56263-45-7Relevant academic research and scientific papers
The crystal and molecular structure of syn-9-phenyl-2,11-dithiametacyclophane
Anker, Willem,Beveridge, Kathy A.,Bushnell, Gordon W.,Mitchell, Reginald H.
, p. 661 - 666 (2007/10/02)
The crystal structure of syn-9-phenyl-2,11-dithiametacyclophane, 6, has been determined by single crystal X-ray diffraction and refined to an R value of 0.0723.The crystal structure is triclinic with a = 9.573(2), b = 12.010(4), c = 8.433(2) Angstroem, α = 108.02(2), β = 95.95(2), γ = 102.25(3) deg, and the space group P with two molecules per cell, D(meas) = 1.313 g cm-3, D(calc) = 1.306 g cm-3.The bridging S atom differ in their conformations so that the S...S distance is 6.931 Angstroem.The metacyclophane rings have a distance of 3.57 Angstroem between their centres and form a dihedral angle of 20.5 deg.The phenyl substituent forms an angle of 78.6 deg with the adjacent ring and has an ortho H-atom very close to the internal H-atom of the opposite ring.The phenyl substituted aromatic ring is non planar and in a shallow boat form, the ring atoms C(11) (internal and C(14) being 0.038(4) and 0.037(5) Angstroem out-of-plane on the outside, the methylene C substituents are 0.212(5) and 0.199(5) Angstroem out plane on the inside.The first atom of the phenyl group is in the bowsprit position and is 0.274(4) Angstroem above the mean plane on the outer side of the molecule.The opposite metacyclophane ring is less strained but in similar boat forma with the methylene C-atoms 0.092(4) and 0.067((6) Angstroem to the inside.The mean bond angle at S is 103.5(2) deg, the angles at C (methylene) range from 113.3(3) deg to 118.0(3) deg.The variable temperature 1Hmr spectra results are consistent with the syn conformer 6 being dominant in solution and frozen at temperatures 60 deg C as conformer A, with only relatively restricted further twisting of the biphenyl being found at ambient temperature.
Intraanular phenyl-substituierte Phane - Synthese und dynamische Stereochemie
Boeckmann, Klaus,Voegtle, Fritz
, p. 1048 - 1064 (2007/10/02)
The synthesis and properties of phanes of different ring size, substituted intraanularly by phenyl groups, and of new biphenylophanes 3, 38 - 43 with "pseudo-syn/anti"-structure are described.Barriers for the hindered rotation of intraanular phenyl substituents have been determined by D-NMR spectroscopy. syn/anti conformers of -, -, - and metacyclophanes are found.A better method for the preparation of mediocyclic bisdisulfides is reported.The pyrolysis of (2-biphenylyl)methyl sulfones leads to fluorenes; pyrolysis of the thiosulfonic S-ester 44 yields bibenzyl and dibenzyl sulfide.
