Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
  • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/40—Radicals substituted by oxygen atoms
  • C07D307/42—Singly bound oxygen atoms

Definitions

• the present invention relates to a method for producing a compound.
• it relates to a method for reductively aminating a formyl group of a carboxylic acid having a formyl group such as formylfurancarboxylic acid.
• Non-Patent Document 1 discloses the following reaction mechanism.
• An object of the present invention is to solve such problems by aminating a compound having a formyl group and a carboxyl group to produce an aminomethylcarboxylic acid compound while effectively suppressing the formation of by-products.
• the object is to provide a manufacturing method.
• a method for producing a compound represented by Formula (2) which comprises reacting a compound represented by Formula (1) with an ammonium salt.
• formula (2) HOOC- X1 - CH2NH2 (In formula (2), X 1 is a divalent organic group.)
• ⁇ 2> The production method according to ⁇ 1>, wherein X 1 in formulas (1) and (2) has an aromatic ring.
• ⁇ 7> The production method according to any one of ⁇ 1> to ⁇ 4>, wherein the ammonium salt contains ammonium acetate.
• ⁇ 8> The production method according to any one of ⁇ 1> to ⁇ 7>, wherein the reaction is performed in the presence of cobalt phosphide.
• ⁇ 9> The production method according to any one of ⁇ 1> to ⁇ 8>, wherein the reaction is performed in the presence of a solvent containing water.
• the reaction is performed in the presence of a solvent containing a compound represented by A-(OH)m (where A is a hydrocarbon group having 1 to 10 carbon atoms and m is 1 or 2).
• the production method according to any one of ⁇ 1> to ⁇ 9>.
• ⁇ 11> The production method according to ⁇ 10>, wherein m in the compound represented by A-(OH)m is 1.
• ⁇ 12> The production method according to ⁇ 10>, wherein the compound represented by A-(OH)m contains methanol.
• the reaction was performed in the presence of a solvent containing water and a compound represented by A-(OH)m (where A is a hydrocarbon group having 1 to 10 carbon atoms and m is 1 or 2).
• ⁇ 1> to ⁇ 12> wherein the volume ratio of water and the compound represented by A-(OH)m is more than 0 and 10 or less with respect to 1 water Production method.
• ⁇ 14> The production method according to any one of ⁇ 1> to ⁇ 13>, wherein the reaction is performed in the presence of a primary alkylamine.
• ⁇ 15> The production method according to ⁇ 14>, wherein the primary alkylamine is n-butylamine.
• ⁇ 16> The production method according to any one of ⁇ 1> to ⁇ 15>, wherein the compound represented by formula (3) is produced together with the compound represented by formula (2).
• Formula (3) HOOC- X1 - CH2OH (In formula (3), X 1 is a divalent organic group.)
• X 1 is a divalent organic group.
• Formula (3-1) ⁇ 18> A composition containing a compound represented by formula (2-1) and a compound represented by formula (3-1).
• Formula (2-1) Formula (3-1)
• an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• the notations that do not describe substituted and unsubstituted are preferably unsubstituted. If the standards shown in this specification differ from year to year in terms of measurement methods, etc., the standards as of January 1, 2021 shall be used unless otherwise specified.
• the method for producing the compound of the present embodiment is a method for producing the compound represented by Formula (2), including reacting the compound represented by Formula (1) with an ammonium salt.
• formula (2) HOOC- X1 - CH2NH2 (In formula (2), X 1 is a divalent organic group.)
• the compound represented by Formula (1) is a starting material for the reaction in the present embodiment.
• the compound represented by formula (1) is put into the reaction system, but it may be an intermediate using another compound as a starting material.
• X 1 in formula (1) is a divalent organic group, and at least one or two of an aliphatic group, an aromatic group, -O-, -NH- and -S- Groups consisting of combinations of one or more are preferred.
• X 1 preferably has an alicyclic ring or an aromatic ring, and more preferably has an aromatic ring.
• the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, preferably an aromatic heterocyclic ring.
• the aromatic ring is preferably a 5- or 6-membered ring, more preferably a 5-membered ring.
• the aromatic ring may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring.
• the aromatic hydrocarbon ring is preferably a benzene ring
• the aromatic heterocyclic ring includes a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, and a pyrimidine ring.
• a pyran ring, etc., and a furan ring is preferred.
• the substituent (substituent A) includes an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 1 carbon atom.
