WO2019028600A1 - Procédé de production de dérivés de phénol carboxylés - Google Patents

Procédé de production de dérivés de phénol carboxylés Download PDF

Info

Publication number
WO2019028600A1
WO2019028600A1 PCT/CN2017/096254 CN2017096254W WO2019028600A1 WO 2019028600 A1 WO2019028600 A1 WO 2019028600A1 CN 2017096254 W CN2017096254 W CN 2017096254W WO 2019028600 A1 WO2019028600 A1 WO 2019028600A1
Authority
WO
WIPO (PCT)
Prior art keywords
derivative
phenol derivative
mixture
process according
anyone
Prior art date
Application number
PCT/CN2017/096254
Other languages
English (en)
Inventor
Howard Hao
Ding Wang
Chunli CAO
Original Assignee
Rhodia Operations
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 Rhodia Operations filed Critical Rhodia Operations
Priority to PCT/CN2017/096254 priority Critical patent/WO2019028600A1/fr
Publication of WO2019028600A1 publication Critical patent/WO2019028600A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis

Definitions

  • the present invention concerns a new process for the production of carboxylated phenol derivatives comprising at least a step of carboxylation of a mixture of (i) phenol derivative and (ii) phenolate derivative, wherein the molar ratio of (i) / (ii) is comprised between 0.8 and 1.2, in presence of CO 2 .
  • the invention also concerns a process for the production of said mixture of (i) phenol derivative and (ii) phenolate derivative.
  • Carboxylated phenol derivatives also called phenolic acids or phenolcarboxylic acids, such as vanillic acid (4-hydroxy-3-methoxybenzoic acid)
  • phenolic acids or phenolcarboxylic acids such as vanillic acid (4-hydroxy-3-methoxybenzoic acid)
  • vanillic acid (4-hydroxy-3-methoxybenzoic acid)
  • WO9626176 discloses a process for production of vanillic acid comprising:
  • NMP N-methyl-2-pyrrolidone
  • the present invention relates now to a process for the production of carboxylated phenol derivatives, such as vanillic acid, with a high conversion and selectivity from a phenol derivative, such as guaiacol, in comparison with processes of the prior art; without the involvement of solvents having a negative effects on humans and the environment, such as toluene for instance. Moreover, it appears that the addition of a phenol derivative during the process after an initial heat treatment permits to increase production of carboxylated phenol derivatives, notably its conversion and selectivity.
  • the present invention concerns then a process for the production of a carboxylatedphenol derivative, comprising at least the following steps:
  • step b) adding an aprotic organic solvent to the mixture treated in step a) and optionally aphenol derivative;
  • step d) proceeding with carboxylation of the mixture obtained in step c) in presence of CO 2 ; in order to obtain a salt of carboxylated phenol derivative;
  • the invention also relates to a process for the production of a mixture of (i) phenol derivative and (ii) phenolate derivative, comprising at least the following steps:
  • step b) adding an aprotic organic solvent to the mixture treated in step a) and optionally a phenol derivative;
  • the invention also concerns a process for the production of a salt of carboxylated phenol derivative comprising at least a step of carboxylation of a mixture of (i) phenol derivative and (ii) phenolate derivative, wherein the molar ratio of (i) / (ii) is comprised between 0.8 and 1.2, in presence of CO 2 .
  • the present invention also concerns a mixture of (i) phenol derivative and (ii) phenolate derivative, wherein the molar ratio of (i) / (ii) is comprised between 0.8 and 1.2, notably comprising an aprotic organic solvent.
  • hydrocarbon group refers to a group consisting of carbon atoms and hydrogen atoms, which group may be saturated or unsaturated, linear, branched or cyclic, aliphatic or aromatic. Hydrocarbon groups of the present invention may be alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkylaryl groups, aryalkyl groups, heterocyclic groups, and/or alkylheterocyclic groups.
  • alkyl groups include saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclic alkyl groups (or "cycloalkyl” or “alicyclic” or “carbocyclic” groups) , such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, branched-chain alkyl groups, such as isopropyl, tert-butyl, sec-butyl, and isobutyl, and alkyl-substituted alkyl groups, such as alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups.
