JPS6222979B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel aminosulfonic acid compound, a method for producing the same, and a reaction catalyst for isocyanate groups formed from the compound. Amphoteric compounds that 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. Regarding compounds that have an amino group as a basic group, research has been relatively advanced, such as amino acids, proteins, and amphoteric polymer compounds, but as for compounds that have a sulfonic acid group as an acidic group and an amino group as a basic group, At present, little research has been conducted other than various aromatic compounds as dye intermediates, and only a few compounds such as amidosulfonic acid and taurine are known. The present inventors have completed the present invention as a result of a series of studies on aliphatic aminosulfonic acid compounds. That is, in the present invention, the following general formula () A novel compound represented by is provided. During the ceremony,
R ₁ and R ₂ each represent H or an alkyl group having 1 to 18 carbon atoms, except when R ₁ and R ₂ are both H, and R ₁ and R ₂ represent the bond between them. A morpholine nucleus or a piperidine nucleus is formed with the nitrogen atom, R ₃ is an alkylene group having 1 to 6 carbon atoms, and R ₄ represents H or an alkyl group having 1 to 4 carbon atoms. The compound of the present invention is produced as follows. That is, method (a) Sodium vinyl sulfonate represented by the following formula () CH ₂ = CH−SO ₃ Na () and the formula () [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are as described above. ] By reacting with the diamine compound shown by the formula () A method for obtaining a sodium sulfonate derivative of and converting it into a free acid. Or method (b): a vinyl sulfonic acid ester represented by the formula () CH ₂ =CH-SO ₃ R () [In the formula, R is an alkyl group having 1 to 4 carbon atoms] and a vinyl sulfonic acid ester represented by the formula () [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are as described above. ] By reacting the diamine compound shown by the formula () [In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R are as described above. ] A sulfonic acid ester compound represented by
By the method of hydrolyzing this, the general formula ()
A compound represented by can be obtained. The reaction of sodium vinyl sulfonate () and diamine compound () and the reaction of vinyl sulfonic acid ester () and diamine compound () are preferably carried out using a suitable inert solvent, such as water, alcohol, ethylene glycol monoalkyl ether,
Dissolve the above diamine compound () in a mixture of one or more types of chlormethylene, etc., and dropwise add a solution of sodium vinyl sulfonate () or vinyl sulfonate (), or directly into a reaction vessel. The reaction is carried out by charging these reaction materials and a solvent and stirring and mixing at a temperature of 0 to 150°C for 10 minutes to 48 hours. 〓〓〓〓〓
These raw material compounds represented by formulas (), (), and () are all available on the market, and some of the diamine compounds represented by formula () can be obtained by alkylating commercially available diamine compounds. Easily synthesized. Representative examples of diamine compounds represented by formula () include N-methylaminopropylamine, N.N.
N'-trimethylethylenediamine, N/N-dimethylaminopropylamine, N/N'-dimethylhexamethylenediamine, N/N-dimethyl-
N'-butylethylenediamine, N.N-dimethylamino-N'-ethylethylenediamine, N.
N'-diethylpropylene diamine, 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, stearyl aminopropylamine, N-aminopropylmorpholine, N-aminohexylmorpholine, N-aminoethylmorpholine, N-aminoethylpiperidine, etc. can be given. Thus, the resulting formula (V) For example, a sodium sulfonate compound represented by the formula () is dissolved in water and converted into a free acid represented by the formula () by the usual neutralization means of adding a calculated amount of hydrochloric acid; The sulfonic acid ester compound represented by can be converted into the free acid of formula () by conventional hydrolysis means, and can be isolated and purified using a combination of techniques such as concentration, desalting, recrystallization, and solvent extraction. . Table 1 shows the NMR spectra of typical sodium salts of the compounds of the present invention produced as described above.

