AbstractIn studies of the synthesis of alkyl titanates from anhydrous butyl alcohol and titanium tetrachloride employing ammonia or an amine to neutralize the hydrogen chloride formed, Speer has reported uniformly unsuccessful results in repeating the examples of Nelles' patents on this process. Kraitzer, Winter, and others followed Nelles' process successfully employing a large excess of anhydrous butyl alcohol. Repetition of Nelles' patent examples is awkward because the ammonium chloride formed in the reaction produces a thick slurry too inconvenient to handle. However, if this slurry was diluted or extracted with an anhydrous hydrocarbon solvent, i.e., toluene, yields of 80% were achieved. Furthermore, since it is difficult to obtain rigorously anhydrous alcohols, it is more convenient to carry out the synthesis of alkyl titanates using an inert anhydrous solvent, i.e., toluene or carbon tetrachloride, as a reaction medium along with the stoichiometric quantity of alcohol instead of using a large excess of the alcohol as the reaction medium. The formation of nonvolatile residues was avoided.If the proper quantity of water dissolved in a low‐boiling alcohol is added slowly with stirring to a solution of the corresponding ester of orthotitanic acid, it is possible to obtain esters of polyorthotitanic acid of controlled average molecular weight. If less than 1 mole of water per mole of orthotitanate esters is employed, the amount of cross‐linked polymer derived is vanishingly little. When the butylorthotitanate was treated with 1.5–2.25 moles of water per mole of titanium, 1.4–1.5 moles of water were consumed per mole of titanium. Water was recovered from the system. Water in excess of 2.25‐3 moles of water per mole of titanium caused complete conversion of butylorthotitanate to titanium dioxide. The polyorthotitanates were soluble in benzene, toluene, and butyl alcohol. The uncross‐linked polymers vary in appearance from very viscous liquids to waxy solids. The polyorthotitanates enter into ester interchange reactions with alcohols in which one to all of the lower boiling alkyl groups may be replaced by the higher one. Long‐chain organic acids react with the alkyl polyorthotitanates or the alkyl titanates to replace one to all of the alkyl groups.