  • aliphatic group includes organic moieties characterized by straight or branched-chains, typically having between 1 and 22 carbon atoms. In complex structures, the chains may be branched, bridged, or cross-linked. Aliphatic groups include alkyl groups, alkenyl groups, and alkynyl groups.
  • alkenyl or “alkenyl group” refers to an aliphatic hydrocarbon radical which can be straight or branched, containing at least one carbon-carbon double bond.
  • alkenyl groups include, but are not limited to, ethenyl, propenyl, n-butenyl, i-butenyl, 3-methylbut-2-enyl, n-pentenyl, heptenyl, octenyl, decenyl, and the like.
  • alkynyl refers to straight or branched chain hydrocarbon groups having at least one triple carbon to carbon bond, such as ethynyl.
  • aryl group includes unsaturated and aromatic cyclic hydrocarbons as well as unsaturated and aromatic heterocycles containing one or more rings.
  • Aryl groups may also be fused or bridged with alicyclic or heterocyclic rings that are not aromatic so as to form a polycycle, such as tetralin.
  • An "arylene” group is a divalent analog of an aryl group.
  • heterocyclic group includes closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur, or oxygen. Heterocyclic groups may be saturated or unsaturated. Additionally, heterocyclic groups, such as pyrrolyl, pyridyl, isoquinolyl, quinolyl, purinyl, and furyl, may have aromatic character, in which case they may be referred to as “heteroaryl” or “heteroaromatic” groups.
  • Aryl and heterocyclic including heteroaryl groups may also be substituted at one or more constituent atoms.
  • heteroaromatic and heteroalicyclic groups may have 1 to 3 separate or fused rings with 3 to about 8 members per ring and one or more N, O, or S heteroatoms.
  • heteroatom includes atoms of any element other than carbon or hydrogen, preferred examples of which include nitrogen, oxygen, sulfur, and phosphorus. Heterocyclic groups may be saturated or unsaturated or aromatic.
  • aralkyl or “arylalkyl” means an alkyl group substituted with one or more aryl groups, such as, for example, phenylmethyl, phenylethyl, triphenylmethyl.
  • alkylaryl means an alkyl moiety bound to an aryl moiety.
  • phenol derivatives may be used according to the present invention, notably those ones that can be carboxylated in the condition of the reaction.
  • the phenol derivative is an ether phenol of formula (I)
  • -n is a number comprised between 0 and 3, preferably 0, 1, 2 or 3,
  • -R' represents hydrogen or a linear or branched alkyl group comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl ouphenyl,
  • -R is chosen in the group consisting of:
  • -linear or branched alkyl group comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl or phenyl,
  • -linear or branched alkoxy group comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy,
  • -halogen atom such as F, Cl, Br, and
  • phenol derivatives of the invention will be carboxylated in para position of the hydroxyle function and will then carry no groupment or function in para position of the hydroxyle function.
  • Phenol derivatives are preferably chosen in the group consisting of: guaiacol, catechol, 3-methoxyphenol, guetol, 3-ethoxyphenol, 2-isopropoxyphenol, 3-isopropoxyphenol, 2-methoxy-6-methylphenol, 2-methoxy-6-tertbutylphenol, 3-chloro-5-methoxyphenol, and 2-methoxy-1-naphthol.
  • alkoxide is the conjugate base of an alcohol and therefore consists of an organic group bonded to a negatively charged oxygen atom. They can be written as R-O - , where R is the organic substituent. Phenoxides are close relatives of the alkoxides, in which the alkyl group is replaced by a derivative of benzene, and are also called phenate. A phenolate derivative is a salt of phenoxide derivative, such as sodium phenolate for instance.
  • Phenolate derivative of the invention preferably relates to phenolate corresponding compounds of phenol derivatives of formula (I) .
  • Phenolate derivatives are preferably salts of alkali metals, such as sodium or potassium.
  • Phenolate derivatives of the present invention are preferably chosen in the group consisting of: potassium 2-hydroxyphenolate, potassium 2-methoxyphenolate, potassium 3-methoxyphenolate, potassium 2-ethoxyphenolate, potassium 3-ethoxyphenolate, potassium 2-isopropoxyphenolate, potassium 3-isopropoxyphenolate, potassium 2-methoxy-6-methylphenolate, potassium 2- (tert-butyl) -6-methoxyphenolate, potassium 3-chloro-5-methoxyphenolate, sodium 2-hydroxyphenolate, sodium 2-methoxyphenolate, sodium 3-methoxyphenolate, sodium 2-ethoxyphenolate, sodium 3-ethoxyphenolate, sodium 2-isopropoxyphenolate, sodium 3-isopropoxyphenolate, sodium 2-methoxy-6-methylphenolate, sodium 2- (tert-butyl) -6-methoxyphenolate, and sodium 3-chloro-5-methoxyphenolate.
