JPS5813562B2 - Kakusan Enkiofukumu Koubun Shidenkai Shitsuno Seihou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer electrolyte containing a nucleobase.

To explain in more detail, the following general formula (1) (where R
1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R2 is a hydrocarbon group having 1 to 4 carbon atoms.

R3 and R4 are hydrocarbon groups having 1 to 6 carbon atoms.

) and a polymer containing one monomer unit represented by the following general formula (2) (where B is adenine, thymine, uracil, cytosine and related compounds thereof).

The purine ring reacts at the 91st position, and the pyrimidine ring reacts at the 1st position.

X is a chloro and bromine atom. ) in a solvent.

One object of the present invention is to provide a material for producing a resin for separating and purifying nucleic acid bases and their related compounds.

This can be attributed to at least the following four factors.

(1) Contains nucleobases.

(2) High molecular weight.

(3) Be polycationic.

(4) Possible to crosslink.

It is.

The method of the present invention solves these problems as follows.

Regarding ([), the specificity of nucleic acids in living organisms is based on the interaction between their constituent units, nucleobases, through hydrogen bonds.

That is, adenine → thymine (uracil), guanine →
Found in cytosine.

The present invention attempts to separate and purify nucleobases and their related compounds by utilizing this interaction.

Regarding (2), various polymers containing nucleobases have been produced in the past.

Generally, these polymers are obtained by vinyl polymerization or condensation polymerization, and have the disadvantage that high molecular weight polymers cannot be obtained.

On the other hand, in the present invention, since it is based on a polymer reaction,
Polymers with fairly high molecular weights can be produced.

Regarding (3), the units constituting the nucleic acid are neutral or anionic.

Therefore, as a method for efficient interaction between nucleic acid bases, cationicity is more advantageous.

Regarding (4), when a polymer containing a nucleobase is used as a separation and purification resin, it is necessary to make it insolubilized.

Two methods can be considered for the polymer reaction in the present invention.

(a) A method using a polymer that has already been crosslinked as a material;
(b) A method in which a soluble polymer is used to first produce a polymer containing a nucleic acid base, and then crosslinked to make it insolubilized.

The former method has the drawbacks that the system becomes non-uniform, the reaction takes time and the reaction rate is low, and is therefore not very preferable.

In the latter method, a crosslinkable group may be introduced into the polymer used.

However, in this case, there are problems such as the density of the nucleobases being reduced by the content of the introduced groups, and the materials being used are limited.

In order to solve these problems, it is only necessary to introduce a crosslinkable group simultaneously with the quaternization reaction.

In this respect, the polythionic polymers produced according to the invention are satisfactory.

The polymer used for producing the polymer electrolyte containing a nucleobase of the present invention is represented by the general formula (1), and examples of these polymers include dimethylaminoacrylate, diethylaminoethyl acrylate, dibutylethyl acrylate, tertiary Butylaminomethyl acrylate:
Dialkylaminoalkyl acrylates such as dimethylaminobutyl methacrylate, dimethylaminobutyl methacrylate, tert-butylaminoethyl methacrylate, or homopolymers of such methacrylates (and substituted styrenes such as styrene or α-methylstyrene; substituted acrylonitriles such as acrylonitrile or methacrylonitrile) Examples include copolymers with vinyl monomers that do not form electrolyte polymers, such as.

The nucleobase derivative used in the quaternization reaction with general formula (1) is the 2'-hydroxy-3 represented by general formula (2).
Examples of the nucleobases and related compounds of the '-halopropyl derivatives include adenine, thymine, uracil, cytosine, 3-N-alkylpyrimidine, 6-mercaptopurine, theophylline, and hypoxanthine.

The units represented by general formula (1) in the polymer can be changed appropriately.

2'-Hydroxy-3 of nucleobases and related compounds
The '-halopropyl derivative can be appropriately changed with respect to one monomer unit represented by general formula (1).

2'-Hydroxy-3 of nucleobases and related compounds
The '-haloprovir derivative may be used in an amount of 1 to 1.5 times equivalent to one unit of the monomer represented by the general formula (1) in the polymer.

It is preferable to carry out the reaction in a homogeneous system, since a non-uniform system will take time and reduce the reaction rate.

Therefore, a solvent may be used, and examples of the solvent include methanol, N-N-dimethylformamide, N-N-dimethylacetamide, dimethylsulfoxide, and the like.

The purpose can be achieved not only by using these solvents alone but also by using a mixture of two or more components.