• aryloxy groups 1 to 10 aryloxy groups, arylthio groups having 1 to 10 carbon atoms, halogen atoms, hydroxyl groups or mercapto groups are exemplified, and alkyl groups having 1 to 10 carbon atoms, alkyloxy groups having 1 to 10 carbon atoms, halogen atoms or hydroxyl groups. child is preferred.
• the number of substituents is preferably 0-3, more preferably 0-2.
• an alicyclic or aliphatic heterocyclic ring such as a cyclohexane ring or a tetrahydrofuran ring.
• These rings may also have a substituent (substituent A) or a linking group, but preferably do not.
• the molecular weight of the compound represented by formula (1) is preferably 125 or more, and preferably 500 or less.
• the compound represented by formula (2) is the product compound. Usually, the compound represented by formula (2) is removed from the reaction system. However, compounds of formula (2) may also be intermediates for the preparation of other compounds.
• formula (2) HOOC- X1 - CH2NH2 (In formula (2), X 1 is a divalent organic group.) X 1 in formula (2) is the same as in formula (1).
• the compound represented by formula (1) is preferably the compound represented by formula (1-1).
• the compound represented by formula (2) is preferably the compound represented by formula (2-1).
• Formula (1-1) Formula (2-1)
• the compound represented by formula (3) may be produced together with the compound represented by formula (2). However, it is preferred that the product contains the compound of formula (2) and does not contain the compound of formula (3).
• Formula (3) HOOC- X1 - CH2OH (In formula (3), X 1 is a divalent organic group.) X 1 in formula (3) is the same as in formula (1). Further, the compound represented by formula (3) is preferably the compound represented by formula (3-1). Formula (3-1)
• the mass ratio (formula (2): Formula (3)) is preferably 99.9:0.1 to 50:50, more preferably 99.9:0.1 to 60:40, and 99.9:0.1 to More preferably 70:30, more preferably 99.9:0.1 to 80:20.
• the compound represented by formula (1) is reacted with an ammonium salt.
• an ammonium salt By reacting with an ammonium salt, the progress of side reactions of formyl groups can be effectively suppressed.
• the ammonium salt a salt obtained by neutralizing an organic acid or an inorganic acid with ammonia can be used.
• Ammonium salts of organic acids include ammonium carbonate, ammonium formate, ammonium acetate, ammonium propionate, ammonium butyrate, ammonium isobutyrate, ammonium oxalate, ammonium succinate, ammonium adipate, ammonium benzoate, and diammonium phthalate.
• ammonium salts of inorganic acids include ammonium phosphate, monoammonium phosphate, diammonium phosphate, ammonium borate, ammonium pentaborate, and ammonium tetraborate.
• ammonium salts of organic acids are preferable, and more preferably at least one selected from the group consisting of ammonium carbonate, ammonium formate, ammonium acetate, ammonium propionate, and ammonium butyrate, including ammonium acetate. is more preferred.
• the amount of the nitrogen source is preferably 1 mol or more, preferably 4 mol or more, relative to the raw material (1 mol of formyl group contained in the compound represented by formula (1)). may be 8 mol or more. Further, the amount of the nitrogen source is preferably 50 mol or less, may be 40 mol or less, or may be 30 mol or less per 1 mol of the raw material (compound represented by formula (1)). well, it may be 20 moles or less, or it may be 15 moles or less. In the production method of the present embodiment, one type of ammonium salt may be used, or two or more types may be used. When two or more are used, the total amount is preferably within the above range.
• the reaction is preferably allowed to proceed in the presence of a solvent.
• the mass ratio (raw material concentration) of the compound represented by formula (1) to the amount of solvent is preferably 0.1% by mass or more, even if it is 0.5% by mass or more. It may be 1.0% by mass or more, 1.5% by mass or more, or 2.0% by mass or more. By making it more than the said lower limit, there exists a tendency for reaction to become quick.
• the upper limit of the raw material concentration is not particularly limited, but if the raw material concentration increases, the raw material may not dissolve. % or less, 20 mass % or less, 15 mass % or less, or 9 mass % or less.
• only one kind of compound represented by formula (1) as a starting material may be used, or two or more kinds thereof may be used, but one kind is preferable. When two or more are used, the total amount is preferably within the above range.
• the reaction is preferably allowed to proceed under a solvent containing water. It is speculated that the inclusion of water in the solvent causes the ammonium salt to dissolve in water, promoting the reaction.
• a solvent containing a compound represented by A-(OH)m (where A is a hydrocarbon group having 1 to 10 carbon atoms and m is 1 or 2) It is preferable to proceed the reaction at .
• A-(OH)m where A is a hydrocarbon group having 1 to 10 carbon atoms and m is 1 or 2
• A is preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. 3 is more preferably a hydrocarbon group.
