Process for producing acrylic acid derivatives

Abstract

The present application addresses the technical problem of providing a novel method for producing an acrylic acid derivative with high conversion rate and / or high yield. The technical problem is solved by a method for producing an acrylic acid derivative represented by formula (1), [in formula (1), R 1 represents a hydrogen atom or the like, R 3 represents a hydrogen atom or the like, and X represents a hydrogen atom or the like]; the method comprising: a process B in which an organometallic compound represented by formula (A3A), or an organometallic compound represented by formula (A3B), or a combination thereof, is brought into contact with a proton donor and an aldehyde compound, to obtain the compound represented by formula (1), [in formula (A3A), R 2 represents a hydrogen atom or the like at each occurrence, R 3 represents a hydrogen atom or the like, and X represents a hydrogen atom or the like, and M represents a hydrogen atom or the like]. [The symbols in formula (A3B) represent the same meanings as described above.]

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a method for producing an acrylic acid derivative, and the like. BACKGROUND

[0002] An acrylic acid derivative is widely used as a raw material for a water-absorbing polymer, a substitute for inorganic glass, and a raw material for an acrylic resin, a raw material for an acrylic resin paint, which is used in window materials for buildings and vehicles, covers for lighting fixtures, lantern signs, road signs, daily necessities, office supplies, artware, windshields for watches, and the like. In addition, a fluorine-containing acrylic acid derivative can be used as a synthetic intermediate for medicines (e.g., antibiotics), a synthetic intermediate for a sheath material for optical fibers, a synthetic intermediate for a coating material, a synthetic intermediate for a semiconductor resist material, and a monomer for a functional polymer, and the like.

[0003] As a method for producing an α-fluoroacrylate, in Patent Literature 1, it is disclosed that an α-fluoroacrylate is produced by reacting an equimolar amount of CH2FCOOR [in the formula, R represents a lower alkyl group] with an aldehyde in the presence of a strong base represented by sodium methoxide.

[0004] Prior Art Documents

[0005] Patent Literature

[0006] Patent Literature 1: U.S. Patent No. 3262968 Specification SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, there is still a demand for providing a new production method capable of producing an acrylic acid derivative. The present inventors and the like have found that, in the method described in Patent Literature 1, it is actually impossible to produce an acrylic acid derivative with a high conversion rate and / or a high yield, regardless of how the reaction conditions are optimized.

[0009] Therefore, an object of the present disclosure is to provide a new production method for an acrylic acid derivative.

[0010] MEANS FOR SOLVING THE PROBLEMS

[0011] The present inventors and the like have conducted intensive studies, and as a result, have found that the production method for an acrylic acid derivative represented by Formula (1) can solve the problems described above:

[0012] [Chemical Formula 1]

[0013]

[0014] [In Formula (1),

[0015] R 1represents a hydrogen atom, an alkyl group, a fluoroalkyl group, an aryl group optionally having one or more substituents, or a halogen atom,

[0016] R 3 represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or an aryl group optionally having one or more substituents, and

[0017] X represents a hydrogen atom, a fluoroalkyl group, an alkyl group, or a halogen atom.

[0018] The production method includes:

[0019] Step B, wherein a compound represented by formula (A3A), or a compound represented by formula (A3B), or a combination thereof is contacted with a proton donor and an aldehyde compound to obtain the compound represented by formula (1),

[0020] [Chemical Formula 2]

[0021]

[0022] [In formula (A3A),

[0023] R 2 represents a hydrogen atom, an alkyl group, or an aryl group,

[0024] R 3 represents the same meaning as described above,

[0025] X represents the same meaning as described above, and

[0026] M represents a hydrogen atom or a metal.

[0027] [Chemical Formula 3]

[0028]

[0029] [In formula (A3B), the symbols represent the same meanings as described above.

[0030] The present disclosure includes the following aspects.

[0031] Item 1.

[0032] A production method of an acrylic acid derivative represented by formula (1):

[0033] [Chemical Formula 4]

[0034]

[0035] [In formula (1),

[0036] R 1 represents a hydrogen atom, an alkyl group, a fluoroalkyl group, an aryl group optionally having one or more substituents, or a halogen atom,

[0037] R3 represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or an aryl group optionally having one or more substituents, and

[0038] X represents a hydrogen atom, a fluoroalkyl group, an alkyl group, or a halogen atom.

[0039] The production method includes:

[0040] Step B, wherein a compound represented by formula (A3A), or a compound represented by formula (A3B), or a combination thereof, is contacted with a proton donor and an aldehyde compound to obtain the compound represented by formula (1),

[0041] [Chemical Formula 5]

[0042]

[0043] [In formula (A3A),

[0044] R 2 represents a hydrogen atom, an alkyl group, or an aryl group,

[0045] R 3 represents the same meaning as described above,

[0046] X represents the same meaning as described above, and

[0047] M represents a hydrogen atom or a metal.

[0048] [Chemical Formula 6]

[0049]

[0050] [In formula (A3B), the symbols represent the same meanings as described above.]

[0051] Item 2.

[0052] The production method according to item 1, wherein R 1 is a hydrogen atom, a linear or branched C1-6 alkyl group, or an aryl group.

[0053] Item 3.

[0054] The production method according to item 2, wherein R 1 is a hydrogen atom, or a linear or branched C1-6 alkyl group.

[0055] Item 4.

[0056] The production method according to any one of items 1 to 3, wherein R 3 is a C1-6 alkyl group or a C1-6 fluoroalkyl group.

[0057] Item 5.

[0058] The production method according to item 4, wherein R 3 is a C1-4 alkyl group or a C1-4 fluoroalkyl group.

[0059] Item 6.

[0060] The production method according to any one of items 1 to 5, wherein X is a halogen atom or a fluoroalkyl group.

[0061] Item 7.

[0062] The production method according to item 6, wherein X is a halogen atom.

[0063] Item 8.

[0064] The production method according to item 6, wherein X is a fluorine atom.

[0065] Item 9.

[0066] The production method according to any one of items 1 to 8, wherein the production method further comprises:

[0067] Process A, wherein a compound represented by formula (A1) is reacted with an oxalic acid compound represented by formula (A2) in the presence of a base to obtain the compound represented by formula (A3A), or the compound represented by formula (A3B), or a combination thereof:

[0068] X-CH2-CO-O-R 3 (A1)

[0069] [The symbols in formula (A1) represent the same meanings as described above];

[0070] (CO2R 2 )2(A2)

[0071] [In formula (A2), R 2 is the same or different at each occurrence, represents a hydrogen atom, an alkyl group, or an aryl group].

[0072] Item 10.

[0073] The production method according to item 9, wherein

[0074] the base is selected from

[0075] (1) a hydroxide of an alkali metal or an alkaline earth metal;

[0076] (2) an alkoxide of an alkali metal or an alkaline earth metal;

[0077] (3) an alkyl lithium;

[0078] (4) an alkyl sodium; and

[0079] (5) an alkyl metal halide

[0080] one or more of the above bases.

[0081] Item 11.

[0082] The production method according to Item 10, wherein

[0083] The base is represented by the formula: ROM

[0084] (in the formula, R is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a t-pentyl group, a neopentyl group, an iso-pentyl group, a sec-pentyl group, a 3-pentyl group, an n-hexyl group, a tertiary carbon-containing hexyl group, a quaternary carbon-containing hexyl group, an n-heptyl group, or an iso-heptyl group; and

[0085] M is sodium, potassium, or lithium)

[0086] The alkoxide represented by the formula: ROM

[0087] Item 12.

