EP1349876A1 - Procede d'oxydation d'alcools primaires - Google Patents

Procede d'oxydation d'alcools primaires

Info

Publication number
EP1349876A1
EP1349876A1 EP01270556A EP01270556A EP1349876A1 EP 1349876 A1 EP1349876 A1 EP 1349876A1 EP 01270556 A EP01270556 A EP 01270556A EP 01270556 A EP01270556 A EP 01270556A EP 1349876 A1 EP1349876 A1 EP 1349876A1
Authority
EP
European Patent Office
Prior art keywords
oxidation
process according
primary
substrate
oxidant
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP01270556A
Other languages
German (de)
English (en)
Inventor
Petter Bragd
Arie Cornelis Besemer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Essity Nederlands BV
Original Assignee
SCA Hygiene Products Zeist BV
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 SCA Hygiene Products Zeist BV filed Critical SCA Hygiene Products Zeist BV
Priority to EP01270556A priority Critical patent/EP1349876A1/fr
Priority claimed from PCT/NL2001/000903 external-priority patent/WO2002048197A1/fr
Publication of EP1349876A1 publication Critical patent/EP1349876A1/fr
Withdrawn legal-status Critical Current

Links

Definitions

  • the invention relates to the selective oxidation of primary alcohols, using an oxidising agent in the presence of a catalytic amount of a di-tertiary-alkyl nitroxyl compound, especially 2,2,6,6-tetramethylpiperidin- 1 -oxyl (TEMPO) .
  • TEMPO 2,2,6,6-tetramethylpiperidin- 1 -oxyl
  • TEMPO cyclic and/or di-tert-alkyl nitroxyls
  • Doxyl 4,4-dimethyloxazolidine-N-oxyl
  • Proxy 2,2,5,5-tetramethylpyrrolidine-N-oxyl
  • 4-hydroxy-TEMPO and derivatives thereof, especially 4-acetamido TEMPO, and those described in WO 95/07303 can be substituted for TEMPO.
  • the catalytic amount of nitroxyl is preferably 0.1-10%, more preferably 0.2-3% by weight, based on the primary alcohol, or 0.1-10 mol% (0.2-3%) with respect to the primary alcohol.
  • the peroxosulphate present in the process of the invention serves for regenerating TEMPO.
  • the peroxosulphate may be a straight peroxomonosulphate, MHSO 5 , M 2 SO 5 or the persulphuric acid H 2 SO 5 , wherein M is an alkali metal or other metal (taking account of its valency in the formula), ammonium or substituted ammonium.
  • M is an alkali metal or other metal (taking account of its valency in the formula), ammonium or substituted ammonium.
  • the peroxosulphate is Oxone® (2KHSO 5 .KHSO 4 .K 2 SO 4 ), which is commercially available. It is not necessary and not recommended to use any halogen, as a co-oxidant.
  • the amount of peroxosulphate is equivalent to the amount of primary hydroxyl groups to be oxidised. If complete oxidation of -CH 2 OH groups to carboxyl groups -COOH is desired, 2 - 2.4 moles of peroxosulphate per mol of primary hydroxyl groups is advantageously used.
  • the process of the invention results in oxidation of primary alcohols initially to the corresponding aldehydes, and eventually to the corresponding carboxylic acids.
  • the second oxidation step from aldehyde to carboxylic acid, proceeds at a faster rate than the first step, i.e. the oxidation from alcohol to aldehyde.
  • the maximum fraction of aldehyde functions present will be below about 10 (based on the number of primary hydroxyls available for oxidation).
  • the present process is especially favourable for the selective oxidation of primary hydroxyl groups in alcohols having a secondary alcohol function in addition to the primary alcohol, such as 1,6-octanediol, 1,9-octadecanediol, sugar alcohols, glycosides, and in particular carbohydrates having primary alcohol functions, especially polysaccharides having chain lengths of at least 5 anhydroglycose units, such as glucans (starch, cellulose), furano- fructans, galactans, (galacto)mannans, and the like.
  • a particular group of compounds suitable for oxidation with the present process are hydroxyalkylated, especially hydroxyethylated carbohydrates such as hydroxyethyl starch or hydroxyethyl inulin. These derivatives result in an alternative way for producing formylmethyl and carboxymethyl carbohydrates.
  • Potato starch (3.0 g, 18.5 mmol anhydroglucose units) was gelatinised in demi- water (200 ml) at 95°C with effective mechanical stirring.
  • 4-Acetamido-TEMPO (61 mg, 0.29 mmol) was added and dissolved.
  • the solution was cooled on ice and the temperature was maintained ⁇ 10°C throughout the reaction.
  • the reaction was initiated by the addition of Oxone (11.38 g, 2 mol HSO 5 7mol primary alcohol), which was added under mechanical stirring in small portions throughout the oxidation to minimise unwanted side reactions.
  • pH was raised to 8.2 and then kept constant by the addition of 0.5 M NaOH using a pH stat apparatus.
  • Example 2 Methyl ⁇ -D-glucopyranoside (1.0 g, 5.1 mmol) and 4-acetamido-TEMPO (20 mg, 0.09 mmol) were dissolved in water (50 ml). The solution was cooled on ice and the temperature was maintained at ⁇ 10°C throughout the reaction. The reaction was initiated by the addition of Oxone (3.17 g, 2 mol HSO 5 7mol primary alcohol), which was added in small portions under mechanical stirring throughout the oxidation to minimise unwanted side reactions. After each addition of the acidic oxidant, pH was raised to 8.2 and then kept constant by the addition of 0.5 M NaOH using a pH stat apparatus.
  • Oxone 3.17 g, 2 mol HSO 5 7mol primary alcohol
  • Amylopectin (waxy starch maize) (3.0 g, 18.5 mmol anhydroglucose units) was gelatinised in demi-water (200 ml) at 95°C with effective mechanical stirring. 4-Acetamido-TEMPO (61 mg, 0.29 mmol) was added and dissolved. The reaction was initiated by the addition of Oxone (11.38 g, 2 mol HSO 5 7mol primary alcohol), which was added under mechanical stirring in small portions throughout the oxidation to minimise unwanted side reactions. The reaction procedure was identical to that in Example 1. The conversion of the primary hydroxyls to carboxyls was estimated by C NMR to be 58 mol%.