[Table] 〓〓〓〓〓

[Table] Next, the method for producing the compound of the present invention will be described in more detail with reference to Examples. Note that parts are "parts by weight." Example 1 N-3-(N'・N'-dimethylamino)propyl taurine (Compound No. 2) 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. Then, the mixture was heated under reflux for 17 hours, and after being allowed to cool, the reaction solution was concentrated under reduced pressure to obtain a colored oil. It was confirmed by NMR that the reaction had progressed 100%. Acetone 4 was added to this, and after stirring well, the white precipitate was centrifuged. Repeat this operation twice,
Excessive dimethylaminopropylamine was extracted and removed. The obtained white precipitate of sodium N-3-(N'·N'-dimethylamino)propyl taurate was dried under reduced pressure, dissolved in 530 parts of pure water, and neutralized by adding 530 ml of concentrated hydrochloric acid. The neutralized solution was concentrated under reduced pressure, and 700 parts of methanol was added to separate insoluble sodium chloride. The liquid was concentrated under reduced pressure and dried, and the pale yellow solid obtained was dissolved in 1000 parts of chloroform. Insoluble impurities were removed by centrifugation, and the solvent was distilled off from the chloroform solution under reduced pressure to obtain the white solid N-3.
-(N′・N′-dimethylamino)propyl taurine
Obtained 370 copies. NMR spectrum ( _D2O ): δ1.93 (2H, ddd, −
〓〓〓〓〓
_CH2CH2CH2- ) _, 2.845 (6H, _S , CH3 ) _,
2.76-3.04 (2H, m, ( _CH3 ) _2N - CH2 ) _,
3.04-3.44 (6H, m , -C H2 _-N -C H2C _H
2 SO ₃ H) Compounds Nos. 1 to 18 were produced in the same manner. Example 2 N-3-(N′・N′-dimethylamino)propyl taurine (compound No. 2) 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 dropping, stir for 30 minutes, then slowly evaporate the methanol at low temperature.
Next, the mixture was treated with ethanol to obtain a white solid of N-3-(N'·N'-dimethylamino)propyl taurine. The NMR spectrum of this product matched that of the compound obtained in Example 1. In addition, compounds No. 1 to 12, 16,
17 and 18 were manufactured. The compound of the present invention is an amphoteric compound having a sulfonic acid group as an acidic group and two amino groups as basic groups. Its ionic structure changes depending on the environment; for example, by controlling the pH of the aminosulfonic acid solution, It changes like this. Therefore, by controlling the environment, it exhibits a variety of reactivity, interfacial properties, electrochemical properties, and biochemical properties. The compounds of the present invention are generally hygroscopic solids at room temperature, and are characterized by being soluble in water and various organic solvents. The present inventors discovered that this amphoteric compound has characteristic functional groups of an amino group and a sulfonic acid group.
It must also have some kind of interaction affinity for NCO groups, and unlike conventional amino acids, it is soluble in organic solvents, so it is difficult to react with isocyanate compounds that exhibit aggressive behavior toward water. We thought that the compound of the present invention could act safely and directly, and as a result of continued research, we found that the compound of the present invention has a catalytic effect on the reaction between an isocyanate compound and a compound having active hydrogen, as well as on the polyaddition reaction of isocyanate. I discovered that. That is, the compound of the present invention is mixed with benzene carbon tetrachloride, dioxane,
〓〓〓〓〓
Dissolve in a neutral solvent that cannot release protons into the reaction system, such as ether, toluene, DMSO, THF, etc., and perform a urethane bond formation reaction between isocyanate and a compound having active hydrogen, such as a hydroxyl group-containing compound, or an isocyanate compound. It has been found that when present in catalytic amounts in multiplexed reactions, each increases the reaction rate and exhibits catalytic activity. The reaction catalytic action of the isocyanate group of such aminosulfonic acid compounds has been completely unknown until now, and together with the fact that they are soluble in organic solvents, this has led to various developments in polymerization, addition, and condensation reactions of compounds having isocyanate groups. is expected. The catalytic action of the compounds of the present invention will be explained below with reference to Examples. In addition, in the reaction of isocyanate and alcohol to give urethane, when no catalyst is added, If the concentrations after a certain time t are [RNCO] = [A] [R'OH] = [B], then the reaction rate Rate = -d/dt [A] = k [A] [B] ...