Cyanoethylation. I. Weakly Basic Catalysts in the Reaction of Acrylonitrile with Active Methylene Compounds<sup>1</sup>

Adamcik, Joe A.; Miklasiewicz, Edward J

doi:10.1021/jo01037a015

Cited by 14 publications

(4 citation statements)

References 4 publications

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“…Subsequent treatment with a convenient base, such as triethylamine ( n = 1) or aqueous sodium hydroxide solution ( n = 2 and 3), and acrylonitrile afforded the expected Michael adducts 8 , 9 , and 10 in high yields. This modification of the original technique, which employed sodium tert -butoxide as the base, reduced the reaction time from 72 to 3 h for compound 5 . In addition, the purification of sodium tert -butoxide by sublimation was avoided.…”

Section: Resultsmentioning

confidence: 99%

Studies on the Intramolecular Cyclizations of Bicyclic δ-Hydroxynitriles Promoted by Triflic Anhydride

2007

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Studies have been conducted to investigate the reactivity of several bicyclic delta-hydroxynitriles with triflic anhydride in dichloromethane. The reactions of the analogues derived from 1-indanone and 1-tetralone lead to annulated enones. These products arise from an initial elimination reaction that generates an alkene, followed by the addition of the carbon-carbon double bond to the activated cyano group. The intramolecular cyclization of the derivative obtained from 1-benzosuberone unexpectedly followed a different path, giving a cyclic imidate as the major product. In this case, the activated cyano group is directly attacked by the hydroxyl group of the starting delta-hydroxynitrile. Theoretical calculations provide a rationale for the observed reactivity pattern. Both the formation of the triflate via its protonated form, its subsequent ionization to the carbocation, and the cyclization of the resulting alkene to the enone become less favorable when the size of the ring increases due to conformational effects. The opposite trend is observed for the competing Pinner-type cyclization to the imidate. An alternative mechanism for the formation of the lactams from the cyclic imidates under acid-catalyzed conditions has also been proposed.

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Section: Resultsmentioning

confidence: 99%

Studies on the Intramolecular Cyclizations of Bicyclic δ-Hydroxynitriles Promoted by Triflic Anhydride

2007

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“…In 1963, the addition of different methylene compounds onto acrylonitrile catalyzed by triethylamine was reported. 34 Following this early research, a wide range of catalysts has been developed, including for instance ruthenium complexes and enolatoiron(II) compounds. [34][35][36][37][38] 1-methyl-3-butylimidazolium hydroxide (an ionic liquid) has also been used as the reaction medium to promote different Michael additions, leading exclusively to bisadducts.…”

Section: Introductionmentioning

confidence: 99%

“…34 Following this early research, a wide range of catalysts has been developed, including for instance ruthenium complexes and enolatoiron(II) compounds. [34][35][36][37][38] 1-methyl-3-butylimidazolium hydroxide (an ionic liquid) has also been used as the reaction medium to promote different Michael additions, leading exclusively to bisadducts. 39,40 Synthesized basic cesium-beta zeolite proved as well to be an effective catalyst for the addition of malonitrile to terpenoid acceptors.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of polyester thermosets via internally catalyzed Michael-addition of methylene compounds on a 2-(trifluoromethyl)acrylate-derived building block

Berne

Caillol

Ladmiral

et al. 2022

European Polymer Journal

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“…Quite a few research groups have reported the double Michael reactions of active methylene compounds. Adamcik and Miklasiewicz1 reported the double Michael addition of acac, methyl acetoacetate, ethyl acetoacetate, malononitrile, and α‐cyanoacetamide with acrylonitrile to afford dicyanoethylated compounds in high yields in protic solvents catalyzed by triethylamine. The reaction of cyanoacetate with acrylonitrile was found to take place by the catalysis of ruthenium complexes or enolatoiron(II) compounds to produce double Michael addition compounds 2–6.…”

Section: Introductionmentioning

confidence: 99%

Novel anionic polyaddition of 2‐trifluoromethylacrylate by double Michael reaction with ethyl cyanoacetate

Umino

Nozaki

Hamana

et al. 2009

J. Polym. Sci. A Polym. Chem.

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Novel fluorinated polymer synthesis with anionic polyaddition by double Michael addition reaction of 2‐trifluoromethylacrylate derivatives with ethyl cyanoacetate (ECA) was proposed. Diaddition product of ECA with phenyl 2‐trifluoromethylacrylate was yielded in high yield by the catalysis of sodium ethoxide in tetrahydrofuran at 60 °C. Sodium hydroxide catalyzed double Michael addition reaction also produced diaddition product in high yield. Novel anionic polyaddition of 1,4‐phenylene bis(2‐trifluoromethylacrylate) [CH2C(CF3)COOC6H4OCOC(CF3)CH2] (PBFA) with ECA afforded the polymer of 1.2 × 104 as the highest molecular weight. The isolated polymer gave the polymer of 2.8 × 104 as a molecular weight by the reaction of the isolated polymer with PBFA in the presence of sodium ethoxide; which proved that the polymer end groups were mainly ECA moieties. The reaction mechanism that the proton abstraction from ECA followed by the addition of 2trifluoromethylacrylate was proposed. The reaction of acetylacetone with PBFA was also examined to give the polymer of 7.6 × 103 as the highest molecular weight catalyzed by sodium hydroxide at room temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5698–5708, 2009

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Cyanoethylation. I. Weakly Basic Catalysts in the Reaction of Acrylonitrile with Active Methylene Compounds¹

Cited by 14 publications

References 4 publications

Studies on the Intramolecular Cyclizations of Bicyclic δ-Hydroxynitriles Promoted by Triflic Anhydride

Studies on the Intramolecular Cyclizations of Bicyclic δ-Hydroxynitriles Promoted by Triflic Anhydride

Synthesis of polyester thermosets via internally catalyzed Michael-addition of methylene compounds on a 2-(trifluoromethyl)acrylate-derived building block

Novel anionic polyaddition of 2‐trifluoromethylacrylate by double Michael reaction with ethyl cyanoacetate

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Cyanoethylation. I. Weakly Basic Catalysts in the Reaction of Acrylonitrile with Active Methylene Compounds1

Cited by 14 publications

References 4 publications

Studies on the Intramolecular Cyclizations of Bicyclic δ-Hydroxynitriles Promoted by Triflic Anhydride

Studies on the Intramolecular Cyclizations of Bicyclic δ-Hydroxynitriles Promoted by Triflic Anhydride

Synthesis of polyester thermosets via internally catalyzed Michael-addition of methylene compounds on a 2-(trifluoromethyl)acrylate-derived building block

Novel anionic polyaddition of 2‐trifluoromethylacrylate by double Michael reaction with ethyl cyanoacetate

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Cyanoethylation. I. Weakly Basic Catalysts in the Reaction of Acrylonitrile with Active Methylene Compounds¹