WO2017023123A1 - Nouveau procédé de préparation d'un dérivé de chromanone - Google Patents

Nouveau procédé de préparation d'un dérivé de chromanone Download PDF

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Publication number
WO2017023123A1
WO2017023123A1 PCT/KR2016/008579 KR2016008579W WO2017023123A1 WO 2017023123 A1 WO2017023123 A1 WO 2017023123A1 KR 2016008579 W KR2016008579 W KR 2016008579W WO 2017023123 A1 WO2017023123 A1 WO 2017023123A1
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WIPO (PCT)
Prior art keywords
formula
compound represented
preparing
acid
reacting
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Application number
PCT/KR2016/008579
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English (en)
Korean (ko)
Inventor
김은선
고동현
권재홍
김영주
이성아
최광도
허승평
이지윤
Original Assignee
씨제이헬스케어 주식회사
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 씨제이헬스케어 주식회사 filed Critical 씨제이헬스케어 주식회사
Priority to JP2018505681A priority Critical patent/JP6770057B2/ja
Priority to CN201680045379.5A priority patent/CN107848943A/zh
Publication of WO2017023123A1 publication Critical patent/WO2017023123A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • 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
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring

Definitions

  • the present invention relates to a novel process for the preparation of 5,7-difluorochroman-4-one derivatives.
  • Chromanone derivatives are substances that are used in medicine and chemistry in a variety of ways, such as the substance itself, or material synthesis process. However, despite the importance of chromanone derivatives, many methods for easily synthesizing them have not been reported.
  • the present invention does not require a separate purification process, has a low manufacturing cost, and can be industrially mass-produced using commercially available reagents and solvents.
  • Provided is a method for preparing a man-4-one derivative.
  • the present invention is a.
  • the preparation method of the present invention does not require a separate purification process, has a low manufacturing cost, and uses 5,7-difluorochroman-4-one derivatives using commercially available reagents and solvents that are not regulated by the environment. Can mass produce effectively.
  • the present invention is a.
  • Reaction of the compound represented by the formula (II) comprising the step of reacting the compound represented by the formula (V) with 2-iodobenzoic acid and potassium peroxymonosulfate (Potassium peroxymonosulfate) It provides a manufacturing method.
  • X may be selected from fluoro, chlorine or iodine with halogen atoms.
  • the reaction is an O-alkylation reaction.
  • the O-alkylation reaction may be used alone or mixed with tetrahydrofuran, dioxane, dichloromethane, 1,2-dimethoxyethane, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) as an organic solvent.
  • Dimethylformamide can be preferably used.
  • potassium hydride sodium hydride, lithium hydride, potassium t-butoxide or the like can be used, and preferably sodium hydride can be used.
  • the compound and base represented by the formula (I) under the organic solvent are stirred at 10 ° C. or lower, preferably 0 ° C. to 10 ° C., and then mixed with the compound represented by the formula to perform an O-alkylation reaction at 60 ° C. to 90 ° C. Can be.
  • X is preferably chlorine.
  • a reaction is a polar solvent, such as Water, methanol, acetonitrile or mixed solvents thereof are used.
  • the compound represented by the formula under a polar solvent may be reacted with 2-Iodobenzoic acid and potassium peroxymonosulfate at 60 ° C to 90 ° C.
  • the reaction is mass-produced by using 2-iodobenzoic acid and potassium peroxymonosulfate, which are generally available without risk, and are not regulatory reagents due to environmental pollution. It is suitable for the process and shows high production yield.
  • the present invention is a.
  • the reaction using copper hydroxide as a base in the Michael addition reaction (Michael addition reaction)
  • the reaction is carried out.
  • copper hydroxide in the Michael addition reaction the present reaction can greatly improve the reaction yield compared to using other base sources.
  • Preparation of the compound represented by the formula (VI) is preferably carried out at 75 °C to 85 °C.
  • the compound represented by the formula (VI) is synthesized by hydrolysis in the presence of an acid or a base.
  • the acid may be selected from sulfuric acid, hydrochloric acid or phosphoric acid, preferably the acid is sulfuric acid.
  • the base may be selected from sodium hydroxide or potassium hydroxide, preferably the base is sodium hydroxide.
  • the step of preparing the compound represented by Formula (II) is preferably performed at 40 ° C. to 60 ° C. under acidic conditions, and under reflux under basic conditions.
