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WO1990009975A1 - Oxydation d'aldehydes - Google Patents

Oxydation d'aldehydes Download PDF

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Publication number
WO1990009975A1
WO1990009975A1 PCT/GB1990/000313 GB9000313W WO9009975A1 WO 1990009975 A1 WO1990009975 A1 WO 1990009975A1 GB 9000313 W GB9000313 W GB 9000313W WO 9009975 A1 WO9009975 A1 WO 9009975A1
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WO
WIPO (PCT)
Prior art keywords
aldehyde
substituent
process according
carboxylic acid
aromatic
Prior art date
Application number
PCT/GB1990/000313
Other languages
English (en)
Inventor
Alexander Mckillop
Duncan Kemp
Original Assignee
Interox Chemicals Limited
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 Interox Chemicals Limited filed Critical Interox Chemicals Limited
Publication of WO1990009975A1 publication Critical patent/WO1990009975A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered

Definitions

  • the present invention relates to the oxidation of aldehydes, and more specifically to the oxidation of aromatic aldehydes to the corresponding carboxylic acids
  • oxidising systems that were not only widely available, storage stable, easy to handle and relatively cheap, but would also perform the desired reaction under mild conditions.
  • oxidants such as permanganate or dichro ate may be employed, but they inevitably introduce toxic materials, thereby creating waste disposal problems.
  • n represents an interger from 1 to 3
  • the or each X represents hydrogen or an electron-withdrawing substituent or a mildly electron-donating substituent that is ortho, meta or para to the aldehyde substituent or a strongly electron-donating substituent that is meta to the aldehyde substituent, provided that at least one ortho position is occupied by hydrogen, is brought into contact with an alkali metal perborate and acetic acid at a mild temperature and permitted to react until at least a proportion of the aldehyde has been oxidised to the corresponding aromatic carboxylic acid.
  • the substituent X it will be recognised, conveniently can be chosen from a very wide range of substituents, thereby demonstrating the inherent usefulness and widespread applicability of the instant invention process.
  • it can be chosen from halo, aldehyde, nitrilo, carboxylic acid, nitro, thioalkyl, alkyl or alkoxy substituents.
  • the halo group can be fluoro, chloro, bromo or iodo group, and the alkyl or thioalkyl preferably contains only a small number of carbon atoms.
  • the substituent can also comprise a nitrogen hetero-atom within the aromatic nucleus or in a yet further variation the benzene nucleus can be replaced by a di or poly-cyclic aromatic nucleus in which the aldehyde substituent is located at the 2 carbon atom.
  • present invention encompasses the oxidation of those aromatic aldehydes that are substituted by a plurality of non-aldehyde substituents, such as two or three.
  • a plurality of such substituents each can each be the same as or different from the other or others. It is most advantageous to so array them as to minimise or eliminate steric hindrance effects.
  • Suitable examples include di-halo benzaldehydes and 3,5-dimethoxy benzaldehyde.
  • the present invention process relates specifically to compounds in which the aldehyde group is a direct and immediate substituent of the aromatic nucleus. It does not extend to the oxidation of saturated aliphatic aldehydes, demonstrated by n-butanal and n-heptanal, or to aromatic compounds in which one or more aliphatic carbons are interposed between the nucleus and the aldehyde, such as phenylacetaldehyde or 2,2-diphenyl cetaldehyde.
  • the alkali perborate is particularly conveniently a sodium perborate on account of the bulk availability and excellent storage and handling properties of the two industrially available products sodium perborate monohydrate and sodium perborate tetrahydrate, which have respectively the empirical formulae NaB ⁇ 3.H 2 0 and aB ⁇ 3.4H 2 0, though these do not properly represent the structure of the compounds.
  • a particularly safe way comprises introducing it progressively, such as in small portions or continuously during an introductory period, either at or below the desired reaction temperature.
  • the invention reaction conditions permit the oxidation of the aldehyde to be effected using only a small excess of perborate beyond the stoichiometric amount of 1 mole per mole of aldehyde.
  • a mole ratio for perborateraldehyde selected in the range of from 1:1 to 2:1 and particularly from 1.1:1 to 1.5:1.
  • the reaction medium particularly conveniently comprises glacial acetic acid.
  • concentration of substrate in the reaction medium can be selected within a very wide range, for example from 0.1M to a saturated solution.
  • concentration of substrate in the reaction medium can be selected within a very wide range, for example from 0.1M to a saturated solution.
  • concentration of substrate in the reaction medium can be selected within a very wide range, for example from 0.1M to a saturated solution.
