Solid-state aromatization

Supercritical Mixtures Dehenedetti-Reid showed that conven-tionaf correlations based on the Stokes-Einstein relation (for hquid phase) tend to overpredict diffusivities in the supercritical state. Nevertheless, they observed that the Stokes-Einstein group D g l/T was constant. Thus, although no general correlation ap es, only one data point is necessaiy to examine variations of fluid viscosity and/or temperature effects. They explored certain combinations of aromatic solids in SFg and COg. 

In most of the papers discussing tautomerism in dihydropyrimidines, the possibility of the existence of 4,5-dihydro isomer 47c (Scheme 19) was not even considered or was ruled out on the basis of H NMR spectra. In 1985, however, Kashima et al. (85TL5057) reported that, although dihydropyrimidines 47 with r = H or Pr (R = R = R = Me, R = H) indeed exist only as mixtures of 47a and 47b tautomers, for analogs with r = Ph, OEt, or SMe, 4,5-dihydro tautomers 47c were also observed in CDCI3 solution in relative amounts of 10%, 20%, and 31%, respectively. The proportion of this tautomer rises to 45% in the case of the 2-dimethylamino-substituted derivative. The electronic effects of a heteroatom or an aromatic group in the 2 position were proposed as an explanation for this phenomenon. No 4,5-dihydropyrimidine has ever been found in the solid state. 

Kaeriyama et al. [10] reported on the Ni(0)-catalyzed coupling of 1,4-dibromo-2-methoxycarbonylbenzene to poly(2-methoxycarbonyl-l,4-phenylene) (4) as a soluble, processable precursor for parent PPP 1. The aromatic polyester-type PPP precursor 4 was then saponified to carboxylated PPP 5 and thermally decarboxy-latcd to 1 with CuO catalysts. However, due to the harsh reaction conditions in the final step, the reaction cannot be carried out satisfactorily in the solid state (film). 

The reactions of some aromatic metal carboxylates are on the borderline of classification as solid-state processes. While there is no evidence of liquefaction, rates of decomposition in the poorly crystallized or vitreous reactant obey kinetic expressions more characteristic of reactions proceeding in a homogeneous phase. 

Fig. 9. Solid-state NMR spectra of stiff chain aromatic polyesters containing sulfur bonds and tentative assignements of their signals, 401. A contact time of 2 ms and a pulse repetition time of 10 s were used...

PET, PTT, and PBT have similar molecular structure and general properties and find similar applications as engineering thermoplastic polymers in fibers, films, and solid-state molding resins. PEN is significantly superior in terms of thermal and mechanical resistance and barrier properties. The thermal properties of aromatic-aliphatic polyesters are summarized in Table 2.6 and are discussed above (Section 2.2.1.1). 

The carboxy-ester interchange melt polyesterification used for the preparation of this wholly aromatic copolyester is followed by a solid-state postpolyesterification (Scheme 2.65). (Reprinted from ref. 439. Copyright 1990 John Wiley Sons, Inc., by permission of the copyright owner.)... 

Solid-state [4 + 2] cycloaddition of fullerene C60 with condensed aromatics using a high-speed vibration milling technique [100]... 

The stability of polyanhydrides composed of the diacids sebacic acid (SA), bis( -carboxyphenoxy)methane (CPM), l,3-bis(g-carboxyphe-noxy)propane (CPP), l,6-bis( -carboxyphenoxy)hexane (CPH), and phenylenedipropionic acid (PDP), in solid state and in organic solutions, was studied over a 1-year period. Aromatic polyanhydrides such as poly(CPM) and poly(CPH) maintained their original molecular weight for at least a year in both solid state and solution (20). 

Stability studies under anhydrous conditions were also conducted using the aliphatic-aromatic homopolyanhydrides. These polymers were completely stable in the solid state in vacuo for over 6 months at 25°C (8). 

REFSGAARD H F, SCHAUMBURG, K and SKIBSTED L H (1996) Solid-state C NMR investigations of insoluble deposit in aromatic bitters, Z Lebesm IJnters Forsch, 203, 287-92. 

The solid state structure of complex 7b is shown in Figure 25.1. Similar to parent chelating ether complex [9b], the solid-state structure of 7b shows a distorted square-pyramidal structure with the benzylidene moiety at the apical position. The N-aryl ring is located above the benzylidene moiety resulting in the relatively close contact of the benzylidene proton with the 7r-aromatic system of the mesityl group. 

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