Bonding bifunctional molecules

As the name implies, an amino acid is a bifunctional molecule with a carboxylic acid group at one end and an amine group at the other. All proteins are polyamides made from condensation reactions of amino acids. Every amino acid in proteins has a central carbon atom bonded to one hydrogen atom and to a second group, symbolized in Figure 13-31 as R. 

In the presence of a proper second molecule bimolecular photochemical processes occur. Obviously such reactions can also occur in an intramolecular fashion in bifunctional molecules containing both reactive centres. These reactions are a) hydrogen abstraction by the excited molecule if the second molecule (or reactive centre) is a hydrogen donor RH (1.14) b) photodimerisation (1.15) c) photoaddition or photocycloaddition (1.16) d) electron transfer (1.17), if no bonding takes place between the reactants (or reactive centres). ... 

MacGillivray s group has employed rigid bifunctional molecules [42], such as 1,3-dihydroxybenzene and 1,8-naphthalenedicarboxyHc acid [42a], as linear templates to organize reactants such as fra s-l,2-bis(4-pyridyl)ethylene via hydrogen bonds for single and multiple photoinduced [2+2] cycloadditions, for the template-controlled synthesis of a l,2,3,4-(4-pyridyl)cyclobutane] [42b] and also of paracyclophanes [42d]. Very recently, [ ]ladderanes ( =2,3) have been synthesized in the solid state by UV irradiation of 2(5-methoxyresorci-nol) 2(4-pyr-poly-m-ene) (m=2,3) [42e]. 

Studies of fluorescence quenching in 8-bond pairs in solvents such as diethylether and acetonitrile, allowed a rate of the photoinduced intramolecular electron transfer of the order of 109s 1 to be estimated, showing that very rapid intramolecular transfer can also occur in the excited bifunctional molecule. 

To enable linear templates to be used as general devices for building molecules, we have identified an ability of rigid bifunctional molecules to serve as linear templates in the organized environment of the solid state [6-12], The templates operate by assembling two complementary molecules by way of hydrogen bonds for a UV-induced [2 + 2] cycloaddition reaction [18]. By using the solid state as a medium for reaction, we have been able to circumvent the structure effects of... 

In the discussion of the loading and curing step, we have focused on the conformation of the silicon side of the aminosilane molecules. Siloxane bond formation and effect of hydrolysis of the alkoxy groups have been characterized clearly. The special reactivity of aminosilanes, compared to other organosilanes, however, is due to the presence of the amino group inside the molecule. The inter- and intramolecular interactions of this group cause special stability and reactivity according to the conditions used. Therefore we will now focus on this side of the bifunctional molecule. 

So far we have discussed polymerization that has been essentially of one kind—bifunctional molecules have combined in normal ionic reactions familiar from the rest of organic chemistry where a nucleophilic functional group attacks an electrophilic functional group. The new bonds have generally been G-O or C-N. We need now to look at the polymerization of alkenes. In these reactions, n r knnric will bp for ed and many of the reactions may be new to you,... 

In the early 1970s Stetter and co-workers succeeded in transferring the concept of the thiazolium catalyzed nucleophilic acylation to the substrate class of Michael acceptors (Stetter 1976 Stetter and Schreck-enberg 1973). Since then, the catalytic 1,4-addition of aldehydes 6 to an acceptor bearing an activated double bond 131 carries his name. The Stetter reaction enables a new catalytic pathway for the synthesis of 1,4-bifunctional molecules 132, such as 1,4-diketones, 4-ketoesters and 4-ketonitriles (Stetter and Kuhlmann 1991 for a short review, see Christmann 2005). The reaction can be catalyzed by a broad range of thiazolium salts. Stetter and co-workers found the benzyl-substituted thiazolium salt 86a to give the best results for the addition of aliphatic aldehydes, whereas 86b and 86c were chosen for the addition of aromatic aldehydes. Any one of these three was found to be suitable for additions with heterocyclic aldehydes. Salt 86d was utilized with a, )-unsaturated esters (Fig. 15). 

In addition to a bifunctional molecule, a trifunctional molecule has been illustrated to self-assemble to give a homodimer. Specifically, Alajarin and Steed have demonstrated the ability of a tris(o-ureido-benzyl)amine to form a homodimer in the solid state (Fig. 5).13 Urea residues formed a belt of 12 hydrogen bonds along the equator to hold the two components together. 

If the two halogens are on the same or adjacent carbons, two consecutive E2 dehydrohalogenations can result in the formation of a triple bond. The Williamson ether synthesis involves the reaction of an alkyl halide with an alkoxide ion. If the two functional groups of a bifunctional molecule can react with each other, both intermolecular and intramolecular reactions can occur. The reaction that is more likely to occur depends on the concentration of the bifunctional molecule and the size of the ring that will be formed in the intramolecular reaction. 

I) covalent bonding, (2) noncovalent interactions (including physical adsorption and electrostatic interactions), and (3) encapsulation. Additionally, for the first two types of immobilization procedures, interaction with the support can occur directly between the support and the molecular species or through bifunctional molecules, previously attached to the support or reacted with the metallic complex, usually termed spacers or linkers. 

---