SU722912A1 - Method of preparing 5-methyl-4-oxo-3,6,8-trioxabicyclo-(3,2,1)-octane - Google Patents
Method of preparing 5-methyl-4-oxo-3,6,8-trioxabicyclo-(3,2,1)-octane Download PDFInfo
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- SU722912A1 SU722912A1 SU782587627A SU2587627A SU722912A1 SU 722912 A1 SU722912 A1 SU 722912A1 SU 782587627 A SU782587627 A SU 782587627A SU 2587627 A SU2587627 A SU 2587627A SU 722912 A1 SU722912 A1 SU 722912A1
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Изобретение относитс к усовершенствованному способу получени 5-метил-4-оксо-З ,6,8-триоксабицикло- (3,2,1)-октана формулыThe invention relates to an improved process for the preparation of 5-methyl-4-oxo-3, 6,8-trioxabicyclo- (3,2,1) -octane of the formula
да Yes
который может быть использован дл производства термостойких пластмасс ингибиторов коррозии и наполнителей дл Масло- и светостойких каучуков и резин,which can be used to produce heat resistant plastics, corrosion inhibitors and fillers for oil and light resistant rubbers and rubbers,
Изве&тен способ получени 5-меТИЛ-1-ОКСО-3 ,6,8-триоксабицикло-(3, 2,1)-октана взаимодействием эфира пировиноградной кислоты с глицерином в присутствии в качестве кислотного катализатора п-толуолсульфокислоты в среде бензола при кип чении с выходом не выше 50% 1.A known method of producing 5-methyl-1-OXO-3, 6,8-trioxabicyclo- (3, 2,1) -octane by reacting pyruvic acid ester with glycerol in the presence of p-toluenesulfonic acid as an acid catalyst in benzene medium at refluxing with yield not higher than 50% 1.
Недостатками этого способа вл ютс низкий выход целевого продукта и применение катализатора, после которого реакционную смесь необходимо нейтрализовать.The disadvantages of this method are the low yield of the desired product and the use of a catalyst, after which the reaction mixture must be neutralized.
Целью изобретени вл етс увеличение выхода целевого продукта.The aim of the invention is to increase the yield of the target product.
Это достигаетс тем, что 2-метил-2-алкоксикарбонил-1 ,3-диоксолан формулыThis is achieved by the fact that a 2-methyl-2-alkoxycarbonyl-1, 3-dioxolane of the formula
(lO(lO
соон soon
где R - метил, зтил, подвергают взаимодействию с глицерином в присутствии в качестве кислотного катализатора КУ-2 в среде бензола при кип чении.where R is methyl, ztil, is reacted with glycerol in the presence of KU-2 as an acid catalyst in benzene at boiling.
Предлагаемый способ отличаетс The proposed method is different.
тем, что в качестве эфира к рбоновой кислоты используют 2-метил-2-алкоксикарбонил-1 ,3-диоксолан, а в качестве кислотного катализатора КУ-2. Исходные 2-метил-2-алкоксикарбонил-1 ,3-диоксоланы получают взаимоействием пировиноградной кислоты, ее эфиров либо эфиров мезоксалевой кислоты с 1,2-диалами в присутствии катионита КУ-2 в Н-форме. При этомthe fact that 2-methyl-2-alkoxycarbonyl-1, 3-dioxolane is used as the ester of the carboxylic acid, and KU-2 as the acid catalyst. The starting 2-methyl-2-alkoxycarbonyl-1, 3-dioxolanes are obtained by reacting pyruvic acid, its esters or esters of mesoxalic acid with 1,2-dialyes in the presence of cation exchanger KU-2 in the H-form. Wherein
выход 2-метил-2-алкоксикарбонил-1, 3-диоксоланов достигает 70-88%.the yield of 2-methyl-2-alkoxycarbonyl-1, 3-dioxolanes reaches 70-88%.
Пример 1.В трехгорлую колбу , снабженную мешалкой, обратным холодильником и термометром, помеают 0,5 мол (73 г) 2-метил-2-метоксикарбонил-1 ,3-диоксолана, 0,5 мол (46 г) глицерина, 150 мл бензола (из расчета 300 мл на 1 мол глицерина) и 20 г катализатора КУ-2 (из расчета 40 г на 1 моль глицерина . Реакцию провод т в течение 56 ч при температуре кипени бензола Затем обратный холодильник замен ют нисход щим и медленно отгон ют образовавшийс метиловый спирт (16 г, т.е. расчетное количество). Реакционную смесь охлаждают, отфильтровывают и перегон ют под вакуумом. Получают 57 г (выход 79%) 5-метил-4-оксо-З ,6,8-триоксабицикло-(3,2, 1)-октана. Т.кип. мм; Т.пл .Example 1. In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 0.5 mol (73 g) of 2-methyl-2-methoxycarbonyl-1, 3-dioxolane, 0.5 mol (46 g) of glycerin, 150 ml benzene (at the rate of 300 ml per 1 mol of glycerol) and 20 g of catalyst KU-2 (at the rate of 40 g per 1 mol of glycerin. The reaction is carried out for 56 hours at the boiling point of benzene. Then the reflux condenser is replaced by a descending and slowly distilled off the resulting methyl alcohol (16 g, i.e., the calculated amount). The reaction mixture is cooled, filtered and distilled under vacuum. 57 g (yield 79%) of 5-methyl-4-oxo-3, 6,8-trioxabicyclo- (3,2, 1) -octane are obtained, bp mm; So pl.
Р8«8°4 . Найдено,%: С 51,70; Н 6,30;Р8 «8 ° 4. Found,%: C, 51.70; H 6.30;
Вычислено,%: С 50,00; Н 5,55.Calculated,%: C 50.00; H 5.55.
ИК-спектры (ОСе) : 1000-1200 (С-0-С-О-С) ; 1750 () .IR spectra (AEC): 1000-1200 (C-0-C-O-C); 1750 ().
Пример 2. В прибор, указанный в примере 1, помещают 0,5 мол (80 г) 2-метил-2-этоксикарбонил-1 ,3-диоксолана, 0,5 мол (46 глицерина, 150 мл бензола и 20 г катализатора КУ-2. Реакцию провод т в течение 6-7 ч при температуре кипени бензола. Затем обратный холодильник замен ют нисход щим и медленно отгон ют образовавшийс этиловый спирт (23 г, т.е. расчетное количество). Реакционную смесь охлаждают , отфильтровывают и перегон ют под вакуумом. Получают 55 г (выход 77%) 5-метил-4-оксо-3,6,8-триоксабицикло- (3,2,1)-октайа, Т.кип. мм; т. пл. 51°С. Идентификацию провод т по примеру 1Example 2. In the device specified in example 1, put 0.5 mol (80 g) of 2-methyl-2-ethoxycarbonyl-1, 3-dioxolane, 0.5 mol (46 glycerol, 150 ml of benzene and 20 g of catalyst KU The reaction is carried out for 6-7 hours at the boiling point of benzene. Then the reflux condenser is replaced by a descending one and the ethanol formed is slowly distilled off (23 g, i.e., the calculated amount). The reaction mixture is cooled, filtered and distilled 55 g (yield 77%) of 5-methyl-4-oxo-3,6,8-trioxabicyclo- (3,2,1) -oqtai, bp mm; melting point 55 ° C are obtained under vacuum. C. Identification is carried out by approx. ru 1
Предлагаемый способ позвол ет увеличить выход целевого продукта до 77-79% (против 50% в известномThe proposed method allows to increase the yield of the target product up to 77-79% (against 50% in the known
способе) а также, упростить выделение целевого соединени за счет замены катализатора.method) and also, to simplify the selection of the target compound by replacing the catalyst.
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