864. ------. [GREESHAM, W. F., AND BROOKS, R. E.] (E. I. du Pont de Nemours & Co.). 1,1,2-Trialkoxyethanes. United States Patent 2,449,470. Sept. 14, 1948. Chem. Abs., vol. 43. 1949. p. 675.

Patent Abstracts

1,1,2-trialkoxyethanes are prepared by heating dialkyl formals with CO and H₂ in the presence of an alkanol and 0.1-20% (based on the total weight of the reaction mixture) Ni or Co catalyst at 100º-350º, preferably 125º-170º, under a pressure of at least 10 atm., preferably 400-1,000 atm., the initial molecular ratio of dialkyl formal to alkanol being 2:1-1:20 and of CO to H₂ 3:1-1:3. For example, 38.1 gm. H₂C(OMe)₂, 160 gm. MeOH, and 20 gm. reduced sintered Co oxide catalyst are treated with a mixture of CO and H₂(1:1) injected into an Ag-lined shaker tube at 550-750 atm., the mixture shaken 15 min. at 160º-170º with intermittent additions of CO-H mixture to maintain a pressure of at least 600 atm., unconverted H₂C(OMe)₂ (50%) and MeOH (88%) recovered by fractional distillation, and 25 ml. distilled H₂O added to the residue, giving (MeO)₂CHCH₂OMe (I) as homogenous H₂O azeotrope, b. 93º-94º, containing 30% H₂O and 70% (I). Saturation of the azeotrope with K₂CO₃ yielded an upper layer (30 gm.). which was dried with Na₂SO₄ and distilled to yield (I) b₅₀56º-59º, b. 126º-127.5º, n²⁰ 1.3901. Substituting iso-BuOH for MeOH in the above example gave a mixture of (iso-BuO)₂XHXH₂OCH₂CHMc₂ and (iso-BuO)₂CHCH₂OMc. Similarly, 83.2 gm. H₂C(OEt)₂. 92 gm. absolute EtOH, and 20 gm. reduced, fused Co catalyst heated 30 min. at 200º-214º with CO : H₂(2:1) at 700 atm., and the products cooled and distilled yielded 6.0 gm. EtOCH₂CH₂OH, b₃₀, 53º-56º, and 7.5 gm. (EtO)₂CHCH₂OEt, b₃₀ 73º-75º. The compounds thus prepared are useful as solvents and intermediates for the manufacture of unsaturated ethers.