1-苯基-2-丙酮的合成新方法

以苯胺为原料,经重氮化反应和改进的Meerwein芳基化反应合成了1-苯基-2-丙酮(2)。优化的Meer-wein芳基化反应条件为:醋酸异丙烯酯为溶剂,氧化亚铜为催化剂,n(氟硼酸重氮盐)∶n(氧化亚铜)=10∶1,反应温度35℃~40℃,反应时间6 h。在优化反应条件下,2的收率达91%。     

1,3-二芳基-1丙酮类化合物的合成

以取代苯乙酮和取代芳香醛为原料,制得一系列1,3-二芳基-1-氧代丙烯类化合物(1a~1j); 1a~1j和对甲苯磺酰肼(2)经还原反应合成了10个1,3-二苯基-1-丙酮类化合物(3a~3j, 3h为新化合物),其结构经¹H NMR, ¹³C NMR, IR和HR-MS（ESI）确证。研究了碱、溶剂、温度和投料比γ[n(1a)/n(2)/n(碱)]对3a产率的影响。结果表明：γ=1/2/2,磷酸钾为碱,乙醇为溶剂,于80 ℃反应4 h, 3a产率最高（80%）。     

芳基丙酮酸的合成

本文报道用Meerwein芳基化反应由2-取代丙烯酸合成芳基丙酮酸的方法。     

2-芳基-2-吗啉醇的合成

醇胺分别与2-溴-4′-甲氧基苯乙酮、2-溴-3′-氯苯丙酮、2-溴-4′-苄氧基苯基丙酮、2-溴-4′-苄氧基苯戊酮、6-甲氧基-2-溴乙酰基萘和6-甲氧基-2-(2-溴丙酰基)萘反应,合成相应的2-芳基-2-吗啉醇(产率80.7%～97.5%)及其盐酸盐.其结构经1H NMR,IR,MS确证.     

5-芳基-1,3,4-噻二唑-2-胺衍生物的合成

在冰醋酸催化下,芳香醛(2a～2g)分别和氨基硫脲(3)反应合成得到芳亚胺基硫脲衍生物(4a～4g),中间体4无需经柱层析纯化,然后在三氯化铁作用下反应关环,得到7个目标化合物5-芳基-1,3,4-噻二唑-2-胺(1a～1g).产物结构经1 H NMR、13 C NMR和ESI-MS确证.然后分别以中间体(E)-2-苄...     

盐酸2-芳基-3,5,5-三甲基-2-吗啉醇的合成

盐酸2-芳基-3; 5; 5-三甲基-2-吗啉醇的合成;盐酸芳基三甲基吗啉醇; 胺化; 合成     

铑(I)催化的不对称硅氢化反应合成手性2-氨基-1-芳基乙醇研究

报道了以Rh()-手性2-(2-吡啶基)-4-羧甲基-1,3-噻唑烷为催化剂,2-氨基芳香酮的不对称硅氢化反应,在常温常压下手性2-氨基-1-芳基乙醇的产率几乎可达定量,产品光学纯度可达80%e.e以上.     

2,5-二甲基-3,4-二乙酰基-1-芳基吡咯的合成

多取代吡咯;二乙酰基己二酮;取代苯胺;2;5-二甲基-3;4-二乙酰基-1-芳基吡咯的合成     

铑(Ⅰ)催化的不对称硅氢化反应合成手性2-氨基-1-芳基乙醇研究

报道了以Rh(I)－手性2－（2－吡啶基）－4－羧甲基－1，3－噻唑烷为催化剂，2－氨基芳香酮的不对称硅氢化反应，在常温常压下手性2－氨基－1－芳基乙醇的产率几乎可达定量，产品光学纯度可达80％e.e以上。     

