2-芳基-3,4-二氮杂芴酮和2-芳基-3,4-二氮杂螺二芴衍生物的合成

水合茚三酮与芳甲基酮、水合肼缩合环化制得2-芳基-3,4-二氮杂芴酮(2); 2经还原得2-芳基-3,4-二氮杂芴(3).2与2-溴联苯格氏试剂反应得到中间体叔醇(4); 4在酸性条件下关环合成了2-芳基-3,4-二氮杂螺二芴,其结构经1H NMR,13C NMR和元素分析表征.     

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.     

One-Pot Synthesis of 2-Aryl- and 2-Alkyl-pyrimidines

Reaction of 1,1,3,3-tetramethoxypropane with amidine hydrochloride salts at elevated temperatures in a sealed tube gave 2-substituted pyrimidines.     

2-Aryl-1,2,3-thiadiazolium salts

When arylhydrazones of -methyleneketones are treated with thionyl chloride they form 2-aryl-1,2,3-thiadiazolium chlorides in high yield, via the intermediate 1,2,3-thiadiazol-3-ine 1-oxides. The effect of substituents on the course of the cyclization was investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1550–1551, November, 1989.     

2-Aryl-4-azaindain-1,3-diones

2-Pheny1-4-azaindan-1,3-dione and 2-(p-dimethylaminophenyl)-4-azaindan-1,3-dione are synthesized by condensing 4-azaphthalide with benzaldehyde and p-dimethylaminobenzaldehyde. 4-Azaphthalide reacts with p-nitrobenzaldehyde in hot acetic anhydride to give 3-(p-nitrobenzylidene)-4-azaphthalide, rearranged by sodium methoxide to 2-(p-nitrophenyl)-4-azaindan-1,3-dione. 2-Phenyl-and 2-(p-nitrophenyl)-4-azaindandiones are also obtained by sodium methoxide rearrangement of the products of reaction of quinolinic anhydride with phenylacetic and p-nitrophenylacetic acids. 2-Aryl-4-azaindandiones are deeply colored substances only slightly soluble, and without sharp melting points. They undergo methylation at the nitrogen atom, to give N-methylbetaines. The IR absorption spectra show that 2-ary]-4-azaindandiones exist in a strongly polarized enol form in the solid state.     

2-Aryl-3,5-dinitro-1,2-dihydropyridines

The reaction of -nitroacetaldehyde with paraformaldehyde or aromatic aldehydes and ammonium acetate in acetic acid yielded 2-aryl-3,5-dinitro-1,2-dihydropyridines. Aromatic aldehydes, in an ethanol and acetic acid mixture, gave isomeric 3,5-dinitro-1,4-dihydropyridines in addition to 1,2-dihydropyridines. Physicochemical properties and reactivities of the compounds have been studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 64–70, January, 1993.     

3-Aryl-2-benzyl -1,2-dihydroquinoxalines

The reaction of 1,2-phenylenediamine with 2-bromo-1,3-diaryl-1-propanones led to stable and crystalline 3-(4-R-phenyl)-2-(4-R-benzyl)-1,2-dihydroquinoxalines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 830–832, June, 1987.     

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     

An Efficient Method for the Selective Reduction of 2-Aryl-1-Nitroalkenes to 2-Aryl-1-Nitroalkanes by 2-Phenylbenzimidazoline

Nitroalkanes have recently been demonstrated to be useful synthetic intermediates for a variety of trans- formations. They have, for example, been converted to carbonyl, la) nitrile oxide,^lb) and amino compounds.^1c) Especially, 2-aryl-1-nitroalkanes are important in connection with the synthesis of biochemically and pharmacologically interesting compounds. ²⁾ They have also been used as synthetically equivalent to enamines and enolates.³⁾ A widely employed method⁴⁾ for the synthesis of nitroalkanes involves NaBH₄ reduction of conjugated nitroalkenes. The NaBH₄ reduction of nitro- alkenes derived from aliphatic aldehydes^4b) or ketones⁵⁾ usually proceeds smoothly in good yields. However, the reduction of 2-aryl-1-nitroalkenes with NaBH₄ produces low yields of products due to undesired side reactions such as dimerization.⁴⁾     

Synthesis of 2-Aryl-3-cyanophthalimidines and Related Analogs

A series of novel 3-cyano- and related 3-substituted phthalmidines have been synthesized from acyclic precursors, some of which were isolated.     

2-芳氧基-1,8-邻苯二甲酰基萘的合成及光致变色性

合成了3种2-芳氧基-1,8-邻苯二甲酰基萘类光致变色化合物,通过核磁共振谱、红外光谱、质谱和元素分析确定了结构.对产物进行了荧光光谱测定,3种光致变色化合物的荧光强度和Stoke位移都较大.用紫外-可见分光光度计对其在丙酮溶液中的光致变色行为进行了测定,3种光致变色化合物在300-600 nm范围内都具有一定的光致变色性能和较大的吸光系数.     

Hypervalent Iodine Oxidation of 2-Aryl-1,2,3,4-tetrahydro-4-quinolones: An Easy Access to 2-Aryl-4-quinolones

Oxidation of 2-aryl-1,2,3,4-tetrahydro-4-quinolones (1a-e) using iodobenzene diacetate in methanolic potassium hydroxide leads to dehydrogenation of 1 thereby providing an easy access to 2-aryl-4-quinolones (2a-e).     

1-芳基-2-丙酮的合成研究

以芳香胺为原料, 经重氮化和改进的Meerwein芳基取代反应, 合成了一系列的1-芳基-2-丙酮, 其中1-(3,5-二三氟甲基苯基)-2-丙酮是一个新化合物. 改进后的方法简化了合成步骤, 提高了收率, 可方便地用于在苯环上具有不同取代基的芳基丙酮的合成.     

Recyclization of 2-Aryl-4-cyano-5-hydrazinooxazoles

The available 2-benzoylamino-3,3-dichloroacrylonitrile and its analogs when treated with excess hydrazine hydrate convert to 2-aryl-4-cyano-5-hydrazinooxazoles. The products are fairly stable in usual conditions but undergo recyclization on heating in acetic acid to give previously unknown derivatives of 2-methyl-1,3,4-oxadiazole with a 5-acylamino(carbamoyl)methyl substituent, whose structure was established by spectroscopy and X-ray diffraction. An important role in this complex transformation is probably played by prototropic forms of 4-cyano-5-hydrazinooxazoles, viz. hydrazones of substituted 2-oxazolin-5-ones which are not aromatic and thus can be cleaved with acetic acid and then recyclize.     

Heterocycles. 9. 2-Aryl-2H-1,4-tetrahydrooxazines

Reaction of 2-bromo-1-phenylethanones with diethanolamine gave 2-hydroxymorpholines. Acetylation gave mono or diacetates. Acid catalyzed dehydrations gave several types of products whose structures are discussed.     

2-芳基-5-苄氧苯基-1,3,4-噁二唑类化合物的合成

由苄氧基苯甲酰肼与各种芳酰氯反应制得N-取代苯甲酰基-4-苄氧苯酰肼(2),2在三氯氧磷存在下发生脱水闭环反应,合成了一系列2-芳基-5-苄氧苯基-1,3,4-噁二唑类化合物,其结构经1H NMR,IR,MS和元素分析表征。     

Synthesis of 4-Aryl-1,5-benzodiazepine-2-carboxamides

4,N-Diaryl-1,5-benzodiazepine-2-carboxamides were synthesized by acid-catalyzed reaction of (Z)-4,N-diaryl-2-hydroxy-4-oxo-2-butenamides with o-phenylenediamine or N,N'-bis(triphenylphosphoranediyl)-o-phenylenediamine. The reaction mechanism is discussed.     

Synthese von 1-Aryl-2-azido-2-alken-1-onen

Zusammenfassung Durch Kondensation von -Azidoacetophenonen mit aliphatischen Aldehyden wurden 1-Aryl-2-azido-2-alken-1-one erhalten. Die Thermolyse dieser Verbindungen gab Azirine, die sich mit Cyclopentadien in 2-Azatricyclo[3.2.1.0^2.4]-6-octene überführen lassen.

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Synthesis of 1-aryl-2-azido-2-alken-1-ones (ene-azides, V)

1-Aryl-2-azido-2-alken-1-ones were obtained by condensing -azidoacetophenones with aliphatic aldehydes. Thermolysis of these compounds gave azirines, which can be converted to 2-azatricyclo[3.2.1.0^2.4]-6-octenes by reaction with cyclopentadiene.

     

(2-Aryl-2-cyanoethenyl)ketenes---annulated cyanophenols from azidoquinones

Annulated cyanophenols are the products derived from the thermolysis of 3,6-diaryl-2,5-diazido-1,4-benzoquinones in the presence of an alkyne. The transformation is envisaged to involve the following steps: 1)thermal fragmentation of the azidoquinones to arylcyanoketenes, 2) cycloaddition of the ketenes to an alkyne to give 4-aryl-4-cyanocyclobutenones, 3) electrocyclic ring opening of the cyclobutenone to generate (2-aryl-2-cyanoethenyl)ketenes, and 4) ring closure of the conjugated ketenes to give the annulated cyanophenol products. Similarly, analogous products are obtained from the thermolysis of 4-aryl-3-azido-6-chloro-5-ethoxy-1,2-benzoquinones.