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1.
Induced hydroxyhalogenation of alkyl cyclohexenyl ketones in the systems [MHlg-HX or HHlg]-H2O2 or (NaClO) was performed and the optimal conditions of this reaction were elucidated. It is established that in the system in situ is induced a hypohaloid acid HClO or HBrO is produced that then enters into electrophilic addition at the ring double bond affording hydroxyhalo derivatives of the cycloaliphatic ketones. The alkyl cyclohexenyl ketone chloro(bromo)hydrines and the oxiranes obtained from them are very reactive compounds and can be used as initial compounds for the synthesis of many individual organic compounds  相似文献   

2.
Optimal conditions were found for induced hydroxyhalogenation of cyclic dienes (tetrahydroindene, 4-vinylcyclohexene and 5-vinyl- and 5-cyclohexenylbicyclo[2.2.1]hept-2-enes) in the system [MHlg-HA or HHlg]-H2O2 (or NaClO). Dehydrohalogenation of the chloro- and bromohydrins thus obtained with powdered potassium carbonate gave the corresponding diepoxy derivatives, and their hydrolysis led to mixtures of stereoisomeric tetrahydric alcohols.  相似文献   

3.
Abstract

Recently it has been shown that the interaction of equimolar amount of HHlg witii phosphinosubstituted ylides (I) and phosphoryl- and thiophosphorylsubstituted ylides (II) leads to monoprotonation products: at the carbon or phosphorus of (I) and at the carbon or oxygen (sulfur) of (II)1. We have found that products of double protonation, diphosphoniomethanes with P-H (III) and P-OH (IV) bonds respectively, are formed by the action of excess acid (HSO3F, HHlg).  相似文献   

4.
A series of insoluble salts of Keggin heteropoly compounds were prepared and used as catalysts for the Mannich-type reaction of benzaldehyde, aniline, and cyclohexanone in water. Among them, Cs2.5H0.5PW12O40 showed excellent catalytic activity. Effects of surfactant, catalyst loading and temperature were studied to introduce the best reaction condition. The optimized reaction conditions were extended to Mannich reaction of various aldehydes, ketones, and amines in water. This rapid procedure afforded structurally divers β-amino ketones with major anti diastereoselectivity. Additionally, four new compounds were reported. The catalyst was recovered and reused for subsequent runs.  相似文献   

5.
Primary alcohols and diols with various structures were subjected to transformations into esters, aldehydes, ketones, and lactones under the action of carbon tetrachloride in the presence of manganese compounds (MnCl2, MnO2, Mn(OAc)2, Mn(acac)3) and vanadium compounds (VCl5, V2O5, VO(acac)2) as catalysts. These transformation proceeded with the involvement of alkyl hypochlorites, which were generated in the course of oxidation of alcohols with carbon tetrachloride catalyzed by manganese or vanadium compounds. The optimum molar ratios between the catalyst and reagents were determined, and the reaction conditions for the highly selective synthesis of esters, aldehydes, ketones, and lactones from alcohols were found.  相似文献   

6.
D.J. Costa  N.E. Boutin  J.G. Riess 《Tetrahedron》1974,30(20):3793-3797
The reaction of phenyltetrafluorophosphorane with secondary or tertiary α- or β -hydroxy esters, ketones, nitriles, ethers and nitro derivatives has been investigated. The formation of the alkoxyfluorophosphorane 3 has been established in several cases. Good yields of isolated fluoro compounds were obtained with MeCHFCOOEt, MeCHFCH2COOEt and Me2CFCH2NO2. These compounds eliminate HF readily.  相似文献   

7.
Ka Young Lee 《Tetrahedron》2005,61(36):8705-8710
α,β-Acetylenic ketones were synthesized from the reaction of acid chlorides and acetylenic compounds in the presence of ZnBr2 and DIEA in acetonitrile. From the acetylenic ketones having nearby methylene unit, 2,5-disubstituted furan derivatives could be synthesized under the same reaction conditions.  相似文献   

8.
Starting from trifluoromethyl β-dicarbonyl compounds, a rare loss of CF3CO was observed in the amination reactions performed under heterogeneous conditions using NsONHCO2Et as the aminating agent and CaO or NaH as the base, while corresponding nonfluorinated β-dicarbonyl compounds under analogous conditions give non deacylated aminated compounds. This reaction can facilitate a direct synthesis of N-substituted α-amino esters or α-amino ketones.  相似文献   

9.
A zirconium borohydride piperazine complex (Ppyz)Zr(BH4)2Cl2, obtained by the reaction of an ethereal solution of ZrCl4 and LiBH4 with piperazine is a stable, selective and efficient reducing agent. (Ppyz)Zr(BH4)2Cl2 reduces aldehydes, ketones, silylethers, α,β-unsaturated carbonyl compounds and esters. The reactions were performed in diethyl ether at room temperature or under reflux, and the yields of the corresponding alcohols were excellent. The selective reduction of aldehydes in the presence of ketones and complete regioselectivity in the reduction of α,β-unsaturated carbonyl groups were observed.  相似文献   

10.
The protonation of cyclic enamino ketones of the pyrrolidine, piperidine, and hexahydroazepine series, as well as their noncyclic analogs, was studied by PMR spectroscopy. It is shown that the presence of a CH2 or CH3 group in the “enamine” position leads to C protonation (in CF3COOH). In the case of enamino ketones that do not contain substituents in the “enamine” α position N-and O-protonated forms are observed in CF3COOH. The measured pKa values (in 10% alcohol) and the ΔpKa values (in nitromethane) of the enamino ketones show that the compounds for which C protonation is characteristic are two to three orders of magnitude more basic than in the case of compounds that do not contain substituents in the “enamine” α position; this is explained by the different character of protonation. See [1] for communication 30. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 344–348, March, 1980  相似文献   

