碘催化的2,2,2-三氟-1-(1H-吲哚-3-基)-乙醇与取代苯胺的傅-克苄基化反应

首次报道了分子碘I₂催化的吲哚衍生物与取代苯胺的傅-克苄基化反应, 合成了8个新型的3-取代吲哚的苯胺类衍生物,收率６５%～９８%,其结构经¹H NMR, ¹³C NMR和HR-ESI-MS表征。     

2,2,2-三氟-1-(9-蒽基)乙醇对映体在涂敷型手性固定相上的液相色谱分离

涂敷１５％三苯基氨基甲酸纤维素酯于大孔硅胶担体,制备手性柱。考察柱温在分离２,２,２－三氟－１－（９－蒽基）乙醇对映体性能方面的影响,发现柱温升高,分离度下降,计算分离过程中,地映体在相与洗脱液之间分配的自由能变、焓变和熵变之差;考察洗脱液正己烷／异丙醇流速在分离性能方面的影响,发现洗脱液流速增加,分离度降低,在流速炎０．５ｍＬ／ｍｉｎ时,分离度最大,Ｒｓ＝１．３３。     

2,2,2-三氟-1-(9-蒽基)乙醇对映体在涂敷型手性固定相上的拆分

用高效液相色谱法在涂敷１５％（Ｗｔ）三苯基氨基甲酸纤维素醌手性柱上,考察了洗脱液正己烷／醇（Ｖ／Ｖ）中醇对分离－２,２,２－三氟－１（９－蒽基）乙醇对映体的影响,初步认为,在对映体分离过程中,洗脱液中醇与手性固定相的ＮＨ和Ｃ＝Ｏ形成氢键作用,此过程与对映体和手性固定相的ＮＨ和Ｃ＝Ｏ所形成氢键作用相竞争;洗脱液中醇的结构不同之所以影响对映体的分离效果,还与洗脱中醇改变固定相中手性空穴的立体环境有关,     

Reaction of ethyl 3-(1-adamantyl)-3-oxopropanoate with fluorobenzoyl chlorides

Russian Journal of Organic Chemistry -     

Synthesis of N-[1-(1H-Benzimidazol-2-ylsulfanyl)-2,2,2-trichloroethyl]arenesulfonamides by Reaction of N-(2,2,2-Trichloroethylidene)arenesulfonamides with 1H-benzimidazole-2-thiol

Russian Journal of Organic Chemistry -     

N-(2,2,2-Trichloroethylidene)- and N-(1-Hydroxy-2,2,2-trichloroethyl)amides in C-Amidoalkylation Reaction of Functionally-substituted Aromatic Compounds

A reaction with phenol and pyrocatechol of N-(2,2,2-trichloroethylidene)arenesulfonyl-, ethoxycarbonylamides and 1-hydroxy-substituted N-(2,2,2-trichloroethyl)amides of arenesulfonic, carbamic, and acetic acids in the presence of oleum or in sulfuric acid provided the corresponding (1-amido-2,2,2-trichloroethyl)-substituted phenols. N-(2,2,2-Trichloroethylidene)-4-chlorobenzenesulfonamide reacted with salicylamide in the presence of oleum to afford 3-aminocarbonyl-4-[2,2,2-trichloro-1-(4-chlorobenzenesulfonamido)ethyl]benzene whereas the 1-hydroxy-2,2,2-trichloroethylamides of the acetic, carbamic, and arenesulfonic acids did not enter into such reactions.     

Reaction of phenoxazine and phenothiazine with 1,1-dicyano-2-(trifluoromethyl)ethylenes

1,1-Dicyano-2,2-bis(triflüoronietliyl)etliylene alkylates phenoxazine and phenothiazine at 20 °C at thepara-position relative to the N atom.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 1026–1027, April, 1996.     

Magnetic and Luminescence Properties of 8-Coordinate Holmium(III) Complexes Containing 4,4,4-Trifluoro-1-Phenyl- and 1-(Naphthalen-2-yl)-1,3-Butanedionates

A new series of mononuclear Ho³⁺ complexes derived from the β-diketonate anions: 4,4,4-trifluoro-1-phenyl-1,3-butanedioneate (btfa⁻) and 4,4,4-trifuoro-1-(naphthalen-2-yl)-1,3-butanedionate (ntfa⁻) have been synthesized, [Ho(btfa)₃(H₂O)₂] (1a), [Ho(ntfa)₃(MeOH)₂] (1b), (1), [Ho(btfa)₃(phen)] (2), [Ho(btfa)₃(bipy)] (3), [Ho(btfa)₃(di-^tbubipy)] (4), [Ho(ntfa)₃(Me₂bipy)] (5), and [Ho(ntfa)₃(bipy)] (6), where phen is 1,10-phenantroline, bipy is 2,2′-bipyridyl, di-^tbubipy is 4,4′-di-tert-butyl-2,2′-bipyridyl, and Me₂bipy is 4,4′-dimethyl-2,2′-bipyridyl. These compounds have been characterized by elemental microanalysis and infrared spectroscopy as well as single-crystal X-ray difraction for 2–6. The central Ho³⁺ ions in these compounds display coordination number 8. The luminescence-emission properties of the pyridyl adducts 2–6 display a strong characteristic band in the visible region at 661 nm and a series of bands in the NIR region (excitation wavelengths (λ_ex) of 367 nm for 2–4 and 380 nm for 5 and 6). The magnetic properties of the complexes revealed magnetically uncoupled Ho³⁺ compounds with no field-induced, single-molecule magnet (SMMs).     

Reaction of 2,5-bis(trifluoromethyl)-1,3,4-oxadiazole with primary amines. Synthesis of 4-substituted-3,5-bis(trifluoromethyl)-4H-1,2,4-triazoles

Reaction of 3,5-bis(trifluoromethyl)-1,3,4-oxadiazole ( 1a ) with primary amines under a variety of conditions conveniently produced 4-substituted-3,5-bis(trifluoromethyl)-4H-1.2,4-triazoles 4a in 26-85% yield. Alkyl amines reacted with 1a in methanol at ?42° to provide hydrogen-bonded monoadduct-methanol complexes 5a , as determined by X-ray. The reaction of 1a with sterically hindered or strongly electron deficient anilines required high temperatures in the absence of solvent.     

Synthesis and characterization of trifluoromethyl heterocyclic compounds: 4-hydroxy-4-methyl-5-(2,2,2-trifluoro-1-trifluoromethylethyl)-1,3-thiazoline derivatives

We report the synthesis of two new bis-trifluoromethyl 4-hydroxy-1,3-thiazoline, and one thiazole derivatives from 5,5,5-trifluoro-4-(trifluoromethyl)-3-penten-2-one (1) by anti-Michael addition and condensation with thioamides. Spectroscopical properties, such as IR and Raman, ¹H, ¹³C and ¹⁹F NMR, as well as the crystalline structure of the 2-methyl-derivative are described. The crystalline structure shows short intermolecular F–F contacts. The 2-phenyl thiazole derivative was obtained by dehydration of the correspondent hydroxythiazoline, attempts to obtain the 2-methyl derivative were unsuccessful.     

Heteroatomic derivatives of aziridine. 15. Reaction of 1-(triethylsilyl)- and 1-[2-(trialkylsilyl)ethyl]-aziridines with thiols

The reaction of 1-(triethylsilyl)aziridine with alkanethiols proceeds with splitting out of aziridine and the formation of (alkylthio)triethylsilanes. The reaction of 1-(triethylsilyl)aziridine with 2-mercaptoethanol leads to 2-(triethylsilyloxy)ethanethiol; the same reaction in a closed system leads to [2-(2-aminoethylthiol)ethoxy]triethylsilane. 1-[2-(Trialkylsilyl)ethyl]aziridines react with 2-mercaptoethanol and with mercapto carboyxlic acids with opening of the aziridine ring.See [1] for Communication 14.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 891–893, July, 1988.     

Reaction of N-acetyl- and N-[1-(arylsulfonylimino)ethyl]-1,4-benzoquinone imines with sodium arenesulfinates

N-Acetyl- and N-[1-(arylsulfonylimino)ethyl]-1,4-benzoquinone imines having no substituent in the 2- and/or 6-position of the quinoid ring react with sodium arenesulfinates preferentially according to the 1,4-addition pattern. The presence of an ArSO₂N group favors radical ion reaction with formation of 1,6-addition products.     

Alkylation of Phenols with N-(2,2,2-Trichloroethylidene)- and N-(2,2,2-Trichloroethyl)arenesulfonamides

N-(2,2,2-Trichloroethylidene)- and N-(2,2,2-trichloroethyl)arenesulfonamides react with phenol, 2-chlorophenol, and 2-methylphenol in the presence of oleum or sulfuric acid to give the corresponding 4-(2,2,2-trichloro-1-arylsulfonylaminoethyl)phenols in good yields.     

Generation of 1-(trifluoromethyl)-1,2-dihydroisoquinolines via a silver(I)-catalyzed reaction of 2-alkynylaryl aldimine with trimethyl(trifluoromethyl)silane

A silver(I)-catalyzed reaction of 2-alkynylaryl aldimine with trimethyl(trifluoromethyl)silane is reported. This reaction proceeds efficiently under extremely mild conditions to generate 1-(trifluoromethyl)-1,2-dihydroisoquinolines in good yields. A three-component reaction of 2-alkynylbenzaldehyde, amine, with trimethyl(trifluoromethyl)silane is presented as well.     

Synthesis of 1-(N-perfluoroalkanesulfonylamino)-2,2,2-(trichloroethyl)dialkylphosphonates and phosphonic Acids

A series of 1-(perfluoroalkanesulfonylamino)-2,2,2-(trichloroethyl)dialkylphosphonates R_fSO₂NHCH-(CCl₃)P(O)(OR)₂ has been synthesized in good yields by addition of dialkyl phosphite to N-perfluoroalkanesulfonyltrichloroaldimines R_fSO₂N=CHCCl₃ that were prepared by treatment of N,N-dichloroperfluoroalkanesulfonylamines with trichloroethylene. Acidic hydrolysis of the phosphonates gave the corresponding phosphonic acids. © 1997 John Wiley & Sons, Inc.