzo[4,5]imidazo[1,2‐c ]pyrido[1,2‐a ]quinazoline derivatives, respectively. This domino‐type reaction formed two new heterocycles and three new covalent bonds in one‐pot procedure and provided a green method for the synthesis of fused pentacyclic heterocycles bearing both quinazoline and benzimidazole moieties in ionic liquids.     

Syntheses of thiopyrone and pyrone derivatives by photocyclization reaction of 3‐aryl‐2‐( Benzothien‐3‐yl)propenoic acids

Naphtho[1,2‐b][1]benzothiophene‐6‐carboxylic acids, 6H‐benzo[b]naphtho[2,3‐d]thiopyran‐6‐ones and 6H‐benzo[b]naphtho[2,3‐d]pyran‐6‐ones were synthesized in one step by the photocyclization reaction of 3‐aryl‐2‐([1]benzothien‐3‐yl)propenoic acids. The photocyclization reaction did not occur when the 3‐aryl group contained the electron‐withdrawing nitro group. The assignment of the ¹H and ¹³C nmr spectra of 6H‐benzo[b]naphtho[2,3‐d]thiopyran‐6‐one and 6H‐benzo[b]naphtho[2,3‐d]pyran‐6‐one by two‐dimensional nmr methods is described. The difference between the chemical shift values of H12 for these two compounds is attributed to different molecular geometries.     

A new approach for the synthesis of some pyrazolo[5,1‐c]triazines and pyrazolo[1,5‐a]pyrimidines containing naphtofuran moiety

Naphtho[2,1‐b]furan‐2‐yl)(8‐phenylpyrazolo[5,1‐c][1,2,4]triazin‐3‐yl)methanone, ([1,2,4]triazolo[3,4‐c][1,2,4]triazin‐6‐yl)(naphtho[2,1‐b]furan‐2‐yl)methanone, benzo[4,5]imidazo[2,1‐c][1,2,4]triazin‐3‐yl‐naphtho[2,1‐b]furan‐2‐yl‐methanone, 5‐(naphtho[2,1‐b]furan‐2‐yl)pyrazolo[1,5‐a]pyrimidine, 7‐(naphtho[2,1‐b]furan‐2‐yl)‐[1,2,4]triazolo[4,3‐a]pyrimidine, 2‐naphtho[2,1‐b]furan‐2‐yl‐benzo[4,5]imidazo[1,2‐a]pyrimidine, pyridine, and pyrazole derivatives are synthesized from sodium salt of 5‐hydroxy‐1‐naphtho[2,1‐b]furan‐2‐ylpropenone and various reagents. The newly synthesized compounds were elucidated by elemental analysis, spectral data, chemical transformation, and alternative synthetic route whenever possible. J. Heterocyclic Chem., (2012).     

Synthesis of Benzo[c]thiophene Analogs Containing Benzimidazole,Benzothiazole, and Oxazole

Iodine-mediated cyclization of benzo[c]thiophene aldehyde with 1,2-diphenylamine/2-aminophenylthiol led to the formation of benzimidazole/benzothiazole-incorporated benzo[c]thiophenes. Similarly, reaction of benzo[c]thiophene aldehyde with p-toluenesulfonylmethyl isocyanide (TOSMIC) reagent in the presence of K₂CO₃ as a base furnished oxazole-containing benzo[c]thiophene analogs.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 23 . Naphtho[2′,1′:4,5]thieno‐[2,3‐c]naphtho[2,1‐f]quinoline

A previously unknown heterocyclic ring system, naphtho[2′,1′:4,5]thieno[2,3‐c]naphtho[2,1‐f]quinoline ( 14 ), was synthesized via oxidative photocyclization of 3‐chloro‐N‐(2‐phenanthryl)naphtho[1,2‐b]‐thiophene‐2‐carboxamide ( 9 ). Further elaboration of the lactam 10 yielded the unsubstituted ring system 14 . Structural confirmation of compound 14 was accomplished by a total assignment of its ¹H and ¹³C nmr spectra utilizing the concerted two‐dimensional nmr spectroscopic methods.     

Synthesis of benzo[b]phenanthro[d]thiophenes

The synthesis of benzo[b]phenanthro[1,2-d]thiphene ( 1 ), benzo[b]phenanthro[4,3-d]thiophene ( 2 ), benzo-[b]phenanthro[2,1-d]thiophene ( 3 ) and benzo[b]phenanthro[3,4-d]thiophene ( 4 ) from appropriately substituted olefines by photochemical cyclodehydrogenation is described. The photolysis of olefin 9 gave a mixture of 4 and anthra[1,2-b]benzo[d]thiophene ( 5 ).