JPH02225424A - Separating agent - Google Patents

Abstract

NEW MATERIAL:Optically active carbamoylated polyamide of formulae I and II (R is 1-15C aliphatic, aromatic hydrocarbon group or aralkyl which may have substituent respectively; A is residue obtained by removing one active hydrogen from each of two amines of primary or secondary diamine). USE:A separating agent used in chromatography for optical resolution. PREPARATION:For example, from an anti.head-head coumarin dimer and hexamethylenediamine a corresponding polyamide is prepared and excess isocyanate is reacted with phenolic hydroxyl groups in the resultant polymer in the presence of a small amount of triethylamine, thus obtaining the objective material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel separating agent, particularly a separating agent for chromatography for optically resolving racemic compounds.

[Conventional technology]

Conventional separation agents based on optically active polymers include optically active acrylamide polyamides. -CG,
Blaschke, Angew, Chem, In
t, Ed.

已ngl, 19. 13 (1980)) or optically active polymethacrylate esters (H, Yuki,
Y, Okamoto.

! , Okamoto, J.A+++, Chem.
Soc, 101.6356 (1980) E.
Polyamides using optically active anti-head-to-head coumarin dimers (K, Saigo, Y, ChenN, Y
onezawa, T., Kanoe, K., Tac
hibana and M, ) tasega, wa,
Macromolecules, 19. 15
52 (t986)) or those using naturally occurring polysaccharide derivatives such as cellulose are known.

[Problem to be solved by the invention]

The conventionally used separation agents based on optically active polymers cannot necessarily separate all racemic compounds, and the target objects are limited.

Therefore, the development of new separation agents that can resolve a wider range of racemic compounds is awaited.

[Means to solve the problem]

In view of the above, the present inventors have focused on research on polyamides using optically active anti-head-head marine dimer derivatives. discovered that selectivity could be imparted to the asymmetric discrimination ability, leading to the present invention.

That is, the present invention provides a separating agent containing an optically active carbamoylated polyamide represented by the following general formula (I) or (n) as a main component.

In the formula, R represents an aliphatic or aromatic hydrocarbon group having 1 to 15 carbon atoms or an aralkyl group, and the structure thereof may contain a substituent that does not participate in the reaction.

Further, A represents a residue obtained by removing one active hydrogen from each of the two amino groups of the first or second diamine.

For example, when R is a chain alkyl group,
-(CHz), -C11,I(n·0-14), or one Ctt (C) with a side chain! -) 2. -CHa
CH([:H3) 2 is also aromatic, and as substituents, in addition to alkyl groups, halogen (CI, Or),
Any group that does not participate in the reaction, such as an ester group, may be used. Sara C1l.

On the other hand, examples of the diamino group corresponding to 8 include the following.

HN (C1,) 2-NH-.

-HN-(CH2)S-NH-, -N-(C1lz)s
-N-c+b c++* The optically active carbamoylated polyamide of the present invention can be prepared by a known method [: Macromolecules, 19
1552 (1986): 1 by synthesizing a polyamide and then reacting it with an excess of incyanate corresponding to the phenolic hydroxyl groups in the polymer.

In order to use the optically active polyamide of the present invention as a separating agent for the purpose of separating compounds and their optical isomers, chromatography methods such as gas chromatography, liquid chromatography, and thin layer chromatography are generally used. However, this geomembrane separation can also be performed.

In order to apply the optically active polyamide of the present invention to a liquid chromatography method as a separating agent, it is common to fill a column as a powder, and it is preferable to crush it or form it into beads. is more preferably porous. Furthermore, improving the pressure resistance of the separating agent,
In order to prevent swelling and shrinkage caused by solvent substitution and to improve the number of theoretical plates, it is preferable to support the optically active polyamide on a carrier.

When used as a powder, the size of the particles and the size of the carrier vary depending on the size of the column used, but from 1 μm to
l+y+m, preferably 1 μm to 300 μm. The carrier is preferably porous, with an average pore size of 10 to 100 μm, preferably 50 to 50 μm.
．． 000 people. The amount of the optically active polyamide supported on the carrier is 1 to 100% by weight, preferably 5 to 50% by weight, based on the carrier.

