SU596571A1 - Method of preparing 1,2-glycols - Google Patents

Description

The invention relates to the field of organic synthesis. in particular, to improve the methods of producing .ls2-rnHKojie from C-olefins, and can be used in the industry related to the processing of olefin-containing raw materials. A known method for producing 1,2-glycol from α-olefins by the reaction of D-o-fines (mixture Cj, -C) with hydrogen peroxide in formic acid in the presence of tungstic acid as a catalyst. The reaction mass is neutralized with a 10% sodium hydroxide solution and the target product is isolated by distillation in a yield. A product contaminated with oxo alcohol and ketones is obtained, the separation of which is difficult. The chain of the invention is to increase the yield and purity of 1.2g glycols. The delivered chain is achieved by the fact that before isolating the desired product is2 glycopaeum, paicreceptor of tetrachloride is introduced into the reaction mass (} tntaya i salt -at-CHg + Tl ittHsaIT10g) YTs4 OflH ОЯ Ф -СН-СЯ ;; Oil ek) eu rriUlH-tOg-HHiQ globes of ocviuecTBiiMioT for 10 hours, then 10 molTEC, is introduced into the reagion mixture. ((L 1 mol O11efnia; {(i.;,) QD N..ojib PdR per 1 mol of Oyefin, uocfie of which the temperature is raised to GO C okopcha. Edepe-1PH of the acidification process irek .152 - D) 1 FOOTING TESC. Le of the Finns with a discharge of 99, 9%. Exit,. P o m i r Is the three-neck flask is loaded 500 ml of E-non-formic acid and 50 ml of 1-g-xiaa. Then, 25 ml of 33% hydrogen peroxide are added to the solution for 5 minutes. The total reaction time is 20-24 hours. After the reaction, 5 ml of n is added to the solution TiCl solution, in 1N hydrochloric acid, 25 mg palladium acetate and 20 mg of pyridine. The mixture becomes intensely red in color due to the formation of the propidate of titanium acid. The mixture is stirred into the distillation copba and gradually heated. When the oxygen is released, the mixture becomes slightly yellow when it is released. The mixture is distilled in vacuo at 6 mmHg to collect 5O mp fractions, ours at 102-104 ° C (crude glycol). Chromatographic analysis shows the potassium in the product of 85% 1,2-hexanediol and 15% monoformate 152-hexanediol. After additional distillation over potassium hydroxide to decompose the monoformate ester according to the reaction: H-CH-ttlg-f KIO® B-YH-YNa-LKON I t I I totH he HE it. 48 g of the fraction boiling at 103–6 mm Hg are recovered. Art. Chromatography and NMR spectroscopy data show the presence of a single compound, 1,2-exanediol. Purity according to iodometry of 99.85%, Output on the taken 1-hexene 9O%. Example 2: Heptanediol is synthesized from 1-heptene. Methods for the synthesis, isolation, purification and analysis of the product analogue of INNIPr and (lera 1. 50 g of 1,2-heptanediol are obtained, since n 110 C / 6 mmHg, st ,, purity according to chromatography and iodometry of 99.87 and 99 , 85%, respectively. The yield on the taken 1- -eptene is 93%. PRI me R 3, The synthesis of 1,2 decocdiol from 1 decene is carried out analogously to the example 58 g, n.4j kip, 138- 140 ° C / 6 mm of mercury., Chistg.cha according to iodometry 99.47%, the yield of the product per PUMP 1-depen 97%. Example 4: In three (1H), a bloody copba is captured 720 ivn ants} OY kispotr., 240 MP "-olefin fraction composition. C-C and 270 ml of 33% hydrogen peroxide, which is introduced gradually to avoid heating the mixture. The longest reaction time is 18-2O Cho. At the end of the reaction, 5 ml OD 1 N are added to the solution. a 1N hydrochloric acid solution and 25 NfrPdCE is heated and the mixture is heated to 50-60 ° C. At the end of the oxygen evolution, the favine acid is distilled off and the crude glycode is distilled over caustic potash. Get 168 ml fraction: ®4 Glycopyum, t, kip. 86-130 C / 6 mm Hg, containing 99.8% e-glycopy (sample with hydroxy-hydroxypamine) "rmula.isobre. shadow 1., A method of obtaining 1s2 glycols by reacting oC α-olefins with hydrogen peroxide in the presence of an organic acid, followed by separation of the target product from the resulting reaction mass, which differs from that to increase the yield and purity. Before isolating the latter, a solution of titanium tetrachloride and palladium PdKg., where x-ce is precipitated, is introduced into the reaction mass. 2. The method according to 1, about tl and h and yy and ys - the fact that tetraporous titanium is taken in an amount of (2-4) ° 10 mop and salt of palladium in an amount of (0.5-2) 10 units per 1 mole olefin. . Sources of information taken into account in the examination: 1. Japan patent No. 2725, cl. 16 to 422, 197 O,