ION-PAIRING AND REACTIVITY OF BETA-KETOENOLATES

被引:11
作者
ARNETT, EM
DEPALMA, V
MAROLDO, S
SMALL, LS
机构
[1] Department of Chemistry, University of Pittsburgh
关键词
D O I
10.1351/pac197951010131
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Relationships between structure and reactivity for alkali salts of the following symmetrical $-diketones in dimethyl sulfoxide solution are considered: dibenzoylmethane; dipivaloylmethane; 3-methylpentane-2,4-dione; 2-methyldimedone; dimethyl methylmalonate and isopropylidene methylmalonate (methyl Meldrum's Acid). Lithium, sodium, potassium, cesium and tetrabutylammonium salts were compared in several cases. The stabilities and structures of the ion-pairs were studied by conductance, nmr, far infrared and by the rates and heats of reaction with methyl iodide. The results, for the most part, are consistent with a simple two- state equilibrium and imply that the cyclic enolate anions are more stable than their acylic analogues both in terms of dissociation from the ion pair and also in terms of their reactivities to proton transfer and alkylation. © 1979, Walter de Gruyter. All rights reserved.
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页码:131 / 137
页数:7
相关论文
共 22 条
  • [1] Acree S.F., 1912, AM CHEM J, V48, P352
  • [2] CATION AND SOLVENT EFFECTS ON ALKYLATION OF 2 ALKALI BETA-KETOENOLATES
    ARNETT, EM
    DEPALMA, VM
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (17) : 5828 - 5829
  • [3] ALKALI BETA-KETOENOLATES AS ION-PAIRS
    ARNETT, EM
    DEPALMA, VM
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (23) : 7447 - 7448
  • [4] WEAK ACIDS IN STRONG BASES .1. THERMOCHEMICAL METHOD FOR COMPARING ACIDITIES
    ARNETT, EM
    MORIARIT.TC
    SMALL, LE
    RUDOLPH, JP
    QUIRK, RP
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (05) : 1492 - 1495
  • [5] ARNETT EM, 1978, J AM CHEM SOC, V100
  • [6] ARNETT EM, 1975, FARADAY S CHEM SOC, V10, P20
  • [7] BORDWELL F, 1975, J AM CHEM SOC, V97, P7006
  • [8] BRANDSTROM A, 1958, ARK KEMI, V13, P51
  • [9] EATOUGH DJ, 1973, EXPT THERMOMETRIC TI
  • [10] FUNCK E, 1960, Z PHYSIK CHEM FRANKF, V23, P297