JPS6365061B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel amino acid metal salt compound, a method for producing the same, and a reaction catalyst for isocyanate groups formed from the compound. Amphoteric compounds, which have an acidic group and a basic group in their molecules, are interesting compounds that exhibit the effects of a base on acidic substances and an acidic effect on basic substances, but they are particularly difficult to find in terms of physiological activity. Various types of α that are attracting attention
-Currently, little research has progressed on anything other than amino acids, proteins, or taurine. The inventors previously proposed the formula [In the formula, R ₁ and R ₂ are each H or a carbon number of 1 to
18 represents an alkyl group, and R ₁ and R ₂ form a morpholine nucleus or piperidine nucleus with the nitrogen atom to which they are bonded; R ₃ is an alkylene group having 1 to 6 carbon atoms; R ₄ is H Or 1 carbon atom
- represents an alkyl group of 4] A novel aminosulfonic acid compound represented by
It is an amphoteric compound that exhibits various reactivity, interfacial properties, electrochemical properties, and biochemical properties depending on environmental control, and is particularly suitable for reactions between isocyanate compounds and compounds containing active hydrogen or polyaddition reactions of isocyanates. I learned that it had a suitable catalytic effect and applied for a patent (Japanese Patent Application No. 159310/1983).
No. 62-22979), filed on October 5, 1982, and entitled "Aminosulfonic Acid Compound, Process for Producing the Same, and Catalyst"), and the present invention is a further development of the aforementioned invention. That is, in the present invention, the following general formula () [In the formula, R ₁ and R ₂ are each H or a carbon number of 1 to
18 represents an alkyl group, and R ₁ and R ₂ form a morpholine nucleus or piperidine nucleus with the nitrogen atom to which they are bonded; R ₃ is an alkylene group having 1 to 6 carbon atoms; R ₄ is H Or carbon number 1-4
represents an alkyl group; A is COO ^- or SO ₃ ^-
represents the anion of; M is periodic table b,
a, b, represents a metal atom belonging to group;
n represents an integer corresponding to the valence of metal M] An amino acid metal salt compound represented by the following is provided. The compound of the present invention is produced as follows. That is, method (a): General formula () [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are as described above, B represents an acid group of -COOH or -SO ₃ H] in an aqueous medium, Treated with an alkali metal salt compound represented by the formula M′OH [M′ is an alkali metal atom],
general formula [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A , and M' are as described above.] An alkali metal salt compound () of an aminosulfonic acid or an aminocarboxylic acid represented by the formula is obtained, and then the alkali metal salt is The compound () has the formula MXn [wherein M represents a metal atom belonging to b, a, b or group of the periodic table; n is an integer corresponding to the valence of metal M; X is a halogen atom] The represented metal halide is reacted to obtain the compound of the present invention represented by the general formula []. The first step of the above reaction, that is, the reaction between the aminosulfonic acid or aminocarboxylic acid of the general formula () and the alkali metal hydroxide, proceeds by simply stirring and mixing in an aqueous medium, but heating may be performed if desired. can. By removing the aqueous medium after the reaction, an alkali metal salt compound represented by the general formula () is obtained. Next, the above alkali metal salt compound () has the formula
The second step, in which the metal halide represented by MXn is reacted, can proceed extremely easily by simply stirring and mixing the two in an appropriate solvent at room temperature. Examples of solvents include methanol, ethanol,
Water, ethylene glycol monoalkyl ether,
