DE2620994A1 - POLYMETHACRYLIC ACID ESTERS WITH IMIDAZOLE SIDE GROUPS AND THEIR PRODUCTION PROCESS - Google Patents

Description

Patent attorneys Dipl.-Ing. R. B E E T Z sen. Dipl.-Ing. K. LAMPRECHT Dr.-Ing. R. B E E T Z jr.

8000 Munich 22

Steinsdorfstrasse 1O

Tel. (089) 227201/227244/295910

Telegr. Allpatent Munich Telex 522O48

233-25.588P

May 12, 1976

Ceskoslovenskä academy ved, PRAGUE - CSSR

Polymethacrylic acid esters with imldazole rare groups and their manufacturing process

The invention relates to new polymethacrylic acid esters which contain imidazole side groups, as well as a process for their Manufacturing.

It is known that imidazole, benzimidazole and their derivatives both in low molecular weight and in polymeric form Can form complexes of all kinds.

The formation of such complexes is with regard to the structure and puncture of protein compounds, z. B. at the Coordination reaction of the imidazole group of histidine in the polypeptide chain with iron of the prosthetic group

233- (S 8892) -SFE

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262U994

(Fe-protoporphyrin) in hemoproteins, of vital importance.

Synthetic polymeric systems with covalently bonded iridazole groups have also been described and used as ion exchangers, chelating polymers or catalysts are used. Their disadvantage is their low mechanical Strength, the low resistance to hydrolysis, the small porosityj the low swellability or in the hydrophobic Character of the polymeric framework. Because of these properties, such previously known imidazole polymers have only low effectiveness and short lifespan.

The invention provides micro- and macroporous polymers with covalently bonded imidazole groups that have not yet been described and a method for their manufacture.

The polymethacrylates according to the invention with imidazole groups have units of the general formula I,

CH ₀
I ³

-CH ₂ - C -

C -f- 0 - CH ₀ - CH ₀ -fc- R (I),

r d. C. ΠΙ

in which m is 1 or 2 and
R means:

(a) the grouping —N

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^R l

with R. = R _n = H, C ₁ -C ₁ J-AIlCyI, -CgH ₅ or

-COOC ₂ H ₅

or

R ₁ + R ₂ = -CH = CH-CH = CH- or

R ₁ = H, R ₂ = -COOCH ₃ , -COOC ₂ H ₅ , -COOH, -NO ₂ , -NH ₂ , -CH ₂ -CH ₂ -NH ₂ or -CH ₂ -CH ₂ -NH-CO- C ₆ H,

(b) the grouping -X- (CHg) _n -N

with 1 £ = η <£ 5,

X = -NH-, -0- or -S- and

R ₁ = R ₂ = H, C ₁ -C ₁₁ -AlCyI, -C ₆ H ₅ , -COOCH ₃ or

-COOC _n H ₁ - or R ₁ , R ₂ =.-CH = CH-CH = CH- or R ₁ = H, R ₂ = -NO ₂ or NH ₃

(c) the grouping

NH-CH-CH _n -

R _n with

R ₁ = H, -COOCH ₃ , -COOC ₂ H ₅ , -COOH, -CONH-NH ₂ , -CO-NH-C ₁ -C ₁₁ -AlCyI, -CO-NH-CH ₂ -C ₆ H ₅

or -CO-NH-C ^ H ₁ - and

6 5

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R - TT OTJ / ™ * TT a J λ γ. / " ¹ TT O TJ

_o - H · - oil _ «""O ₀ IIi- UCltiX ·" ΟΓ1 _n "U / -n _r .

ii j ί- 5 top

As starting materials according to the invention Process polyglycol methacrylate aryl sulfonates of the general formula II used,

CH ₃

- CH "-C-

(ID

C.

O = CG 0 - CH ₂ - CH ₂ ^ - 0 - SO ₂ _ ^ O> -

with

m is 1 or 2 and
R '= H or -CH ₃ ,

which are reacted with imidazole derivatives of the general formula RH with R as defined above at temperatures up to 100 ^° C. for 5 min to 8 h, advantageously in the presence of solvents and, if necessary, after the compound RH has been converted into an alkali salt.

The polyglycol methacrylate aryl sulfonates of the formula II used can have a micro- or macroporous structure and after the CS inventor's certificate ......... (see the CS patent application PV 375 ^ -73).

