水介质中2-氨基-4-芳基-7,7-二甲基-5-氧代-4H-5,6,7,8-四氢苯并[b]吡喃-3-羧酸酯的有效合成

水介质中在三乙基苄基氯化铵(TEBA)存在下, 芳亚甲基氰乙酸酯与5,5-二甲基-1,3-环己二酮反应为2-氨基-4-芳基-7,7-二甲基-5-氧代-4H-5,6,7,8-四氢苯并[b]吡喃-3-羧酸酯提供了一种快速、方便、高效和洁净的合成方法. 产物的结构通过红外光谱、核磁共振氢谱、元素分析和单晶X射线衍射确定.     

Palladium-Catalyzed N-Arylation of 3-Functionalized 2-Amino-4,5-dimethylpyrroles

A versatile class of 2-aminopyrroles containing various electron-withdrawing substituents at the 3-position have been N-arylated on the amine using a palladium-catalyzed cross-coupling reaction. Using this methodology, a pyrimidone-based tricyclic system has been prepared in just one step from a starting 2-aminopyrrole.

Copper-Catalyzed Amination of Aryl Halides with Aqueous Ammonia under Mild Conditions

A Cu(I) generated in situ from CuSO₄·5H₂O/sodium ascorbate catalyzed cross‐coupling reaction of aryl halides with aqueous ammonia for the synthesis of primary aromatic amines has been developed. Key to the success included the application of aqueous ammonia under a homogeneous condition.     

The Synthesis of 2-(Arylthio)arylcyanamides via Copper-Catalyzed Domino Intermolecular C-S Cross-Coupling Reaction of 2-Aminobenzothiazoles with Aryl Iodides

Abstract

A series of 2-(arylthio)arylcyanamide derivatives were obtained in excellent yields via a copper-catalyzed domino C–S cross-coupling of 2-aminobenzothiazoles with aryl iodides. This reaction occurred via an intermolecular C–S bond formation, associated with C–S bond cleavage, followed by an intermolecular S-arylation under ligand-free conditions. Their structures were unambiguously determined by the analytic tools, such as HRMS, ¹H, and ¹³C NMR analysis.     

3-(2-苯并呋喃酰基)薁-1-羧酸甲酯的有效合成

以苯基三甲铵三溴盐(PTAB)为溴化试剂, 对3-乙酰基薁-1-羧酸甲酯进行了溴代反应研究, 将其单溴代产物与水杨醛在温和反应条件下进行缩合, 以极优的收率高选择性得到3-(2-苯并[b]呋喃酰基)薁-1-羧酸甲酯类衍生物, 其结构经¹H NMR, IR及元素分析等得以证实.     

微波辐射下"一锅煮"法合成2-氨基-3-氰基-4-芳基-4H,5H-吡喃-[3,2-c]苯并吡喃-5-酮

以芳醛、4-羟基香豆素、丙二腈为原料,乙醇为能量转移剂,哌啶为催化剂,在微波辐射下一步合成了一系列2-氨基-3-氰基-4-芳基-4H,5H-吡喃-[3,2-c]苯并吡喃-5-酮,反应在40～60s时间内完成,产率60%～97%.     

Photochemical Synthesis of 3, 4-Annulated Tetrahydrothiophenes

Abstract

Irradiation of 2(5H)-thiophenones 4 in either methanol containing 1, 4-pentadiene or in allyl alcohol affords as major products the cis-fused 3, 4-annulated tetrahydrothiophenes 10 and 12, respectively.     

苯并噻吩类稠环化合物的合成及其在有机场效应晶体管中研究的进展

总结了苯并噻吩类稠环化合物半导体材料的最新研究进展,对其合成方法及结构与性能进行了归纳,介绍了它们在有机场效应晶体管中的应用,并对其研究和应用前景进行了展望。     

Reaction of 3-Cyano-2-diazo-4,5,6,7-tetrahydrobenzo[ b ]thiophene with 3-Imino-butyronitrile: Synthesis of Pyridazines,Thiophenes and Their Fused Derivatives

The reaction of the 3-cyano-2-diazo-4,5,6,7-tetrahydrobenzo[ b ]thiophene 1 with 3-imino-butyronitrile 2 gave the azo derivative ( 3 ). The reactivity of the latter product toward different reagents was studied to give fused derivatives with potential biological activities.     