[0088] The production method according to any one of Items 9 to 11, wherein R 2 independently at each occurrence is an alkyl group.

[0089] Item 13.

[0090] The production method according to any one of Items 1 to 12, wherein the proton donor is water and / or an organic acid, an inorganic acid, or a solid acid.

[0091] Item 14.

[0092] The production method according to Item 13, wherein the proton donor is water and / or an organic acid.

[0093] Item 15.

[0094] The production method according to any one of Items 9 to 14, wherein, after the reaction of Step A, the compound represented by Formula (A3A) or Formula (A3B) is not separated as a solid.

[0095] Effects of the Invention

[0096] According to the production method of the present disclosure, it is possible to produce an acrylic acid derivative with high conversion rate and / or high yield. DETAILED DESCRIPTION

[0097] Terminology

[0098] In the present specification, symbols and abbreviations not specifically mentioned can be understood in the meanings commonly used in the technical field to which the present invention pertains, in the context of the present specification.

[0099] In the present specification, the phrase "comprising" is used in the sense of "including", "containing", and "comprehending", and is intended not to be limiting.

[0100] In the present specification, the "reaction product" can be a reaction product compound or a reaction product composition. The "reaction product composition" can contain, for example, one or more unreacted reactants, in addition to one or more reaction product compounds.

[0101] The processes, treatments, or operations described in the present specification can be performed at room temperature, unless otherwise specified.

[0102] In the present specification, room temperature refers to a temperature within the range of 10°C to 40°C.

[0103] As generally understood by those skilled in the art, the expression "Cn-m" (here, n and m are numbers) written together with a substituent or the like means that the number of carbon atoms of the substituent or the like is n or more and m or less.

[0104] In the present specification, "alkyl" (the term "alkyl" includes "alkyl" in "fluoroalkyl" and the like) can be cyclic, linear, or branched, or an alkyl thereof. That is, in the present specification, the term "alkyl" is intended to broadly include, in addition to (acyclic) alkyl groups, cyclic alkyl groups.

[0105] In the present specification, "alkyl" can be, for example, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.

[0106] In the present specification, as "alkyl", specifically, for example, straight-chain or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, neopentyl, and hexyl can be mentioned.

[0107] In the present specification, as "alkyl", specifically, for example, cyclic alkyl groups (cycloalkyl groups) having 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl can be mentioned.

[0108] In the present specification, "fluoroalkyl" is an alkyl group in which at least one hydrogen atom is replaced with a fluorine atom.

[0109] In the present specification, the number of fluorine atoms that "fluoroalkyl" has can be one or more (for example: 1 to 3, 1 to 6, 1 to 12, 1 to the maximum number of replaceable).

[0110] "Fluoroalkyl" includes perfluoroalkyl. "Perfluoroalkyl" is an alkyl group in which all hydrogen atoms are replaced with fluorine atoms.

[0111] In the present specification, a "fluoroalkyl group" can be, for example, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms.

[0112] In the present specification, a "fluoroalkyl group" can be a straight-chain or branched fluoroalkyl group.

[0113] In the present specification, as the "fluoroalkyl group", specifically, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a tetrafluoropropyl group (for example: HCF2CF2CH2-), a hexafluoropropyl group (for example: (CF3)2CH-), a nonafluorobutyl group, an octafluoropentyl group (for example: HCF2CF2CF2CF2CH2-), a tridecafluorohexyl group, or the like can be mentioned.

[0114] In the present specification, as the "aryl group", for example, a phenyl group and a naphthyl group can be mentioned.

[0115] In the present specification, as the "halogen atom", for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like can be mentioned.

[0116] [Manufacturing method]

[0117] The manufacturing method of the present disclosure is a manufacturing method of an acrylic acid derivative represented by formula (1) [in the present specification, sometimes referred to as acrylic acid derivative (1)].

[0118] [Chemical formula 7]

[0119]

[0120] [In formula (1),

[0121] R 1 represents a hydrogen atom, an alkyl group, a fluoroalkyl group, an aryl group optionally having one or more substituents, or a halogen atom,

[0122] R 3 represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or an aryl group optionally having one or more substituents, and

[0123] X represents a fluoroalkyl group, an alkyl group, a halogen atom, or a hydrogen atom.

[0124] The manufacturing method includes a step B in which a compound represented by formula (A3A) [in the present specification, sometimes referred to as compound (A3A)], or an organometallic compound represented by formula (A3B) [in the present specification, sometimes referred to as compound (A3B)], or a combination thereof (in the present specification, sometimes referred to as substance A collectively and simply as the compound and the combination thereof) is contacted with a proton donor and an aldehyde compound, to obtain the compound represented by formula (1).

[0125] [Chemical formula 8]

[0126]

[0127] [In formula (A3A),

[0128] R 2 represents a hydrogen atom, an alkyl group or an aryl group,

[0129] R 3 represents the same meaning as described above,

[0130] X represents the same meaning as described above, and

[0131] M represents a hydrogen atom or a metal.

[0132] [Chemical Formula 9]

[0133]

[0134] [The symbols in the formula represent the same meanings as described above.]

[0135] As is generally understood by those skilled in the art, formula (1) includes

[0136] [Chemical Formula 10]

[0137]

[0138] and

[0139] [Chemical Formula 11]

[0140]

[0141] , and combinations (or mixtures) thereof.

[0142] R 1 is preferably a hydrogen atom, a linear or branched C1-6 alkyl group, or an aryl group, more preferably a hydrogen atom, or a linear or branched C1-6 alkyl group.

[0143] R 1 is preferably a hydrogen atom.

[0144] R 3 is preferably a C1-6 alkyl group or a C1-6 fluoroalkyl group.

[0145] R 3 is preferably a C1-4 alkyl group or a C1-4 fluoroalkyl group. R 3 is preferably a methyl group.

[0146] X is preferably a halogen atom or a fluoroalkyl group.

[0147] X is preferably a halogen atom.

[0148] X is preferably a fluorine atom.

[0149] M is preferably an alkali metal (e.g., Li, Na, K) or an alkaline earth metal (e.g., Ca, Sr, Ba).

[0150] The substance A can be obtained, for example, by a method comprising a process A in which a compound represented by formula (Al) [hereinafter sometimes referred to as compound (Al)] is reacted with an oxalic acid compound represented by formula (A2) [hereinafter sometimes referred to as compound (A2)] in the presence of a base:

[0151] X-CH2-CO-O-R 3 (A1)

[0152] [The symbols in formula (Al) represent the same meanings as described above];

[0153] (CO2R 2 )2(A2)

[0154] [In formula (A2), R 2 is the same or different at each occurrence and represents a hydrogen atom, an alkyl group, or an aryl group].

[0155] The base is preferably selected from the group consisting of

[0156] (1) a hydroxide of an alkali metal, an alkaline earth metal, or a transition metal;

[0157] (2) a (mono-, or di-)hydrocarboxide (Japanese: hydorokarubokishido) of an alkali metal, an alkaline earth metal, or a transition metal (e.g., an alkoxide, and an aryloxide);

[0158] (3) a lithium hydrocarbyl (e.g., aryl, and alkyl);

[0159] (4) a sodium hydrocarbyl (e.g., aryl, and alkyl); and

[0160] (5) a metal halide of a hydrocarbyl (e.g., aryl, and alkyl)

[0161] in the above.

