JP4250211B2 - Novel aminocarboxylic acid ester salt derivatives - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel aminocarboxylic acid ester salt derivative and a method for producing the same.
[0002]
[Prior art]
Conventionally, amide derivatives, particularly N-acylaminocarboxylic acid esters, have been used as starting materials in the production of various industrially useful compounds. In the production of these amide derivatives, aminocarboxylic acid is used as a starting material. Specifically, (1) aminocarboxylic acid in the presence of sodium hydroxide or the like in water or a water-alcohol solvent. And then acylating (Schotten-Baumann method) followed by esterification. (2) Once the aminocarboxylic acid is esterified with an acid catalyst, the acid catalyst is neutralized to extract the free aminocarboxylic acid ester. A method of acylation, (3) a method in which an aminocarboxylic acid is esterified with an acid catalyst and then an aminocarboxylic acid ester salt in which an amino group is neutralized with an acid is taken out and acylated. ing. However, although the production method (1) is useful as a production method of aminocarboxylic acids having high water solubility such as amino acids, aminocarboxylic acids having low water solubility such as ω-aminoalkylcarboxylic acids having a large number of carbon atoms. However, since the product has the property that the product precipitates in the reaction system, the operation is complicated. In addition, the production method (2) has a problem that a high yield cannot be expected because the produced free aminocarboxylic acid ester has a property of being extremely easily polymerized. Furthermore, the production method (3) has a problem that the production process becomes complicated because the aminocarboxylic acid ester salt produced is a solid having a high melting point.
[0003]
As described above, a compound useful as a raw material for easily producing an amide carboxylic acid ester industrially at low cost has not been known yet.
[0004]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide an aminocarboxylic acid ester salt derivative that is liquid at room temperature to about 100 ° C. and is useful as an intermediate for producing an amide carboxylic acid, and a method for producing the same.
[0005]
[Means for Solving the Problems]
As a result of intensive studies in view of such circumstances, the present inventors have conducted esterification of aminocarboxylic acid or cyclic lactam in the presence of a specific acid catalyst, and then obtained amino acid obtained by distilling off excess alcohol as it is. The present inventors have found that the carboxylic acid ester salt derivative is liquid at room temperature to about 100 ° C. and is useful as an intermediate for producing amide carboxylic acid, and has completed the present invention.
[0006]
That is, the present invention provides the following general formula (1)
[0007]
[Formula 4]
[0008]
Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or a straight-chain alkyl group having 1 to 6 carbon atoms, R ³ represents a linear or branched alkyl group having 2 to 4 carbon atoms, ^- AO represents a residue of one divalent or trivalent inorganic acid hydrogen ion is ^{desorbed, - a '(oR 3)} (R 3 as defined above are) has one hydrogen ion desorption An aminocarboxylic acid ester salt derivative represented by the following formula : n represents a number of 2 to 16, and m represents a number of 0 to 1.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the formula (1), examples of the linear alkyl group having 1 to 6 carbon atoms represented by R ¹ or R ^2, is not particularly limited, a hydrogen atom, a methyl group, an ethyl group are preferable. Further, n R ¹ and R ² may be the same or different.
[0010]
Moreover, as n, although it does not restrict | limit, 2-12 are preferable.
[0011]
Further, the linear, branched or cyclic alkyl group having 2 to 40 carbon atoms represented by R ³ is not particularly limited, but a linear, branched or cyclic alkyl group having 2 to 12 carbon atoms is preferable, and carbon A linear, branched or cyclic alkyl group having 2 to 8 carbon atoms is more preferable, and a branched alkyl group having 2 to 8 carbon atoms is particularly preferable.
[0012]
^Moreover, - as the acid residue represented by AO, sulfuric acid residue ^(- HSO _4), phosphoric acid residue ^(- H ₂ PO _4). Among them sulfate residue are preferred.