Insoluble crosslinked polymers with a gel structure are referred to as microporous, those for soluble, interacting or reacting components are only accessible in the entire mass after greater swelling (swelling porosity,

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latent porosity). Strongly crosslinked polymers are referred to as macroporous, even when they are not swollen contain accessible macropores (true porosity).

According to the invention, reactive polymers of the formula II, advantageously in the form of regular beads, are replaced by polymer-analogs Conversions converted into insoluble polymeric products with heterocyclic groups.

The invention is based on the finding that polymeric compounds of the general formula I with R as defined in (a) by reacting reactive polymers of the formula II with alkali metal salts of imidazole, optionally imidazole derivatives RH with R as defined in (a) can be. The reaction is advantageously carried out in aprotic solvents such as benzene, toluene, tetrahydrofuran, dimethylformamide or dimethyl sulfoxide, but can also be carried out in alcohols, for example in methanol and ethanol. Alkali salts of imidazole derivatives are produced by the action of alkali hydrides (LiH, NaH), alkali amides (NaNH), optionally alcohol and sodium. The actual reaction is carried out at a temperature of 20-100 ^° C. within 5 minutes to 8 hours.

Polymeric compounds of the general formula I with R as defined in (a), R ^ = H and R ₂ = -NO ₂ or -NH ₂ are prepared in such a way that the sodium salt of 4- (5) -nitroimidazole is first carried out Represents the action of dilute lye; the isolated salt is reacted with the polymers II in solvents customary for nitro derivatives. The amino derivative is prepared by subsequent reduction with an alkaline, aqueous-alcoholic solution of sodium dithionite or tin (II) chloride in concentrated hydrochloric acid. The primary

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Grouping of the histamine must be protected from binding to polymer II by acylation, advantageously by benzoylation will. After the binding of the imidazole residue of histamine to the polymer II, the protective group is through Split off hydrolysis in an alkaline or acidic medium.

The invention is also based on the position that polymeric compounds of the general formula I in which R is as is defined in (b), by polymer-analogous conversion of reactive polymers of the formula II with imidazole derivatives RH with R according to (b) can be produced. In the case of the derivatives with X = -OH and -SH, alkali metal salts are first formed through action of sodium or lithium hydride or sodium amide in aprotic solvents, of sodium in absolute Methanol, optionally ethanol, or NaOH in dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriainide and in the case of Mercaptoalkylimidazoles of NaOH in an aqueous lower alcohol (C. - C ^) manufactured. The alkali salts are with the Polymer II in common solvents such as benzene, toluene, xylene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, Hexamethylphosphoric triamide, methanol, ethanol, optionally aqueous methanol and ethanol, including polymeric compounds of the general formula I with R according to (b) and with X = S or 0 reacted.

If in the general formula RH R is defined according to (b) and X = -NH_, the imidazole derivatives are used as free bases used and with the polymer II in a medium of water, methanol, ethanol or aqueous alcohols, dioxane, Tetrahydrofuran, dimethyl sulfoxide, dimethylformamide or hexamethylphosphoric triamide reacted. All reactions to the Preparation of compounds of general formula I with R

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according to (b) are ^{carried out at 20 to 100 °} C. and require a reaction time of 15 min to 8 h.

The polymeric compounds of the general formula I with R according to (b) and R = H and R "= -NHp are obtained by reduction of the corresponding 4- (5) -nitroimidazole with the sodium dithionite or tin (II) chloride in an environment containing hydrochloric acid manufactured.

The invention is also based on the further plague position, that polymeric compounds of the general formula I with R according to (c) by polymer-analogous conversion of reactive Polymers II prepared with histamine, optionally histidine derivatives of the general formula RH with R according to (c) can be.

The polymers I and R according to (c) are produced by converting II with derivatives RH (R according to (c)) in aqueous methanolic or ethanolic mixtures in methanol, ethanol, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide and others. The reaction time is between 30 min and 8 h at 50-100 ^° C.

Histidine itself must be added to the reaction in the presence of an inorganic base, advantageously sodium hydrogen carbonate; this histidine derivative can also be obtained by saponifying the histidine ester I with R according to (c) and R. = COOCH or COOC ₂ H ₅ with 1-5 N sodium hydroxide solution, advantageously 5N. The hydrazide is accessible by reacting the histidine ester I with R according to - (c) and R. = COOCH ₀ or COOC _n H ₁ - with 98 tiger hydrazine hydrate.

The polymers produced by the process according to the invention have a number of advantages over up to

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known comparable products. They are insoluble in water, but hydrophilic and easily wettable with water. They swell in organic solvents and can also in these media are used. They have a regular spherical shape suitable for use in columns and columns as well as adjustable micro- and macro-porosity, which can be changed as required and adapted to the size of the substrate. she are chemically stable and have good mechanical strength. The imidazole groupings can be sufficient on the long side chains are localized so that they form complexes with the metals contained in biopolymers can. Due to these properties, the products according to the invention can, for. B. as selective sorbents, catalysts, Ion exchangers or carriers of biological functions are used.

The preparation of the polymers according to the invention with imidazole groups is illustrated below by means of examples.

example 1

To 1.7 g (0.025 mol) of irnidazole in 30 ml of absolute tetrahydrofuran if the equivalent amount of NaH or LiH was added, the alkali salt formed immediately with evolution of hydrogen. The suspension was heated to the boil with constant stirring and kept at this temperature for 30 minutes. The reaction mixture 2 g of polymer II with a microporous or macroporous structure were added, according to the method according to the CS inventor's certificate (CS registration PV

5754-73). The suspension was then

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heated to boiling with stirring for 8 h. After cooling, the sample was sucked off, successively with ethanol, water, ethanol, Acetone and ether washed and dried in vacuo. The amount of bound imidazole was determined by elemental analysis calculated specific nitrogen content.

Amount of bound imidazole mg / g

calculated found

microporous sample 370 174

macroporous sample 8l 76

In the same way, the reactions were also carried out with other imidazole derivatives of the general formula RH with R according to (a) and R. = R "using the reactive polymer II carried out according to Example 1. Reactive polymers of the general formula II with m = 2 have also been found to be suitable. In the process according to Example 1, the alkali salts can also be used in other aprotic after removal of the tetrahydrofuran Solvents such as benzene, toluene, xylene, dimethylformamide, Dimethyl sulfoxide, hexamethylphosphoric triamide or dioxane are implemented. The alkali salts were also by the action of Alkali metals in liquid ammonia or absolute methanol, optionally ethanol, prepared on imidazole derivatives. These Solvents were separated from the salts; those mentioned above became the actual nucleophilic substitution aprotic solvent used. The amount of bound imidazole depends on the reaction conditions, especially on the concentration of the reaction components, the reaction temperature, the solvent used and, if appropriate, of the duration of action and can therefore be varied and adjusted as required.

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Example 2

The equivalent amount of sodium or lithium hydride was added to 2.95 F- (0.025 mol) benzimidazole in 30 ml of absolute tetrahydrofuran. The alkali salt formed immediately with the evolution of hydrogen. The suspension was heated to boiling with constant stirring and kept at this temperature for 30 minutes. 2 g of macroporous polymer II (m = 2) were then added to the reaction mixture. The suspension was heated to boiling for 8 h with stirring. The product was processed as in Example 1. Amount of bound imidazole according to the elemental analysis: found 108 mg / g; calculated 120 mg / g.

Example 3

1.4 g (0.02 mol) of imidazole were added to a solution of sodium ethylate from 25 ml of absolute ethanol and 0.46 g (0.02 mol) of sodium. The solution was ^{kept at 90 °} C. for 30 min, after which it was reacted with 2 g of reactive polymer II (m = 2) and the suspension was ^{kept at 90 °} C. for a further 60 min with stirring. The polymeric product was filtered off with suction, washed with water, ethanol, acetone and ether, dried in vacuo and the amount of bound imidazole was determined as in Example 1.

Amount of bound imidazole, calculated mg / g found

macroporous sample 120 43

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Example 4

1.4 g of imidazole were added to a solution of sodium ethylate from 25 ml of absolute ethanol and 0.46 g (0.02 mol) of sodium. The solution was boiled for 30 min and then reacted with 2 g of macroporous polymer II (m = 1) for 15 min while stirring while boiling. The product was processed
as in Example 3. Amount of bound imidazole after
Elemental analysis: found 52 mg / g; calculated 125 mg / g.

Example 5

1.4 g of imidazole were added to a solution of sodium ethylate from 25 ml of absolute ethanol and 0.46 g (0.02 mol) of sodium admitted. The solution was boiled for 30 minutes and then reacted with 2 g of macroporous polymer II (m = 1) for 60 min while stirring at the boil. The product was processed as in Example 3 · Amount of bound imidazole according to elemental analysis: found 73 mg / g; calculated 125 mg / g.

Example 6

1.4 g of imidazole were added to a solution of sodium ethylate from 25 ml of absolute ethanol and 0.46 g (0.02 mol) of sodium admitted. The solution was boiled for 30 min and then with stirring while boiling for 120 min with 2 g of macroporous polymer II (m = 1) implemented. The product was processed as in Example 3. Amount of bound imidazole according to the elemental analysis: found 91 mg / g; calculated 125 nig / g.

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Example 7

The alkali salt of imidazole-4 (5) -carboxylic acid methyl ester (optionally the ethyl ester) was prepared by the process described in Example 1. The ester was reacted with the reactive polymer II (m = 1) in the aprotic solvents listed above under the conditions listed in Example 1. The polymeric product (1 g) was heated to boiling with excess 5N NaOH with stirring for 2 h. The saponified sample was filtered off with suction and washed successively with water, 20% acetic acid, water, ethanol, acetone and ether and dried in vacuo. The amount of bound
Imidazole was determined as in Example 1.

Amount of bound imidazole mg / g

calculated found

microporous sample 269 139

macroporous sample 8l 41

Example 8

From 2.83 g (0.025 mol) of 4- (5) -nitroimidazole, the action of the equivalent amount of sodium hydroxide solution in 20 ml
Water produced the sodium salt, which was filtered off with suction, carefully dried and suspended in 30 ml of absolute tetrahydrofuran. Then 2 g of macroporous reactive polymer II (m = 2) were added and the reaction mixture was added for 8 h on
Simmered and stirred. The polymeric product was filtered off with suction, washed successively with water, ethanol, acetone and ether and dried in vacuo.

The content of bound imidazole moieties was
in a similar manner to Example 1 by elemental analysis

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determined: calculated 149 mg / g; found 97

In the same catfish, 4- (5) -nitro derivatives of 1- (2-hydroxyethyl) imidazole and 1- (2-mercaptoethyl) imidazole were bound to the microporous and macroporous reactive polymer II. The polymeric derivative of 4- (5) -nitroimidazole (1 g) prepared in the manner described above was treated with 50 ml of concentrated hydrochloric acid and 5 g of SnCl _? suspended. The reaction mixture 'was ^{heated to 90 °} C. for 2 h with stirring and the polymeric product was filtered off with suction, successively with conc. HCl, absolute ethanol and anhydrous acetone and dried in vacuo over PpO, -. The free base was obtained by the action of dilute alkali. The reduction of the nitro groupings was also carried out by the action of Na ^ SpOi. The polymer sample (1 g) was first in a mixture of water (25 ml), ethanol (10 ml) and conc. Ammonia (3 ml) suspended, after which NapSpOj. (3 g)

pp

added and the reaction mixture was ^{heated to 90 °} C. for 3 h with stirring. The product was washed successively with water, ethanol, acetone and ether and dried in vacuo over KOH. The amino groups in the polymer were detected qualitatively with trinitrobenzenesulfonic acid (TNBS) and ninhydrin. The samples obtained had a macroporous structure; the content of bound imidazole derivative (mg / g) was determined by elemental analysis similar to example 1:

Amount of bound imidazole, calculated mg / g found

reduced with SnCl ₂ / HCl 149 85

reduced with Na ₃ S ₃ O ₁₄ 149 78

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In the same catfish were 1- (2-hydroxyethyl) -4- (5) -nitroimldazole and l- (2-mercaptoethyl) -4- (5) -nitroimidazole to the Polymer bound and reduced.

Example 9

N-benzoylhistamine (2.15 g; 0.01 mol) was admixed with 2 g of macroporous reactive polymer II (m = 2) under the conditions given in Example 1. The polymeric product (1 g) with an imidazole content of 54 mg / g was ^{saponified by heating to 90 °} C. with 30 ml of 5 N NaOH with constant stirring. The sample was filtered off with suction, washed successively with water, ethanol, acetone and ether and dried in vacuo.

The saponification was also carried out in an acidic medium. In this case, the polymer was heated (1 g) with an excess of concentrated acid salts 3 h at 80 ⁰ C. The product was filtered off with suction, washed successively with water, 1 N NaOH, water, ethanol, acetone and ether and dried in vacuo. The amino groups were detected qualitatively with TNBS and ninhydrin. The content of bound imidazoI groups was determined as in Example 1: calculated 120 mg / g; found 53 mg / g (elemental analysis).

Example 10

2.8 g of l- (2-hydroxyethyl) imidazole (0.025 mol) became the sodium salt prepared by the method of Example 1 or 2 and dissolved in 50 ml of anhydrous tetrahydrofuran in 2 h under boiling of the reactive polymer II (2 g) with macro-

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porous and microporous structure bound. The polymer was filtered off with suction, washed with water, ethanol, acetone and ether and dried in vacuo. The content of imidazole groups was determined as in Example 1:

calculated mg / g found mg / p

microporous sample 225 12 ¹ I.

macroporous sample 150 100

In a similar way, further polymeric products I for R according to (b) and X = O or S were made from microporous or macroporous reactive polymers II and corresponding imidazole derivatives with the hydroxy or mercapto group.

Example 11

2.1 g of 1- (3-aminopropyl) imidazole (0.025 mol) were dissolved in dioxane (30 ml), 2 g of macroporous reactive polymer II (m = 2) were added and the reaction mixture was ^{heated to 90 °} C. for 30 minutes while stirring . The polymeric product was filtered off with suction, washed with ethanol, acetone and ether and dried in vacuo. The content of imidazole groups was determined as in Example 1: calculated 118 mg / g; found 36 mg / g (elemental analysis)

Example 12

To a suspension of 1.55 g of histidine (0.01 mol) and 0.84 g of NaHCO (0.01 mol) in 30 ml of aqueous methanol (1: 1) (optionally ethanol) were 2 g macroporous reactive

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Polymer II (m = 2) was added and the reaction mixture was stirred at boiling for 2 h. The polymer product was sucked off, washed with water, ethanol, acetone and ether and dried in vacuo. The content of imidazole moieties was determined as in Example 1 by elemental analysis: calculated 120 mg / g; found 16 mg / g.

Example 13

1.69 g of the methyl ester of histidine (0.01 mol) were dissolved in dioxane (30 ml); the solution was ^{stirred at 100 °} C. for 90 min with 2 g of macroporous reactive polymer II (m = 2). The product was filtered off with suction, washed and dried as in the previous example. The content of imidazole bound to the polymer was determined as in Example 1: found 38 mg / g; calculated 120 mg / g.

In the same way, further polymeric products I were prepared from microporous or macroporous reactive polymers II and imidazole derivatives with R according to (c) with the exception of the imidazole derivatives with R according to (c) and R ₁ = CONH-NH ₂ .

example

The polymer prepared according to Example 13 with the bound methyl ester of histidine (1 g) was shaken Reacted for 3 h at room temperature with 20 ml of 98 tiger hydrazine hydrate, suctioned off, washed successively with water, 1 N HCl, water, 1 N NaOH, water, ethanol, acetone and ether and im Vacuum dried. The hydrazide groups in the polymer

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were detected qualitatively with TNBS and the content of imidazole groups was determined as in Example 1: calculated 120 mg / g, found 39 mg / g.

example

Polymer prepared according to Example 13 (1 g) was saponified as in Example 3. It became a polymeric product recovered containing histidine with free carboxyl groups; the content of imidazole groups was as in Example 3 determined by elemental analysis: calculated 120 mg / g, found 40 mg / g.

Example 16

3.2 g of l- (2-mercaptoethyl) imidazole (0.025 mol) became as in Example 1 in 50 ml of absolute tetrahydrofuran Sodium salt prepared and reacted with reactive macroporous polymer II (m = 2) while stirring at the boil for 4 h. The product was processed as in Example 10. Amount of bound imidazole according to elemental analysis: found 115 nig / g, calculated 116 mg / g.

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Claims (1)

Claims 1. Polymethacrylic acid esters with imidazole side groups, marked by units of the general formula I, -CH ₂ - C - C - { O - CH ₂ - CH ₂ ^ - R (I), in which m is 1 or 2 and R means: (a) the grouping with R ₁ = R ₀ = H, C ₁ -Ci ₁ -AllCyI, -Cx-Hp. or -COOCH ₁ - or + R ₂ = -CH = CH-CH = CH- or R ₁ = H, R ₂ = -COOCH, -COOC ₂ H, -COOH, -NO ₂ , -NH ₂ , -CH ₂ -CH ₂ -NH ₂ or (b) the grouping -X- (CH ₂ ) _n -N 609848/0889 with X = -NH-, -O- or -S- and R ₁ = R ₂ = H, C ₁ -C ₂₁ -AlCyI, -CgH ₅ , -COOCH ₃ or -COOC _n H, - or R ₁ , R ₂ = -CH = CH-CH = CH- or R ₁ = H, R ₂ = -NO ₂ or NH ₂ or R ₁ (c) the grouping ' NH-CH- ( with = H, -COOCH_, -COOC ₂ H, -COOH, -CONH-NH ₂ , -CO-NH-C ₁ -C ₁₁ -AlCyI, -CO-NH-CH ₂ -C ₆ H or -CO-NH-C ^ H ₁ - and 6 5 ₀ = H, -CH ₀ , -C ₀ H ₁ - or - Process for the production of the polymethacrylic acid esters according to Claim 1, characterized by the reaction of polyglycol methacrylate aryl sulfonates of the general formula II - CH ₀ - C - O = C (0 - CH ₂ - CH ₂ -) ^ j - 0 - 609848/0889 with m is 1 or 2 and
R '= H or CH-, with imidazole derivatives of the general formula RH with R as in claim 1 at temperatures up to 100 ^° C. and a reaction time of 5 min to 8 h, advantageously in the presence of solvents and optionally after conversion of the compound RH into an alkali salt. 3. The method according to claim 2, characterized in that the imidazole derivative RH with R according to (a) converted into its alkali metal salt and then 5 to 8 min at 20 h - 100 ⁰ C is reacted with the compound of formula II. 4. The method according to claims 2 or 3, characterized in that that the imidazole derivative after the action of alkali hydrides, amides or alcoholates in aprotic Solvents such as benzene, toluene, xylene, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide or hexamethylphosphoric triamide is converted into its alkali salt. 5. Process according to claims 2 or 3, characterized in that the imidazole derivative RH is converted into its alkali salt by the action of an alkali metal alcoholate in the medium of a lower aliphatic alcohol (C _{1 -C ^).} 6. The method according to any one of claims 2-5, characterized in that the imidazole derivative RH with R according to (a) and R ₁ = H and R ₂ = NO _{2 is} first converted into the alkali salt, this isolated in an aprotic solvent 6098 4 8/0889 rait the compound of type II implemented and possibly. Subsequently with sodium dithionite or tin (II) chloride in concentrated form Hydrochloric acid is reduced. 7. The method according to any one of claims 2-5, characterized in that the imidazo1derivat RH with R according to (a) and R ₁ = -CH ₀ -CHp-NH _{2 is} first acylated, advantageously benzoylated, after which the aeyl group after the reaction is split off again with the compound of formula II. 8. The method according to claim 2, characterized in that the Imxdazolderivat RH with R according to (b), optionally after conversion into the sodium salt, 15 min up to B h at 25 - 100 ⁰ C in the solvent with the compound of formula reacted II. . 9. The method according to claim 2 or 8, characterized in that the imidazole derivative RH with R according to (b) and X = O or S. initially under the action of sodium hydride, lithium hydride, sodium amide or caustic soda in an aprotic solvent converted into its alkali salt and then reacted with the compound of formula II. 10. The method according to claim 2 or 8, characterized in that the imidazole derivative RH with R according to (b) and X = O or S. by the action of an alkali metal in a lower aliphatic Alcohol (C, - C ^,) converted into its alkali salt and is then reacted with the compound of formula II in the same solvent. 11. The method according to claim 1 or 8, characterized in that the imidazole derivative RH with R according to (b) and X = S also in 609848/0889 Water, lower aliphatic alcohols (C - C ^) or in their mixtures with water in the presence of an inorganic base, preferably sodium hydroxide solution, is reacted. 12. The method according to claim 2 or #, characterized in that the inidazole derivative RII with R according to (b) and R ₁ = H and Rp = NO «after binding to the polymer of formula II with ilodium dithionite or tin (II) chloride in concentrated hydrochloric acid is reduced. 13. The method according to claim 2 or 8, characterized in that the imidazole derivative RH with R according to (b) and X = NEp in an environment of water, methanol, ethanol, their mixtures with water, dioxane, tetrahydrofuran, diine thylsulf oxide or hexamethylphosphoric triamide is reacted. 14. The method according to claim 2, characterized in that the imidazole derivative RH with R according to (c) with the compound of type II 30 min to 8 h at 50-100 ⁰ C in an environment of water, methanol, ethanol, their mixtures with Water, dioxane, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide or hexamethylphosphoric triamide reacted and then if necessary: fs. is chemically reacted further. 15. Use of the polymethacrylates according to claim 1 for the production of selective sorbents, catalysts, ion exchangers, biologically active materials and metal complexes. 609848/0889