5-三氟甲基-2-茚酮的合成及表征

三氟甲基化合物和茚酮化合物具有许多独特的理化性质和生物活性,在农药、医药、染料和功能材料领域应用广泛。以对三氟甲基苯甲醛为原料,经Knoevenagel缩合、分子内Friedel-Crafts酰化、环氧化物不对称开环等步骤,经9步反应以总收率22%得目标化合物5-三氟甲基-2-茚酮,其结构经1H NMR、13C NMR、DEPT、HR-ESI-MS和元素分析表征。     

Aldol dimerization of 1-indanone and 1-tetralones

The aldol dimerization of 1-indanone and 1-tetralones using titanium tetrachloride and triethylamine as condensing agents provides α,β- and β, γ-unsaturated ketones, respectively, in 53–58% yield.     

6-氯-1-茚酮的合成

以对氯氯苄和丙二酸二乙酯为原料,经缩合、碱性水解、脱羧、酰氯化、Friedel-Crafts酰基化等反应得到6-氯-1-茚酮,总收率62%,纯度99%.其结构经核磁共振谱(1H NMR)、质谱(MS)和元素分析确认.     

Phosphorescence of 1-indanone and related compounds

Dual phosphorescence of 1-indanone and related molecules is shown to arise from two nearby triplet states of different orbital origin.     

新方法合成4-氰基-1-茚酮

以邻氰基氯苄和丙二酸二乙酯为原料,经缩合、碱水解、脱羧和Friedel-Crafts酰化反应合成了4-氰基-1-茚酮,总收率32.1%,其结构经1H NMR和13C NMR确证。     

Conversion of perfluoro-1-indanone to perfluorochroman in the H2O2-HF-SbF5 system

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2463–2464, October, 1990.     

3-取代-3-苯基-1-茚酮类化合物的合成

以3-苯基-1-茚酮（1）为原料,THF为溶剂,二异丙基氨基锂（LDA）为碱,与碘代烷（RI）经亲核取代反应合成了4个3-取代-3-苯基-1-茚酮类化合物（3a~3d),其中3b~3d为新化合物,其结构经¹H NMR, ¹³C NMR 和EI-GC-MS表征。在最佳反应条件［1 1.0 eq., LDA/RI=2.1/1.5（当量比）,于0 ℃~rt反应5 h］下,3a~3d收率为70％～80％。     

Enantioselective synthesis of 2-hydroxy-1-indanone,a key precursor of enantiomerically pure 1-amino-2-indanol

Enantiomerically pure (R)- or (S)-2-hydroxy-1-indanone was synthesized by enzymatic kinetic resolution of racemic 2-acetoxy-1-indanone through hydrolysis or transesterification.     

The structure of cis and trans lsomers of 1-(p-Bromobenzylidene)-2-indanone

Abstract

In this communication we wish to report an interesting case of the isolation and characterization of the cis and trans isomers of 1-(p-bromobenzylidene)-2-indanone and their ketals. Prior to this work, Hoogstreen and Trenner² had reported on the cis and trans isomers of 1-(p-chlorobenzylidene)-2-methyl-5-methoxyindenylacetic acid. The condensation of 2-(N-morpholinyl)-indene (1, prepared by the reaction of 2-indanone³ and morpholine) with P-bromobenzaldehyde was conducted by refluxing them in the presence of acetic acid for 4 hours. Acid hydrolysis of the reaction mixture followed by dry column chrcmatography over sillica gel using a fraction collector afforded two iscmeric monobenzylidenes, compounds 2(36.6%, mp 110–111°)and 3(1.3%, mp 115–116°) and a dibenylidene, compound 4 (8.7%, mp 205°). The relative rations of the mono- and dibenzylidenes seemed to depend on the reaction conditions. Higher yields of the monobenzylidenes 2 and 3 were obtained by conducting the reaction in the presence of UV light. The structures of these monobenzylidenes were established as cis and trans isomers of 1-(p-bromobenzylidenes)-2-indanone on the Basis of elemental analyses and ir and nmr spectroscopy. The ir spectra⁴ (CHCl₃)

