WO2020159007A1 - Procédé de préparation d'un composé acyloxybenzène sulfonate - Google Patents

Procédé de préparation d'un composé acyloxybenzène sulfonate Download PDF

Info

Publication number
WO2020159007A1
WO2020159007A1 PCT/KR2019/005829 KR2019005829W WO2020159007A1 WO 2020159007 A1 WO2020159007 A1 WO 2020159007A1 KR 2019005829 W KR2019005829 W KR 2019005829W WO 2020159007 A1 WO2020159007 A1 WO 2020159007A1
Authority
WO
WIPO (PCT)
Prior art keywords
chloride
sodium
reaction
distilled water
yield
Prior art date
Application number
PCT/KR2019/005829
Other languages
English (en)
Korean (ko)
Inventor
김선기
Original Assignee
주식회사 비제이바이오켐
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 주식회사 비제이바이오켐 filed Critical 주식회사 비제이바이오켐
Publication of WO2020159007A1 publication Critical patent/WO2020159007A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C07C309/58—Carboxylic acid groups or esters thereof

Definitions

  • the present invention relates to a method for preparing an acyloxybenzenesulfonate compound which is a bleaching activator.
  • U.S. Patent Publication No. 1,437,724 discloses a method for preparing acyloxybenzenesulfonates by reacting a hydroxybenzene sulfonate salt and an aryl ester with an organic solvent at 200 to 350°C have.
  • the prior art is manufactured by using an organic solvent at a high temperature, resulting in high production cost, using a large amount of organic solvents harmful to the human body, and harmful to the environment. Therefore, it is required to develop an economical and eco-friendly manufacturing process due to easy production.
  • the present inventors confirmed that the target compound can be obtained with a high yield even when reacted in an aqueous solution at a low temperature in order to develop an easy and eco-friendly process.
  • One object of the present invention is a method for preparing sodium acyloxybenzenesulfonate represented by Chemical Formula 1, comprising reacting acyl chloride and sodium hydroxybenzenesulfonate under a reaction solvent as in Reaction Scheme I. Is to provide.
  • R in Reaction Scheme I and Formula 1 is a C6 to C22 linear or pulverized saturated alkyl group, and the reaction solvent is water and acetone mixed in a weight ratio of 10:0 to 6.5:3.5.
  • the present invention relates to a method for synthesizing a bleach activator acyloxybenzenesulfonate in an aqueous solution at low temperature. Since it is manufactured in an aqueous solution at low temperature, the production cost can be lowered, and acyloxybenzenesulfonate, an environmentally friendly bleaching active material, can be produced.
  • the present invention includes, in one embodiment, a reaction of acyl chloride and sodium hydroxybenzenesulfonate under reaction solvent as shown in Reaction Scheme I, sodium acyloxybenzene represented by Chemical Formula 1 It is to provide a method for preparing a sulfonate.
  • the R of Formula 1 and Formula 1 is a C6 to C22 linear or pulverized saturated alkyl group, and the reaction solvent is water and acetone mixed in a weight ratio of 10:0 to 6.5:3.5.
  • the sodium acyloxybenzenesulfonate of the present invention is represented by Formula 1 above.
  • the sodium acyloxybenzenesulfonate can be used as a bleaching active material.
  • R of Formula 1 is a C6 to C22 linear or pulverized saturated alkyl group.
  • the sodium acyloxybenzenesulfonate represented by Formula 1 specifically includes lauryloxybenzenesulfonate or nonanoyloxybenzenesulfonate.
  • Sodium acyloxybenzenesulfonate represented by Chemical Formula 1 may be prepared by reacting acyl chloride and sodium hydroxybenzenesulfonate under a reaction solvent as in Reaction Scheme I.
  • R of Reaction Scheme I is as defined in Chemical Formula 1.
