SU536162A1 - The method of obtaining-benzoyl-α-amino-methyl-α-ethyl acrylic acid - Google Patents

The method of obtaining-benzoyl-α-amino-methyl-α-ethyl acrylic acid

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Publication number
SU536162A1
SU536162A1 SU2128205A SU2128205A SU536162A1 SU 536162 A1 SU536162 A1 SU 536162A1 SU 2128205 A SU2128205 A SU 2128205A SU 2128205 A SU2128205 A SU 2128205A SU 536162 A1 SU536162 A1 SU 536162A1
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USSR - Soviet Union
Prior art keywords
acid
methyl
benzoyl
amino
obtaining
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SU2128205A
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Russian (ru)
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Инара Карловна Калнинь
Ида Элиасовна Хацкевич
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Предприятие П/Я М-5043
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Priority to SU2128205A priority Critical patent/SU536162A1/en
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Publication of SU536162A1 publication Critical patent/SU536162A1/en

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обработки,что значительно упрощает процесс получени  Й-бензоил-а-амимо-/ -мётил-0-этйд рило вой кислоты. Возможность применени  этанола вместо метанола улучшает услови  проведени  прюцесса. Способ заключаетс  в следующем: при взаимодействии гиппуровой кислоты с метилэтилкетоном в среде Уксусного ангидрида в присутствии ацетата натри  после упаривани  реакционной массы и обработки водой получают технический 2-фенил-4-втор-бутилиденрксазолон-5 (красное масло). Оксазолон Б раствор ют в этиловом спирте, опиртовый раствор подкисл ют концентрированной сол ной кислотой до -сильнокислой реакции и выдерживают при lO-SOC 5-8 ч. По окончании гидролиза раствор частично упаривают в вакууме при 20- 30 мм рт.ст., в упаренную шссу доливают воду д|1Я растворени  neopraHHiecKHX примесей и выделени  кислоты А. Пример 1. Загружают 54 г (0,3 мол ) гиппуровой кислоты, 1300мл метилэтилкетона, 24 г (0,29 мол ) ацетата натри  и при перемепшвании в течение ЗОмин добавл ют 76 мл (0,75 мол ) уксусного ашидрида. Реакдаонную смесь кип т т при нагревании в течение 6 ч. По охлаждении реакционную смесь отфильтровывают и упаривают. Остаток выпивают в 1 л воды и выдерживают при 15-20°С в течение 6 ч. Затем красное масло отдел ют на делительной воронке и раствор ют в 300 мл этилового спирта. Спиртовьш раствор, подкисл ют 40мл концентрированной сол ной кислоты. После сто ни  в течение 5 ч. при 2Q-22C гидролизную смесь упаривают до 1/2 первоначального объема, добавл ют 300 мл дистиллированной-воды и отфильтровьшают 34 г N-бензоил -о -амино-/3-метил-/3-этилакриловой кислоты. Кислоту А промьшают водно-спиртовым раствором. Выход 48,6%, счита  на гиппуровую кислоту; т.пл.196- 99С. Найдено,%: С 65,29; И 6,55; N 5,58. CijH.sOjN Вьпшслено,%:С66,92; Н6,49; N6,12. Пример 2. Загружают 54 г (0,3 мол ) гиппуровой кислоты, 1300 мл метилэтилкетона, 24 г (0,29 мол ) ацетата натр«  и. при перемешивании в течение 30 мин добавл ют 76 мл (0,75 мол ) yKcycHOjo ангидрида. Реакционную смесь кип т т при нагревании в течение 6 ч. По охлаждении реакциоЩ1ую смесь отфилыровьгеают и упаривают. Остаток выливают в 1 л воды и выдерживают при 15-20°С в течение 6ч. Затем красное масло .отдел ют на делительной ворюнке и раствор ют в 250мл этилового спирта. Спиртовьш раствор подкисл ют 55 мл концентрированной сол ной кислоты. После сто ни  в течение 8 ч при 20-22° С гидролизнзто смесь упаривают до половины первоначального объема, добавл ют 400 мл дистиллированной воды и отфильтровывают 35,2 г кислоты А. Кислоту А промывают водно-спиртовым раствором. Выход 50,3%, счита  на гипцуровую кислоту. Пример 3. Загружают 27 г (0,15 мол ) ги4пуровой кислоты, 650 мл метилэтилкетона, 12 г (0,145 мол ) ацетата натри  и при перемешивании в тече1ше 30 мин добавл ют 38 мл (О, 38 мол ) уксусАого ангидрида. Реакционную смесь кип т т при нагревании в течение 7 ч. По охлаждении реакционную смесь отфильтровьюают и упаривают, упаренный остаток раствор ют в 250 мл этилового спирта. Спиртовой раствор фильтруют и фильтрат подкис г ют 25 мл концентрированной сол ной кислоты до рН 0,3. : После сто ни  в течение 6ч при 20-22° С к гидролизной смеси добавл ют 1 л дистиллированной воды. Отфильтровьшают 18,12 г N-бензоил-а-амино-Д-метил-/3-этилакриловой кислоты. Выход 51,4% в расчете на га пуровую кислоту; Т.ПЛ. 195-197°С. Найдено, %: С 65,53; Н6,46; N6,19 CijHisOjN Вычислено,%: С66,92; Н6,49; N6,12 Хроматографшкски однородный. Пример 4. Технический 2-фенил- 4-втор- бутилиденоксаэолон- 5, полученный аналогично примеру 3, раствор ют в 250-300мл этилового спирта, спиртовый раствор фильтруют, фильтрат довод т до заданной температуры, добавл ют 20-25 мл концентрированной сол ной кислоты (рН 0,2-0,5) и выдерживают гидролизуемую смесь при этой температуре. Кристагты М-бензош1Ч1 -амино-13-метил-| -этилакриловой кислоты отфипьтровьюают. Результаты приведены в таблице.treatment, which greatly simplifies the process for the preparation of th-benzoyl-a-amimo-1-methyl-0-etryl acid. The possibility of using ethanol instead of methanol improves the conditions of the process. The method is as follows: by reacting hippuric acid with methyl ethyl ketone in acetic anhydride medium in the presence of sodium acetate, after technical evaporation of the reaction mass and treatment with water, technical 2-phenyl-4-sec-butylidenexazolone-5 (red oil) is obtained. Oxazolone B is dissolved in ethyl alcohol, the alcoholic solution is acidified with concentrated hydrochloric acid to a strongly acidic reaction and kept at lO-SOC for 5-8 hours. At the end of the hydrolysis, the solution is partially evaporated in vacuo at 20-30 mm Hg, in one hundred percent of the shssu is added with water to dissolve neopraHHiecKHX impurities and release of acid A. Example 1. Load 54 g (0.3 mol) of hippuric acid, 1300 ml of methyl ethyl ketone, 24 g (0.29 mol) of sodium acetate and stirring during 3 h. 76 ml (0.75 mol) of acetic acidhydride. The reaction mixture is boiled under heating for 6 hours. After cooling, the reaction mixture is filtered and evaporated. The residue is drunk in 1 liter of water and maintained at 15-20 ° C for 6 hours. Then the red oil is separated in a separatory funnel and dissolved in 300 ml of ethanol. The alcoholic solution is acidified with 40 ml of concentrated hydrochloric acid. After standing for 5 hours at 2Q-22C, the hydrolysis mixture is evaporated to 1/2 of the original volume, 300 ml of distilled water is added and 34 g of N-benzoyl -o-amino- / 3-methyl- / 3-ethyl acrylic are filtered off acid. Acid A is washed with a water-alcohol solution. Yield 48.6%, calculated on hippuric acid; mp.196-99C. Found,%: C 65.29; And 6.55; N 5.58. CijH.sOjN,%: C66.92; H6.49; N6.12. Example 2. Download 54 g (0.3 mol) of hippuric acid, 1300 ml of methyl ethyl ketone, 24 g (0.29 mol) of sodium acetate and. while stirring, 76 ml (0.75 mol) of yKcycHOjo anhydride are added over 30 minutes. The reaction mixture is boiled under heating for 6 hours. After cooling, the reaction mixture is filtered and evaporated. The residue is poured into 1 liter of water and maintained at 15-20 ° C for 6 hours. Then the red oil is separated on a dunnel and dissolved in 250 ml of ethanol. The alcoholic solution is acidified with 55 ml of concentrated hydrochloric acid. After standing for 8 hours at 20–22 ° C, the hydrolysis mixture is evaporated to half the original volume, 400 ml of distilled water is added and 35.2 g of acid A is filtered. Acid A is washed with an aqueous-alcoholic solution. Yield 50.3%, based on gypsum acid. Example 3. A load of 27 g (0.15 mol) of hydrous acid, 650 ml of methyl ethyl ketone, 12 g (0.145 mol) of sodium acetate and 38 ml (O, 38 mol) of acetic anhydride are added with stirring over 30 minutes. The reaction mixture is boiled under heating for 7 hours. After cooling, the reaction mixture is filtered and evaporated, the evaporated residue is dissolved in 250 ml of ethyl alcohol. The alcoholic solution is filtered and the filtrate is acidified with 25 ml of concentrated hydrochloric acid to pH 0.3. After standing for 6 hours at 20-22 ° C, 1 liter of distilled water was added to the hydrolysis mixture. 18.12 g of N-benzoyl-a-amino-D-methyl- / 3-ethylacrylic acid are filtered out. Yield 51.4% based on hecturine acid; T.PL. 195-197 ° C. Found,%: C 65.53; H6.46; N6.19 CijHisOjN Calculated: C66.92; H6.49; N6,12 Chromatographic homogeneous. Example 4. Technical 2-phenyl-4-sec-butylidenoxaaolone-5, prepared as in Example 3, is dissolved in 250-300 ml of ethyl alcohol, the alcoholic solution is filtered, the filtrate is brought to a predetermined temperature, and 20-25 ml of concentrated hydrochloric acid is added. acid (pH 0.2-0.5) and maintain the hydrolyzable mixture at this temperature. Cristags M-benzoshch1ch1-amino-13-methyl- | -ethyl acrylic acid is washed out. The results are shown in the table.

Claims (2)

1.F.P. Doyle и др. .Experiments in the synthesis of D,L-iso- LeucineY Cnem Soc,1955,1719.1.F.P. Doyle et al. Experiments in the synthesis of D, L-iso- LeucineY Cnem Soc, 1955.1719. 2.Лурье G. И., Вдовина P. Г. Исследова ше в области аминокислот, цис-транс-изомери  в р ду оксазолонов (азлактонов), ЖОХ, 1883, 1952 (прототш).2. Lurie, G.I., Vdovina, P.G. Research in the field of amino acids, cis-trans-isomerism in the row of oxazolones (azlactones), JOH, 1883, 1952 (prototisch).
SU2128205A 1975-04-28 1975-04-28 The method of obtaining-benzoyl-α-amino-methyl-α-ethyl acrylic acid SU536162A1 (en)

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