WO1999064428A1 - Synthesis of aryl boronic acids - Google Patents

Synthesis of aryl boronic acids Download PDF

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Publication number
WO1999064428A1
WO1999064428A1 PCT/US1999/013105 US9913105W WO9964428A1 WO 1999064428 A1 WO1999064428 A1 WO 1999064428A1 US 9913105 W US9913105 W US 9913105W WO 9964428 A1 WO9964428 A1 WO 9964428A1
Authority
WO
WIPO (PCT)
Prior art keywords
aryl
boronic acid
reaction mixture
borate
aryl boronic
Prior art date
Application number
PCT/US1999/013105
Other languages
English (en)
French (fr)
Inventor
Jeffrey M. Sullivan
Hamlin H. Barnes
Original Assignee
Boulder Scientific Company
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 Boulder Scientific Company filed Critical Boulder Scientific Company
Priority to JP2000553436A priority Critical patent/JP2002517503A/ja
Priority to NZ502612A priority patent/NZ502612A/en
Priority to CA002297780A priority patent/CA2297780A1/en
Priority to EP99930198A priority patent/EP1064286A1/en
Priority to AU46786/99A priority patent/AU4678699A/en
Publication of WO1999064428A1 publication Critical patent/WO1999064428A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds

Definitions

  • This invention relates to the synthesis of aryl boronic acids .
  • Known aryl boronic acid synthesis typically entails concurrent or dual addition of substantially equimolar amounts of a trialkyl borate ester and an aromatic Grignard reagent to a reaction vessel at a temperature of less than -60°C, wherein a reaction mixture containing an aryl boronic acid ester is produced in a 30% to 50% yield. The ester is separated and hydrolyzed to provide the desired aryl boronic acid.
  • Aryl boronic acids are now in substantial commercial use to synthesize biaryl compounds by the palladium catalyzed cross-coupling "Suzuki" reaction. See, e.g., A. Suzuki, et al., Syn . Commun .
  • aryl borate diesters is accomplished at a temperature of from about -10° to 0°C by direct addition of the Grignard to the trialkyl borate or conversely in any desired mole ratio.
  • Hydrolysis of the aryl borate diesters may be accomplished in situ in synthesis reaction mixture with an aqueous mineral, preferably, aqueous sulfuric acid, in known manner .
  • This invention typically provides aryl boronic yields approximately 20-40% greater than those achieved by the prior art. More specifically, the invention may provide aryl boronic acid yields of from about 50% to about 70% based on the trialkyl borate reactant.
  • the invention may, but need not be, practiced as a one pot method.
  • a Grignard reagent is prepared in known manner in an appropriate ethereal solvent, preferably at the greatest concentration resulting in a solution. Any ethereal solvent compatible with
  • Useful solvents may be ethers which are cyclic, e.g. , tetrahydrofuran, or which have the formula ROR, in which R is an alkyl group preferably having 2 to 6 carbon atoms .
  • an aryl boronic acid triester is synthesized at a temperature of -10°C to
  • the Grignard aryl (Ar) groups may be substituted at one, some, or all available positions by any halogen (chlorine, bromine, fluorine or iodine) , or by any straight or branched chain, substituted or unsubstituted alkyl group, or by any functional group compatible with or protected by standard methods to be compatible with the Grignard function.
  • Phenyl, 4-fluorophenyl and naphthyl groups are typical Grignard aryl groups .
  • the alkyl borate reactant (B (OR 3 ) ) is preferably used in an amount greater than stoichiometric with respect to the ArMgX reagent. For example, from about 1.1 to 2.0, preferably about 1.5 moles, of B(OR 3 ) may be used for each mole of ArMgX.
  • Each of the R groups may be any alkyl group.
  • Appropriate R groups have one to ten carbon atoms .
  • R is preferably methyl .
  • the hydrolysis of the aryl boronic acid diester (equation 2) may be performed in known manner, e.g., by combining a mineral acid, preferably aqueous H 2 S0 4 , directly with the Grignard reaction mixture: ArB(OR) 2 +H 2 S0 4(aq) > ArB (OH) 2 +2ROH (2)
  • EXAMPLE 1 (General Example) The Grignard reagent is prepared in known manner in an appropriate ethereal solvent, preferably at the greatest concentration resulting in a solution.
  • a flask of appropriate size to accommodate the reaction volume as well as the volume of the aqueous acid hydrolysis solution is set up under a sweep of inert atmosphere and equipped for reflux and cooling.
  • Trialkyl borate e.g., trimethyl borate diluted with an equal weight of an ethereal solvent, preferably THF, is charged to the lask in an amount to provide a mole ratio of ArMgX:B (0CH 3 ) 3 of 1:1.5.
  • the flask is cooled with dry ice:acetone to -10°C and addition of Grignard reagent begun, wherein a reaction mixture containing an aryl borate dialkyl ester is produced.
  • the reaction mixture Upon completion of the Grignard addition, the reaction mixture is stirred to room temperature (1-2 hours) .
  • the dialkyl ester is hydrolyzed in situ by directly adding a 10% w/v H 2 S0 4 aqueous solution in an amount equal to 2 mole H 2 S0 4 with vigorous stirring for 30 minutes .
  • the reaction mixture is then allowed to settle for 30 minutes .
  • the hydrolysis reaction mixture forms an upper organic layer and a lower aqueous layer.
  • the organic layer is separated, and then dried over sodium sulfate.
  • Solvent is distilled until solids begin to precipitate. Hexanes are added, and the precipitated product collected by filtration.
  • reaction flask was charged with trimethyl borate (1.5 moles, 155.7g) and tetrahydrofuran (300g) .
  • the mixture was cooled to a temperature of -5°C to 0°C.
  • One mole of phenyl magnesium bromide was added slowly with maintenance of the temperature between -5°C and 0°C.
  • the reaction mixture was stirred for thirty minutes .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
PCT/US1999/013105 1998-06-10 1999-06-10 Synthesis of aryl boronic acids WO1999064428A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2000553436A JP2002517503A (ja) 1998-06-10 1999-06-10 アリール硼酸の合成
NZ502612A NZ502612A (en) 1998-06-10 1999-06-10 Synthesis of aryl boronic acids
CA002297780A CA2297780A1 (en) 1998-06-10 1999-06-10 Synthesis of aryl boronic acids
EP99930198A EP1064286A1 (en) 1998-06-10 1999-06-10 Synthesis of aryl boronic acids
AU46786/99A AU4678699A (en) 1998-06-10 1999-06-10 Synthesis of aryl boronic acids

