JPH0213664B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel amino acid 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 action of a base against acidic substances and the action of an acid against basic substances, but they have received particular attention in terms of their physiological activity. Various α
-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 their bonded nitrogen atoms; R ₃ represents an alkylene group having 1 to 6 carbon atoms] The aminosulfonic acid compound is an amphoteric compound that exhibits various reactivity, interfacial properties, electrochemical properties, and biochemical properties depending on environmental control.
In particular, I learned that it exhibits a suitable catalytic effect for the reaction between isocyanate compounds and compounds having active hydrogen, or for the polyaddition reaction of isocyanates, and filed a patent application (Japanese Patent Application No. 159310-1981, October 5, 1982). Application, title of invention "Aminosulfonic acid compound, method for producing the same, and catalyst"). The structural features of the aminosulfonic acid compound represented by the above general formula are two basic nitrogen atoms present in the carbon chain and a sulfonic group present at the end, and these show extremely specific amphoteric properties. This is what is being done. However, for the purpose of having a basic group and an acidic group in the same molecule, the sulfone group may be a carboxyl group, and the hydrogen atom of the imino group can be used not only for an alkyl group but also for other groups. It does not matter if it is substituted with a substituent. From this point of view, the present inventors further developed the above invention and arrived at the present invention. That is, according to the present invention, the general formula () [In the formula, R ₁ and R ₂ each independently represent 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; A represents -COOH or -SO ₃ H group; R ₄ is an alkyl group having 1 to 7 carbon atoms, phenyl alkyl group, phenyl group, substituted phenyl group or naphthyl group A novel amino acid compound represented by the following is provided. This compound has the general formula () [In the formula, R ₁ and R ₂ each independently have 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 atoms to which they are bonded; A represents a COOH or SO ₃ H group] and a compound represented by the general formula () R ₄ NCO () [In the formula, R ₄ represents an alkyl group having 1 to 7 carbon atoms, a phenyl alkyl group, a phenyl group, a substituted phenyl group or a naphthyl group] By reacting with an isocyanate represented by Manufactured. The compound of the general formula () as a reaction raw material is described in Japanese Patent Application No. 159310/1983 filed by the same applicant, and is also detailed in the latter part. On the other hand, isocyanates of general formula () are easily available on the market, and representative examples include methyl isocyanate, ethyl isocyanate, n-propylisocyanate, isopropylisocyanate, cyclopropylisocyanate, allyl isocyanate, n-Butyl isocyanate, isobutyl isocyanate, t-butyl isocyanate, isoamyl isocyanate, cyclohexyl isocyanate, n-hexyl isocyanate, α-propyl butyl isocyanate, α-methyl-α-ethyl butyl isocyanate, β- Phenethyl isocyanate, β-phenyl isopropyl isocyanate, α-methylbenzyl isocyanate, phenyl isocyanate, 2-chlorophenyl isocyanate, tolyl isocyanate, benzyl isocyanate, methoxyphenyl isocyanate, bromophenyl Isocyanate, iodophenyl isocyanate,
Nitrophenyl isocyanate, 5-nitro-2
-Methyl phenyl isocyanate, 4-nitro-
2-methylphenyl isocyanate, 4-fluorophenyl isocyanate, 2,4-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 6-nitro-2,4-dimethylphenyl isocyanate, 5-nitro-2,4
-dimethylphenyl isocyanate, 4-ethoxyphenyl isocyanate, 2,4,5-trimethylphenyl isocyanate, 2,4,6-trimethylphenyl isocyanate, naphthyl isocyanate, and the like. The above reaction proceeds very easily by simply mixing both reaction materials, preferably in an inert solvent. To control the reaction rate,
It is particularly preferred to drop a solution of the isocyanate () under ice-cooling into a solution of the general formula () in an inert solvent, and then continue stirring at room temperature to complete the reaction. Since isocyanate is active, an inert solvent that does not react with isocyanate must be used as the reaction solvent, such as aromatic hydrocarbons such as benzene, toluene, and xylene, and chlorine such as chloroform, dichloroethylene, and trichloroethylene. Preferably used are hydrogenated hydrocarbons, aliphatic hydrocarbons such as n-hexane and n-heptane, ethers such as ethylene glycol and dimethyl ether, esters such as ethyl acetate and butyl acetate, and ketones such as acetone and methyl ethyl ketone. . The compounds of the present invention are generally crystalline solids that dissolve in organic solvents, but their solubility varies depending on the solvent. Therefore, the product can be precipitated by appropriately selecting the reaction medium, and the product can be isolated and purified by appropriately combining methods such as solvent distillation, concentration, recrystallization, and solvent extraction. be. In addition, the compound represented by the general formula () used as a raw material can be prepared using the formula () according to the method described in the above-mentioned Japanese Patent Application No. [In the formula, R ₁ and R ₂ are each an alkyl group having 1 to 18 carbon atoms, or R ₁ and R ₂ form a morpholine or piperidine nucleus with the nitrogen atom to which they are bonded, and R ₃ is an alkyl group having 1 to 18 carbon atoms. ~6 alkylene group] is reacted with a vinyl compound represented by the formula () CH ₂ = CH-X () [wherein X is COONa or SO ₃ Na] in a suitable inert solvent. , neutralization treatment, or by reacting and hydrolyzing a vinyl compound represented by CH ₂ = CH-Y () [wherein Y is COOR or SO ₃ R; R is an alkyl group] In the case of aminocarboxylic acids, they can also be obtained by direct reaction with acrylic acid. However, since these amino acid compounds represented by the general formula () are generally hygroscopic, when used as a starting material in the method of the present invention, it is necessary to use sufficiently dehydrated and dried compounds together with the solvent. Next, Tables 1 and 2 show representative examples of compounds represented by the general formula () used as raw materials in the method of the present invention and representative examples of amino acid compounds obtained by the method of the present invention.