The production of the polymer electrolyte containing a nucleobase produced by the present invention is simple; first, a polymer containing one monomer unit represented by general formula (1) is dissolved in a solvent, and then the nucleobase and its related compounds are dissolved. 2'-hydroxy-37 -7
- Add lopropyl derivative and heat the reaction.

The reaction temperature is suitably in the range of 50°C to 120°C, and the reaction time is 10 to 40 hours.

In the present invention, the introduction rate of the 2'-hydroxy-3'-haloprobyl derivative of the nucleobase and its related compounds relative to one unit of the monomer of general formula (1) can be appropriately changed.

The ultraviolet absorption spectra of the polyelectrolytes containing nucleobases produced according to the present invention were measured using water as a solvent, and the results showed that the corresponding nucleobases and related compounds were 27-hydroxy-3'-1...loprovir derivatives. showed a maximum peak at the same wavelength.

From this result, it was found that the polymer electrolyte containing a nucleobase obtained in the present invention had the desired structure.

The polyelectrolyte produced according to the method of the invention was a highly hygroscopic solid material.

Furthermore, the viscosity of these aqueous solutions was extremely high, similar to that of general polymer electrolytes.

The polyelectrolyte produced by the present invention comprises nucleobases,
It is extremely effective as a raw material for resins for separating and purifying nucleic acid-related compounds such as nucleosides and nucleotides, and as a raw material for polyion complexes.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these examples.

Example 1 Polydimethylaminomethyl acrylate (molecular weight 1.3
After dissolving X105)12'P in 18 ml of N-N-dimethylformamide, 1-(2'-hydroxy-3'-bromoprovir) monothymine was added, and the reaction was carried out by heating at 80°C to 85°C for 24 hours. .

After the reaction was completed, the mixture was poured into a mixture of ethyl acetate and ethyl alcohol to obtain a product.

The degree of quaternization was 72%.

Elemental analysis was as follows. As a result of measuring the ultraviolet absorption spectrum of the elemental analysis product in water,
It exhibited extremely thick absorption at the same wavelength (272 mμ) as 1-(2'-hydroxy-3'-bromprovir)-thymine.

The product obtained from the above results was estimated to have the following structure.

Example 2 Dimethylamine methyl methacrylate-styrene copolymer (78:22, molecular weight 27X105) 1M' was converted into N-
After dissolving in 1-5 ml of N-dimethylformamide,
(2) = (2'-Hydroxy-3'-chlorpyrol)-thymine 142 was added, and a heating reaction was carried out at 80°C to 85°C for 30 hours.

After the reaction was completed, the mixture was poured into a mixture of ethyl acetate and ethyl alcohol to obtain a product.

The degree of quaternization was 61%.

Elemental analysis was as follows.

When the ultraviolet absorption spectrum of the product was measured in water, it was found that 1
It showed maximum absorption at the same wavelength (272 mμ) as -(2'-hydroxy-3'-chlorprobyl)-thymine.

The product obtained from the above results was estimated to have the following structure.

Example 3 Example 2 No-1-(2'-hydroxy-3'-chlorprovir)-thymine was converted into 1-(2'-hydroxy-3'-
-bromupropyl) except that it was replaced with uracil 12r.
Reactions and treatments were carried out in the same manner.

As a result, the product was estimated to have the following structure.

Example 4 Diethylamine methyl methacrylate-styrene copolymer (25:75, molecular weight 3X105) 121
After dissolving in 20rrLl of -N-dimethylformamide, 1-(2'-hydroxy-37-bromoprobyl)-4-ethoxypyrimidine was added, and the reaction and treatment were carried out in the same manner as in Example 2.

The degree of quaternization was 71%.

The results of elemental analysis were as follows.

Measuring ultraviolet absorption spectra of elemental analysis products in water
-(2'-hydroxy-3'-bromprovir)-4-
It showed maximum absorption at the same wavelength (275 mμ) as ethoxypyrimidine.

The product obtained from the above results was estimated to have the following structure.

Claims (1)

[Scope of Claims] 1 General formula (1) below (wherein R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R2 is a hydrocarbon group having 1 to 4 carbon atoms. R3 and R4 are A polymer containing one monomer unit represented by the following general formula (2) (where B is adenine, thymine, uracil, cytosine and related compounds thereof. A method for producing a polymer electrolyte, characterized in that the purine ring is reacted at the 91-position and the pyrimidine ring is reacted at the 1-position.