- 1-aryl-2-acetone compound preparation method
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The invention discloses a 1-aryl-2-acetone compound preparation method, which comprises: (1) carrying out a reaction on (E)-2-methyl-3-aryl acrylic acid (I) as a starting raw material and diphenyl azidophosphate (DPPPA) in the presence of an organic alkali; (2) carrying out a heating reaction; and (3) adding an acidic aqueous solution into the reaction solution, and carrying out a reaction to obtain the 1-aryl-2-acetone compound with a structural formula (IV). According to the present invention, the method can solve the technical problems of difficultly available, highly-corrosive, highly toxic and highly explosive reagents, long steps, low yield, tedious operation and the like in the 1-aryl-2-acetone synthesis in the prior art, has characteristics of easily available raw materials, safe and simple operation, mild condition and high yield, and is suitable for industrial production.
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Paragraph 0045-0046
(2020/01/08)
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- Salicylic Acid-Catalyzed Arylation of Enol Acetates with Anilines
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α-Aryl ketones are both structure moieties commonly found in bioactive compounds and versatile synthetic intermediates for the preparation of drug-like molecules. An operationally simple and scalable protocol has been developed to prepare α-aryl ketones from readily available aromatic amines and enol acetates (or silyl enol ethers). This metal-free methodology features the use of salicylic acid as a convenient catalyst to promote the formation of aryl radicals from in-situ generated aryl diazonium salts, without demanding thermal or photochemical activation. The mild reaction conditions used are compatible with anilines substituted with diverse functionalities. Structural elaboration of some prepared α-aryl ketones was accomplished to illustrate their usefulness as building blocks. (Figure presented.).
- Felipe-Blanco, Diego,Gonzalez-Gomez, Jose C.
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supporting information
p. 2773 - 2778
(2018/07/29)
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- Application of piperidine-containing thiazole compound and preparation method thereof
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The invention discloses application of a piperidine-containing thiazole compound as a bactericide in controlling cucumber downy mildew and rice sheath blight, and a preparation method of the piperidine-containing thiazole compound. The invention provides a novel application of the piperidine-containing thiazole compound. The compound is a new compound with bactericidal activity and provides a foundation for the research and development of piperidine thiazole pesticides. The preparation method of the invention provides a raw material foundation for the preparation of a bactericide.
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Paragraph 0006; 0027
(2018/04/02)
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- A convenient and efficient one-pot synthesis of arylacetones from (E)-3-aryl-2-methylacrylic acids by curtius rearrangement
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A convenient and efficient method was developed for the synthesis of arylacetones from (E)-3-aryl-2-methylacrylic acids through a Curtius rearrangement. The Curtius rearrangement of (E)-3-aryl-2-methylacryloyl azides and subsequent hydrolysis proceeded at mild temperatures in a two-phase medium of carbon tetrachloride and water containing a catalytic amount of tetrabutylammonium bromide to give the corresponding derivatives in 82-93% yield.
- He, Xin,Cao, Chong,Liang, Jingwei,Li, Xinyang,Zhang, Tingjian,Meng, Fanhao
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p. 386 - 390
(2017/02/10)
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- Direct Asymmetric Reductive Amination for the Synthesis of Chiral β-Arylamines
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The highly efficient and direct asymmetric reductive amination of arylacetones catalyzed by an iridium complex for the preparation of enantiomerically pure β-arylamines is described. The monodentate phosphoramidite ligand exhibits superb reactivity (TONs of up to 20 000) and enantioselectivity (up to 99 % ee). Additives played important roles in this reductive coupling reaction. Asymmetric reductive coupling of a ketone and an amine is a straightforward and atom-economic approach for preparing optically enriched amines. The highly efficient and direct asymmetric reductive amination of arylacetones, catalyzed by an iridium complex, supplies enantiomerically pure β-arylamines. The new phosphoramidite ligands reported show superb reactivity and enantioselectivity in this reductive coupling. M.S.=molecular sieves, TFA=trifluoroacetic acid.
