Inclusion solid state

Potrzebowski MJ, Kazmierski S (2005) High-Resolution Solid-State NMR Studies of Inclusion Complexes. 246 91-140 Poulin P, see Loudet JC (2003) 226 173-196 Raghuraman K, see Katti KV (2003) 229 121-141... 

A regio- and stereoselective Beckmann rearrangement utilized diastereose-lective host guest interactions of the inclusion complexes 225 and 228 in a solid state reaction. Initially, a 1 1 mixture of the chiral host 223 and the racemic oximes 224 and 227, respectively, was treated with ultra sound in the solid state to induce the optical resolution. Then H2SO4 was added to start the Beckmann rearrangement, the corresponding c-caprolactams 226 and 229 were isolated in 68 % and 64 % yields and ee of about 80 % and 69 % (determined by HPLC analysis on chiracel OC) (Scheme 43) [46]. 

Over the last few years, we have made a number of novel discoveries using reactive salt fluxes in the crystal growth experiment of mixed-metal oxides. The most important outcome that these salt-inclusion solids have demonstrated is the propensity for structure- directing effects of the employed salt. These hybrid solids have revealed fascinating solid-state structures ranging from nanoclusters to three-dimensional open frameworks of current interest. Solids featuring mag-... 

When a solution of 10a and 11 in ether was kept at room temperature for 12 h, a 2 1 inclusion complex of 10a and 11 was obtained as colorless prisms (m.p. 134-137 °C) in 72% yield. When a powdered mixture of the inclusion crystal and 7 was kept at room temperature in the solid state for 3 days, (+)-trans-1,2-dibromocyclohexane (12) of 12% ee was obtained in 56% yield by distillation of the reaction mixture [3]. Much more efficient enantioselective reactions in the solid state are described in Sect. 6. 

Enantioselective Br2 addition to cyclohexene (11) was accomplished by the solid-state reaction of a 2 1 inclusion complex of 10b and 11 with 7, although the optical yield was low (Sect. 2.1). However, some successful enantioselective solid-state reactions have been reported. For example, reaction of a 1 1 complex of 68 and acetophenone (64a) with borane-ethylenediamine complex (130) in the solid state gave the (i )-(+)-2-hydroxyethylbenzene (65a) of 44% ee in 96%... 

An enantioselective Michael addition reaction was also accomplished in an inclusion complex with a chiral host compound. Treatment of a 1 1 complex of 10c and 66b with 2-mercaptopyridine (137) in the solid state gave (+)-138 of 80% ee in 51% yield. By a similar method, 3-methyl-3-buten-2-one (139) gave (+)-140 of 49% ee in 76% yield [30]. 

Starting with Volume 30, the title of the series. Thin Films, is being changed to Thin Films and Nanostructures. We feel that this new title reflects more accurately the rapidly growing inclusion of research and development efforts on nanostructures, especially in relation to novel solid-state device formats. 

The phenomenon of pseudopolymorphism is also observed, i.e., compounds can crystallize with one or more molecules of solvent in the crystal lattice. Conversion from solvated to nonsolvated, or hydrate to anhydrous, and vice versa, can lead to changes in solid-state properties. For example, a moisture-mediated phase transformation of carbamazepine to the dihydrate has been reported to be responsible for whisker growth on the surface of tablets. The effect can be retarded by the inclusion of Polyoxamer 184 in the tablet formulation [61]. 

The unequivocal proof is furnished by the crystal inclusion behavior of simple 2-hydroxy-3-naphthalenecarboxylic acid 25a46 , and its 1-chloro derivative 25b37 since both allow the formation of a crystalline adduct ( clathratocomplex 19)) with dimethylformamide with the expected 1 1 stoichiometric ratio37. Thus, the salicylic acid function (2-hydroxycarboxylic acid group) is shown to be an excellent sensor, or a good complementary site for the dimethylformamide molecule in solid state inclusion. 

