Open AccessThe mixed diol–dithiol 2,2‐bis(sulfanylmethyl)propane‐1,3‐diol: characterization of key intermediates on a new synthetic pathway
Author(s) -
Simmons Trevor R.,
Pickett Christopher J.,
Wright Joseph A.
Publication year - 2011
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
eISSN - 1600-5759
pISSN - 0108-2701
DOI - 10.1107/s0108270110049371
Subject(s) - chemistry , thiocyanate , diol , intramolecular force , hydrogen bond , hydroxymethyl , propane , stereochemistry , crystal structure , molecule , crystallography , medicinal chemistry , polymer chemistry , organic chemistry
A new synthetic route to 2,2‐bis(sulfanylmethyl)propane‐1,3‐diol, (II), is described starting from the commercially available 2,2‐bis(hydroxymethyl)propane‐1,3‐diol. The structures of two intermediates on this route are described. 5,5‐Dimethenyl‐2,2‐dimethyl‐1,3‐dioxane bis(thiocyanate) (systematic name: {[5‐(cyanosulfanyl)‐2,2‐dimethyl‐1,3‐dioxan‐5‐yl]sulfanyl}formonitrile), C 10 H 14 N 2 O 2 S 2 , (X), crystallizes in the space group P 2 1 / c with no symmetry relationship between the two thiocyanate groups. There is a short intramolecular N...S contact for one thiocyanate group, while the second group is positioned such that this type of interaction is not possible. 1,3‐(Hydroxymethyl)propane‐1,3‐diyl bis(thiocyanate), C 7 H 10 N 2 O 2 S 2 , (XI), also features a single short N...S contact in the solid state. Hydrogen bonding between two molecules of compound (XI) results in the formation of dimers in the crystal, which are then linked together by a second hydrogen‐bond interaction between the dimers. In addition, the structures of two intermediates from an unsuccessful alternative synthesis of (II) are reported. 2,2‐Bis(chloromethyl)propane‐1,3‐diol, C 5 H 10 Cl 2 O 2 , (VI), crystallized as an inversion twin with a minor twin fraction of 0.43 (6). It forms a zigzag structure as a result of intermolecular hydrogen bonding. The structure of 9,9‐dimethyl‐2,4,8,10‐tetraoxa‐3λ 4 ‐thiaspiro[5.5]undecan‐3‐one, C 8 H 14 O 5 S, (VII), shows evidence for a weak S...O contact with a distance of 3.2529 (11) Å.