- Huang, Haizhou,Liu, Xiaoyan,Zhou, Le,Chang, Mingxin,Zhang, Xumu
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supporting information
p. 5309 - 5312
(2016/04/26)
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- A family of low molecular-weight, organic catalysts for reductive C-C bond formation
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Hydrazines form a new family of low molecular-weight reducing agents for diazonium salts. Using only small amounts of hydrazine catalyst, the coupling of diazonium salts to a variety of reactive partners has been achieved, without the requirement for either metal adjuvants or irradiation with visible or ultraviolet light. The generality of the concept proposed herein as well as its advantages in the preparative scale is outlined and discussed.
- Shaaban, Saad,Jolit, Ana?s,Petkova, Desislava,Maulide, Nuno
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p. 13902 - 13905
(2015/09/15)
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- Pinacolatoboron fluoride (pinBF) is an efficient fluoride transfer agent for diastereoselective synthesis of benzylic fluorides
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The incorporation of alkoxy ligands within a range of alkoxyfluoroboranes and dialkoxyfluoroboranes results in fluoroborane reagents with attenuated Lewis acidity and increased ability to donate fluoride ion(s) when compared to boron trifluoride itself. Pinacolatoboron fluoride (pinBF), prepared in situ from BF3·OEt2 and bis(O-trimethylsilyl)pinacol, has been identified as an efficient fluoride donor which allows highly stereoselective SN1-type epoxide ring-opening (with retention of configuration) of a range of trans-β-methyl-substituted aryl epoxides to give the corresponding syn-fluorohydrins. The substrate scope of this transformation is more broad than the analogous protocol using boron trifluoride alone.
- Cresswell, Alexander J.,Davies, Stephen G.,Figuccia, Aude L.A.,Fletcher, Ai M.,Heijnen, Dorus,Lee, James A.,Morris, Melloney J.,Kennett, Alice M.R.,Roberts, Paul M.,Thomson, James E.
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p. 3373 - 3377
(2015/06/02)
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- Palladium-catalyzed mono-α-arylation of acetone with aryl imidazolylsulfonates
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Set the ace(tone): A palladium catalyst derived from the bidentate XantPhos ligand and Pd(OAc)2 has enabled broadly applicable mono-α-arylations of acetone to be performed with air- and moisture-stable aryl imidazolylsulfonates as most user-friendly electrophiles (see scheme). Copyright
- Ackermann, Lutz,Mehta, Vaibhav P.
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supporting information; experimental part
p. 10230 - 10233
(2012/09/22)
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- β-fluoroamphetamines via the stereoselective synthesis of benzylic fluorides
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A range of substituted aryl epoxides undergo efficient ring-opening hydrofluorination upon treatment with 0.33 equiv of BF3-OEt 2 in CH2Cl2 at -20 -°C to give the corresponding syn-fluorohydrins, consistent with a mechanism involving a stereoselective SN1-type epoxide ring-opening process. The benzylic fluoride products of these reactions are valuable templates for further elaboration, as demonstrated by the preparation of a range of aryl-substituted β-fluoroamphetamines.
- Cresswell, Alexander J.,Davies, Stephen G.,Lee, James A.,Roberts, Paul M.,Russell, Angela J.,Thomson, James E.,Tyte, Melloney J.
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supporting information; experimental part
p. 2936 - 2939
(2010/09/10)
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- Facile synthesis of 1-aryl-2-propanones from aromatic amine
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A facile synthesis of aryl propanones using aromatic amines as precursors, via an improved Meerwein arylation reaction under mild conditions, is reported. Copyright Taylor & Francis Group, LLC.
- Li, Li,Chen, Hongbiao,Lin, Yuanbin
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p. 985 - 991
(2007/10/03)
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- An Effective System to Synthesize Arylacetones. Substrate-ionic Liquid-ultrasonic Irradiation
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Manganese(III) acetate-promoted aromatic acetonylation has been accomplished with ultrasonic irradiation in ionic liquids, [N-n-pentyl-4- picolinium] [closo-CB11H12] (1), [OMIM] [BF4] and [BMIM] [PF6] in 62-93% yields, with excellent chemical selectivity.
- Yinghuai, Zhu,Bahnmueller, Stefan,Hosmane, Narayan S.,Maguire, John A.
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p. 730 - 731
(2007/10/03)
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- Regioselectivity of the Base-Induced Ring Cleavage of 1-Oxygenated Derivatives of Cyclobutabenzene
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Oxy anions 3 generated from 1,2-dihydrocyclobutabenzen-1-ones 1 through addition of a charged nucleophile or from 1-hydroxy-1,2-dihydrocyclobutabenzenes 2 by deprotonation with base lead to stable products through distal and/or proximal cleavage of the strained four-membered ring via benzyl carbanion 4 and/or aryl carbanion 5. A systematic study of this process reveals the relative stability of the two isomeric carbanions 4 and 5 as a key factor in determining the course of the ring-cleavage reaction. While benzyl carbanions 4 can be trapped with carbon electrophiles, attempts at trapping aryl carbanions 5 with electrophiles other than H+ failed. In protic solvents, the magnesium salt of the tertiary alcohol 2 shows an increased rate of proximal cleavage as compared to its alkali salts. From this, we conclude that, in contrast to benzyl carbanions 4, free aryl carbanions 5 are of transient existence only. Proximal C,C-bond cleavage seems to occur either through protonation of 5 from a fast, reversible equilibrium 3?5 in which 3 strongly predominates, or in protic solvents possibly even through a rate-limiting protonation of 3 at the aromatic C-atom, bypassing free anion 5 altogether. Thus, additional factors other than just the relative stability of isomeric carbanions 4 and 5 are of importance in determining the regiochemistry of the base-induced C,C-bond cleavage in ketones 1 and in alcohols 2.
- Gokhale, Abha,Schiess, Peter
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p. 251 - 267
(2007/10/03)
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- Mass spectrometric investigations on phenylacetic acid derivatives, IV: Loss of ortho-substituents from ionized phenyl-2-propanones upon electron impact
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In the gas phase, the phenyl-2-propanone molecules 2a-4a lose upon electron impact chloro-, bromo-, and iodo-radicals specifically at the orthopOsition of the phenyl group giving rise to strong (M-Hal.)+-ions (70/12 eV; 1st and 2nd FFR) of identical structure as confirmed by their MIKE-CAD-spectra. The daughter ions at m/z 133 from o-chlorophenyl-2-propanone (2a) and 2,2-dimethyl-2,3-dihydro[b]furane (11) are structurally similar but not identical (similarity index 99.8). The collisionally activated (2nd FFR) (M-Br.)+-ions from o-bromophenyl-2-propanone (3a) and 1-bromo-1-phenyl-2-propanone (12) produce virtually congruent spectra. The most impOrtant subsequent fragmentation of the (M-Hal-)+-ions from 2a-4a is the loss of CO which incorporates the C-atom of the carbonyl group exclusively (13C labelling). Mechanistic aspects of the fragmentation sequences are discussed (Figs. 5 and 8).
- Striegel,Mayer,Wiegrebe,Schlunegger,Siegrist,Aebi
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p. 751 - 760
(2007/10/02)
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- SYNTHESIS, TAUTOMERIZATION AND ACYLATION OF 1-PHENYLPROPANE-2-IMINES
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1-Phenylpropane-2-imines and its derivatives substituted in a benzene ring were synthesized in reaction of proper ketones with ammonia.The keto-enol and imine-enamine tautomerisms in starting compounds and reaction products, respectively, were examined by proton nuclear magnetic resonance spectrometry and chemical methods.The determined constants of tautomeric equilibria were correlated with the Hammett ? constants.Electronic effects occurring in the systems under study were discussed basing on the correlations found.A possible use of 1-phenylpropane-2-imines in synthesis of N-acyl derivatives of 2-phenyl-1-methylvinylamines was examined.
- Zielinski, W.,Mazik, M.
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p. 661 - 668
(2007/10/02)
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- Studies on nucleophilic substitution reactions with cyclopentadienyliron complexes of some chloroarenes and nitorarenes and syntheses of substituted arenes by demetallation of the substitution products
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Nucleophilic substitution reactions with the cyclopentadienyliron (CpFe) complex of m- or p-dichlorobenzene with carbanion nucleophiles derived from ethyl acetoacetate (EAA), dibenzoylmethane (DBM) or diacetylmethane (DAM) were found to give only monosubstitution as previously observed for the CpFe complex of o-dichlorobenzene.Reaction of the CpFe complex of 2,6-dimethylchlorobenzene (XIVa) or 2,6-dimethylnitorbenzene (XIVb) with nucleophiles derived from ammonia, dimethylamine, n-butylamine, pyrrolidine, ethanol, phenol, o-thiocresol and EAA all gave SNAr products, without significant steric hindrance.However, no reaction was observed in the treatment of XIVa or XIVb with DBM, suggesting that only with a bulky nucleophile such as that derived from DBM were steric hindrance effects sufficiently large to prevent an SNAr reaction with XIVa or XIVb.Pyrolytic sublimation of the various SNAr products was found to cause decomposition in some cases, but in most instances, demetallation took place giving rise to substituted arenes.New substituted arenes prepared in this way in the present work included RC6H4CH(COC6H5)2, with R = p-CH3, o-Cl, m-Cl or p-Cl, and 2,6-(CH3)2C6H3Y, with Y = CH3(CH2)3NH, C2H5O or o-CH3C6H4S.
- Abd-El-Aziz, A.S.,Lee, C. C.,Piorko, A.,Sutherland, R. G.
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- Aromatic Acetonylation Promoted by Manganese(III) and Cerium(IV) Salts
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Treatment of aromatic hydrocarbons with acetone and manganese(III) acetate gave rise to arylacetones in yields ranging from 25 percent with chlorobenzene to 74 percent with anisole.Cerium(IV) salts were also successfully used as promoters but gave lower yields.The reactions were relatively free of side products except with toluene.Isomer distributions, relative rates, and partial rate factors were determined for acetonylation of anisole, toluene, chlorobenzene, and fluorobenzene.A Hammett plot of the log of the partial rate factors for the manganese(III) system vs. ?-constants gave a slope, ρ, of -2.4 +/- 0.3.An isotope effect kH/kD = 3.8 was observed for the manganese(III)-promoted reaction with acetone-d6, indicating rate-determining proton loss from acetone.The overall mechanism involves formation and attack of acetonyl radicals onto the aromatic hydrocarbon followed by subsequent oxidative deprotonation of the resulting ?-radical complex.The acetonyl radical exhibits appreciable electron-deficient character in its substitution behavior with aromatic hydrocarbons.
- Kurz, Michael E.,Baru, Vijayalakshmi,Nguyen, P-Nhi
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p. 1603 - 1607
(2007/10/02)
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- ACETONYLATION AROMATIQUE HOMOLYTIQUE
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Treatment of monosubstituted benzene derivatives with acetone and manganese(III) acetate in acetic acid gave rise to products of homolytic aromatic substitution in fairly good yields and high purity except for toluene.Isomer distribution, relative rates and partial rate factors were determeined for toluene, anisole, chlorobenzene, bromobenzene and benzonitrile.A Hammet plot of the logarithm of the partial rate factors for meta and para positions vs. ?-constants gave a slope ρ of -1.74 +/- 0.40 (confidence interval at the level 95percent).When using ?+-constants the slope becomes ρ+ = -1.25 +/- 0.36.The negative velues of ρ and ρ+ indicated that the acetonyl radical has an appreciable electrophilic character.
- Gardrat, C.
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p. 897 - 902
(2007/10/02)
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