The synthesis of polycyclic thiophenes derived from phenanthrene intermediates

The synthesis of benzo[b]triphenyleno[2,1-d]thiophene ( 9 ), benzo[b]triphenyleno[1,2-d]thiophene ( 13 ), 5-methylbenz[7,8]anthra[2,1-b]thiophene ( 17 ), l-methylchryseno[3,4-b]thiophene ( 18 ), triphenyleno[1,2-c]dibenzothiophene ( 22 ), triphenyleno[2,1-a]dibenzothiophene ( 26 ), triphenyleno[1,2-a]dibenzothiophene ( 29 ), and triphenyleno[2,1-b]dibenzothiophene ( 30 ) is described.     

两种非对称芳基二噻吩并[2,3-b:3',2'-d]噻吩的合成与光谱特性

合成了两种非对称芳基取代的并三噻吩化合物.以2-溴-5-三甲基硅-二噻吩并[2,3-b:3',2'-d]噻吩为原料,经脱除四甲基硅烷(TMS)和Suzuki偶联两步反应制备了2-噻吩基二噻吩并[2,3-b:3',2'-d]噻吩,总产率为67.4%;以2-苯基二噻吩并[2,3-b:3',2'-d]噻吩为原料,经N-溴代琥...     

Synthesis and spectral analysis of 8-substituted dinaphtho [2,1-d:1′,2′-g] [1,3,6,2]dioxathiaphosphocin 8-oxides

Synthesis and spectral analysis of several 8-substituted dinaphtho[2,1-d:1′,2′-g][1,3,6,2]dioxathiaphosphocin 8-oxides have been described. An X-ray crystallographic study of 8-(2′,3′- dimethylphenoxy)dinaphtho[2,1 - d:1′,2′-g][1,3,6,2]dioxathiaphosphocin 8-oxide has indicated that, in the solid state, the dioxathiaphosphocin ring is in a distorted-boat–like conformation with the P = O group and bridged S atom directed away from each other. Electron impact mass spectra showed M⁺ and (M–OR)⁺ ions, containing the dioxathiaphosphocin ring system, confirming the structures of the esters. © 1995 John Wiley & Sons, Inc.     

二氰基乙烯基并三噻吩的光谱行为

本文设计合成了两种二氰基乙烯基并三噻吩化合物,即2-二氰基乙烯基二噻吩并[3,2-b:2’,3-’d]噻吩(DCTT)与2-二氰基乙烯基二噻吩并[2,3-b:3’,2-’d]噻吩(DCST).研究了介质极性对吸收与发射光谱行为的影响,考察了化合物的分子结构与其发光能力的关系.溶剂效应显示化合物DCST随介质的极性增加,分子内电荷转移态(ICT)的荧光发射峰位红移现象更为明显,展示出较大的Stokes位移.化合物DCTT随介质的极性增加,发光行为表现出负的溶致变色效应,与"能级邻近效应"有关.溶剂效应说明了DCTT分子中并三噻吩部分给出电子的能力较弱,而DCST分子中的并三噻吩部分给出电子的能力较强,是导致二者ICT态的发光能力的差异的主要原因.     

并三噻吩及其三种衍生物电子光谱的密度泛函理论研究

采用B3LYP/6-31G(d,p)方法优化得到了并三噻吩(DTT)及其三种衍生物苯基并三噻吩(PDTT)、萘基并三噻吩(TDTT)和噻吩基并三噻吩(NDTT)基态(S0)的稳定几何构型,并通过频率分析加以验证.在TD-B3LYP/cc-pVTZ水平下,计算了它们的电子吸收光谱,计算值与实验值符合得很好.计算结果表明:它们的吸收波长顺序为λNDTTλTDTTλPDTTλDTT.采用TD-B3LYP/6-31G(d,p)方法,优化得到了TDTT和NDTT第一激发态(S1)的几何结构,并在TD-B3LYP/cc-pVTZ水平下计算了它们的发射光谱.     

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.     

Synthesis of Unsymmetric Monosubstituted and Disubstituted Dinaphthothiophenes

Dinaphthothiophenes (DNTs) are a class of compounds with potential uses in organic semiconductors and the synthesis of unsymmetric catalysts. Symmetrical or asymmetrical addition of functional groups to the DNT structure may be desired for steric bulk in binaphthyl catalyst synthesis or tuning the electronic properties of semiconductors. Thus, versatility of functional group addition is a great asset in DNT synthesis. Until now, no versatile and concise methods for the synthesis of unsymmetrically substituted DNTs have been reported. Herein, we report three synthetic routes for the creation of three different classes of DNTs. Each route involves the successive addition of two functionalized styryl groups to a thiophene ring, followed by a photocyclization to form the desired asymmetric DNT. Various novel unsymmetrically monosubstituted and disubstituted dinaphtho[2,1‐b :1′,2′‐d ]thiophenes, dinaphtho[1,2‐b :1′,2′‐d ]thiophenes, and dinaphtho[1,2‐b :2′,1′‐d ]thiophenes were synthesized from 2‐bromothiophene,2,4‐dibromothiophene, and 3,4‐dibromothiophene in three or four steps. These methods can be used to synthesize a wide variety of unsymmetrically functionalized DNTs.     

