WO2006001562A1 - Procede de fabrication de derives d'acide (r)-2-phenoxypropionique purs optiquement actifs - Google Patents

Procede de fabrication de derives d'acide (r)-2-phenoxypropionique purs optiquement actifs Download PDF

Info

Publication number
WO2006001562A1
WO2006001562A1 PCT/KR2004/002984 KR2004002984W WO2006001562A1 WO 2006001562 A1 WO2006001562 A1 WO 2006001562A1 KR 2004002984 W KR2004002984 W KR 2004002984W WO 2006001562 A1 WO2006001562 A1 WO 2006001562A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
acid derivatives
phenoxypropionic acid
cyclohexane
alkali metal
Prior art date
Application number
PCT/KR2004/002984
Other languages
English (en)
Inventor
Dae Whang Kim
Kun Hoe Chung
Hae Sung Chang
Young Kwan Ko
Jae Wook Ryu
Jae Chun Woo
Dong Wan Koo
Original Assignee
Korea Research Institute Of Chemical Technology
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 Korea Research Institute Of Chemical Technology filed Critical Korea Research Institute Of Chemical Technology
Publication of WO2006001562A1 publication Critical patent/WO2006001562A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/73—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • 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
    • C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Definitions

  • the present invention relates to a method for manufacturing optically active (R)-2-phenoxypropionic acid derivatives. More particularly, the present invention relates to a method for manufacturing optically active (R)-2-phenoxypropionic acid derivatives of the following formula 1 with high purity by using a p-substituted phenol derivative and alkyl (S)-2-arylsulfonyloxypropionate as starting materials and reacting them at 60 to 100 0 C in the presence of an alkali metal salt as a base and a hydrocarbon solvent.
  • A is a benzoyloxy (BzO) group, an acetoxy (AcO) group, p- toluenesulfonyloxy (p-TsO) group, or a Ci-C 6 aliphatic acyl group; and R is H or a Ci-C 6 alkyl group.
  • the (R)-2-phenoxypropionic acid derivative of the above formula 1 is a precursor of (R)-2-(p-hydroxyphenoxy)propionic acid known as important intermediates in synthesizing aryloxylphenoxypropionic acid based agrochemicals.
  • the methods of chemical synthesis of (R)-2-phenoxypropionic acid derivatives of the above formula 1 are disclosed in many references [U.S. Pat. Nos. 4,625,053, 4,760,172, 4,908,476, 4,935,522, 5,801,272, German Pat. No. 3,902,372(1989), Japanese Pat. Nos. Sho 58-188889(1983), Sho 59-230873(1984)].
  • an object of the present invention is to provide a novel method for industrial manufacture of (R)-2-phenoxypropionic acid derivatives in a most cost- effective manner.
  • the present invention relates to a method for manufacturing optically active (R)-2-phenoxypropionic acid derivatives of the following formula 1 by reacting the p-substituted phenol derivatives of the following formula 2 with alkyl (S)-2- arylsulfonyloxypropionate of the following formula 3 at 60 to 100 0 C in the presence of an alkali metal salt as a base and a hydrocarbon solvent,
  • A is a benzoyloxy (BzO) group, an acetoxy (AcO) group, ⁇ - toluenesulfonyloxy (p-TsO) group, or a C 1 -C 6 aliphatic acyl group;
  • R is H or a C 1 - C 6 alkyl group; and
  • Y is an arylsulfonyloxy group.
  • the present invention relates to an improved method of manufacturing (R)- 2-phenoxy propionic acid derivatives by reacting a ⁇ -substituted phenol derivative with alkyl (S)-2-arylsulfonyloxypropionate under a predetermined specific condition maintaining a certain temperature by using an appropriate solvent and an appropriate base thereby obtaining only optically pure (R)-compounds in a most cost-effective manner.
  • the selection of a reaction solvent, a base and a leaving group (Y) as well as control of a reaction temperature plays a very crucial role.
  • the p-substituted phenol derivative of the above formula 2 used as a starting material for the reaction, is selected from the group consisting of p-benzoyloxyphenol, p- acetoxyphenol, p-(p- toluenesulfonyloxy)phenol or p-acylphenol.
  • the alkyl (S)-2- arylsulfonyloxypropionate of the above formula 3, used as another starting material for the reaction, is preferably alkyl (S)-(p-toluenesulfonyloxy)propionate.
  • the compounds of the above formulas 2 and 3 used in the present invention are all known compounds and they can be easily synthesized by the known methods.
  • reaction solvent to be used in the present invention examples include aliphatic or aromatic hydrocarbon solvents such as cyclopentane, n-hexane, cyclohexane, methylcyclohexane, cycloheptane, benzene, toluene, and xylene, preferably n-hexane, cyclohexane, and xylene.
