GB1266391A - - Google Patents

Abstract

1,266,391. Esters. HALCON INTERNATIONAL Inc. 20 June, 1969 [21 June, 1968], No. 31363/69. Heading C2C. Esters are prepared by reacting an olefinically unsaturated compound with a carboxylic acid anion at elevated temperature and in the presence of iodine and at least one metal-containing or nitrogen-containing compound. The olefinic compounds may be ethylene, propylene, butene-2, allyl alcohol and acetate and methyl butene-2 and many others are listed. The iodine may be provided as such, or by reacting oxygen and an iodine producing compound in the presence of an acid. The presence of oxygen enables the iodine to be regenerated in a continuous process. The metal containing compounds are alkali metal compounds, or compounds of metals of atomic number 21 to 30 and 48 capable of producing cations in solution and nitrogen-containing bases such as trialkylamines, ammonium acetate, piperidine and pyridine are specified. Many carboxylic acids are listed and acetic acid is preferred. Examples describe the reaction of ethylene with acetic acid and oxygen with potassium, manganese, iron, nickel, chromium, copper, cobalt, zinc or cadmium acetates and iodine or potassium iodide to yield ethylene diacetate; propylene to yield propylene glycol mono- or diacetate; allyl alcohol or acetate to yield triacetin; butene-2 to yield 2, 3 butane diacetate; 2, methylbutene-2 to yield methyl butene-2-2,3-diacetate; hexadiene to yield 5-hexene-1,2-diacetate; styrene to yield ethyl benzene 2,#-diacetate. Butene-2 or tetradecene, or decene-1, are also reacted with propionic, pentanoic, n-undecylic, suocinic, cyclohexane carboxylic or picolinic acids to form the corresponding carboxylates. Cyclohexene may be reacted with #-chloropropionic acid to form cyclohexane 1,2-di-#-chloropropionate, and propylene may be reacted with o-methoxybenzoic acid to form propane 1,2-di-o-methoxy benzoate.