WO2009056293A1 - Process for the preparation of alkyl 3,3-dialkoxypropionates - Google Patents
Process for the preparation of alkyl 3,3-dialkoxypropionates Download PDFInfo
- Publication number
- WO2009056293A1 WO2009056293A1 PCT/EP2008/009128 EP2008009128W WO2009056293A1 WO 2009056293 A1 WO2009056293 A1 WO 2009056293A1 EP 2008009128 W EP2008009128 W EP 2008009128W WO 2009056293 A1 WO2009056293 A1 WO 2009056293A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- acidic
- orthoformate
- alkyl
- polysilicates
- Prior art date
Links
Classifications
-
- 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
- C07C67/327—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 by elimination of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/46—Preparation of carboxylic acid esters from ketenes or polyketenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a continuous process for preparing alkyl 3,3-dialkoxy- propionates of the formula (RO) 2 CHCH 2 CO 2 R, wherein R is Ci_ 6 alkyl.
- Alkyl 3,3-dialkoxypropionates are important C-3 building blocks, which themselves are intermediates for various products, such as pyrimidine, quinoline, uracil, fluvastatin, vitamin A and agrochemicals like the herbicide l-methyl-5-hydroxypyrazole.
- One possible synthetic route for alkyl 3,3-dialkoxypropionates is the preparation from the corresponding orthoformate by reaction with ketene in the presence of an acidic catalyst.
- G. Buchi prepares methyl 3,3-dimethoxypropionate in a yield of 19% at a reaction temperature of -70 °C (Biichi et al., J Am. Chem. Soc. 1973, 95, 540-545).
- C 1- ⁇ alkyl is to be understood to mean any linear or branched alkyl group containing 1 to 6 carbon atoms.
- Examples of C 1- ⁇ alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), hexyl, isohexyl (4-methylpentyl) and the like.
- the orthoformate is selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate and tributyl orthoformate. More preferably, the orthoformate is trimethyl orthoformate.
- Continuous operation means that both the reaction partners and the reaction products are continuously added and removed, respectively.
- the ketene gas, the orthoformate and the acidic catalyst are continuously reacted with one another in a loop reactor.
- the term "loop reactor” does not denote a certain design, but only the principle of operation.
- the loop reactor consists of a circularly closed tube (loop) equipped with a circulating pump.
- the loop has at least one connection for withdrawing a product stream and at least two connections for feeding the starting materials.
- the reaction can be carried out in a solvent or in the absence of a solvent.
- the acidic catalyst can be directly added into the reactor, or it can be mixed beforehand with the orthoformate and/or the solvent. The number and the positions of the feed connections have to be chosen accordingly.
- the orthoformate is firstly mixed with the acidic catalyst and optionally with the solvent, whereupon the catalyst goes into solution or just forms a suspension. The resulting mixture is then fed into the loop reactor.
- the reaction is carried out in the absence of a solvent.
- the ketene gas can be fed into the reaction mixture by any suitable gas distribution system, for example, by using a sparger, which is optionally provided with a frit or a nozzle.
- a gas-liquid ejector consists of different units described as follows. The liquid flow passes through a nozzle which generates a high velocity jet of fluid, thus creating suction of the ketene and entraining it into the ejector.
- the accelerated liquid-gaseous jet collides with the wall of an adjacent mixing tube, resulting in a rapid dissipation of kinetic energy.
- the ability to generate and finally disperse very small ketene bubbles into the liquid mixture leads to a favourable gas-liquid ratio of, for example, between 0.5 and 2.0, and to a much better dispersion of ketene in the liquid.
- the thus obtained two-phase mixture is finally injected into the fluid phase in the reactor, leading to an optimal efficacy in the subsequent chemical reaction.
- this way of gas distribution allows a consistent, pressure-free flowing of ketene into the gas-liquid ejector, which is particularly desired as ketene is prone to polymerization under pressure.