(1 ) k = reaction rate constant, and since RNCO and R′OH are equimolar reactions, [A] = [B]. Therefore, equation (1) is Rate = -d/dt [A] = k[ A] ² ...(2) -d[A]/[A] ² = kdt ...(3) If we integrate equation (3) from t=t to t=0 (however, [A ₀ ] is t = _RNCO concentration when A ₀ ]=1 Therefore, 1/1-α-1/1=kt α/1-α=kt (5) It can be seen that α/1-α is proportional to time t. Also, from equation (3), the reaction is quadratic with respect to [RNCO]. On the other hand, the reaction when a catalyst is added is The first stage is rate-determining, and the second stage is extremely fast. Therefore, the reaction rate is Rate=-d[A]/dt= _k1 [A][D]...(3) [A] is the RNCO concentration and [D] is the catalyst concentration. Here, since the catalyst is regenerated in the second stage reaction, its concentration does not change. That is, k ₁ [D]=
When k ₁ ' is substituted into equation (3), -d[A]/dt= _k1 '[A]...(4), and -d[A]/[A]= _k1'dt . Now, integrating from t=t to t=0, ln[A ₀ ]/[A]=k ₁ 't [A ₀ ] is the rate of change when t=0, that is, [A ₀ ]=
If the rate of change when 1t=t is α, then [A]=1−
Since α, ln1/1−α=k ₁ ′t (5) In other words, it can be seen that ln1/1−α is proportional to time. From equation (4), the reaction is first-order with respect to [RNCO]. Example 3 5.04 parts of isocyanate KL-2444 (HMDI isocyanurate) and 0.315 parts of N-3-(N'・N'-
Add dimethylamino)propyl taurine〓〓〓〓〓
An isocyanate solution was prepared by dissolving it in 8.76 parts of a mixed solvent of DMSO/xylene (=1/5). Add 3.06 parts of n-hexyl alcohol to this solution/DMSO/
A solution of 11.06 parts of xylene (=1/5) was added and stirred well. This mixed solution was filled in a 0.025 mm liquid cell and kept at 100° C. in a heating cell, and the change in absorbance over time at 2270 cm ⁻¹ (ν _NCO ) was measured using a 1R-spectrum. The measurement results are shown in Figure 2 as a correlation diagram between the NCO change rate (vertical axis) and time (horizontal axis). From the same measurement results, the order of the reaction to give tri(n-hexyloxycarbonylamino)hexyl isocyanurate was first order, and the reaction rate constant was 1.26 sec ^-1 . Comparative Example 1 The same experiment as in Example 1 was carried out except that N-3-(N'・
The test was carried out without adding N'-dimethylamino)propyl taurine, and the change in absorbance over time was measured in the same manner, and the results are shown in FIG. The reaction order is 2
Next, the reaction rate constant was 2.19 gmol ^-1 sec ^-1 . Example 4 50.4 parts of isocyanate KL-2444 (HMDI isocyanurate) and 0.21 parts of N-3-(N'・N'-
Add dimethylamino)propyl taurine
An isocyanate solution was prepared by dissolving it in 87.6 parts of a mixed solvent of DMSO/xylene (=1/5). Add 30.6 parts of n-hexyl alcohol to this solution/DMSO/
A solution of 110.6 parts of xylene (=1/5) was added and stirred well. This mixed solution was filled in a 0.025 mm liquid cell, kept at 100° C. in a heating cell, and the change in absorbance decrease over time at 2270 cm ⁻¹ (ν _NCO ) was measured using IR spectroscopy. The measurement results are shown in Figure 3. From the same measurement results, the reaction order of this reaction to give tri(n-hexyloxycarbonylamino)hexyl isocyanurate is first order, and the reaction rate constant is
It was 0.209 gmol ^-1 sec ^-1 . Comparative Example 2 5.04 parts of isocyanate KL-2444 (HMDI isocyanurate) and 3.06 parts of n-hexyl alcohol
A solution of 18.82 parts of DMSO/xylene (=1/5) was added and stirred well. This mixed solution
It was filled into a 0.025 mm liquid cell and kept at 100°C in a heating cell, and the time course of the decrease in absorbance at 2270 cm ^-1 (ν _NCO ) was measured using IR spectroscopy. The measurement results are shown in Figure 3. From the same measurement results, the reaction order was 2nd order and the reaction rate constant was 0.093 gmol ^-1 sec ^-1 . From the above results, when N-3-(N'・N'-dimethylamino)propyl taurine is added, the reaction is as follows.