[0162] Examples of the alkali metal, the alkaline earth metal, or the transition metal include zinc, iron, aluminum, titanium, zirconium, magnesium, tin, silane, and vanadium.

[0163] Specific examples of the alkoxide include Al(O-i-C3H7)3, Ba(OC2H5)2, Bi(O-t-C5H 11)3, Ca(OC2H5)2, Fe(O-i-C3H7)3, Ga(O-i-C3H7)3, Ge(OC2H5)4, Hf(O-i-C3H7)4, In(O-i-C3H7)3, KOC2H5, La(O-i-C3H7)3, LiOCH3, Mg(OC2H5)2, Mo(OC2H5)5, NaOC2H5, Nb(OC2H5)5, Pb(O-i-C3H7)2, Sb(OC2H5)3, Sn(O-i-C3H7)4, Sr(O-i-C3H7)2, Ta(OC2H5)5, Ti(O-i-C3H7)4, VO(C2H5)3, W(OC2H5)5, Y(O-i-C3H7)3, Zn(OC2H5)2, Zr(O-i-C3H7)4, Zr(O-t-C4H9)4, and Zr(O-n-C4H9)4.

[0164] The base is preferably a strong base.

[0165] Examples of the base are:

[0166] (1) hydroxides of alkali metals or alkaline earth metals (e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide) ;

[0167] (2) alkoxides of alkali metals or alkaline earth metals;

[0168] [for example, alkoxides of formula ROM

[0169] (in the formula, R is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a t-pentyl group, a neopentyl group, an iso-pentyl group, a sec-pentyl group, a 3-pentyl group, an n-hexyl group, a t-carbon-containing hexyl group, a quaternary carbon-containing hexyl group, an n-heptyl group, or an iso-heptyl group; and M is sodium, potassium, or lithium).

[0170] (3) alkyl lithium (e.g., n-butyllithium, sec-butyllithium, t-butyllithium) ;

[0171] (4) alkyl sodium (e.g., n-butyllithium, sec-butyllithium, t-butyllithium) ; and

[0172] (5) alkyl magnesium halide [e.g., Grignard reagent].

[0173] The base is preferably of formula: ROM

[0174] (in the formula, R is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a t-pentyl group, a neopentyl group, an iso-pentyl group, a sec-pentyl group, a 3-pentyl group, an n-hexyl group, a t-carbon-containing hexyl group, a quaternary carbon-containing hexyl group, an n-heptyl group, or an iso-heptyl group; and M is sodium, potassium, or lithium).

[0175] (3) alkyl lithium (e.g., n-butyllithium, sec-butyllithium, t-butyllithium) ;

[0176] The base is preferably of formula: ROM

[0177] (in the formula, R is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a t-pentyl group, a neopentyl group, an iso-pentyl group, a sec-pentyl group, a 3-pentyl group, an n-hexyl group, a t-carbon-containing hexyl group, a quaternary carbon-containing hexyl group, an n-heptyl group, or an iso-heptyl group; and M is sodium, potassium, or lithium).

[0178] R is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, or an isoheptyl group; and

[0179] M is sodium, potassium, or lithium.

[0180] The alkoxide represented by the formula (2).

[0181] The base can be used alone or in combination with two or more kinds.

[0182] The base can be used in an amount in the range of 0.9 to 1.7 mol, preferably in the range of 1.0 to 1.5 mol, and further preferably in the range of 1.1 to 1.3 mol, per 1 mol of the compound (A1).

[0183] In the oxalic acid compound, R 2 Preferably, R is independently an alkyl group at each occurrence. Examples of the oxalic acid compound include dimethyl oxalate, methyl ethyl oxalate, diethyl oxalate, dipropyl oxalate, and dibutyl oxalate.

[0184] The oxalic acid compound can be used alone or in combination with two or more kinds.

[0185] The oxalic acid compound can be used in an amount of 1 mol or more (preferably in excess), for example, in the range of 0.9 to 1.7 mol, preferably in the range of 1.0 to 1.5 mol, and further preferably in the range of 1.1 to 1.2 mol, per 1 mol of the compound (A1).

[0186] The molar ratio of the dimethyl oxalate to the base (preferably, for example, sodium methoxide) can be in the range of 1:10 to 10:1, preferably in the range of 1:5 to 5:1, and more preferably in the range of 1:3 to 3:1.

[0187] The ratio is preferably in the range of 1:3 to 1:1, 1:2.5 to 1:1, 1:2 to 1:1.01, 1:1.5 to 1:1.05, 1:1.3 to 1:1.07, or 1:1.2 to 1:1.1 in one embodiment of the present disclosure.

[0188] The ratio is preferably in the range of 3:1 to 1:1, 2.5:1 to 1:1, 2:1 to 1:1.01, 1.5:1 to 1.01:1, 1.3:1 to 1.05:1, or 1.2:1 to 1.07:1 in another embodiment of the present disclosure.

[0189] The oxalic acid compound preferably makes R 2 and R 3The same compound is contacted with each other. On the other hand, from the viewpoint of general use, oxalic acid diphenyl ester, oxalic acid dipropyl ester, oxalic acid dimethyl ester, and oxalic acid diethyl ester are preferred, and oxalic acid dimethyl ester and oxalic acid diethyl ester are further preferred.

[0190] Examples of the proton donor include water and / or an organic acid, an inorganic acid, or a solid acid.

[0191] The organic acid, the inorganic acid, or the solid acid can be used together with water, and an aqueous liquid (e.g., an aqueous solution, an aqueous suspension, an aqueous impregnate) thereof can be used.

[0192] The proton donor can be a liquid, or can also be a solid.

[0193] Examples of the organic acid include acetic acid, monomethyl acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, phenol, benzoic acid, citric acid, succinic acid, and oxalic acid.

[0194] Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, hydroiodic acid, and hydrobromic acid.

[0195] Examples of the solid acid include silica-alumina, silica-magnesia, and ion exchange resins or ion exchange membranes each having an acid group (e.g., a sulfonic acid group, a carboxylic acid group).

[0196] The proton donor can be used alone at 1 kind, or can also be used in combination at 2 or more kinds.

[0197] For example, the proton donor can be used in the form of an aqueous solution of an acid (e.g., an organic acid, an inorganic acid).

[0198] The proton donor is preferably water and / or an organic acid, and more preferably water (e.g., ion exchange water, pure water) or an aqueous solution of an organic acid.

[0199] The organic acid can be used in a range of usually 0.01 to 0.3 mol, and preferably 0.02 to 0.25 mol, relative to 1 mol of the compound (A1).

[0200] The proton donor can preferably be a Bronsted acid in relation to the base.

[0201] The proton donor can be used in a range of usually 0.01 to 0.3 mol, and preferably 0.02 to 0.25 mol, relative to 1 mol of the compound (A1).

[0202] R 1 Can be derived from an aldehyde compound.

[0203] The aldehyde compound can be

[0204] [1] gaseous formaldehyde,

[0205] [2] a formaldehyde aqueous solution having a high concentration (e.g., 90% by mass or more), and

[0206] [3] one or more compounds selected from the group consisting of an aliphatic aldehyde and an aromatic aldehyde optionally substituted with one or more substituents,

[0207] [4] a polyformaldehyde, and

[0208] a combination of two or more of these.