- a swirl device directs, orientates and stabilizes the pumped liquid flow, before the liquid flow passes through the nozzle.
- a type of reactor as described above is also known as BUSS Loop ® reactor.
- reaction components are fed into the loop reactor in a simultaneous and continuous manner. This means that there are no major interruptions or strong variations in the molar ratio of the reactants within the reaction mixture.
- the circulation in the loop ensures good or even ideal mixing. However, it is not necessary to enforce an ideal mixing.
- a product stream is withdrawn from the loop reactor, in a volume which corresponds to the volume of the reactants charged, for subjecting to the following work-up procedure. This may take place, for example, via a simple overflow pipe or by pumping-off, while the pumping-off may be controlled using a level detector.
- efficient cooling may be required due to the highly exothermic reaction. It can be achieved by known means, like by use of a cooling jacket covering a substantial part of the tube length or by a heat exchanger of conventional construction being incorporated into the loop.
- the reaction is advantageously carried out at a temperature between —40 °C and 50 0 C.
- the reactants may be pre-cooled before feeding into the loop reactor.
- the reaction temperature is between —30 °C and 30 °C, more preferably between -10 °C and 10 °C.
- the ketene used may be essentially pure or may contain inert gases, such as nitrogen, carbon monoxide and/or carbon dioxide, which advantageously are removed from the loop reactor by means of a suitable air-relief vent in order to prevent excessive pressure buildup.
- inert gases such as nitrogen, carbon monoxide and/or carbon dioxide
- the molar ratio of orthoformate to ketene is preferably between 0.9 and 1.2, more preferably between 1.0 and 1.1. These values refer to the amounts charged. The ratios actually present in the reaction mixture may differ more or less from these values.
- each organic solvent in which the orthoformate is sufficiently soluble and which does not react with ketene or any other component can be used as solvent.
- Suitable solvents are, for example, aliphatic or aromatic hydrocarbons and ethers.
- trimethyl orthoformate is directly reacted with ketene, i.e. without solvent, in the presence of an acidic catalyst.
- Suitable acidic catalysts are both "classic” Lewis acids and “classic” Br ⁇ nsted acids, and also acidic polysilicates.
- the "classic” Lewis acids used are zinc(II) chloride, iron(III) chloride, aluminum chloride, boron trifiuoride and its adducts with ethers, esters and similar compounds.
- a preferred adduct of boron trifiuoride is the diethyl ether adduct.
- Preferred examples of "classic" Br ⁇ nsted acids are sulfuric acid, phosphoric acid, methanesulfonic acid and benzenesulfonic acid.
- Acidic polysilicates have Lewis and/or Br ⁇ nsted acid properties and are therefore likewise suitable for the process according to the invention.
- the acidic polysilicates can also be employed in modified form or as mixtures.
- the formulae below are only given to illustrate the polysilicates but are not meant to be interpreted as a limitation.
- Suitable acidic polysilicates are, for example, amorphous polysilicates of the allophane type; chain polysilicates of the hormite type, such as “polygorskite”; two-layer polysilicates of the kaolin type, such as “kaolinite” Al 2 (OH) 4 [Si 2 O 5 ] and “halloysite” Al 2 (OH) 4 [Si 2 O 5 ] x 2 H 2 O; three-layer polysilicates of the smectite type, such as "sauconite” Na 0 3 Zn 3 (Si 5 Al) 4 O 1O (OH) 2 x 4 H 2 O, "saponite” (Ca 5 Na) 03 (Mg 5 Fe 11 MSiAl) 4 O 10 (OH) 2 x 4 H 2 O, "montmorillonite” M 03 (Al 5 Mg) 2 Si 4 O 10 (OH) 2 x n H 2 O 5 wherein M in natural montmorillon
- the acidic polysilicates of the process according to the invention may be activated by treatment with acid and/or by treatment with a metal salt solution and/or by drying, and in the case of zeolites preferably by ion-exchange and/or by heating.