• the hydrocarbon group is preferably an alkyl group.
• A is preferably a methyl group or an ethyl group, more preferably a methyl group.
• A is preferably an ethylene group, a propylene group, or a butylene group.
• m is preferably 1.
• compounds represented by A-(OH)m include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, 3-pentanol, 2 -methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, alkyl monoalcohols such as neopentyl alcohol, ethylene glycol, 1,3-propanediol, Examples include alkylene diols such as 1,4-butanediol, alkyl monoalcohols are preferred, methanol and ethanol are more preferred, and methanol is even more preferred.
• the solvent used in this embodiment preferably contains a compound represented by A-(OH)m and water.
• a compound represented by A-(OH)m By using both water and the compound represented by A-(OH)m as the solvent, the formation of the compound of formula (3) can also be effectively suppressed.
• the volume ratio of water and the compound represented by A-(OH)m is, with respect to water 1, It is preferably greater than 0, may be 0.1 or greater, may be greater than 1.0, or may be 1.5 or greater. Further, the volume ratio of the water and the compound represented by A-(OH)m is preferably 10 or less, more preferably 5 or less, and may be 3 or less with respect to 1 water. .
• only one kind of compound represented by A-(OH)m may be used, or two or more kinds thereof may be used. When two or more are used, the total amount is preferably within the above range.
• the total amount of the compound represented by A-(OH)m and water accounts for 90% by volume or more of the solvent. preferably 95% by volume or more, more preferably 99% by volume or more.
• the primary alkylamine is treated as an additive, not as a solvent, in the present embodiment.
• the amination reaction is preferably further carried out in the presence of a primary alkylamine.
• a primary alkylamine By adding a primary alkylamine, the formyl group can be protected and the formation of the compound represented by formula (3) can be effectively suppressed. That is, as shown below, a primary alkylamine (eg, n-butylamine (BA)) promotes imination and can effectively suppress the side reaction (formation of the compound represented by formula (3)).
• a primary alkylamine eg, n-butylamine (BA)
• the primary alkylamine is preferably a primary alkylamine having 1 to 10 carbon atoms, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, t-butylamine, isobutylamine, n-pentylamine, t-pentyl.
• Amine, isopentylamine, 2-methylbutylamine, n-hexylamine, n-heptylamine are more preferred, and methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, t-butylamine, isobutylamine are further preferred.
• it is n-butylamine.
• the blending amount is preferably 0.1 mol or more per 1 mol of the formyl group of the raw material (compound represented by formula (1)). It is preferably 0.4 mol or more, more preferably 0.4 mol or more. When the amount is at least the above lower limit, the effect of protecting the formyl group tends to be further improved.
• the amount of the primary alkylamine is preferably less than 10 mol, more preferably 5 mol or less, and 2 mol or less per 1 mol of the formyl group of the raw material (compound represented by formula (1)). is more preferable.
• the blending amount is preferably 1 mol or less, more preferably 0.5 mol or less, more preferably 0.3 mol or less per 1 mol of the ammonium salt. It may be mol or less.
• the content is equal to or less than the above upper limit, there is a tendency to effectively promote the exchange reaction between the primary alkylamine-protected imine compound and the ammonium salt (trans-imination described above).
• the lower limit is not particularly defined, for example, 0.01 mol or more is practical with respect to 1 mol of the ammonium salt.
• one type of primary alkylamine may be used, or two or more types may be used. When two or more are used, the total amount is preferably within the above range.
• a catalyst may be used to promote the reaction.
• the type of the catalyst is not particularly limited, but metallic nickel, metallic cobalt, nickel compounds, and cobalt compounds are preferred, and for example, nickel, cobalt, nickel phosphide, and cobalt phosphide are more preferred. Among these, cobalt phosphide is preferred, and particles of cobalt phosphide are more preferred. Details of cobalt phosphide can be referred to the description of JP-A-2021-013923, the content of which is incorporated herein.
• the amount of the catalyst is preferably 0.01 mol or more, preferably 0.05, per 1 mol of the formyl group of the raw material (compound represented by formula (1)). It may be mol or more, or may be 0.08 mol or more. Further, the catalyst may be 10 mol or less, 5 mol or less, or 3 mol or less per 1 mol of the raw material (compound represented by formula (1)), It may be 0.4 mol or less, or may be 0.2 mol or less. In the production method of the present embodiment, one type of catalyst may be used, or two or more types may be used. When two or more are used, the total amount is preferably within the above range.
