Study of plant coumarins 1. Transformations of peucedanin

The structure of 2-bromooreoselon, which was prepared by bromination of peucedanin or oreoselon with molecular bromine, was established. The compositions and structures of the reaction products of this bromide with amines, such as pyridine, triethylamine, and morpholine, as well as with sodium acetate and potassium hydroxide were studied. The reaction of peucedanin with m-chloroperoxybenzoic acid affords peuruthenicin isobutyrate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 362—366, February, 2006.     

Synthesis of brominated 2-(tert-butyl-NNO-azoxy)anilmes

2-(tert-Butyl-NNO-azoxy)aniline was prepared by selective reduction of 2-(tert-butyl-NNO-azoxy)nitrobenzene. Its bromination yielded the correspondingpara-bromo- andortho, para-dibromoanilines (3a,b).meta-Bromoanilines (6a,b) were synthesized by selective replacement of theortho-bromine atoms in ortho,para-bromo(tert-butylazoxy)benzenes (5a,b) by ammonia in toluene under pressure.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1620–1623, September, 1994.This work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 93-03-18461).     

Cu（OTf）2催化苄基卤代物与三丁基烯丙基锡的偶联反应

研究了苄基卤代物与三丁基烯丙基锡的偶联反应,当以10mol%Cu(OTf)2为催化剂,CH2Cl2为溶剂时,1-氯甲基-4-苯基萘与三丁基烯丙基锡于室温反应1h,交叉偶联反应产物1-(3-丁烯基)-4-苯基萘(3b)收率即达93%.结果表明,芳环含供电子基的底物反应活性较高,在室温反应几分钟即可完成,而芳环含吸电子基的底物反应活性低.反应产物3b,1-溴-4-(3-丁烯基)萘(3c)和1-(3-丁烯基)-4-硝基萘(3f)未见报道,且其结构经表征确认.     

An efficient, rapid and regioselective nuclear bromination of aromatics and heteroaromatics with NBS using sulfonic-acid-functionalized silica as a heterogeneous recyclable catalyst

A simple, efficient and rapid method has been developed for high-yielding regioselective nuclear monobromination of aromatic and heteroaromatic compounds using NBS in the presence of sulfonic-acid-functionalized silica at room temperature. The catalyst works under heterogeneous conditions and can be recycled.     

铜三氟柳配合物的合成,结构和仿生催化溴化

合成了一系列2-羟基-4-三氟甲基苯甲酸（h₂tba）-铜配合物：[Cu（htba）₂（pz）₂]（1）,[Cu（htba）（2,2''-bipy）]（htba）（2）和[Cu（htba）₂（4,4''-bipy）]（3）（h₂tba=2-羟基-4-三氟甲基苯甲酸,pz=吡唑,2,2''-bipy=2,2''-联吡啶,4,4''-bipy=4,4''-联吡啶）,并且通过元素分析、红外光谱、紫外光谱、粉末X射线衍射、单晶X射线衍射和热重分析方法对配合物结构进行了表征。这些配合物能够在过氧化氢和溴化物存在的条件下催化苯酚红溴化,并且展示出了较高的催化溴化活性。     

Improved Synthesis of 1-Bromo-3-buten-2-one

A convenient procedure for the synthesis of 1-bromo-3-buten-2-one, 4, from commercially available 2-ethyl-2-methyl-1,3-dioxolane, 1, is described. The procedure involves three reaction steps: (1) The acetal 1 is converted to 2-(1-bromoethyl)-2-bromomethyl-1,3-dioxolane, 2, by reacting 1 with elemental bromine in dichloromethane to yield 98% of 2. (2) Dehydrobromination of 2 with potassium tert-butoxide in tetrahydrofuran gives 2-bromomethyl-2-vinyl-1,3-dioxolane, 3, in 84–93% yield. (3) Removal of the acetal protection from 3 by formolysis for 6–10 h afforded 1-bromo-3-buten-2-one, 4, in 85–94% yield. A more rapid method is acid hydrolysis of 3 under microwave activation (100 °C, 8–10 min), by which 4 was obtained in 75% yield. Full experimental details are given.

Catalytic Asymmetric Bromination of Unfunctionalized Olefins with H2O as a Nucleophile

The dimeric cinchona alkaloid (DHQD)₂PHAL is used to catalyze an effective asymmetric bromohydroxylation of unfunctionalized olefins with H₂O as nucleophile an N‐bromobenzamide as a bromine source. A variety of optically active bromohydrins are formed with up to 88 % ee.     

4-hydroxy-2-quinolones. 110. Bromination of 1-r-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid anilides

1-R-4-Hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid anilides have been prepared. It has been shown experimentally that these compounds are brominated by molecular bromine in glacial acetic acid at position 4 of the anilide fragment. The antitubercular properties of the compounds synthesized are discussed. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1508–1516, October, 2006.     

Peripheral Hexabromination,Hexaphenylation, and Hexaethynylation of meso‐Aryl‐Substituted Subporphyrins

Effective peripheral fabrication methods of meso‐aryl‐substituted subporphyrins were explored for the first time. Hexabrominated subporphyrins 2 were prepared quantitatively from the bromination of subporphyrins 1 with bromine. Hexaphenylated subporphyrins 3 and hexaethynylated subporphyrins 4 and 5 were synthesized by Suzuki–Miyaura coupling and Stille coupling, respectively, in good yields. X‐ray crystal structures of 2 b , 3 b , 4 b , and 5 a revealed preservation of the bowl‐shaped bent structures with bowl depths similar to that of 1 . Hexaethynylated subporphyrins exhibit large two‐photon‐absorption cross‐sections due to effective delocalization of the conjugated network to the ethynyl substituents.