New Monomers for Organometallic Poly-p-xylylenes: Synthesis of Silyl-, Germyl- and Stannyl[2.2]paracyclophane Derivatives

Abstract

Symmetrically 4,16‐disubstituted (3a–c) and bridged (6a, b) organometallic paracyclophane derivatives have been synthesized for use as monomeric precursors of organometallic poly‐p‐xylylenes. Both types of compounds were obtained by lithiation of the appropriately substituted paracyclophane bromides (1 or 4) and subsequent quenching of the resulting lithioparacyclophane derivatives with organometallic electrophiles. For the synthesis of 4,16‐bis(trimethylsilyl)[2.2]paracyclophane (3a) we also examined the Grignard reaction, and as a result the first successful use of a 4,16‐bis Grignard reagent is described. According to the spectral data, the bridged compounds 6a, c are formed as diastereomeric mixtures of a meso‐ and a d,l form. The diastereomers were separated by fractional recrystallization and characterized.

An exploration of Suzuki aryl cross coupling chemistry involving [2.2]paracyclophane derivatives

“…Such compounds are also of interest as they serve as monomers for cross linked Parylene type polymers. 19 Our initial attempts to use the above Suzuki methodology to prepare diPCP, or PCP-OFP dicyclophanes were not successful, with sterics being the most likely cause. So we turned our attention to the formation of a dicyclophane with a spacer group.…”

Suzuki aryl cross-coupling chemistry using derivatives of 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane

“…1,2,2,9,9,10,paracyclophane (3) This compound was prepared from 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane [1] by the published procedure [2]. 13 C NMR data for this compound have not been previously reported; 13 C{ 1 H} NMR d 141.90,133.72 (dd,J = 14.2,3.8 Hz),130.58,130.18,129.96,129.46,126.69 90 (dd,J = 170.6,6.7 Hz),133.72 (d,J = 170.6 Hz),130.58 (dd,J = 167.5,6.5 Hz),130.18 (dd,J = 166.9,6.7 Hz),129.96 (dd,J = 166.1,6.7 Hz),129.46 (dd,J = 168.4,6.7 Hz),126.69 (dd,J = 166.8,6.7 Hz) (aryl C-Hs); 94.85 (d, J = 9.3 Hz) (C-I); 136.67 (t, J = 7.3 Hz), 135.93 (d,J = 8.6 Hz),135.10 (t,J = 8.1 Hz),134.33 (t,J = 7.8 Hz) (cyclophane bridgeheads). 4.1.5.…”

Computational Study about Through-Bond and Through-Space Interactions in [2.2]Cyclophanes

“…5 The cyclophanes have applications not only in different synthetic processes but also in supramolecular chemistry 6 and in the biomedical areas. 7 Polymers prepared from cyclophanes by chemical deposition on vapor phase (CVD) 8 can compose biomimetical layers with incorporated functional groups (proteins, antigens, cell receptors) which allow the control of the interactions between biomaterials and the organisms. 7 These compounds also act as selective synthetic receptors of anions that exhibit biological function, for example, carboxylates and phosphates.…”