Acid/pyridine complexation, hydrogen bonding

Figure 12. Stereoview of the morellic acid pyridine complex showing more explicitly the function of the pyridine molecule. Hydrogen bonds are indicated. Notice the hairpin shape of the acid molecules.

In addition, taper-shaped and dendritic units were connected either covalently (at the apex or at the periphery) [133,135, 383,405] or by means of self assembly (e.g., hydrogen bonding [399]) to a polymer backbone. For example, polymers based on poly[4-(3-methacryloylpropyl]pyridine] form hydrogen bonded complexes with partially fluorinated mono-, di-, or trisubstituted benzoic acids (see complex 221 in Fig. 72). The type of mesophase formed by these complexes varies from smectic via columnar to cubic, most probably micellar cubic, with rising... 

Langner. R. Zundel, C. FTIR investigation of polarizable hydrogen bonds in carboxylic acid-pyridine complexes in... 

Tertiary amines can be converted to amine oxides by oxidation. Hydrogen peroxide is often used, but peroxyacids are also important reagents for this purpose. Pyridine and its derivatives are oxidized only by peroxyacids. In the attack by hydrogen peroxide there is first formed a trialkylammonium peroxide, a hydrogen-bonded complex represented as R3N-H202, which can be isolated. The decomposition of this complex probably involves an attack by the OH moiety of the H2O2. Oxidation with Caro s acid has been shown to proceed in this manner ... 

However, the hydrogen-bonded mesogens that are of most interest in the context of this article are those elaborated initially by Kato and Frechet in the early 1990s [24-33]. In this approach, a pyridine, which may or may not have liquid crystal properties, was hydrogen bonded with a 4-substituted benzoic acid to form a new species with its own, distinct mesomorphism. For example, complex 9 shows a SmA phase that persists to 238 °C (n = 2, m = 4), while its free component pyridine is nematic to 213 °C the component benzoic acid is also nematic (as the H-bonded dimer) to 147 °C (although note that the notional monomer would not be liquid crystalline). 

Bis(oxazolinyl)pyridine-Ce(IV) triflate complex 78 catalyzed the enantioselective 1,3-DC of acyclic nitrones with a, 3-unsaturated 2-acyl imidazoles. For example, C-phenyl 7V-benzyl nitrone reacted with 77 in the presence of 78 to give the adduct 79 with excellent diastereo-and enantioselectivity. Isoxazolidine 79 was then converted into P -hydroxy-P-amino acid derivatives by hydrogenation of the N-0 bond in the presence of Pd(OH)2/C and cleavage of the 2-acyl imidazole with MeOTf in MeCN <06OL3351>. 

We have referred to the influence of hydrogen bonding in one-component systems and mentioned the two-component system benzoic acid-pyridine (108). A variety of acid-base systems in addition to the latter are known to give 1 1 complexes. Pfeiffer gives in his book (88) a wealth of information from the older literature on such complexes, as well as on two-component organic-inorganic systems and charge-transfer complexes. 

Koga et al. complexed oxo acids like methyl phenylphosphonate with bis(resorcinol) quinoline derivative 57 [83], Anslyn and coworkers presented a more rigid polyazacleft containing hydrogen bond acceptor and donor sites in form of pyridine rings and amino groups, respectively. The formation of the 3 1 complex 58 with dibenzyl phosphate is assumed, in which the four components are spatially fixed by a net of H-bonds [84]. 

A potential way to avoid the formation of undesired side products, like in 7.2., is the use of such boron compounds that have only one transferable group. In most cases boronic acids are the compounds of choice, as they are easy to prepare, insensitive to moisture and air, and usually form crystalline solids. In certain cases, however the transmetalation of the heteroaryl group might be hindered by the formation of stable hydrogen bonded complexes. In such cases the use of a boronate ester, such as in equation 7.4., provides better yields. For example pyridine-2-boronic acid dimethylester coupled readily with a bromoquinoline derivative under conditions similar to 7.3. (potassium hydroxide was used as base and tetrabutylammonium bromide as phase transfer catalyst).6... 

Maciel et al. (370,371,374) combined l3C and 15N CP/MAS NMR to study the adsorption of pyridine on silica-alumina. Hydrogen bonding was found to be the dominant interaction at high loading levels (0.5 to 1 monolayer). At lower coverages, a Lewis acid-base complex dominates and the pyridine is significantly less mobile. Bronsted complexes are found when the surface has been pretreated with HC1 gas. 

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