A new method for the synthesis of dinaphtho[1,2‐b;2′,1′‐d]thiophenes and selenophenes

Naphthalene‐1‐sulfonic acid dimethylamides were treated with n‐BuLi and elemental sulfur or selenium to afford dinaphtho[1,2‐b:2′,1′‐d]thiophenes and selenophenes, respectively. This is the first example of making two C S/Se bonds and a C C bond in a single step at room temperature and also demonstrates a useful method for the synthesis of both thiophenes and selenophenes on naphthalene. In the case of the reactions of elemental selenium, diselenides were also obtained along with dinaphtho[1,2‐b:2′,1′‐d]selenophenes. The structure of dinaphtho[1,2‐b:′,1′‐d]thiophene was characterized by X‐ray crystallography as a representative molecule. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:239–248, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20291     

Donor-acceptor copolymers from cyclopentannulation polymerizations with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm] perylene acceptors

A series of donor-acceptor copolymers with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm]perylene acceptor units was prepared via palladium catalyzed cyclopenta-annulation reactions. The acceptor units were paired with diethynyl containing donor groups based on benzo[1,2-b:4,5-b’]dithiophene, thieno[3,2-b]thiophene, and 4-octyl-4H-dithieno[3,2-b:2′,3′-d]pyrrole to create six polymer variants. The cyclopentannulation polymerization resulted in copolymers with molecular weights (Mn) of 6–14 kDa and broad light absorption in the visible region with band gaps of 1.38–1.85 eV. The synthetic methodology, as well as optoelectronic properties, including thin-film absorption and cyclic voltammetry, of the donor-acceptor copolymers are presented.     

Electrophilic chemistry of thia-PAHs: stable carbocations (NMR and DFT), S-alkylated onium salts, model electrophilic substitutions (nitration and bromination), and mutagenicity assay

First examples of stable carbocations are reported from several classes of thia-PAHs with four fused rings, namely, benzo[b]naphtho[2,1-d]thiophene (1) and its 3-methoxy derivative (2), phenanthro[4,3-b]thiophene (3) and its 7-methoxy (4), 10-methoxy (5), and 9-methoxy (6) derivatives, phenanthro[3,4-b]thiophene (7) and its 7-methoxy (8) and 9-methoxy (9) derivatives, and 3-methoxybenzo[b]naphtha[1,2-d]thiophene (11). In several cases, the resulting carbocations were also studied by GIAO-DFT. Charge delocalization modes in the resulting carbocations were probed. A series of S-alkylated onium tetrafluoroborates, namely, 1Me+, 1Et+, 2Et+, and 7Me+ (from 1, 2, and 7), 10Me+ and 10Et+ (from benzo[b]naphtha[1,2-d]thiophene 10), 12Me+ and 12Et+ (from phenanthro[3,2-b][1]benzothiophene 12), 13Me+ (from 3-methoxyphenanthro[3,2-b]benzothiophene 13), 14Me+ (from phenanthro[4,3-b][1]benzothiophene 14), and 15Me+ (from 3-methoxyphenanthro[4,3-b][1]benzothiophene 15), were synthesized. PAH-sulfonium salts 1Me+, 1Et+, 10Me+, 10Et+, 12Me+, and 14Me+ proved to be efficient akylating agents toward model nitrogen nucleophile receptors (imidazole and azaindole). Facile transalkylation to model nucleophiles (including guanine) is also supported by favorable reaction energies computed by DFT. Ring opening energies in thia-PAH-epoxides from 1, 3, and 7 and charge delocalization modes in the resulting carbocations were also evaluated. The four-ring-fused thia-PAHs 1, 2, 3, 4, 5, 7, 8, and 11 are effectively nitrated under extremely mild conditions. Nitration regioselectivity corresponds closely to protonation under stable ion conditions. Bromination of 4 and 6 is also reported. Comparative mutagenicity assays (Ames test) were performed on 1 versus 1NO2, 5 versus 5NO2, and 11 versus 11NO2. Compound 5NO2 was found to be a potent direct acting mutagen.     