  • the present invention is a.
  • a method for preparing a compound represented by the formula (III) comprising a third step of preparing a compound represented by the formula (III) by cyclizing the compound represented by the formula (II).
  • the cyclization reaction may be performed under acidic conditions.
  • the acid may be selected from sulfuric acid, hydrochloric acid or phosphoric acid, preferably sulfuric acid.
  • the reaction in the presence of an acid is preferably reacted at 40 ° C to 60 ° C.
  • the present invention is a.
  • the cyclization reaction may be performed under acidic conditions.
  • Reaction conditions may be applied to the content of the third step of preparing a compound represented by the formula (III) by cyclizing the compound represented by the formula (II) described above.
  • the reaction from formula (VI) to formula (III) may be carried out in an in-situ reaction.
  • the preparation of the compound represented by the formula (I) to the compound represented by the formula (II) is treated with the compound represented by the formula (IV) to the compound represented by the formula (I) after the O-alkylation reaction to 2-benzoic iodide ( 2-Iodobenzoic acid) and potassium peroxymonosulfate (Potassium peroxymonosulfate) may be treated to synthesize the compound represented by Formula II, or may be prepared by hydrolysis after performing a reaction with acrylonitrile.
  • Preparation of the compound represented by the formula (III) from the compound represented by the formula (II) can be prepared by adding a compound represented by the formula (II) in the presence of an acid, and then carrying out a cyclization reaction.
  • the method for preparing a compound represented by Formula (II) according to the present invention may be represented by the following Scheme -1.
  • a compound represented by Formula V is prepared by reacting a compound represented by Formula I with sodium hydride under dimethylformamide, and performing an O-alkylation reaction with a compound of Formula IV.
  • the compound represented by the formula (V) is reacted with 2-iodic benzoic acid and potassium peroxymonosulfate to prepare the compound represented by the formula (II).
  • the preparation method of the compound represented by the formula (III) according to the present invention may be preferably represented by the following reaction scheme (I-1).
  • a compound represented by Formula V is prepared by reacting a compound represented by Formula I with sodium hydride under dimethylformamide, and performing an O-alkylation reaction with a compound of Formula IV.
  • the compound represented by formula (V) is reacted with 2-iodic benzoic acid and potassium peroxymonosulfate to prepare the compound represented by formula (II), and then the sulfuric acid is treated to prepare a compound represented by formula (III) through a cyclization reaction. do.
  • the preparation method of the compound represented by the formula (III) according to the present invention may be preferably represented by the following reaction scheme (I-2).
  • acrylonitrile is reacted under copper hydroxide to prepare a compound of formula VI, and hydrolysis is performed through acid treatment, followed by a cyclization reaction to prepare a compound of formula III.
  • the sulfuric acid treatment reaction may be carried out in the In-situ reaction.
  • the preparation method of the present invention does not require a separate purification process, has a low manufacturing cost, and effectively utilizes 5,7-difluorochroman-4-one using commercially available reagents and solvents that are not regulated by the environment. Can be mass produced industrially.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyrane Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un nouveau procédé de préparation d'un dérivé de 5,7-difluorochroman-4-one. Le procédé de préparation selon la présente invention permet la production industrielle de masse en utilisant d'une manière générale un réactif et un solvant utilisables ne nécessitant pas de processus de raffinage distinct, ayant de faibles coûts de production, et n'étant soumis à aucune réglementation sur l'environnement, ce qui permet la production efficace d'un dérivé de 5,7-difluorochroman-4-one.
PCT/KR2016/008579 2015-08-04 2016-08-03 Nouveau procédé de préparation d'un dérivé de chromanone WO2017023123A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2018505681A JP6770057B2 (ja) 2015-08-04 2016-08-03 クロマノン誘導体の新規な製造方法
CN201680045379.5A CN107848943A (zh) 2015-08-04 2016-08-03 制备色满酮衍生物的新方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2015-0110245 2015-08-04
KR1020150110245A KR20170016754A (ko) 2015-08-04 2015-08-04 크로마논 유도체의 신규한 제조방법

Publications (1)

Publication Number Publication Date
WO2017023123A1 true WO2017023123A1 (fr) 2017-02-09

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PCT/KR2016/008579 WO2017023123A1 (fr) 2015-08-04 2016-08-03 Nouveau procédé de préparation d'un dérivé de chromanone

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JP (3) JP6770057B2 (fr)
KR (1) KR20170016754A (fr)
CN (1) CN107848943A (fr)
WO (1) WO2017023123A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11377434B2 (en) * 2020-07-20 2022-07-05 Hangzhou Duyi Technology Co. Ltd. Methods for preparing substituted chromanone derivatives
WO2023278729A1 (fr) * 2021-06-30 2023-01-05 The General Hospital Corporation Ligands d'imagerie à base de chromane

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210020403A (ko) 2019-08-14 2021-02-24 엘지전자 주식회사 의류 처리장치
KR20210020406A (ko) 2019-08-14 2021-02-24 엘지전자 주식회사 의류 처리장치
KR20210111556A (ko) 2020-03-03 2021-09-13 엘지전자 주식회사 의류 처리장치
KR20210111555A (ko) 2020-03-03 2021-09-13 엘지전자 주식회사 의류 처리장치
KR20210121402A (ko) 2020-03-30 2021-10-08 엘지전자 주식회사 의류 처리장치 및 이의 운전 제어방법

Citations (3)

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US4625042A (en) * 1984-07-09 1986-11-25 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for preparing 6-fluoro-4-chromanone using 3-(4-fluorophenoxy)propionitrile
KR20060060007A (ko) * 2003-08-08 2006-06-02 얀센 파마슈티카 엔.브이. Ｃｃｋ2 조절제로서의2-(퀴녹살린-5-일설포닐아미노)-벤즈아미드 화합물
KR20110023895A (ko) * 2008-06-25 2011-03-08 바이엘 쉐링 파마 악티엔게젤샤프트 치환된 ７-술파닐메틸, ７-술피닐메틸 및 ７-술포닐메틸 인돌, 및 그의 용도

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KR100915417B1 (ko) 2002-06-28 2009-09-03 디일 베게테 디펜스 게엠베하 운트 코 카게 피보호 물체의 자체 방어 장치
WO2008151927A2 (fr) * 2007-06-15 2008-12-18 Nycomed Gmbh Dérivés de benzimidazole à substitution 6-n pharmaceutiquement actifs
TW201348231A (zh) * 2012-02-29 2013-12-01 Amgen Inc 雜雙環化合物

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US4625042A (en) * 1984-07-09 1986-11-25 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for preparing 6-fluoro-4-chromanone using 3-(4-fluorophenoxy)propionitrile
KR20060060007A (ko) * 2003-08-08 2006-06-02 얀센 파마슈티카 엔.브이. Ｃｃｋ2 조절제로서의2-(퀴녹살린-5-일설포닐아미노)-벤즈아미드 화합물
KR20110023895A (ko) * 2008-06-25 2011-03-08 바이엘 쉐링 파마 악티엔게젤샤프트 치환된 ７-술파닐메틸, ７-술피닐메틸 및 ７-술포닐메틸 인돌, 및 그의 용도

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THOTTUMKARA, ARUN P. ET AL.: "In Situ Generation of o-Iodoxybenzoic Acid (IBX) and the Catalytic Use of It in Oxidation Reactions in the Presence of Qxone as a Co-oxidan", ORG. LETT., vol. 7, no. 14, 2005, pages 2933 - 2936, XP055361796 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11377434B2 (en) * 2020-07-20 2022-07-05 Hangzhou Duyi Technology Co. Ltd. Methods for preparing substituted chromanone derivatives
WO2023278729A1 (fr) * 2021-06-30 2023-01-05 The General Hospital Corporation Ligands d'imagerie à base de chromane

Also Published As

Publication number Publication date
KR20170016754A (ko) 2017-02-14
JP2018523662A (ja) 2018-08-23
JP2020180134A (ja) 2020-11-05
JP2020097607A (ja) 2020-06-25
CN107848943A (zh) 2018-03-27
JP6948419B2 (ja) 2021-10-13
JP6770057B2 (ja) 2020-10-14

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