[0209] The "aliphatic aldehyde" can be a straight-chain or branched aliphatic aldehyde, and can be a saturated or unsaturated aliphatic aldehyde.

[0210] The aldehyde is preferably a straight-chain saturated aldehyde having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, still further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms).

[0211] In the present specification, the "aliphatic aldehyde" is, for example, a compound represented by the formula: R-CHO (in the formula, R represents an aliphatic hydrocarbon group). Here, the aliphatic hydrocarbon group represented by R is preferably an aliphatic hydrocarbon group.

[0212] In the present specification, the "aromatic aldehyde" is, for example, a compound represented by the formula: R-CHO (in the formula, R represents an aryl group optionally substituted with one or more substituents).

[0213] R can correspond to R 1 .

[0214] The aldehyde compound is preferably selected from the group consisting of

[0215] one or more of formaldehyde, acetaldehyde, n-propyl aldehyde, isopropyl aldehyde, n-butyl aldehyde, isobutyl aldehyde, neopentyl aldehyde, n-pentyl aldehyde, n-hexyl aldehyde, n-heptyl aldehyde, n-octyl aldehyde, nonyl aldehyde, decyl aldehyde, undecyl aldehyde, dodecyl aldehyde, tridecyl aldehyde, benzaldehyde, o-anisic aldehyde, m-anisic aldehyde, p-anisic aldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, and p-methylbenzaldehyde.

[0216] The polyformaldehyde compound described above can be a polymer composed of two or more formaldehyde compounds (e.g., formaldehyde), and can be linear or cyclic. As examples thereof, polyoxymethylene and 1,3,5-trioxane can be given.

[0217] The number average degree of polymerization of the polyformaldehyde compound (e.g., polyoxymethylene) is preferably 2 to 100.

[0218] The above formaldehyde compound can be used in a range of 1.0 to 1.5 moles, preferably in a range of 1.0 to 1.2 moles, relative to 1 mole of the compound (Al).

[0219] The reaction time of the step A is preferably in a range of 0.1 to 72 hours, more preferably in a range of 0.1 to 48 hours, and further preferably in a range of 0.1 to 24 hours.

[0220] The lower limit of the reaction temperature of the step A can be -78°C, -50°C, -40°C, -30°C, -20°C, -10°C or 0°C.

[0221] The upper limit of the reaction temperature of the step A can be 200°C, 180°C, 150°C, 120°C, 100°C, 80°C, 60°C, 40°C or 25°C.

[0222] In the above step B, the above reaction product obtained in the step A is contacted with a proton donor and an aldehyde compound, and the compound represented by the above formula (1) can be obtained.

[0223] The means and order of the contacting are not particularly limited.

[0224] The contacting of the reaction product obtained in the step A with the proton donor and the contacting of the reaction product obtained in the step A with the aldehyde compound can be performed simultaneously, successively, or alternately.

[0225] The reaction product can be a reaction compound or a reaction composition. The "reaction composition" can contain, for example, the compound (Al), the base and the oxalic acid compound (A2) in addition to one or more reaction compounds.

[0226] In the step B, the reaction product obtained in the step A is reacted with the aldehyde compound, and thereby the compound represented by the formula (1) is produced.

[0227] Specifically, the step B can be performed, for example, by introducing a proton donor and the aldehyde compound into a reaction system containing the reaction product obtained in the step A.

[0228] Specifically, for example, the reaction product obtained in the step A can be mixed with a proton donor and the aldehyde compound.

[0229] The operation of the step A is also described later in this specification.

[0230] The above-mentioned process A and the process B can be performed in parallel. In other words, the process B can be started before the reaction of the process A is completed. However, from the viewpoint of high conversion and / or high yield, it is preferable that the process B be started after the reaction of the process A is completed or almost completed.

[0231] The process B can be started after a prescribed time elapses from the start of the reaction of the process A (for example, after 1 hour or more elapses or after 2 hours or more elapses).

[0232] After the reaction of the process A, purification or removal of part or all of the unnecessary substances can be performed as needed.

[0233] The removal can be performed by using a publicly known method such as distillation removal, rectification, filtration, extraction, and the like.

[0234] By performing the removal by distillation under reduced pressure, an appropriate temperature can be selected depending on the compound to be removed, and the temperature for the removal by distillation under reduced pressure can be 100°C or lower, and can be preferably 50°C or lower. The lower limit of the temperature for the removal by distillation under reduced pressure can be, for example, 0°C.

[0235] Examples of the above-mentioned unnecessary substances include:

[0236] an alcohol adduct, a product in which an alcohol is added to a double bond site of a target substance,

[0237] a proton adduct, a product in which a proton donor is added to a double bond site of a target substance,

[0238] a carbonic diester, R'-O-CO-O-R',

[0239] a monofluoroacetate,

[0240] an oxalic diester, and

[0241] formic acid or a formate, H-CO-O-R'

[0242] (these formulas, R' is the same or different at each occurrence, and represents a hydrogen atom, an alkyl group, or an aryl group).

[0243] The removal can be such that the content of the unnecessary substance is, for example, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less.

[0244] The removal does not necessarily need to completely remove the unnecessary substance, and the lower limit of the content thereof can be, for example, 1 ppm.

[0245] In a preferable embodiment of the present disclosure, it is preferable that purification (or removal of part or all of the unnecessary substances) not be performed after the reaction of the process A.

[0246] In a particularly preferable embodiment of the present disclosure, the compound represented by formula (A3A) or formula (A3B) is not isolated as a solid after the reaction of step A.

[0247] The separation includes filtration separation, powderization by drying, recrystallization, and the like of the above-mentioned compound.

[0248] Based on general technical knowledge, the intermediate or product is often separated from the reaction system, thereby achieving an increase in the reaction yield and selectivity.

[0249] However, in this embodiment, by not performing the separation, decomposition caused by drying of the compound represented by formula (A3A) or formula (A3B) when taken out as a solid can be suppressed.

[0250] In addition, in this embodiment, by not performing the separation, the advantage of eliminating the limitation of the reaction solvent of step A required for such separation is obtained.

[0251] In this embodiment, the separation or drying process of the compound represented by formula (A3A) or formula (A3B) is not required, thereby enabling an increase in productivity, and enabling a high yield of the target product, and thus enabling a reduction in manufacturing cost.

[0252] That is, in the present disclosure, unlike general technical knowledge, even if the intermediate or product is not separated from the reaction system, a high reaction yield and high selectivity can be achieved. Further, in the present disclosure, on the contrary, by not separating the intermediate or product from the reaction system, the reaction yield and selectivity can be increased, and the manufacturing cost can be reduced.

[0253] The reaction time (or implementation time) of step B is preferably in the range of 0.1 to 72 hours, more preferably in the range of 0.1 to 48 hours, and further preferably in the range of 0.1 to 24 hours.

[0254] The lower limit of the reaction temperature (or the temperature of the reaction system) of step B can be -78°C, -50°C, -40°C, -30°C, -20°C, -10°C, or 0°C.

[0255] The upper limit of the reaction temperature of step B can be 200°C, 180°C, 150°C, 120°C, 100°C, 80°C, 60°C, 40°C, or 25°C.

[0256] The reaction temperature of step B can be the same as or different from the reaction temperature of step A. In terms of operational convenience, it is preferable that the reaction temperature (or the temperature of the reaction system) of step B be the same as or substantially the same as the reaction temperature of step A.