A CONVENIENT SYNTHESIS OF NEW PYRIDOTHIENOPYRIMIDIN-4 (3H) ONES AND PYRIDOTHIENOPYRIMIDIN-2, 4(1H, 3H) DIONES

New derivatives of 2-substituted pyrido[3′,2′:4,5]thieno[3,2-d]pyri-midin-4(3H) ones and 3-substituted pyrido[3′,2′:4,5]thieno[3,2-d]pyri-midin-2,4(1H,3H) diones have been prepared by base catalyzed cyclocondensation of ethyl-3-aminothieno[3,2-b]pyridine-2-carboxylate with aryl nitriles and aryl- or alkyl isocyanates respectively.     

Syntheses of dibenzo[c,e][1,2]diselenin and related novel chalcogenide heterocyclic compounds

Reaction of 2,2′-dilithio-1,1′-binaphthyl with selenium followed by air oxidation gives a mixture of dinaph-thoselenophene and dimer and oligomers of 2,2′-diseleno-1,1′-binaphthyl. 2,2′-Dilithio-1,1′-biphenyl reacts with selenium to afford dibenzo[c,e][1,2]diselenin. Structures of the dimeric 2,2′-diseleno-1,1′-binaphthyl and dibenzo[c,e][1,2]diselenin have been confirmed by X-ray crystallographic analyses. Similar reaction of 2,2′-dilithio-1,1′-binaphthyl with sulfur or tellurium gives a mixture of dinaphthothiophene and dinaphtho[2,1-c:-1′,2′-e][1,2]dithiin or a mixture of dinaphthotellurophene and oligomer of 2,2′-ditelluro-1,1′-binaphthyl, respectively. Dibenzotellurophene and oligomer of 2,2′-ditelluro-1,1′-biphenyl are obtained from reaction of 2,2′-dilithio-1,1′-biphenyl with tellurium.     

Cyclic isothioureido compounds. II. Reaction of trans-3a,4,5,9b-tetrahydronaphth[1,2-d]-imidazoline-2-thiones with α-bromoketones

The reaction of trans-3a,4,5,9b-tetrahydronaphth[1,2-d]imidazoline-2-thiones ( 8 ) with α-bromoketones gave, depending upon the structure of the α-bromoketones, reaction solvent and reaction temperature, the hydrobromides of tetrahydronaphth[1,2-d]imidazolin-2-ylthiomethyl ketone ( 10 ), hexahydro-8-hydroxynaphth[1′,2′:4,5]imidazo[2,1-b]thiazoles ( 5, 11, 19 and 20 ) or tetrahydronaphth[1′,2′:4,5]imidazo[2,1-b]-thiazoles ( 12 and 16 ). Structural determinations based on ir and nmr spectroscopies are discussed.     

Thermolyzed products of naphth[1,2-d]imidazo[2,1-b]-thiazole-2,3-dione

Themolysis of naphth[1,2-d]imidazo[2,1-b]thiazole-2,3-dione ( 1 ) in dimethylformamide gave an intermediate 2-isocyanatonaphtho[1,2-d]thiazole ( 2 ), which underwent [4 + 4] cyclodimerization to yield dinaphtho-[1″,2″:4,5;1′″,2′″:4′,5′]dithiazolo[3,2-a:3′,2′-e]-1,3,5,7-tetrazocine-9,19-dione ( 3 ). The possible [4 + 2] cycloadduct, 3-(2-naphtho-[1,2-d]-thiazolyl)naphtho[1′,2′:4,5]thiazolo[3,2-a]-1,3,5-triazine-2,4-dione ( 4 ), an usual dimer type of heterocyclic isocyanates was not produced. Discrimination between the two isomers was established on the basis of spectral analyses.     

Action of 1,2-diamines and o-aminophenols on 1-alkyl-3-carboxyindole-2-acetic acid anhydrides. Preparation of new ring systems

1-Alkyl-3-carboxyindole-2-acetic acid anhydrides (I) react with ethylenediamine and with o-phenylenediamine to give directly 10-alkylimidazo[3,2:1′,2′]pyrido[4,5-b]indol-5(1H)-ones (II) and 5,6-dihydro-5-alkyl-13H-indolo[2′,3′:4,5]pyrido[1,2-a]benzimidazol-13-one (V), respectively. However, anhydrides I react with o-aminophenol and with o-aminothiophenol to give carboxyindole-acetanilide derivatives IX, which can be cyclised to indolo[2′,3′:4,5]pyrido[2,1-b]benzoxazolone and indolo[2′,3′:4,5]pyrido[2,1-b]benzthiazolone (XI). Some derivatives of II and V were prepared to help in elucidating the structures.     