By way of contrast, irradiation for 6 h in the solid state of the 1 2 inclusion complex 12a composed of 1 and 11a which has been prepared by recrystallization of the two components from a solvent gave the syn-head-to-tail dimer 13a selectively in 90% yield 7,8>. Similar irradiation of the 1 2 inclusion complexes 12b-12d composed of 1... 

Table 2. Reaction time, products, and yields of photocycloaddition reactions of inclusion complexes involving 11,17, and 21 in the solid state...

The freeze of equilibrium by the complexation method is also applicable to some other compounds. 2-Mercapto substituted tropone 32 has been reported to exist as an equilibrium mixture of 2-mercaptotropone (32 a) and 2-hydroxytropothione (32 b), and the latter is predominant both in solution 17) and in the solid state 18). The equilibrium is frozen and the former was isolated by inclusion complexation with 1. When a solution of 1 and 32 in petrol ether was kept, a 1 1 complex 33 composed of 1 and 32a was obtained in 90% yield as orange prisms of mp 101 to 103 °C19). The structure of 32a in 33 was elucidated by IR spectroscopy which showed vSH at 2482 cm-1 33 gave also absorptions of a strongly hydrogen-bonded hydroxyl group at 3270 cm 1. 

An enantioselective photoreaction of a guest compound is expected when an inclusion complex of the guest with an optically active host compound is irradiated in the solid state. 

When 8 a is used instead of 2a for complexation with 50a, two kinds of 1 1 inclusion complexes 57 were obtained one (57a) is photoreactive and the other (57b) is photostable. Thus when a solution of 8a and an equimolar amount of 50a in benzene was kept at room temperature for 10 h, a 1 1 inclusion complex between both (57a) was obtained as colorless fine needles of mp 110 to 123 °C which upon irradiation in the solid state for 49 h gave (1 R,5S)-(+)-52a of 3.6% ee in 30% yield 13). However, recrystallization of 57a from benzene gave a different kind of 1 1 inclusion complex (57b) as colorless needles of mp 123-125 °C which is photostable. Photocyclization of 50a in 57b is probably prevented by a steric hindrance. The different behavior of 57a and 57b may be clarified in future by X-ray structural studies. 

Irradiation of cycloocta-2,4-dien-l-one (55) in pentane gives a racemic photodimer, anti-tricyclofSAO.O Jhexadeca- , 11 -diene-3,16-dione (60) in 10% yield along with polymeric materials 34). Efficient and enantioselective photodimerization of 58 was achieved by irradiation of the 2 1 inclusion complex 59 formed between 2 a and 5813). When a solution of 2a and an equimolar amount of 58 in ether-hexane (1 1) was kept at room temperature for 12 h, 59 was obtained as colorless needles of mp 105 to 108 °C. Irradiation of 59 in the solid state for 48 h gave (—)-60 of 78 % ee in 55 % yield. 

Inclusion complexation of racemic 63 with the meso isomer of 2 was also examined. The host compound included racemic 63 as did 2a, and photoreaction of the complex in the solid state gave racemic 65 again 23). 

The 1 1 inclusion complexes 68 composed of 2a and nitrones 67 were prepared by keeping a solution of 2a and an equimolar amount of 67 in benzene-hexane (1 1) at room temperature for 12 h 40). Melting points of the complexes 68 are shown in Table 8. Irradiation of 68 in the solid state gave optically active oxaziridines 69. Irradiation time, yields and optical purity of the products are summarized in Table 8 40). Enantioselectivity in the formation of 67d, 67f, and 67g is high, but that of 69b, 69 c, and 69 e is low. This suggests a distinct influence coming from the substituents. 

Table 10. Solid-state photocyclization of oxoamides to p-lactams using inclusion complexation...

Contrarily, irradiation of the 1 1 inclusion complex between 4 and 88 for 40 h in the solid state gave 89 selectively in 60% yield 47). By the similar irradiation of the 1 1 inclusion complex between 4 and N,N-dimethylacetylformamide (91) in the solid state, p-lactam derivative 92 was obtained as the sole product in 56 % yield 47). 

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