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[Table] Conventionally known amphoteric compounds such as α-amino acids and taurine are soluble in water but generally poorly soluble in organic solvents, whereas the amino acid compounds according to the present invention are soluble in water, alcohol, and methyl cellosolve. , ethyl cellosolve, chloroform, acetone, acetonitrile, DMSO, DMF and other organic solvents with strong hydrogen bonding strength are extremely characteristic in that they are easily soluble.
In aqueous media, for example, in the case of sulfonic acid derivatives 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 since the compounds of the present invention have characteristic functional groups such as an amino group and a sulfonic acid group or a carboxyl group, they should have some kind of interactive affinity for NCO groups, and also for conventional amino acids, etc. Since the compound of the present invention is soluble in organic solvents, unlike other organic solvents, we thought that it would be able to safely and directly affect the reaction of isocyanate compounds that behave violently with water, and as a result of continued research, we found that the compound of the present invention is soluble in isocyanate compounds. It has been found that the present invention exhibits a catalyzing effect on the reaction between a compound and a compound having active hydrogen, the polyaddition reaction of isocyanates, or the block dissociation reaction of blocked isocyanates. That is, the compound of the present invention is mixed with acetonitrile,
Multiplexing reaction of isocyanate compounds dissolved in a neutral solvent that does not release protons into the reaction system such as DMSO or DMF, urethane bond formation reaction between isocyanate and a compound having active hydrogen, or isocyanate compounds blocked with ketoxime etc. It has been found that when a sufficient amount of dissociation solvent is present in the block dissociation reactions, these reactions exhibit catalytic action with increased reaction rates. The reaction catalytic action of the isocyanate group of aminosulfonic acid or carboxylic acid has not been previously known at all, and together with the fact that it is soluble in organic solvents, it can be used for deprotection, polymerization, addition, and condensation reactions of compounds having isocyanate groups. Various developments are expected in the future. The present invention will be explained below with reference to Examples. In these examples, parts are by weight unless otherwise specified. Example 1 A solution of 25 g of phenyl isocyanate in chloroform (40 ml) was added dropwise to 152 g (0.21 mol) of a 29% chloroform solution of dimethylaminopropyl taurine while cooling in an ice bath. After stirring for 20 hours after dropping, a white precipitate is formed, which is expressed by the formula 66.5 g of the compound was obtained. The yield was 96%. The structure of this compound was confirmed by IR spectrum, NMR spectrum, etc. as described above. IR (KBr): 1640 cm ^-1 (ν _NHCO ) NMR (DMSOd ₆ −MeOHd ₄ D) δ: 1.8 to 2.2 (m,
2H, CH ₂ ), 2.83 (m, 6H, CH ₃ ), 2.7-3.3
(m, 4H, CH ₂ ), 3.3-3.6 (m, 2H, CH ₂ ),
3.6-3.9 (m, 2H, CH2 ) _, 6.92-7.7 (m, 5H,
(aromatic proton), 9.25 (broad, 1H, NH ) The compounds of the present invention listed in Table 2 were prepared using the aminosulfonic acids and aminocarboxylic acids listed in Table 1 in the same manner. Example 2 5.04 parts of isocyanate KL-2444 (HMDI isocyanurate) and 0.494 parts (5/100 equivalent) of N-3-(N',N'-dimethylamino)propyl-N-phenylcarbamoyl taurine were mixed in DMSO/ An isocyanate solution was prepared by dissolving it in 8.76 parts of a mixed solvent of xylene (5/1). Add 3.06 parts of n-hexyl alcohol and DMSO/xylene (5/1) to this solution.