of compounds 2 [1725 (c=0), 1620 (c=c)cm^?1] and 3[1710 (c=o), 1570, 1600 (c=c) cm^?1] were consistent with the structures. The molecular ion peaks as well as the fragmentation patterns in the mass spectra of both these compounds were consistent with the assigned structures. Before going into the omr discussion it should be pointed out that treatment of compound 2 with athylene glycol in the presence of p-toluene sulfonic acid produced two ketals, 5 (38.3% mp, 118–120°) and 6 (30.6% mp, 125–126°). As depicted; the ketals 5and 6 were also found (by omr) to be related to each other as cis and trans isomers. Furthermore, each of them could be hydrolyzed with acid to the corresponding monobenzylidenes 2 and 3 without any isomerization. However, UV irradiation of compounds 2 and 3 gave equilibrium mixtures containing both the isomers, indicating isomerization had occurred under photolytic conditions.     

Structure of the photoproduct from the cycloadduct of 2,3-diphenyl-2,3-epoxy-1-indanone and dibenzoylacetylene

A single crystal x-ray analysis of the photoproduct, from the cycloadduct (1) of 2,3-dipheny1–2,3-epoxy-1-indanone and dibenzoylacetylene, has shown that its structure is 3,3a-dibenzoyl-3a,8b-dihydro-2, 8b-diphenylindeno[l,2-b]furan-4-one (8a) and not the earlier reported benzoxocinone structure (3a). Reasonable pathways for the formation of 8a and analogous products are presented. Contribution No. NDRL-3312 and No. RRLT-PRU-10 from the Regional Research Laboratory, Trivandrum.     

Mechanism of CO loss for protonated 1-indanone and isomeric [C9H9O]+ ions

In order to establish the mechanism of CO loss occurring during metastable decomposition of protonated 1-indanone, fragmentations of monocyclic [C₉H₉O]⁺ isomers have been studied. These ions of known structure were prepared by CI protonation and fragmentation of the corresponding acids chlorides. It is demonstrated that the wide component of the [MH? CO]⁺ metastable peak induced by protonated 1-indanone fragmentation is the result of fragmentation of the [C₆H₅CH₂CH₂CO]⁺ isomer ion.     

CIDNP assisted assignment of carbon-13 NMR lines in α-tetralone and α-indanone

The reversible abstraction of hydrogen from benzene-1,3,5-triol by photoexcited α-tetralone or α-indanone in solutions of methanol leads to CIDNP in the ¹³C NMR spectra of these compounds. The information gained from the phase of the polarization in the CIDNP spectra is used to resolve the ambiguities in the assignment of the ¹³C NMR lines for α-indanone and α-tetralone, arising from conflicting literature data. Chemical shifts for both compounds in methanol are reported. 2′-Methylacetophenone does not exhibit CIDNP in the ¹³C spectrum under similar conditions.     

2-[(4-Aminobutyl)ferrocenylmethylidene]-5,6-dimethoxy-1-indanone derivatives: Synthesis,characterization, and investigation of electro-optical properties

A ferrocenyl-based, chromophore-containing 1-indanone derivative was synthesized through crotonic condensation between 4-chlorobutylferrocenecarboxaldehyde and 5,6-dimethoxy-1-indanone followed by the nucleophilic substitution of chlorine atom of the obtained dyad with different aromatic and aliphatic amines. The electrochemical and optical properties of the synthesized compounds were investigated to explore the relationship between their structures and optical and electrochemical properties. The bandgaps determined from optical absorption spectra ranged from 2.05 to 2.15 eV. The important electrochemical parameters, including the peak potential separation, peak current ratios, and the dependence of peak currents on the scan rate, were studied. Results showed an electrochemically reversible redox system with diffusion-controlled redox process for the synthesized compounds. The study of quantum chemistry was performed on the synthesized compounds using the density functional theory approach. The B3LYP method and 6-311 G(d) basis set were used for optimizing the structures in the gas phase. The theoretical and experimental results show that these compounds can be considered as candidates to be used in optical applications.     

Synthesis of 5-Cyanoindazole and 1-Methyl and 1-Aryl-5-Cyanoindazoles

5-Cyanoindazoles are conveniently prepared in two to three steps from commercially available 5-bromo-2-fluorobenzaldehyde.