- the catalysts used are acidic polysilicates of the smectite type and zeolites.
- a particularly preferred acidic polysilicate of the smectite type is montmorillonite, especially the types available under the names "montmorillonite K 10" and “montmorillonite KSF/O", which are available, for example, from the company S ⁇ d-Chemie.
- the acidic catalyst is advantageously employed in the process of the invention in an amount between 0.1% by weight and 20% by weight (based on oithoformate), preferably between 0.5 and 10% by weight. However, the amount depends on the activity of the catalyst and the reaction temperature.
- a solid acid catalyst is used which is filtered off in a first work-up step.
- the residue thus obtained is then either discarded or re-used in the reaction mixture as acidic catalyst, after its purification and optional re-activation if required.
- the filtrate is worked up in a known manner, preferably by distillation, to obtain the formed alkyl 3,3-dialkoxypropionate in neat form.
- the unreacted orthoformate which usually has a lower boiling point than the desired product, is distilled off after filtration and is then re-cycled into the reaction mixture, which significantly increases the total conversion of the reaction.
- Alkyl 3-alkoxyprop-2-enoates are likewise important C-3 building blocks and are used, for example, for preparing alkyl 2,2,3-trichloro-3-alkoxypropionates, pyrazoles, furanones, thio- phenes, aminothiazoles, isoxazole and vitamin A.
- Suitable acids are both liquid acids and solid acids, like acidic salts, acidically activated silica gel, acidic clay minerals, acidically activated carbon, acidic zeolites and cation exchange resins in their H-form.
- the salts can be attached to carrier materials or can be modified.
- Suitable acids are, for example, sulfuric acid, orthoboric acid, orthophosphoric acid, methane- sulfonic acid, j ⁇ -toluenesulfonic acid, sulfanilic acid, sodium bisulfate, phosphorus pentoxide, aluminum phosphate, zinc chloride, aluminum chloride and acidic zeolites.
- the amount of acid employed is between 0.05% by weight and 15% by weight (based on alkyl 3,3-dialkoxypropionate), particularly preferably between 0.1% by weight and 10% by weight.
- the solvent used may be any solvent which does not react with the reaction components, such as, for example, ligroin. However, the elimination can also be carried out without solvent. Preferably, the reaction is carried out in the absence of a solvent.
- the elimination is carried out at a temperature between 50 °C and 250 °C, more preferably between 80 °C and 200 °C, and the reaction time is advantageously between 1 hour and 15 hours, preferably between 1 hour and 10 hours.
- the reaction may also be carried out under reduced pressure.
- the E-isomer of alkyl 3-alkoxyprop-2- enoate is formed with preference.
- the formed alcohol (ROH) is directly distilled off during reaction.
- the alkyl 3-alkoxyprop-2-enoate obtained can be purified in a known manner, for example by rectification.
- Figure 1 shows, schematically, a device for the continuous preparation of alkyl 3,3-dialkoxy- propionate.
- the specific meanings of the reference signs are as follows:
- the reaction mixture was kept at a temperature of about 0 °C and circulated in the loop via a circulating pump. Corresponding to the amount of starting materials added, and also continuously, a corresponding part of the reaction mixture flowed over into a collecting tank. After filtration, the purity of the filtrate was determined by GC as 80% methyl 3,3-dimethoxypropionate, 8% unreacted trimethyl orthoformate, 4% methyl 3-methoxyprop-2-enoate and 4% methyl acetate.
- the reaction was carried out analogously to example 2 using 5 g (content 99%, 34 mmol) of pure-distilled methyl 3,3-dimethoxypropionate and 25 mg (0.13 mmol) of/?-toluenesulfonic acid monohydrate (Fluka).
- the resulting crude product had a content of 91% (GC) of methyl 3- methoxyprop-2-enoate.