11.
A series of magnesium(II) complexes bearing the sterically demanding phosphinoamide ligand, L?=Ph2PNDip?, Dip=2,6‐diisopropylphenyl, including heteroleptic magnesium alkyl and hydride complexes are described. The ligand geometry enforces various novel ring and cluster geometries for the heteroleptic compounds. We have studied the stoichiometric reactivity of [(LMgH)4] towards unsaturated substrates, and investigated catalytic hydroborations and hydrosilylations of ketones and pyridines. We found that hydroborations of two ketones with pinacolborane using various Mg precatalysts is very rapid at room temperature with very low catalyst loadings, and ketone hydrosilylation using phenylsilane is rapid at 70 °C. Our studies point to an insertion/σ‐bond metathesis catalytic cycle of an in situ formed “MgH2” active species.  相似文献   

12.
The use of MoO2Cl2 as a novel catalyst for Friedel-Crafts acylation and sulfonylation is described. A series of aromatic ketones and sulfones were prepared in moderate to good yields using acyl chloride or sulfonyl chloride in the presence of MoO2Cl2 (20 mol %), under solvent-free conditions.  相似文献   

13.
2,3,4‐Trisubstituted quinolines, substituted with adamantan‐1‐yl or (adamantan‐1‐yl)methyl in the 4‐position, were prepared from the corresponding admantan‐1‐yl 2‐aminophenyl ketones or admantan‐1‐ylmethyl 2‐aminophenyl ketones and ketones with an α‐CH2 group. These reactions were carried out under neat conditions or in toluene, and the products were obtained in moderate‐to‐excellent yields. The scope and limitations of the examined procedures are discussed. All new compounds are fully characterized by IR and NMR spectroscopy and mass spectrometry. The molecular structures of five new quinolines, obtained via single‐crystal X‐ray diffraction analyses, are discussed.  相似文献   

14.
Deuterodifluoromethyl ketones and sulfones were assembled in three synthetic steps from methyl ketones and sulfones, respectively. The key synthetic transformation is the deuteration of the difluorocarbanion generated by the release of trifluoroacetate from highly α-fluorinated gem-diols. High levels of deuterium on the “CF2D” group were routinely observed. This strategy is mild and versatile and it can be applied to both ketones and sulfones without additional concerns of over- or under-fluorination. Additional examples address issues of over-deuteration when compounds with other acidic protons are subjected to the reaction conditions. This process not only demonstrates a new method to install a “CF2D” group but also extends the scope of trifluoroacetate release to sulfones.  相似文献   

15.
Oxidation of secondary alkanols with the system Ce(NH4)2(NO3)6—LiBr in aqueous acetonitrile gave ketones, α-bromo ketones, or α,α′-dibromo ketones. The selectivity of the reaction under standard conditions depends only on the molar ratio of the reagents (alkanol: CeIV: LiBr).  相似文献   

16.
A series of ferrocene-based organosilicon compounds have been prepared via hydrosilylation or double silylation of carbonyl compounds with 1,1′-bis(dimethylsilyl)ferrocene using (C2H4)Pt(PPh3)2 or Ni(PEt3)4 catalysts. In general, while the platinum catalyst (C2H4)Pt(PPh3)2 preferentially produced cyclic double-silylated products, the Ni(PEt3)4 catalyst led to the hydrosilylated ferrocene products from aldehydes or ketones.  相似文献   

17.
Depending on the reaction conditions, the reactions of (E)-3,3,3-trichloro-1-nitropropene with cyclohexanone enamines led to bicyclo[4.2.0]octanes or trisubstituted enamines, which are the ring-chain tautomers capable of reversible transformations. Diastereoselectivity of the reactions of (E)-3,3,3-trichloro(trifluoro)-1-nitropropenes with cycloalkanone enamines were studied, a series of hitherto unknown CX3-containing nitroalkylated enamines and γ-nitro ketones were synthesized, the structures of novel compounds were determined by NMR spectroscopy and X-ray diffraction.  相似文献   

18.
An extension of the scope of the Grignard reaction of fluorinated compounds is reported. Fluorohalogenoethanes of the general formula CF3CXYZ ( X = F,Cl,Br ; Y,Z = Cl,Br ) were found to undergo smoothly the metal-halogen exchange reaction with alkyl- or aryl-magnesium halides at low temperature to yield organometallic compounds CF3CXYMgHal. The Grignard compounds were reacted with a series of aldehydes and ketones to give the corresponding alcohols in good to moderate preparative yields.  相似文献   

19.
Highly selective one-pot synthesis of N-substituted aminocyclohexanols has been performed by hydroxyhalogenation of the corresponding cyclohexenes with electrophilic reagents formed in situ in the system Н2О2 + HHlg (Hlg = Cl, Br), with subsequent substitution of halogen atoms with amines. Some products were tested as antimicrobial additives to motor oils and cooling lubricants and showed high antibacterial and antifungal activity.  相似文献   

20.
A series of new piano‐stool iron(II) complexes comprising N‐heterocyclic carbene ligands [Fe(Cp)(CO)2(NHC)]I (NHC = 1,3‐disubstituted imidazolidin‐2‐ylidene) have been synthesized and analyzed by 1H NMR, 13C NMR, IR, elemental analysis and mass spectrometric techniques. These compounds were easily prepared from the reaction of disubstituted imidazolidin‐2‐ylidene with [FeI(Cp)(CO)2] in toluene at room temperature. These complexes were tested in the catalytic hydrosilylation reaction of aldehydes and ketones with phenylsilane in solvent‐free conditions. After a basic hydrolysis step, the corresponding alcohols were obtained in good yields. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

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