Reaction of zinc enolates prepared from 2,2-dibromoindan-1-one or 2,2-dibromo-1-tetralone and zinc with 2-oxochromen-3-carboxylic acid derivatives

Zinc enolates obtained from 2,2-dibromonidan-1-one or 2,2-dibromo-1-tetralone and zinc reacted with alkyl esters and amides of 2-oxochromen-3-carboxylic acid giving the corresponding derivatives of 2,1′-dioxo-spiro(1a,7b-dihydrocyclopropa[c]chromen-1,2′-indan)-or 1′,2′,3′,4′-tetrahydro-2,1′-dioxospiro(1a,7b-dihydrocyclopropa[c]chromen-1,2′-naphthalene)-1a-carboxylic acids prevailingly in the form of a single geometric isomer.     

Three-Component Spiro Heterocyclization of Pyrrolediones,Indane-1,3-dione,and Heterocyclic Enamines

Russian Journal of Organic Chemistry - 3-Methyl-2′,5-dioxo-5′-phenyl-1′,2′,5,10-tetrahydrospiro(indeno[1,2-b]isoxazolo[4,3-e]pyridine-4,3′-pyrroles) and...     

SYNTHESIS AND CHEMISTRY OF SOME NEW 2-MERCAPTOIMIDAZOLE DERIVATIVES OF POSSIBLE ANTIMICROBIAL ACTIVITY

4,5-Diaryl-2,3-dihydro-2-mercaptoimidazoles (2a–e) were synthesized. They reacted with chloroacetic acid in gl. acetic acid/Ac ₂ O in presence of anhyd. sodium acetate afforded 5,6-diaryl-2,3-dihydro-imidazo[2,1-b]thiazol-3-ones (3a–d). Also these compounds were prepared by the action of chloroacetyl chloride on compounds (2) in pyridine. Compounds (3a–d) on condensation with aromatic aldehydes yield 2-arylmethylene-5,6-diaryl-2,3-dihydroimidazo[2,1-b]-thiazol-3-ones (4a–q). The latter compounds were prepared directly by the reaction of (2) with chloroacetic acid and the aromatic aldehydes. Compounds (3a–d) coupled with aryldiazonium salts in pyridine to give 2-arylhydrazono-5,6-diaryl-2,3-dihydroimidazo[2,1-b]thiazol-3-ones (5a–r). Also compounds (2) when reacted with 2 or 3-bromopropionic acid afford 2,3-di-hydro-5,6-diaryl-2-methylimidazo[2,1-b]thiazol-3-ones (6a–d) and 2,3-di-hydro-6,7-diaryl imidazo-[2,1-b]-1,3-thiazin-4-ones (7a–d), respectively. Compounds (3, 6, and 7) have been cleaved by aromatic amines to give the corresponding 2-(4′,5′-diaryl-2′,3′-dihydroimidazol-2′-yl)thioacetanilide (8a–f), 2-(2′,3′-dihydro-4′,5′-diaryl imidazol-2′-yl)thiopropionamide (9a–c), and 3-(2′,3′-dihydro-4′,5′-diaryl-imidazol-2′-yl)thiopropionamide (10a–d) respectively. All the prepared compounds show considerable antimicrobial activity against bacteria, yeast, and fungi.     

Benzofurano derivatives of coumarins as possible antifertility agents

Synthesis and medicinal importance of 4-methyl-6-nitro-8,9,10,11-tetrahydro-2H-benzofuro[2,3-b]-1-benzo-pyran-2-one (I), 4-ethyl-11-nitro-6,7,8,9-tetrahydro-2H-benzofuro[3,2-g]-1-benzopyran-2-one (II), and 6,7-di-hydro-4,13-dimethylbis-1-benzopyrano[6,7-d:7′,6′-d']-2H,11H-benzo[1,2-b:3,4-b']difuran-2,11-dione (III) is presented. The structures of these compounds were confirmed by elemental analysis and spectral studies.     

Nickel-catalyzed asymmetric grignard cross-coupling of dinaphthothiophene giving axially chiral 1,1'-binaphthyls

Asymmetric cross-coupling of dinaphtho[2,1-b:1',2'-d]thiophene with ArMgBr (Ar = Ph, 4-MeC6H4, 4-MeOC6H4) proceeded with high enantioselectivity in THF at 20 degrees C in the presence of 3 mol % of a nickel catalyst generated from Ni(cod)2 and a chiral oxazoline-phosphine ligand to give high yields of axially chiral 2-mercapto-2'-aryl-1,1'-binaphthyls, whose enantiomeric excesses are over 93%. The mercapto group in the chiral binaphthyl was converted into iodo, boryl, and phosphino groups without racemization.