- Example 4 Preparation of methyl 3-methoxyprop-2-enoate The reaction was carried out analogously to example 2 using 5 g (content 99%, 34 mmol) of pure-distilled methyl 3,3-dimethoxypropionate and 47 mg (0.27 mmol) of sulfanilic acid (Fluka). The resulting crude product had a content of 92% (GC) of methyl 3-methoxyprop-2- enoate.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08844650A EP2207765A1 (en) | 2007-10-29 | 2008-10-29 | Process for the preparation of alkyl 3,3-dialkoxypropionates |
CN200880114018.7A CN101842344B (en) | 2007-10-29 | 2008-10-29 | Process for the preparation of alkyl 3,3-dialkoxypropionates |
MX2010004565A MX2010004565A (en) | 2007-10-29 | 2008-10-29 | Process for the preparation of alkyl 3,3-dialkoxypropionates. |
JP2010531453A JP5496902B2 (en) | 2007-10-29 | 2008-10-29 | Process for preparing alkyl 3,3-dialkoxypropionates |
US12/679,045 US20100217031A1 (en) | 2007-10-29 | 2008-10-29 | Process for the preparation of alkyl 3,3-dialkoxypropionates |
CA2700240A CA2700240A1 (en) | 2007-10-29 | 2008-10-29 | Process for the preparation of alkyl 3,3-dialkoxypropionates |
HK10111403.6A HK1144682A1 (en) | 2007-10-29 | 2010-12-08 | Process for the preparation of alkyl 3,3-dialkoxypropionates 33- |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07021098.4 | 2007-10-29 | ||
EP07021104A EP2055694A1 (en) | 2007-10-29 | 2007-10-29 | Method for manufacturing alkyl-3-alkoxyprop-2-enoates |
EP07021098 | 2007-10-29 | ||
EP07021104.0 | 2007-10-29 | ||
US9572808P | 2008-09-10 | 2008-09-10 | |
US61/095,728 | 2008-09-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009056293A1 true WO2009056293A1 (en) | 2009-05-07 |
Family
ID=40042623
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2008/009128 WO2009056293A1 (en) | 2007-10-29 | 2008-10-29 | Process for the preparation of alkyl 3,3-dialkoxypropionates |
Country Status (8)
Country | Link |
---|---|
US (1) | US20100217031A1 (en) |
EP (1) | EP2207765A1 (en) |
JP (1) | JP5496902B2 (en) |
CN (1) | CN101842344B (en) |
CA (1) | CA2700240A1 (en) |
HK (1) | HK1144682A1 (en) |
MX (1) | MX2010004565A (en) |
WO (1) | WO2009056293A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8948753B2 (en) | 2010-04-30 | 2015-02-03 | Alcatel Lucent | Method of providing notification of abnormal conditions during non-access stratum (NAS) message tunneling |
EP2995658A2 (en) | 2014-09-09 | 2016-03-16 | Fujifilm Corporation | Polymerizable composition, ink composition for inkjet recording, inkkjet recording method and recorded matter |
EP3650442A1 (en) | 2018-11-09 | 2020-05-13 | Lonza Limited | Method for the preparation of difluoromethyl pyrazole carboxylic alkyl ester and its acid |
CN111995519A (en) * | 2020-09-26 | 2020-11-27 | 安徽金禾实业股份有限公司 | Preparation method of 3-methoxy methyl acrylate |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102603588A (en) * | 2012-03-13 | 2012-07-25 | 浙江工业大学 | Method for preparing vitamin A derivative |
CN102746156A (en) * | 2012-05-31 | 2012-10-24 | 上海海事大学 | Production technology of methyl 3-methoxyacrylate |
CN105418421A (en) * | 2015-10-23 | 2016-03-23 | 吴清来 | Synthesizing method for 3-methoxyacrylate |
CN109438237B (en) * | 2018-12-12 | 2021-05-28 | 浙江华方药业股份有限公司 | Preparation method of 3-ethoxy ethyl acrylate |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2449471A (en) * | 1946-11-01 | 1948-09-14 | Du Pont | Preparation of ether esters |