  • concentration of substrate in the reaction medium can be selected within a very wide range, for example from 0.1M to a saturated solution.
  • millid temperature in the context of the present reaction is meant that there is no need to maintain a high temperature during the reaction or even approach closely reflux temperature for the medium. In many instances, it is convenient to employ a temperature that is above ambient, and preferably above 40 & C, up to about 70°C. Very effective oxidations have been achieved in the region of or around 45 to 50°C throughout the reaction period.
  • the precise mechanism for the present invention is open to discussion at present. It is speculated that there may be some mode or modes of interaction between the perborate oxidant and the reaction medium which can result in the generation in situ of one or more active species that is or are resposible for the effective oxidation reaction. It will be recognised, though, that the present invention stands by virtue of its demonstrated results and not by the truth or otherwise of any particular point of speculation.
  • the total reaction period will usually be determined in practice by taking into account the reaction temperature and the substrate and will often include a period during which perborate is introduced and a subsequent period in which the reaction is allowed to progress.
  • the perborate introduction period is often chosen within the range of 10 to 60 minutes.
  • the subsequent period is often chosen in the range of from 15 minutes to 10 hours and for many of the substrates in the range of from 15 minutes to 120 minutes.
  • Some reaction can occur whilst the perborate is being introduced so that the total reaction period is often selected in the range of from 30 minutes to 10 hours, and for many substrates from 30 to to 150 minutes.
  • the presence of an electron-withdrawing substituent tends to enable a shorter reaction period to be selected and an electron-donating substituent tends to demand a longer reaction period.
  • the reaction can be monitored, for example by thin layer chromatography and recovery of the product commenced when the monitoring indicates that either a desired proportion of the substrate has been converted to the product, or the reaction rate has slowed thereby indicating that little further product could be obtained.
  • reaction periods can be gauged in small scale trials and refined in bulk-scale operation.
  • the invention process is particularly suitable for a batch style reaction procedure, but it will be recognised that by a suitable choice of reactor design such a tubular once through reactor, it is a practical proposition to carry out the reaction continuously, especially for those substrates that employ a relatively short reaction period.
  • the product can be recovered from the reaction mixture by-removal of at least part of the reaction medium and preferably all of it, such as by evaporation, preferably under reduced pressure, and subsequent addition of water to the residue, thereby causing formation of a solid product.
  • a suitable amount of water is often chosen in the range of 10 to 100 parts w/w per part of substrate.
  • the solid can then be separated using conventional solid/liquid separating techniques such as centrifugation, filtration or settling.
  • the aqueous residue comprises a saturated solution of the product. Accordingly, a further amount of product can be recovered by subsequently contacting the aqueous residue with a low molecular weight aliphatic ester such as ethyl acetate or a similar solvent having low boiling point and low miscibility with water, separating the two phases and removing the solvent, such as by evaporation, preferably under reduced pressure.
  • a convenient ratio of stripping solvent to aqueous residue is often chosen in a total v/v ratio of 1:1 to 3:1.
  • the conventional techniques of solvent stripping, viz continuous co- or counter-current contact or multiple batch contact are applicable.
  • product losses can be reduced additionally to the solvent stripping technique or alternatively instead of that technique by recycling the aqueous residue, either before or after its contact with the above-mentioned solvent, in place of at least a fraction of the water that is added to the reaction mixture residue in an early phase of the product recovery.
  • the acetic acid was removed from the reaction mixture by evaporation under reduced pressure and water, 50 mis, added to the residue.
  • the solid which separated out, crude product was recovered by filtration, and dried in air.
  • the - filtrate was contacted with ethyl acetate, 3 x 25 mis portions, and the combined organic phase was dried with anhydrous magnesium sulphate, and evaporated under reduced pressure, thereby precipitating a further amount of crude product.
  • the two crude products were combined, dried and recrystallised to provide the yield given in the Table, which is the molar percentage of purified carboxylic acid product, based on the substrate present initially. The identity of the product was subsequently confirmed by melting point comparison with the reading given in the literature and by infra red spectral analysis.

