Synthesis of quinazolinones from anthranilamides and aldehydes via metal-free aerobic oxidation in DMSO

A highly environmentally benign protocol for the synthesis of quinazolinones from anthranilamides and aldehydes via aerobic oxidation was developed in wet DMSO. This protocol is operationally simple, exhibits broad substrate scope, and does not need toxic metal catalysts and bases. In addition, the utility of this transformation was further demonstrated by converting the resulting quinazolinones into other useful products in the same-pot without their isolation.     

Claisen重排反应合成5-烯丙基-4-羟基异吲哚啉-2-羧酸叔丁酯

以2,3-二甲基苯酚(2)和烯丙基溴为原料,经过醚化、溴代、关环及Claisen重排等四步反应,合成得到5-烯丙基-4-羟基异吲哚啉-2-羧酸叔丁酯(1),4步反应总收率为17.8％.中间体及产物结构经1 H NMR和ESI-MS表征,产物结构进一步经过FT-IR、13 C NMR及X-射线单晶衍射进行确认.同时,重点...     

Synthesis of carbostyril derivatives by reaction of aldehydes with oxazolines

Carbostyril derivatives are obtained on reaction of o-chlorobenzaldehyde and derivatives with 2-alkyl-4,4-dimelhyl-2-oxazolines with elimination of methallyl chloride. Phenylethenyloxazolines are presumed intermediates.     

Efficient method for the oxidation of aldehydes and diols with tert-butylhydroperoxide under transition metal-free conditions

An efficient, mild, and simple protocol is presented for the oxidation of aldehydes and diols to carboxylic acids utilizing 70% aq TBHP as oxidant and t-BuOK as additive. The oxidation of aldehydes could be achieved by two methods under aqueous medium. Excellent yields of products were obtained in short reaction times. Notably, the products were isolated by simple filtration technique and do not involve chromatographic separation. These reactions may prove to be valuable alternatives to traditional metal-mediated oxidations. Oxidation does not require any transition metals or organic solvents in reaction, making this protocol green.     

Synthesis of organotin polymers by the reaction of diallyl carbonates with Bu3SNH

Tri-n-butyltin hydride (Bu₃SnH) was employed for the synthesis of organotin polymers via radical process. The polymers having both organotin and carbonate groups were obtained by the reaction of Bu₃SnH with monomers such as diallylcarbonate and diethylene glycol bis(allyl carbonate) via hydrostannation. The copolymerization of diethylene glycol bis(allyl carbonate) and the mono-hydrostannated derivative was also conducted to obtain the corresponding polymers.     

Bu4NI-Catalyzed Synthesis of Pyrophosphate Esters from H-Phosphonates

Abstract

A n-Bu₄NI/t-BuOOH catalysis system has been developed to promote oxidative dehydrogenative coupling of H-phosphonates to form pyrophosphate tetraesters. This novel iodide (I^?) ion-catalyzed reaction provides easy access to pyrophosphate derivatives in the absence of a metal and solvent.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Transition metal-free synthesis of primary amides from aldehydes and hydroxylamine hydrochloride

Primary aromatic amides can be synthesized from aldehydes and hydroxylamine hydrochloride in the presence of Cs₂CO₃. Various aromatic aldehydes (include some heteroaromatic aldehydes) are able to generate the corresponding aromatic amides in moderate to excellent yields.     

Synthesis of higher epoxides by the joint catalytic oxidation of aldehydes and olefins

Conclusions The selective catalytic epoxidation of 1-alkenes by molecular oxygen was accomplished in the presence of C₂-C₅ alipahtic aldehydes and catalysts, viz., the salts of Cu(II), Ni(II), Fe(III), or Zr(IV).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2269–2272, October, 1985.     

A theoretical investigation of the gas-phase oxidation reaction of the saturated tert-butyl radical.

The radical-radical reaction mechanisms and dynamics of ground-state atomic oxygen [O(3P)] with the saturated tert-butyl radical (t-C4H9) are investigated using the density functional method and the complete basis set model. Two distinctive reaction pathways are predicted to be in competition: addition and abstraction. The barrierless addition of O(3P) to t-C4H9 leads to the formation of an energy-rich intermediate (OC4H9) on the lowest doublet potential energy surface, which undergoes subsequent direct elimination or isomerization-elimination leading to various products: C3H6O + CH3, iso-C4H8O + H, C3H7O + CH2, and iso-C4H8 + OH. The respective microscopic reaction processes examined with the aid of statistical calculations, predict that the major addition pathway is the formation of acetone (C3H6O) + CH3 through a low-barrier, single-step cleavage. For the direct, barrierless H-atom abstraction mechanism producing iso-C4H8 (isobutene) + OH, which was recently reported in gas-phase crossed-beam investigations, the reaction is described in terms of both an abstraction process (major) and a short-lived addition dynamic complex (minor).     

Synthesis of 1H-isochromenes, 4H-chromenes,and ortho-aminocarbonitrile tetrahydronaphthalenes from the same reactants by using metal-free catalyst

A facile and rapid multicomponent synthesis of pharmaceutically diverse 1H-isochromenes, 4H-chromenes, and ortho-aminocarbonitrile tetrahydronaphthalenes has been developed from benzaldehyde, malononitrile, and cyclohexanone. Three different methods from the same reactants, solvent, temperature, and catalyst lead to three products with excellent yields. All the reactions were followed with the Michael addition and cyclization. In this study, morpholine was used as an active metal-free base catalyst that increases the yields of products and decreases the time of reactions.     

Synthesis of poly(4-vinylbenzocyclobutene) and its reaction with dienophiles

4-Vinylbenzocyclobutene ( 1 ) was prepared by the nickel-catalyzed coupling reaction of 4-bromobenzocyclobutene with vinylbromide in 70% yield. Radical homopolymerization of 1 at 60°C for 24 h afforded poly(4 vinylbenzocyclobutene) [poly( 1 )] in 89% yield and radical copolymerizations of 1 with styrene (St) or methyl methacrylate (MMA) were carried out to obtain the corresponding copolymers. The Q = 1.07, e = 0.046. As a model reaction of the polymer reaction of the polymer reaction of poly( 1 ) and poly(4-vinylbenzocyclobutene-co-styrene) [copoly( 1 -St)] with dienophiles, the Diels-Alder reaction of benzocyclobutene with N-phenylmaleimide (MI) or maleic anhydride (MANH) was carried out to determine the optimum reaction conditions. Under the optimum condition, the Diels-Alder reaction of poly( 1 ) and copoly( 1 -St) with MI and MANH in the presence of 4-tert-butyl-catechol as an inhibitor were carried out to yield the corresponding polymers in good yields. The properties (solubilities, T_g, and temperature of 10% weight loss) of the products obtained from the polymer reaction were different from these of poly( 1 ). © 1995 John Wiley & Sons, Inc.