  • lauryl chloride or nonanoyl chloride was reacted with sodium hydroxybenzenesulfonate in a reaction solvent to prepare sodium lauryloxybenzenesulfonate or sodium nonanoyloxybenzenesulfonate.
  • the acyl chloride includes lauryl chloride or nonanoyl chloride.
  • sodium lauryloxybenzenesulfonate using a mixed solvent of water and an organic solvent acetone, ethyl acetate, toluene, isopar-G or tetrahydrofuran (THF)
  • an organic solvent acetone, ethyl acetate, toluene, isopar-G or tetrahydrofuran (THF)
  • sodium nonanoyloxybenzenesulfonate was prepared, and the yield according to the type and mixing ratio of the organic solvent was analyzed.
  • reaction solvent water or an organic solvent (acetone, ethyl acetate, toluene, isopa-G, and tetrahydrofuran (tetrahydrofuran, THF)) was used as a result of the reaction, acetone, ethyl acetate, toluene, The reaction did not proceed when the reaction was carried out using isopha-G or tetrahydrofuran (THF) alone, but it was confirmed that sodium acyloxybenzenesulfonate can be prepared when water is used as the reaction solvent. Did.
  • a sodium acyloxybenzenesulfonate was prepared using a mixed solution of water and an organic solvent as a reaction solvent, and the yield was compared.
  • ethyl acetate, toluene, isopar-G, or tetrahydrofuran (THF) was used.
  • THF tetrahydrofuran
  • the yield was lower than when only distilled water was used.
  • the solvent mixed with water and acetone 9:1 to 7:3 was used as a reaction solvent, it was confirmed that the yield increased than when only distilled water was used.
  • the reaction solvent is a mixed solvent of water and acetone, water and acetone are mixed in a weight ratio of 10:0 to 6.5:3.5, and specifically water and acetone are mixed in a weight ratio of 9.5:0.5 to 6.5:3.5. It may be, and more specifically, may be a mixture of water and acetone in a weight ratio of 9:1 to 7:3.
  • a catalyst was added to 1 g of sodium hydroxybenzene sulfonate and 40 g of a 50% sodium hydroxide aqueous solution in 1000 g of the reaction solvent, followed by stirring, while 0.95 mol of lauryl chloride was slowly added dropwise thereto. After the dropping was completed, the reaction was performed for 1 hour while maintaining the temperature of the reactor at 28°C and the pH at 7 to 9.
  • the catalyst used was tetra-n-butylammonium bromide (TBAB), a quaternary ammonium salt, based on the total weight of the reaction solvent, sodium hydroxybenzene sulfonate, aqueous sodium hydroxide solution and lauryl chloride.
  • Sodium lauryloxybenzenesulfonate was prepared by adding 0.4% by weight.
  • sodium lauronyloxybenzenesulfonate was prepared by performing the reaction in the same manner, except that lauryl chloride was changed to nonanoyl chloride.
  • the step of reacting the present invention includes adding the reaction solvent to the reactor, adding sodium hydroxybenzenesulfonate, adding a sodium hydroxide aqueous solution, adding a catalyst and stirring, and the acyl chloride It may include the step of adding to proceed the reaction.
  • the acyl chloride may be slowly added dropwise to the reactor, and the reaction may be performed for 0.5 to 4 hours after the dropping is completed.
  • the sodium hydroxybenzene sulfonate 0.5 to 1.5 mol (mol)
  • 20 to 80% sodium hydroxide aqueous solution 50 to 100 g
  • the acyl chloride 0.5 to 1.5 mol (mol)
  • the catalyst may be added in an amount of 0.1 to 1.5% by weight based on the total weight of the reaction solvent, the sodium hydroxybenzene sulfonate, the aqueous sodium hydroxide solution and the acyl chloride added in the step of reacting.