  • a carboxylated phenol derivative is a phenol derivative compound comprising at least one carboxylic acid function, for instance one carboxylic acid function or two carboxylic functions.
  • carboxylic acid function for instance one carboxylic acid function or two carboxylic functions.
  • phenolic acids or phenolcarboxylic acids that are containing a phenolic ring and an organic carboxylic acid function.
  • Carboxylated phenol derivatives of the invention are preferably chosen in the group consisting of: para vanillic acid (ie. vanillic acid) , ortho vanillic acid, meta vanillic acid, 3, 4-dihydroxylbenzoic acid, 2-methoxy-4-hydroxybenzoic acid, 3-ethoxy-4-hydroxybenzonic acid, 2-ethoxy-4-hydroxybenzoic acid, 2-isopropoxy-4-hydroxybenzoic acid, and 3-isopropoxy-4-hydroxybenzoic acid.
  • para vanillic acid ie. vanillic acid
  • ortho vanillic acid ortho vanillic acid
  • meta vanillic acid 3, 4-dihydroxylbenzoic acid, 2-methoxy-4-hydroxybenzoic acid, 3-ethoxy-4-hydroxybenzonic acid, 2-ethoxy-4-hydroxybenzoic acid, 2-isopropoxy-4-hydroxybenzoic acid, and 3-isopropoxy-4-hydroxybenzoic acid.
  • Bases used in the present invention may be an organic base or an inorganic base.
  • Inorganic bases are preferably chosen in the group consisting of: alkali metal carbonate, alkali metal bicarbonate, alkaline-earth metal hydroxide or alkali metal hydroxide, such as sodium hydroxide and potassium hydroxide.
  • Organic bases are preferably chosen in the group consisting of: ammonia, alkylamine, trialkylamine, ammonium hydroxide, and alkylammonium hydroxide, aniline, aminophenol, and alkali metal tert-butoxide, such as potassium tert-butoxide or sodium tert-butoxide.
  • Heat treatment is preferably carried out at a temperature comprised between 50 and 200°C, more preferably between 100 and 160°C. Such a heat treatment may be preferably carried out at atmospheric pressure.
  • the water content in the medium may be partially or totally removed, notably by distillation.
  • Heat treatment of step a) allows production of phenolate derivative from phenol derivative, preferably with a conversion comprised from 80%to 100%of phenol derivative reactant.
  • the molar ratio between the phenol derivative and the base is comprised between 0.4 and 2.2, more preferably between 0.8 and 2.1, more preferably between 0.95 and 2.05, in the mixture.
  • the molar ratio between the phenol derivative and the base may also be comprised between 0.8 and 1.2.
  • the mass concentration of base preferably in water, may be for instance comprised between 30 and 50%by weight, more preferably comprised between 35 and 45%by weight.
  • Mixture as obtained at the end of step a) may comprise a phenolate derivative and a phenol derivative, depending on the amount of phenol derivative and base added at the start of the reaction.
  • a phenolate derivative may be below 0.9
  • fresh phenol derivative may be charged into the mixture in order to ensure the molar ratio between phenol derivative and phenolate derivative is between 0.9 and 1.1, more preferably between 0.95 to 1.05.
  • Phenol derivatives as optionally used in step b) may be similar or different with respect to phenol derivative as used in step a) .
  • phenol derivative used in step a) and b) is the same chemical compound.
  • the aprotic organic solvent is preferably chosen in the group consisting of: tetrahydrofuran, ethyl acetate, acetone, 2-butanone, dimethylformamide, acetonitrile, dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP) , hexane, perfluorohexane, pyridine, N, N-dimethylacetamide, N, N-diethylacetamide, and hexamethylphosphoric triamide.
  • NMP N-methyl-2-pyrrolidone
  • the aprotic organic solvent may dissolve both phenol derivatives and phenolate derivatives.
  • NMP is preferably used for its toxicological and ecological properties, notably as a low toxicity alternative solvent towards toluene.
  • Addition of a phenol derivative in an aprotic organic solvent to the mixture treated in step a) may be made at room temperature with usual appropriated device.
  • Weight ratio of aprotic organic solvent added to the mixture with respect to phenolate derivative present in the mixture may be comprised between 1 and 10, preferably 2 and 6, more preferably 3 and 5.
