EP0423182A1 - Oxydation von epoxyalkoholen in epoxycarbonsäuren - Google Patents

Oxydation von epoxyalkoholen in epoxycarbonsäuren

Info

Publication number
EP0423182A1
EP0423182A1 EP89907770A EP89907770A EP0423182A1 EP 0423182 A1 EP0423182 A1 EP 0423182A1 EP 89907770 A EP89907770 A EP 89907770A EP 89907770 A EP89907770 A EP 89907770A EP 0423182 A1 EP0423182 A1 EP 0423182A1
Authority
EP
European Patent Office
Prior art keywords
epoxy
water
alcohol
organic solvent
moles
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Withdrawn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
EP89907770A
Other languages
English (en)
French (fr)
Inventor
Jean-Pierre Genet
Dominique Pons
Sylvain Juge
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.)
Societe National Elf Aquitaine
Societe Nationale Elf Aquitaine Production SA
Original Assignee
Societe National Elf Aquitaine
Societe Nationale Elf Aquitaine Production SA
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 Societe National Elf Aquitaine, Societe Nationale Elf Aquitaine Production SA filed Critical Societe National Elf Aquitaine
Publication of EP0423182A1 publication Critical patent/EP0423182A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals

Definitions

  • the present invention relates to the preparation of epoxy carboxylic acids. It is in particular based on the oxidation in liquid medium of alcohols carrying an epoxy bridge.
  • the process of this invention is in particular useful for obtaining acidic epoxies of relatively low molecular masses, very soluble in water , whose industrial recovery of the aqueous medium is generally difficult.
  • epoxidized acids, with aliphatic chain, in C 3 to C 10 , and particularly in C 3 to C 5 are favorably amenable to the process of one invention.
  • Epoxy carboxylic acids have various industrial applications, in particular for the synthesis of different derivatives of acids, esters or corresponding salts. Thus, for example, are they used for the synthesis of compounds of biological interest, such as amino acids, pheromones, antibiotics etc.
  • the invention provides a marked advantage in that it makes it possible to obtain, from an optically active alcohol, an epoxy-acid, without loss of the desired chirality for the continuation of the synthesis.
  • the invention allows easy and economical recovery of epoxidized acids from their preparation medium. This recovery takes place by the evaporation of an organic solvent, more volatile than the acid prepared, in which this acid is found at the end of the preparation.
  • the process according to the invention which consists in oxidizing epoxy alcohols, in a medium containing an organic solvent and water, by means of an oxidizing compound, in the presence of a catalyst based on a salt of ruthenium, is characterized eh that the proportion of water is sufficiently low compared to that of organic solvent, so that at least a large part of the oxidant is in the solid state in the reaction medium, heterogeneous.
  • the various salts of the oxygenated anions of halogens may be suitable, such as hypo-chlorites, hypo-bromites, chlorites, bromites, iodites, chlorates, bromates, iodates, perbromates or alkaline, alkaline-earth and periodate , those of Zn, Al, Fe, etc.
  • Preferred oxidants are hypochlorites and periodates of Na, K or Ca.
  • the catalysts used in the process of the invention are salts of Ru and in particular RuCl 3 .
  • An important characteristic of the invention is a water content of the reaction medium not exceeding 20 moles H2O per mole of alcohol to be oxidized, the volume of organic solvent being greater than that of water, preferably at least double.
  • the preferred conditions, in this process, reside in a proportion of H 2 O of 0.2 to 20 moles per mole of alcohol, better still 0.5 to 5, and more particularly 1 to 2 moles. This is assured, while the volume of solvent is set to about 5 to 250 times that of water, and preferably 10 to 100 times.
  • H or C 1 to C 7 alkyl, and especially H, C 1 or C 2 , the acid formed can only be practically recovered by evaporation of the solvent, at the end of the reaction, if the content of H 2 O, in the reaction medium, is less than 20 moles H 2 O per mole of alcohol to be oxidized, and preferably does not exceed 2 moles H 2 O per mole of alcohol (compared to 166 moles in the aforementioned prior art) .
  • the process is preferably carried out with
  • oxidant per alcohol group to be oxidized 1.5 to 3 equivalents of oxidant per alcohol group to be oxidized; thus particularly suitable 1.5 to 3 moles NalO 4 or 0.75 to 1.5 moles Ca (ClO) 2 per group -OH, the oxidant being introduced in the form of a fine powder into the reaction mixture.
  • the amounts of oxidant per unit volume of total solvent + water are preferably of the order of 0.5 to 2 equivalents per liter, and especially from 0.7 to 1.5 eq / l.
  • the particularly advantageous catalyst, RuCl 3 can advantageously be used in an amount of 0.1 to 5% by weight of the reaction mixture.
  • the process of the invention can be practiced at various temperatures, in particular from -20o to + 80oC, preferably between 10o and 40oC, and especially between 20o and
  • the optimal duration depends on various factors, notably the nature of the alcohol treated, the temperature and the excess of oxidizing salt; most often, at room temperature, the appropriate reaction times are from 1 to 16 hours, and mainly from 2 to 12 hours.
  • the yield is improved and the duration of the operation can be shortened by the addition of a surfactant compound to the reaction medium.
  • a surfactant compound Generally about 0.1 to 1% by weight of surfactant is sufficient relative to the weight of the mixture.
  • the surfactant is chosen from those which do not contain an alcohol function; suitable, for example, compounds of the ether, sulphate or sulphonate type, such as polyoxyethylene fatty acid esters, in particular polyoxyethylene laurate or stearate (“NONISOLS”), Na dodecyl sulphate (“SDS”), alkane sulphonates of Na (petroleum, "PETRONATE HL”), alkyl-aryl sulfonates of Na, such as phenyl-octadecane sulfonate of Na, or lauryl benzene-sulfonate of Na, etc.
  • suitable for example, compounds of the ether, sulphate or sulphonate type,
  • the reaction mixture consists in each case of 0.01 mol (0.88 g) of in 20 ml of CCl 4 ,
  • the initial water content should not not exceed 1.46 moles per mole of epoxy-butyl alcohol.
  • Example 5 the Na metaperiodate is replaced by 1.5 equivalents of calcium hypochlorite Ca (ClO) 2 . After 5 hours at 25oC, the yield of epoxy-butyric acid is 76%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP89907770A 1988-07-01 1989-06-23 Oxydation von epoxyalkoholen in epoxycarbonsäuren Withdrawn EP0423182A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8808905 1988-07-01
FR8808905A FR2633620B1 (fr) 1988-07-01 1988-07-01 Oxydation d'epoxy-alcools en epoxy-acides carboxyliques

