JPH0370702B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel basic nitrogen-containing monomer.
Many basic monomers have been known so far, and are used as raw materials for functional polymers or as pharmaceutical raw materials. Examples of those having a benzimidazole skeleton include Collect.Czech.Chem.Commun, 31
(12) 4682 (1966) with 2-(o-isopropenylphenyl)benzimidazole or 2-[o-
(1-ethylpropenyl)phenyl]benzimidazole and the like are known. However, since these have low polymerizability and high ceiling temperature, they cannot be made into polymers. Furthermore, regarding double bonds, some compounds having α,β-disubstituted benzimidazole-containing skeletons are known, but these have no polymerizability at all. The present inventors have a benzimidazole skeleton,
Moreover, as a result of repeated studies aimed at synthesizing a monomer with polymerizability comparable to that of styrene, they have finally synthesized a new basic monomer. That is, the present invention relates to a basic nitrogen-containing monomer represented by the following structural formula (). Here, R represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. Also, Z represents the following (a) or (b).

【formula】

[Formula] Here, R ₁ and R ₂ are hydrogen or carbon atoms 1 to 10
represents a hydrocarbon group. X ^- represents a counteranion. Preferred examples of R are hydrogen, methyl group, ethyl group, etc. Among these, hydrogen is preferred. Preferred examples of R ₁ and R ₂ are:
Examples include hydrogen, methyl group, ethyl group, propyl group, butyl group, and benzyl group. The positions of R and Z in () may be any position, but with respect to the vinyl group, Z may be at the m-position or the p-position.
R is preferably at m-position or p-position. X ^- represents a counter anion to the imidazolium cation in formula (b), and is not particularly limited as long as it can easily become an anion. It may be a polyvalent anion such as sulfate ion or phosphate ion. Specific examples include halogen ions, hydroxy ions, carbonate ions, nitrate ions, sulfate ions, and phosphate ions. Next, a method for producing the substance according to the present invention will be described. Among the substances of the present invention, those represented by Z=(a) are vinylbenzalcohols represented by the following structural formula ().

