Crystallizing reaction

When colorless crystals of rac-s-trans-3,8-di-tert-butyl-l,5,6,10-tetraphenyl-deca-3,4,6,7-tetraene-l,9-diyne (123) were heated at 140 °C for 2 h, the ben-zodicylobutadiene derivative (126) was produced as green crystals. As shown in the sequence (Scheme 20), 123 is first isomerized to its s-ds-isomer (124), and intramolecular thermal reaction of the two allene moieties through a [2+2] conrotatory cyclization gives the intermediate 125, which upon further thermal reaction between acetylene moieties gives the final product 126 [19,22].This is another example of the crystal-to-crystal reaction. 

Figure 7.27. ORTEP representations from X-ray data of the salts 76a with (S)-PEA, and (a) chiral product 76a-(S)-PEA, and (b) the overlap of both starting material and product at 50% conversion of the crystal-to-crystal reaction. (Taken from reference 174.)...

Single crystal-to-single crystal reactions are quite rare in solid-state organic photochemistry, and we were fortunate to discover a second example in the Yang photocyclization of the 1-phenylethylamine salt of 2-methyl-2-benzoyl-p-carboxylic acid 39 [37]. 

In this article, the features and mechanism of the crystal-to-crystal reactions of 1,3-diene compounds are described on the basis of the molecular packing structure and intermolecular interactions in the crystals for starting materials and products. The dimerization and isomerization of unsaturated compounds as well as addition polymerization via a chain reaction mechanism are ideal sohd-state reactions, because they produce no leaving group during the reac-... 

In contrast to cyclization and rearrangement as the unimolecular reaction, the EZ isomerization of olefins is difficult due to a drastic and unenviable change in the size and shape of the occupied space by substituents on the double bond during isomerization in the crystalline state. Some (Z,Z)-muconic derivatives provide a geometrical isomer as the photoproduct in a high yield, but not a polymer, under UV irradiation in the crystalline state, as is described in the Introduction (Scheme 1 and Table 1). This isomerization is a crystal-to-crystal reaction with an excellent selectivity, which is completely different from ordinary photoisomerizations. 

Powder X-ray diffraction has verified that the isomerization occurs via a crys-tal-to-crystal reaction process, and that the diffraction profiles of the crystals after photoirradiation consist of overlapped patterns of diffraction due to the crystals of 10 and 11. This indicates that the crystal domains of each isomer exist simultaneously in the crystals accompanied by crystal phase separation during the photoisomerization. Single crystal structure analysis has disclosed that the crystals of 11 as the photoproduct have a symmetry different from that of the starting crystals of 10 (Fig. 14). 

Crystallization processes are very important in chemical processes whenever there are solid products in a reactor. We saw in Chapter 9 that crystallization and dissolution particle sizes could be handled with the same equations as chemical vapor deposition and reactive etching. We note here that crystallization reactions can be handled with the same equations as polymerization. 

Optical and electron microscopy provide information about crystal reactions at a more macroscopic level. They are particularly good at revealing when reaction is favored near pre-existing lattice defects rather than occurring uniformly through the bulk of the crystal. Sometimes reaction products can be observed directly other times their presence is revealed by chemical etching, fluorescence, or the development of lattice strain [39]. 

Crystal reaction study mechanistic tools, 296 computer simulation, 297 electronic spectroscopy, 298 electron microscopy, 298 electron paramagnetic resonance (EPR), 299 nuclear magnetic resonance (NMR), 298 Raman spectroscopy, 299 Crystal reaction study techniques crystal mounting, 308 decomposition limiting, 309 polarized IR spectroscopy, 309 temperature control, 308 Cycloreversions, adiabatic photochemical involving anthracenes, 203 excited state properties of lepidopterenes, 206... 

Crystallization, by definition, implies that the initial structure be a glass, followed by the nucleation and growth of a crystalline phase, be it the equilibrium one or a metastable phase. The process is a first-order transformation and involves atomic diffusion, or at least atomic shuttles. Types of crystallization reactions that occur include polymorphous crystallization, which is a composition invariant transformation such as that in Fe-B, and eutectic crystallization, T, in FeNiPB glass, where line lamellae of iron-nickel austenite and mclastable (FeNiJj PB phases grow cooperatively. 

Returning now to the observed effect of particle size on catalytic activity, van Hardeveld and Hartog 219) have calculated that the relative concentration of C7 sites on octahedral iron crystallites decreases with decreasing particle size and that, in general, the C7 site is not a small-particle surface site. The above correlation of increased catalytic activity with increased C7 site surface concentration thus also explains the observed structure sensitivity (particle size dependence) for this reaction. Finally, this correlation is consistent with results obtained from field electron microscopy of iron (220), single crystal reaction studies on tungsten (also a bee metal) (227), and symmetry considerations (222). 

Keywords 2-benzoylbenzamide, absolute asymmetric synthesis, single-crystal-to-single-crystal reaction, photoirradiation, 3-(Al-methylanilino)-3-phenylphthalide... 

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