S-2-(Adamant-1-yl)-4-methylphenyl N,N-dimethylthiocarbamate

The title compound, C20H27NOS, was obtained from the corresponding O-thiocarbamate. The structure features a C=O bond distance of 1.209 (2) Å and an sp 3-hybridized S atom [C—S—C = 101.66 (1)°]. The steric bulk of the 1-adamantyl substituent on the 2-position of the aromatic ring is reflected in the S—C—C—C torsion angle [−7.5 (3)°].

The title compound, C 20 H 27 NOS, was obtained from the corresponding O-thiocarbamate. The structure features a C O bond distance of 1.209 (2) Å and an sp 3 -hybridized S atom [C-S-C = 101.66 (1) ]. The steric bulk of the 1adamantyl substituent on the 2-position of the aromatic ring is reflected in the S-C-C-C torsion angle [À7.5 (3) ].
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GW2030).

S-2-(Adamant-1-yl)-4-methylphenyl N,N-dimethylthiocarbamate
R. Huerta, I. Castillo and S. Hernández-Ortega Comment Newman-Kwart thermal rearrangement of O-thiocarbamates to the corresponding S-thiocarbamates is a widely used reaction for the preparation of benzenethiols (Newman & Karnes, 1966). The presence of bulky substituents on the 2-position of phenols represents a synthetic challenge in this methodology, and the experimental difficulties have been attributed by our group to the steric congestion around the thiocarbamate moiety (Flores-Figueroa et al., 2005). We herein report the preparation (see Experimental and Scheme) of the title compound S-2-adamant-1-yl-4-methylphenyl N,N-dimethylthiocarbamate (I).
Compound (I) crystallizes in the triclinic space group P-1 by slow evaporation of a concentrated 2-propanol solution. A search of the Cambridge Crystallographic Database (Version 5.19; Allen, 2002) using CONQUEST, Version 1.4; Bruno et al., 2002) revealed that (I) represents one of the very few examples of aromatic S-thiocarbamates with sterically demanding substituents adjacent to the S atom. Its structure, which is depicted with atom numbering scheme in Fig. 1, features a C=O bond length of 1.209 (2) Å, and C-S 1.780 (3) Å (Table 1). The bond lengths and angles of the thiocarbamate group of (I) are comparable to those of related compounds (Higgs & Carrano, 2002, Bennett et al., 1999. The steric congestion around the S-thiocarbamate group is reflected in the torsion angle of −7.5 (3)° between the S-C(aromatic) and the adjacent C(aromatic)-C(orthosubsituent) bond (S-C1-C2-C10).
Molecules of (I) pack in chains on the 100 plane, as shown in Fig. 2. These chains are formed by intermolecular C-H···O interactions between the O atom of one molecule and C8-H8B on an adjacent molecule, with C8···O and H8B···O distances of 3.294 (3) and 2.534 (2) Å, respectively. The C and H atoms are located on one of the NMe 2 groups of a the S-thiocarbamate moiety, and the corresponding C-H···O angle is 136.1 (2)°. -2-adamant-1-yl-4-methylphenyl N,N-dimethylthiocarbamate (0.26 g, 0.80 mmol) was heated to 593-603 K for 2 h in a round bottom flask equipped with a teflon stopcock. After cooling to room temperature, the material was disolved in dichloromethane, filtered, and evaporated to dryness (30 ml). The solid obtained was disolved in hot 2-propanol, and upon cooling starting material precipitated. After filtering, the mother liquor yielded yellow crystals of (I) by slow evaporation of the solvent. Yield: 0.06 g (23%); m.p. 407-408 K; IR (CHCl 3 ) 3011, 2903,2852,1710,1655,1598,1451,1406,1365,1261,1170,1100,1066,1029,910 Fig. 1. Molecular structure of (I) with atom numbering scheme. Thermal ellipsoids are shown at the 50% probability level.   as large as those based on F, and R-factors based on ALL data will be even larger. Hydrogen atoms were placed in idealized positions, and the isotropic thermal parameters were assigned the values U iso = 1.2 times the thermal parameter of the parent atom.