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
  • C07D211/68—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 one double bond between ring members or between a ring member and a non-ring member
  • C07D211/72—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 one double bond between ring members or between a ring member and a non-ring member 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
  • C07D211/74—Oxygen atoms
  • C07D211/76—Oxygen atoms attached in position 2 or 6
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
  • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D207/24—Oxygen or sulfur atoms
  • C07D207/26—2-Pyrrolidones
  • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
  • C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D207/36—Oxygen or sulfur atoms
  • C07D207/40—2,5-Pyrrolidine-diones
  • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
  • C07D207/408—Radicals containing only hydrogen and carbon atoms attached to ring carbon atoms
• • 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
  • C07D211/80—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 two double bonds between ring members or between ring members and non-ring members
  • C07D211/84—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 two double bonds between ring members or between ring members and non-ring members 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
  • C07D211/86—Oxygen atoms
  • C07D211/88—Oxygen atoms attached in positions 2 and 6, e.g. glutarimide

Definitions

• the present invention relates to a process for preparing lactams from cyclic imide compounds.
• Lactams are cyclic amides well known to those skilled in the art.
• Lactams can be prepared, for example, by cyclization of an amino acid such as lysine. They can also be prepared by reacting an aminonitrile with water in the presence of a catalyst to effect cyclizing hydrolysis of the aminonitrile to lactam.
• Lactams are used in various fields, and in particular in the manufacture of polyamides.
• the lactams can also be used as plasticizers or as solvents, for example for N-alkyl lactams such as NMP, or as intermediates for syntheses of pharmaceutical and agrochemical products.
• Heterogeneous catalytic reactions are the most commonly used catalysis reactions and involve the use of a non-soluble catalyst in the reaction medium; it can therefore easily be recovered.
• the catalyst is generally supported on an inert support.
• WO2005 / 0501907 describes the preparation of N-methyl-pyrrolidone by hydrogenation of N-methyl succinimide in the presence of a catalyst soluble in the reaction medium.
• the catalyst used is Ruthenium bound to a phosphine-type organic ligand, in particular Ru-acethylacetonate is used as a precursor. This type of ligand has health and environmental disadvantages;
• the present invention also aims to provide lactams with satisfactory yields, especially greater than 50%, and preferably greater than 75%, or even 80% or 90%.
• the present invention relates to a process for the preparation of lactam, by hydrogenation of at least one compound of formula (I) below:
• A represents a radical of formula ( ⁇ ) or ( ⁇ ) following:
• R 1, R 2 and R 3 represent independently of each other H, OH, an alkyl radical or a cycloalkyl radical,
• Ri and R 2 can be connected together to form with the carbon atoms which carry them an aliphatic ring comprising from 4 to 6 carbon atoms;
• R 2 and R 3 may be connected together to form with the carbon atoms which carry them an aliphatic ring comprising from 4 to 6 carbon atoms;
• R represents H or a linear or branched alkyl radical comprising from 1 to 20, preferably from 1 to 10, preferably from 1 to 4, carbon atoms; said process being carried out at a pressure of less than 60 bar, preferably from 10 bar to 50 bar, in the presence of a solid hydrogenation catalyst, comprising at least two metals selected from the group of noble metals and transition metals , and an inert substance as a carrier; said compound of formula (I) may be alone or in admixture.
• lactam denotes cyclic amides which may be represented by the following formula (II):
• R being as defined above in formula (I) and A 'representing a radical of formula Ri, R 2 and R 3 being as defined above in formulas ( ⁇ ) and ( ⁇ ).
• the "alkyl” radicals represent straight or branched chain saturated hydrocarbon radicals comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms (they can typically be represented by the formula C n H 2n + i, where n is the number of carbon atoms). Mention may in particular be made, when they are linear, the methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl and decyl radicals.
• alkyl radicals When they are branched or substituted by one or more alkyl radicals, mention may be made especially of the isopropyl, tert-butyl, 2-ethylhexyl, 2-methylbutyl, 2-methylpentyl, 1-methylpentyl and 3-methylheptyl radicals.
• cycloalkyl radical is a saturated, nonaromatic, saturated mono-, bi- or tricyclic hydrocarbon radical preferably comprising 5 or 6 carbon atoms, such as in particular cyclopentyl or cyclohexyl.
• the process according to the invention can be carried out for a compound of formula (I) alone or for a mixture of different compounds of formula (I).
• the compound subjected to the hydrogenation step may be a mixture of compounds of formula (I), with A and / or R being different.
• the process of the invention consists of hydrogenating one of the carbonyl functions of imide (I).
• the starting compound may be represented by the following formula:
• these two compounds may be the same or different.
• the lactam obtained can be a mixture of several compounds, i.e. position isomers.
• the product obtained is a mixture of positional isomers.
• A corresponds to the formula ( ⁇ ) or ( ⁇ ) as defined above.
