Adamantane functionalization

Fig. 23 Structure of [(CH3)8l Zn] used in ref. 134 and the adamantane-functionalized, hexa-anionic water-soluble Zn(ii) phthalocyanine used in ref. 132.

The dendrimer molecules are large, this fact results in the increase of the x values of 32-34 upon complexation. The EPR spectra of 32 in the presence of each dendrimer were measured. For all dendrimers the increase of the x values was observed, the most significant changes occurring for D16. Dendrimers D8 and D64 cause smaller, similar with each other, changes in x values, this fact being due to their considerable flexibility. The x values can serve for calculation of binding constants for complexation of 32 with adamantane functionalized dendrimers. 

Low temperature fluorination techniques (—78° C) are promising for the preparation of complex fluorinated molecules, especiaUy where functional groups are present (30), eg, fluorination of hexamethjiethane to perfluorohexamethylethane [39902-62-0] of norbomane to perfluoro- (CyF 2) 1-hydro undecafluoronorbomane [4934-61 -6] C HF, and of adamantane to 1-hydropentadecafluoroadamantane [54767-15-6]. 

The imminium chloride formed was transformed, in-situ, into the corresponding carboxyhc acid derivative, this was added to a solution of cellulose in LiCl/DMAc. Palmitic, stearic, adamantane-1-carboxylic, and 4-nitrobenzoic acids were employed. The DS of the corresponding esters increased as a function of increasing the ratio oxalyl chloride/AGU. The solubihty of the products obtained in aprotic solvents was tested GPC results have indicated negligible degradation of the polymer [200]. 

A number of other thermodynamic properties of adamantane and diamantane in different phases are reported by Kabo et al. [5]. They include (1) standard molar thermodynamic functions for adamantane in the ideal gas state as calculated by statistical thermodynamics methods and (2) temperature dependence of the heat capacities of adamantane in the condensed state between 340 and 600 K as measured by a scanning calorimeter and reported here in Fig. 8. According to this figure, liquid adamantane converts to a solid plastic with simple cubic crystal structure upon freezing. After further cooling it moves into another solid state, an fee crystalline phase. 

Star polymers are a class of polymers with interesting rheological and physical properties. The tetra-functionalized adamantane cores (adamantyls) have been employed as initiators in the atom transfer radical polymerization (ATRP) method applied to styrene and various acrylate monomers (see Fig. 21). 

Adamantane can be used to construct peptidic scaffolding and synthesis of artificial proteins. It has been introduced into different types of synthetic peptidic macrocycles, which are useful tools in peptide chemistry and stereochemistry studies and have many other applications as well. Introduction of amino acid-functionalized adamantane to the DNA nanostmctures might lead to construction of DNA-adamantane-amino acid nanostmctures with desirable stiffness and integrity. Diamondoids can be employed to constmct molecular rods, cages, and containers and also for utilization in different methods of self-assembly. In fact, through the development of self-assembly approaches and utilization of diamondoids in these processes, it would be possible to design and constmct novel nanostmctures for effective and specific carriers for each dmg. 

The condensation reactions described above are unique in yet another sense. The conversion of an amine, a basic residue, to a neutral imide occurs with the simultaneous creation of a carboxylic acid nearby. In one synthetic event, an amine acts as the template and is converted into a structure that is the complement of an amine in size, shape and functionality. In this manner the triacid 15 shows high selectivity toward the parent triamine in binding experiments. Complementarity in binding is self-evident. Cyclodextrins for example, provide a hydrophobic inner surface complementary to structures such as benzenes, adamantanes and ferrocenes having appropriate shapes and sizes 12) (cf. 1). Complementary functionality has been harder to arrange in macrocycles the lone pairs of the oxygens of crown ethers and the 7t-surfaces of the cyclo-phanes are relatively inert13). Catalytically useful functionality such as carboxylic acids and their derivatives are available for the first time within these new molecular clefts. 

One of the advances in the field of PET is the design of molecular devices, in which D and A pairs are ingeniously linked by covalent bridges (B) to form D-B-A dyads. Electron transfers between D and A across B in a controlled manner may thus display useful functionalities, such as molecular rectifiers [25], switches [26], biosensors [27], photovoltaic cells [28], and nonlinear optical materials [29]. Spacers that have been utilized are versatile, including small molecules, such as cyclohexane [30], adamantane [31], bicyclo[2.2.2]octane [32], steroids [33], and oligomers of... 