It has become clear that this is a first-order reaction that depends only on the concentration of isocyanate and exhibits catalytic action. Example 5 Trimerization reaction of phenyl isocyanate In a 200 ml three-necked flask equipped with a nitrogen inlet tube, magnetic stirrer, dropping funnel, and thermometer.
Add 50 g of an acetonitrile solution (concentration: 1 mol Kg ^-1 ) of phenyl isocyanate, and add 50 g of a chloroform solution of N-3-(N'・N'-dimethylamino)propyltaurine (concentration: 1 mol Kg -1 ) under stirring in a nitrogen stream.
0.05 molKg ^-1 ) was added at once. After stirring at 20-22° C. for about 20 hours, 4.34 g (73%) of the precipitated trimeric triphenyl isocyanurate was collected. The trimer was recrystallized from acetonitrile to obtain mp282.5~
It becomes a colorless prismatic crystal at 283.0℃. (Literature value*
mp281℃). IR spectrum (KBr): 1700cm ^-1
(ν _CO ), (literature value*1700cm ^-1 ). In addition, if N-3-(N'・N'-dimethylamino)propyl taurine is not added in the above,
Trimeric triphenyl isocyanurate was not obtained. From the above results, it was revealed that N-3-(N'·N'-dimethylamino)propyl taurine exhibits isocyanate trimerization catalytic activity. *JEKresta, CSShen, KCFrisch.
Makromol.Chem., 178, 2495 (1977)

[Brief explanation of the drawing]

Figure 1 shows a representative compound N-3- according to the present invention.
(N′・N′-dimethylamino)propyl taurine Sodium
The NMR spectrum of the salt is shown. Figure 2 shows Example 3
Figure 3 shows the relationship between NCO change rate and time for each reaction in Comparative Example 1, and Figure 3 shows Example 4 and Comparative Example 2.
A diagram showing the relationship between the NCO change rate and time in each reaction. 1 is NCO in a system without the addition of N-3-(N′・N′-dimethylamino)propyl taurine (DMAPT)
Change rate α/1-α, 2 is NCO change rate α/1-α in DMAPT-added system, 3 is ln in DMAPT-added system 〓〓〓〓〓
1/1-α. 〓〓〓〓〓

Claims (1)

[Claims] 1 Formula () [In the formula, R ₁ and R ₂ are each H or a carbon number of 1 to 18
represents an alkyl group, provided that R ₁ and R ₂ are both H
R ₁ and R ₂ form a morpholine nucleus or piperidine nucleus with their bonded nitrogen atoms, R ₃ is an alkylene group having 1 to 6 carbon atoms, and R ₄ is H or Represents an alkyl group having 1 to 4 carbon atoms. ] An aminosulfonic acid compound represented by 2. Claim 1, wherein the compound of formula () is N-3-(methylamino)propyl taurine.