  • the catalyst When the catalyst is added in an amount of less than 0.1% by weight, the yield decreases when reacting, and many side reaction products are produced. When the catalyst is added in an amount of more than 1.5% by weight, the yield does not significantly increase and efficiency is deteriorated.
  • the reacting may further include maintaining the temperature of the reactor at 10 to 40°C.
  • the temperature of the reactor is less than 10°C, the reaction is slow, and the number of side reaction products generated increases, so the yield may drop. If it is more than 40°C, the reaction rate is fast, but acyl chloride is easily decomposed and soap is generated more There is a problem that the yield is lowered or the reaction does not proceed.
  • the reacting may further include maintaining the pH at 7 to 9.
  • the acyl chloride and the sodium hydroxybenzene sulfonate may be reacted by adding in a molar ratio of 0.8 to 1.0: 1.0 to 1.2.
  • the catalyst may be at least one selected from the group consisting of acid compounds, base compounds, metal compounds and ammonium salt compounds.
  • the acid compound is at least one selected from paratoluene sulfonic acid, phosphoric acid, hypophosphorous acid, sodium hypophosphite and sulfuric acid
  • the base compound is an alkali metal hydroxide
  • the metal compound is Fe, Cu, Co, Ti, Sn and Mn It is a compound containing at least one metal selected from the above, and the ammonium salt may be a quaternary ammonium salt.
  • the alkali metal may be at least one selected from lithium, sodium, potassium, rubidium, cesium, francium, and ununennium.
  • the ammonium salt is specifically, cetyltrimethylammonium chloride, (3-chloro-2-hydroxypropyl) trimethylammonium chloride ((3-Chloro-2-hydroxypropyl)trimethylammonium chloride), diaryldimethylammonium chloride ( Diallyldimethylammonium chloride), Didodecyldimethylammonium bromide, Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, (Hydrazinocarbonylmethyl) ) Trimethylammonium Chloride ((Hydrazinocarbonylmethyl)trimethylammonium chloride), Glycidyltrimethylammonium chloride, Hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate (Hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate), Hexadecyltrimethylammonium bro
  • the presence or absence of the reaction is confirmed by using thin layer chromatography (TLC), and when there is no residual sodium hydroxybenzenesulfonate, soap generated as an unreacted material and a side reactant is removed.
  • TLC thin layer chromatography
  • distilled water was added to the reactor, stirred for about 30 minutes, filtered through a filter, and the filtered composite was dried to obtain sodium lauryloxybenzenesulfonate or sodium nonanoyloxybenzenesulfonate.
  • the production method according to the present invention may further include the step of obtaining by filtration.
  • the step obtained by filtration means that the solution after the step of reacting is separated from the solvent and solid sodium acyloxybenzenesulfonate through a filter to obtain sodium acyloxybenzenesulfonate.
  • the obtained sodium acyloxybenzenesulfonate can be dried at 80 to 140°C.
  • lauroyloxybenzenesulfonate was prepared by changing the reaction solvent as shown in Table 1. According to Table 1, tetra-n-butylammonium bromide (TBAB)/ NaOH catalyst was reacted at 28° C. for 2 hours under distilled water as a reaction solvent to yield 4-Lauroyloxybenzenesulfonate sodium with a yield of 73%. It was confirmed that this was prepared (Example 1-1).
  • Example 1-1 Distilled water 28 TBAB / NaOH 2 73 Comparative Example 1-1 Acetone 28 TBAB / NaOH 2 - Comparative Example 1-2 Ethyl acetate 28 TBAB / NaOH 2 - Comparative Example 1-3 toluene 28 TBAB / NaOH 2 - Comparative Example 1-4 Isopha-G 28 TBAB / NaOH 2 - Comparative Example 1-5 THF 28 TBAB / NaOH 2 - Comparative Example 1-6 Ethyl acetate 28 TBAB 2 - Comparative Example 1-7 toluene 28 TBAB 2 - Comparative Example 1-8 Isopha-G 28 TBAB 2 - Comparative Example 1-9 THF 28 TBAB 2 -