  • an alkali metal salt is generally used, preferably an alkali metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate and the like, more preferably potassium carbonate.
  • the reaction temperature is a very important factor closely related with racemization and thus it should be carefully controlled.
  • a temperature in the range of from about 60 to about 100 0 C, and more preferably in the range of from about 65 to about 85 0 C considering the reaction time.
  • sulfonic acid salt produced at a relatively high temperature is filtered and then concentrated to recover the (R)-2-phenoxypropionic acid derivatives of the above formula 1 with high purity and high yield.
  • several steps of recrystallization process is performed for purification purpose to recover the resulting product of (R)- compounds.
  • the method according to the present invention enables to obtain highly pure optically active (R)-compounds without an additional purification process and is thus very useful for its industrial application.
  • Example 1 Synethesis of (R)-2-(p- acetylphenoxy)propionic acid ethylester
  • a 250 mL flask equipped with Dean-Stock was added with 13.6 g (0.1 mole) of p-hydroxyacetophenone, 27.2 g (0.1 mole) of ethyl (S)-2-(p- toluenesulfonyloxy)propionate, 27.6 g(0.2 mole) of potassium carbonate along with 136 mL of cyclohexane and allowed to react for 16 hrs under heat reflux.
  • Example 2 Synethesis of (JR)-2-(p-acetylphenoxy)propionic acid A 100 mL flask was added with 23.6 g (0.1 mol) of (R)-2-(p- acetylphenoxy)propionic acid ethylester and 50 mL of 20% sulfuric acid and then allowed to react while stirring at 80 0 C for 5 hrs. Upon completion of the reaction, the mixture was cooled, extracted with 100 mL of dichlomethane, and then dried. The solvent was removed under reduced pressure to remove 20.4 g of (R)-2-(p- acetylphenoxy)propionic acid.
  • Example 3 Synethesis of (R)-2-[p-(p-toluenesulfonyl)oxyphenoxy] ⁇ ropionic acid (K)-2-[/?-(p-toluenesulfonyl)oxyphenoxy]propionic acid ethylester was treated same as in the above example 2 to obtain a target compound.
  • Example 4 Synethesis of (R)-2-(/?-hydroxylphenoxy) propionic acid ethylester
  • Twenty five point two grams (0.1 mole) of (R)-2-(p- acetoxyphenoxy)propionic acid ethylester prepared in the above example 1 was dissolved in 5% HCl-95% ethanol and stirred at 30 0 C for 2 hrs.
  • Ethanol was collected by distillation under reduced pressure and then dissolved by adding 100 mL of 5% sodium hydrogen carbonate. It was extracted using 100 mL of ethyl acetate, dried using anhydrous magnesiumsulfate and then concentrated to obtain 20.5 g of (R)-2-(p-hydroxyphenoxy)propionic acid ethylester.
  • Example 5 Synethesis of (R)-2-( ⁇ -hydroxylphenoxy)propionic acid Twenty five point two grams (0.1 mole) of (R)-2-(p- acetoxyphenoxy)propionic acid ethylester prepared in the above example 1 was dissolved in 50 mL of 5% NaOH and stirred at 25 - 30 0 C for 2 hrs. The reaction solution was neutralized, extracted 3 times with 50 mL of ethyl acetate, dried with magnesium sulfate and then concentrated to obtain 17.3 g of (R)-2-(p- hydroxyphenoxy)propionic acid.
  • Comparative Example 1 The optical purities of compounds prepared according to the known methods are shown in the following table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de fabrication de dérivés d'acide (R)-2-phénoxypropionique optiquement actifs. Plus particulièrement, la présente invention concerne un procédé destiné à fabriquer des dérivés d'acide (R)-2-phénoxypropionique optiquement actifs présentant une haute pureté, et consistant à utiliser des dérivés de phénol p-substitués et de l'alkyle-(S)-2-arylsulfonyloxypropionate comme matières de départ, et à les faire réagir à 60-100 °C en présence d'un sel de métal alcalin comme base et d'un solvant hydrocarboné.
PCT/KR2004/002984 2004-06-23 2004-11-18 Procede de fabrication de derives d'acide (r)-2-phenoxypropionique purs optiquement actifs WO2006001562A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2004-0047240 2004-06-23
KR1020040047240A KR100597259B1 (ko) 2004-06-23 2004-06-23 광학활성 (ｒ)-2-페녹시프로피온산 유도체의 제조방법

Publications (1)

Publication Number Publication Date
WO2006001562A1 true WO2006001562A1 (fr) 2006-01-05

Family

ID=35781952

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2004/002984 WO2006001562A1 (fr) 2004-06-23 2004-11-18 Procede de fabrication de derives d'acide (r)-2-phenoxypropionique purs optiquement actifs

