新型3-吲哚-四取代氧化吲哚的无催化剂合成

以3-氯氧化吲哚为原料,在无催化剂条件下发生S_N1反应,合成了18个新型的3-吲哚-四取代氧化吲哚,产率34%~77%,其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF）表征。     

新型多取代3-烯基吲哚的合成

开发了一种以吲哚为起始原料,合成具有多个反应位点的多取代3-烯基吲哚的新方法,合成了9个目标化合物,其中8个为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI)表征。     

新型吲哚衍生物的合成及其光学性质

以吲哚为原料,经Vilsmeier-Haack, Ullmannhe和Witting-Hornor反应合成了两个新型的含吲哚环共轭化合物--1,4-二(3-苯乙烯基吲哚基)苯（4a）和1,4-二(3-萘乙烯基吲哚基)苯（4b）,其结构经¹H NMR, ¹³C NMR, IR和ESI-MS表征。光学性能研究结果表明,4a和4b的λ_max分别位于330 nm和348 nm;在330 nm波长激发下,λ_em分别位于410 nm和425 nm。     

新型5-取代吲哚-3-甲酰胺化合物的合成

以5-取代吲哚为原料,经维尔斯迈尔-哈克反应制得5-取代吲哚-3-甲醛(2a~2e); 2a~2e在DMF催化下,与盐酸羟胺反应制得5-取代吲哚-3-甲腈（3a~3e）; 3a~3e在H₂O₂和NaOH溶液中水解合成了5-取代吲哚-3-甲酰胺（4a~4e, 4b~4e为新化合物）,产率62.0%~75.0%,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。     

3-异硫氰酸酯氧化吲哚与色胺酮的[3+2]环加成反应合成螺环氧化吲哚类化合物

以3-异硫氰酸酯氧化吲哚和色胺酮为原料,在催化剂Et₃N作用下发生[3+2]环加成反应,合成了13个结构新颖的含双螺环骨架的氧化吲哚类化合物3a~3m,收率为63~93%,dr值>19:1,并对这些化合物进行¹H NMR、¹³C NMR和HR-MS(ESI-TOF)表征。该类化合物含有两个连续的螺环季碳中心,可为后续的生物活性筛选提供候选化合物。     

BINOL双酰胺绿色催化吲哚与硝基烯烃的 Friedel-Crafts烷基化反应

合成了3种BINOL双酰胺(Ⅰ~Ⅲ)，其结构经¹H NMR, ¹³C NMR, HR-MS(ESI)和元素分析确证。研究了I~III对取代吲哚和硝基烯烃的Friedel-Crafts烷基化反应的催化性能，并对反应条件进行了优化。结果表明：在最优条件(CH₂Cl₂为溶剂，Ⅰ为催化剂，于40 ℃反应12 h)下，吲哚及取代吲哚与硝基烯烃均能有效的进行Friedel-Crafts烷基化反应，收率和ee值最高可达88%和90%。     

碱调节的磺酰基吲哚的膦氢化反应

含磷吲哚衍生物是一类重要的有机磷化合物，不仅广泛存在于医药制剂中，而且作为配体和中间体广泛存在于材料学和有机合成中。利用膦亲核试剂对磺酰吲哚原位生成的插烯亚胺中间体进行迈克尔加成，能够以较高收率得到一系列3-膦取代吲哚化合物。以磺酰基吲哚和二苯基氧磷为原料，在无机碱碳酸铯作用下发生迈克尔加成反应，合成了11个结构新颖的3-(1-磷酰基)甲基吲哚类化合物3a～3k,产率为72%～98%,并对这些化合物进行¹H NMR、¹³C NMR、³¹P NMR、熔点和HR-MS(ESI-TOF)表征。     

新型甘油拼接3-四取代氧化吲哚的无催化剂无溶剂合成

以3-氯氧化吲哚为原料，在无催化剂、无溶剂条件下于80 ℃发生亲核取代反应，合成了10个新型的甘油拼接3-四取代氧化吲哚，收率54%~72%， dr值10/9~>10/7, 其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF）表征。     

3-卤氧化吲哚参与胺基化反应合成3-胺基四取代氧化吲哚

以3-卤氧化吲哚为起始原料，DMAP为有机催化剂，在甲苯中于60 ℃和苄胺发生3-胺基化取代反应后，用Boc基团对氮原子进行保护，合成了7个新型的N-Boc-3-胺基四取代氧化吲哚，收率85%~93%，其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF）表征。     

新型3-烷氧基-四取代氧化吲哚的无催化剂无溶剂合成

以3-氯氧化吲哚和甲醇（或甘油）为原料，在无催化剂无溶剂条件下经S_N1反应合成了10个新型的3-甲氧基-四取代氧化吲哚(产率36%~93%)和10个新型的3-甘油拼接四取代氧化吲哚（产率71%~87%）,其结构经¹H NMR, C N¹³MR和HR-MS（ESI-TOF）表征。     

Fluorinated and Trifluoromethylated Corannulenes

The syntheses and properties of corannulenes carrying electron‐withdrawing groups (F, CF₃, C₆F₅) are reported. Direct fluorination of corannulene (C₂₀H₁₀) was carried out with xenon difluoride, and the crystal structure of the product was confirmed by the X‐ray analysis. Novel trifluoromethylated corannulenes, including the versatile 4,9‐dibromo‐1,2‐bis(trifluoromethyl)corannulene, were obtained by various established ring‐closing reactions. Besides the use of hexafluorobutyne for the construction of fluoranthenes by Diels–Alder reaction as precursor molecules to form 1,2‐disubstituted corannulenes, bis(pentafluorophenyl)acetylene was employed as dienophile. The molecular structure and crystal packing of a trifluoromethylated corannulene was determined by single‐crystal X‐ray analysis and compared with those known brominated and trifluoromethylated corannulenes. The general electron‐acceptor properties of corannulenes bearing substituents introduced in particular positions by liquid‐phase synthesis are discussed together with published computational results.     

Indoles

The reaction of arylhydrazines and cyclic semiacetals (α-hydroxytetrahydropyran and α-hydroxytetrahydrofuran) on heating leads, with the evolution of water and ammonia, respectively, to homotryptophols and tryptophols.     

Indoles

A new method is proposed for the synthesis of 1,2-disubstituted tryptophols by reaction of N_α-substituted arylhydrazines with α-acyl-γ-butyrolactones by refluxing the components in an acidic aqueous alcohol media.     

Indoles

A number of tryptamines were obtained by the reaction of arylhydrazines with-chlorobutyraldehyde.See [1] for communication XXXV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 213–218, February, 1973.     

Indoles

The corresponding tryptophols are obtained when arylhydrazine salts are heated with dihydrofuran in dioxane.See [1] for communication XXXI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1366–1367, October, 1972.     

Indoles

It has been found that the heating of arylhydrazine salts and dihydropyran in dioxane leads to the corresponding homotryptophols.For Communication IX, see [6].See I. I. Grandberg and N. I. Bobrova, USSR Patent No. 239,341, Byull. Izobr., No. 11 (1969).Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 7, pp. 942–944, July, 1970.     

Indoles

In a study of the Fischer cyclization of cyclohexanone mono-p-substituted α, α-diphenylhydrazones (in which the substituents were donor and acceptor groups) it was found that isomeric (formed during cyclization at the substituted and unsubstituted rings) indoles are formed in close ratios. The results were interpreted in terms of sigmatropic processes as a confirmation of the Fischer reaction via a scheme involving a sigmatropic shift.     

Indoles

The formation of tryptamines instead of the usual Fischer cyclization is observed when salts of arylhydrazines are heated with -halo carbonyl compounds. Bisulfite derivatives of -halo carbonyl compounds with both arylhydrazines themselves and with their salts can also be used in the synthesis of the tryptamines.For Communication XLV see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1085–1088, August, 1974.     

Indoles

A new method for the synthesis of the tricyclic system of eserine on the basis of the reaction of arylhydrazines with -halogenocarbonyl compounds possessing an -methyl group in neutral media [2] has been proposed.For Part VI, see [1].