WO2017209458A1 - Nouvelle méthode de préparation de l'acide 4'-hydroxy-4-biphénylcarboxylique - Google Patents

Nouvelle méthode de préparation de l'acide 4'-hydroxy-4-biphénylcarboxylique Download PDF

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Publication number
WO2017209458A1
WO2017209458A1 PCT/KR2017/005524 KR2017005524W WO2017209458A1 WO 2017209458 A1 WO2017209458 A1 WO 2017209458A1 KR 2017005524 W KR2017005524 W KR 2017005524W WO 2017209458 A1 WO2017209458 A1 WO 2017209458A1
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formula
hydroxy
compound
biphenylcarboxylic acid
reaction
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PCT/KR2017/005524
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English (en)
Korean (ko)
Inventor
이석원
오재민
정현윤
이원지
조양래
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(주)위즈켐
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/50—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
    • C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids

Definitions

  • the present invention relates to a novel process for preparing 4'-hydroxy-4-biphenylcarboxylic acid, and more particularly to 4'-hydroxy-4- ratio useful as a liquid crystal, a liquid crystal polymer, and a high heat dissipation high heat resistant resin material. It relates to an industrially useful process for preparing phenylcarboxylic acid from 4-phenylphenol.
  • Suzuki coupling reactions require the use of expensive boronic acid compounds or expensive palladium catalysts, and thus are not industrially feasible.
  • the hydroxy group of phenylphenol is protected with acetyl group, then acetylated, deacetylated, and then protected with benzyl, and then hypochlorous acid is reacted and carboxylated under alkaline conditions, followed by deprotection of the protecting group benzyl by hydrogen reaction under palladium catalyst. It is reported that the target compound 4'-hydroxy-4-biphenyl carboxylic acid was synthesized.
  • This process consists of complex multistage reactions such as multistage protection-deprotection, as well as the use of a large amount of hypochlorite salts and commercially dangerous hydrogen reactions required for deprotection of benzyl protecting groups. It is evaluated as a process that lacks much economic feasibility.
  • Huaxue Shiji 2005, 13 (6), 614 has a method similar to that of [Chemical Scheme 2]. As shown in [Chemical Reaction Formula 3], the hydroxy group of phenylphenol is first protected with a methyl group, and then the hypochlorite salt is reacted under alkaline conditions to be carboxylated. It is reported that the target compound 4'-hydroxy-4-biphenylcarboxylic acid is obtained as a step of deprotecting the methyl group.
  • this method also uses a large amount of hypochlorite salt, and in order to deprotect the methyl protecting group, it is evaluated as a process lacking in economical efficiency in terms of manufacturing cost such as acetic acid as a solvent and high temperature reaction using expensive bromic acid. do.
  • Japanese Patent No. 04243851 uses phosgene derivatives to protect two 4-phenylphenol hydroxy groups and to carboxylate them using oxalyl chloride to target compound 4'-hydroxy-4.
  • the phosgene derivative N, N-dimethyl chloroformamide is obtained as shown in the following [Chemical Reaction Scheme 4] by reacting with 4-phenylphenol and hydrolysis. Methods of synthesizing the desired compound 4'-hydroxy-4-biphenylcarboxylic acid are known.
  • an object of the present invention is to provide a novel method of producing 4'-hydroxy-4-biphenylcarboxylic acid having a simple process and high productivity.
  • the novel process for preparing 4'-hydroxy-4-biphenylcarboxylic acid of formula (1) of the present invention is characterized in that it is prepared through a hydrolysis reaction from a compound of formula (2).
  • R 1 is an alkyl, cycloalkyl, or aryl group having 1 to 6 carbon atoms
  • R is hydrogen or an alkyl group
  • X is a leaving group selected from chlorine, bromine, iodine, methanesulfonate, benzenesulfonate, toluenesulfonate,
  • Quaternary amine salts are amine salts consisting of three identical or different alkyl groups or aromatic hydrocarbons, or cyclized aromatic amine salts such as pyridine.
  • the hydrolysis refers to a reaction for heating if necessary in an alkaline aqueous solution or a mixed solution of an alkaline aqueous solution and an organic solvent
  • the alkali used is NaOH, KOH, CsOH, Na 2 CO 3 , K 2 CO 3 , Cs Alkali salts such as 2 CO 3 .
  • the alkali is used in the amount of 2 to 5 equivalents, preferably 2 to 3 equivalents based on the compound of formula (2).
  • the hydrolysis reaction temperature is 20-100 degreeC, Preferably it is 60-100 degreeC.
  • the compound of Formula 2 is prepared through the reaction of a compound of Formula 3 with a tertiary amine.
  • R 1 is an alkyl, cycloalkyl or aryl group having 1 to 6 carbon atoms
  • R is hydrogen or an alkyl group
  • X is a leaving group such as chlorine, bromine, iodine, methanesulfonate, benzenesulfonate, toluenesulfonate.