  • molar amount of phenol derivative added in step b) is between 0.8 and 1.2 equivalent with respect to molar amount of phenol derivative used in step a) , more preferably between 0.9 and 1.1 equivalent, particularly between 0.95 and 1.05 equivalent, specifically about 1 equivalent.
  • Removing of water and aprotic organic solvent from the reaction medium in step c) may be carried out by various means and device, such as distillation, for instance classical distillation or vacuum distillation. It has to be noticed that removal of aprotic organic solvent may be partial and that the obtained mixture may also comprise then a part of the aprotic organic solvent.
  • the mixture is heated at a temperature comprised between 90 and 110°C under a pressure comprised between 10 and 180 mbar with a further distillation.
  • the vacuum varies according to the boiling point of the solvent.
  • Carboxylation step d) of phenolate derivatives is well known in the prior art.
  • the reaction mixture is usually charged into a reactor in which CO 2 is introduced at a pressure comprised between 5 and 50 barg, preferably 18 and 22 barg and usually heated at a temperature comprised between 90 and 150°C, preferably 110 and 125°C, for a duration usually comprised between 1 and 10 hours, preferably 1.5 and 3 hours.
  • Cool down of the reaction temperature may occur between 80 and 90 °C.
  • HPLC High Performance Liquid Chromatography
  • Carboxylation of the mixture obtain in step c) may be obtained by using CO 2 or a compound able to generate CO 2 during the reaction.
  • CO 2 may be used pure or diluted, preferably pure.
  • An isolation of the salt of carboxylated phenol derivative may be made at the end of step d) .
  • Such an isolation may be carried out by several methods usually known in the technical field, such as for instance centrifugation or filtration, notably vacuum filtration or pressure filtration, and distillation.
  • the salt of carboxylated phenol derivative may be isolated by filtration followed by a vacuum distillation, at a temperature comprised between 100 and 200°C and at apressure comprised between 50 and 300 mbar.
  • step b) It is notably possible to recycle the phenol derivative and the aprotic organic solvent to step b) .
  • the phenol derivative and the aprotic organic solvent present at the end of step d) are preferably recycled to step b) .
  • the filtrate comprising notably NMP and guaiacol is preferably recycled to step b) .
  • Recycle ratio of phenol derivative may be comprised from 70 to 99%, preferably from 80 to 99%, more preferably from 90 to 99%.
  • Recycle ratio of aprotic organic solvent may be comprised from 50 to 99%, preferably from 80 to 99%.
  • Step e) refers to conversion of the salt of carboxylated phenol derivative to the corresponding carboxylated phenol derivative, notably its carboxylic acid form. It may be notably made by adding an acid to the carboxylated phenol derivative. It is notably possible to first dissolve in water a solid obtained by filtration at the end of step d) and adjust pH from 1 to 5, notably 2 to 3, for instance by adding an acid, such as for instance sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid, with a subsequent filtration to isolate the carboxylic phenol derivative. Isolated carboxylated phenol derivative may be further washed with water and dried at a temperature comprised between 60 and 120°C.
  • carboxylated phenol derivatives may be obtained in accordance with the process of the present invention such as ortho, meta and/or para carboxylated phenol derivatives with respect to the position of the hydroxyl function. It is also possible that carboxylated phenol derivatives comprise one or two carboxylic acid functions.
  • carboxylated phenol derivatives may comprises 2-hydroxy-3-methoxybenzoic acid (ortho-vanillic acid) , 4-hydroxy-3-methoxybenzoic acid (vanillic acid) , 4-hydroxy-5- methoxyisophthalic acid (di-vanillic acid) and dimers of vanillic acid like for instance 5, 5'-dihydroxy-4, 4'-dimethoxy- [1, 1'-biphenyl] -2, 2'-dicarboxylic acid.
  • Para/Ortho selectivity of carboxylated phenol derivative may be comprised from 70/30 to 99/1, for instance from 70/30 to 90/10.
  • step d) It is notably possible to recycle carboxylated phenol derivatives after filtration expressed at the end of step d) . It is for instance possible to recycle para carboxylated phenol derivatives and/or ortho carboxylated phenol derivatives, notably in mixture, after filtration expressed at the end of step d) .