• the lactam obtained will be in the form of a mixture comprising the isomers of position, it is that is to say a mixture of lactams obtained by the hydrogenation of each of the carbonyl functions.
• the lactam obtained will be in the form of a mixture comprising the position isomers, that is to say a mixture of lactams obtained by the hydrogenation of each of the carbonyl functions.
• R 1 or R 3 is an alkyl radical (the other two being H), or R 1, R 2 and R 3 are alkyl radicals, R- ⁇ and R 3 being different, either R 1 and R 2 are alkyl radicals (R 3 being H), which are identical or different, or R 2 and R 3 are alkyl radicals (R 1 being H), which are identical or different, or R 1 and R 2; 3 are different alkyl radicals (R 2 being H), then the lactam obtained will be in the form of a mixture comprising the position isomers, that is to say a mixture of lactams obtained by the hydrogenation of each of the functions carbonyls.
• the hydrogenation process according to the invention is carried out in the absence of a solvent.
• This embodiment makes it possible to work in a more concentrated environment. Such a process makes it possible to be more competitive on an industrial level.
• the process is less energy consuming and generates less effluents related to the presence of solvent compared to solvent processes.
• the hydrogenation process according to the invention is carried out in the liquid phase.
• the process of the invention can therefore be carried out in conventional hydrogenation reactors.
• the starting imide compound, subjected to the hydrogenation process may be a single compound or a mixture of several compounds of formula (I) as defined above.
• the imide compounds of the process of the invention are compounds of formula (I), in which A corresponds to the formula ( ⁇ ) or ( ⁇ ) as defined above, each of R- ⁇ , R 2 and R 3 representing H or an alkyl radical, especially (CrC 4 ) alkyl.
• A is a radical of formula -CH 2 -CH 2 -CH (R ') -, R' representing a radical (CC 4 ) alkyl, and preferably methyl or ethyl.
• group A As specific examples of group A according to the invention, mention may be made of ethylene (-CH 2 -CH 2 -) or propylene (-CH 2 -CH 2 -CH 2 -), or else 1-methylpropylene (-CH 2 -CH 2 -CH (CH 3 ) -).
• radicals will be chosen: ethylene (-CH 2 -CH 2 -), propylene (-CH 2 -CH 2 -CH 2 -), ethyl-ethylene (-CH (and ) -CH 2 -), 1-methylpropylene (-CH 2 -CH 2 -CH (CH 3 ) -) and mixtures thereof.
• A represents a radical -CH 2 -CH 2 -CH (CH 3 ) -.
• R is H or Me.
• R is H.
• the present invention therefore also relates to the preparation of lactams by the hydrogenation of a mixture of compounds of formula (I).
• the invention relates to the preparation of lactams by the hydrogenation of a mixture comprising the following compounds:
• the present invention therefore also relates to a process as defined above, for preparing a mixture of lactams of formulas (11-5) and (11-6) as follows:
• the present invention also relates to a process as defined above, for preparing a mixture of lactams of formulas (11-1) and (II-2) as follows:
• R ' represents a radical (C 1 -C 4 ) alkyl, and preferably methyl or ethyl.
• the present invention also relates to a process as defined above, for preparing a mixture of lactams of formulas (II-3) and (II):
• the starting imide of formula (I) may be methylglutarimide (MGI) obtained from methylglutaronitrile (MGN), or from a mixture of dinitriles resulting from the method of manufacture of adiponitrile by double hydrocyanation of butadiene.
• MGN methylglutaronitrile
• This mixture preferably corresponds to the distillation fraction making it possible to separate the branched dinitriles (2-methylglutaronitrile, ethylsuccinonitrile) from adiponitrile.
• This mixture of dinitriles generally has the following composition by weight:
• 2-methylglutaronitrile between 70% and 95%, preferably between 80% and 85%;
• 2-ethylsuccinonitrile between 5% and 30%, preferably between 8% and 12%;
• adiponitrile between 0% and 10%, preferably between 1% and 5%, the 100% complement corresponding to different impurities.
• the starting imide of formula (I), especially in the case of methylglutarimide (MGI), can be obtained from methylglutaronitrile (MGN), or from a mixture of dinitriles such as described above, for example according to a reaction method of MGN or the mixture of dinitriles with an acid, as described in the international application WO201 1/144619. It can also be obtained by a hydrolysis method in the presence of water of the MGN or the dinitrile mixture, which corresponds to the first step of the process described for example in the international application WO2009 / 056477.
• the process of the invention is carried out at a pressure of less than 60 bar, preferably less than 50 bar, in order to avoid the hydrogenation of the two carbonyl functions, which would make it impossible to obtain lactams.
• the process of the invention is carried out at a pressure ranging from 10 bar to 50 bar, and preferably at a pressure ranging from 10 to 40 bar, in particular from 20 to 40 bar, and preferably equal to 20 bar. bar.
• the pressure is from 20 to 25 bar.
• the process of the invention thus makes it possible to work at low pressures, which is particularly advantageous from an industrial point of view.
