JP2019059695A - Process for producing N-substituted (meth) acrylamide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially produce high-yield, high-purity β-alkoxypropionic acid amide, β-aminopropionic acid amide and N-substituted (meth) acrylamide using (meth) acrylic acid ester as a starting material. Provide a method. SOLUTION: A β-substituted propionic acid ester, which is a product of a Michael addition reaction between a (meth) acrylic acid ester and an alcohol or an amine, is used to carry out an amidation reaction with an amine in the presence of a metal complex as a catalyst. To obtain the β-substituted propionic acid amide. Further, the thermal decomposition reaction of β-substituted propionic acid amide is carried out in the presence of a metal complex as a catalyst to eliminate alcohol or amine to obtain the target compound N-substituted (meth) acrylamide. [Selection diagram] None

Description

  The present invention relates to a convenient industrial process for the preparation of N-substituted (meth) acrylamides.

  The N-substituted (meth) acrylamide includes monofunctional (meth) acrylamide having one (meth) acrylamide group and polyfunctional (meth) acrylamide having two or more (meth) acrylamide groups, and Depending on the type and number of substituents, the structures vary widely, and can cover a wide range of physical properties and functions from liquid to solid, from hydrophilic to hydrophobic, and paints, adhesives, adhesives, various coating agents, It is used in a wide variety of fields such as papermaking chemicals, polymer flocculants, synthetic raw materials such as contact lenses, reactive diluents for UV curable resins, and crosslinking agents for thermal polymerization or photopolymerization, and its production method is Has been actively studied.

  One of the industrial production methods of N-substituted (meth) acrylamide is a method using (meth) acrylic acid ester as a starting material, and specifically, (1) (meth) acrylic acid ester and amine Method of directly performing amidation reaction in the presence of a strongly basic catalyst; (2) Michael addition reaction of (meth) acrylic acid ester with amine, followed by further amidation reaction with amine, then its formation N-substituted (meth) acrylamides by liquid phase thermal decomposition in the presence of no catalyst or acidic catalyst in the presence of an aminoamide which is an organic compound (patent documents 1 to 3).

  However, in the method (1), the Michael addition reaction of (meth) acrylic acid ester and amine proceeds simultaneously with the amidation reaction, and there is a problem that a large amount of amino ester is by-produced. (2) First, an amino ester was synthesized as a Michael adduct of (meth) acrylic acid ester and an amine, and then an amidation reaction of the amino ester with an amine was performed in the presence of a basic catalyst. It is a method of thermally decomposing aminoamide in the presence of no catalyst or acidic catalyst. In this method, high purity aminoamide can be easily obtained, but if the basic catalyst can be neutralized before it is introduced into the thermal decomposition step, polymerization problems can not be avoided. In addition, removal of the neutralization salt by-produced by neutralization takes cost and effort. Furthermore, when the thermal decomposition reaction is carried out without a catalyst, the decomposition reaction of the deamination does not have a sufficient rate, so that the recombination between the amine and the (meth) acrylic acid amide after decomposition tends to occur, and a high yield is aimed. I can not get the product. In the thermal decomposition reaction in the presence of an acidic catalyst, there is a problem that the acidic catalyst by the amine after decomposition is neutralized and the catalytic activity is lost.

JP-A-4-208258 Unexamined-Japanese-Patent No. 6-199752 JP 2012-97005 A

  An object of the present invention is to use an easily handled (meth) acrylic ester as a starting material and N-substituted (meth) acrylamides, particularly bulky cyclic substituents (meth) acrylamides, long-chain alkyls even under mild reaction conditions. High purity, high yield, high yield, convenient and inexpensive industrial production of N-substituted (meth) acrylamides which are high boiling point and solid at room temperature such as (meth) acrylamides and polyfunctional (meth) acrylamides by known methods To provide a way to

  The inventors of the present invention conducted intensive studies to solve these problems, and as a result, Michael addition reaction of (meth) acrylic acid ester with alcohol and / or amine was carried out to obtain β-alkoxy propionic acid ester, β-alkoxy ester. After synthesizing an aminopropionic acid ester, a metal complex is added as a catalyst, and an amidation reaction is performed with an amine compound to obtain β-alkoxypropionic acid amide and β-aminopropionic acid amide as an intermediate, and then a metal as a catalyst The present inventors have found that the target compound N-substituted (meth) acrylamide can be obtained by liquid phase thermal decomposition reaction of β-alkoxy propionic acid amide and β-amino propionic acid amide in the presence of a complex.

That is, the present invention
(1) N represented by the general formula [2] characterized in that liquid phase thermal decomposition reaction is carried out in the presence of a metal complex as a catalyst using the β-substituted propionic acid amide represented by the general formula [1] A process for producing substituted (meth) acrylamides,
(In each formula, R ₁ represents a hydrogen atom or a methyl group. N is an integer of 1 to 10, and when n = 1, R ₂ is a linear or branched chain having 11 to 36 carbon atoms alkyl group, alkyl ether group, an alicyclic hydrocarbon, an aromatic hydrocarbon, for integer n = 2 to 10, R ₂ is a hydrogen atom or a linear or branched carbon atoms 1 to 36 A represents an alkoxy group or an amino group represented by the general formula [3] or [4] (wherein R ₃ represents Represents a linear or branched alkyl group having 1 to 6 carbon atoms, an alkyl ether group, or an alicyclic hydrocarbon R ₄ and R ₅ each independently represent a hydrogen atom or a linear or branched chain having 1 to 10 carbon atoms List of linear alkyl group, alkyl ether group, alicyclic hydrocarbon, aromatic hydrocarbon . Further, R ₄ and R ₅ together with the nitrogen atom carrying them, represent a saturated 5 to 7 membered ring may be made by forming a (including those having an oxygen atom)), D is hydrogen Or a linear or branched alkylene group having 1 to 10 carbon atoms, an alkylene ether group, an alicyclic hydrocarbon, an aromatic hydrocarbon, or a cyclic ether group having an oxygen atom, E represents an n-valent linking group .)
(2) A metal complex in which the β-substituted propionic acid amide represented by the general formula [1] is a β-substituted propionate ester represented by the general formula [5] and an amine compound represented by the general formula [6] as a catalyst The reaction according to (1), which is obtained by reacting in the presence of
(In each formula, R ₁ , R ₂ , n, A, D and E are as defined above. R ₆ represents a linear or branched alkyl group having 1 to 4 carbon atoms.)
(3) The metal complex is a mononuclear metal complex having one metal atom or metal ion in one molecule, or a polynuclear metal complex having two or more metal atoms or metal ions in one molecule, And the metal atom or metal ion is a hard Lewis acid in HSAB law or a Lewis acid of intermediate hardness, the production method according to the above (1) or (2),
(4) The metal complex has two or more organic ligands or inorganic ligands in one molecule, and at least one or more ligands have a hard base or an intermediate hardness in the HSAB rule. A manufacturing method according to any one of the above (1) to (3), which is any one of a combination of a Lewis acid and a Lewis base.
(5) The metal atom or the metal ion of the metal complex has a coordination number of 4 to 12, and an ion radius of 0.5 to 1.5 Å, any of the above (1) to (4) The manufacturing method according to item 1 or
(6) Lewis bases are halide ion, hydroxide ion, acetate ion, toluene sulfonate ion, methane sulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, fluorosulfonate ion And trifluoromethanesulfonate ion, trifluoroacetate ion, 2- (trifluoromethyl) benzenesulfonate ion, water, an amine and at least one selected from the group consisting of alcohols, 1) The manufacturing method according to any one of (5),
(7) The metal (atom or ion) is selected from the group consisting of iron, nickel, copper (divalent), titanium, cobalt, ruthenium, tin, indium, manganese, zinc, gallium, scandium, vanadium, yttrium and lanthanoid The manufacturing method according to any one of the above (1) to (6) is provided, which is at least one kind of organic acid.

