EP3405452A1 - Procédé de préparation d'analogues de la méthionine - Google Patents

Procédé de préparation d'analogues de la méthionine

Info

Publication number
EP3405452A1
EP3405452A1 EP17706536.4A EP17706536A EP3405452A1 EP 3405452 A1 EP3405452 A1 EP 3405452A1 EP 17706536 A EP17706536 A EP 17706536A EP 3405452 A1 EP3405452 A1 EP 3405452A1
Authority
EP
European Patent Office
Prior art keywords
compound
alkyl group
group
alkyl
formula
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Withdrawn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
EP17706536.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Robert Huet
Vivien Henryon
Jérôme MONBRUN
Etienne AIRIAU
Sylvain AUBRY
Patrick Rey
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.)
Adisseo France SAS
Original Assignee
Adisseo France SAS
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 Adisseo France SAS filed Critical Adisseo France SAS
Publication of EP3405452A1 publication Critical patent/EP3405452A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/22—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by oxygen atoms
    • 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
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/02—Thiols having mercapto groups bound to acyclic carbon atoms
    • C07C321/04—Thiols having mercapto groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/15—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/04—Sodium compounds

Definitions

  • the present invention relates to a process for preparing analogs of methionine, as well as to the selenium derivatives of methionine analogs, from abundant and accessible compounds derived from biomass.
  • Methionine and its analogs such as 2-hydroxy-4-methylthiobutanoic acid (HMTBA) and 2-oxo-4-methylthiobutane acid (KMB), as well as salts, chelates, especially metal chelates (from Zn, Ca, M n, Mg, Cu, Na ...) and esters of these acids, such as isopropyl and tert-butyl esters of H MTBA, are widely used in animal nutrition.
  • the selenium derivatives of methionine and its hydroxyanalogues are also constituents of major interests in animal nutrition.
  • this process makes it possible to prepare a compound or one of its salts, said compound corresponding to formula I,
  • R 1 represents H or a C1-C6 alkyl group
  • R 2 represents H, a C 1 -C 6 alkyl group, or an alkylaryl group
  • R 3 is CH 2 SR 4 or CH 2 SeR 4 with R 4 is H or an alkyl group
  • R 1 , R 2 and X are as defined above;
  • R 5 represents H or COOR 6 with R 6 represents H or a C 1 -C 6 alkyl group.
  • R 7 with R 7 represents H, a C 1 -C 6 alkyl group or an acyl group of formula CO-R 4 with R 4 as defined above; SR 4 or SeR 4 with R 4 as defined above; or NR 8 R 9 , with R 8 and R 9 , which may be identical or different, represent, each or together, a C 1 -C 6 alkyl group, or an alkylaryl group;
  • Z which is the same or different from Y, represents OR 10 with R 10 represents H; a C 1 -C 6 alkyl group, or CO-R 4 with R 4 as defined above; a group N (COR 4 ) (COR 4 ), cyclic or acyclic, with R 4 as defined above; or a group NR 1: L R 12 , with R 11 and R 12 , which are identical or different, represent, each or together, a C 1 -C 6 alkyl group or an alkylaryl group;
  • reaction of the compound (IV) with R 4 SH or one of its salts, or R 4 SeH or one of its salts, with R 4 according to the preceding definition, already present in the reaction medium or added during the process may lead to a compound having the structure (V) F ⁇ OOC-AMBKHF ⁇ -CHZZ (V)
  • A represents OH; HN-R 'where R' is H or a C1-C6 alkyl group; or HN-OR "where R” is H, a C1-C6 alkyl group, or an alkylaryl group; and
  • B represents SR 4 or SeR 4 with R 4 as defined above.
  • alkyl denotes a monovalent hydrocarbon radical linear or branched having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, such as methyl ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, ⁇ -hexyl or a monovalent cyclic hydrocarbon radical containing from 3 to 20 carbon atoms, advantageously from 3 to 6 carbon atoms, such as cyclopropyl, cyclohexyl.
  • alkylaryl group is meant an aryl group comprising from 6 to 20 carbon atoms, said aryl group being substituted by at least one alkyl group as defined above.
  • a first route preferably consists in reacting a compound (II) with formaldehyde or paraformaldehyde, in hydrated form or otherwise, in a basic medium and in the presence of MeSH or of one of its salts, such as sodium salts. , potassium or calcium methylmercaptan.
  • a second route comprises reacting a compound (II) with a compound (III), said compound (III) being chosen from 1 - [(methylsulfanyl) methyl] - piperidine, 1 - [(methylsulfanyl) methyl] pyrrolidine and 1 - [(methylsulfanyl) methyl] diethylamine.
  • This second route leads to an intermediate compound that can be isolated or not, which is an object of the present invention.
