Mechanistic Study on Polymerization of Acrylamide Induced by Cyclohexanone Based on the Interaction Between the Carbonyl and Amide Groups

Zhong, Xu-Dong; Ishifune, Manabu; Yamashita, Nami

doi:10.1081/ma-100101530

Cited by 5 publications

(2 citation statements)

References 14 publications

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“…The reactions of CHn with N, N-dimethylacrylamide, N-iso-propylacrylamide and N-tert-butylacrylamide produced the expected α-alkylation derivatives, 2- (N, N-dimethyl-2-carbamoylethyl)cyclohexanone (1), 2-(N-iso-propyl-2-carbamoylethyl)cyclohexanone (2a) and, 2-(N-tert-butyl-2-carbamoylethyl) cyclohexanone (2b), respectively (Scheme 2). It was similar to the cyclohexanone α-alkylation by acrylonitrile and methyl acrylate [18,22] . In the case of acrylamide, however, the reaction did not yield the corresponding α-alkylation derivatives 2-(2-carbamoylethyl)cyclohexanone (3), but resulted unexpectedly in the formation of one dicyclo ene-lactam, 3,4,5,6,7,8-hexahydro-2(lH)-quinolinone (3) that was confirmed by the single-crystal X-ray diffraction ( Figure 1).…”

Section: The Effect Of N-substituents Of Amides On the Michael Reactionmentioning

confidence: 91%

“…For example, cyclohexanone (CHn) reacts with the Michael acceptor acrylonitrile and methyl acrylate at 130℃ to give the α-alkylation products, 2-(2-cyanoethyl) cyclohexanone and 2-(2-methoxycarbonyl-ethyl) cyclohexanone, in the high yields [19] . However, the reaction of CHn with acrylamide (AAm) under the same reaction condition does not produce the desired α-alkylation product but the acrylamide homopolymer because cyclanone can induce the homopolymerization of AAm [22] . The polymerization was confirmed to proceed through a radical-initiated mechanism from the resulting polymerization equation.…”

Section: The Michael Addition Reaction Of Cyclanones With Acrylamidesmentioning

confidence: 99%

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Michael addition reactions of cyclanones with acrylamides: Producing 2-carbamoylethyl derivatives or ene-lactams

Dai

Wang

Zhang

et al. 2008

Sci. China Ser. B-Chem.

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The electron-withdrawing groups (EWGs) in the electrophilic alkenes employed in the Michael addition reaction are almost only CO 2 R, CN, COR, NO 2 , and SO 2 Ph. Although amides (CONR 1 R 2 ) are also typical electron-withdrawing groups and are of great importance in organic synthesis, they are scarcely employed as the EWGs of the electrophilic alkenes in the Michael addition reaction. In this work, the Michael reactions of acrylamide and its derivatives with cyclanones were successfully carried out in the presence of enough radical inhibitors. The amide groups play a key role in producing the preferred products. The N-substituted acrylamides, including N-monosubstituted and N,N-disubstituted acrylamides could react with cyclohexanone (CHn) to give the expected 2-carbamoylethyl derivatives; however, acrylamide reacting with cyclohexanone only produced ene-lactam. Cyclanones also have effects on the products, while the ring size of cyclanones influences the reaction yield and the α-substituent decides the ratio of resulting isomeric ene-lactams.

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Section: The Effect Of N-substituents Of Amides On the Michael Reactionmentioning

confidence: 91%

Section: The Michael Addition Reaction Of Cyclanones With Acrylamidesmentioning

confidence: 99%

Michael addition reactions of cyclanones with acrylamides: Producing 2-carbamoylethyl derivatives or ene-lactams

Dai

Wang

Zhang

et al. 2008

Sci. China Ser. B-Chem.

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Allyl ethers as apparent initiators of radical polymerizations

Bevington

2001

European Polymer Journal

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Polymerization of Acrylamide in Aqueous Solution of Poly(N‐isopropylacrylamide) at Lower Critical Solution Temperature

Ishifune

Suzuki

Yamane

et al. 2008

Journal of Macromolecular Science, Part A

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Acrylamide (AAm) was found to polymerize in a solution of poly(N-isopropylacrylamide) (PNIPAAm) in water at around its lower critical solution temperature (LCST) (328C) without any initiators. This phenomenon was specifically observed in aqueous solutions of the polymers having LCST such as PNIPAAm and poly(methylvinylether) (PMVE). AAm polymerized only when PNIPAAm and AAm were dissolved in water below LCST of PNIPAAm and then the solution was warmed up to the polymerization temperature (408C). On the other hand, the polymerization of AAm did not proceed when AAm was added into aqueous PNIPAAm solution during and after the phase separation above 328C. Furthermore the polymerizability of AAm was remarkably affected by the concentration and molecular weight of the PNIPAAm additives. Under the condition of lower PNIPAAm concentration (0.30 mol/L), the increase in the molecular weight of PNIPAAm considerably increased the molecular weight of the resulting PAAm but decreased the yield of PAAm. Under the condition of higher PNIPAAm concentration (0.60 mol/L) the polymerizability was not so affected by the molecular weight of PNIPAAm, while the molecular weight of PAAm formed by using higher molecular weight PNIPAAm was higher than those of PAAm formed by using lower molecular weight PNIPAAm. Moreover, the molecular weight of PAAm formed by the PNIPAAm induced polymerization of AAm was much higher than that of the polymer obtained by the radical polymerization using AIBN in THF or VA-061 in water.

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Mechanistic Study on Polymerization of Acrylamide Induced by Cyclohexanone Based on the Interaction Between the Carbonyl and Amide Groups

Cited by 5 publications

References 14 publications

Michael addition reactions of cyclanones with acrylamides: Producing 2-carbamoylethyl derivatives or ene-lactams

Michael addition reactions of cyclanones with acrylamides: Producing 2-carbamoylethyl derivatives or ene-lactams

Allyl ethers as apparent initiators of radical polymerizations

Polymerization of Acrylamide in Aqueous Solution of Poly(N‐isopropylacrylamide) at Lower Critical Solution Temperature

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