[0013]
Furthermore, ^- A 'group represented by (OR ^3), as shown in the ester one hydrogen ions are eliminated, in particular with divalent or trivalent inorganic acid (AOH) R ³ OH (R ³ is the same as that described above), wherein one hydrogen ion is desorbed from the inorganic acid residue of the ester formed by the above, and specific examples of the divalent or trivalent inorganic acid (AOH) include hydrogen. There wherein by desorption ^- AO can be mentioned those which produce, specifically, sulfuric acid (H ₂ SO _4), include phosphoric acid (H ₃ PO _4), among others sulfate is preferred. Examples of R ³ are the same as those described above.
[0014]
Here, although m shows the number of 0-1, it is normally considered to be the state of the number of 0.5-1.
[0015]
The aminocarboxylic acid ester salt derivative (1) of the present invention can be produced according to the following steps.
[0016]
[Chemical formula 5]
[0017]
[Wherein R ¹ , R ² , R ³ , n and m are the same as above]
[0018]
In other words, the aminocarboxylic acid represented by the general formula (2) or the cyclic lactam represented by the general formula (3) has a carbon number of 2 to 4 in the presence of a divalent or trivalent inorganic acid (AOH). The aminocarboxylic acid ester salt derivative represented by the general formula (1) can be obtained by reacting the monohydric alcohol (R ³ OH) and distilling off the unreacted alcohol. Hereinafter, the production method of the present invention will be described for each step.
[0019]
(Process 1)
This step is a step of reacting the aminocarboxylic acid (2) or the cyclic lactam (3) with a monohydric alcohol (R ³ OH) in the presence of a divalent or trivalent inorganic acid (AOH).
[0020]
The reaction may be performed in the absence of a solvent or in an inert solvent.
Examples of the inert solvent used here include hexane, toluene, xylene, diethyl ether, tetrahydrofuran, methylene chloride, and chloroform.
[0021]
This step is performed by heating the reaction solution under normal pressure or reduced pressure as necessary. Here, the reaction temperature ranges from room temperature to 200 ° C., preferably from 50 ° C. to the boiling point of the monohydric alcohol (R ³ OH) used under the atmospheric pressure.
[0022]
(Process 2)
This step is a step of distilling off excess alcohol in the reaction solution obtained in step 1. Such distillation is carried out under normal pressure or reduced pressure and, if necessary, under heating or cooling. Here, the reaction temperature ranges from 0 to 200 ° C., preferably from 20 ° C. to the boiling point of the monohydric alcohol (R ³ OH) used under the atmospheric pressure.
[0023]
Through this step, the aminocarboxylic acid ester salt derivative (1) of the present invention can be produced.
[0024]
In addition, this invention aminocarboxylic acid ester salt derivative (1) can obtain desired N-acylaminocarboxylic acid ester (4) by passing through the following process 3.
[0025]
[Chemical 6]
[0026]
Wherein in R ⁴ COX (wherein, R ⁴ is a linear, indicates a branched chain or cyclic hydrocarbon group, X is a halogen atom or an acid anhydride residue (R ⁴ COO- (R ⁴ is as defined above )) Represents a carboxylic acid halide when X is a halogen atom, and represents an acid anhydride when X is an acid anhydride residue (R ⁴ COO—). And R ¹ , R ² , R ³ , m and n are the same as above]
[0027]
(Process 3)
This reaction is a step of reacting the aminocarboxylic acid ester salt derivative (1) obtained in Step 2 with a carboxylic acid halide or acid anhydride (R ⁴ COX) in the presence of a tertiary amine in an inert solvent. .
[0028]
In the carboxylic acid halide or acid anhydride (R ⁴ COX) used here, R ⁴ preferably represents a hydrocarbon group having 1 to 40 carbon atoms, more preferably a linear or branched chain having 1 to 22 carbon atoms. Or a cyclic hydrocarbon group is shown. X represents a halogen atom such as chlorine, bromine or iodine, or an acid anhydride residue (R ⁴ COO—). Specific examples of such carboxylic acid halides include acetic acid chloride, propionic acid chloride, butanoic acid chloride, hexanoic acid chloride, octanoic acid chloride, decanoic acid chloride, dodecanoic acid chloride, tetradecanoic acid chloride, hexadecanoic acid chloride, behenic acid chloride, isobutanoic acid. Examples include chloride, 2-ethylhexanoic acid chloride, isononanoic acid chloride, isostearic acid chloride and the like, and specific examples of the acid anhydride include acetic anhydride and the like.