  • This compound has the following formula (V):
  • R 1 represents H or a C 1 -C 6 alkyl group
  • R 2 represents H, a C 1 -C 6 alkyl group, or an alkylaryl group
  • A represents OH; HN-R 'where R' is H or a C1-C6 alkyl group; or HN-OR “or R” represents H or a C1-C6 alkyl group or an alkylaryl group;
  • B is SR 4 or SeR 4 with R 4 is H or C 1 -C 6 alkyl
  • Z is OR with R is H; a C1-C6 alkyl group; a CO-R 4 group with R 4 represents H or a C 1 -C 6 alkyl group; a group N (COR 4 ) (COR 4 ), cyclic or acyclic, with R 4 as defined above; or NR 1: L R 12 , with R 11 and R 12 , identical or different, represent, each or together, a C 1 -C 6 alkyl group, or an alkylaryl group.
  • the second route advantageously involves oxaloacetic acid or an ester thereof, that is to say a compound of formula (II) in which X represents 0, R 2 represents H and R 5 represents C0 2 R 6 with R 6 is H or C1-C6 alkyl, with a compound of formula (III) type CH 2 (Y) (Z) wherein Y and Z respectively represent the group SCH 3 and the group NR 1: L R 12 as defined above; preferably the NR 1 group : L R 12 represents the piperidinyl group.
  • the invention therefore also relates to the compound of formula (V) in which A represents OH, B represents SCH 3 , R 2 represents H and Z represents the piperidinyl group.
  • X is selected from 0; N-R 'where R' is H or a C1-C6 alkyl group; and N-OR "wherein R" represents H, a C1-C6 alkyl group, or an aryl group;
  • R 1 represents H or a C1-C6 alkyl group
  • R 2 represents H, a C 1 -C 6 alkyl group, or an alkylaryl group
  • Z is NR 8 R 9 , with R 8 and R 9 , which are the same or different, each represent together or together a C 1 -C 6 alkyl group or an alkylaryl group.
  • a compound of formula (III) in which Y and Z respectively represent the group NR 8 R 9 and the group NR 1: L R 12 as defined previously.
  • at least one of NR 8 R 9 and NR 1: L R 12 but more preferably both, represent the same piperidinyl group.
  • the invention relates to the intermediate compound of formula (IV) in which X represents O, R 2 represents H and Z represents the piperidinyl group, R 1 being as defined above, namely H when the compound (II) is oxaloacetic acid or a C1-C6 alkyl group when the compound (II) is the corresponding ester of oxaloacetic acid.
  • the compound (II) is advantageously chosen from oxaloacetic acid and pyruvic acid.
  • the process of the invention makes it possible to obtain different analogs of methionine.
  • 2-oxo-4-methylthiobutanoic acid (KMB) or one of its salts, such as its calcium, magnesium, manganese, copper, zinc, sodium or ammonium salts and its corresponding selenium or one of its salts are products of the process of the invention under economically interesting conditions and yields.
  • Another subject of the invention is a process of D, L-methionine, D- or L-methionine, D, L-2-hydroxy-4-methylthiobutanoic acid (HMTBA), or D- or L- -HMTBA, starting from 2-oxo-4-methylthiobutanoic acid (KMB), said process comprising the preparation of KMB according to the process of the invention as defined above and then converting the KMB thus obtained into methionine or HMTBA, chemically or biologically, by techniques known to those skilled in the art.
  • HMTBA 2-oxo-4-methylthiobutanoic acid
  • reaction medium is cooled to 10 ° C. and then the MeSH is added by bubbling into the reaction medium at 10 ° C. until the required amount (1 eq). The addition is completed in 4 hours then the set temperature is raised to 20 ° C. The reaction medium is stirred for 3h this temperature.
  • a GC-FID control (column Equity-1) indicates that the conversion of piperidine is complete and the RRdose in species "thiomethyl activated" is 97%.
  • reaction medium is withdrawn and then concentrated under reduced pressure (1mbar, 20 ° C., 6 h).
  • KM B piperidinium is obtained as a yellow oil without further purification.
  • Step 2 Condensation with pyruvic acid 0 2 C .piperidinium
  • reaction medium is cooled to 20 ° C. and the solvent is then evaporated under reduced pressure (10 °, 20 ° C., 1 h) to give (IV) as a pale yellow oil (1.2 g).
  • the MeSH gas is introduced in Iesel (via a syringe pump).
  • the reaction medium is then heated to 60 ° C in 1 hour and then this temperature is maintained for 30 minutes.
  • HPLC control indicates a complete transformation of the intermediate and the majority formation of KM B piperidinium.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogenated Pyridines (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
EP17706536.4A 2016-01-18 2017-01-17 Procédé de préparation d'analogues de la méthionine Withdrawn EP3405452A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1650366A FR3046791B1 (fr) 2016-01-18 2016-01-18 Procede de preparation d'analogues de la methionine
PCT/FR2017/050096 WO2017125673A1 (fr) 2016-01-18 2017-01-17 Procédé de préparation d'analogues de la méthionine

