WO2001096277A1 - Procede de production d'acide 2,3,4,6-tetramethylmandelique et d'acetate d'acide 2,3,4,6-tetramethylmandelique - Google Patents

Procede de production d'acide 2,3,4,6-tetramethylmandelique et d'acetate d'acide 2,3,4,6-tetramethylmandelique Download PDF

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Publication number
WO2001096277A1
WO2001096277A1 PCT/EP2001/006381 EP0106381W WO0196277A1 WO 2001096277 A1 WO2001096277 A1 WO 2001096277A1 EP 0106381 W EP0106381 W EP 0106381W WO 0196277 A1 WO0196277 A1 WO 0196277A1
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WO
WIPO (PCT)
Prior art keywords
acid
tetramethylbenzene
glyoxylic acid
isodurol
tetramethylmandelic
Prior art date
Application number
PCT/EP2001/006381
Other languages
German (de)
English (en)
Inventor
Thomas Himmler
Original Assignee
Bayer Aktiengesellschaft
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 Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU67524/01A priority Critical patent/AU6752401A/en
Publication of WO2001096277A1 publication Critical patent/WO2001096277A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
    • C07C69/157—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds

Definitions

  • the present invention relates to a new process for the preparation of 2,3,4,6-
  • 2,3,4,6-tetramethylmandelic acid is known (Chem. Ber. 20 (1887) 3097-3104; J. Amer. Chem. Soc. 61 (1939) 3246-3249). They are produced either by Friedel-Crafts acylation of 1,2,3,5-tetramethylbenzene (isodurol) to give 2,3,4,6-
  • Tetramethylacetophenone its oxidation to isodurylglyoxylic acid with potassium permanganate and subsequent reduction with sodium amalgam (Chem. Ber. 20 (1887) 3097-3104); or by Friedel-Crafts acylation of 1,2,3,5-tetramethylbenzene (isodurol) to 2,3,4,6-tetramethylacetophenone, its oxidation to the isodurylglyoxal with selenium dioxide and conversion to 2,3,4,6- Tetramethylmandelic acid with
  • mandelic acids substituted on the aromatic can be prepared in such a way that the aromatic is reacted with glyoxylic acid or glyoxylic acid hydrate in the presence of a base or acid.
  • the reactions are preferably carried out in the presence of a base when a phenol is reacted with glyoxylic acid or glyoxylic acid hydrate as the substituted aromatic.
  • EP-A-023 459 it is known from EP-A-023 459 that the reaction of 4-methylphenol (p-cresol) with glyoxylic acid in dilute aqueous sodium hydroxide solution leads to 2-hydroxy-5-methyl-mandanic acid.
  • 2,3,4,6-tetramethylmandelic acid can thus be prepared by an analogous reaction of 1,2,3,5-tetramethylbenzene (isodurol) with glyoxylic acid or glyoxylic acid hydrate.
  • 1,2,3,5-tetramethylbenzene is not commercially available in large (technically relevant) quantities.
  • 1,2,3,5-tetramethylbenzene (isodurol) is only available in a mixture with 1,2,4,5-tetramethylbenzene (Durol).
  • other alkyl aromatics may also be present in a mixture; called his here for example dimethyl ethyl benzenes.
  • the properties of these various alkyl aromatics (boiling point; melting point) are so similar to one another that separation is not possible or is possible only with disproportionate effort.
  • R represents hydrogen or a radical -CO-R
  • R 2 represents methyl, ethyl or propyl
  • Tetramethylbenzene which may contain other alkyl aromatics such as dimethyl ethyl benzenes, optionally in the presence of a solvent and a catalyst at a temperature between 0 and 100 ° C with 0.5 to 1.75 mol of glyoxylic acid or glyoxylic acid hydrate per mole of 1,2,3,5-tetramethylbenzene (isodurol).
  • R represents a radical -CO-R 2