【formula】

[Formula] Obtained by reacting dehydes with o-phenylenediamines represented by ().
(Here, R and R ₁ are the same as above. ()
The substituents in the formula may be placed in any position. ) To give a preferable specific example of (), m
-, and p-vinylbenzaldehyde, 1-methyl-3-vinyl-5-formylbenzene, 1-
Ethyl-3-vinyl-5-formylbenzene and the like. To give a preferable specific example of (), o-
Phenylenediamine, N-methyl-o-phenylenediamine, N-ethyl-o-phenylenediamine, N-propyl-o-phenylenediamine, N
-benzyl-o-phenylenediamine and the like. o-Phenylenediamines are easily oxidized in the air. There is no problem with using them in the form of salts, including hydrochlorides. The amount of () relative to () is not particularly limited, but is preferably 0.1 to 10 times the molar amount. There is no particular restriction on the reaction temperature, but it is preferably 0.
-100°C, more preferably 20-70°C. The reaction time is also not particularly limited, but is preferably 30 minutes to 10 hours. When this reaction is carried out, it may be carried out in the presence of an inert liquid. The inert liquid in the present invention refers to a liquid that is inert to the raw material aldehyde, o-phenylenediamines, and products. Specific examples include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, alcohols such as methanol, ethanol, and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and diethyl ketone, diethyl ether, and methyl. Ethers such as ethyl ether, dibutyl ether, dioxane, tetrahydrofuran, diphenyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, esters such as ethyl formate, ethyl acetate, butyl acetate, dimethylformamide (DMF), Amides including dimethylacetamide (DMAc), aliphatic halides such as chloroform, methylene chloride, dichloroethane,
Aromatic halides, including chlorobenzene, and polar liquids, such as dimethyl sulfoxide and water, can also be used. These liquids can be used alone or as a mixture of two or more liquids. It has been found that carrying out this reaction in the presence of a polymerization inhibitor has a positive effect on the reaction temperature, the concentration of the reaction substrate, and even the yield. As a polymerization inhibitor, tert-butylhydroxylanisole, 2,6-ditert-butyl-4
-Methylphenol, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,
Phenol derivatives including 4'-butylidene-bis-(6-tert-butyl-3-methylphenol), hydroquinones including tert-butylhydroquinone and 2,5-ditertiary-butylhydroquinone, butyl night Compounds having a nitroso or hydroxylamino group, such as nitrosophenyl nitrosophenylhydroxylamine ammonium salt (clopene), or organic halides may also be used. The use of commercially available polymerization inhibitors is a preferred example due to its convenience. Furthermore, in this reaction, it is preferable to carry out the reaction in the presence of an aldehyde activator. Aldehyde activation aids react with aldehydes and o-
It enhances the reaction of phenylenediamine and has the general formula M _k H _l S _n O _o (M is an alkali metal (the valence is a), k, l, m, and n are integers of 0 or more, ak + 1
=2(m+n). ). Specific examples include sulfur dioxide, sodium sulfite, sodium hydrogen sulfite, sodium bisulfite, and sodium thiosulfate. These active aids may be reacted with aldehydes before reacting with o-phenylenediamine, or may be reacted in the presence of the aldehydes. As a method for synthesizing a compound in which R ₁ is a hydrocarbon group, there is also a method in which a compound in which R ₁ is hydrogen is synthesized and then reacted with R ₁ X or the like. To synthesize the compound represented by Z=(b), Z
A compound represented by R ₂ X may be reacted with the compound of =(a). (R ₂ , X are the same as above, but
is preferably a halogen) The amount of R ₂ There is no particular limit to the reaction temperature and time, but usually 20
~100℃, 1 hour ~ 50 hours is adopted. The reaction may be carried out in the presence of an inert liquid. Additionally, in this reaction, it may be advantageous to add a basic substance. Basic substances include alkali metal salts such as potassium hydroxide, sodium hydroxide, and sodium carbonate, and alkali metal alcoholates such as sodium ethylate. There is no particular restriction on the amount of the basic substance used, but it is preferably 0.1 to 10 times the number of moles of the functional group (a), more preferably 1 to 3 times the number of moles. If R ₁ and R ₂ are particularly equal, Z = (a) and R ₁ =
It can also be obtained by reacting a compound corresponding to H with R ₁ X (=R ₂ X) in twice the molar amount. When R ₁ or R ₂ is hydrogen, () is (Z=(b)), which is a so-called salt and can be tautomerically converted with acids and bases. The substance of the present invention can be polymerized by a conventional polymerization method to easily synthesize a polymer having a functional group, and is useful as an adsorbent. Examples are shown below. Example 1 In a 2000 ml three-necked flask, 105.8 g of p-vinylbenzaldehyde, 400 ml of methanol, and 400 ml of water were mixed and dissolved under stirring. Separately, a solution of 87 g of sodium bisulfite dissolved in 400 ml of water was prepared, and this solution was dropped into the three-necked flask. The reaction was allowed to proceed for 30 minutes at room temperature while stirring. The generated precipitate was separated, washed with methanol, and then dried. The amount of product was 35.1 g. To 23.6 g of this product, 150 ml of DMF and 10.0 g of o-
Phenyl diamine and 0.1 g of t-butylcatechol were mixed and reacted at 50°C for 1.5 hours.
Add 1N sodium hydroxide solution to the reaction mixture to a pH of 10.
After it was placed in a freezer at -15°C, it was left overnight. After separating the precipitated yellow crystals,
The product was washed successively with 18% sodium sulfite solution, 2% sodium sulfide solution, and water, and dried under reduced pressure to obtain a product. The yield of product was 17.2g. The results of elemental analysis of the product were as follows. However, the values in parentheses represent theoretical values. C: 81.76 (81.79), H: 5.54 (5.49), N: 12.70 (12.72) The mass spectrum analysis results are as follows. 220 (M ⁺ /e), 193, 117, 103, 27, etc. The results of measuring the NMR spectrum after dissolving it in _d6 -DMSO are shown below. 5.2 to 6.0 (two doublets, 2H) 6.5 to 7.0 (double of doublets, 1H) 7.1 to 7.9 (multiplet, 9H) The main peaks of the infrared absorption spectrum are as follows. 3100, 1640, 1620, 1490, 1470, 1410, 1390,