Publications (1)

Publication Number Publication Date
EP0423182A1 true EP0423182A1 (de) 1991-04-24

Family

ID=9367963

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89907770A Withdrawn EP0423182A1 (de) 1988-07-01 1989-06-23 Oxydation von epoxyalkoholen in epoxycarbonsäuren

Country Status (4)

Country Link
US (1) US5084582A (de)
EP (1) EP0423182A1 (de)
FR (1) FR2633620B1 (de)
WO (1) WO1990000167A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5252759A (en) * 1993-01-29 1993-10-12 Arco Chemical Technology, L.P. Process for producing optically active epoxy alcohol derivatives
DE4304756C1 (de) * 1993-02-17 1994-09-08 Hoechst Ag Verfahren zur Darstellung von Salzen, chiraler, alpha-sauerstoffunktionalisierter Carbonsäuren
FR2776292B1 (fr) * 1998-03-20 2004-09-10 Oncopharm Cephalotaxanes porteurs de chaine laterale et leur procede de synthese

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5116633A (en) * 1974-07-27 1976-02-10 Nisshin Flour Milling Co 22 hidorokishi 33 butensanjudotaino seizoho
FR2609032B1 (fr) * 1986-12-30 1990-01-05 Centre Nat Rech Scient Epoxydes fonctionnels enantiomeriquement purs, leur procede de preparation et leur application comme synthons chiraux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9000167A1 *

Also Published As

Publication number Publication date
FR2633620B1 (fr) 1992-02-21
US5084582A (en) 1992-01-28
WO1990000167A1 (fr) 1990-01-11
FR2633620A1 (fr) 1990-01-05

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