CRYSTAL-STRUCTURE AND GAS-PHASE INVESTIGATIONS OF LITHIATED TERT-BUTYL ACETOACETATE

被引：11

作者：

WALDMULLER, D

MAYER, B

BRAUN, M

HANUSCHIK, A

KRUGER, C

GUENOT, P

机构：

[1] MAX PLANCK INST COAL RES,W-4330 MULHEIM,GERMANY

[2] UNIV RENNES 1,CRMPO,F-35042 RENNES,FRANCE

[3] UNIV DUSSELDORF,INST ORGAN CHEM,UNIV STR 1,W-4000 DUSSELDORF 1,GERMANY

来源：

CHEMISCHE BERICHTE-RECUEIL | 1992年 / 125卷 / 12期

关键词：

LITHIUM ENOLATE; PE SPECTROSCOPY; MASS SPECTROMETRY;

D O I：

10.1002/cber.19921251225

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The lithium enolate 2, generated either by deprotonation of tert-butyl acetoacetate (1) or by pyrolysis of lithiated tert-butyl acetate (3) is crystallized from toluene. The X-ray diffraction analysis of unsolvatized 2 reveals a hexameric structure. Thereby, the central skeleton is formed by two Li-O six-membered rings, and the carbonyl group of the ester moiety serves to complete the fourfold coordination of the lithium atom. The thermal stability of 2 enables the very first mass spectrometric and photoelectron spectroscopic investigation of a lithium enolate. The lithium compound 2 forms aggregates even in the gas phase. The first vertical ionization energy of 2 is found to be significantly lower than those observed in the photoelectron spectra of both the enol ether 5 and the ester 1.

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页码：2779 / 2782

页数：4

相关论文

共 26 条

[1] CRYSTAL STRUCTURE OF (1-PHENYLBUTANE-1,3-DIONATO)(ETHYLENE GLYCOL)-SODIUM [J].

BRIGHT, D ;

MILBURN, GHW ;

TRUTER, MR .

JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1971, (10) :1582-&

[2] VINYL ETHER HYDROLYSIS .2. GENERAL ACID CATALYZED HYDRATION OF 3-ALKYLOXYCROTONIC AND 3-ARYLOXYCROTONIC ACID DERIVATIVES [J].

BRYNES, SD ;

FEDOR, LR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (20) :7016-&

[3]

CAMBILLAU C, 1979, NOUV J CHIM, V3, P9

[4] COMPLEXES FORMED BY THE ADDITION OF ETHER CROWNS TO NA+ AND K+ ETHYL-ACETYLACETATE-ENOLATES - CRYSTALLINE-STRUCTURES AND EQUILIBRIUM SYSTEM IN SOLUTION IN THF AND DMSO [J].

CAMBILLAU, C ;

BRAM, G ;

CORSET, J ;

RICHE, C .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1982, 60 (20) :2554-2565

[5] ENOLATES OF ETHYL ACETYLACETATE - STRUCTURE AND REACTIVITY OF POTASSIUM-SALT IN PRESENCE OF CROWN-ETHER AND CRYPTAND [J].

CAMBILLAU, C ;

BRAM, G ;

CORSET, J ;

RICHE, C ;

PASCARDBILLY, C .

TETRAHEDRON, 1978, 34 (17) :2675-2685

[6] STEREOSELECTIVE ALDOL REACTIONS WITH (R)-2-HYDROXY-1,2,2-TRIPHENYLETHYL AND (S)-2-HYDROXY-1,2,2-TRIPHENYLETHYL ACETATE AND RELATED GLYCOL MONOACETATES [J].

DEVANT, R ;

MAHLER, U ;

BRAUN, M .

CHEMISCHE BERICHTE-RECUEIL, 1988, 121 (03) :397-406

[7] GROUND-STATES OF MOLECULES .38. MNDO METHOD - APPROXIMATIONS AND PARAMETERS [J].

DEWAR, MJS ;

THIEL, W .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (15) :4899-4907

[8] Heats of organic reactions VI Heats of hydrogenation of some oxygen-containing compounds [J].

Dolliver, MA ;

Gresham, TL ;

Kistiakowsky, GB ;

Smith, EA ;

Vaughan, WE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1938, 60 :440-450

[9] ANIONIC HEXAFLUOROACETYLACETONATO COMPLEXES OF ALKALI AND OTHER OTHER METALS AND CRYSTAL-STRUCTURE OF DIRUBIDIUM TRIS(HEXAFLUOROACETYLACETONATO)-SODATE [J].

FENTON, DE ;

NAVE, C ;

TRUTER, MR .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1973, (20) :2188-2194

[10] NUCLEOPHILIC ADDITIONS TO KETENES BY (TRIMETHYLSILYL)LITHIUM AND BY ENOLATES [J].

GONG, LY ;

LEUNGTOUNG, R ;

TIDWELL, TT .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (11) :3634-3639