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

Abstract

Procédé permettant l'oxydation d'aldéhydes aromatiques par un aldéhyde ayant la formule générale (1) où n est un nombre entier entre 1 et 3, et X ou chaque X est hydrogène ou un substituant preneur d'électrons ou un substituant légèrement donneur d'électrons qui est ortho, méta ou para pour le substituant d'aldéhyde, ou un substituant fortement donneur d'électrons qui est méta pour le substituant d'aldéhyde, à condition qu'une position ortho au moins soit occupée par l'hydrogène. L'aldéhyde en question est mis en contact avec un perborate de métal alcalin et un acide acétique à une température modérée et la réaction se poursuit jusqu'à ce qu'une partie au moins de l'aldéhyde s'oxyde en un acide carboxylique aromatique correspondant.
PCT/GB1990/000313 1989-03-02 1990-02-28 Oxydation d'aldehydes WO1990009975A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8904798.9 1989-03-02
GB898904798A GB8904798D0 (en) 1989-03-02 1989-03-02 Aldehyde oxidation

Publications (1)

Publication Number Publication Date
WO1990009975A1 true WO1990009975A1 (fr) 1990-09-07

Family

ID=10652607

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1990/000313 WO1990009975A1 (fr) 1989-03-02 1990-02-28 Oxydation d'aldehydes

Country Status (2)

Country Link
GB (1) GB8904798D0 (fr)
WO (1) WO1990009975A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5866723A (en) * 1991-09-25 1999-02-02 Monsanto Company Benzoyl derivatives and synthesis thereof
US5869688A (en) * 1994-07-20 1999-02-09 Monsanto Company Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity
US5883263A (en) * 1996-06-20 1999-03-16 Monsanto Company Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1793671A1 (de) * 1965-04-21 1972-03-30 Rhone Poulenc Sa Verfahren zur Herstellung von phenolischen Verbindungen
DE2252674A1 (de) * 1972-10-27 1974-05-09 Bayer Ag Verfahren zur herstellung von aldehyden aus olefinen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1793671A1 (de) * 1965-04-21 1972-03-30 Rhone Poulenc Sa Verfahren zur Herstellung von phenolischen Verbindungen
DE2252674A1 (de) * 1972-10-27 1974-05-09 Bayer Ag Verfahren zur herstellung von aldehyden aus olefinen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
The Merck Index, 10th Edition, 1983, Merck & Co., Inc., (Rahway, US), see page 1239, Item No. 8492,: "Sodium Perborate" *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5866723A (en) * 1991-09-25 1999-02-02 Monsanto Company Benzoyl derivatives and synthesis thereof
US5869688A (en) * 1994-07-20 1999-02-09 Monsanto Company Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity
US5973164A (en) * 1994-07-20 1999-10-26 Monsanto Company Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity
US5986104A (en) * 1994-07-20 1999-11-16 Monsanto Company Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity
US6121458A (en) * 1994-07-20 2000-09-19 Monsanto Company Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity
US5883263A (en) * 1996-06-20 1999-03-16 Monsanto Company Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity
US5900489A (en) * 1996-06-20 1999-05-04 Monsanto Company Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity
US5910596A (en) * 1996-06-20 1999-06-08 Monsanto Company Esterification of benzoic acid substituents of 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity
US5969153A (en) * 1996-06-20 1999-10-19 Monsanto Company Preparation of substituted 3-aryl-5-haloalkyl-pyrazoles having herbicidal activity

Also Published As

Publication number Publication date
GB8904798D0 (en) 1989-04-12

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