• the production method of the present embodiment is preferably carried out under hydrogen pressure.
• the pressure with hydrogen is preferably greater than or equal to 1 bar and preferably less than or equal to 10 bar.
• the reaction temperature of the amination reaction in the production method of the present embodiment is preferably 50° C. or higher, more preferably 90° C. or higher, even more preferably 95° C. or higher, and 100° C. or higher. is more preferable, and 105° C. or higher is even more preferable.
• the reaction temperature of the amination reaction is preferably 200° C. or lower, more preferably 150° C. or lower, even more preferably 140° C. or lower, even more preferably 130° C. or lower, 125° C. or lower is even more preferable.
• the reaction temperature may be the same temperature (however, a variation of ⁇ 5 ° C.
• reaction temperature is the same (however, a variation of ⁇ 5° C. is regarded as an error) except for the initial temperature increase and the final temperature decrease.
• the reaction time of the amination reaction in the production method of the present embodiment is preferably 1 minute or longer, may be 30 minutes or longer, may be 1 hour or longer, or may be 2 hours or longer. Moreover, the reaction time of the amination reaction may be 50 hours or less, 30 hours or less, or 20 hours or less.
• Separation of the reaction mixture and the catalyst after the reaction can be performed by general methods such as sedimentation, centrifugation, and filtration. Separation of the catalyst is preferably carried out under an atmosphere of an inert gas such as nitrogen or argon, depending on the catalyst to be used, in order to prevent ignition.
• the reaction mixture may be used as a raw material or an intermediate as it is, or the reaction mixture may be purified by post-treatment as appropriate. Specific post-treatment methods include known purification methods such as extraction, distillation, and chromatography. These purification methods may be performed in combination of two or more.
• the higher the conversion rate of the raw material the better, preferably 50 mol % or more, more preferably 80 mol % or more.
• the ideal upper limit is 100 mol %.
• the higher the yield of the compound represented by formula (2) the better, preferably 30% or more, more preferably 50% or more, and 70% or more. is more preferable.
• the ideal upper limit is 100 mol %.
• the yield of by-products other than the compound represented by formula (3) is preferably low, more preferably 40% or less, and further preferably 30% or less. Preferably, it is 20% or less, and even more preferably 10% or less.
• the lower limit is 0%.
• the compound represented by the formula (2) obtained in the present embodiment, and the composition containing the compound represented by the formula (2) and the compound represented by the formula (3) are preferably used as various industrial materials. .
• Example 1 An autoclave was charged with 0.5 mmol of raw material (formylfurancarboxylic acid (FFCA)), water (an amount that gives a raw material concentration of 2.5% by mass), 0.05 mmol of the cobalt phosphide catalyst obtained above, a nitrogen source (ammonium acetate salt ) was charged and reacted at a hydrogen pressure of 5 bar and a reaction temperature of 120° C. for 16 hours.
• FFCA formylfurancarboxylic acid
• water an amount that gives a raw material concentration of 2.5% by mass
• a nitrogen source ammonium acetate salt
• the conversion rate was calculated by quantifying the raw material by HPLC (High Performance Liquid Chromatography) measurement. The unit of conversion is %. Table 1 shows the results.
• HPLC measurement of the reaction solution was performed to identify and quantify raw materials and products.
• the amount of by-products that could not be detected by HPLC measurement was calculated from the amounts of starting materials and products.
• the unit of each component of the product is shown as %. Table 1 shows the results.
• Example 1 the conditions shown in Table 1 were changed, and the others were carried out in the same manner. Methanol and/or n-butylamine were added to the reaction system at the same time as an aqueous solution of 0.5 mmol of formylfurancarboxylic acid (FFCA).
• FFCA formylfurancarboxylic acid
• MeOH indicates methanol
• NH 4 OAc indicates ammonium acetate
• NH 3 aq indicates aqueous ammonia.
• the solvent ratio indicates the volume ratio of water (H 2 O) and methanol (MeOH).
• AMFCA indicates aminomethylfurancarboxylic acid
• HMFCA indicates hydroxymethylfurancarboxylic acid.

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• 2022
  • 2022-09-05 JP JP2023546926A patent/JPWO2023037992A1/ja active Pending
  • 2022-09-05 WO PCT/JP2022/033205 patent/WO2023037992A1/ja not_active Ceased
  • 2022-09-05 CN CN202280060291.6A patent/CN117916226A/zh active Pending
  • 2022-09-05 EP EP22867314.1A patent/EP4400496A4/en active Pending
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  • 2022-09-05 US US18/689,222 patent/US20250011294A1/en active Pending

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