Kollner et al. (29) prepared a Josiphos derivative containing an amine functionality that was reacted with benzene-1,3,5-tricarboxylic acid trichloride (11) and adamantane-l,3,5,7-tetracarboxylic acid tetrachloride (12). The second generation of these two types of dendrimers (13 and 14) were synthesized convergently through esterification of benzene-1,3,5-tricarboxylic acid trichloride and adamantane-1,3,5,7-tetracarboxylic acid with a phenol bearing the Josiphos derivative in the 1,3 positions. The rhodium complexes of the dendrimers were used as chiral dendritic catalysts in the asymmetric hydrogenation of dimethyl itaconate in methanol (1 mol% catalyst, 1 bar H2 partial pressure). The enantioselectivities were only... 

More recently, and based on the same concept, O Neill and coworkers have prepared a series of related systems (80a-c) based on Vennerstrom s adamantyl trioxolane unit". These derivatives, which are synthesized in only three steps from adamantan-2-one, have activity in the low nanomolar region (<3 nM versus K1 P. falciparum). Like the prototypes synthesized by the groups of Meunier" and Singh", these compounds can be formulated as water-soluble salts and it is anticipated that these agents may have the capacity to hit the parasite by two distinctive mechanisms. Indeed, any chemical or metabolic degradation of the endoperoxide bridge in these compounds will result in metabolites that may still have the ability to function as inhibitors of heme polymerization provided that they do not become covalently attached to proteins in the bioactivation process. 

Itoh et al. used Cu yd-diketiminato complexes with general formula 4, and their reactivity has been described as a functional model for pMMO (particulate methane monooxygenase). Initially, the Hgands were reacted with both Cu and Cu precursors, with a variety of species formed, depending on the specific conditions employed [111, 112]. It was then shown that both Cu and Cu complexes ultimately led to bis(/z-oxo)(Cu )2 species upon reaction with O2 and H2O2, respectively. Use of these Cu complexes as the pre-catalysts for the oxidation of alkanes (cyclohexane and adamantane) in the presence of H2O2 resulted in low yields ( 20%). 

Adsorption of a condensed 1-hydroxy-adamantane layer at the Hg elec-trode/(Na2S04 or NaF) solution interface has been studied as a function of temperature by Stenina et al. [174]. Later, Stenina etal. [175] have determined adsorption parameters and their temperature dependence for a two-dimensional condensation of adamantanol-1 at a mercury electrode in Na2S04 solutions. They have also studied coadsorption of halide (F , Cl , Br ) anions and 1-adamantanol molecules on Hg electrode [176]. More recently, Stenina etal. [177] have described a new type of an adsorption layer comprising organic molecules of a cage structure condensed at the electrode/solution interface. This phenomenon was discovered for adsorption of cubane derivatives at mercury electrode. 

Furukawa et al. (1) prepared a functional resin composition containing di-substituted adamantane, (I), which was used as a resist in semiconductor production processes. Monosubstituted analogs, (II), were prepared by Kodama et al. (2). Cyano-containing adamantyl derivatives, ( 1) and (IV), were prepared by Ito et al. (3) and Bae et al. (4), respectively, and used in preparing semiconductor devices. 

POLYHYDROGEN FLUORIDE REAGENT 1-FLUORO-ADAMANTANE. Dichloroalkane synthesis is shown in cis-DI-CHLOROALKANES FROM EPOXIDES cis-1,2-DICHLORO-CYCLOHEXANE. Nitrile functionality can be introduced from a ketone, as in NITRILES FROM KETONES CYCLOHEXANENITRILE, or from a reactive diene, as shown in 2,3-DICYANOBUTADIENE AS A REACTIVE INTERMEDIATE BY in situ GENERATION FROM 1,2-DICYANO CYCLOBUTENE 2,3-DICYANO-1,4,4a,9a -TETRAHYDRO-FLUORENE. 

Like adamantane,6 diamantane (also known as congressane4), the second member of the diamond family, may also be prepared by aluminum halide-catalyzed isomerization. A variety of starting materials have been shown to give diamantane,2 4,7,8 but the very best results are obtained by the present procedure2 8 starting with Binor-S.2,3,9 Diamantane may be converted to a variety of functionalized derivatives.2,5,10,11 4-Methyldiamantane may also be prepared by rearrangement.10... 

---