Method for production of methionine from homoserine
View Patent ↗The invention relates to a method for production of D- and/or L-methionine via D- and/or L-homoserine with subsequent chemical transformation to give methionine.
1. A method for producing L-methionine, D-methionine or a mixture of L— and D-methionine starting from homoserine, comprising converting L-homoserine, D-homoserine or mixtures of L- and D-homoserine of the formula I:
to methionine by chemical transformation, without passing through any of the intermediates N-carbamoylhomoserine, 4—(2-bromoethyl)hydantoin and 4—(2-methyl-thioethyl)hydantoin; wherein the chemical transformation of L—and/or D-homoserine is carried out in a manner that comprises:
a) using an acylating agent to produce N-acyl-L—and/or D-homoserine lactone of the formula VIII:
where R is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tertbutyl, phenyl, mono-, di- or trihaloalkyl, where halogen=F or Cl, CF 3 or CCl 3 , benzyloxycarbonyl or C 1 — to C 4 -alkyloxycarbonyl,
b) reacting the N-acylhomoserine lactone obtained in step a) with MeSH in the presence of a basic or acid catalyst to give N-acylmethionine of formula VII:
c) hydrolyzing the N-acylmethionine obtained in step b) at temperatures of >95° C. to give methionine.
2. The method of claim 1 , wherein said method is used to produce L-methionine from L-homoserine.
3. The method of claim 1 , wherein said method is used to produce D-methionine from D-homoserine.
4. The method of claim 1 , wherein R is hydrogen.
5. The method of claim 1 , wherein R is methyl, ethyl or n-propyl.
6. The method of claim 1 , wherein, in step a), said acylating agent is of the general formula R—CO—X 1 , where X 1 can be R 1 COO, OR 2 (R 2 = methyl or ethyl), Cl, Br, and R and R 1 can be identical or different and are selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, mono-, di- or trihaloalkyl, where halogen=F or Cl, CF 3 or CCl 3 , benzyloxycarbonyl, or C 1 - to C 4 - alkyloxycarbonyl, preferably tert-butyloxycarbonyl, or methyloxycarbonyl.
7. The method of claim 6 , wherein R and R 1 are hydrogen.
8. The method of claim 6 , wherein R and R 1 are selected from the group consisting of methyl, ethyl, n-propyl.
9. The method of claim 6 , wherein X 1 is R 1 COO.
10. The method of claim 6 , wherein X 1 is OR 2 .
11. The method of claim 1 , wherein, the reaction in step b) is carried out in the presence of a basic catalyst selected from the group consisting of: NaOH; KOH; pyridine; trimethylamine; triethylamine; or an acetate, carbonate or hydrogencarbonate of an alkali metal or alkaline earth metal; tertiary amines having a maximum of 36 carbon atoms and 1 to 4 nitrogen atoms, tetra(C 1 —C 4 -alkyl)guanidine, bicyclic amines, preferably DBU (1,8-diazobicyclo[5.4.0]undec-7-ene) and TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene), and pyridine.
12. The method of claim 1 , wherein, the reaction in step b) is carried out in the presence of a strongly alkaline ion-exchange resin.
13. The method of claim 1 , wherein, the reaction in step b) is carried out in the presence of a Brönstedt acid selected from the group consisting of: HCl, HBr, HI, H 2 SO 4 , alkali metal HSO 4 , H 3 PO 4 , alkali metal H 2 PO 4 , where alkali metal is lithium, sodium, potassium, rubidium or cesium, polyphosphoric acid, C 1 —C 12 -alkylsulphonic acid, C 6 —C 10 -arylsulphonic acid, trifluoromethanesulphonic acid, trifluoroacetic acid, or a copolymer of tetrafluoroethylene and perfluoro-3,6-dioxo-4-methyl-7-octenesulphonic acid (Nafion).
14. The method of claim 1 , wherein, the reaction in step b) is carried out in the presence of a Lewis acid selected from the group consisting of: AlCl 3 , ZnCl 2 , BF 3 ·OEt 2 , SnCl 2 , and FeCl 3 .
15. The method of claim 1 , wherein the reaction in step b) is carried out in the presence of a strongly acidic ion-exchange resin.
16. The method of claim 1 , wherein, the reaction in step b) is carried out in the presence of a heterogeneous acid catalyst selected from the group consisting of:
(WO 3 - and Cs 2 O)-containing aluminium oxide, zeolite and montmorrillonite.
17. The method of claim 1 , wherein the reaction in step b) is carried out in solution and/or in suspension in an organic solvent.
18. The method claim 1 , wherein said the reaction in step b) is carried out in a solution and/or suspension in the presence of water and/or an organic solvent selected from the group consisting of: C 3 to C 6 ketones; straight-chain or branched C 1 to C 4 alcohols; C 4 to C 10 carboxylic esters; C 3 to C 6 carboxamides; C 6 to C 10 aromatics; and
C 3 to C 7 cyclic carbonates.
19. The method of claim 1 , wherein said method utilizes only homoserine having an L configuration and produced by fermenting bacteria of the genus Corynebacterium or Escherichia.
20. The method of claim 1 , wherein said method utilizes only homoserine having a D configuration and produced by fermenting bacteria of the genus Corynebacterium or Escherichia.