Topochemical control

Topochemical control of solid state dimerizations is well illustrated by the example of the frows-cinnamic acids.(112) The a form of ftmv-cinnamic acid is known to have a molecular separation of 3.6 A between double bonds and the molecules are arranged in a head-to-tail fashion. -Cinnamic acid has approximately the same intermolecular distance in the crystal but the molecules are arranged in a parallel head-to-head manner. a-Truxillic (101) and /3-truxinic (102) acids are the products expected and observed ... 

Topochemical control is also revealed by closely related compounds showing significant differences in chemical behavior in the solid state. For example, cinnamylidenemalonic acid (103) dimerizes in the solid state to cyclobutane (104), while cinnamylideneacetic acid (105) dimerizes to cyclobutane (106)(113) ... 

Topochemical control will also be revealed in causing a given compound to react differently in the solid phase than in solution. Crystalline 2,5-di-methylbenzoquinone yields dimers (111) and (112) upon irradiation 2,5-dimethylbenzoquinone in ethyl acetate solution yields primarily the oxetane (113)[Pg.544]

Electronic excitation energy in a crystal is in many cases highly mobile It may diffuse very rapidly through many thousands of molecules and eventually be trapped at some appropriate defect site. If, then, photoreaction occurs at this site, the stereochemistry of the reaction pathway will be determined by the symmetry of this site, and not by the symmetry of the bulk crystal. Nevertheless, the bulk symmetry is found empirically to be the determining factor in most cases studied (topochemical control). 

Photodimerization of cinnamic acids and its derivatives generally proceeds with high efficiency in the crystal (176), but very inefficiently in fluid phases (177). This low efficiency in the latter phases is apparently due to the rapid deactivation of excited monomers in such phases. However, in systems in which pairs of molecules are constrained so that potentially reactive double bonds are close to one another, the reaction may proceed in reasonable yield even in fluid and disordered states. The major practical application has been for production of photoresists, that is, insoluble photoformed polymers used for image-transfer systems (printed circuits, lithography, etc.) (178). Another application, of more interest here, is the use that has been made of mono- and dicinnamates for asymmetric synthesis (179), in studies of molecular association (180), and in the mapping of the geometry of complex molecules in fluid phases (181). In all of these it is tacitly assumed that there is quasi-topochemical control in other words, that the stereochemistry of the cyclobutane dimer is related to the prereaction geometry of the monomers in the same way as for the solid-state processes. 

McBride and co-workers have studied extensively the reactions of such free-radical precursors as azoalkanes and diacyl peroxides (246). By employing a variety of techniques, including X-ray structure analysis, electron paramagnetic resonance (EPR), and product studies, and comparing reactions in the crystal and in fluid and rigid solvents, they have been able to obtain extremely detailed pictures of the solid-state processes. We will describe here some of the types of lattice control they have elucidated, and the mechanisms that they suggest limit the efficacy of topochemical control. 

Solvent-drop grinding was next applied as an eco-friendly modification to a previously described preparation of a crystalline organic inclusion compound. Initial work had demonstrated solution-mediated supramolecular organisation and solid-state topochemically controlled reactivity in a system involving l,2-bis(4-pyridyl)ethylene (bpe) 32 and 1,2,4,5-benzenetetracar-boxylic acid (bta) 33 [57]. A single crystal of a 2 1 bpe bta 32 33 cocrystal was... 

A further distinction has to be made between reactions taking place within a molecular crystal and reactions of a molecular crystal A with a molecular crystaT B (see Scheme 2 A and B can also be the same crystal) [7bj. Reactions of the former type, or intra-solid reactions, can be either under topochemical control, depending on the proximity of the reactants, or may imply extensive molecular motion within the crystal lattice. Reactions of the second type, or inter-solid reactions, can either take place on the crystallite surface or require molecular diffusion through the lattice. Inter-solid reactions are often accompanied by formation of eutectics. 

Lauher and Fowler et al. have proposed an elegant strategy for the control of topochemical polymerization based on the host-guest cocrystal concept. They used the ureylene and oxalamide functionality to form layered supramolecu-lar structures for the topochemically controlled polymerization of diacetylenes and 1,3-butadienes in the solid state [62,63]. 

Scheme 10.13 Topochemically controlled solid-state synthesis of bisadduct 61 and subsequent cyclopropanation to give [2 4]-hexakisadduct 62. (i) 180°C, 10 min (ii) 40 equiv. diethyl bromomalonate, 40 equiv. DBU.

When the reactivity of a solid is controlled by the crystal structure, rather than by the chemical constituents of the crystal, the reaction is said to be topochemically controlled. The nature of products obtained in a decomposition reaction is frequently decided by topochemical factors, particularly when the reaction occurs within the solid without separation of a new phase (Thomas, 1974 Manohar, 1974). A topotactic reaction is a solid state reaction where the atomic arrangement in the reactant crystal remains largely unaffected during the course of the reaction, except for changes in dimension in one or more directions. Dehydration of Mo03-2H20 is a typical example of a topotactic reaction ... 

