Poly adamantane

Covalent attachment of adamantane molecules is a key strategy to string them together and construct molecular rods. The McMurry coupling reaction was employed to obtain poly-adamantane molecular rods (Figure 3.18) [71]. As another example, synthesis of tetrameric 1,3-adamantane and its butyl derivative has been reported [72] (see Figure 3.19). 

Ayres, F.D., Khan, S.I., and Chapman, O.L. Synthesis and x-ray crystal structures of poly-adamantane molecular rods. Tetrahedron Lett 1994, 35 8561-8564. 

Mathias et al. synthesized poly(ether sulfone)s and poly(ether ether ketone)s with pendent adamantane groups.192 Incorporating adamantane into a polymer as a pendent group has been demonstrated to significantly increase the glass transition temperature. 

It has been also found that PhIO as an oxidant in the presence of a catalytic amount of sulfonated manganese and iron porphyrin supported on poly(vinylpyridinium) polymers in olefin epoxidation and alkane hydroxylation is a better oxidant than Bu4NHS05 °. Oxidation of adamantane to 1-adamantanol in good yield using BU4NHSO5 and acetone in the presence of aqueous NaHCOs was also reported . ... 

Adamantane and other tertiary hydrocarbons have been converted by applying this method [nitrosonium tetrafluoroborate/pyridinium poly(hydrogen fluoride) (PPHF)] into the corresponding fluorohydrocarbons in excellent yields.88... 

Nitronium tetrafluoroborate in the presence of pyridine poly(hydrogen fluoride) (PPHF) can be used to substitute chlorine or bromine in adamantanes and other hydrocarbons (see Table 21).90... 

Selective poly hydroxylation of adamantane is possible.87 A concerted insertion mechanism closely resembling to the mechanism of ozonation has been... 

The AcBr-2AlX3 (X = Cl, Br) complexes display high activity in the alkylation of adamantane with alkanes to form poly alkylated adamantanes (Cn < C < C33) and bisadamantylalkanes (C23 < C < C50)119 [Eq. (5.70)]. The suggested pathway includes the 1-adamantyl cation and alkyl cations generated by hydride removal by the superacidic complexes. The 1-adamantyl cation then alkylates alkenes equilibrating with the alkyl cations. Various transformations may follow, resulting in the formation of additional products. 

At even higher pH values, metal catalysis is required for chlorination to proceed. Thus, at pH =11, nickel(salen) catalyzes the chlorination of adamantane, cyclohexane and toluene785 and manganese porphyrin promotes the chlorination of cyclohexane786. Selective side-chain chlorination by sodium hypochlorite under PTCs at pH = 8.5 has been used for benzylic chlorinations787,788 and for the functionalization of poly(4-methyl-styrene)789,790. Similarly, with calcium hypochlorite in acetic acid, ring chlorination is reported for toluene, xylenes, anisole and other activated aromatics791. 

With adamantan-2-onc (4), additional substitution of hydrogen atoms can lead to poly-fluorinated compounds 6 as well as 5, depending on the reaction conditions. 

Poly(maleic acid-aft-isobutene) 1-Adamantane-amide 0.1 P-CD 22 [190]... 

Figure 12. The light-harvesting polyrotaxane 15 [71] is composed of a poly(ethyleneglycol) axle encircled by an average of 15 a-cyclodextrin units, each bearing approximately two naphthalenesulfonate groups therefore, 15 contains about 30 naphthyl chromophoric groups held together mechanically. In aqueous solution, the dansyl-modifled /3-cyclodextrin 16 is able to bind to the adamantane stoppers of 15 under such conditions, a photoinduced energy transfer process from the excited naphthalenesulfonate moieties of 15 to the dansyl group of 16 is observed.

Weickenmeier and Wenz [84] investigated the inclusion complex formation of poly[(N-vinyl-2-pyrrolidone)-co-(maleic acid)] modified with j8-CD moieties with 1-adamantanamine and with 1-adamantanecarboxylic acid by isothermal titration calorimetry. They reported 1 1 inclusion complexes between -CD moieties and adamantane derivatives with relatively large binding constants (ca. 3-5 x 10 M ). 

Figure 2-7. Ordered networks. 0, Adamantane as an example of a cage polymer (type 0) I, Cyclized and dehydrogenated l,2-poly(butadiene) as an example of a ladder or double-strand polymer (type 1) 2, graphite as a layer or parquet polymer (type 2). ( ) Carbon-to-hydrogen bonds (— and =) carbon-to-carbon bonds.

A. Kulkarni, W. Deng, S.-H. Hyun, D. Thompson, Development of a low toxicity, effective pDNA vector based on noncovalent assembly of bioresponsive amino- 3-cyclodextrin adamantane-poly(vinyl alcohol)-poly(ethylene glycol) transfection complexes, Bioconjug. Chem. 23 (2012) 933-940. 

Supramolecular polymeric complexes yielding graft copolymers based on the inclusion interactions of P-cydodextrin groups in poly(N-vinyl-2-pyrrolidone-co-6-deoxy-6-methacrylate ethylamino-p-cyclodextrin) with the adamantane group on the end of PGL were also reported by Ren et... 

Rings s. a. Adamantanes, Alcohols, cyclic, Hetero-cyclics, Isocyclics, Ketones, cyclic, Macrocyclics, Poly-cyclics, Propellanes -, condensed highly condensed s. Cage compds. 

Scheme 20 Solvent-free electrochemical fluorination of adamantanes in poly HF salt...

TE, tissue engineering Hap, hydroxyapatite PNIPAAm, poly(A -isopropylacrylamide AD, adamantane CD, p-cyclodextrin. High degree of methacrylation. 

Thermochemical properties of difluoramino-substituted cage hydrocarbons, specifically, poly(difluoramino)cubanes [154] and poly(difluoramino)-adamantanes [155], have been estimated by Ju et al. in order to compare results from a variety of computational methods density fimctional the-... 

Procesring of Polyamides.—Fibre Formation, Structure, and Properties. The equipment used for production of fibres by wet spinning of limited quantities of materials has been described, together with physical characterization methods for spun filaments of poly(m-phenylene adamantane l,3 dicarboxamide). ... 

Two interesting dendrimer-based approaches to novel cancer therapeutics are the water-soluble adamantane terminated rhenium-cored aromatic polyethers, reported by Reinhoudt and co-workers [55], and the porphyrin-cored polyester-poly( ethylene glycol) dendrimer system described by Frechet and co-workers [56]. 

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