Any inert solvent such as chloroform, acetone, acetonitrile, benzene, toluene, chlormethylene, and DMSO can be used, but methanol, ethanol, etc. Particular preference is given to using lower alcohols. After the completion of the reaction, the by-product alkali halide is separated, and the reaction solution is concentrated and the by-product alkali halide is subjected to another operation to obtain the target amino acid metal salt compound represented by the general formula () in high yield. be able to. The metal halide of the formula MXn that is reacted with the alkali metal salt compound of the general formula () includes metals of Group B of the periodic table (e.g. Cu,
Ag, Au) group metals (e.g. Mg, Ca, Zn, Sr,
Ba), group a metals (e.g. Al), group a metals (e.g. Ti, Zr), group b metals (e.g. Si, Sn,
Pb), group b metals (e.g. Mn), chlorides, bromides and fluorides of group metals (e.g. Fe, Co, Ni), especially halides, especially chlorides of Cu, Ca, Fe, Ni and Sn. Preferably used. Most of the starting materials in the above method, aminosulfonic acids or aminocarboxylic acids represented by the general formula (), are new compounds; issue),
For example, according to the method described in the patent application filed on October 5, 1981, entitled "Aminosulfonic acid compound, its production method and catalyst", or according to the method, for example, the formula () [In the formula, R ₁ and R ₂ each represent H or an alkyl group having 1 to 18 carbon atoms, and R ₁ and R ₂ form a morpholine nucleus or piperidine nucleus with the nitrogen atom to which they are bonded; R ₃ is an alkylene group having 1 to 6 carbon atoms; R ₄ is H or C 1
~4 alkyl group] is reacted with a vinyl sulfonic acid ester represented by the formula CH ₂ =CH-SO ₃ R [wherein R is an alkyl group having 1 to 4 carbon atoms] to obtain a diamine compound represented by It can be easily synthesized by a method of hydrolyzing an aminosulfonic acid ester, or a method of reacting a diamine compound represented by the above general formula () with acrylic acid. Representative examples of aminosulfonic acids or aminocarboxylic acids obtained by such a method and used as starting materials in the present invention include N-aminomethyltaurine, N-2-aminoethyltaurine, N-3-aminopropyltaurine, -6-aminohexyltaurine, N-3
-(Methylamino)propyl taurine, N-3
(N′,N′-dimethylamino)propyl taurine,
N-3-(N',N'-dimethylamino)ethyl-N
-Methyltaurine, N-6-(N'-methylamino)hexyl-N-methyltaurine, N-2-
(N',N'-dimethylamino)ethyl-N-butyltaurine, N-2-(N',N'-dimethylamino)
Ethyl-N-ethyltaurine, N-3-(N'-ethylamino)propyl-N-ethyltaurine, N
-4-(N',N'-diethylamino)-1-methylbutyltaurine, N-4-(N',N'-dipropylamino)butyl-N-propyltaurine, N-2
-(N′-isopropylamino)ethyltaurine,
N-2-(N'-isopropylamino)-1,1-
Dimethylethyltaurine, N-3-(N',N'-dibutylamino)propyltaurine, N-4-
(N'-dodecylamino)butyltaurine, N-2
-(N'-dodecylamino)ethyl-N-methyltaurine, N-3-(N'-stearylamino)propyltaurine, N-3-morpholinopropyltaurine, N-6-morpholinohexyltaurine, N
Examples include aminosulfonic acids such as -2-piperidinoethyltaurine, and their respective corresponding aminocarboxylic acids. Compounds according to the invention may also alternatively be of the general formula () [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are respectively as described above] A diamine compound represented by the formula () CH ₂ =CH-A M' () [In the formula, A is COO ^- or SO ₃ ^- represents an anion; M' represents an alkali metal cation] by reacting an alkali metal salt of vinyl carboxylic acid or sulfonic acid with the general formula [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A and M′ are as described above] An amino acid alkali metal salt compound () represented by the formula
MXn [In the formula, M is b, , a, , b of the periodic table
or represents a metal atom belonging to the group; n is an integer corresponding to the valence of metal M; X represents a halogen atom] It can also be produced by a method of reacting a metal halide. The diamine compounds represented by the general formula () used as starting materials in the above method are commercially available, and some are easily synthesized by alkylation of commercially available diamine compounds. Representative examples of such diamine compounds include diaminomethane, ethylene diamine, 1,3-propylene diamine, 1,6-hexamethylene diamine, N-
Methylaminopropylamine, N,N,N'-trimethylethylenediamine, N,N-dimethylaminopropylamine, N,N'-dimethylhexamethylenediamine, N,N-dimethyl-N'-butylethylenediamine, N,N- Dimethylamino-N'-ethylethylenediamine, 1,4-diaminobutane, N,N'-diethylpropylenediamine, 2-amino-5-diethylaminopentane, N,N,N'-tripropyltetramethylenediamine, N'- isopropyl-2-methyl-1,
2-propanediamine, N-isopropylethylenediamine, N,N-dibutylaminopropylamine, lauryl aminobutylamine, N-lauryl-N'-methylethylenediamine, stearylaminopropylamine, N-aminopropylmorpholine, N-aminohexylmorpholine, Examples include N-aminoethylmorpholine and N-aminoethylpiperidine. The reaction between the diamine compound and the alkali metal salt of vinyl sulfonic acid or carboxylic acid is preferably carried out in a suitable inert solvent such as water, alcohol, ethylene glycol monoalkyl ether, chlormethylene, etc., or a mixture of two or more thereof. 0~150
It is carried out by stirring and mixing at a temperature of 10 minutes to 48 hours. After the reaction is complete, the solvent is distilled off and the general formula () [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A and M' are respectively as described above] After obtaining the alkali metal salt of aminosulfonic acid or carboxylic acid, the following method (a) is carried out. In the same manner as in the second step, the formula MXn [where M is b, , a, , b of the periodic table]
or represents a metal atom belonging to the group; n is an integer corresponding to the valence of metal M; X represents a halogen atom] By reacting a metal halide represented by [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A, n, and M are each as described above] The amino acid metal salt compound represented by the formula can be obtained in high yield. The amino acid metal salt compound according to the present invention thus obtained is a solid with a relatively high melting point, but is soluble in water, alcohol, methyl cellosolve, ethyl cellosolve, chloroform, acetonitrile, DMSO, etc., and is soluble in ordinary amino acids or It is extremely unique in that it is soluble in organic solvents, whereas its metal salts are sparingly soluble in organic solvents. The compound of the present invention can be used in an aqueous medium, for example, in the case of a sulfonic acid derivative. The ionic structure changes variously depending on the environment. Therefore, various reactivity, interfacial properties, electrochemical properties, and biochemical properties can be exhibited by controlling the environment. The same applies to carboxylic acid derivatives. The present inventors believe that the compound of the present invention has an amino group and
Because it has a latent acid group, such as a sulfonic acid group or a carboxylic acid group, it may have some kind of interactive affinity for NCO groups, and because it is soluble in organic solvents, it behaves violently toward water. We thought that the compound of the present invention could have a safe and direct effect on the reaction of isocyanate compounds exhibiting We found that this shows that That is, the compound of the present invention can be mixed with benzene, carbon tetrachloride, dioxane, ether, toluene,
When dissolved in a neutral solvent that cannot release protons into the reaction system, such as DMSO or THF, and present in a catalytic amount in a multiplex reaction of isocyanate compounds, or added in a catalytic amount to isocyanate compounds blocked with ketoxime, etc. It has been found that when the block dissociation reaction is carried out by heating, the reaction rate increases and catalytic action is exhibited. The reaction catalytic action of the isocyanate group of the metal salt of aminosulfonic acid or carboxylic acid has not been known at all, and together with the fact that it is soluble in organic solvents, it is difficult to protect compounds having an isocyanate group and dissociate the protecting group. A variety of developments are expected in polymerization, addition, and condensation reactions. Next, production examples of aminosulfonic acids and aminocarboxylic acids represented by the general formula () as starting materials used for producing the compounds of the present invention will be shown. Parts are by weight. Production example 1 N-3-(N',N'-dimethylamino)propyl taurine 10.2 parts of dimethylaminopropylamine and 100 parts of methanol were placed in a reactor equipped with a stirrer.
Cooled with ice water. A solution of 12.2 parts of vinyl sulfonic acid methyl ester dissolved in 100 parts of methanol was added dropwise to this solution at 0°C. After the addition was completed, the solution was stirred for 30 minutes, and then the methanol was slowly evaporated, treated with ethanol, and N-3- A white solid of (N',N'-dimethylamino)propyl taurine was obtained. The NMR spectrum (D ₂ O) for the sodium salt is δ1.91 (2H, ddd, -CH ₂ C H ₂ CH ₂ -), 2.845
(6H, s, CH ₃ ), 2.76-3.04 (2H, m,
( _CH3 ) _2N - CH2 ), 3.04-3.44 ( _6H , m, _-CH2-
N-C H ₂ -C H ₂ SO ₃ H). Production Example 2 Production of N-3-(N',N'-dimethylamino)propyl-β-alanine A solution of 153 parts of N,N-dimethylaminopropylamine in 50 ml of toluene was placed in a reactor equipped with a stirrer and mixed with ice water. Cooled. To this solution, while stirring, a solution of 150 parts of ethyl acrylate in 50 ml of toluene was added dropwise at about 12° C. over a period of 2 hours. After stirring for 1 hour after dropping, the mixture was heated to 100°C, and while 950 parts of ion-exchanged water was added dropwise, toluene and ethanol produced by hydrolysis were azeotropically removed. After about 2.5 hours, it was left to cool. Water was distilled off from the resulting aqueous solution under reduced pressure to obtain a white solid, which was recrystallized from methanol and acetone to give N-
3-(N′,N′-dimethylamino)propyl-β-
Obtained 129.5 parts of alanine. Production Example 3 Production of N-3-(N',N'-dimethylamino)propyl-β-alanine (alternative method) Add a solution of 204 parts (2 moles) of N,N-dimethylaminopropylamine in 300 ml of chloroform to a stirrer. The mixture was placed in an attached reactor and cooled with ice water. A solution of 144 parts (2 mol) of acrylic acid in 200 ml of chloroform was added dropwise to this solution at 0 to 10°C. Next, the reaction mixture was stirred at room temperature for 24 hours, and chloroform was distilled off under reduced pressure to obtain 348 parts of N-3-(N',N'-dimethylamino)propyl-β-alanine as a yellow oil. When left in a dryer, it became a white solid. Next, typical aminosulfonic acids and aminocarboxylic acids obtained by these methods and their properties are shown in Tables 1 and 2.

【table】

【table】

【table】

[Table] The present invention will be explained below with reference to Examples. Parts are by weight. Example 1 Production of N-3-(N',N'-dimethylamino)propyl-β-alanine nickel salt Ion exchange of 348 parts of N-3-(N',N'-dimethylamino)propyl-β-alanine It was dissolved in 500 parts of water, and while stirring, a solution of 80 parts of sodium hydroxide dissolved in 300 parts of ion-exchanged water was added. After stirring at about 40°C for 3 hours, water was distilled off under reduced pressure, acetone was added, washed well, and crystallized to give N-3-
231 parts of sodium (N',N'-dimethylamino)propyl-β-alanine were obtained. Next, dissolve 98 parts of the sodium salt obtained above in 600 ml of methanol, and add nickel chloride while stirring.
A solution of 59.4 parts in 400 ml of methanol was added dropwise. After stirring at room temperature for 1 hour, the formed sodium chloride precipitate was separated, the liquid was concentrated under reduced pressure, and the formed precipitate (NaCl) was separated. This operation was continued until no sodium chloride precipitate was formed. Methanol was distilled off from the liquid under reduced pressure, and acetone was added for crystallization to obtain 57 parts of nickel salt. By fluorescence X-rays, using nickel oxide (NiO) as a standard,
Quantification of nickel was carried out. From this result, the above compound is It was confirmed that it has the structural formula (hereinafter, this compound is referred to as DMAPA ₂ Ni). This compound is a green solid with a melting point of 188-200℃ (decomposition), which can be used in water, alcohol, methyl cellosolve, ethyl cellosolve, chloroform, acetonitrile,
It was soluble in DMSO. Example 2 Production of N-3-(N',N'-dimethylamino)propyl-β-alanine nickel salt 72 parts of acrylic acid was dissolved in 150 parts of ion-exchanged water,
A solution of 40 parts of sodium hydroxide dissolved in 150 parts of water at room temperature was added under ice cooling to prepare an aqueous solution of sodium acrylate. 122 parts of N,N-dimethylaminopropylamine and 250 parts of ion-exchanged water were placed in a reactor equipped with a stirrer and heated to about 70°C. The above aqueous solution of sodium acrylate was added dropwise to this solution over a period of 2 hours. then 70
After stirring at °C for 11 hours, the mixture was allowed to cool. Water was distilled off under reduced pressure, and 800 parts of acetone was added to the resulting oily substance.
Stir well and decant. This operation was repeated four times, and the resulting white solid was collected and dried to obtain 159 parts of sodium N-3-(N',N'-dimethylamino)propyl-β-alanine. Dissolve 98 parts of the above sodium salt in 600 ml of methanol, dropwise add a solution of 59.4 parts of nickel chloride and 400 ml of methanol while stirring, and proceed as in Example 1 to obtain N-3-(N',N'-dimethyl 57.5 parts of a green solid of amino)propyl-β-alanine nickel salt was obtained. This did not show any melting point depression in the blending test with the product of Example 1. Example 3 Production of copper salt of N-3-(N',N'-dimethylamino)propyl taurine 306 parts of dimethylaminopropylamine was placed in a reactor equipped with a stirrer, and 25 parts of sodium vinylsulfonate was added at room temperature. % aqueous solution was added dropwise while stirring. After heating under reflux for 17 hours, the mixture was allowed to cool and the reaction solution was concentrated under reduced pressure to obtain a brown oil. Acetone 4 was added to this mixture and stirred well, and then the white precipitate was centrifuged. This operation was repeated twice to extract and remove the excess dimethylaminopropylamine and dry under reduced pressure to produce N-3-(N',N'-dimethylamino).
Sodium propyl taurate was obtained as a white solid. Amount obtained: 403 parts (yield: 87%) 23.2 parts of the sodium salt obtained above was dissolved in 500 ml of methanol, and a solution of 6.72 parts of cupric chloride in 100 ml of methanol was added dropwise while stirring. 1 at room temperature
After stirring for an hour, separate the formed sodium chloride precipitate, concentrate the liquid under reduced pressure, and precipitate NaCl.
The precipitate was separated. This operation was repeated until no sodium chloride precipitate was formed, methanol was distilled off from the liquid under reduced pressure, and acetone was added to crystallize to obtain 13 parts of copper salt. The metal salts of aminocarboxylic acids and metal salts of aminosulfonic acids listed in Tables 3 and 4 below were prepared in the same manner as in the above examples.

【table】

【table】

【table】

[Table] Example 4 Trimerization reaction of phenyl isocyanate Add 0.05 mol/Kg of DMAPA 2 Ni to 50 parts of an acetonitrile solution of ₁ mol/Kg of phenyl isocyanate at room temperature (20 to 22°C) in a nitrogen stream. 50 parts of the solution were added at once. After about 6 hours, a white precipitate was deposited, but stirring was continued. After 24 hours, 5.05 parts (yield: 85%) of precipitated trimeric triphenyl isocyanurate was obtained. The melting point of the product recrystallized from acetonitrile is 282.5-283℃*
It was a colorless prismatic crystal. (*Literature value mp.281℃, JEKresta, CSShen,
KCFrisch, MaKromol.Chem.178, 2495
(1977)) It was found that all of the metal salts listed in Tables 3 and 4 exhibited similar catalytic activity in the trimerization reaction of phenyl isocyanate. Example 5 Dissociation effect of blocked isocyanate A sample was prepared by adding 10 mol % (0.05 eq) of DMAPA ₂ Cu to blocked isocyanate obtained by blocking hexamethylene diisocyanate with methyl ethyl ketoxime. This sample was kneaded with an equal weight of liquid paraffin, sandwiched between KBr crystal plates,
While increasing the temperature in a heating cell, the development of isocyanate absorption (ν _NCO 2270 cm ^-1 ) was observed in terms of transmission % by IR spectroscopy. As a control, tests similar to those described above were conducted for a sample without additives (STD) and a sample containing 10 mol% (0.05 eq) of dibutyltin dilaurate (DBTL). IR (2270cm ^-1 )
As a result of measurement, all of these systems dissociated isocyanate at 110 to 120℃, but DMAPA ₂ Cu
It was observed that the additives suddenly absorbed isocyanate at 120-140°C and generated isocyanate more rapidly than the STD and DBTL additives. The metal salts listed in Tables 3 and 4 all exhibited the effect of promoting the dissociation action of blocked isocyanate as described above.

Claims (1)

[Claims] 1 General formula () [In the formula, R ₁ and R ₂ are each H or a carbon number of 1 to
18 represents an alkyl group, and R ₁ and R ₂ form a morpholine nucleus or piperidine nucleus with the nitrogen atom to which they are bonded; R ₃ is an alkylene group having 1 to 6 carbon atoms; R ₄ is H or represents an alkyl group having 1 to 4 carbon atoms; A represents COO ^- or SO ₃ ^- anion; M represents b, a, a of the periodic table;
, b, represents a metal atom belonging to group; n represents an integer corresponding to the valence of metal M]. 2. Claim 1, wherein M is a metal atom selected from the group consisting of Ca, Cu, Ni, Fe, and Sn.
Compounds described in Section. 3 General formula () [In the formula, R ₁ and R ₂ are each H or a carbon number of 1 to
18 represents an alkyl group, and R ₁ and R ₂ form a morpholine nucleus or piperidine nucleus with the nitrogen atom to which they are bonded; R ₃ is an alkylene group having 1 to 6 carbon atoms; R ₄ is H Or carbon number 1-4
represents an alkyl group; B represents an acid group of -COOH or -SO ₃ H]
By treating with an alkali metal hydroxide represented by [M′ is an alkali metal atom], the general formula [R ₁ , R ₂ , R ₃ , R ₄ and M′ are A
represents a COO ^- or SO ₃ ^- anion] A step of obtaining an amino acid alkali metal salt compound () represented by the formula MXn [where M represents b, a, , b or a metal atom belonging to the group; n is an integer corresponding to the valence of the metal M; X is a halogen atom]. formula() [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A, M and n are as described above] A method for producing an amino acid metal salt compound represented by the following. 4 General formula () [In the formula, R ₁ and R ₂ are each H or a carbon number of 1 to
18 represents an alkyl group, and R ₁ and R ₂ form a morpholine nucleus or piperidine nucleus with the nitrogen atom to which they are bonded; R ₃ is an alkylene group having 1 to 6 carbon atoms; R ₄ is H Or carbon number 1-4
[represents an alkyl group of ] ] to a diamine compound represented by the formula CH ₂ =CH-A M' () [wherein A represents a COO ^- or SO ₃ ^- anion; M' represents an alkali metal cation] The general formula is [R ₁ , R ₂ , R ₃ , R ₄ , A and M′ are as described above] Amino acid alkali metal salt compound ()
and the amino acid alkali metal salt compound has the formula MXn [wherein M represents a metal atom belonging to b, a, b or groups of the periodic table; n is an integer corresponding to the valence of the metal M; and X represents a halogen atom] [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , A, n and M are as described above] A method for producing an amino acid metal salt compound represented by the following. 5 Metal halide is Ca, Cu, Ni, Fe or
The method according to claim 3 or 4, wherein the method is a chloride of Sn. 6 General formula () [In the formula, R ₁ and R ₂ are each H or a carbon number of 1 to
18 represents an alkyl group, and R ₁ and R ₂ form a morpholine nucleus or piperidine nucleus with the nitrogen atom to which they are bonded; R ₃ is an alkylene group having 1 to 6 carbon atoms; R ₄ is H Or carbon number 1-4
is an alkyl group; A represents an anion of COO or SO ₃ ; M is an alkyl group of periodic table b, , a,
, b or a metal atom belonging to the group; n represents an integer corresponding to the valence of the metal M] A reaction catalyst of an isocyanate group consisting of an amino acid metal salt compound represented by the following. 7. Claim 6, wherein M is a metal atom selected from the group consisting of Ca, Cu, Ni, Fe, and Sn.
Reaction catalyst described in section.