Expanded Tetrahedral Molecules from 1,3,5,7-Tetraphenyladamantane

Abstract

The goal of this and two succeeding papers was to investigate the effects of rigid tetrahedral cores (such as adamantane) on the properties of aramid and poly (phenylene) dendrimers as well as dendrimers that form single molecule micelles. This paper deals with model compound studies dealing with generating tetrasubstituted derivatives of adamantane. A previously reported procedure (for making tetraphenyladamantane) using tert-butyl bromide-AlCL catalyzed arylation of 1-bromoadamantane was found not to be a general synthetic method for the preparation of other substituted adamantane derivatives. Adamantane derivatives with multiple phenyl substituents were isolated only when benzene and bromobenzene were used in the Friedel-Crafts reaction. Tetraphenyl-substituted adamantane derivatives were formed, however, by the traditional Friedel-Crafts arylation of 1,3,5,7-tetrabromoadamantane with bromobenzene and 1,3dibromobenzene. A lack of regioselectivity for these reactions (isolated mixtures of the meta/para isomers or ortho/meta isomers) was observed. Large quantities (50-100 g) of 1,3,5,7-tetraphenyladamantane (1) were prepared from 1-bromoadamantane using a slightly modified literature procedure. This organic insoluble compound was iodinated with [bis(trifluoroacetoxy)iodo]benzene to give the all-para-substituted compound, 5. Compound 5 was further reacted to give numerous derivatives and used as a core in the synthesis of first generation dendrimers.

Nickel-catalyzed synthesis of nanoporous organic frameworks and their potential use in gas storage applications

“…1,5-cyclooctadiene (COD) was distilled from calcium hydride, and toluene was distilled from sodium. 1,3,5,7-tetrakis (4-iodophenyl)adamantane, 1,3,5-tris(4-bromophenyl)benzene, and 1,2,4,5-tetrakis (4-bromophenyl)benzene were prepared according to literature methods [46][47][48][49][50][51]. All reactions were performed under a nitrogen atmosphere using glovebox or Schlenk line techniques.…”

Synthesis of an azobenzene-linker-conjugate with tetrahedrical shape

“…20,21 The following Sonogashira-coupling with trimethylsilylacetylene and the carboxylation with t-BuLi and CO 2 gave precursor 2a as previously reported. 12 By following the literature protocol, compound 2a is obtained as a mixture of the tri-and dicarboxylic acid (2a,b, see Scheme 1) which was used in the next step to avoid the difficult separation by column chromatography.…”

New Epoxy Resins Cured with Tetraaminophenyladamantane (TAPA)

“…Epon resin 828, the diglycidyl ether of bisphenol A, (EEW ¼ 190) was purchased from Shell Chemical Co. 1,3,5,7-tetraphenyladamantane (2) was prepared from 1-bromoadamantane (1) (99 wt.-%, from ACROS) following a known procedure. [16] NMR and High Resolution Mass Spectra Characterization NMR spectra were obtained on a Varian INOVA 500 spectrometer operating at 499.90 MHz for 1 H and 124.98 MHz for 13 C and collected in DMSO-d 6 at ambient probe temperature. 1 H NMR spectrum of TAPA is shown in Figure 1.…”

“…The commercially available 1-bromoadamantane (1) was reacted with benzene in a Friedel-Crafts reaction to produce 1,3,5,7-tetraphenyladamantane (2) following a procedure reported by Mathias and coworkers. [16] The nitration of 2 and the reduction of the tetranitroderivative (3) were performed by adapting standard procedures employed for the synthesis of tetrakis(4-aminophenyl)-methane. [21] The solubility of 4 in organic solvents, as well as that of intermediate 2 and 3, was very low.…”

“…This compound is thermodynamically very stable [7,8] and it has been incorporated as a pendant group or into the backbones of many polymers including polyacrylates, polyesters, polysulfones, polyimides, [9,10] acetylenic adamantane polymers [11] and thermal polymers based on acetylene-terminated adamantanes, [12] leading to increased thermal stability and glass transition temperature, as well as low dielectric constants. [13,14] More recently, a variety of adamantanes tetrahedrally substituted at the four bridgehead positions have been employed to prepare dendrimers, [15,16] star polymers, [17] aramids [17] and other materials. [18,19] In each case, an increase in the glass transition temperature (T g ) and the thermal properties was observed over the linear, unsubstituted polymer.…”