The method for supporting the optically active polyamide on a carrier may be a chemical method or a physical method. Physical methods include dissolving the optically active polyamide in a soluble solvent, mixing well with a carrier, and distilling off the solvent with an air stream under reduced pressure or heating, and dissolving the optically active polyamide in a soluble solvent. There is also a method in which the optically active polyamide is dispersed in a solvent insoluble to the optically active polyamide after being thoroughly mixed with a carrier, thereby diffusing the soluble solvent. It is also possible to improve the separation ability of the separation agent obtained in this way by subjecting it to appropriate treatments such as heating, addition of a solvent, and washing.

The carrier used may be a porous organic carrier or a porous inorganic carrier, preferably a porous inorganic carrier. Suitable porous organic carriers include polymeric substances such as polystyrene, polyacrylamide, polyacrylate, etc. Suitable porous inorganic carriers include silica,
These materials include alumina, magnesia, glass, kaolin, titanium oxide, and silicate, and their surfaces are treated to improve their affinity with the optically active polyamide or to modify the surface characteristics of the carrier itself. You may use the one that has been applied.

Examples of surface treatment methods include silanization using an organic silane compound and surface treatment using plasma polymerization.

There are no particular restrictions on the developing solvent used in liquid chromatography or thin layer chromatography, as long as it dissolves or reacts with the optically active polyamide. When the optically active polyamide is bonded to a carrier by a chemical method or made insolubilized by crosslinking, there are no particular restrictions except for those that react with the carrier.

On the other hand, when performing thin layer chromatography, 0.1
μm to Q, thickness Q of the separation agent consisting of particles of about 1 mm and a small amount of binder if necessary, 1 mm to 5
A layer of mm may be formed on the support plate.

In addition, when performing membrane separation, it is used as a hollow fiber or film.

〔Example〕

Hereinafter, synthesis examples and examples of the separating agent of the present invention will be shown together with comparative examples, but the present invention is not limited to these examples.

Synthesis Example 1 The reaction of the (-)anti head-head marine dimer with hexamethylene diamine was carried out by a known method [Macr.

molecules, 19.1552 (1986)
) to obtain the corresponding polyamide.

Synthesis Example 2 A reaction between the (-)anti-head-head marine dimer and p-phenylenediamine was carried out according to Synthesis Example 1 to obtain a corresponding polyamide.

Synthesis Example 3 The polyamide obtained in Synthesis Example 1 and isopropyl isocyanate (4 equivalents) were mixed in the presence of a small amount of triethylamine.
The reaction was carried out in dimethylacetamide at 70° C. for 24 hours with stirring. After cooling, the reaction mixture was poured into water, and the precipitate was dried under reduced pressure to obtain a carbamoylated polyamide.

Synthesis Example 4 The polyamide of Synthesis Example 1 and phenyl isocyanate were reacted in the same manner as in Synthesis Example 3.

Synthesis Example 5 The polyamide obtained in Synthesis Example 2 and isopropyl isocyanate were reacted in the same manner as in Synthesis Example 3.

Synthesis Example 6 The polyamide of Synthesis Example 2 and phenyl isocyanate were reacted in the same manner as in Synthesis Example 3.

Example 1 The yield and properties of the carbamoylated polyamides obtained in Synthesis Examples 3 to 6 above were investigated. The results are shown in Table-1.

Table note) Book 1: 0.3 g-J-', dimethylacetamide solvent, 30°C Book 2: 0.15 g-dl! -', for dimethylacetamide solvent, 400MHz 'H-N indicates that the phenolic hydroxyl group is completely carbamoylated.
Confirmed by MR.

Example 2 The optically active carbamoylated polyamide obtained in Synthesis Examples 3 to 6 was dissolved in dimethylacetamide, and silica gel treated with diphenylsilane (Lichrospher) was prepared.
1QQQ, particle size 10 μm) was supported (20% coating) to prepare a filler.

Each of the obtained fillers was packed into a stainless steel column (inner diameter 0.46 cm x length 20 cm) by a slurry method. Using these columns, various racemates shown in Table 2 were separated. The separation coefficient (α) at that time is shown in Table-2.

table

Claims (1)

[Scope of Claims] A separating agent whose main component is an optically active carbamoylated polyamide represented by the following general formula (I) or (II). (I)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is an aliphatic or aromatic hydrocarbon group having 1 to 15 carbon atoms, or an aralkyl group. The structure may contain a substituent that does not participate in the reaction.Also, A represents a residue obtained by removing one active hydrogen from each of the two amino groups of the primary or secondary diamine. .)