Country Status (2)

Country Link
KR (1) KR100597259B1 (fr)
WO (1) WO2006001562A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108727187A (zh) * 2018-07-10 2018-11-02 淮安国瑞化工有限公司 一种（r）-（+）-2-对羟基苯氧基丙酸的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4625053A (en) * 1984-12-28 1986-11-25 Nissan Chemical Industries Ltd. Process for preparing optically active 2-(4-hydroxy-phenoxy) propionic acid compounds
US4760172A (en) * 1986-12-22 1988-07-26 The Dow Chemical Company Process for the preparation of optically active 2-(4-methoxyphenoxy) propionic acid
US4908476A (en) * 1988-03-21 1990-03-13 Hoechst Celanese Corporation Synthesis of 2-(4-hydroxyphenoxy)alkanoic acids
US4978774A (en) * 1989-01-27 1990-12-18 Hoechst Aktiengesellschaft Process for the preparation of D(+)-2-(4-acetylphenoxy)-propionic esters

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4625053A (en) * 1984-12-28 1986-11-25 Nissan Chemical Industries Ltd. Process for preparing optically active 2-(4-hydroxy-phenoxy) propionic acid compounds
US4760172A (en) * 1986-12-22 1988-07-26 The Dow Chemical Company Process for the preparation of optically active 2-(4-methoxyphenoxy) propionic acid
US4908476A (en) * 1988-03-21 1990-03-13 Hoechst Celanese Corporation Synthesis of 2-(4-hydroxyphenoxy)alkanoic acids
US4978774A (en) * 1989-01-27 1990-12-18 Hoechst Aktiengesellschaft Process for the preparation of D(+)-2-(4-acetylphenoxy)-propionic esters

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108727187A (zh) * 2018-07-10 2018-11-02 淮安国瑞化工有限公司 一种（r）-（+）-2-对羟基苯氧基丙酸的制备方法
CN108727187B (zh) * 2018-07-10 2020-04-24 淮安国瑞化工有限公司 一种(r)-(+)-2-对羟基苯氧基丙酸的制备方法

Also Published As

Publication number Publication date
KR100597259B1 (ko) 2006-07-06
KR20050122087A (ko) 2005-12-28

Similar Documents

Publication Publication Date Title
EP2247572B1 (fr) Procédé de préparation en enceinte unique de dihydrate de 3-(2,2,2-triméthylhydrazinium)-propionate
JPS61158947A (ja) 光学活性２−（４−ヒドロキシフエノキシ）プロピオン酸の製法
EP3524592B1 (fr) Procédé de préparation d'un composé phénylalanine
WO2006001562A1 (fr) Procede de fabrication de derives d'acide (r)-2-phenoxypropionique purs optiquement actifs
CN114315609A (zh) 一种制备顺式2-氨基环己醇的工艺方法
KR101525493B1 (ko) 고순도 탐술로신 또는 이의 염 제조방법
JPS5915901B2 (ja) ｕ↓−アミノアルコ−ルの製造方法
CN109265385B (zh) 一种手性催化剂的合成工艺
JP5463051B2 (ja) １，４―ジヒドロピリジン誘導体の製造法
JPH0794420B2 (ja) 置換フェノキシアセトアルデヒドオキシム類の製造方法
JP4968066B2 (ja) ４−アミノ−２−アルキルチオ−５−ピリミジンカルバルデヒドの製法
JP4397990B2 (ja) ３−アルキルフラバノノール誘導体の精製法
CN111039838B (zh) 一种3-乙酰巯基-2-甲基丙酸的制备方法
JPH05140034A (ja) ｏ−アルコキシ安息香酸の製造方法
CN109574894B (zh) 一种n-(3-(二甲基胺基)-3-丙硫酰基)-取代的苯甲酰胺的（i）合成方法
CN107827811B (zh) 一种制备n-取代-1,2,3,6-四氢吡啶的方法
CN117903043A (zh) 一种顺式-2-吡啶-2-基环己醇的制备方法
KR100730766B1 (ko) 비페닐아세트산의 신규 제조방법
JP4039026B2 (ja) ３−アミノ−２−チオフェンカルボン酸エステルの製法
JPH0120150B2 (fr)
JPH02295951A (ja) ニトロ安息香酸アルキルの製造方法
KR101315751B1 (ko) 로페라미드 옥사이드 모노하이드레이트의 신규한 제조방법
JPH0440355B2 (fr)
JP2008308458A (ja) ピリジンカルボニル化合物の製造方法
JPH11240869A (ja) ラクタムカルボン酸誘導体およびその製法、ならびにそれを用いたピペリジン誘導体の製法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase