ES2662800T3 - Proceso para la fabricación de fluoroacrilato de alquilo - Google Patents
Proceso para la fabricación de fluoroacrilato de alquilo Download PDFInfo
- Publication number
- ES2662800T3 ES2662800T3 ES13730917.5T ES13730917T ES2662800T3 ES 2662800 T3 ES2662800 T3 ES 2662800T3 ES 13730917 T ES13730917 T ES 13730917T ES 2662800 T3 ES2662800 T3 ES 2662800T3
- Authority
- ES
- Spain
- Prior art keywords
- claisen
- alkyl
- alkane
- manufacture
- suitable solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 alkyl fluoroacrylate Chemical compound 0.000 title abstract 4
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 title abstract 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 5
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 2
- 229920002866 paraformaldehyde Polymers 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract 3
- 238000003512 Claisen condensation reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 150000003901 oxalic acid esters Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZTZJVAOTIOAZGZ-UHFFFAOYSA-N methyl 2-fluoroacrylate Chemical compound COC(=O)C(F)=C ZTZJVAOTIOAZGZ-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C67/32—Decarboxylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Proceso para la fabricación de un fluoroacrilato de alquilo, que comprende las siguientes etapas: A. un fluoroacetato de alquilo con un éster de ácido oxálico se hace reaccionar en presencia de una base y un disolvente adecuado en una condensación de Claisen cruzada dando como resultado una sal de Claisen, B. la sal de Claisen obtenida en la etapa A se elimina por filtración opcionalmente y se lava con un disolvente adecuado, C. la sal de Claisen obtenida en la etapa A o B se hace reaccionar con paraformaldehído y D. el fluoroacrilato de alquilo obtenido en la etapa C se aísla usando un disolvente adecuado, en el que el disolvente en al menos la etapa C y opcionalmente en una de las etapas A, B o D comprende un alcano que es líquido en las condiciones de reacción de las etapas en las que se aplica el alcano, y en el que el alcano es pentano o hexano.
Description
30 % de NaOMe en metanol (48,9 g, 1,25 equiv.). La solución resultante se agita durante 24 h a 20-25 °C.
Etapa B
5 La suspensión se enfría a 0 °C, la sal de Claisen se elimina por filtración y se lava con pentano (3 x 40 ml).
Etapa C
La sal húmeda y el pentano (120 ml) se cargan en el reactor y la suspensión se enfría a 5-10 ºC. Se añade en 10 10 porciones paraformaldehído (4,0 g, 1,2 equiv.) y la suspensión se agita a 5-10 ºC durante 5 h más.
Etapa D
La mezcla de reacción se inactiva con agua (115 ml) y la fase acuosa se extrajo una vez con pentano (2 x 60 ml). 15 Las fases orgánicas se combinan y el producto se purifica mediante destilación al vacío.
Se espera que el rendimiento alcanzado antes de la destilación esté en línea con el rendimiento obtenido para los ejemplos de fluoroacrilato de metilo.
8
Claims (1)
-
imagen1
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12173485 | 2012-06-25 | ||
| EP12173485 | 2012-06-25 | ||
| PCT/EP2013/063324 WO2014001365A1 (en) | 2012-06-25 | 2013-06-25 | Process for the manufacture of alkylfluoroacrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2662800T3 true ES2662800T3 (es) | 2018-04-09 |
Family
ID=48672654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES13730917.5T Active ES2662800T3 (es) | 2012-06-25 | 2013-06-25 | Proceso para la fabricación de fluoroacrilato de alquilo |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US11420927B2 (es) |
| EP (1) | EP2864286B1 (es) |
| JP (1) | JP6146724B2 (es) |
| CN (2) | CN109456187B (es) |
| CA (1) | CA2877548C (es) |
| ES (1) | ES2662800T3 (es) |
| IN (1) | IN2015DN00531A (es) |
| WO (1) | WO2014001365A1 (es) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2558147C1 (ru) * | 2014-07-17 | 2015-07-27 | Закрытое акционерное общество научно-производственное Объединение "ПиМ-Инвест" (ЗАО НПО "Пим-Инвест") | Способ получения метил-2-фторакрилата |
| CN104478715B (zh) * | 2014-11-21 | 2016-07-20 | 湖北华世通生物医药科技有限公司 | 化合物的制备方法 |
| WO2017013683A1 (en) | 2015-07-22 | 2017-01-26 | Srf Limited | Process for the preparation of fluoroacrylic acid esters |
| CN105646216B (zh) * | 2016-02-23 | 2018-04-03 | 湖北工程学院 | 2‑氟‑3‑羟基丙酸甲酯合成方法 |
| CN115956065A (zh) * | 2020-08-19 | 2023-04-11 | 大金工业株式会社 | 含卤素（甲基）丙烯酸酯的精制方法 |
| EP4212508A4 (en) * | 2020-09-11 | 2024-10-30 | Daikin Industries, Ltd. | PROCESS FOR PRODUCING ACRYLIC ACID DERIVATIVE |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2454663A (en) | 1945-04-09 | 1948-11-23 | Ici Ltd | Fluorodihalo esters |
| US3075002A (en) | 1962-02-21 | 1963-01-22 | American Cyanamid Co | Process for preparing alpha-fluoroacrylates |
| US3262967A (en) * | 1963-10-31 | 1966-07-26 | American Cyanamid Co | Process for the preparation of alpha-fluoroacrylates |
| US3262968A (en) | 1963-11-07 | 1966-07-26 | American Cyanamid Co | Process for the preparation of alpha-fluoroacrylates |
| US6509134B2 (en) * | 2001-01-26 | 2003-01-21 | International Business Machines Corporation | Norbornene fluoroacrylate copolymers and process for the use thereof |
| DE102009030681A1 (de) | 2009-06-26 | 2010-12-30 | Saltigo Gmbh | Herstellung von substituierten 2-Fluoracrylsäurederivaten |
| CN102211998A (zh) * | 2011-04-08 | 2011-10-12 | 镇江蓝德特药业科技有限公司 | α-氟代丙烯酸甲酯及其类似物的合成方法 |
| CN102731304B (zh) | 2011-04-11 | 2016-05-25 | 天津泰瑞倍药研科技有限公司 | α-氟代丙烯酸酯的制备方法 |
| CN102212000A (zh) * | 2011-05-25 | 2011-10-12 | 原平市同利化工有限责任公司 | 2-氟-3羟基丙酸烷基酯的合成方法 |
| CN102757347A (zh) | 2012-07-23 | 2012-10-31 | 太仓中化环保化工有限公司 | 一种2-卤代丙烯酸烷基酯的制备方法 |
-
2013
- 2013-06-25 CA CA2877548A patent/CA2877548C/en active Active
- 2013-06-25 US US14/409,522 patent/US11420927B2/en active Active
- 2013-06-25 JP JP2015517811A patent/JP6146724B2/ja active Active
- 2013-06-25 EP EP13730917.5A patent/EP2864286B1/en active Active
- 2013-06-25 IN IN531DEN2015 patent/IN2015DN00531A/en unknown
- 2013-06-25 CN CN201811196178.2A patent/CN109456187B/zh active Active
- 2013-06-25 CN CN201380033307.5A patent/CN104520264A/zh active Pending
- 2013-06-25 ES ES13730917.5T patent/ES2662800T3/es active Active
- 2013-06-25 WO PCT/EP2013/063324 patent/WO2014001365A1/en not_active Ceased
-
2020
- 2020-06-08 US US16/895,830 patent/US11492323B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP6146724B2 (ja) | 2017-06-14 |
| CN104520264A (zh) | 2015-04-15 |
| CA2877548C (en) | 2020-09-01 |
| US11420927B2 (en) | 2022-08-23 |
| EP2864286B1 (en) | 2018-02-14 |
| CN109456187B (zh) | 2022-08-30 |
| WO2014001365A1 (en) | 2014-01-03 |
| US20150368178A1 (en) | 2015-12-24 |
| IN2015DN00531A (es) | 2015-06-26 |
| CN109456187A (zh) | 2019-03-12 |
| EP2864286A1 (en) | 2015-04-29 |
| CA2877548A1 (en) | 2014-01-03 |
| JP2015523993A (ja) | 2015-08-20 |
| US11492323B2 (en) | 2022-11-08 |
| US20200369593A1 (en) | 2020-11-26 |
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