US2571212A (en) * | 1948-10-02 | 1951-10-16 | Rohm & Haas | Preparation of ether-substituted unsaturated esters |
DE1087123B (en) * | 1959-01-31 | 1960-08-18 | Wacker Chemie Gmbh | Process and device for the continuous production of ª ‰ -alkoxycarboxylic acid esters |
US3049560A (en) * | 1958-08-04 | 1962-08-14 | Wacker Chemie Gmbh | Process for the production of betaalkoxy substituted carboxylic acid esters |
EP0346852A2 (en) * | 1988-06-14 | 1989-12-20 | Lonza Ag | Process for producing 4-chloro-3-alkoxybut-2E-ene acid alkyl esters |
WO1998007707A1 (en) * | 1996-08-19 | 1998-02-26 | Zeneca Limited | Process for the preparation of pyrimidine compounds |
US20040152894A1 (en) * | 2001-06-26 | 2004-08-05 | Nippon Soda Co. Ltd | Process for producing acrylic acid derivative |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4031136A (en) * | 1975-01-28 | 1977-06-21 | Hoechst Aktiengesellschaft | Process for the preparation of trans, trans-muconic acid |
KR930007731B1 (en) * | 1991-06-18 | 1993-08-18 | 한국과학기술연구원 | Preparation of preparing for diketene |
DE4243464A1 (en) * | 1992-12-22 | 1994-06-23 | Basf Ag | Process for the preparation of alpha-tocopherol and alpha-tocopheryl acetate in liquid or supercritical carbon dioxide |
JP2003286282A (en) * | 2002-03-19 | 2003-10-10 | Council Scient Ind Res | Method for selectively producing 2-nitrothiophene from thiophene by using metal-exchanged clay catalyst |
US20060165566A1 (en) * | 2005-01-25 | 2006-07-27 | Fina Technology, Inc. | Loop reactor design |
-
2008
- 2008-10-29 EP EP08844650A patent/EP2207765A1/en not_active Withdrawn
- 2008-10-29 WO PCT/EP2008/009128 patent/WO2009056293A1/en active Application Filing
- 2008-10-29 CN CN200880114018.7A patent/CN101842344B/en not_active Expired - Fee Related
- 2008-10-29 US US12/679,045 patent/US20100217031A1/en not_active Abandoned
- 2008-10-29 CA CA2700240A patent/CA2700240A1/en not_active Abandoned
- 2008-10-29 JP JP2010531453A patent/JP5496902B2/en not_active Expired - Fee Related
- 2008-10-29 MX MX2010004565A patent/MX2010004565A/en not_active Application Discontinuation
-
2010
- 2010-12-08 HK HK10111403.6A patent/HK1144682A1/en not_active IP Right Cessation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2449471A (en) * | 1946-11-01 | 1948-09-14 | Du Pont | Preparation of ether esters |
US2571212A (en) * | 1948-10-02 | 1951-10-16 | Rohm & Haas | Preparation of ether-substituted unsaturated esters |
US3049560A (en) * | 1958-08-04 | 1962-08-14 | Wacker Chemie Gmbh | Process for the production of betaalkoxy substituted carboxylic acid esters |
DE1087123B (en) * | 1959-01-31 | 1960-08-18 | Wacker Chemie Gmbh | Process and device for the continuous production of ª ‰ -alkoxycarboxylic acid esters |
EP0346852A2 (en) * | 1988-06-14 | 1989-12-20 | Lonza Ag | Process for producing 4-chloro-3-alkoxybut-2E-ene acid alkyl esters |
WO1998007707A1 (en) * | 1996-08-19 | 1998-02-26 | Zeneca Limited | Process for the preparation of pyrimidine compounds |
US20040152894A1 (en) * | 2001-06-26 | 2004-08-05 | Nippon Soda Co. Ltd | Process for producing acrylic acid derivative |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8948753B2 (en) | 2010-04-30 | 2015-02-03 | Alcatel Lucent | Method of providing notification of abnormal conditions during non-access stratum (NAS) message tunneling |
EP2995658A2 (en) | 2014-09-09 | 2016-03-16 | Fujifilm Corporation | Polymerizable composition, ink composition for inkjet recording, inkkjet recording method and recorded matter |
EP3650442A1 (en) | 2018-11-09 | 2020-05-13 | Lonza Limited | Method for the preparation of difluoromethyl pyrazole carboxylic alkyl ester and its acid |
CN111995519A (en) * | 2020-09-26 | 2020-11-27 | 安徽金禾实业股份有限公司 | Preparation method of 3-methoxy methyl acrylate |
CN111995519B (en) * | 2020-09-26 | 2022-08-26 | 安徽金禾实业股份有限公司 | Preparation method of 3-methoxy methyl acrylate |
Also Published As
Publication number | Publication date |
---|---|
CA2700240A1 (en) | 2009-05-07 |
EP2207765A1 (en) | 2010-07-21 |
MX2010004565A (en) | 2010-05-20 |
US20100217031A1 (en) | 2010-08-26 |
JP5496902B2 (en) | 2014-05-21 |
JP2011500861A (en) | 2011-01-06 |
CN101842344A (en) | 2010-09-22 |
CN101842344B (en) | 2014-04-30 |
HK1144682A1 (en) | 2011-03-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20100217031A1 (en) | Process for the preparation of alkyl 3,3-dialkoxypropionates | |
EP2123631B1 (en) | PROCESS FOR PRODUCING ß-ALKOXYPROPIONAMIDE | |
CN111094237A (en) | Amide compounds and nitrile compounds and methods of making and using the same | |
EP1435358A2 (en) | Process for preparing phosphoric ester | |
WO2010121768A1 (en) | Process for the preparation of dialkyl glutaconates | |
CN109970580A (en) | A kind of extraction preparation method of R-3- amino butanol | |
US8969600B2 (en) | Method for producing glycidol | |
US7683221B2 (en) | Process for the production of alkylene glycols using homogeneous catalysts | |
US9199950B2 (en) | Method for producing glycidol by successive catalytic reactions | |
CN102753515B (en) | A kind of method preparing carboxylicesters | |
JP4106494B2 (en) | Method for producing carboxylic acid ester using HF catalyst | |
EP3650442B1 (en) | Method for the preparation of difluoromethyl pyrazole carboxylic alkyl ester and its acid | |
CN103261159A (en) | Process for the preparation of imides, of derivatives thereof and uses | |
JP2002529440A (en) | Method for producing tris (ether-amine) | |
JP2004285068A (en) | METHOD FOR CONTINUOUSLY PRODUCING ACETAL OF alpha,beta-DICARBONYL COMPOUND | |
JP4091361B2 (en) | Method for producing dialkyl carbonate | |
CN107235832B (en) | Method for producing guaiacol | |
EP1057822B1 (en) | Process for the preparation of alcohol derivatives | |
US20080027241A1 (en) | Process for Producing Cyclopentanone-2, 3, 5-Tricarboxylic Acid Triester | |
TW201402538A (en) | Transesterification process | |
JP4131025B2 (en) | Method for producing ketazine and hydrated hydrazine | |
WO2017204155A1 (en) | Method for producing acetal compound | |
CN113677654B (en) | method | |
JPH03188089A (en) | Continuous production of phosphoric monoester | |
JP3709651B2 (en) | Production method of dihydric phenol monoalkyl ether |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880114018.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08844650 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2008844650 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2008844650 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2700240 Country of ref document: CA Ref document number: 12679045 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2123/DELNP/2010 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2010/004565 Country of ref document: MX |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010531453 Country of ref document: JP |