1330, 1300 From the above results, it was found that this product was 2-(p-vinylphenyl)benzimidazole. Example 2 N-methyl-o-phenylenediamine was used instead of o-phenylenediamine in Example 1.
12.2 g was used to react with 23.6 g of the intermediate product. The yield was 21.3g. The results of elemental analysis of the product are as follows. However, the values in parentheses represent theoretical values. C; 81.97 (82.02), H; 6.10 (6.02), N; 12.03
(11.96) The results of mass spectrum measurement were as follows. 232 (M ⁺ /e), 217, 205, 129, 103 and others The results of NMR spectra using d ₆ -DMSO as a solvent are as follows. (δ-value (ppm)) 3.75 (singlet, 3H) 5.2 to 6.0 (two doublets, 2H) 6.5 to 7.0 (doublet of doublets, 1H) 7.1 to 7.9 (multiplet, 8H) The main peaks of the infrared absorption spectrum are as follows. 3100, 1640, 1620, 1490, 1470, 1445, 1410,
1390, 1330, 1300, etc. As a result, the product is 1-methyl-2-(p-
It was found to be vinylphenylbenzimidazole. 8.5 g of this product and 1.5 g of divinylbenzene
g, 8 g of toluene and 0.1 g of azobisisobutyronitrile were placed in an ampoule and reacted at 90°C for 16 hours. The produced polymer was pulverized and then washed with acetone. The ion exchange capacity of this product was measured and found to be 3.20 meq/g. When a potassium iodide solution was passed through this CI type polymer, 3.20 mmol of iodine ions were adsorbed per gram of polymer. Example 3 22.0 g of the product obtained in Example 1, 200 ml of dimethylformamide and 0.1 t-butylcatechol
14.2 g of methyl iodide was added dropwise under stirring. The reaction mixture was poured into a large amount of ether, and the formed precipitate was separated. Then add this one to 80
It was dissolved in 500 ml of 1N hydrochloric acid heated to 0.degree. C. and subsequently neutralized with sodium hydroxide solution. The precipitate formed at this time was separated to obtain a product. This was the same product obtained in Example 2. The yield was 45%. Example 4 In the same manner as in Example 3, ethyl bromide,
The reaction was carried out using benzyl chloride, respectively.
1-Ethyl-2-(p-vinylphenyl)benzimidazole, 1-phenylmethyl-2-(p-
Vinylphenyl)benzimidazole was obtained. Example 5 Using 1-methyl-(p-vinylphenyl)benzimidazole obtained in Example 2, Example 3
By the same method as above, butyl bromide and benzyl chloride were reacted to form 1-methyl-2
-(p-vinylphenyl)-3-butylbenzimidazolium bromide, and 1-methyl-2-
(p-vinylphenyl)-3-benzylimidazolium chloride was obtained. Example 6 16.0 g of 1-ethyl-3-vinyl-5-formylbenzene, 24.4 g of N-methyl-o-phenylenediamine, 10.4 g of sodium bisulfite, 0.05 g of t-butylcatechol, and 100 ml of DMAc in a 300 ml flask. The mixture was mixed and reacted at 50°C for 5 hours. 300 ml of 1N sodium hydroxide solution was added little by little to the reaction mixture while stirring. After separating the formed precipitate, it was thoroughly washed with water. This crude product
Recrystallization was performed with DMAc to obtain a product. The yield was 5.0g (Y=19%). The results of elemental analysis of the product were C; 82.32 (82.41) H; 6.99 (6.92) N; 10.69 (10.68). However, the numbers in parentheses represent theoretical values. The main peaks of the mass spectrum are as follows. 262 (M ⁺ /e), 247, 235, 233, 132, 130, etc. The results of the NMR spectra are as follows. 1.15 (Triple line, 3H) 2.60 (Quadruple line, 2H) 3.75 (Single line, 3H) 5.2~6.0 (Two double lines, 2H) 6.5~7.0 (Double line of double line, 1H) 7.1~ 7.9 (multiplet, 7H) The main peaks of the infrared absorption spectrum are 3100, 2950, 1640, 1620, 1490, 1475, 1450,
They were 1385, 1330, 1300, 1260, 860, and 760. The product obtained from these results is 2-(3
-Ethyl-5-vinylphenyl)-1-methylbenzimidazole. Example 7 Vinylbenzaldehyde (m/p=6/4)
13.2g and 19g of sodium metabisulfite were used in the same manner as in Example 6, with a yield of 16%.
Methyl-2-(vinylphenyl)benzimidazole was obtained. As a result of analysis by gas chromatography, m-
The ratio of isomer to p-isomer was 43/57. Example 8 11.0 g of the product obtained in Example 7 was dissolved in methanol.
It was dissolved in 100ml and 20g of hydrochloric acid gas was bubbled into it. The product was reprecipitated from ether to obtain the product. From the results of elemental analysis, the product is 1-methyl-2
-(m/p-vinylphenyl)-3H-benzimidazolium chloride. Cl; 13.22 (13.09) Example 9 11.0 g of the product obtained in Example 7 was dissolved in methanol.
The mixture was dissolved in 100 ml, and 3.0 g of sodium methylate was added thereto, followed by stirring at 50°C in a 200 ml flask. To this mixture, 21 g of methyl iodide was added dropwise from the dropping funnel over about 30 minutes, and the reaction was continued with stirring at the same temperature for 6 hours. Pour the reaction mixture into water,
Extraction washing was performed three times with ether. The aqueous layer was concentrated to dryness and then recrystallized from a methanol-water mixed solvent to obtain a product. The yield was 15.1g. The elemental analysis of this product is C; 54.18 (54.27) H; 4.63 (4.55) N; 7.45 (7.45) I; 33.74 (33.73), and the product is 1,3-dimethyl-2-(m/
It was found to be p-vinylphenyl)benzimidazolium iodide.

Claims (1)

[Scope of Claims] 1. A basic nitrogen-containing monomer represented by the following structural formula (). Here, R represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. Also, Z represents the following (a) or (b). [Formula] [Formula] Here, R ₁ and R ₂ are hydrogen or carbon atoms from 1 to 10
represents a hydrocarbon group. X ^- represents a counteranion. 2 Structural formula () characterized by reacting vinylbenzaldehydes represented by structural formula () with o-phenylenediamines represented by ()
A method for producing a basic nitrogen-containing monomer represented by [Formula] [Formula] [Formula] [Formula] Here, Z represents (a), R is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and R ₁ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. represents a group. 3. After reacting the basic nitrogen-containing monomer represented by the structural formula () with R ₂ Y (Y represents a halogen), a compound other than Y used as necessary
It is represented by the structural formula () characterized in that it is treated with a liquid containing X ^- (X ^- represents a counter anion), and Z =
(b) A method for producing a basic monomer. Here, R represents hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. Also, Z represents the following (a) or (b). [Formula] [Formula] Here, R ₁ and R ₂ are hydrogen or carbon atoms from 1 to 10
represents a hydrocarbon group.