  • R 2 represents methyl, ethyl or propyl
  • Preferred compounds of the formula (I) are the compounds of the formula (Ia)
  • R represents hydrogen or a radical -CO-CH 3 ,
  • Glyoxylic acid for selective alkylation by the process according to the invention can be used, for example, as a commercially available 50% aqueous solution or as a glyoxylic acid hydrate. If a 50% aqueous solution of glyoxylic acid is used, enough water can be distilled off, if necessary, with a suitable solvent so that the residual water content corresponds to that of the monohydrate. However, it is also possible to use the 50% aqueous solution.
  • the amount of glyoxylic acid or glyoxylic acid hydrate to be used by the process according to the invention is based on the amount of 1,2,3,5-tetramethylbenzene (isodurol), which, such as for example, dimethyl ethyl benzene is calculated. 0.5 to 1.75 mol of glyoxylic acid or glyoxylic acid hydrate are used per mol of 1,2,3,5-tetramethylbenzene (isodurol).
  • the inventive method can be carried out at temperatures between 0 and 100 ° C.
  • the amount of glyoxylic acid or glyoxylic acid hydrate to be used by the process according to the invention per mole of 1,2,3,5-tetramethylbenzene can depend on the reaction temperature and the following preferred combinations result: 1.4 to 1.75 moles of glyoxylic acid or glyoxylic acid hydrate per mole 1, 2,3,5-tetramethylbenzene at 30 to 50 ° C, or 0.8 to 1.3 moles of glyoxylic acid or glyoxylic acid hydrate per mole of 1,2,3,5-tetramethylbenzene at 10 to 90 ° C.
  • Particularly preferred combinations are 1.45 to 1.75 mol of glyoxylic acid or glyoxylic acid hydrate per mole of 1,2,3,5-tetramethylbenzene at 35 to 50 ° C., or 0.9 to 1.25 mol of glyoxylic acid or glyoxylic acid hydrate per mole 1, 2,3,5-tetramethylbenzene at 20 to 60 ° C. At high molar ratios, the dependence on the temperature is therefore more pronounced.
  • Acids can typically be used as catalysts for the reaction of 1,2,3,5-tetramethylbenzene (isodurol), which is present in a mixture with 1,2,4,5-tetramethylbenzene (durol) and optionally further alkyl aromatics such as dimethyl ethyl benzene such as sulfuric acid, hydrochloric acid or p-toluenesulfonic acid can be used.
  • the acids can be used in amounts of 0.1 to 200 mole percent, based on the amount of glyoxylic acid or glyoxylic acid hydrate used. Amounts of 1 to 180 mole percent are preferred; Amounts of 5 to 150 mole percent are particularly preferred.
  • suitable solvents for the process according to the invention are carboxylic acids such as formic acid, acetic acid, propionic acid, etc., mixtures of these solvents or mixtures of these solvents with water.
  • Acetic acid or propionic acid are preferred; acetic acid is particularly preferred.
  • the reaction usually takes place under normal pressure, but in principle it can also be carried out under elevated or reduced pressure.
  • reaction times of the process according to the invention are between 1 and 24 hours.
  • Phenylacetic acid derivatives are important precursors for active substances in crop protection or are used as pharmaceutical active substances (cf. WO 97/36868).
  • reaction mixture is heated and stirred at 105 to 110 ° C for 15 hours.
  • the reaction mixture is then mixed with 500 ml of ice water and extracted once with 200 ml and three times with 100 ml of methylene chloride.
  • the combined organic phases are dried over sodium sulfate and concentrated in vacuo. This gives 67.6 g of a viscous oil which, according to GC / MS (after silylation), has the following composition (area%):