• the process of the invention is carried out at a temperature higher than the melting temperature of the imides.
• the hydrogenation is carried out at a temperature greater than or equal to 105 ° C., and preferably below 230 ° C.
• the hydrogenation is carried out at a temperature ranging from 150 ° C. to 220 ° C., and preferably equal to 200 ° C.
• the process of the invention is carried out in the presence of a solid hydrogenation catalyst.
• solid hydrogenation catalyst refers to any solid catalyst well known to those skilled in the art for catalyzing hydrogenation reactions.
• This catalyst may be free or fixed on an inert support, in particular on charcoal, silica or alumina.
• the hydrogenation catalyst used in the context of the invention comprises a mixture of metals selected from the group of noble metals and transition metals, and optionally an inert substance as a support.
• the hydrogenation catalyst used in the context of the invention comprises a mixture of two or three metals selected from the group of noble metals and transition metals, and optionally an inert substance as a support.
• the hydrogenation catalyst comprises an inert substance bearing the metals as defined above.
• the catalyst according to the invention may comprise a support on which a mixture of metals is supported or may be a mixture of several metals, each of the metals being able to be supported independently of one another.
• non-noble metals refers to a metal that is resistant to corrosion and oxidation. Among these metals, mention may be made of gold, silver and platinum.
• the term "transition metals" refers to those elements which have an incomplete d-sublayer or which may give a cation having an incomplete d-sublayer. In the context of the present invention, this term refers to elements which are not noble metals.
• the transition metals are chosen from the elements of columns 3 to 12, with the exception of lutetium and lawrencium.
• the hydrogenation catalyst as defined above comprises two metals M1 and M2, each of the metals being able to be supported independently of one another or the M1 + M2 mixture being able to be supported.
• M1 is supported by an inert substance S1 and M2 is supported by an inert substance S2, S1 and S2 being two distinct supports, of identical or different nature.
• the hydrogenation catalyst can also be designated as a catalyst mixture.
• the mixture formed by metals M1 and M2 is supported by a single inert substance S1.
• the hydrogenation catalyst may be a mixture of two metals selected from the group consisting of ruthenium, platinum, palladium, iridium and rhodium, said mixture being supported by an inert substance , especially coal.
• the hydrogenation catalyst comprises, supported by charcoal, ruthenium mixed with a metal selected from the group consisting of platinum, palladium, iridium and rhodium.
• the hydrogenation catalyst may be in the form of a mixture comprising ruthenium supported by carbon and another metal as defined above, supported by coal.
• the hydrogenation catalyst comprises a mixture of ruthenium and palladium, said mixture being supported by coal.
• the mass content of catalyst is preferably from 1% to 10% relative to the total weight of compound (s) of formula (I).
• the mass content of catalyst corresponds to the mass content of the assembly formed by the metal and the support if it is present.
• the mass content of catalyst is 5% relative to the total weight of compound (s) of formula (I).
• the catalyst is a mixture of ruthenium and palladium supported on charcoal, comprising from 2% to 7% of ruthenium and from 0.5% to 1.5% of palladium relative to the total mass. of the catalyst, the bulk complement corresponding to the carbon support.
• the catalyst is a mixture of ruthenium and palladium supported on charcoal, comprising 5% ruthenium, 1% palladium and 94% coal based on the total weight of the catalyst.
• the examples which follow make it possible to further illustrate the invention without limiting it.
• reaction medium is then analyzed by gas chromatography.
• N-methyl-3-methylglutarimide N-Me-MGI
• the reaction medium is then analyzed by gas chromatography.
• the conversion of N-methyl-MGI is 40% and the mixture yield of the two lactams is 29%.
• N-octyl-3-methylglutarimide N-Oc-MGI
• the reaction medium is then analyzed by gas chromatography.
• the MGI conversion is 32% and the mixture yield of the two lactams is 25%.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Hydrogenated Pyridines (AREA)
• Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Other In-Based Heterocyclic Compounds (AREA)
• Pyrrole Compounds (AREA)

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• 2012
  • 2012-04-27 FR FR1253946A patent/FR2989971B1/fr not_active Expired - Fee Related
• 2013
  • 2013-04-25 BR BR112014026874A patent/BR112014026874A2/pt not_active IP Right Cessation
  • 2013-04-25 US US14/395,994 patent/US20150051401A1/en not_active Abandoned
  • 2013-04-25 KR KR1020147033196A patent/KR20150003885A/ko not_active Application Discontinuation
  • 2013-04-25 EP EP13719504.6A patent/EP2841420A1/fr not_active Withdrawn
  • 2013-04-25 WO PCT/EP2013/058591 patent/WO2013160389A1/fr active Application Filing
  • 2013-04-25 JP JP2015507530A patent/JP2015521162A/ja active Pending
  • 2013-04-25 CN CN201380022043.3A patent/CN104284889A/zh active Pending
  • 2013-04-25 SG SG11201406494QA patent/SG11201406494QA/en unknown

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