一株红球菌脱硫菌株脱硫特性的研究

从炼油厂污水排放口取得的土样中筛选到一株能降解二苯并噻吩 (DBT)的菌株 ,用GC/MS方法 ,证明其降解DBT走硫专一脱除途径 ,即“4S途径” .该菌株被命名为SDUZAWQ ,用微生物生理生化实验及 16SrDNA序列分析初步鉴定为红球菌属 (Rhodococcussp .) .实验结果表明 ,红球菌SDUZAWQ可有效降解苯并噻吩 (BT)和DBT及其甲基衍生物 .在 2d内 ,BT与DBT可同时完全降解 ,0 .5mmol·L-1的BT在 1d内可降解掉 86% ,降解速度高于DBT的降解 .5 MBT的降解率也高于 4,6 DMDBT和 4 MDBT .4 MDBT较 4,6 DMDBT更难降解 ,在 2d内 ,红球菌SDUZAWQ可降解 62 %的 4,6 DMDBT ,而相同条件下 ,4 MDBT仅能被降解 3 6% .     

Susceptibility of Methyl 3-Amino-1H-pyrazole-5-carboxylate to Acylation

In the search for a new method of synthesis of hybrid peptides with aminopyrazole carboxylic acid, we tried to force selective acylation at the aromatic amino group instead of at the ring nitrogen atom with fairly gentle acylating agents. The acylating agents used were acid anhydrides: acetic anhydride, tert-butyl pyrocarbonate, and 2-(2-methoxyethoxy)ethoxyacetic acid/dicyclohexylcarbodiimide. We succceded in acylation at this amino group with almost none at the ring nitrogen atom. Sometimes, however, acylation in small quantities at the ring nitrogen atom was observed as a by-product. To remove this by-product, imidazole was used. Thus, we were able to obtain the hybrid peptides in question with no protection and subsequent removal required. We synthesized a few these free peptides with no protection of the pyrazole ring. This is a simpler method than that being used currently.     

Simple Access to 2-Arylbenzo[b]tellurophenes

Arguably, the simplest way for the preparation of benzo[b]tellurophenes has been elaborated. Cyclization of o-haloarylalkynes in the presence of Te-NaOH-DMSO triad occurs by simple mixing of starting materials and heating overnight without the need for dry and inert atmosphere and provides the corresponding benzo[b]tellurophenes in up to 90 % GC-yield. Catalytic telluration of aryl iodide substrates extends the applicability of the developed cyclization cascade to substrates that are not suitable for the direct S_NAr/5-endo-dig cyclization approach. Successful S_EAr in the third position of benzo[b]tellurophene provides a synthetic intermediate for the preparation of Te analogues of selective estrogen receptor modulator (SERM) raloxifene.     

Synthesis,Reactions, and Characterization of 6-Amino-4-(Benzo[b]Thiophen-2-YL)-2-Thioxo-1, 2-Dihydropyridine-3, 5-Dicarbonitrile

Abstract

Benzothiophene -2- carbaldehyde 1 reacted with 2-cyanoethanethioamide 2 in 1:2 molar ratios to give the corresponding 6-amino-4-(benzo[b]thiophen-2-yl)-2-thioxo-1, 2-dihydropyridine-3,5-dicarbonitrile 6. The synthetic potentiality of compound 6 was investigated via its reaction with active halogen-containing reagents to afford the corresponding thieno[2,3-b]pyridine derivatives 11a,b, 14, 16, and 19. Also, compound 6 reacted with hydrazine hydrate to give the pyrazolo[3,4-b]pyridine derivative 21. Compound 21 condensed with 4-(2-thienyl)benzaldehyde to afford pyrazolo[3,4-b]pyridine derivative 23. Structural elucidation of all the newly synthesized heterocyclic compounds was based on elemental analyses, IR, ¹H NMR, and mass spectra.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

金催化的炔烃羟基化反应: 合成2取代苯并呋喃化合物

本文报道了一种以邻炔基苯酚为原料,通过金催化的炔烃羟基化反应合成2取代苯并呋喃的方法. 该方法可以在温和的条件下快速以高产率得到各种2取代苯并呋喃. 关键前体邻炔基苯酚可以很容易由Sonogashira 反应制备.     