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

Abstract

La présente invention concerne un nouveau procédé de production d'acide 2,3,4,6-tétraméthylmandélique et d'acétate d'acide 2,3,4,6-tétraméthylmandélique, par réaction d'un mélange constitué de 1,2,3,5-tétraméthylbenzène (isodurène) et de 1,2,4,5-tétraméthylbenzène (durène) avec 0,5 à 1,75 moles d'acide glyoxylique ou d'hydrate d'acide glyoxylique par mole de 1,2,3,5-tétraméthylbenzène (isodurène), à une température située entre 0 et 100 DEG C.
PCT/EP2001/006381 2000-06-15 2001-06-05 Procede de production d'acide 2,3,4,6-tetramethylmandelique et d'acetate d'acide 2,3,4,6-tetramethylmandelique WO2001096277A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU67524/01A AU6752401A (en) 2000-06-15 2001-06-05 Method for producing 2,3,4,6-tetramethyl mandelic acid and 2,3,4,6-tetramethyl mandelic acid acetate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10029413.8 2000-06-15
DE2000129413 DE10029413A1 (de) 2000-06-15 2000-06-15 Verfahren zur Herstellung von 2,3,4,6-Tetramethylmandelsäure und 2,3,4,6-Tetramethylmandelsäureacetat

Publications (1)

Publication Number Publication Date
WO2001096277A1 true WO2001096277A1 (fr) 2001-12-20

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PCT/EP2001/006381 WO2001096277A1 (fr) 2000-06-15 2001-06-05 Procede de production d'acide 2,3,4,6-tetramethylmandelique et d'acetate d'acide 2,3,4,6-tetramethylmandelique

Country Status (3)

Country Link
AU (1) AU6752401A (fr)
DE (1) DE10029413A1 (fr)
WO (1) WO2001096277A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010069525A1 (fr) 2008-12-19 2010-06-24 Bayer Cropscience Ag Pyridazinone substituée en 4 par un phényle, à activité herbicide et insecticide
WO2011035878A1 (fr) 2009-09-25 2011-03-31 Bayer Cropscience Ag Pyridazinones à activité herbicide substitués par un phényle
WO2011045271A1 (fr) 2009-10-15 2011-04-21 Bayer Cropscience Ag Pyridazinones à substitution hétérocyclyle, à effet herbicide
WO2012028582A1 (fr) 2010-09-01 2012-03-08 Bayer Cropscience Ag Cétosultames et dicétopyridines herbicides

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023459A1 (fr) * 1979-07-25 1981-02-04 SOCIETE FRANCAISE HOECHST Société anonyme dite: Procédé de préparation d'acides hydroxyarylglycoliques racémiques

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023459A1 (fr) * 1979-07-25 1981-02-04 SOCIETE FRANCAISE HOECHST Société anonyme dite: Procédé de préparation d'acides hydroxyarylglycoliques racémiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FUSON ET AL.: "1,2-Diacylethylene Glycols", J. AMER. CHEM. SOC., vol. 61, 1939, pages 3246 - 3249, XP001021797 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010069525A1 (fr) 2008-12-19 2010-06-24 Bayer Cropscience Ag Pyridazinone substituée en 4 par un phényle, à activité herbicide et insecticide
EP2204366A1 (fr) 2008-12-19 2010-07-07 Bayer CropScience AG Pyridazinones substitués par phényle agissant en tant qu'herbicide et insecticide
WO2010078912A1 (fr) 2008-12-19 2010-07-15 Bayer Cropscience Ag Pyridazinones à substitution phényle à effet herbicide et insecticide
WO2011035878A1 (fr) 2009-09-25 2011-03-31 Bayer Cropscience Ag Pyridazinones à activité herbicide substitués par un phényle
WO2011045271A1 (fr) 2009-10-15 2011-04-21 Bayer Cropscience Ag Pyridazinones à substitution hétérocyclyle, à effet herbicide
WO2012028582A1 (fr) 2010-09-01 2012-03-08 Bayer Cropscience Ag Cétosultames et dicétopyridines herbicides

Also Published As

Publication number Publication date
AU6752401A (en) 2001-12-24
DE10029413A1 (de) 2001-12-20

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