  According to the process of the present invention, N-substituted (meth) acrylamide can be produced inexpensively and conveniently from starting material (meth) acrylic acid ester in high yield. Further, in the method of the present invention, a metal complex which is recyclable and has a low environmental load is used as a catalyst, and (meth) acrylamide having a bulky cyclic substituent, long chain alkyl (meth) acrylamide, polyfunctional (meth) ) Even in N-substituted (meth) acrylamides such as acrylamide, the reaction proceeds with sufficient speed and high selectivity, no troubles such as polymerization occur, little by-product of impurities, and high purity products with high yield It can be acquired.

  In the production method of the present invention, the reaction mechanism is not necessarily clear with respect to the catalytic mechanism of the metal complex consisting of a Lewis acid and a Lewis base in the amidation reaction of an amine compound and a β-substituted propionic acid ester. For this reason, it is easy to coordinate to an empty coordination site of the metal or to substitute by replacing the existing metal ligand, whereby the amine is activated and the reaction becomes smooth even under mild conditions. The inventors speculate that it will progress. In addition, even in the liquid phase thermal decomposition of β-substituted propionic acid amide, since alcohol and amine are easily coordinated to the metal complex, they are easily eliminated from β-substituted propionic acid amide, and the decomposition reaction is sufficient even at low temperatures. The inventors speculate that it will progress at a reasonable speed.

The present invention is a β-substituted propionic acid amide comprising the following two steps (i) and (ii), β-alkoxy propionic acid amide (general formula [7]) and β-amino propionic acid amide (general formula 8]) (In each formula, R _{1 to} R ₅ , n, A, D and E are as defined above.) A method for efficiently and industrially producing the compound is provided.

The present invention comprises a general formula [9] comprising the following three steps (i) to (iii): wherein R ₁ , R ₂ , n, D and E are as defined above. It is an object of the present invention to provide a method for efficiently and industrially producing the indicated N-substituted (meth) acrylamide.

(I) Production of β-substituted propionate ester (i-1) Process for producing β-alkoxy propionate ester (Meth) acrylic acid ester and alcohol in the presence of a basic catalyst at a molar ratio (alcohol It is made to react in / (meth) acrylic acid ester) in 1.0 or more, reaction temperature in the range of 0-120 degreeC, and (beta) -alkoxy propionic acid ester can be manufactured.

(B-2) Process for producing β-aminopropionic acid ester (Meth) acrylic acid ester and primary or secondary monofunctional amine in a molar ratio (amine / (meth) acrylic acid ester) of 1.0 or more, reaction The reaction can be carried out at a temperature in the range of -10 to 120 ° C to produce β-aminopropionic acid ester.

(B) Process for producing β-substituted propionic acid amide
An amine compound represented by the general formula [6] and a β-substituted propionic acid ester (β-alkoxypropionic acid ester and β-aminopropionic acid ester) represented by the general formula [5] and produced in the step (i) Can be reacted in the presence of a metal complex to produce β-substituted propionic acid amide (β-alkoxy propionic acid amide and β-amino propionic acid amide) represented by the general formula [1].

(Iii) Process for producing N-substituted (meth) acrylamide (ii) The β-substituted propionic acid amide produced in the process undergoes an alcohol or amine at the β position by liquid phase thermal decomposition reaction in the presence of a metal complex It can be eliminated to produce N-substituted (meth) acrylamide.

Hereafter, each process of this invention is explained in full detail.
Step (a) This step is carried out by reacting (meth) acrylic acid ester with alcohol in the presence of a basic catalyst, and the alkoxypropionic acid ester is obtained in good yield without complicated operation. It can be acquired (B-1). In addition, it is carried out by reacting (meth) acrylic acid ester with a primary or secondary monofunctional amine in the presence of a basic catalyst or under non-catalytic conditions, and the yield is high without complicated operations. An amino propionate can be obtained (1-2). Since the (meth) acrylic acid ester used in the step is easy to polymerize, it is preferably carried out in the presence of a radical polymerization inhibitor.

  In the step (b), using a stoichiometric amount of alcohol or amine as the compounding ratio of alcohol or primary or secondary monofunctional amine to (meth) acrylic acid ester Or the use of an excess thereof to promote completion of the reaction, which is preferable. In general, an alcohol or an amine is used in a range of 1 to 30 times mol with respect to 1 mol of (meth) acrylic acid ester. Moreover, the range of 1.05-20 times mole is preferable, and the range of 1.1-10 times mole is particularly preferable. The alcohol or amine can be used as a solvent for the reaction simultaneously with the starting material for the reaction. Furthermore, since the amine has basic catalysis, the reaction can proceed rapidly without the addition of a separate catalyst. When the compounding ratio of alcohol or amine is more than 30 times the molar amount of (meth) acrylic acid ester, it is disadvantageous for economic aspect such as recovery after reaction.

The basic compound used in the step (i) is not particularly limited, and may be either an inorganic base or an organic base. Examples of the inorganic base include hydroxides of alkali metals such as lithium, sodium and potassium, carbonates, hydrogencarbonates and phosphates. Examples of organic bases include tertiary amines, pyridines and alkoxides of the above alkali metals. Etc. From the viewpoint of preventing the generation of impurities, lithium methoxide, lithium ethoxide, lithium propoxide, lithium butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium methoxide, potassium methoxide, potassium ethoxide, potassium propoxide Potassium butoxide is preferable, and it is most preferable to use a metal alkoxide composed of the same alcohol as that used in the step.

  The basic compounds may be used alone or in combination of two or more. Among these, basic metal alkoxides that are not usually commercially available can be prepared using the boiling point difference of alcohol. For example, when the primary alcohol of the raw material is butyl alcohol, sodium butoxide, potassium butoxide and lithium butoxide are preferred. However, since the catalyst itself is expensive, butanol is added to inexpensive sodium methoxide and the reaction is carried out after sodium butoxide is easily obtained by distilling off methanol by distillation. Is preferred. In addition, as for the addition amount of these basic compounds, 0.05-20 mol% is preferable with respect to the (meth) acrylic acid ester of (i) process.