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9451198A 1998-06-10 1998-06-10
US09/094,511 1998-06-10

Publications (1)

Publication Number Publication Date
WO1999064428A1 true WO1999064428A1 (en) 1999-12-16

Family

ID=22245595

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/013105 WO1999064428A1 (en) 1998-06-10 1999-06-10 Synthesis of aryl boronic acids

Country Status (6)

Country Link
EP (1) EP1064286A1 (ja)
JP (1) JP2002517503A (ja)
AU (1) AU4678699A (ja)
CA (1) CA2297780A1 (ja)
NZ (1) NZ502612A (ja)
WO (1) WO1999064428A1 (ja)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1285924A1 (de) * 2001-08-21 2003-02-26 Clariant GmbH Verfahren zur Herstellung von Aryl- und Alkyl-Bor-Verbindungen in Mikroreaktoren
GB2415193A (en) * 2004-06-19 2005-12-21 F2 Chemicals Ltd Fluorinated arylboronic acids
US7507262B2 (en) 2006-03-07 2009-03-24 The Procter & Gamble Company Compositions for oxidatively dyeing keratin fibers and methods for using such compositions
WO2010094406A1 (de) 2009-02-17 2010-08-26 Bayer Cropscience Aktiengesellschaft Aminopyrimidinamide als schädlingsbekämpfungsmittel
EP2266973A1 (de) 2009-05-29 2010-12-29 Bayer CropScience AG Pyrazinylpyrazole
EP2275422A1 (de) 2006-12-20 2011-01-19 Bayer CropScience AG Pyrimidinylpyrazole als insektizide und parasitizide Wirkstoffe
EP2374791A1 (de) 2008-08-14 2011-10-12 Bayer CropScience Aktiengesellschaft Insektizide 4-Phenyl-1H-pyrazole
CN104119367A (zh) * 2014-07-09 2014-10-29 中国科学技术大学苏州研究院 一种芳基硼酸的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2898365A (en) * 1956-12-05 1959-08-04 American Potash & Chem Corp Process for manufacture of areneboronic acids

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2898365A (en) * 1956-12-05 1959-08-04 American Potash & Chem Corp Process for manufacture of areneboronic acids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SEAMAN W., JOHNSON J. R.: "DERIVATIVES OF PHENYLBORIC ACID, THEIR PREPARATION AND ACTION UPON BACTERIA.", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, US, vol. 53., 1 February 1931 (1931-02-01), US, pages 711 - 723., XP002919981, ISSN: 0002-7863, DOI: 10.1021/ja01353a039 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1285924A1 (de) * 2001-08-21 2003-02-26 Clariant GmbH Verfahren zur Herstellung von Aryl- und Alkyl-Bor-Verbindungen in Mikroreaktoren
GB2415193A (en) * 2004-06-19 2005-12-21 F2 Chemicals Ltd Fluorinated arylboronic acids
US7507262B2 (en) 2006-03-07 2009-03-24 The Procter & Gamble Company Compositions for oxidatively dyeing keratin fibers and methods for using such compositions
US7678158B2 (en) 2006-03-07 2010-03-16 The Procter & Gamble Company Compositions for oxidatively dyeing keratin fibers and methods for using such compositions
EP2275422A1 (de) 2006-12-20 2011-01-19 Bayer CropScience AG Pyrimidinylpyrazole als insektizide und parasitizide Wirkstoffe
EP2374791A1 (de) 2008-08-14 2011-10-12 Bayer CropScience Aktiengesellschaft Insektizide 4-Phenyl-1H-pyrazole
WO2010094406A1 (de) 2009-02-17 2010-08-26 Bayer Cropscience Aktiengesellschaft Aminopyrimidinamide als schädlingsbekämpfungsmittel
EP2246335A1 (de) 2009-02-17 2010-11-03 Bayer CropScience AG Aminopyrimidinamide als Schädlingsbekämpfungsmittel
US8202877B2 (en) 2009-02-17 2012-06-19 Bayer Cropscience Ag Aminopyrimidinamides as pesticides
EP2266973A1 (de) 2009-05-29 2010-12-29 Bayer CropScience AG Pyrazinylpyrazole
US8513260B2 (en) 2009-05-29 2013-08-20 Bayer Cropscience Ag Pyrazinylpyrazoles
CN104119367A (zh) * 2014-07-09 2014-10-29 中国科学技术大学苏州研究院 一种芳基硼酸的制备方法

Also Published As

Publication number Publication date
CA2297780A1 (en) 1999-12-16
AU4678699A (en) 1999-12-30
EP1064286A1 (en) 2001-01-03
NZ502612A (en) 2001-06-29
JP2002517503A (ja) 2002-06-18

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