[0257] The process A and the process B can be continuously performed in a flow type, can be performed in a batch type, or can be performed in a one-pot method.

[0258] The process A and the process B can be suitably performed in the presence of a reaction solvent.

[0259] Examples of the reaction solvent include

[0260] methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and the like alcohol;

[0261] acetone, methyl ethyl ketone (MEK), and the like ketone;

[0262] diethyl ether, tetrahydrofuran (THF), and the like ether;

[0263] carboxylic acids such as acetic acid and propionic acid, sulfoxide solvents such as dimethyl sulfoxide (DMSO) and sulfolane, amide solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 1-methyl-2-pyrrolidinone (NMP), 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacrylamide, N,N-dimethylacetoacetamide, N,N-diethylformamide, and N,N-diethylacetamide, and

[0264] water

[0265] and the like combination of two or more thereof

[0266] water-soluble solvent (or hydrophilic solvent or high-polar solvent).

[0267] The solvent used in the process A and the solvent used in the process B can be the same or different.

[0268] In the case where the solvent used in the process A contains a proton donor, part or all of the proton donor can serve as the proton donor used in the process A described above.

[0269] As the solvent, for example, there can be mentioned

[0270] pentane, hexane, heptane, octane, cyclohexane, decalin, n-decane, isododecane, and tridecane, and the like non-aromatic hydrocarbon solvent;

[0271] benzene, toluene, xylene, tetralin, veratrole, diethylbenzene, methylnaphthalene, nitrobenzene, o-nitrotoluene, mesitylene, indene, and diphenyl sulfide, and the like aromatic hydrocarbon solvent;

[0272] acetone, methyl ethyl ketone, methyl isobutyl ketone, phenylacetone, phenylpropionone, diisobutyl ketone, and isophorone, and the like ketone;

[0273] dichloromethane, chloroform, and chlorobenzene, and the like halogenated hydrocarbon solvent;

[0274] ether solvents such as diethyl ether, tetrahydrofuran, diisopropyl ether, methyl tert-butyl ether, dioxane, dimethoxyethane, diglycol dimethyl ether, phenyl ethyl ether, 1,1-dimethoxycyclohexane, diisopentyl ether, and cyclopentyl methyl ether;

[0275] ester solvents such as ethyl acetate, isopropyl acetate, diethyl malonate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, α-acetyl-γ-butyrolactone; nitrile solvents such as acetonitrile, benzonitrile; sulfoxide solvents such as dimethyl sulfoxide, and sulfolane; and

[0276] amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacrylamide, N,N-dimethylacetoacetamide, N,N-diethylformamide, and N,N-diethylacetamide.

[0277] The solvent is preferably, for example, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, ethylene glycol, propylene glycol, diethylene glycol, tetrahydrofuran, dioxane, dimethoxyethane, diglycol dimethyl ether, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, chloroform, dichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, acetonitrile, benzonitrile, dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacrylamide, N,N-dimethylacetoacetamide, N,N-diethylformamide, N,N-diethylacetamide, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, benzoic acid, p-toluenesulfonic acid, and the like.

[0278] non-aromatic hydrocarbons such as heptane, octane, and cyclohexane;

[0279] aromatic hydrocarbon solvents such as toluene, xylene, and the like;

[0280] ether solvents such as diethyl ether, tetrahydrofuran, diisopropyl ether, methyl tert-butyl ether, dioxane, dimethoxyethane, diglycol dimethyl ether, phenyl ethyl ether, 1,1-dimethoxycyclohexane, diisopentyl ether, and cyclopentyl methyl ether; or

[0281] amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacrylamide, N,N-dimethylacetoacetamide, N,N-diethylformamide, and N,N-diethylacetamide.

[0282] As the reaction solvent, methanol, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, cyclopentyl methyl ether, methyl tert-butyl ether, or 1-methyl-2-pyrrolidinone is preferable.

[0283] The amount of the reaction solvent is usually in the range of 1 to 10 parts by weight, preferably in the range of 2 to 8 parts by weight, and more preferably in the range of 3 to 5 parts by weight, relative to 1 part by weight of the compound (A1).

[0284] The solvent can be used singly or in combination of two or more.

[0285] The reaction solvent in the process A and the process B can be the same or different.

[0286] In the production method of the present disclosure, a stabilizer can be appropriately used.

[0287] In the present specification, the "stabilizer" can be a "polymerization inhibitor", a "decomposition inhibitor", or a "polymerization inhibitor" and a "decomposition inhibitor". The stabilizer can be added to the reaction system at any timing before and during the reaction of Step B. Further, the "before the reaction of Step B" can be any timing before and during the reaction of Step A performed before Step B.

[0288] By performing Step B in the presence of the stabilizer, the stability of the product of Step B, that is, the acrylic acid derivative represented by formula (1) can be improved.

[0289] Examples of the stabilizer include amides having 1 to 6 carbon atoms [for example, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetoacetamide, N,N-dimethylformamide, N,N-diethylformamide, and N,N-diethylacetamide].

[0290] Another example of the stabilizer includes alcohols having 1 to 6 carbon atoms [for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, and hexanol].

[0291] Another example of the stabilizer includes aldehydes.

[0292] The preferred example of the aldehyde can be one or more selected from the group consisting of aliphatic aldehydes and aromatic aldehydes which can be substituted with one or more substituents.

[0293] The aliphatic aldehyde can be an aliphatic aldehyde which is linear or branched, and can be a saturated or unsaturated aliphatic aldehyde.

[0294] The aldehyde can preferably be a linear saturated aldehyde having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, still further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms).

[0295] The aliphatic aldehyde is, for example, a compound represented by the formula: R'-CHO (in the formula, R' represents an aliphatic hydrocarbon group). Here, the aliphatic hydrocarbon group represented by R' is preferably an aliphatic hydrocarbon group.

[0296] The aromatic aldehyde is, for example, a compound represented by the formula: R'-CHO (in the formula, R' represents an aryl group which can be substituted with one or more substituents).

[0297] The aldehyde is specifically preferably one or more kinds (preferably one kind) selected from the group consisting of formaldehyde, acetaldehyde, n-propyl aldehyde, isopropyl aldehyde, n-butyl aldehyde, isobutyl aldehyde, neopentyl aldehyde, n-pentyl aldehyde, n-hexyl aldehyde, n-heptyl aldehyde, n-octyl aldehyde, nonyl aldehyde, decyl aldehyde, undecyl aldehyde, dodecyl aldehyde, tridecyl aldehyde, benzaldehyde, o-anisaldehyde, m-anisaldehyde, p-anisaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, and p-methylbenzaldehyde, and more preferably n-butyl aldehyde.

[0298] The amount of the aldehyde is preferably 0.1 mol or less, more preferably 0.05 mol or less, and further preferably 0.02 mol or less, relative to 1 mol of the acrylic acid derivative (1).

[0299] The aldehyde is able to stabilize the acrylic acid derivative (1) even in a trace amount, but the amount of the aldehyde (B) relative to 1 mol of the acrylic acid derivative (1) is, for example, 0.0005 mol or more.

[0300] The molar ratio of the acrylic acid derivative (1) to the aldehyde is preferably 1 : 0.1 or less, more preferably in the range of 1 : 0.0005 to 1 : 0.05, and further preferably in the range of 1 : 0.0005 to 1 : 0.02.