  The reaction temperature and reaction time of the step (i) are appropriately selected according to the (meth) acrylate and alcohol which are the starting materials of the reaction, the type of the amine, the type of the catalyst, and the compounding ratio. However, generally, the reaction temperature is about 0 to 120 ° C., and the reaction time is in the range of 0.5 to 48 hours. The preferred reaction temperature is about 20 to 100 ° C., and the reaction time is in the range of 1 to 36 hours. If the reaction temperature is less than 0 ° C. or the reaction time is less than 0.5 hours, the rate of the Michael addition reaction is significantly reduced, while if the reaction temperature exceeds 120 ° C., the alcohol or amine goes out of the reaction system It is not preferable because the decomposition of the product and other side reactions increase at the same time as desorption becomes easy. In addition, if the reaction time exceeds 48 hours, the productivity and the cost have disadvantages.

  Although an action as a reaction solvent can be provided by blending an alcohol or an amine which is a starting material of the reaction in excess, a solvent may be used if necessary. The reaction solvent in the step (b) is not particularly limited, and any common solvent can be used as long as it does not cause a side reaction with the starting material for the reaction, the product and the basic compound.

  After completion of the reaction in step (a), the reaction solution is neutralized with an inorganic or organic acidic compound such as hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid as required, or by contact treatment of a strongly acidic cation exchange resin Neutralization can be implemented. Then, if there is a precipitated salt, it is separated by filtration, and the reaction solvent, unreacted alcohol, amine and other by-products in the filtrate are removed under normal pressure or reduced pressure, and the target compound of the process is obtained. [Beta] -alkoxypropionic acid ester and [beta] -aminopropionic acid ester can be obtained. Furthermore, it can be highly purified by a purification method such as vacuum distillation, if necessary.

  The reaction in step (i) is preferably carried out in the presence of a radical polymerization inhibitor. As the polymerization inhibitor, known ones can be used, for example, hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl parahydroquinone, 2,5-di-tert-butyl hydroquinone, 2, 4-Dimethyl-6-tert-butylphenol, phenolic compounds such as hydroquinone monomethyl ether, N-isopropyl-N'-phenyl-para-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl -Para-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-para-phenylenediamine, N, N'-diphenyl-para-phenylenediamine, N, N'-di-2-naphthyl-para- P-phenylenediamines such as phenylenediamine, thiodiphenylamine etc. Amine compounds, piperidine such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, acetamidotetramethylpiperidine-1-oxyl, etc. -1- oxy free radical compounds etc. can be illustrated. These polymerization inhibitors may be used alone or in combination of two or more. Moreover, the addition amount of the polymerization inhibitor is 1 to 10000 ppm, preferably 5 to 5000 ppm with respect to (meth) acrylic acid.

Step (ii) In this step, the β-substituted propionate ester obtained in the step (i) is used in the presence of a metal complex as a catalyst, and the compound of the general formula 6] is to produce the β-substituted propionic acid amide represented by the general formula [1] by an amidation reaction with an amine compound represented by 6].

  The amine compound used in the present invention has a monofunctional amine compound having only one secondary amino group in one molecule and one or more primary amino groups in one molecule, or / and Included are polyfunctional amine compounds having two or more secondary amino groups. These monofunctional amine compounds or polyfunctional amine compounds may be used alone or in combination of two or more.

  The monofunctional amine compound is an N-monosubstituted or N, N-disubstituted substituent having 11 to 36 carbon atoms (a linear or branched alkyl group, an alkyl ether group, an alicyclic hydrocarbon, an aromatic group A saturated or unsaturated, linear or branched or cyclic aliphatic monofunctional primary amine and a monofunctional secondary amine (including those having an aromatic ring) having a hydrocarbon); A monofunctional primary aromatic amine having a substituent having 11 to 36 carbon atoms and a monofunctional secondary aromatic amine having a substituent having 11 to 36 carbon atoms, and a monofunctional primary alkano having a substituent having 11 to 36 carbon atoms as described above And monofunctional secondary alkanolamines, monofunctional primary ether amines having the same substituent having 11 to 36 carbon atoms and monofunctional secondary ether amines, and the same substitution of 11 to 36 carbon atoms as described above Monofunctional primary amino acid having a group It is down and monofunctional secondary amino amine. As specific examples of the linear or branched alkyl group having 11 to 36 carbon atoms, undecyl group (C11), lauryl group (C12), tridecyl group (C13), myristyl group (C14), cetyl group ( C16), stearyl group (C18), oleyl group (C18), aralyl group (C20), behenyl group (C22), lignoceryl group (C24), serotoyl group (C26), montanyl group (C28), melissyl group (C30) And saturated or unsaturated linear or branched chains of dotriacontanoyl group (C32), tetratriacontaylamine (C34), and hexatriacontanoyl group (C36).

  The polyfunctional amine compound is an N-monosubstituted or N, N-disubstituted C1-C36 substituent (a linear or branched alkyl group, an alkyl ether group, an alicyclic hydrocarbon, an aromatic group Saturated or unsaturated, linear or branched or cyclic aliphatic polyfunctional primary amine, polyfunctional secondary amine or polyfunctional primary or secondary having a hydrocarbon Blended amines, polyfunctional primary aromatic amines having the same substituent having 1 to 36 carbon atoms, polyfunctional secondary aromatic amines, or polyfunctional primary and secondary blended aromatic amines And the same as above, polyfunctional primary alkanolamine having a substituent of 1 to 36 carbon atoms, polyfunctional secondary alkanolamine, or polyfunctional primary and secondary blend alkanolamine, as described above First polyfunctional having a C 1 to C 36 substituent group Ether amine and polyfunctional secondary ether amine or polyfunctional primary and secondary blended ether amine, polyfunctional primary amino amine having the same substituent having 1 to 36 carbon atoms, polyfunctional primary amine It is a secondary aminoamine or a multifunctional primary and secondary blended aminoamine. Specific examples of the linear or branched alkyl group having 1 to 36 carbon atoms include methyl group (C1), ethyl group (C2), (iso) propyl group (C3) and (iso) butyl group C4), (iso) pentyl group (C5), (iso) hexyl group (C6), (iso) heptyl group (C7), (iso) octyl group (C8), (iso) nonyl group (C9), (iso ) Decyl group (C10), undecyl group (C11), lauryl group (C12), tridecyl group (C13), myristyl group (C14), cetyl group (C16), stearyl group (C18), oleyl group (C18), aralyl Group (C20), behenyl group (C22), lignoceryl group (C24), serotoyl group (C26), montanyl group (C28), melissyl group (C30), dotriacontanoyl group (C32), tetratritol Contour noil amine (C34), linear or branched, saturated or unsaturated hexa triacontanyl hexanoyl group (C36) can be mentioned.