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.     

Water-Mediated Selective Synthesis of Pyrazolo[1,5-a]quinazolin-5(4H)-ones and [1,2,4]Triazolo[1,5-a]quinazolin-5(4H)-one via Copper-Catalyzed Cascade Reactions

A convenient and sustainable synthesis of pyrazolo[1,5-a]quinazolin-5(4H)-ones and [1,2,4]triazolo[1,5-a]quinazolin-5(4H)-one through copper-catalyzed cascade reactions of 2-bromobenzoates with 1H-pyrazol-5-amines or 1H-1,2,4-triazol-5-amine under ligand-free conditions in water is presented. It is notable that aqueous medium turned out to be crucial for the chemoselective formation of the title compounds. Compared with literature protocols, this new method showed advantages such as simple and sustainable procedure, commercially available starting materials, and convenient reuse of the reaction medium together with the copper catalyst.     

2-(2,6-二烷氧基苯基)苯并呋喃衍生物的合成

以焦性没食子酸、4-羟基苯甲醛和酚为原料, 以邻碘代苯酚与苯乙炔衍生物的Sonogashira偶联及其连串化反应生成苯并呋喃环为关键步骤, 设计合成了一系列2-(2 ,6 -二烷氧基苯基)苯并呋喃衍生物, 并对产物进行了¹H NMR, ¹³C NMR, MS等表征.     

基于苯并[b]萘并[1,2-d]噻吩的可见光驱动光环化荧光turn-on型二芳基乙烯的合成与性能研究

可见光驱动光环化的荧光turn-on型二芳基乙烯分子开关是超分辨显微成像的理想材料, 但目前关于该类型分子的报道仍较少. 本工作合成了一种基于苯并[b]萘并[1,2-d]噻吩(BNTP)的405 nm可见光驱动光环化的荧光turn-on型二芳基乙烯分子BNTP-BTTO4, 同时系统研究了该分子的光物理性能与稳定性, 并借助密度泛函理论(DFT)计算厘清了分子实现可见光驱动光环化及荧光turn-on原因. 另外, 本研究发现BNTP引入后分子表现出比参比分子Ph-BTTO4更优异的抗疲劳性、热稳定性和光稳定性, 尤其是在历经200 min 405 nm可见光照射后, BNTP-BTTO4(c)吸收强度只下降4%, 光稳定性大幅提升. 本研究为设计开发性能优异的可见光驱动光环化的荧光turn-on型二芳基乙烯提供了新的思路.     

2-氨基-3-氰基-7,7-二甲基-4-苯基-5-氧代-5,6,7,8-四氢-4H-苯并吡喃的合成和晶体结构

标题化合物C18H18N2O2是由亚苄基丙二睛和5,5-二甲基-1,3-环己酮在乙二醇中反应2小时得到,结构通过单晶X-射线衍射法确定,其晶体属单斜晶系,空间群P21/c,Mr=294.34,a = 11.3070(1), b= 9.4750(1),c = 14.919(2) ,β= 99.34(1)埃琕 = 1577.1(3) 3,Z = 4,Dc=1.240Mgm-3,μ=0.082mm-1,F(000)=624, 最终的偏离因子为R=0.0381,wR=0.0961,在分子结构中存在3个环:苯环(A)、吡喃环(B)及与吡喃环稠合的六员环(C)。A与B、A与C及B与C之间的两面角分别为 92.5°、85.7°和8.2°。