  • tertiary amines consisting of three identical or different alkyl groups or aromatic hydrocarbons; There are cyclized aromatic amines such as pyridine.
  • Reaction temperature is 20-150 degreeC, especially 80-120 degreeC is efficient.
  • the compound of Formula 3 is prepared by a catalytic condensation reaction of a compound of Formula 4 with a compound of Formula 5.
  • R 1 is an alkyl, cycloalkyl or aryl group having 1 to 6 carbon atoms
  • R is hydrogen or an alkyl group
  • X is a leaving group selected from chlorine, bromine, iodine, methanesulfonate, benzenesulfonate, toluenesulfonate.
  • Lewis acids such as organic sulfonate metal salts, such as metal salts of trifluoromethane sulfonate.
  • the manufacturing process of the present invention has the advantage of providing high manufacturing economics with the simplicity of the process.
  • the manufacturing process of the present invention has the advantage that the synthesis process is simple and the purification process is convenient to provide a process for economically manufacturing high purity products.
  • the present invention provides a novel process for preparing compound 4'-hydroxy-4-biphenylcarboxylic acid of formula (1).
  • the manufacturing process of the present invention can be represented by the chemical reaction path of the following Chemical Scheme 5.
  • an acyl group is introduced to protect an alcohol group of 4-phenylphenol to obtain a compound of Chemical Formula 4.
  • R is an alkyl group having 1 to 6 carbon atoms or an aryl group;
  • X 1 is chlorine, bromine, or acylated compound as acetic anhydride;
  • Acid anhydrides such as propionic anhydride are used.
  • the base used in the reaction step i NaOH, Na 2 CO 3 , KOH, K 2 CO 3 , tertiary amines are used.
  • the reaction solvent used in the reaction step i esters such as ethyl acetate; Ethers such as diisopropyl ether; Ketones such as acetone; Amides such as dimethyl formamide; Nitriles such as acetonitrile; Sulfoxides such as dimethyl sulfoxide are used.
  • reaction step ii an acyl compound, such as Formula 5, substituted with a leaving group having a good 2-position to the compound of Formula 4 obtained through Reaction Step i under a Lewis catalyst to obtain a compound of Formula 3, wherein R is Hydrogen, an alkyl group having 1 to 6 carbon atoms; X is a good leaving group such as chlorine, bromine, iodine, methanesulfonate, toluenesulfonate, benzenesulfonate, and the compound of formula 5 is an acid chloride having such a leaving group.
  • the catalyst used in the reaction step ii may be Lewis acid such as AlCl 3 , FeCl 3 , ZnCl 2 , an organic sulfonate metal salt, and the solvent used in the reaction step ii may include chlorinated hydrocarbons such as dichloromethane and dichloroethane; Nitro alkanes such as nitromethane are used.
  • tertiary amines used to synthesize compounds of formula 2 from compounds of formula 3 include tertiary amines composed of three alkyl groups, the same as or different from each other; Tertiary amines having one or more aryl groups; Tertiary amines which form a ring such as pyridine are used.
  • Solvents used in reaction step iii include tertiary amines such as pyridine used to form the compound of formula (2); Esters such as ethyl acetate; Ethers such as diisopropyl ether; Ketones such as acetone; Amides such as dimethyl formamide; Nitriles such as acetonitrile; Sulfoxides such as dimethyl sulfoxide; Water or a mixed solvent of water and an organic solvent is used.
  • reaction temperature is 20 to 150 ° C, particularly 80 to 120 ° C.
  • reaction step iv which is a hydrolysis step
  • an alkaline aqueous solution Hydrolysis using a mixed solution of an alkaline aqueous solution and an organic solvent, NaOH, Na 2 CO 3 , KOH, K 2 CO 3 , CsOH, Cs2CO 3 and the like are used as the alkali used in the reaction step iv
  • the alkali equivalent is 2 to 5 equivalents, in particular 2 to 3 equivalents.
  • the organic solvent used in the reaction step iv by mixing with the aqueous alkali solution is alcohols such as methyl alcohol; Amides such as dimethylformamide; Nitriles such as acetonitrile; Sulfoxides such as dimethyl sulfoxide; Ketones such as 2-butanone; Ethers such as diisopropyl ether are used.
  • the reaction temperature of the hydrolysis reaction in reaction step iv is 20 to 100 ° C., particularly 60 to 100 ° C.
  • the acid used as a neutralizing agent to obtain the compound of formula 1 from the reaction solution hydrolyzed in reaction step iv is an aqueous hydrochloric acid solution; Inorganic acids such as aqueous bromic acid solution; Organic acids such as acetic acid are used.
  • 4'-hydroxy-4-biphenylcarboxylic acid according to the present invention can be used as a high functional material such as liquid crystal, liquid crystal polymer, high heat dissipation, high heat-resistant resin, and will be described in detail in the following examples.
  • a high functional material such as liquid crystal, liquid crystal polymer, high heat dissipation, high heat-resistant resin, and will be described in detail in the following examples.
  • the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