  The polyfunctional amine compound is one having one or more primary amino groups or two or more secondary amino groups in one molecule, and optionally from the group consisting of the amino groups of the above monofunctional amine compounds. It is composed of a combination of two or more selected amino groups. Also, from the viewpoint of industrial availability and high safety, as the aliphatic polyfunctional amine, ethylenediamine, propylenediamine, isopropylenediamine, 1,3-diamino-2-propanol, 1,2-dihydroxyethylenediamine 2,3-Dihydroxy-1,4-butanediamine, 1,8-diamine-3,6-dioxaoctane, 1,10-diamino-4,7-dioxadecane, 1,1 '-(1,2- (1,2-) Ethanediyl bis (oxy)) bis (3-amino-2-propanol)), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis (hexamethylene) triamine, trimethylhexamethylenediamine, hexamethylenediamine, tris (2-aminoethyl) amine, n-f Phenyl-ethylenediamine, putrescine (1,4-butanediamine), spermidine (N- (3-aminopropyl) -1,4-diaminobutane), spermine (N, N-bis (3-aminopropyl) butane-1, 4-diamine, tris (3-aminopropoxymethyl) aminomethane, 4,7,10-trioxa-1,13-tridecaneamine, 1,4-bis (2-hydroxy-3-amino propoxy) butane, polyether diamine Etc. are preferable, and as alicyclic polyfunctional amines, isophorone diamine, 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-amino Methyl piperazine, menthane diamine, N-aminoethyl piperazine, 3 ,, 9-Bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, Methylenedianiline etc. are preferable, As aromatic polyfunctional amines, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, diaminodiphenylmethane, 1,3,5-triaminobenzene, 1,2,4-4- Triaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, N, N'-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidazole, xylylenediamine, etc. are preferred. The amine compound may be used alone or in combination of two or more.

  The metal complex used in the present invention is selected from the group consisting of mononuclear metal complexes having one metal atom or metal ion in one molecule and polynuclear metal complexes having two or more metal atoms or metal ions in one molecule. One or two or more.

  The metal atom or metal ion of the mononuclear metal complex and polynuclear metal complex is a hard Lewis acid or a Lewis acid of intermediate hardness in the HSAB rule. The HSAB law (Hard and Soft Acids and Bases law) is known to classify the compatibility between Lewis acid and Lewis base using the expression of hard and soft, and "hard Lewis acid" has high charge density, A less polarizable, smaller size cation, "soft Lewis acid", is a cation that has a low charge density, is relatively easy to polarize, and has a large size. On the other hand, the “hard Lewis base” is a small base having high electronegativity and difficult to be polarized, and the “soft Lewis base” is a large base having small electronegativity and easy to be polarized. There are also these intermediate acids (Lewis acids of medium hardness) and intermediate bases (Lewis bases of medium hardness), according to the HSAB rules "hard Lewis acids" and "hard Lewis bases" , "Soft Lewis acid" and "soft Lewis base" are the rule of thumb that they are easy to interact with each other.

  The metal atom or metal ion of the metal complex used in the present invention is characterized by having a coordination number of 4 to 12 and an ion radius of 0.5 to 1.5 Å. If the coordination number and ionic radius are within this range, the metal atom or metal ion corresponds to a hard Lewis acid of HSAB law or a Lewis acid of intermediate hardness, and a hard Lewis base or a Lewis of intermediate hardness The combination with a base can exhibit a sufficiently high activity as a catalyst such as the amidation reaction of the present invention. Specifically, it consists of iron, nickel, copper (divalent), titanium, ruthenium, tin, indium, magnesium, calcium, manganese, zinc, gallium, scandium, vanadium, yttrium, lanthanoid metal as metal (atom or ion) It is at least one metal selected from the group.

  The metal complex used in the present invention has two or more organic ligands or inorganic ligands in one molecule, and at least one or more ligands are hard Lewis bases or intermediates in the HSAB rule. Lewis base of good hardness.

  The Lewis base used in the present invention includes halide ion, hydroxide ion, acetate ion, toluene sulfonate ion, methane sulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, fluorosulfone It is at least one ligand selected from the group consisting of an acid ion, a trifluoromethanesulfonic acid ion, a trifluoroacetic acid ion, a 2- (trifluoromethyl) benzenesulfonic acid ion, water, an amine and an alcohol.

  When any combination of at least one metal atom or metal ion selected from the group of Lewis acids and at least one ligand selected from the group of Lewis bases, any one or more metal complexes You can get The metal complex catalyst used in the present invention is a mononuclear metal complex composed of two or more same kind or different kinds of ligands centering on one metal atom or metal ion in one molecule, and in one molecule A multinuclear metal complex is composed of two or more same or different metal atoms or metal ions, and composed of two or more same or different ligands per metal atom or metal ion. Furthermore, it is to include a metal cluster having a bond between metal atoms as a polynuclear metal complex. Specifically, catalysts usable in the steps (ii) and (iii) of the present invention include, as metals, iron, nickel, copper (divalent), titanium, cobalt, ruthenium, tin, indium, magnesium, calcium, manganese, Zinc, gallium, scandium, vanadium, yttrium, lanthanoid, halide ion as a ligand, hydroxide ion, hydroxide ion, acetate ion, toluene sulfonate ion, methane sulfonate ion, perchlorate ion, tetrafluoroborate ion, hexa ion Fluorinated phosphate ion, fluorosulfonic acid ion, trifluoromethanesulfonic acid ion, trifluoroacetic acid ion, 2- (trifluoromethyl) benzenesulfonic acid ion, water, an amine, and an optional combination with an alcohol Containing mononuclear metal complexes and / or clusters Polynuclear metal catalyst. These metal complexes can be used alone or in combination of two or more. Iron, nickel, copper, tin, indium, manganese, zinc, scandium, vanadium, yttrium, lanthanoid acetate, toluene sulfonate, methane sulfonate, perchlorate from the viewpoint of industrialization and availability in general Tetrafluoroborate, fluorosulfonate, trifluoromethanesulfonate, and trifluoroacetate are more preferable.

  The reaction of the step (b) may be a batch system or a continuous system. For example, in the case of a batch reaction, the shape of the metal complex is preferably powdery or particulate. In addition, in the powdery or fine particulate catalyst, a state uniformly dissolved or dispersed by the amine compound as the raw material, the β-substituted propionate ester obtained in the step (i), and the organic solvent added as necessary It is more preferable to use because it is easy to handle. For example, in the case of a continuous reaction, it is preferable to use for the reaction in a state where the metal complex is fixed to a suitable catalyst carrier.

  In the step (b), the molar ratio of the β-substituted propionic acid ester to the amine compound is excessive using either one of the functional group (amino group) of the amine compound and the functional group (ester group) of the β-substituted propionic acid ester This promotes the completion of the reaction. In the present invention, from the viewpoint that the product β-substituted propionic acid amide in the step (ii) is easily separated and purified from the reaction liquid, the blending amount of the ester group is in the range of 1.00 to 20 times the molar amount with respect to the amino group. Is preferable, and the range of 1.01 to 10 times mol is more preferable. The β-substituted propionate ester used in excess can simultaneously be used as a solvent for the reaction, but if it exceeds this compounding amount, it is disadvantageous for economic aspects such as recovery of the excess charged after the reaction.

