Patent GB-962453-A (GB)
Title: Diethers of oligo-oxymethylene glycols and the production thereof
Inventor: DUKE ANGUS JOHN
IPC: C07C41/00
Filed: 1960-03-07
Abstract: The invention comprises compounds having the formula: <FORM:0962453/C1/1> wherein R represents the residue, after removal of the hydroxyl radical, of an aliphatic, cycloaliphatic or araliphatic monohydric alcohol of the formula ROH where R contains at least one reactive grouping selected from non-terminal ethylenic double bonds, halogen atoms, and nitrile, nitro, ester, thioester and cyclic imide groups, and wherein X is an integer from 2 to 6. The invention also comprises the preparation of mixtures of compounds of the above formula wherein R is a radical as defined above except that it may also contain terminal ethylenic double bonds and X has an average value greater than 1 and less than 10, by reacting formaldehyde, or a substance capable of yielding formaldehyde under the conditions of the reaction, e.g. paraformaldehyde or trioxane, with a monohydric alcohol of the formula ROH at 25-200 DEG C., the molar ratio of formaldehyde to monohydric alcohol being greater than 0.5 and not more than 5, in the presence of a catalyst selected from elemental iodine, and the halides and oxyhalides (where existent) of the ammonium cation and of lithium, beryllium, magnesium, calcium, boron, aluminium, gallium, silicon, germanium, tin, bismuth, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, mercury and thorium, and isolating, and removing the said catalyst from, the said mixture.  In a modification, the reaction is effected, optionally in the presence of water, with a catalyst selected from the catalysts defined above or from acids of pKa less than 4, acid salts of inorganic polybasic acids, ion exchange resins bearing ionizable groups in the hydrogen form derived from acids of pKa less than 4, and substances which are substantially hydrolysed to yield acids of pKa less than 4 under the reaction conditions, at 25-200 DEG C. under conditions such that water, whether initially present or formed during the reaction, is continuously removed from the reaction zone, e.g. by azeotropic distillation, whereupon the desired mixture is isolated and the catalyst removed therefrom. Suitable acidic catalysts for the above process include hydrochloric, sulphuric, p-toluenesulphonic, benzenesulphonic, phosphoric and trifluoroacetic acids and aluminium sulphate, ferric nitrate and phosphorus halides.  Suitable alcohols ROH for use in the preparations of the invention include allyl alcohol, 2-methylallyl alcohol, but-2-enol, but-3-enol, cyclopent-2-enol, cyclohex-2-enol, cyclohex-3-enol, bicyclo [2,2,1] hept-2-en-5-ol, 1,2,3,6-tetrahydrobenzyl alcohol, 2-methyl-1,2,3,6-tetrahydrobenzyl alcohol, tricyclo (5,2,1,02, 6) dec-3-en-8 (or 9)-ol, ethylene chlorohydrin, ethylene bromohydrin, propylene chlorohydrin, cyclohexene chlorohydrin, 2-acetoxy-ethanol, methyl glycollate, ethyl lactate, ethyl 3-hydroxypropionate, ethyl 3-hydroxybutyrate, 2-cyanoethanol, 5 - acetyl - 2 - thioethanol, N - (2 - hydroxyethyl)-phthalimide, N-(2-hydroxy ethyl)-succinimide and 2-nitro ethanol.  The above processes may be carried out using two different alcohols in the same preparation and consequently the two R values in the above formula may be different. Also, recovered alcohol, formaldehyde and its polymers, monoformal or undesired diethers of oligo-oxymethylene glycols can be used in subsequent reaction mixtures.  In most of the examples the diethers (and monoformal formed) are separated by fractional distillation.  In Example 9, a mixture of di-allyl ethers of oligo-oxymethylene glycols is catalytically hydrogenated to form a mixture of the corresponding di-n-propyl ethers.  The compounds of the invention are useful as intermediates in the production of polymeric materials, epoxy resins and insecticides.  According to the Provisional Specification the value of X in the above formula is from 2 to 10.