Abstract

Selon l'invention, on peut sélectivement oxyder des groupes hydroxyles primaires dans un substrat comportant à la fois des groupes hydroxyles primaires et secondaires pour obtenir un carbaldéhyde et/ou des groupes carboxyles, en mettant en contact le substrat avec un composé nitroxyle cyclique en présence d'un peroxosulfate utilisé comme cooxydant et en menant la réaction à 30 °C avec un pH inférieur à 9. Ce procédé est exempt d'halogène et de métal et convient particulièrement à l'oxydation de polysaccharides.
EP01270556A 2000-12-13 2001-12-12 Procede d'oxydation d'alcools primaires Withdrawn EP1349876A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01270556A EP1349876A1 (fr) 2000-12-13 2001-12-12 Procede d'oxydation d'alcools primaires

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP00204483 2000-12-13
EP00204483 2000-12-13
US25589900P 2000-12-18 2000-12-18
US255899P 2000-12-18
EP01270556A EP1349876A1 (fr) 2000-12-13 2001-12-12 Procede d'oxydation d'alcools primaires
PCT/NL2001/000903 WO2002048197A1 (fr) 2000-12-13 2001-12-12 Procede d'oxydation d'alcools primaires

Publications (1)

Publication Number Publication Date
EP1349876A1 true EP1349876A1 (fr) 2003-10-08

Family

ID=28045905

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01270556A Withdrawn EP1349876A1 (fr) 2000-12-13 2001-12-12 Procede d'oxydation d'alcools primaires

Country Status (1)

Country Link
EP (1) EP1349876A1 (fr)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0248197A1 *

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