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

Abstract

La présente invention concerne une nouvelle méthode de préparation de l'acide 4'-hydroxy-4-biphénylcarboxylique, qui est préparé par une réaction d'hydrolyse à partir d'un composé de R1-COO-Ph-Ph-CO-CR-Y. Dans la formule: R1 est un C1-6 alkyle, un groupe cycloalkyle ou aryle; Ph est le phényle; R est hydrogène ou un groupe alkyle; Y est > N+-(X-); X est un groupe partant sélectionné parmi le chlorure, le bromure, l'iodure, le sulfonate de méthane, le sulfonate de benzène et le sulfonate de toluène; et >N+-est un sel amine quaternaire, qui est un sel amine comprenant trois identiques ou différents groupes alkyles ou des hydrocarbones aromatiques ou un sel amine aromatique cyclique comme la pyridine.
PCT/KR2017/005524 2016-06-01 2017-05-26 Nouvelle méthode de préparation de l'acide 4'-hydroxy-4-biphénylcarboxylique WO2017209458A1 (fr)

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KR1020160067854A KR101856566B1 (ko) 2016-06-01 2016-06-01 4'-히드록시-4-비페닐카르복실산의 신규 제조 방법
KR10-2016-0067854 2016-06-01

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KR102309073B1 (ko) * 2019-11-07 2021-10-05 조혜수 비페닐디카복실산의 제조 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990660A (en) * 1987-12-22 1991-02-05 Basf Aktiengesellschaft Preparation of aromatic hydroxycarboxylic acids
JPH03275641A (ja) * 1990-03-26 1991-12-06 Iwaki Seiyaku Kk ヒドロキシビフェニル化合物及びその製造法
JPH07107021B2 (ja) * 1986-11-06 1995-11-15 三井東圧化学株式会社 ４′−ヒドロキシビフエニル−４−カルボン酸の製造方法
US5854245A (en) * 1996-06-28 1998-12-29 Merck & Co., Inc. Fibrinogen receptor antagonists

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US4755617A (en) 1986-04-04 1988-07-05 Mitsui Toatsu Chemicals, Incorporated Process for the preparation of 4'-hydroxybiphenyl-4-carboxyl acid
JP2598173B2 (ja) 1991-01-22 1997-04-09 帝人株式会社 ４´ −ヒドロキシビフェニル−４−カルボン酸の製造方法
JP3648729B2 (ja) 2002-08-19 2005-05-18 松屋電工株式会社 天井収納用梯子
JP5222632B2 (ja) 2008-06-13 2013-06-26 白鳥製薬株式会社 ビアリール化合物の製造方法

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JPH07107021B2 (ja) * 1986-11-06 1995-11-15 三井東圧化学株式会社 ４′−ヒドロキシビフエニル−４−カルボン酸の製造方法
US4990660A (en) * 1987-12-22 1991-02-05 Basf Aktiengesellschaft Preparation of aromatic hydroxycarboxylic acids
JPH03275641A (ja) * 1990-03-26 1991-12-06 Iwaki Seiyaku Kk ヒドロキシビフェニル化合物及びその製造法
US5854245A (en) * 1996-06-28 1998-12-29 Merck & Co., Inc. Fibrinogen receptor antagonists

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CAP???H, ?. T. ET AL.: "??????????????? CT?????? AMMOH?????? CO???, ?????????? PI-X???-? ?-METO??????????????? ????????", X????????? ?????? ???????, vol. 57, no. 3, 2004, pages 41 - 49 *

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