  The amount of the metal complex used in step (b) depends on the type and properties of the β-substituted propionate and amine compound (liquid or solid at reaction temperature), number of amino groups, solubility, reaction temperature and solvent used Although there is an optimum range, it is usually in the range of 0.1 to 50 mol%, preferably in the range of 0.5 to 20 mol%, particularly preferably in the range of 1 to 10 mol% relative to the amino group.

  The reaction temperature and reaction time of the step (b) are appropriately selected according to the type and mixing ratio of the β-substituted propionate ester synthesized in the step (b) and the raw material amine compound, but the reaction selectivity The reaction temperature is about 0 to 150 ° C., and the reaction time is in the range of 0.1 to 48 hours because the reaction rate is relatively fast. The preferred reaction temperature is about 20 to 150 ° C., the reaction time is 0.5 to 36 hours, the particularly preferable reaction temperature is 40 to 100 ° C., and the reaction time is 1.0 to 24 hours. It is. Although the effect | action as a reaction solvent can also be provided by mix | blending excess (beta) -substituted propionic acid ester obtained by (i) process, a solvent may be used as needed. The reaction can be carried out under normal pressure, under reduced pressure or under pressure using an apparatus that can be pressurized such as an autoclave. The reaction solvent is not particularly limited, and any common solvent can be used as long as it does not cause a side reaction with the starting material for the reaction, the product and the metal complex. Examples thereof include hydrophobic solvents such as toluene and xylene, and hydrophilic solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), ethylene glycol and glycerin. When a solvent is used, the amount thereof used is usually in the range of 20 to 1000% by weight, preferably 50 to 500% by weight, particularly preferably 100 to 100% by weight based on the total of the β-substituted propionic acid ester and the amine compound. It is in the range of 300 to 300% by weight. When the reaction solvent is used for the purpose of dissolving the raw materials or improving the stirring efficiency, it may not be expected to have a sufficient effect with less than 20% by weight, and when it exceeds 1000% by weight, it is uneconomical at the same time The reaction rate may be reduced.

  When the reaction in step (b) is carried out in a batch mode, for example, the β-substituted propionate ester obtained in step (a), an amine compound as a raw material, a metal complex and a solvent are charged into a reaction vessel, and if necessary After replacing the inside of the reaction vessel and the reaction liquid with an inert gas, the reaction temperature is adjusted to a predetermined value while maintaining the suspended or dissolved state by stirring, and the reaction is performed for a predetermined time. In addition, when the metal complex is present in a solid state, for example, the reaction liquid mixture after completion of the reaction may be separated and recovered by filtration or filtration and separation of the solid liquid by a filter, or separated. Alternatively, decantation, concentration, precipitation with water or other solvent, extraction, etc. may be carried out, and then it may be reused as it is (step B) or carried over to the next step (step C). On the other hand, when the metal complex after completion of the reaction is dissolved in the reaction solution, the reaction solution may be concentrated and then reused as it is (step B) or carried over to the next step (step B). Furthermore, regardless of the state of dissolution or dispersion of the metal complex after completion of the reaction, the reaction solution can be carried over to the next step (step III) without being concentrated.

  In the steps (ii) and (iii) of the present invention, as the reaction proceeds, the coordination structure of the metal complex as the catalyst may be changed, and a hard acid or an intermediate in the aforementioned HSAB rule may be used. Combination of a metal atom or metal ion corresponding to an acid and various ligands corresponding to a hard base or a base of intermediate hardness according to HSAB rules, such as a raw material amine compound, a reaction product or an intermediate, etc. The metal complex is not particularly limited as long as it is a metal complex composed of That is, the type, concentration, and proportion of the ligand change with the progress of the reaction, and the type and number of metal complexes may change according to the change, and as a result, the metal complex An optimal coordination structure in the reaction system will be taken. The reason why the amidation reaction of the amine compound of the present invention and the β-substituted propionic acid ester can proceed at a low temperature and with a high yield and a high selectivity is not clearly elucidated, but the inventors Accordingly, it is presumed that the high activity of the catalyst is provided by the fact that the structure of the metal complex can always maintain the optimum state by self-adjustment.

Step (iii) In this step, using the β-substituted propionic acid amide obtained in step (ii), the alcohol or amine is eliminated by liquid phase thermal decomposition reaction at a predetermined reaction temperature and operating pressure. (B) Distilling and recovering in the order of boiling point together with the reaction solvent, unreacted starting materials, by-products, etc. introduced from step (b) to obtain the desired N-substituted (meth) acrylamide as a distillation component or distillation residue be able to. Also, depending on the physical properties of the target product, raw materials, byproducts and reaction solvent, the target product is separated and purified by known methods such as precipitation, washing, extraction, centrifugation, separation with ion exchange resin instead of distillation. Can be acquired. Furthermore, if necessary, the desired product obtained can be obtained by a known method such as precision distillation, recrystallization, sublimation, permeation, adsorption, etc. to obtain a desired product of high purity. The reaction of this step can be carried out using a mixture of crude β-substituted propionic acid amide and metal complex obtained from step (ii), and addition of metal complex to the separated and purified β-substituted propionic acid amide Can be done. It is preferable to carry out in the presence of a polymerization inhibitor as in step (a). As the polymerization inhibitor, those known in the step (i) can be used.

  The step (iii) may use the same or different metal complex catalyst as the step (ii), and may use the same or different polymerization inhibitor as the step (ii). The addition amount of the metal complex is preferably 1 to 50 mol% with respect to the raw material β-substituted propionic acid amide (alkoxy propionic acid amide or amino propionic acid amide) in the step (iii). The addition amount of the polymerization inhibitor is 1 to 10000 ppm, preferably 5 to 5000 ppm with respect to the β-substituted propionic acid amide.

  (C) The reaction temperature in the step is usually about 80 to 200 ° C., and the reaction time is in the range of 1 to 40 hours. The preferred reaction temperature is about 100 to 150 ° C., and the reaction time is in the range of 2 to 30 hours. If the reaction temperature is less than 80 ° C. or the reaction time is less than 1 hour, the thermal decomposition reaction rate is significantly reduced, while if the reaction temperature is more than 200 ° C., the polymerization of products and other side reactions increase. Not desirable. In addition, when the reaction time exceeds 40 hours, the productivity and the cost have disadvantages.

  (C) A solvent may be used in the process as needed. The reaction solvent is not particularly limited, and any common solvent can be used as long as it does not cause a side reaction with a reaction starting material, a product or a metal complex. An appropriate range when a solvent is used is usually in the range of 10 to 1000% by weight, preferably in the range of 50 to 500% by weight, based on the β-substituted propionic acid amide.

  The catalysts used in Examples of the present invention and Comparative Examples are shown in Table 1. The metal complexes shown here are merely for the purpose of illustrating the present invention, and are not intended to limit the present invention in any way.

Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited thereto. Abbreviated-names of the (beta) -substituted propionic acid ester described in the Example and the comparative example, (beta) -substituted propionic acid amide, N-substituted (meth) acrylamide, and the used material are as follows.
(1) (Meth) acrylic acid ester MA: methyl acrylate EA: ethyl acrylate BA: butyl acrylate MMA: methyl methacrylate (2) amine compound DMA: dimethylamine DEA: diethylamine DBA: dibutylamine LA: laurylamine SA : Stearyl amine
BAN: bis (aminomethyl) norbornane
EDA: ethylenediamine
IPDA: Isopropylene diamine
BDA: butylene diamine
OBBA: 4,4'-oxybis (benzeneamine)
DTA: Diethylenetriamine
APDA: N- (3-aminopropyl) -1,3-propanediamine
TETA: triethylenetetramine
BPDA: N, N'-bis (2-aminoethyl) -1,3-propanediamine
TEPA: tetraethylenepentamine
NEDA: nona ethylene decamine
BABB: 1,4-bis (2-hydroxy-3-aminopropoxy) butane
DAHO: 1,6-diamino-2,5-hexanediol
DADO: 1, 8-diamine-3, 6-dioxaoctane
DADD: 1, 10-diamino-4, 7-dioxadecane
BHBA: N, N'-bis (2-hydroxyethyl) -1,4-butanediamine
BMHA: N, N'-bismethoxymethyl-1,6-hexanediamine
TAPA: tris (3-aminopropoxymethyl) aminomethane
TODA: 4,7,10-trioxatridecane-1,3-diamine
PTPA: 3,3 ', 3 "-(1,2,3-propanetriyltris (oxy) tris (1-propanamine)
(3) β-substituted propionate ester MPM: methyl β-methoxypropionate MPE: ethyl β-methoxypropionate EPE: ethyl β-ethoxypropionate EPM: methyl β-ethoxypropionate MPB: butyl β-methoxypropionate DMAPM : Methyl β-dimethylaminopropionate DEAPM: Methyl β-diethylaminopropionate DMAPE: Ethyl β-dimethylaminopropionate DEAPE: Ethyl β-diethylaminopropionate DBAPM: Methyl β-dibutylaminopropionate (4) β-alkoxypropionic acid Amide EPM-LA: Amidation reaction product of MPM and LA MPM-SA: Amidation reaction product of EPM and SA MPM-BAN: Amidation reaction product of MPM and BAN EPE-EDA: APE of EPE and EDA Deoxidation reaction product MPB-BDA: Amidation reaction product of MPB and BDA MPM-OBBA: Amidation reaction product of MPM and OBBA MPM-DAHO: Amidation reaction product of MPM and DAHO MPE-BPDA: MPE with Amidation reaction product of BPDA MPM-BHBA: Amidation reaction product of MPM and BHBA MPE-BMHA: Amidation reaction product of MPE and BMHA (5) .beta.-aminopropionic acid amide DMAPM-DTA: DMAPA and DTA Amidation reaction product DEAPM-IPDA: Amidation reaction product of DEAPM and IPDA DBAPM-SA: Amidation reaction product of DBAPM and SA DEAPM-APDA: Amidation reaction product of DEAPM and APDA DMAPE-TETA: DMAPE Amidation reaction product of TETA EAPM-TEPA: Deamidation reaction product of DEAPM and TEPA DEAPE-NEDA: Amidation reaction product of DEAPE and NEDA DMAPM-BABB: Amidation reaction product of DMAPM and BABB DEAPE-DADO: Amidation reaction of DEAPE and DADO Product DEAPE-DADD: Amidification reaction product of DEAPE and DADD DBAPM-TAPA: Amidification reaction product of DBAPM and TAPA DEAPM-TODA: Amidification reaction product of DEAPM and TODA DEAPE-PTPA: An amide of DEAPE and PTPA Reaction product (6) N-substituted (meth) acrylamide LMAM: lauryl methacrylamide SAM: stearyl acrylamide
NBBAM: norbornane bisacrylamide EBA: N, N'-ethylenebisacrylamide IPBA: isopropylene bisacrylamide
BBA: butylene bis acrylamide
OBBAM: 4,4'-oxybis (benzene acrylamide)
TADTA: N, N ', N "-trisacryloyldiethylenetriamine
BPPA: N, N-bis (3-((1-oxo-2-propen-1-yl) amino) propyl) -2-propenamide
TAETA: N, N ′, N ′ ′, N ′ ′ ′-tetraacryloyl ethylene tetraamine PPPA: N, N′-1,3-propane ezyl bis (N- (2- (1-oxo-2-propene-1-) Yl) amino) ethyl) -2-propenamide
PAETA: Pentaacryloyl ethylene pentaamine
NAEDA: nonacryloyl ethylene decaamine
BBBA: N, N '-(1,4-butane hexyl bis (oxo (2-hydroxy-3,1-propane hexyl)) bis (2-propenamide)
BAMHO: 1,6-bisacrylamide-2,5-hexanediol
BHBAM: N, N'-bis (2-hydroxyethyl) -1,4-butylenebisacrylamide
BAMDO: 1,8-bisacrylylamido-3,6-dioxaoctane
BMADO: 1,8-bismethacrylamido-3,6-dioxaoctane
BAMDD: 1,10-bisacrylamide-4,7-dioxadecane
BMHAM: N, N'-bismethoxymethyl-1,6-hexyl diacrylamide
TAPAM: N- (Tris (3-acrylamidopropoxymethyl) methyl) acrylamide TDBAM: N, N '-(4,7, 10-trioxatridecamethylene) bisacrylamide PTPAM: N, N'', N ""- (1,2,3-propanetriyl (oxy-3,1-propanediyl)) tris (2-propenamide)
(7) Alcohol compound MeOH: methanol EtOH: ethanol BuOH: butanol (8) basic catalyst SM: sodium methoxide SE: sodium ethoxide LiOMe: lithium methoxide KOMe: potassium methoxide KOEt: potassium ethoxy De-KOBu: Potassium butoxide NaOH: Sodium hydroxide KOH: Potassium hydroxide (9) Polymerization inhibitor TDA: Thiodiphenylamine HQ: Hydroquinone MEHQ: Hydroquinone monomethyl ether TEMPO: 2,2,6,6-Tetramethylpiperidine-1-oxyl TBC: 4-tert-butyl catechol BHT: dibutyl hydroxytoluene DDA: styrylation-N-aminobiphenyl W-300: 4,4′-butylidene bis (6-tert-butyl-m-cresole)

Example 1
(A-1) 259.0 g (3 mol) of methyl acrylate (MA) and 0.13 g of MEHQ were charged into a 1000 mL flask equipped with a stirrer, thermometer, dropping device and condenser, and sodium methoxide (SM) was added thereto. A mixed solution consisting of 0.16 g (3 mmol) and 106.0 g (3.3 mol) of methanol (MeOH) was slowly added with stirring. Meanwhile, the temperature of the reaction mixture was kept below 40 ° C. After completion of the addition, the reaction mixture was heated to 60 ° C. with stirring, and the reaction was continued for 6 hours while refluxing methanol. Thereafter, the reaction solution is returned to room temperature and neutralized with an equivalent amount of sulfuric acid, and the unreacted raw material is removed by distillation to obtain 352.5 g of methyl β-methoxypropionate (abbreviated as MPM). The purity was 99.9%, and the yield was 99%.

(B-1) In a 2000 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 300 g (2.5 mol, 99.9% purity) of the MPM obtained in the step (a-1), 539 g (2 .0 mol), 34.6 g (0.1 mol) of iron (II) trifluoromethanesulfonate as a metal complex and 420 mL of DMF as a solvent, the reaction solution is heated to 80.degree. C. with stirring, and further by-products are added. The reaction was continued at 80 ° C. for 2 hours while removing some methanol. After completion of the reaction, the temperature of the reaction solution was returned to room temperature, and it was confirmed by sampling that the reaction yield reached 98%. Thereafter, the reaction solution was transferred to a distillation apparatus, and the solvent and the unreacted material were recovered. The distillation residue was recrystallized twice using acetone to obtain a white solid. The purity of the product is 99.9% by gas chromatography analysis, and the product is the target compound β-methoxy-N by analysis of infrared absorption spectrum (IR) with nuclear magnetic resonance spectrum ( ¹ H-NMR) -It confirmed that it was stearyl amide (abbreviation MPM-SA).

Examples 2 to 8
(I-2) to (i-10) and (ro-2) to (ro-10) In Example 1, the starting materials, catalyst, solvent, polymerization inhibitor and reaction conditions of each step are as shown in Table 2. The reaction of (a) step and (b) step was performed in the same manner as in Example 1 and the identification of each product was performed by ¹ H-NMR and IR analysis. The reaction yield of each step is shown in Table 2. Depending on the reaction temperature, the alcohol by-produced during the reaction may not be removed, and after completion of the reaction, it may be removed by distillation under normal pressure or reduced pressure. When a solvent is used for the reaction, the solvent can be recovered by distillation after completion of the reaction. Furthermore, purification can be performed by known methods such as neutralization, washing, extraction, recrystallization, ion exchange resin treatment, chromatography, etc., depending on physical properties such as the state of the target compound and solubility.

Example 11
(B-11) After charging 216.0 g (2.5 mol) of MA, 0.11 g of MEHQ, and 0.07 g (1 mmol) of SM in order to a 1000 mL autoclave, the mixture is cooled to 0 ° C., and the liquefied DMA 124 .4 g (2.8 mol) were added. After the addition, the reaction mixture was heated to 40 ° C. with stirring, and the reaction was continued under pressure for 6 hours. Thereafter, the reaction solution is returned to room temperature, neutralized with an equivalent amount of sulfuric acid, and unreacted raw materials are removed by distillation to obtain 323.7 g of methyl β-dimethylamino-propionate (abbr. DMAPM). The purity was 99.9%, and the yield was 98%.

(B-11) In a 2000 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 300 g (2.3 mol, 99.9% purity) of DMAPM obtained in the step (b-11), 51.6 g DTA (0.5 mol), 11.1 g (0.03 mol) of nickel (II) trifluoromethanesulfonate was added, the reaction solution was heated to 60 ° C. with stirring, and the methanol as a by-product was further removed. The reaction was continued for 1 hour at ° C. After completion of the reaction, the temperature of the reaction solution was returned to room temperature, and it was confirmed by sampling that the reaction yield reached 98%. Thereafter, the reaction solution was transferred to a distillation apparatus, and the solvent and unreacted starting materials were recovered to obtain a white solid. The product purity is 99.2% by gas chromatography analysis, and the product is amidated by DMAPM and DTA by analysis of infrared absorption spectrum (IR) with nuclear magnetic resonance spectrum ( ¹ H-NMR) The objective compound (abbr. DMAPM-DTA) obtained in

Examples 12 to 22
(I-12) to (i-22) and (ro-12) to (ro-22) In Example 11, the starting materials, the catalyst, the solvent, the polymerization inhibitor and the reaction conditions of the respective steps are as shown in Table 3. The reaction of (a) step and (b) step was performed in the same manner as in Example 11, and identification of each product was performed by ¹ H-NMR and IR analysis. The reaction yield of each step is shown in Table 3. Depending on the reaction conditions, the alcohol by-produced during the reaction may not be removed and may be removed by distillation under normal pressure or reduced pressure after completion of the reaction. In the reaction under normal pressure, a 1000 mL flask equipped with a stirrer, a thermometer and a condenser was used instead of the autoclave. When a solvent is used for the reaction, the solvent can be recovered by distillation after completion of the reaction. Furthermore, purification can be performed by known methods such as neutralization, washing, extraction, recrystallization, ion exchange resin treatment, chromatography, etc., depending on physical properties such as the state of the target compound and solubility.

Example 23
(Ha-23) Using a 1000 mL reactive distillation apparatus equipped with a stirrer, a thermometer, a gas introduction line and a condenser, MPM-SA 355. 6 g (1.0 mol), 0.711 g of TDA as a polymerization inhibitor, 36.2 g (0.1 mol) of copper (II) trifluoromethanesulfonate as a metal complex, and 250 g of xylene as a solvent were added. Thereafter, a trace amount of nitrogen gas was flowed as a carrier, the temperature of the reaction mixture was raised to 110 ° C. while stirring, and MeOH generated by the liquid phase thermal decomposition reaction was distilled off under normal pressure. After completion of the reaction, the temperature of the reaction solution was returned to room temperature, and the precipitated solid was separated by filtration to obtain a crude monomer. The obtained crude monomer was recrystallized twice with acetone to obtain a white powder having a melting point of 71 to 72 ° C. The purity of the product is 99.4% by gas chromatography analysis, and the product is the target compound stearylacrylamide (abbreviation SMA) by analysis of infrared absorption spectrum (IR) with nuclear magnetic resonance spectrum ( ¹ H-NMR). It confirmed that it was).

Examples 24-32
(HA-24) to (HA-32) In Example 23, the starting materials, catalyst, solvent, polymerization inhibitor and reaction conditions of the respective steps are changed as shown in Table 4, and thermal decomposition is carried out as in Example 23. The reaction was carried out to obtain each desired product. In addition, the thermal decomposition process of (iii) can be used without refine | purifying the reaction liquid obtained by the (ii) process. Also. Purification can be performed by known methods such as washing, extraction, recrystallization, ion exchange resin treatment, chromatography and the like depending on the physical properties of the target compound.

