Cationic Ring‐Opening Polymerization of 1,3‐Dehydroadamantanes

Abstract

Summary: Ring-opening polymerizations of [3.3.1]propellane derivatives, 1,3-dehydroadamantane (1) and 5-butyl-1,3-dehydroadamantane (2), were carried out with CF 3 SO 3 H in CH 2 Cl 2 at 0 8C for 6-42 h. The central s-bonds in 1 and 2 were exclusively opened to afford novel poly ([3.3.1]propellane)s, poly(1,3-adamantane)s, in 52-95% yields. The resulting poly(2) possessing flexible butyl substituent was soluble in chloroform, THF, and 1,2-dichlorobenzene, and the degree of polymerization was estimated to be greater than 30, while the poly(1) was hardly soluble in the common organic solvents. All aliphatic poly(1) and poly(2) showed high thermal stability, their 10% weight loss temperatures were 421 and 486 8C, respectively.

Template Synthesis of Linear‐Chain Nanodiamonds Inside Carbon Nanotubes from Bridgehead‐Halogenated Diamantane Precursors

“…Thep resent templatebased approach for the synthesis of linear-chain diamondoid polymers is entirely different from conventional chemical approaches. [22,[33][34][35][36] We have also developed am ethod for extracting the products formed inside the CNT templates from the template through solution-phase sonication/extraction. [37] Studies on polymer extraction are currently in progress to investigate their tensile strengths or thermal transport properties.W ea lso expect that the present template-based approach will provide access to adiverse range of novel 1D polymers.I np rinciple,t he present strategy is applicable to various dihalogen-substituted molecules.Infact, preliminary experiments indicate that the polymerization can also occur with other precursor molecules.T he present synthetic method may offer an ew strategy for the design and synthesis of one-dimensional nanomaterials.…”

Template Synthesis of Linear‐Chain Nanodiamonds Inside Carbon Nanotubes from Bridgehead‐Halogenated Diamantane Precursors

“…[22,[33][34][35][36] We have also developed am ethod for extracting the products formed inside the CNT templates from the template through solution-phase sonication/extraction. Thep resent templatebased approach for the synthesis of linear-chain diamondoid polymers is entirely different from conventional chemical approaches.…”

Synthesis and Heat Resistance of Arylenedioxy-organosilanylene Polymers with Adamantane Units

“…In an autoclave were placed 0.321 g (1.00 mmol) of 2,2-bis(4-hydroxy phenyl)adamantane, 0.108 g (1.00 mmol) of phenylsilane, 27.8 mg (3.0 mol-%) of RhCl(PPh 3 ) 3 , and 15 mL of toluene, and the mixture was heated at 150 • C for 12 h. Then 0.30 g of triazinetrithiol (Sankyo Kasei Co. Ltd.) was added, and the mixture was stirred for 30 min at r. t. Then it was filtered to remove the catalyst. After removal of the solvent, the residue was reprecipitated from toluenehexane to give 0.24 g of 2a as a pale-yellow solid.…”