11.06 parts of the solution was added and stirred well. Fill a 0.025 mm liquid cell with this mixed solution and place it in a heating cell for 102 m
The time course of the decrease in absorbance at (v _NCO 2270 cm ^-1 ) was measured in the 1R-spectrum while heating to ~104°C. Calculating the reaction order from the reduction rate of isocyanate, it is first order, and the reaction rate constant is
It was 1.34sec ^-1 . When N-3-(N',N'-dimethylamino)propyl-N-phenylcarbamoyltaurine is not added, the reaction order is second order and the reaction rate constant is 2.19g.
It was mol ^-1 sec ^-1 . From this result, N-3-
It was clear that when (N', N'-dimethylamino)propyl N-phenylcarbamoyltaurine was added, the reaction became a first-order reaction that depended only on the concentration of isocyanate and exhibited catalytic activity. Example 3 A 200 ml three-necked flask equipped with a nitrogen inlet tube, magnetic stirrer, dropping funnel, and thermometer was charged with 50
A solution of phenyl isocyanate (concentration: 1 mol Kg ^-1 ) in acetonitrile was added to N-3-(N',N'-dimethylamino)propyl- while stirring in a nitrogen stream.
50 g of a chloroform solution of N-phenylcarbamoylalanine (concentration 0.05 mol Kg ^-1 ) was added at once.
After stirring at 22-24° C. for about 20 hours, 4.69 g (79%) of precipitated trimeric triphenyl isocyanurate was collected. The trimer was recrystallized from acetonitrile. It was a colorless prismatic crystal with a melting point of 282.5-283.0°C. From the above results, it is clear that N-3-(N',N'-dimethylamino)propyl-N-phenylcarbamoylalanine catalyzes isocyanate trimerization. Example 4 N-3-(N',N'-diethylamino)propyl-N-phenylcarbamoyl taurine was added to the blocked isocyanate obtained by blocking hexamethylene diisocyanate with methyl ethyl ketoxime.
A sample with 10 mol% added was prepared, mixed with an equal weight of liquid paraffin, sandwiched between KBr crystal plates, and heated in a heating cell to transmit the development of isocyanate absorption (ν _NCO 2270 cm ^-1 ) using a 1R spectrum. Observed in %. Additive-free (STD), dibutyltin dilaurate as a control
The same test as above was conducted for the one containing 10 mol% (DBTL). From the IR spectra, all of these systems caused dissociation of isocyanate at 110-120℃, but the one containing N-3-(N',N'-dimethylamino)propyl-N-phenylcarbamoyltaurine Absorption of isocyanate suddenly appeared at 130-150°C, and rapid generation of isocyanate was observed compared to those with STD and DBTL addition. It should be noted that all of the amino acid compounds listed in Table 2 exhibited the effect of promoting the dissociation of blocked isocyanate or the same dissociation effect as in Examples 2 and 3, as described above.

Claims (1)

[Claims] 1 General formula () [In the formula, R ₁ and R ₂ each independently represent 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 an alkyl group having 1 to 7 carbon atoms, phenyl alkyl group, phenyl group, substituted phenyl group or naphthyl group; A is COOH or
represents an SO ₃ H group] An amino acid compound represented by: 2 General formula () [In the formula, R ₁ and R ₂ each independently represent 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; A represents a COOH or SO ₃ H group] and a compound represented by the general formula () R ₄ NCO () [wherein R ₄ is an alkyl group having 1 to 7 carbon atoms] group, phenylalkyl group, phenyl group, substituted phenyl group or naphthyl group] [wherein R ₁ , R ₂ , R ₃ , R ₄ and A are as described above] A method for producing an amino acid compound represented by the following. 3 General formula () [In the formula, R ₁ and R ₂ each independently represent an alkyl group having 1 to 18 carbon atoms; 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 an alkyl group having 1 to 7 carbon atoms, phenyl alkyl group, phenyl group, substituted phenyl group or naphthyl group; A is COOH or
A reaction catalyst for a urethane formation reaction between an isocyanate compound and a compound having active hydrogen, a polyaddition reaction of an isocyanate compound, or a block dissociation reaction of a blocked isocyanate, consisting of an amino acid compound represented by SO ₃ H group.