Example 33
(Ha-33) Using 500 g of the reaction liquid after completion of the reaction for 16 hours obtained in the (row 21) step, charge it in the same reaction distillation apparatus as (ha-23), raise the temperature to 80 ° C, and reduce pressure Then, the butylene diamine produced by the thermal decomposition reaction for 6 hours was distilled to obtain a crude monomer. The obtained crude monomer was recrystallized twice with a mixed solvent of methanol and acetone to obtain a white powder having a melting point of 57 to 58 ° C. The purity of the product is 99.0% by gas chromatography analysis, and analysis of the infrared absorption spectrum (IR) with the nuclear magnetic resonance spectrum ( ¹ H-NMR) shows that the product is the target compound N, N′− It was confirmed that it was (4,7,10-trioxatris decamethylene) bisacrylamide (abbreviated as TDBAM).

Examples 34 to 44
(Ha-34) to (Ha-44) In Example 23 or Example 33, the starting materials, catalyst, solvent, polymerization inhibitor and reaction conditions of each step were changed as shown in Table 5, Example 23 or The thermal decomposition reaction was carried out in the same manner as in Example 33 to obtain the intended product of each. Depending on the physical properties of the target compound, neutralization (for example, neutralization and separation of amino group of residual β-aminopropionic acid ester with acid), washing, extraction, recrystallization, adsorption treatment with ion exchange resin, chromatography Purification can be performed by known methods such as

Comparative Examples 1 to 4
The reaction was performed according to the method described in Example 1 except that the starting materials, the catalyst, the solvent, the polymerization inhibitor and the reaction conditions of the respective steps in Example 1 were changed as shown in Table 6. The reaction results are shown in Table 6. In these comparative examples, the purification operation of the product was not performed.

Comparative Examples 5 to 10
A reaction was performed according to the method described in Example 23, except that the starting materials, the catalyst, the solvent, the polymerization inhibitor and the reaction conditions of the respective steps in Example 23 were changed as shown in Table 7. The results are shown in Table 7. In these comparative examples, the purification operation of the product was not performed.

  From the results of Example 1-22 and Comparative Example 1-4, in the amidation reaction in the step (ii), even if the reaction conditions such as the feed ratio of the raw materials, the reaction temperature, and the time are equal, the metal complex of the present invention is proposed It was found that the reaction did not proceed without the presence of.

  From the results of Example 23-44 and Comparative Example 5-10, in the thermal decomposition reaction of (iii) step, even if the reaction conditions such as the feed ratio of the raw materials, the reaction temperature, and the time are equal, the metal complex of the present invention is proposed It was found that the reaction did not proceed without the presence of. In addition, in the thermal decomposition reaction by the conventional acidic catalyst, the reaction does not occur unless the temperature is high, and on the other hand, polymerization troubles due to the high temperature reaction easily occur, and in particular, obtaining polyfunctional N-substituted (meth) acrylamide I could not

As described above, when the method of the present invention uses a (meth) acrylic acid ester as a starting material and a metal complex is used as a catalyst, β-alkoxypropionic acid is efficiently obtained for a short time even under mild reaction conditions. Esters, β-aminopropionic esters and high purity N-substituted (meth) acrylamides can be prepared. In addition, the reaction proceeds at a sufficient speed and high selectivity even under normal pressure and low temperature by the selection of the metal complex catalyst, and troubles such as polymerization do not occur, there is little byproduct of impurities, and high yield of high purity products Can be obtained by
The N-substituted (meth) acrylamide obtained by the method of the present invention is a functional polymer obtained by homopolymerization or copolymerization with another polymerizable monomer, and in the daily life, from the viewpoint of convenience, paints, adhesives, adhesives , Various coating agents, paper strength agents such as paper strength agents, polymer flocculants used in industrial and household wastewater treatment, polymer modifiers, dispersants, thickeners, thickeners, contact lenses and biogels It can be suitably used in a very wide variety of fields such as synthetic raw materials such as, reactive diluents for UV curable resins, and the like.

Claims (7)

The liquid phase thermal decomposition reaction is carried out in the presence of a metal complex as a catalyst using the β-substituted propionic acid amide represented by the general formula [1], and the N-substituted (generally represented by the general formula [2] Method for producing meta) acrylamide.
(In each formula, R ₁ represents a hydrogen atom or a methyl group. N is an integer of 1 to 10, and when n = 1, R ₂ is a linear or branched chain having 11 to 36 carbon atoms alkyl group, alkyl ether group, an alicyclic hydrocarbon, an aromatic hydrocarbon, for integer n = 2 to 10, R ₂ is a hydrogen atom or a linear or branched carbon atoms 1 to 36 A represents an alkoxy group or an amino group represented by the general formula [3] or [4] (wherein R ₃ represents Represents a linear or branched alkyl group having 1 to 6 carbon atoms, an alkyl ether group, or an alicyclic hydrocarbon R ₄ and R ₅ each independently represent a hydrogen atom or a linear or branched chain having 1 to 10 carbon atoms List of linear alkyl group, alkyl ether group, alicyclic hydrocarbon, aromatic hydrocarbon . Further, R ₄ and R ₅ together with the nitrogen atom carrying them, represent a saturated 5 to 7 membered ring may be made by forming a (including those having an oxygen atom)), D is hydrogen Or a linear or branched alkylene group having 1 to 10 carbon atoms, an alkylene ether group, an alicyclic hydrocarbon, an aromatic hydrocarbon, or a cyclic ether group having an oxygen atom, E represents an n-valent linking group .)
In the presence of a metal complex, the β-substituted propionic acid amide represented by the general formula [1] is a β-substituted propionate ester represented by the general formula [5] and an amine compound represented by the general formula [6] The method according to claim 1, wherein the reaction is carried out by
(In each formula, R ₁ , R ₂ , n, A, D and E are as defined above. R ₆ represents a linear or branched alkyl group having 1 to 4 carbon atoms.) The metal complex is a mononuclear metal complex having one metal atom or metal ion in one molecule, or a polynuclear metal complex having two or more metal atoms or metal ions in one molecule, and a metal atom The method according to claim 1 or 2, wherein the metal ion is a hard Lewis acid in HSAB law or a Lewis acid of intermediate hardness. The metal complex has two or more organic ligands or inorganic ligands in one molecule, and at least one or more ligands are hard bases or bases of intermediate hardness in the HSAB rule. The method according to any one of claims 1 to 3, wherein the method is any one of a combination of a Lewis acid and a Lewis base. 5. The metal atom or metal ion of the metal complex has a coordination number of 4 to 12, and an ion radius of 0.5 to 1.5 Å. Production method. Lewis bases include halide ion, hydroxide ion, acetate ion, toluene sulfonate ion, methane sulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, fluorosulfonate ion, trifluoromethane 6. The method according to claim 1, wherein at least one selected from the group consisting of sulfonate ion, trifluoroacetate ion, 2- (trifluoromethyl) benzenesulfonate ion, water, amine, and alcohol. The manufacturing method according to any one of the above. The metal (atom or ion) is at least one selected from the group consisting of iron, nickel, copper (divalent), titanium, cobalt, ruthenium, tin, indium, manganese, zinc, gallium, scandium, vanadium, yttrium, lanthanoid The method according to any one of claims 1 to 6, which is a species.