  • Specific carboxylated phenol derivatives of interest such as para carboxylated phenol derivatives, may be further isolated at the end of step e) .
  • para carboxylated phenol derivatives it’s notably possible to proceed to a recrystallization or distillation of para/ortho mixture.
  • recrystallization can be carried out by adding water or alcohol to the para/ortho mixture and proceed with a subsequent heat treatment and slow cooling to recrystallize the para carboxylated phenol derivative.
  • Isolation of para carboxylated phenol derivatives by distillation may be carried out with a conventional distillation column.
  • Carboxylated phenol derivatives of the invention may be used in various applications such as for instance as food additive, use as a building block for production of ingredients in pharma, agro and flagrance, use as a building block for production of epoxyresins, use as a food preservative or use as a biocide booster in industrial applications.
  • Dihydroxybenzoic acid derivatives such as vanillic acid
  • Vanillic acid may be used as a flavoring agent or intermediates in the production of vanillin.
  • Vanillic acid has been associated with a variety of pharmacologic activities such as inhibiting snake venom activity, carcinogenesis, apoptosis, inflammation and it has become most popular for its pleasant creamy odour that is widely used in fragrances and licensed as a food additive.
  • Aqueous effluents made during the process of the present invention can be further processed according to state of the art techniques to achieve compliant effluents with relevant regulations.
  • NMP N-methyl-pyrrolidone
  • reaction mixture (674g) was charged into the pressure reactor; 20 barg CO 2 was introduced and heated to 118°C, kept CO 2 pressure at 20 barg, and stirred the mixture for 2h at 118°C.
  • the reaction mixture has been filtered at 85°C. 250g of filtration cake was obtained and 433g of filtrate was obtained. The cake was washed with 170g of NMP and filtrated. 223g of filtration cake and 172g of filtrate were obtained. Both filtrates comprising notably NMP and guaiacol have been recycled to the 1L reaction flask for a next batch.
  • the 433 g filtrate which mainly contains NMP, guaiacol and unreacted GAK (potassium guaiacolate) , was mixed with 23.7 g 98%H 2 SO 4 , in order to convert unreacted GAK to guaiacol.
  • NMP and guaiacol was distillated out at 140°C under vacuum (60-250 mbar) .
  • the collected NMP and guaiacol which was totally 383g, including 106g of guaiacol and 277.1g of NMP determined by HPLC, would then be used in next batch by mixing with fresh guaiacol and NMP.
  • the 172 g filtrate, which mainly contains NMP and guaiacol was distillated at 140°C under vacuum (60-250 mbar) .
  • the cake was dissolved into 508g of water and pH of the solution has been adjusted to 2-3 with a 30%sulfuric acid solution for 30 mins and then a filtration was carried out. 258g of filtration cake was obtained and 579g of filtrate was obtained. This filtrate has been then treated as wastewater.
  • the cake is then washed with 508g of water and a filtration is then carried out. 170g of filtration cake was obtained, while 592g filtrate was obtained. This filtrate has been then treated as wastewater.
  • the cake was then dried at 90°C for 4 h in order to obtain 77.5g of white solid, which is 4-hydroxy-3-methoxybenzoic acid, i.e., para-vanillin acid.
  • HPLC High Performance Liquid Chromatograph
  • this normalized weight% was converted to normalized molar%, in order to calculate the conversion of guaiacol.
  • the molar%of guaiacol, vanillic acid, ortho-vanillic acid and diacid derivative were 68.68%, 26.73%, 4.14%, and 0.45%, respectively.
  • HPLC HPLC was used to check the conversion and selectivity as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un nouveau procédé de production de dérivés de phénol carboxylés comprenant au moins une étape de carboxylation d'un mélange (i) de dérivé de phénol et (ii) de phénolate, le rapport molaire de (i)/(ii) étant compris entre 0,8 et 1,2 en présence de CO2. L'invention concerne également un procédé de production dudit mélange de (i) dérivé de phénol et de (ii) dérivé de phénolate.
PCT/CN2017/096254 2017-08-07 2017-08-07 Procédé de production de dérivés de phénol carboxylés WO2019028600A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/096254 WO2019028600A1 (fr) 2017-08-07 2017-08-07 Procédé de production de dérivés de phénol carboxylés