  • Table 2 shows the yield of lauroyloxybenzenesulfonate according to the reaction temperature.
  • the organic solvents acetone, ethyl acetate, toluene, isopar-G, THF
  • the yield was 45%, and it was confirmed that the yield decreased to 20% as the reaction temperature increased to 100°C, and 150°C.
  • the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and organic solvent was analyzed.
  • organic solvent acetone, ethyl acetate, toluene, isopa-G, and tetrahydrofuran (THF) were used.
  • Table 3 shows the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and acetone.
  • Table 4 shows the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and ethyl acetate.
  • Example 1-1 when only distilled water was used, the yield was 73%, and in the solvent mixed with ethyl acetate at 10 to 40%, the yield was 54 to 63%, which was lower than when only distilled water was used.
  • Table 5 shows the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and toluene.
  • Example 1-1 when only distilled water was used, the yield was 73%, and in the solvent mixed with 10 to 40% of toluene, the yield was 50 to 65%, which was lower than when only distilled water was used.
  • Table 6 shows the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and isopar G.
  • Table 7 shows the yield of lauroyloxybenzenesulfonate according to the mixing ratio of distilled water and THF.
  • Example 1-1 when only distilled water was used, a yield of 73% was exhibited, and in a solvent mixed with THF of 10 to 40%, the yield was 53 to 62%, which was lower than when only distilled water was used.
  • the reaction did not proceed when the reaction was performed without using a catalyst under the same conditions as Comparative Example 1-34 in a mixed solution of distilled water 80% and THF 20%.
  • nonanoyloxybenzenesulfonate was prepared by changing the reaction solvent as shown in Table 8. According to Table 8, tetra-n-butylammonium bromide (TBAB)/distilled water is used as a reaction solvent and reacted at 28° C. under NaOH catalyst conditions for 2 hours to obtain 4-nonano with a yield of 65%. It was confirmed that sodium oxybenzenesulfonate was prepared (Example 2-1).
  • Example 2-1 Distilled water 28 TBAB / NaOH 2 65 Comparative Example 2-1 Acetone 28 TBAB / NaOH 2 - Comparative Example 2-2 Ethyl acetate 28 TBAB / NaOH 2 - Comparative Example 2-3 toluene 28 TBAB / NaOH 2 - Comparative Example 2-4 Isopha-G 28 TBAB / NaOH 2 - Comparative Example 2-5 THF 28 TBAB / NaOH 2 - Comparative Example 2-6 Ethyl acetate 28 TBAB 2 - Comparative Example 2-7 toluene 28 TBAB 2 - Comparative Example 2-8 Isopha-G 28 TBAB 2 - Comparative Example 2-9 THF 28 TBAB 2 -
  • Example 2-1 the reaction was carried out by using a solvent in which the reaction did not proceed, and the temperature conditions and the catalyst conditions were changed as shown in Table 9. In addition, the reaction was performed by varying the temperature conditions in distilled water and the yield was confirmed.
  • Table 9 shows the yield of nonanoyloxybenzenesulfonate according to the reaction temperature.
  • an organic solvent acetone, ethyl acetate, toluene, isopar-G, THF
  • Comparative Examples 2-15 to Comparative Examples 2-17 which are distilled water
  • the yield was 30%, and as the reaction temperature increased to 100°C, the yield was reduced to 10%. Also, it was confirmed that the reaction did not proceed at 150°C.
  • the yield was analyzed in a mixed solvent of distilled water and an organic solvent.
