Newly Clarified Structures

Glaucentrine was originally isolated in the 1930 s from three Dicentra species, and subsequently assigned structure XXIV. No degradation 

In 1965, the actual synthesis of (+ )-l-hydroxy-2,9,10-trimethoxy-aporphine (XXIV) (mp 190°-192°) by an unambiguous route was reported, and the synthetic material was found to be different from natural glaucentrine (16). It was then found that natural glaucentrine and natural corydine (XXVI) are identical, so that the name glaucentrine should be eliminated from the record (16). 

A quaternary aporphine possessing one phenolic hydroxyl and three methoxyls had been isolated from the bark of Fagara tinguassoiba Hoehne and assigned structure XXVII (in the A-methyl quaternary form), partly on the basis of a comparison with a derivative of glaucentrine (17). 

The alkaloid isoboldine was first isolated from Nandina domestica Thunb. and correctly assigned structnre XXVIII (19). This structural designation has been further confirmed by a synthesis of the alkaloid through phenolic oxidative coupling (20). 

In 1964, isoboldine, as alkaloid A, methanolate (mp 121°-126°), solvent-free base (mp 180° [a] -p 41.2° in ethanol), was also reported in Symplocos celastrinea Mart., where it was found in large enough quantities that a variety of chemical transformations could be attempted (11). Treatment of either isoboldine (XXVIII) or the well-known boldine (XXX) with dihydropyran, then with diazomethane, and finally acid hydrolysis of the protective dihydropyranyl grouping, resulted in the formation of JV-methyllaurotetanine (XXIX), whose structiu-e had previously been clearly established. The hydroxyl group is therefore more reactive when at C-9 than when situated either at C-1 or C-2 (21). 

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In this chapter, NMR studies for four ILs having a common anion bis(fluoromethylsulfonyl)amine (TFSA) will be described. The cations are N-ethyl-N-methylimidazolium (EMIm), N,2-dimethyl-N-propylimidazolium (DMPIm), N-methyl-N-propylpyrrolidinium (F 13), and N,N-diethyl-N-methyl-N-(2-methoxylethyl)ammonium (DEME). These ILs are important candidates to use as electrolytes in various batteries or cells. The basic properties of molecular weight (MW), viscosity (q) and cation and TFSA diffusion coefficients (Dcaiion and ZTtfsa) measured at 30°C are given in Table 1 for the four ILs. The experimental data have been published in our previous papers for individual ILs.i-4 In the present chapter, the individual experimental data for the four ILs are plotted on a sheet to clarify the cation properties. In addition, newly derived plots of Dcaaon versus correlation times of molecular motion are included. The chemical structures of the ions are shown. 

Nineteen years have passed since the monograph Solid Acids and Bases was published in 1970. During this period many new kinds of solid acids and bases have been found and synthesized. The surface properties (in particular, acidic and basic properties) and the structures of the new solids have been clarified by newly developed measurement methods using modern instruments and techniques. The characterized solid acids and bases have been applied as catalysts for diversified reactions, many good correlations being obtained between the acid-base properties and the catalytic activities or selectivities. Recently, acid-base bifunctional catalysis on solid surfaces is becoming an ever more important and intriguing field of study. 

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