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/096254 WO2019028600A1 (fr) 2017-08-07 2017-08-07 Procédé de production de dérivés de phénol carboxylés

Publications (1)

Publication Number Publication Date
WO2019028600A1 true WO2019028600A1 (fr) 2019-02-14

Family

ID=65273226

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/096254 WO2019028600A1 (fr) 2017-08-07 2017-08-07 Procédé de production de dérivés de phénol carboxylés

Country Status (1)

Country Link
WO (1) WO2019028600A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116082139A (zh) * 2022-12-27 2023-05-09 甘肃省化工研究院有限责任公司 一种制备水杨酸类紫外线吸收剂的方法及装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996026176A1 (fr) * 1995-02-20 1996-08-29 Rhone-Poulenc Chimie Procede de carboxylation d'un ether de phenol
US20060052632A1 (en) * 2002-10-01 2006-03-09 Ryuzo Ueno Process for production of hydroxygbenzoic acids
CN103012123A (zh) * 2012-12-20 2013-04-03 浙江大学 3,6-二氯-2-羟基苯甲酸的合成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996026176A1 (fr) * 1995-02-20 1996-08-29 Rhone-Poulenc Chimie Procede de carboxylation d'un ether de phenol
US20060052632A1 (en) * 2002-10-01 2006-03-09 Ryuzo Ueno Process for production of hydroxygbenzoic acids
CN103012123A (zh) * 2012-12-20 2013-04-03 浙江大学 3,6-二氯-2-羟基苯甲酸的合成方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116082139A (zh) * 2022-12-27 2023-05-09 甘肃省化工研究院有限责任公司 一种制备水杨酸类紫外线吸收剂的方法及装置

Similar Documents

Publication Publication Date Title
US3247262A (en) Process for making polyphenols
JP4588407B2 (ja) 環式ジスルホン酸エステルの製造方法
JP6221771B2 (ja) エーテル化合物の製造方法、および重合性化合物の製造方法
FR2946339A1 (fr) Procede d'hydroxydation de composes amples halogenes
WO2019028600A1 (fr) Procédé de production de dérivés de phénol carboxylés
JPS6339578B2 (fr)
JP2006160663A (ja) １，１’−ビス（２−ヒドロキシナフチル）類の製造方法
CN110143857B (zh) 一种半棉酚、棉酚及它们的类似物的合成方法
EP1868978B1 (fr) Nouveau composé, le 1-bromo-4-(4'-bromophénoxy)-2-pentadécylbenzène, et procédé de synthèse dudit composé
WO2012042532A4 (fr) Procédés de préparation de bicalutamide
JPWO2006006414A1 (ja) ２−アダマンタノンの製造方法
JP5076313B2 (ja) 精製２，２−ジメチル−３−ホルミルシクロプロパンカルボン酸エステルの製造方法およびその中間体
KR20160087908A (ko) 신규한 비스(히드록시페닐)벤즈옥사졸 화합물
US6689921B2 (en) Preparation of biphenols by oxidative coupling of alkylphenols using a recyclable copper catalyst
CN109678687B (zh) 一种邻羟基苯乙酮类化合物的高效制备方法
JP7476448B2 (ja) ４－ヒドロキシ－２－メチル安息香酸の製造方法
CN108623529B (zh) 一种噁嗪草酮的制备方法
JP3040264B2 (ja) カーボネート化合物の製造方法
JP2008266182A (ja) １，２，３，４−ベンゼンテトラカルボン酸の製造方法
CN107531617A (zh) O‑[1‑(2‑羟基丙基)]肟化合物的制造方法
JPH0437814B2 (fr)
JP2023121456A (ja) ビスフェノール化合物の製造方法
CN114591152A (zh) 一种酚基烯烷基醚的合成方法
JP4930668B2 (ja) ジヒドロキシジフェニルスルホン異性体混合物の製造方法
RU2287516C1 (ru) Способ получения мета-феноксифенола

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: 17921038

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: 17921038

Country of ref document: EP

Kind code of ref document: A1