2-[1-芳酰基-1-(芳基偶氮) 亚甲基] 苯并噻唑啉的合成

本实验通过2-(1-芳甲酰基亚甲基)苯并噻唑啉和芳基重氮盐反应, 高产率地制得一系列2-[1-芳酰基-1-(芳基偶氮)亚甲基]苯并噻唑啉。     

Synthesis of 1-aryl-2-propanones

A new convenient synthesis of a series of 1-aryl-2-propanones using aromatic amines as precursors, via diazo-reaction and improved Meerwein arylation reaction under mild conditions, was achieved. In addition, 1-[3,5-bis(trifluoromethyl)phenyl]-2-propanone is a new compound among the synthesized compounds. This approach is an efficient synthetic method for the aryl-propanones with different substituting groups. __________ Translated from Chinese Journal of Organic Chemistry, 2007, 27(10): 1244–1249 [译自: 有机化学]     

Synthesis and reactions of 5-aryl-2-thiophenecarbaldehydes

The reaction of 2-thiophenecarbaldehyde with arene diazonium chlorides in the presence of CuCl₂ catalyst gave 5-aryl-2-thiophenecarbaldehydes. Use of 4-nitrobenzene diazonium chloride in the reaction also gave the isomeric 3-(4-nitrophenyl)-2-thiophenecarbaldehyde. Condensation products of the 5-aryl-2-thiophenecarbaldehydes with cyanoacetic acid esters, cyanoacetamide, and with barbituric and dimethylbarbituric acids were prepared. Communication 16 in the series “Synthesis of heterocycles based on the products of arylation of unsaturated compounds”. For Communication 15 see [1]. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1166–1171, August, 2008.     

Facile Synthesis of 1‐Aryl‐2‐propanones from Aromatic Amine

A facile synthesis of aryl propanones using aromatic amines as precursors, via an improved Meerwein arylation reaction under mild conditions, is reported.     

The Synthesis of 1-Aryl-5-Fluorouracil

5-Fluorouracil (5-Fu,1)1 is an important antitumor drug. Some derivatives2,3 have shown better therapeutic efficacy than 5-Fu. In order to find much more better antitumor drugs of its derivatives, several attempts have been made and many different types of its derivatives have been prepared at N1, N3 position4~7. Moreover, several different ways have been used for alkylation of 5-Fu7~10. However, up to now, the arylation of 5-Fu at N1 or N3 position hasn't been reported, and the compound o…     

Reaction of 1-Aryl-3-methylpyrazol-5-ones with 2-Cyanoaryldiazonium Bisulfates

2-Cyanoaryldiazonium bisulfates, obtained by the action of nitrosyl sulfuric acid on isatin 3-hydrazone and its 5-bromo and 5-nitro derivatives, couple with 1-aryl-3-methylpyrazol-5-ones and form 4-arylhydrazones of 1-aryl-3-methylpyrazole-4,5-diones. It was established on the basis of data of IR, UV, and ¹H NMR spectra and of X-ray structural analysis that the coupling products exist in the hydrazone form stabilized by an intramolecular hydrogen bond.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 210–215, February, 2005.     

Synthesis and Reaction of 2-Mercapto-3-Arylpropanoic Acids

Abstract

Two synthetic pathways for the preparation of 2-mercapto-3-arylpropanoic acids were developed. First, by the reaction of arenediazonium bromides with acrylic esters in the presence of CuBr, alkyl (2-bromo-3-aryl)propanoates were formed. Their cyclization with thiourea produced 5-(R-benzyl)-2-imino-4-thiazolidinones, which yielded 3-aryl-2-mercaptopropanoic acids by alkaline hydrolysis. Second, direct Meerwein arylation of acrylates in the presence of S-nucleophile (NaSH) allowed isolation of 3-phenyl-2-mercaptopropanoic acid in 8% yield. Such acids were used for cyclization with cyanoguanidine and phenyl isothiocyanate yielding 1-[5-(R-benzyl)-4-oxo-1,3-thiazolidin-2-ylidene]guanidines and new 5-(R-benzyl)-3-phenyl-2-thioxo-1,3-thiazolidin-4-one (rhodanine) derivatives correspondingly.