Publications (1)

Publication Number Publication Date
EP3405452A1 true EP3405452A1 (fr) 2018-11-28

Family

ID=56263788

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17706536.4A Withdrawn EP3405452A1 (fr) 2016-01-18 2017-01-17 Procédé de préparation d'analogues de la méthionine

Country Status (12)

Country Link
US (1) US20200283387A1 (zh)
EP (1) EP3405452A1 (zh)
JP (1) JP2019503380A (zh)
KR (1) KR20180101481A (zh)
CN (1) CN108779064A (zh)
AR (1) AR107581A1 (zh)
BR (1) BR112018014391A2 (zh)
FR (1) FR3046791B1 (zh)
RU (1) RU2736212C2 (zh)
SG (1) SG11201806119VA (zh)
TW (1) TW201726613A (zh)
WO (1) WO2017125673A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845454A (zh) * 2020-06-28 2021-12-28 张科春 一种酮基蛋氨酸及其衍生物的制备方法及应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5731299A (en) * 1992-05-29 1998-03-24 The Procter & Gamble Company Phosphonosulfonate compounds, pharmaceutical compositions, and methods for treating abnormal calcium and phosphate metabolism
CN101921203A (zh) * 2009-06-09 2010-12-22 长江大学 N-苯氧苯基取代的α-氨基酸及其衍生物以及用作除草剂的用途
JP2012067073A (ja) * 2010-08-27 2012-04-05 Sumitomo Chemical Co Ltd 含硫黄２−ケトカルボン酸化合物の製造方法
JP2013075885A (ja) * 2011-09-16 2013-04-25 Sumitomo Chemical Co Ltd メチオニンの製造方法
TWI633089B (zh) * 2013-03-28 2018-08-21 拜耳製藥股份有限公司 經取代的酮基吡啶衍生物

Also Published As

Publication number Publication date
FR3046791B1 (fr) 2020-01-10
US20200283387A1 (en) 2020-09-10
AR107581A1 (es) 2018-05-16
FR3046791A1 (fr) 2017-07-21
JP2019503380A (ja) 2019-02-07
SG11201806119VA (en) 2018-08-30
RU2736212C2 (ru) 2020-11-12
TW201726613A (zh) 2017-08-01
BR112018014391A2 (pt) 2018-12-11
KR20180101481A (ko) 2018-09-12
RU2018126611A (ru) 2020-02-20
WO2017125673A1 (fr) 2017-07-27
CN108779064A (zh) 2018-11-09
RU2018126611A3 (zh) 2020-02-28

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