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71.
Polystyrenes, polyacrylates and poly(methyl methacrylate) prepared by atom transfer radical polymerization (ATRP) have predictable molecular weights, low polydispersities and well-defined halogen end groups. The halogen end groups have been substituted by other functionalities such as azides and amines. In order to predict the feasibility and selectivity of nucleophilic substitution reactions, the reactivities of the end groups of the different polymers were studied. First, model studies with benzyl halide (BzX), 1-phenylethyl halide (1-PEX), methyl 2-halopropionate (MXP), ethyl 2-bromoisobutyrate (EBiB) and 2-halopropionitrile (2-XPN) were performed. The models compounds were dissolved in DMF and after adding sodium azide (1.1 eq.), the reaction mixtures were stirred at 25°C. The relative magnitude of the rate constants for the reactions with the chlorinated substrates were found to be BzCl > MClP > 1-PECl ≈ 2-ClPN:22 > 6 > 1. Increased substitution at the carbon center decreased the rate of reaction, benzyl chloride reacted 22 times faster than 1-phenylethyl chloride. The brominated substrates reacted very fast. The rate constant of 1-PEBr, determined by competition experiments, was 4.5 times higher than the rate constant of benzyl chloride. Based on these results, the bromine end groups of different polymers were substituted under reaction conditions simular to those used for the model reactions. The end-functionalized polymers were characterized by 1H-NMR, IR and MALDI-TOFMS.  相似文献   
72.
Copper(I) catalyzed radical benzylation and cyclization reaction of tertiary enamides was investigated and 3,3-disubstituted N-Alkyl isoindolin-1-ones were obtained in moderate to good yields. In this reaction, two new C–C bonds were formed in one step with high atom economy. Possible reaction pathway for the formation of the products was also discussed in this paper.  相似文献   
73.
Ce(IV) as ceric ammonium nitrate can effectively catalyze ring opening of epoxides with halides under very mild conditions and easy procedure to give the corresponding β-chloro-and β-bromohydrins in excellent yields. The reactions occur with both substituted and unsubstituted quaternary ammonium halides and with high regio- and stereoselectivity. The reaction of optically active styrene oxide with chloride ion was found to be highly stereospecific and afforded the corresponding β-halohydrin in 96% ee.  相似文献   
74.
The reactivity ratios of four butyl acrylates versus methyl methacrylate and tert-butyl methacrylate were determined for their radical copolymerization in 2-butanone solution using the Jaacks method. The reactivity ratios values obtained were positively verified by substituting into the Alfrey-Goldfinger equation, yielding correct copolymer composition for a series of samples obtained from different initial mole fractions of the comonomers.  相似文献   
75.
Toluene has been identified as a novel carrier of xanthates. Their corresponding fragmentative precursors proved to behave efficiently in radical group transfer reactions. As examples, unprecedented S-tri/di-chloromethyl xanthates could be prepared, isolated and further used in radical additions to olefins. Their precursors (de-aromatized toluene upon which is grafted, at one end, a tri/di-chloromethyl-group and, at the other end, a dithiocarbonyl group) can also be used directly in the transfer of both groups to olefins. The re-aromatizing loss of toluene by radical initiated fragmentation of the precursors brings thus new opportunities to the chemistry of xanthates, exemplified here in the intermolecular additions to olefins of new S-tri/di-chloromethyl xanthates.  相似文献   
76.
《Tetrahedron》2019,75(43):130624
An Fe(III)-catalyzed efficient method has been developed for the synthesis of selenoester derivatives in high yields through the coupling of α-amino carbonyl/glycine derivatives and diselenides under ambient air. A library of benzoselenoate derivatives having a variety of substituents has been synthesized. A plausible reaction pathway has been predicted. Experimental results suggest that the reaction proceeds through a radical pathway. Operational simplicity, compatibility with various α-amino carbonyls and diselenides, high yields, fast reaction and mild reaction conditions are the notable advantages of this procedure. We have also shown the practical application of the synthesized selenoesters which is useful to generate peptide bonds in biological sciences.  相似文献   
77.
Abstract

The cyclopentylmethyl free radical has been generated in argon matrices by UV irradiation of the corresponding diacyl peroxide at T = 20K. The infrared spectrum of the radical reveals an out-of-plane deformation of the radical center at 563 cm?1 characteristic of primary alkyl radicals.  相似文献   
78.
《Tetrahedron》2019,75(12):1639-1646
An efficient visible-light photocatalytic protocol for the vicinal heteroarylsulfonylation and oximinosulfonylation of unactivated olefins is described. The addition of sulfonyl radicals to alkenes triggers the intramolecular migration of remote heteroaryl and oximino groups via CC bond cleavage. The transformation features a good functional group tolerance and a broad substrate scope. A variety of valuable heteroaryl- and oximino-substituted alkyl sulfones are obtained under mild conditions in synthetically useful yields.  相似文献   
79.
《Tetrahedron》2019,75(28):3856-3863
Without employing any transition metal, organic solvent and base, a facile, economical and environmentally friendly strategy has been developed for the α-hydroxylation of β-keto esters and β-keto amides with peroxides via radical cross-coupling reaction in water under open-air conditions. This protocol allows a convenient access to various α-hydroxy-β-keto esters and α-hydroxy-β-keto amides with up to 92% yield (34 examples). Moreover, the reaction was successfully scaled up to gram quantity and mechanistic studies showed the radical pathway was involved in this hydroxylation.  相似文献   
80.
Microwave catalyzed reaction of a neat mixture of styrene oxide and H-dimethylphosphonate furnished dimethyl methylphosphonate, trimethylphosphate, phenylacetaldehyde, 1-methoxy-2-phenylethanol, 1-phenylethleneglycol, cis- and trans-1,3-diphenylcyclobutanes, hydrogen 1-(2-phenylethyl)methylphosphinate, (1-phenylethyl)dimethylphosphonate, and (1-phenylethyl)dimethylphosphonate via free radical processes.  相似文献   
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