Infrared-Spectroscopic Study of (4-Methylpent-3-en-1-ynyl)methylthiocarbene, Its Photochemical Transformations, and Reactions in an Argon Matrix.

The first representative of singlet carbenes bearing both ethynyl and methylthio groups at the carbene center, (4-methylpent-3-en-1-ynyl)methylthiocarbene, has been generated in a low-temperature Ar matrix upon UV photolysis of 3,3-dimethyl-5-methylthioethynyl-3H-pyrazole and detected by FTIR spectroscopy. The generation of the carbene proceeds via intermediate (3-diazo-5-methylhex-4-en-1-ynyl)methylsulfane. The comparison of FTIR spectroscopy data with the results of quantum chemical calculations (B3LYP/aug-cc-pVTZ) and NRT analysis shows that (4-methylpent-3-en-1-ynyl)methylthiocarbene has a singlet ground state with the localization of the unpaired spins on the carbon atom in the α-position to methylthio moiety.
Two major pathways of further phototransformation of the studied carbene have been found. One of them produces photochemically stable thioketone (S═CMe-C≡C-CH═CMe2) as a result of methyl group migration from sulfur to the neighboring carbon atom, and the other one leads to the formation of labile thioketene (S═C═C(Me)-CH═CH-CMe═CH2). Ability of (4-methylpent-3-en-1-ynyl)methylthiocarbene to insert into the H-Cl bond was established, which additionally confirms the singlet nature of this intermediate.


The title compound congestiflorone, C(28)H(32)O(4), which was isolated from the stem bark of Mesua congestiflora, consists of a benzophenone skeleton with two attached pyran rings to which a cyclo-hexane ring and a C6 side chain are bonded. The benzene ring is significantly distorted from planarity (r.m.s. deviation = 0.0007 Å) due to the constraints imposed by junctions with the two pyran rings. The cyclo-hexane ring is in a chair conformation, one pyran ring is in a boat conformation, while the other is a distorted chair. The phenyl and benzene rings make a dihedral angle of 55.85 (9)°. An intra-molecular O-H⋯O hydrogen bond is observed. In the crystal, mol-ecules are linked via C-H⋯O inter-actions.