DITOPIC THIACYCLOPHANES CONTAINING THE S(CH2)(2)X(CH2)(2)S (X=O,S) LINKAGE - SYNTHESIS AND STRUCTURES OF 2,5,8,17,20,23-HEXATHIA[9](1,2)[9](4,5)CYCLOPHANE AND ETRATHIA[9](1,3)[9](4,6)-2,5-BIS(ETHOXY)CYCLOPHANE
Sj. Loeb et Gkh. Shimizu, DITOPIC THIACYCLOPHANES CONTAINING THE S(CH2)(2)X(CH2)(2)S (X=O,S) LINKAGE - SYNTHESIS AND STRUCTURES OF 2,5,8,17,20,23-HEXATHIA[9](1,2)[9](4,5)CYCLOPHANE AND ETRATHIA[9](1,3)[9](4,6)-2,5-BIS(ETHOXY)CYCLOPHANE, Canadian journal of chemistry, 72(7), 1994, pp. 1728-1734
The Cs+/DMF mediated reactions of 1,2,4,5-tetra(bromomethyl) benzene a
nd 1,2,4,5-tetra(bromomethyl)3,6-bis(ethoxy)benzene with dithiols HSCH
(2)CH(2)XCH(2)CH(2)SH (X = S,O) were explored in order in order to asc
ertain the effect of structural variations on the regioselectivity of
double ring-closure. Although a structure with bis(ortho) geometry was
the target molecule, the major products are those with a bis(meta) st
ructure. Two crystal structures, one with a bis(ortho) structure, 2,5,
8,17,20,23-hexathia[9](1,2)[9](4,S)cyclophane, 1, and one with a bis(m
eta) structure, trathia[9](1,3)[9](4,6)-2,5-bis(ethoxy)cyclophane, 7,
are reported. 1 crystallized in the triclinic space group P $($) over
bar$$ 1 with a = 8.583(3), b = 11.806(3), c = 5.448(2) Angstrom, alpha
= 97.18(2), beta = 107.18(2), gamma = 99.40(2)degrees, V = 511.6(6) A
ngstrom(3), and Z = 1. The structure refined to R = 6.48% and R(w) = 7
.13% for 1020 reflections with F-0(2) > 3 sigma(F-0(2)). 7 crystallize
d in the triclinic space group P $($) over bar$$ 1 with a = 9.568(2),
b = 9.577(2), c = 8.312(2) Angstrom, alpha = 113.53(2), beta = 94.58(2
), gamma = 114.94(2)degrees, V = 604.3(7) Angstrom(3), and Z = 1. The
structure refined to R = 3.86% and R(w) = 4.20% for 1129 reflections w
ith F-0(2) > 3 sigma(F-2(0)). Both compounds sit on a crystallographic
centre of symmetry and have the thioether linkages oriented on opposi
te sides of the central aromatic ring.