Alkyl and arylpropenonitriles

Procházka, M.; Uchytil, B.; Zelinka, J.

doi:10.1135/cccc19741342

Cited by 5 publications

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“…The implications of Scheme II are clear with respect to the use of the mercury method to determine the relative rates of olefin addition to the benzyl radical (and, by inference, to other stabilized radicals as well): One must determine the relative yields not of two products, as with simple alkyl radicals (Scheme I), but rather of all four major products (e.g., [11][12][13][14] of olefin addition and subsequent trapping (Scheme III).…”

Section: Resultsmentioning

confidence: 99%

“…An additional complication might conceivably arise if the benzyl-trapped products 12 and 14 result from radical coupling, rather than from SH2 transfer of a benzyl fragment from mercury.9 One might then anticipate some competitive formation of the disproportionation products 15 and 16 in addition to 11 this question, we prepared 1510 and 1611 (each as a mixture of isomers) and searched the products of competitive addition for evidence of disproportionation. None was found.12 Quantitation of products 11-14 is thus sufficient for reliable determimation of the relative rates of olefin addition.…”

Section: Resultsmentioning

confidence: 99%

“…None was found.12 Quantitation of products 11-14 is thus sufficient for reliable determimation of the relative rates of olefin addition. Higher oligomers of styrene and acrylonitrile are precluded by the rapid capture of the initial adducts 9 and 10, and while the high trapping rate reduces the yields of [11][12][13][14] (by diverting most of the benzyl radicals to toluene and bibenzyl) the relative product yields are readily determined with the required accuracy and precision. Routine quantitation of each of the products 11-14 proved to be inconvenient, as a result of the wide variation in boiling points.…”

Section: Resultsmentioning

confidence: 99%

“…Routine quantitation of each of the products 11-14 proved to be inconvenient, as a result of the wide variation in boiling points. In contrast, determination of the relative yields of the hydrogen-trapped products 11 and 13 was straightforward. Thus it was of interest to determine the partitioning of each of the adducts 9 and 10 between the products of trapping by hydrogen and by benzyl fragments; if the ratios 11:12 and 13:14 are known and independent of reaction conditions, a simple determination of the ratio of products 11 and 13 is sufficient to determine the rate constant ratio ks/kA (Scheme III).…”

Section: Resultsmentioning

confidence: 99%

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Model copolymerization reactions: determination of the relative rates of addition of styrene and acrylonitrile to the benzyl radical

Prementine¹,

Tirrell²

1989

Macromolecules

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Reductive demercuration of benzylmercuric chloride in CH2C12 solutions affords toluene and bibenzyl as major products in a ratio of ca. 4:3. In similar solutions that contain styrene and acrylonitrile, one obtains not only toluene and bibenzyl but also 1,3-diphenylpropane (11), 1,2,4-triphenylbutane (12), 4-phenylbutyronitrile (13), and 2-benzyl-4-phenylbutyronitrile ( 14). Each of these products can be rationalized on the basis of a reaction scheme in which addition of the benzyl radical to styrene or acrylonitrile is followed by trapping of the adduct by transfer of a hydrogen atom or a benzyl fragment. The product ratios 11:12 and 13:14 were found to be independent of reaction conditions within the range of conditions employed in this work. The relative rates of addition of styrene and acrylonitrile (ks/kA) were determined by analysis of relative product yields as a function of the relative starting concentrations of styrene and acrylonitrile. We find kg/kA = 0.33 ± 0.04, a result that is consistent with the known selectivity of the 1-phenylethyl radical and that falls within the range of published reactivity ratios for styrene in its copolymerization with acrylonitrile. These results support the use of the mercury method as a source of simple, reliable models for the macroradicals involved in the growth of copolymer chains.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Model copolymerization reactions: determination of the relative rates of addition of styrene and acrylonitrile to the benzyl radical

Prementine¹,

Tirrell²

1989

Macromolecules

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Trimethylsilylcyanid als Umpolungsreagens, XI. Über den ambidenten Charakter substituierter Allyl‐Anionen

Hünig

Reichelt

1986

Chem. Ber.

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An l-Cyan-3-aryl-l-(trimethylsiloxy)allyl-Anionen (6) wird das Verhaltnis der u/y-Alkylie- The dependence of the u/y-ratio of alkylation products on several factors has been determined with 1 -cyano-3-aryl-l -(trimethylsiloxy)allylic anions. Increasing amounts of y-product are found in more polar solvents, with larger alkali ions, on addition of HMPT, with smaller alkyl groups in the electrophile, and especially with p-cyanophenyl groups. In contrast, temperature and leaving groups have minor effects. On substitution of the 0-silyl group by 0-methyl and 0-ethoxycarbonyl, a-alkylation predominates strongly. The results are compared to known allylic anions. Furthermore, the isomerisation of compounds of type C to type B is described as well as a new addition reaction of cyanoformates to aldehydes.

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ChemInform Abstract: ISOMERIZATION OF UNSATURATED NITRILES PART 2, ALKYL AND ARYLPROPENONITRILES

Procházka¹,

Uchytil²,

Zelinka³

1974

Chemischer Informationsdienst

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Alkyl and arylpropenonitriles

Cited by 5 publications

References 0 publications

Model copolymerization reactions: determination of the relative rates of addition of styrene and acrylonitrile to the benzyl radical

Model copolymerization reactions: determination of the relative rates of addition of styrene and acrylonitrile to the benzyl radical

Trimethylsilylcyanid als Umpolungsreagens, XI. Über den ambidenten Charakter substituierter Allyl‐Anionen

ChemInform Abstract: ISOMERIZATION OF UNSATURATED NITRILES PART 2, ALKYL AND ARYLPROPENONITRILES

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