Titanium(IV) Chloride–2,2,6,6‐Tetramethylpiperidine

(TiCl4) [7550-45-0] Cl4Ti (MW 189.68) InChI = 1S/4ClH.Ti/h4*1H;/q;;;;+4/p-4 InChIKey = XJDNKRIXUMDJCW-UHFFFAOYSA-J (TMP) [768-66-1] C9H19N (MW 141.29) InChI = 1S/C9H19N/c1-8(2)6-5-7-9(3,4)10-8/h10H,5-7H2,1-4H3 InChIKey = RKMGAJGJIURJSJ-UHFFFAOYSA-N (oxophilic Lewis acid for the intramolecular cyclization of unsaturated (Z)-allylic alcohols1) Physical Data: see Titanium(IV) Chloride and 2,2,6,6-Tetramethylpiperidine. Solubility: TiCl4: sol aromatic hydrocarbons, ether, THF, dioxane, chlorohydrocarbons. TMP: sol acid, ethers, chlorohydrocarbons, aromatic solvents. Form Supplied in: TiCl4: colorless liquid, or as a crystalline complex with THF. TMP: colorless liquid. Preparative Methods: TMP (1.5 equiv) is added to a solution of TiCl4 (1.5 equiv) in dichloromethane at 0 °C. It is assumed that a complex, analogous to the TiCl4–N-methylaniline complex,1, 2 is formed. The mixture is then cooled to −23 °C and the (Z)-allylic alcohol added. Handling, Storage, and Precautions: TiCl4 is corrosive and moisture-sensitive. TMP is a flammable liquid which should be stored in colored glass. The reagent will be moisture sensitive so the reactions are best performed under a dry inert atmosphere. Solvents should be dried before use.