[0029]
Examples of the tertiary amine used here include trimethylamine, triethylamine, tripropylamine, tributylamine, pyridine, dimethylpyridine, and the like.
[0030]
Examples of the inert solvent used here include hexane, toluene, xylene, benzene, diethyl ether, tetrahydrofuran, methylene chloride, chloroform and the like.
[0031]
This step is performed within a range of 0 to 100 ° C, and preferably performed within a range of 10 to 80 ° C.
[0032]
After completion of the reaction, the tertiary amine salt generated from the reaction mixture is removed by washing with water and the like, and the solvent is distilled off to easily obtain an N-acylaminocarboxylic acid ester.
[0033]
【The invention's effect】
When the aminocarboxylic acid ester salt derivative of the present invention is used, corresponding amide carboxylic acid esters can be obtained very easily industrially.
[0034]
【Example】
EXAMPLES Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited to this at all.
[0035]
Example 1 Synthesis of 12-aminododecanoic acid isobutyl ester salt:
Charge 12-aminododecanoic acid 100 g into a 1 liter flask, add 344 g of isobutanol and start stirring. Subsequently, it heated at 50 degreeC and 52.2 g of sulfuric acid was dripped. After completion of the dropwise addition, the mixture was heated to reflux, and after 5 hours, cooled to 70 ° C., and isobutanol was distilled off under reduced pressure to obtain 12-aminododecanoic acid isobutyl ester / sulfuric acid / isobutyl sulfate.
[0036]
NMR: (ppm, CDCl ₃ in CHCl ₃ standard)
0.70 (d, J = 6.6Hz, 6H), 0.80 (d, J = 6.6Hz, 6H), 1.12-1.49 (m, 14H),
1.49-1.82 (m, 4H), 1.82-2.12 (m, 2H), 2.32 (t, J = 7.5Hz, 2H),
2.82-3.18 (m, 2H), 3.78 (d, J = 6.6Hz, 2H), 3.87 (d, J = 6.6Hz, 2H)
IR: (cm ^-1 , Kbr plate)
2932, 1740, 1473, 1236, 1203, 1056, 996, 882, 846, 804, 582

Claims (5)

The following general formula (1)
[Wherein, R ¹ and R ² represent a hydrogen atom , R ³ represents a linear or branched alkyl group having 2 to 4 carbon atoms, ^and AO represents a divalent group in which one hydrogen ion is eliminated or represents a residue of a trivalent inorganic ^{acids, - a '(OR 3)} (R 3 is as defined above) represents one hydrogen ions esters of inorganic acids desorbed, n represents the 2-11 An aminocarboxylic acid ester salt derivative represented by the formula: ^- AO sulfate residues ^- aminocarboxylic acid ester salt derivative according to claim 1, wherein the (HSO _4). The following general formula (2)
[Wherein R ¹ and R ² represent a hydrogen atom , and n represents a number of 2 to 11 ] or an aminocarboxylic acid represented by the following general formula (3)
[Wherein R ¹ , R ² and n are as defined above], in the presence of a divalent or trivalent inorganic acid, a monohydric alcohol having 2 to 4 carbon atoms (R ³ OH [ Wherein R ³ is the same as defined above]), and the unreacted alcohol is distilled off. The method for producing an aminocarboxylic acid ester salt derivative according to claim 1 or 2,   The process according to claim 3, wherein the aminocarboxylic acid represented by the general formula (2) is 12-aminododecanoic acid, 11-aminoundecanoic acid or 6-aminohexanoic acid.   The production method according to claim 3 or 4, wherein the cyclic lactam represented by the general formula (3) is ε-caprolactum, undecaractam or laurin lactam.