  • organic solvent acetone, ethyl acetate, toluene, isopa-G, and tetrahydrofuran (THF) were used.
  • Table 10 is a result of comparing the yield of the nonanoyloxybenzenesulfonate yield according to the acetone mixing ratio.
  • Example 2-1 When only distilled water was used in Example 2-1, the yield was 65%, but in a mixed solution of 90% distilled water and 10% acetone (Example 2-4), the yield increased to 73%, 80% distilled water, acetone
  • Example 2-2 When using a 20% mixed solution (Example 2-2), it was confirmed that the yield was highest when using a solution containing 20% acetone as 77% as a reaction solvent.
  • the yield was 52%, confirming that the yield was reduced compared to using only distilled water (Comparative Examples 2-18-1).
  • Example 2-2 Distilled water (8) / Acetone (2) 28 TBAB / NaOH 2 77
  • Example 2-3 Distilled water (7) / Acetone (3) 28 TBAB / NaOH 2 75 Comparative Example 2-18-1
  • Example 2-4 Distilled water (9) / Acetone (1) 28 TBAB / NaOH 2 73 Comparative Example 2-18-2 Distilled water (8) / Acetone (2) 28 - 2 -
  • Table 11 shows the yield of nonanoyloxybenzenesulfonate according to the mixing ratio of distilled water and ethyl acetate.
  • Example 2-1 when only distilled water was used, a yield of 65% was exhibited, and in a solvent mixed with ethyl acetate at 10 to 40%, the yield was 45 to 61%, which was lower than when only distilled water was used.
  • the reaction did not proceed when the reaction was performed without using a catalyst under the same conditions as Comparative Example 2-19 in a mixed solution of distilled water 80% and ethyl acetate 20%.
  • Table 12 shows the yield of nonanoyloxybenzenesulfonate according to the mixing ratio of distilled water and toluene.
  • the yield was 65%, and in the solvent mixed with toluene at 10 to 40%, the yield was 50 to 60%, which was lower than when only distilled water was used.
  • Table 13 shows the yield of nonanoyloxybenzenesulfonate according to the mixing ratio of distilled water and isopar G.
  • Example 2-1 when only distilled water was used, a yield of 65% was exhibited, and in the solvent mixed with isopar G at 10 to 40%, the yield was 50 to 63%, which was lower than when only distilled water was used.
  • Example 2-29 when the reaction was performed without using a catalyst under the same conditions as in Example 2-29 of a mixed solution of 80% distilled water and 20% of isopar G, it was confirmed that the reaction did not proceed.
  • Table 14 shows the yield of nonanoyloxybenzenesulfonate according to the mixing ratio of distilled water and THF.
  • Example 2-1 when only distilled water was used, a yield of 65% was exhibited, and in a solvent in which THF was mixed at 10 to 40%, the yield was 49 to 63%, which was lower than when only distilled water was used.
  • Example 2-34 when the reaction was performed without using a catalyst under the same conditions as in Example 2-34, a mixed solution of distilled water 80% and THF 20%, it was confirmed that the reaction did not proceed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de synthèse d'acyloxybenzène sulfonate, qui est un activateur de blanchiment, à partir d'une solution aqueuse à basse température. Le coût de l'unité de production peut être réduit en raison de la production à partir d'une solution aqueuse à basse température, et un acyloxybenzènesulfonate, qui est un activateur de blanchiment, peut être produit de manière respectueuse de l'environnement.
PCT/KR2019/005829 2019-02-01 2019-05-15 Procédé de préparation d'un composé acyloxybenzène sulfonate WO2020159007A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020190013476A KR102171424B1 (ko) 2019-02-01 2019-02-01 아실옥시벤젠술포네이트 화합물의 제조방법
KR10-2019-0013476 2019-02-01