[0301] In addition, as the stabilizer, for example, an amine compound such as an aliphatic primary amine, an aliphatic secondary amine, an aliphatic tertiary amine, an alicyclic secondary amine, an alicyclic tertiary amine, an aromatic amine, a heterocyclic amine, and a polymer-supported amine compound can be mentioned.

[0302] As the aliphatic primary amine, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, and ethylenediamine can be mentioned.

[0303] As the aliphatic secondary amine, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, and dicyclohexylamine can be mentioned.

[0304] As the aliphatic tertiary amine, for example, trimethylamine, triethylamine, diisopropylethylamine, tributylamine, and N,N,N',N'-tetramethylethylenediamine can be mentioned.

[0305] As the alicyclic secondary amine, for example, piperidine, piperazine, pyrrolidine, and morpholine can be mentioned.

[0306] As the alicyclic tertiary amine, for example, N-methylpiperazine, N-methylpyrrolidine, 5-diazabicyclo[4.3.0]nonene-5, and 1,4-diazabicyclo[2.2.2]octane can be mentioned.

[0307] As the aromatic amine, for example, aniline, methyl aniline, dimethyl aniline, N,N-dimethyl aniline, halogenated aniline, and nitro aniline can be mentioned.

[0308] As the heterocyclic amine, for example, pyridine, melamine, pyrimidine, piperazine, quinoline, and imidazole can be given.

[0309] As the polymer-supported amine compound, for example, polyallylamine and polyvinylpyridine can be given.

[0310] Further, as the stabilizer other than the above (i.e., the stabilizer other than the amine compound), one or more compounds selected from the group consisting of:

[0311] (1) a compound having a hydroxyl group,

[0312] (2) a compound having a sulfide bond,

[0313] (3) a compound having a sulfhydryl group or a mercapto group,

[0314] (4) a sulfurous acid compound, and

[0315] (5) a nitrous acid compound (in the present specification, this group can be referred to as the compound group (C)).

[0316] The compound (C) can be used alone as one kind, or two or more kinds can be used in combination.

[0317] As the above "(1) compound having a hydroxyl group", for example, an alcohol represented by the formula: R'-OH (in the formula, R' represents an alkyl group having 1 to 6 carbon atoms, for example) such as methanol, ethanol, isopropanol, and tert-butyl alcohol; and a compound having a partial structure of a benzene ring substituted with one or more hydroxyl groups (in this case, the hydroxyl group can be oxo (O=) by tautomerism) such as phenol, hydroquinone, 4-methoxyphenol, 2,5-di-tert-butylhydroquinone, methylhydroquinone, tert-butylhydroquinone (TBH), p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and 2,6-di-tert-butyl-4-methylphenol (BHT) (in this case, the number of carbon atoms of the compound is preferably 6 to 20) can be given.

[0318] As the above "(2) compound having a sulfide bond", for example, a dialkyl sulfide (the number of carbon atoms of the two "alkyl groups" is the same or different, and is preferably 1 to 6), and a compound having a diphenyl sulfide structure (for example, a compound having a sulfide bond having 6 to 20 carbon atoms such as diphenyl sulfide and phenothiazine having a benzene sulfide structure) can be given.

[0319] As the above "(3) compound having a sulfhydryl group or a mercapto group", for example, a compound having an R(-SH) group such as benzene sulfhydryl, benzene dithiol, 1,2-ethanedithiol, and 1,3-propanedithiol can be given. n[In the formula, R represents, for example, an alkane having 1 to 6 carbon atoms or an aromatic carbocyclic ring having 6 to 12 carbon atoms (for example, benzene, diphenyl); and n represents, for example, an integer of 1 or 2.]

[0320] As the above-mentioned "(4) sulfurous acid compound", for example, potassium sulfite, calcium sulfite, sodium bisulfite, sodium sulfite, barium sulfite, magnesium sulfite, dimethyl sulfite, diethyl sulfite, dipentyl sulfite, dipropyl sulfite, and diisopropyl sulfite can be given.

[0321] As the above-mentioned "(5) nitrous acid compound", for example, potassium nitrite, sodium nitrite, methyl nitrite, ethyl nitrite, pentyl nitrite, propyl nitrite, and isopropyl nitrite can be given.

[0322] The above-mentioned compound (C) as a stabilizer is preferably the above-mentioned "(1) compound having a hydroxyl group", and more preferably a phenol compound.

[0323] As the above-mentioned stabilizer, for example, diisopropylethylamine, tributylamine, triethylamine, 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol (BHT), pyridine, melamine, and phenothiazine can be given.

[0324] The stabilizer can be used alone or in combination of two or more.

[0325] In a preferred embodiment of the present disclosure, the process B is performed in the presence of (1) one or more amine compounds capable of functioning as a stabilizer and (2) one or more compounds (C).

[0326] In the case where a stabilizer is used in the process B, the total amount thereof is preferably in the range of 100 to 50,000 ppm (w / w) with respect to the acrylic acid derivative represented by formula (1), more preferably in the range of 100 to 10,000 ppm (w / w), further preferably in the range of 100 to 5,000 ppm (w / w), more further preferably in the range of 100 to 3,000 ppm (w / w), particularly preferably in the range of 500 to 2,000 ppm (w / w), and more further preferably in the range of 500 to 1,500 ppm (w / w).

[0327] The reaction of the process A and the process B can be performed, for example, in the presence of air.

[0328] The acrylic acid derivative obtained by the production method of the present disclosure can be purified, as necessary, by a known purification method such as solvent extraction, water washing and dehydration, drying, filtration, distillation, concentration, and a combination thereof, according to its use.

[0329] According to the present disclosure, the compound represented by the above formula (1) can be obtained at a high conversion rate and / or a high yield even when the process A and the process B are carried out in a one-pot method. The present disclosure relates to a relationship in which the reaction product obtained in the process A is reacted with the formaldehyde compound in the presence of a proton donor.

[0330] In the production method of the present disclosure, the compound represented by the above formula (1) can be obtained at a conversion rate in the range of preferably 80% to 98%, more preferably 85% to 95%.

[0331] In the production method of the present disclosure, the compound represented by the above formula (1) can be obtained at a yield in the range of preferably 80% to 98%, more preferably 85% to 95%.

[0332] In the reaction system of the process A, the following order can be adopted:

[0333] the order of the compound (A2), then the base, and then the compound (A1),

[0334] the order of the compound (A2), then the compound (A1), and then the base,

[0335] the order of the base, then the compound (A2), and then the compound (A1),

[0336] the order of the base, then the compound (A1), and then the compound (A2),

[0337] the order of the compound (A1), then the base, and then the compound (A2), or

[0338] the order of the compound (A1), then the compound (A2), and then the base.

[0339] The way in which they are added to the reaction system of the process A is arbitrary, and for example, they can be added directly as they are, or they can be added after being dissolved or dispersed in a solvent;

[0340] They can be added at once, or they can be added in divided portions (for example: 2 portions, 3 portions, 4 portions, 5 portions, 6 portions, 7 portions, 8 portions, 9 portions, 10 portions, 15 portions, 20 portions, 25 portions, 30 portions, 35 portions, 40 portions, 45 portions, 50 portions, 55 portions, 60 portions, 65 portions, 70 portions, 75 portions, 80 portions, 85 portions, 90 portions, 95 portions, 100 portions);

[0341] The divided portions of two of these various materials can be added alternately;

[0342] The divided portions of the same material can be added repeatedly two or more times; and

[0343] Any combination of these methods can also be employed.

[0344] In the reaction system of Step B, the order of addition of the compound (A3A) and / or (A3B), the formaldehyde compound, and the base can be as follows:

[0345] the order of addition of the base, the compound (A3A) and / or (A3B), and then the formaldehyde compound,

[0346] the order of addition of the formaldehyde compound, the compound (A3A) and / or (A3B), and then the base,

[0347] the order of addition of the compound (A3A) and / or (A3B), the base, and then the formaldehyde compound,

[0348] the order of addition of the formaldehyde compound, the compound (A3A) and / or (A3B), and then the base,

[0349] the order of addition of the compound (A3A) and / or (A3B), the formaldehyde compound, and then the base, or

[0350] the order of addition of the formaldehyde compound, the base, and then the compound (A3A) and / or (A3B).

[0351] The order of addition of the compound (A3A) and / or (A3B), the base, and then the formaldehyde compound,

[0352] The addition can be performed at once, or can be divided into a plurality of portions (for example, 2 portions, 3 portions, 4 portions, 5 portions, 6 portions, 7 portions, 8 portions, 9 portions, 10 portions, 15 portions, 20 portions, 25 portions, 30 portions, 35 portions, 40 portions, 45 portions, 50 portions, 55 portions, 60 portions, 65 portions, 70 portions, 75 portions, 80 portions, 85 portions, 90 portions, 95 portions, 100 portions) and added;

[0353] The divided portions of two of these materials can be alternately added;

[0354] The divided portions of the same material can be added two or more times repeatedly; and

[0355] Any combination of these methods can also be used.

[0356] In addition, the order of the operations of Step A or a part thereof, and the order of the operations of Step B or a part thereof can be repeated any number of times and combined arbitrarily as long as the effects of the present disclosure are not significantly impaired.

[0357] Examples

[0358] The present disclosure will be described in more detail by examples below, but the present disclosure is not limited thereto.

[0359] The meanings and structural formulas of the symbols and abbreviations in the examples are shown below.

[0360] DMF: N,N-dimethylformamide

[0361] DMSO: dimethyl sulfoxide

[0362] NMP: 1-methyl-2-pyrrolidinone

[0363] A4A: structural formula

[0364] [Chemical 12]

[0365]

[0366] A4B: structural formula

[0367] [Chemical 13]

[0368]

[0369] A5A: structural formula

[0370] [Chemical 14]

[0371]

[0372] A5B: structural formula

[0373] [Chemical 15]

[0374]

[0375] A6A: structural formula

[0376] [Chemical 16]

[0377]

[0378] A6B: structural formula

[0379] [Chemical 17]

[0380]

[0381] Example A-1

[0382] Into a 3-necked flask, NMP 92 g was charged. The flask was subjected to nitrogen replacement, and the flask was subjected to water bath to make the internal temperature 20°C or less.

[0383] Dimethyl oxalate 177 g was weighed and charged into the above flask. Next, sodium methoxide 70 g was weighed and charged into the above flask. Next, methyl fluoroacetate 92 g was weighed and charged into the above flask. The reaction was allowed to mature by stirring at room temperature for 24 hours, and a solution of a substance A (A4A and A4B in this example) as a substance having a structure corresponding to the above substrate was quantitatively obtained.

[0384] Example A-2

[0385] Into a 3-necked flask was put NMP 92 g. Nitrogen replacement was performed for the flask, and the flask was subjected to water bath so that the inside temperature would be 20°C or lower.

[0386] Oxalic acid diethyl ester 219 g was weighed and put into the flask. Next, sodium ethoxide 116 g was weighed and put into the flask. Next, fluoroacetic acid ethyl ester 106 g was weighed and put into the flask. The reaction was allowed to mature by stirring for 24 hours at room temperature, and a solution of substance A (A5A and A5B in this example) as a substance having a structure corresponding to the above substrate was quantitatively obtained.

[0387] Example A-3

[0388] Into a 3-necked flask was put NMP 92 g. Nitrogen replacement was performed for the flask, and the flask was subjected to water bath so that the inside temperature would be 20°C or lower.

[0389] Oxalic acid diethyl ester 219 g was weighed and put into the flask. Next, sodium ethoxide 116 g was weighed and put into the flask. Next, fluoroacetic acid ethyl ester 106 g was weighed and put into the flask. The reaction was allowed to mature by stirring for 24 hours at room temperature, and a solution of substance A (A5A and A5B in this example) as a substance having a structure corresponding to the above substrate was quantitatively obtained.

[0390] Example A-4

[0391] Into a 3-necked flask was put NMP 92 g. Nitrogen replacement was performed for the flask, and the flask was subjected to water bath so that the inside temperature would be 20°C or lower.

[0392] Oxalic acid diethyl ester 219 g was weighed and put into the flask. Next, sodium ethoxide 116 g was weighed and put into the flask. Next, fluoroacetic acid ethyl ester 106 g was weighed and put into the flask. The reaction was allowed to mature by stirring for 24 hours at room temperature, and a solution of substance A (A5A and A5B in this example) as a substance having a structure corresponding to the above substrate was quantitatively obtained.

[0393] Example A-5

[0394] Into a 3-necked flask was put NMP 92 g. Nitrogen replacement was performed for the flask, and the flask was subjected to water bath so that the inside temperature would be 20°C or lower.

[0395] DMF 92 g was charged in a 3-necked flask. The flask was subjected to nitrogen replacement, and the flask was subjected to water bath to make the internal temperature 20°C or lower.

[0396] Example A-6

[0397] DMF 92 g was charged in a 3-necked flask. The flask was subjected to nitrogen replacement, and the flask was subjected to water bath to make the internal temperature 20°C or lower.

[0398] DMF 92 g was charged in a 3-necked flask. The flask was subjected to nitrogen replacement, and the flask was subjected to water bath to make the internal temperature 20°C or lower.

[0399] Step B

[0400] Using the reaction solution obtained in Examples A-1 to A-6, the following Examples B-1 to B-12 and Comparative Example 1 were carried out.

[0401] Example B-1

[0402] In a 3-necked flask, to the solution 431 g of Example A-1, 431 g of NMP and 1 g of water were charged, and then 30 g of paraformaldehyde was charged in 3 portions, and the reaction was allowed to mature at room temperature for 24 hours, to obtain the target compound (1) (i.e., methyl 2-fluoropropenoate) in a yield of 89%.

[0403] The reaction solution after the reaction obtained in the above procedure was confirmed by gas chromatography, and the by-products other than the compound (1) and the unreacted raw material were confirmed.

[0404] As a result, the target compound was 89.0%, formate was 0.2% (of which the ester portion was the same as that of the target), carbonic acid diester was 0.5% (of which the ester portion was the same as that of the target), fluoroacetic acid ester was 1.0% (of which the ester portion was the same as that of the target), alcohol addition product of the compound (1) was 4.5%, and the base addition product of the compound (1) was 4.8%.

[0405] The alcohol addition product is a product in which an alcohol corresponding to the ester group is added to the double bond portion of the target compound, and the base addition product is a product in which a base is added to the double bond portion of the target compound.

[0406] Example B-2

[0407] In a 3-necked flask, 431 g of the solution of Example A-1 was charged with 431 g of NMP and 4 g of water, and then 30 g of paraformaldehyde was added in three portions. The reaction was allowed to stand at room temperature for 24 hours, and the target compound (1) having a structure corresponding to the above substrate (i.e., methyl 2-fluoropropenoate) was obtained in a yield of 87%.

[0408] Example B-3

[0409] In a 3-necked flask, 431 g of the solution of Example A-1 was charged with 431 g of NMP and 4 g of water, and then 30 g of paraformaldehyde was added in three portions. The reaction was allowed to stand at room temperature for 24 hours, and the target compound (1) having a structure corresponding to the above substrate (i.e., methyl 2-fluoropropenoate) was obtained in a yield of 87%.

[0410] Example B-4

[0411] In a 3-necked flask, 431 g of the solution of Example A-1 was charged with 431 g of NMP and 4 g of water, and then 30 g of paraformaldehyde was added in three portions. The reaction was allowed to stand at room temperature for 24 hours, and the target compound (1) having a structure corresponding to the above substrate (i.e., methyl 2-fluoropropenoate) was obtained in a yield of 87%.

[0412] Example B-5

[0413] In a 3-necked flask, 431 g of the solution of Example A-1 was charged with 431 g of NMP and 4 g of water, and then 30 g of paraformaldehyde was added in three portions. The reaction was allowed to stand at room temperature for 24 hours, and the target compound (1) having a structure corresponding to the above substrate (i.e., methyl 2-fluoropropenoate) was obtained in a yield of 87%.

[0414] Example B-6

[0415] Into a 3-necked round bottom flask was placed 431 g of NMP. Next, 30 g of paraformaldehyde and 1 g of water were added. To the flask was added dropwise 431 g of the solution of Example A-1. The reaction was allowed to mature at room temperature for 24 hours to give the target compound (1) having the structure corresponding to the above substrate (i.e., methyl 2-fluoropropenoate) in 90% yield.

[0416] Example B-7

[0417] Into a 3-necked round bottom flask was placed 312 g of the solution of Example A-2 and 312 g of NMP and 1 g of water, and then 30 g of paraformaldehyde was added in three portions. The reaction was allowed to mature at room temperature for 24 hours to give the target compound (1) having the structure corresponding to the above substrate (i.e., methyl 2-fluoropropenoate) in 88% yield.

[0418] Example B-8

[0419] Into a 3-necked round bottom flask was placed 547 g of the solution of Example A-3 and 547 g of NMP and 1 g of water, and then 30 g of paraformaldehyde was added in three portions. The reaction was allowed to mature at room temperature for 24 hours to give the target compound (1) having the structure corresponding to the above substrate (i.e., ethyl 2-fluoropropenoate) in 89% yield.

[0420] Example B-9

[0421] Into a 3-necked round bottom flask was placed 408 g of the solution of Example A-4 and 408 g of NMP and 1 g of water, and then 30 g of paraformaldehyde was added in three portions. The reaction was allowed to mature at room temperature for 24 hours to give the target compound (1) having the structure corresponding to the above substrate (i.e., methyl 2-fluoropropenoate) in 88% yield.

[0422] Example B-10

[0423] Into a 3-necked round bottom flask was placed 385 g of the solution of Example A-5 and 385 g of DMSO and 1 g of water, and then 30 g of paraformaldehyde was added in three portions. The reaction was allowed to mature at room temperature for 24 hours to give the target compound (1) having the structure corresponding to the above substrate (i.e., methyl 2-fluoropropenoate) in 90% yield.

[0424] Example B-11

[0425] In a 3-necked flask, to a solution of Example A-6, 431 g, was added 431 g of DMF, and 1 g of water, followed by the addition of paraformaldehyde, 30 g in 3 portions. The reaction was allowed to mature at room temperature for 24 hours to give the target compound (1) (i.e., methyl 2-fluoropropenoate) having the structure corresponding to the substrate in 91% yield.

[0426] Comparative Example 1

[0427] In a 3-necked flask, to a solution of Example A-1, 431 g, was added 431 g of NMP, followed by the addition of paraformaldehyde, 30 g in 3 portions, and the reaction was allowed to mature at room temperature for 24 hours to give the target compound (1) (i.e., methyl 2-fluoropropenoate) having the structure corresponding to the substrate in 30% yield.

Claims

1. A method for manufacturing an acrylic acid derivative of formula (1): ; In equation (1), R 1 The term represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having or not having one or more substituents, or a halogen atom, wherein the aryl group is phenyl or naphthyl. R 3 The aryl group represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having or not having one or more substituents, wherein the aryl group is phenyl or naphthyl, and X represents a hydrogen atom, a fluoroalkyl group with 1 to 20 carbon atoms, an alkyl group with 1 to 20 carbon atoms, or a halogen atom; The manufacturing method includes: Process A, in which, Reacting the compound represented by formula (A1) with the oxalic acid compound represented by formula (A2) in the presence of a base yields the compound represented by formula (A3A), or the compound represented by formula (A3B), or a combination thereof: X-CH2-CO-OR 3 (A1) The symbols in equation (A1) have the same meaning as those mentioned above; (CO2R 2 )2(A2) In equation (A2), R 2 The same or different occurrences each time indicate a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, wherein the aryl group is phenyl or naphthyl. After the reaction in step A, the compound represented by formula (A3A) or formula (A3B) is not separated as a solid; and Step B, wherein the compound represented by formula (A3A), or the compound represented by formula (A3B), or a combination thereof, is contacted with a proton donor and an aldehyde compound to obtain the compound represented by formula (1): ; In formula (A3A), R 2 The alkyl or aryl group represents hydrogen atoms and has 1 to 20 carbon atoms, wherein the aryl group is phenyl or naphthyl. R 3 It means the same as above. X represents the same meaning as described above, and M represents a hydrogen atom or a metal; ; The symbols in equation (A3B) have the same meaning as those described above; The proton donor is water. The proton donor is used in an amount ranging from 0.01 to 0.3 moles relative to 1 mole of the compound represented by formula (A1).

2. The manufacturing method according to claim 1, wherein, R 1 It is a hydrogen atom, a straight-chain or branched C1-6 alkyl group, or an aryl group, wherein the aryl group is phenyl or naphthyl.

3. The manufacturing method according to claim 2, wherein, R 1 It consists of hydrogen atoms, or straight-chain or branched C1-6 alkyl groups.

4. The manufacturing method according to any one of claims 1 to 3, wherein, R 3 It is a C1-6 alkyl or C1-6 fluoroalkyl.

5. The manufacturing method according to claim 4, wherein, R 3 It is a C1-4 alkyl or C1-4 fluoroalkyl.

6. The manufacturing method according to any one of claims 1 to 3, wherein, X is a halogen atom or a fluoroalkyl group.

7. The manufacturing method according to claim 6, wherein, X is a halogen atom.

8. The manufacturing method according to claim 6, wherein, X is a fluorine atom.

9. The manufacturing method according to claim 1, wherein, The alkali is selected from... (1) Hydroxides of alkali metals or alkaline earth metals; (2) Alkoxides of alkali metals or alkaline earth metals; (3) Alkyl lithium; (4) Sodium alkylate; and (5) Alkyl metal halides One or more bases in it.

10. The manufacturing method according to claim 9, wherein, The base is an alkoxide represented by the formula: ROM. In this formula, R is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, n-hexyl, hexyl containing a tertiary carbon, hexyl containing a quaternary carbon, n-heptyl, or isoheptyl; and M is sodium, potassium, or lithium.

11. The manufacturing method according to claim 1, wherein, R 2 It is an alkyl group each time it appears.

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