In the absence of defects, the reactivity of organic solids is mainly determined by molecular packing. Reactions in which the crystal structure holds sway over intrinsic molecular reactivity are said to be topochemically controlled (Thomas, 1974). A classic example of a topochemically controlled organic reaction in the solid state is the photodimerization of rrans-cinnamic acids studied by Schmidt et al. (see Ginsburg,... 

The correct alignment of surfactants in some, but not all, SUVs is an essential requirement for polymerization. Polymerization of diacetylenes is topochemically controlled and only occurs below the phase transition temperature of the surfactant. In contrast, SUVs prepared from styrene-containing surfactants could be polymerized in their fluid states [55]. The degree of polymerization varied from very low (10-20 for SUVs prepared from styrene containing surfactants) to rather high (several hundred for SUVs prepared from diacetylene-containing surfactants). 

Scheffer, Trotter, and co-workers have provided elegant demonstrations of the distance and angular dependence between a carbonyl oxygen atom and a gamma hydrogen atom on the ease of initial abstraction [276], Their singlecrystal X-ray structural information allows the various courses of Norrish II reactions of neat solids to be understood in the context of topochemical control [11,13]. For instance, they have noted that the cyclic diones 77 (n = 7,8,10, and 12) follow different Norrish II pathways depending upon the conformations of the individual molecules in their crystals (Eq. 9) [277]. 

The fact that the polyreaction of diacetylenes is topochemically controlled is especially well documented by the polymerization behavior of the sulfolipid (22)23 . (22) forms two condensed phases when spread on an acidic subphase at elevated temperatures (Fig. 10). UV initiated polymerization can only be carried out at low surface pressures in the first condensed phase, where the molecules are less densely packed. Apparently, in the second phase at surface pressures from 20 to 50 mN/m the packing of the diyne groups is either too tight to permit a topochemical polymerization or a vertical shift of the molecules at the gas/water interface causes a transition from head packing to chain packing (Fig. 10), thus preventing the formation of polymer. 

Several reviews deal with the solid-state reactions of simple inorganic salts and of organic compounds.1-8 The essential differences between solid-state reactions and reactions in solution can be ascribed to the fact that solid-state reactions occur within the constraining environment of the crystal lattice. The reactant crystal lattice can control both the kinetic features of a reaction, and the nature of the products. In many solid-phase reactions the separation distances and mutual orientations of reactants in the solid determine the product. Such reactions are said to be topo-chemically controlled.9 Topochemical control of a reaction product is analogous to kinetic control in solution. The product is not necessarily the thermodynamically most stable product available to the system, but is rather the one dictated by the reaction pathway available in the constraining environment of the solid. 

Regardless of whether or not topochemical control is evident in a reaction, there is often a coherence, on the molecular level, between the lattice of the product and that of the reactant the reaction is then described as being topotactic. In other instances, the growth of the product phase proceeds in a less orderly manner, producing a product that is amorphous to X-rays. This situation... 

E (1) Accelerates reaction through lowered AS achieved by restricting configurational space of starting materials (2) Increases yield without acceleration by inhibiting alternative reactions (normal topochemical control) Yes... 

Prior to the development of tether-directed functionalization methods, Krautler and co-workers developed a very elegant topochemically controlled, solid-state group-transfer synthesis [12,13] to obtain the trans-1 bisanthracene adduct 9 (Figure 2). 

On the other hand, since the concept of topochemically-controlled reactions was established, various approaches to asymmetric synthesis using solid-state photoreaction... 

Remarkable changes in the product profiles were recognized when the reaction was carried out at low (5%) conversion or at low temperature (-78°C). In the former case, a good ee value (77% ee) was obtained with exclusive product formation (>95% as observed by H-NMR of the crude mixture). Under these conditions, the molecules were supposed to be still under topochemical control leading to the better stereoselective reaction in the crystals. Additionally, the reaction at -78°C gave similar results (50% yield, 65% ee) for the same reason, where the molecules were strongly frozen in the crystal lattices. Obviously, the topochemical control was much more effective at lower temperature since 65 %ee was obtained even at 50 % conversion, which value corresponded to about 39 %ee for 0°C on estimation of the curve. Apart... 

Topochemically controlled solid reactions are governed by the crystal structure of the solid. Even if the intrinsic reactivity allows for a reaction, the topochemical restrictions circumvent a conversion. The photodimerization of solid anthracene was observed electron microscopically at dislocations [85], The reason for this is the possibility of molecule rotation at the dislocation, and not only the high pressure. 

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