Publications (1)

Publication Number Publication Date
WO2020159007A1 true WO2020159007A1 (fr) 2020-08-06

Family

ID=71841877

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/005829 WO2020159007A1 (fr) 2019-02-01 2019-05-15 Procédé de préparation d'un composé acyloxybenzène sulfonate

Country Status (2)

Country Link
KR (1) KR102171424B1 (fr)
WO (1) WO2020159007A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0853405A (ja) * 1994-08-11 1996-02-27 Kao Corp アシルオキシベンゼンスルホン酸塩の製造方法
US5891838A (en) * 1997-11-20 1999-04-06 The Procter & Gamble Company Detergent composition containing optimally sized bleach activator particles
EP1156035A2 (fr) * 1997-12-11 2001-11-21 The Associated Octel Company Limited Préparation d'esters
CN101293859A (zh) * 2008-05-28 2008-10-29 浙江理工大学 H2o2低温漂白助剂的环保型制备方法
CN102875425A (zh) * 2012-08-29 2013-01-16 昆山铁牛衬衫厂 一种低温氧化助剂的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5830781B2 (ja) 2012-01-25 2015-12-09 ライオン株式会社 衣料用洗剤組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0853405A (ja) * 1994-08-11 1996-02-27 Kao Corp アシルオキシベンゼンスルホン酸塩の製造方法
US5891838A (en) * 1997-11-20 1999-04-06 The Procter & Gamble Company Detergent composition containing optimally sized bleach activator particles
EP1156035A2 (fr) * 1997-12-11 2001-11-21 The Associated Octel Company Limited Préparation d'esters
CN101293859A (zh) * 2008-05-28 2008-10-29 浙江理工大学 H2o2低温漂白助剂的环保型制备方法
CN102875425A (zh) * 2012-08-29 2013-01-16 昆山铁牛衬衫厂 一种低温氧化助剂的制备方法

Also Published As

Publication number Publication date
KR102171424B1 (ko) 2020-10-29
KR20200095741A (ko) 2020-08-11

Similar Documents

Publication Publication Date Title
WO2020145627A1 (fr) Procédé de préparation de glufosinate
WO2020145514A1 (fr) Procédé de production de l-glufosinate
WO2014200232A1 (fr) Stabilisant de dispersion pour exfoliation du graphène, composite graphène-sel de métal alcalin le comprenant, et procédé de préparation de graphène l'utilisant
KR20080026639A (ko) Ｎ－치환 이소치아졸리논 유도체의 제조 방법
WO2010027150A2 (fr) Nouvelle préparation d’hydroxychloroquine
WO2017023123A1 (fr) Nouveau procédé de préparation d'un dérivé de chromanone
EP3204364A2 (fr) Procédé de préparation de gadobutrol
WO2011004980A2 (fr) Procédé de préparation de dérivés tricycliques
WO2022244969A1 (fr) Procédé de préparation d'un composé à base de lactone de méthylène
WO2020159007A1 (fr) Procédé de préparation d'un composé acyloxybenzène sulfonate
WO2010036048A2 (fr) Procédé de préparation de sels montélukast sodiques
WO2019199013A1 (fr) Méthode de préparation de sel de bis(fluorosulfonyl)imide de lithium
WO2019022426A1 (fr) Procédé de préparation de maléimide n-substitué à l'aide d'un photocatalyseur
WO2016076573A2 (fr) Procédé de préparation de blonanserin et son intermédiaire
WO2015199367A1 (fr) Composé de phénol styréné et son procédé de préparation
WO2015053576A1 (fr) Procédé pour la préparation de 3-alkylthio-2-bromopyridine
WO2021107514A2 (fr) Procédé de préparation de lifitegrast
WO2011105649A1 (fr) Nouveau procédé de fabrication de la pitavastatine hémicalcium utilisant un nouvel intermédiaire
WO2010074387A1 (fr) Dérivés d'aza-bicyclo[2.2.1]heptène, leurs méthodes de synthèse, et méthodes de synthèse d'intermédiaires de l'oseltamivir les utilisant
WO2022059948A1 (fr) Procédé de production en masse de taurodésoxycholate de sodium
WO2017209458A1 (fr) Nouvelle méthode de préparation de l'acide 4'-hydroxy-4-biphénylcarboxylique
WO2016153094A1 (fr) Nouveau procédé de préparation d'un dérivé de 3-alcoxy-thiophène
WO2019124674A1 (fr) Procédé de purification de maléimide n-substitué
WO2024058311A1 (fr) Procédé de production d'ectoïne
WO2018128387A1 (fr) Procédé de production d'un composé d'uracile 3-aryle

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19914031

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19914031

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 19914031

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC, EPO FORM 1205A DATED 02.05.2022

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC, EPO FORM 1205A DATED 02.05.2022

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC, EPO FORM 1205A DATED 02.05.2022

122 Ep: pct application non-entry in european phase

Ref document number: 19914031

Country of ref document: EP

Kind code of ref document: A1