Compounds described in Section. 3. The compound according to claim 1, wherein the compound of formula () is N-3-(N'·N'-dimethylamino)propyl taurine. 4. The compound according to claim 1, wherein the compound of formula () is N-3-(N'·N'-dimethylamino)ethyl-N-methyltaurine. 5. The compound according to claim 1, wherein the compound of formula () is N-6-(N'-methylamino)hexyl-N-methyltaurine. 6. The compound according to claim 1, wherein the compound of formula () is N-2-(N'·N'-dimethylamino)ethyl-N-n-butyltaurine. 7. The compound according to claim 1, wherein the compound of formula () is N-2-(N'·N'-dimethylamino)ethyl-N-ethyltaurine. 8. The compound according to claim 1, wherein the compound of formula () is N-3-(N'-ethylamino)propyl-N-ethyltaurine. 9. The compound according to claim 1, wherein the compound of formula () is N-4-(N'·N'-dimethylamino)-1-methylbutyltaurine. 10. The compound according to claim 1, wherein the compound of formula () is N-4-(N'·N'-dipropylamino)butyl-N-propyltaurine. 11. The compound according to claim 1, wherein the compound of formula () is N-2-(N'-isopropylamino)ethyltaurine. 〓〓〓〓〓
12. The compound according to claim 1, wherein the compound of formula () is N-2-(N'-isopropylamino)-1,1-dimethylethyltaurine. 13. The compound according to claim 1, wherein the compound of formula () is N-3-(N'·N'-dibutylamino)propyl taurine. 14. The compound according to claim 1, wherein the compound of formula () is N-4-(N'-dodecylamino)butyltaurine. 15. The compound according to claim 1, wherein the compound of formula () is N-2-(N'-dodecylamino)ethyl-N-methyltaurine. 16. The compound according to claim 1, wherein the compound of formula () is N-3-(N'-stearylamino)propyl taurine. 17. The compound according to claim 1, wherein the compound of formula () is N-3-morpholinopropyltaurine. 18. The compound according to claim 1, wherein the compound of formula () is N-6-morpholinohexyltaurine. 19. The compound according to claim 1, wherein the compound of formula () is N-2-piperidinoethyltaurine. 20 Sodium vinyl sulfonate of formula () CH ₂ = CH−SO ₃ Na () and formula () [In the formula, R ₁ and R ₂ are each H or a carbon number of 1 to 18
represents an alkyl group, provided that R ₁ and R ₂ are both H
R ₁ and R ₂ form a morpholine nucleus or piperidine nucleus with their bonded nitrogen atoms, R ₃ is an alkylene group having 1 to 6 carbon atoms, and R ₄ is H or Represents an alkyl group having 1 to 4 carbon atoms. ] Formula () characterized by reacting a diamine compound represented by the formula () and leading the obtained aminosulfonic acid sodium salt to a free acid. [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are as described above. ] A method for producing an aminosulfonic acid compound represented by: 21 Formula () _CH2 =CH- _SO3R () [In the formula, R represents an alkyl group having 1 to 4 carbon atoms. ] Vinyl sulfonic acid ester of formula () [In the formula, R ₁ and R ₂ are each H or a carbon number of 1 to 18
represents an alkyl group, except when both R ₁ and R ₂ are H, and R ₁ and R ₂ form a morpholine nucleus or piperidine nucleus with the nitrogen atom to which they are bonded, and R ₃ represents an alkyl group. It is an alkylene group having 1 to 6 carbon atoms, and R ₄ is H or 1 to 4 carbon atoms.
represents an alkyl group. ] Formula () characterized by reacting a diamine compound represented by the formula and hydrolyzing the obtained aminosulfonic acid ester. [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are as described above. ] A method for producing an aminosulfonic acid compound represented by: 22 formula () [In the formula, R ₁ and R ₂ are each H or a carbon number of 1 to 18
represents an alkyl group, provided that R ₁ and R ₂ are both H
_{Except when _}
R ₄ represents H or an alkyl group having 1 to 4 carbon atoms. ] An isocyanate group reaction catalyst consisting of an aminosulfonic acid compound represented by: