MXPA98000591A - Derivatives of photoquimically reticulated polysaccharides that do not have functional groups fotopolimerizab - Google Patents

Abstract

The invention relates to substantially photochemically crosslinked polysaccharide derivatives which do not contain photopolymerizable functional groups before crosslinking, which can be used as carrier materials for the chromatographic separation of enantiomers. The present invention relates to photochemically crosslinked polysaccharide derivatives wherein the OH groups as OR groups have been esterified or converted to carbamate (urethane) or mixtures thereof, with the proviso that the OR groups do not contain polymerizable double bonds prior to reticulation. The photochemically crosslinked polysaccharides according to the invention, in a conditioned form, can also be used as the pure polymer for the chromatographic separation of enantiomer

Description

DERIVADOS DE POLISACA IDOS PHOTOQUIMICALLY RETICUL TWO THAT DO NOT HAVE FUNCTIONAL GROUPS FOTOPOLIMERIZABLES The invention relates to substantially photochemically crosslinked polysaccharide derivatives which do not contain photopolymerizable functional groups prior to crosslinking, which can be used as carrier materials for the chromatographic separation of enantiomers. K. Kimata and collaborators describe, in Anal. Methods and Instrumentation, Volume 1, (1993) 23, the preparation of a chiral carrier material which is stable to solvents, and which is obtained by the polymerization of vinyl benzoate of cellulose. The chemically bound stationary phases, which consist of cellulose, are compared with the analogous non-polymerized phases with respect to their chiral selectivity and stability towards the solvents, observing an increase in the stability towards the organic solvents, and a slight decrease in the chiral selectivity of chemically linked cellulose. C. Oliveros et al. Describe, in J. Liquid Chromatogr., 18 (1995) 1521, the stationary phases consisting of 3,5-dimethylphenyl carbamate cellulose which have been immobilized on a carrier. The resulting chiral stationary phases can be immobilized, for example, on carriers, for example silica gel, and then they are resistant to customary solvents, the method of immobilization used in that work having already been known from the prior art (for example , U.S. Patent Number 1,690,620). German Patent Number DE-A-2,422, 365, discloses polymers suitable for photopolymerization, "having groups" which contain anhydride, and which are converted by means of mechanically effective light, into resistant substances which are suitable as compounds for protective printing, or for the preparation of protective printing templates for printing plates. No mention is made of its use as a carrier material for the chromatographic separation of enantiomers. N.R. Bertoniere et al. Describe, in J. Appl. Polymer Sci., Volume 15, (1971) 1743, cotton fabrics "containing cinnamic acid esters (cinnamoyl radicals) as substituents, which upon irradiation with light of a certain wavelength (2573 A), are first isomerized, and then they are dimerized to form trixyl and truxic acid derivatives, but the photochemical reaction essentially takes place only on the surface of the fabric. The two patent specifications of the States United States Nos. 2,682,481 and 2,682,482 disclose methods by which carbohydrates, especially cellulose derivatives, which carry unsaturated functional groups, can be converted by heating with peroxide catalysts, or by dimerization or other crosslinking, to obtain shaped articles that they have an insoluble surface. H. Engelmann et al. Describe, in a publication issued by Staatliches Forschungsinstitut für makromolekulare Chemie, Freiburg i, Breisgau, (1957), 233, a method for the preparation of cellulose tricrotonate and cellulose acetocrotonates, and the reaction of these products in cross-linking, with oxygen or light, and the addition of halogens and diamines. It is noted that all products obtained, including those that have a very low crotonyl content, are then insoluble in organic solvents. There is no indication of the property as a carrier material for the chromatographic separation of enantiomers. In all the cited publications, the starting materials used contain polymerizable groups for crosslinking, that is, the crosslinking is carried out by polymerization of one or more double bonds. The present invention relates to photochemically crosslinked polysaccharide derivatives, wherein the OH groups as OR groups have been esterified or converted to carbamate (urethane) or mixtures thereof, with the proviso that the OR groups do not contain polymerizable double bonds before crosslinking. The invention relates especially to photochemically crosslinked polysaccharide derivatives, wherein the OH groups co or OR groups have been converted to an unsubstituted or substituted aryl, arylalkyl, hetaryl, or heteroaryl ester, or to an aryl carbamate, arylalkyl, hetaryl, or unsubstituted or substituted hetarylalkyl (urethane), or mixtures thereof, with the proviso that the OR groups do not contain polymerizable double bonds before crosslinking. Particular importance is given to the photochemically crosslinked polysaccharide derivatives wherein the OH groups as OR groups have been converted to an unsubstituted or substituted aryl or arylalkyl ester, or an unsubstituted or substituted aryl or arylalkyl carbamate, or mixtures thereof , with the proviso that the OR groups do not contain polymerizable double bonds before crosslinking. Also of particular importance are the photochemically cross-linked cellulose or amylose derivatives, wherein the OH groups as OR groups have been converted to an aryl or arylalkyl ester or an aryl or arylalkyl carbamate, the ester or carbamate being unsubstituted or mono- or poly-substituted by lower alkyl and / or by halogen, or mixtures thereof, with the proviso that the OR groups do not contain polymerizable double bonds before crosslinking. Very special importance is given to the photochemically crosslinked cellulose or amylose derivatives wherein the OH groups as OR groups have been converted to a phenyl or benzyl ester or to a phenyl or benzyl carbamate, the ester or carbamate being unsubstituted or mono - or poly-substituted by lower alkyl and / or by halogen, or mixtures thereof, with the proviso that the OR groups do not contain polymerizable double bonds. In the esterification or in the conversion of carbamate of the OH groups into OR groups, the hydrogen of the OH group is replaced by an acyl radical of the formula R'-C (= 0) -, or by the acyl radical of carbamic acid R '-NH-C (= 0) -. Previously herein and below, the radicals and lower compounds should be understood to be, for example, those having up to and including 7, preferably up to and including 4 carbon atoms (carbon atoms).

C). The polysaccharides are, for example, cellulose, amylose, chitosan, dextrin, xylan, and curdlan, chitin and inulipa, which can be obtained as polysaccharides in a high degree of purity. Preference is given to the use of polysaccharides having a degree of polymerization (number of rings of piraposa and furanose) of at least number 5, and in an especially preferable manner of at least number 10, in order to ensure ease of driving. Lower alkyl is, for example, alkyl of 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl, which may be unsubstituted or substituted by halogen, such as fluorine or chlorine, for example trifluoromethyl or trichloromethyl.

Aryl as such is, for example, phenyl or naphthyl, such as 1- or 2-naphthyl, or substituted phenyl or naphthyl, for example phenyl or naphthyl substituted by lower alkyl, lower haloalkyl, hydroxy, lower alkoxy, lower alkanoyloxy, halogen, and / or by cyano. Aryl is preferably phenyl which is unsubstituted or substituted as indicated above, and is especially phenyl. Arylalkyl is preferably arylalkyl, especially phenylalkyl, more especially phenylethyl or benzyl. Lower alkoxy is, for example, normal propoxy, isopropoxy, normal butoxy, or tertiary butoxy, preferably ethoxy, and especially methoxy. Lower alkanoyloxy is, for example, propionyloxy or pivaloyloxy, preferably acetyloxy. Halogen is, for example, chlorine or fluorine, and also bromine and iodine. Lower haloalkyl is, for example, 2- or 3-lower haloalkyl, for example 2-halopropyl, 3-halopropyl, or 3-halo-2-methylpropyl. Hetaryl should be understood as especially a monocyclic, but also bicyclic or polycyclic radical of an aromatic character. The bicyclic and polycyclic hetaryl may be composed of a number of heterocyclic rings, or preferably of a heterocycle and one or more, for example one or two, but especially a copulated carbocyclic ring, especially a benzo ring. Each individual ring contains, for example, 3, 5, 6, 7, and especially 5 or 6 ring members. Hetaryl is especially an aza-, thia-, oxa-, thiaza-, thiadiaza-, oxaza-, diaza-, or tetraza-cyclic radical. Hetaryl is especially a monacyclic monoaza-, monothia-, or mono-oxa-cyclic radical, for example pyrrhyl, for example 2-pyrryl or 3-pyrryl, pyridyl, for example 2-, 3-, or 4-pyridyl, thienyl, for example 2- or 3-tiepyl, or furyl, for example 2-furyl; a bicyclic radical opoaza-, opo-oxa-, or monotia-cyclic, for example indolyl, for example 2- or 3-indolyl, quinolipyl, for example 2- or 4-quinolinyl, isoquipolinyl, for example 1-isoquinolinyl, benzofuran, for example 2- or 3-benzofuranyl, or benzothienyl, for example 2- or 3-benzothienyl, a diacyl-, triaza-, tetraza-, oxaza-, thiaza-, or thiadiaza-cyclic monocyclic radical, such as i-idazolyl, example 2-imidazolyl, pyrimidinyl, for example 2- or 4-pyridinyl, triazolyl, for example 1, 2,4-triazol-3-yl, tetrazolyl, for example 1- or 5-tetrazolyl, oxazolyl, for example 2- oxazolyl, iso-oxazolyl, for example 3- or 4-isoxazolyl, thiazolyl, for example 2-thiazolyl, isothiazolyl, for example 3- or 4-isothiazolyl, or 1,2,4- or 1, 3,4-thiadiazolyl, for example, 1, 2,4-thiadiazol-3-yl or 1,4-thiadiazol-2-yl, or a bicyclic diaza-, oxaza-, or thiaza-cyclic radical, such as benzyl-idazolyl, for example 2 -benzimidazolyl, benzoxazolyl, for example 2-benzoxazole lyl, or benzothiazolyl, for example 2-benzothiazolyl. Hetaryl radicals are substituted or carry substituents. Suitable substituents on the ring carbon atoms are, for example, the substituents indicated above for the aryl radicals, and in addition oxo (= 0). The nitrogen atoms in the ring may be substituted, for example, by lower alkyl, arylalkyl, lower alkali, benzyl, carboxy, lower alkoxycarbonyl, hydroxy, lower alkoxy., lower alkanoyloxy, or by oxide (-0). Hetaryl is especially pyridyl, thienyl, pyrryl, or furyl. The hetarylalkyl radicals are composed of the aforementioned hetaryl radicals, and the aforementioned alkyl radicals, especially lower alkyl radicals. Heteroxy lower alkyl is especially pyridinyl-, thienyl-, pyrril-, or furyl-methyl. The compounds according to the invention are prepared as follows: the polysaccharide derivatives wherein the OH groups as OR groups have been esterified or converted to carbamate, after being previously coated on a carrier, or after a previous conditioning as a material using an emulsion, they are crosslinked by means of irradiation (hv) to form the compounds according to the invention. The crosslinking can be effected by supplying radiation energy of different wavelengths, for example by means of laser beams, or preferably by irradiation using a conventional submersible mercury discharge lamp. Suitable suspending agents for irradiation are, for example, inert solvents, for example hydrocarbons such as hexane or lower alkanols, such as methanol, ethanol, propanol, or isopropanol, or aqueous mixtures thereof, ethereal solvents, for example ether. diethyl, or carbon tetrachloride or acetonitrile. The photochemical crosslinking can optionally be carried out in the presence of photosensitizers, for example in the presence of thioxanthone. As carriers, it is possible to use silicon dioxides, for example silica gel or modified silica gel, especially aminosilanised silica gel, glass, and also oxides of aluminum (alumina), graphite, or zirconia (zirconia). The polysaccharides used as starting compounds in which the OH groups as OR groups have been esterified or converted to carbamate (urethane), are prepared by esterification of the free OH groups of the polysaccharide compounds, or by converting them to carbamate (urethane). The esterification and the carbamate formation are carried out in a manner known per se, by reaction with an isocyanate or with a reactive functional carboxylic acid derivative. For example, the esterification can be carried out with unsubstituted or substituted benzoyl halides, especially benzoyl chlorides, the corresponding carboxylic acid anhydrides, or alternatively with a mixture of the corresponding carboxylic acid and a suitable dehydrating agent. For esterification, it is possible to use any inert solvent that does not prevent esterification, it being usual to also add a catalyst, for example a tertiary amine, such as 4- (N, N-dimethylamino) pyridine. The formation of the carbamate is normally carried out by reaction with a suitable isocyanate in the presence of a suitable catalyst. As the catalyst, it is possible to use a Lewis base, for example a tertiary amine, or alternatively a Lewis acid, for example a tin compound, for example dibutyl tin dilaurate. The preferred reaction is carried out in the presence of a tertiary base, for example in the presence of pyridine or quinoline, which act simultaneously as a solvent, but it is preferable to use as the tertiary base also 4- (N, N-dimethylamino) pyridine, which is an accelerator of the reaction. For the conversion of the OH groups into the corresponding OR groups by esterification or carbamate formation, in particular, benzoyl chlorides or unsubstituted or substituted phenyl isocyanates are used. Preferably, phenyl isocyanates or benzoyl chlorides substituted by chlorine or methyl are used, it being possible for the methyl groups and the chlorine atoms to be configured in the meta or ortho positions in relation to one another. The photochemically crosslinked polysaccharide derivatives according to the invention, are used as chiral carriers for the chromatographic separation of enantiomers. Surprisingly, by means of the process according to the invention, it is possible to immobilize polysaccharide derivatives that do not have photopolymerizable functional groups, reaching a high degree of stability towards the solvents. Surprisingly, the high separation capacity is completely retained after immobilization. Immobilization allows the use of mobile phases containing, for example, methylene chloride, tetrahydrofuran, chloroform, dioxane, or ethyl acetate, and which would dissolve non-immobilized polysaccharide derivatives. The use of these mobile phases results in better results in the enantiomeric separation of a large number of racemates, and also allows the dissolution of sparingly soluble samples. The photochemically crosslinked polysaccharides according to the invention, in a conditioned form, can also be used as the pure polymer for the chromatographic separation of enantiomers. A possible additional application is the use of cross-linked polysaccharide derivatives in the production of coatings on different materials, such as wood, paper, plastic, and metals. These coatings can also be photo-structured. The photochemically crosslinked polysaccharides according to the invention can also be used as a material for the production of different membranes for any type of application. The different chromatographic enantiomeric separations are described and explained in greater detail after the preparation section (Examples). The following examples (including the preparation of starting materials and intermediates) are given for purposes of illustration and a better understanding of the invention. Temperatures are given in degrees Celsius, and (unless otherwise indicated) the pressures are given in bar.

Example 1 1.53 grams of cellulose tribenzoate (prepared according to the known procedures: Chirality, 3 (1991) 43) are dissolved in 60 milliliters of methylene chloride. In this solution 4 grams of aminosilanized silica (prepared according to a known method of Nucleosil-4000, particle size of 10 microns, Macherey-Nagel) are suspended. The suspension is then concentrated in a rotary evaporator, and dried under a high vacuum.

Immobilization 5 grams of the coated material is suspended in a mixture of 100 milliliters of methanol and 400 milliliters of water, and stirred. The suspension is irradiated for 20 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The suspension is filtered, and the filter cake is washed with methanol and dried. In order to remove the non-immobilized material, the irradiated product is then extracted with methylene chloride in a Soxhlet apparatus for 16 hours. The insoluble residue is suspended in about 30 milliliters of methylene chloride, and stirred for about 30 minutes. Then add 300 milliliters of hexane (addition rate: 1 milliliter / minute). The product is isolated by filtration, and washed with hexane. Elementary analysis: C 6.20 percent.

Example 2 In a manner analogous to Example 1, 4.0 grams of aminosilanized silica is coated with 1.53 grams of cellulose tris (benzoate 4-methyl) (prepared according to the known procedures: J. Chromatogr., 595 (1992) 63) . The photochemical immobilization of the cellulose derivative is carried out in a manner analogous to Example 1, in a mixture of -100 milliliters of methanol and 300 milliliters of water. The removal of non-immobilized material by extraction with methylene chloride, and the reconditioning by its treatment with hexane, are also carried out analogously. Elemental analysis: C 16.97%.

Example 3 3.0 grams of cellulose tris (bepzoate 4-methyl) granules (prepared according to the known procedures: J. Chromatogr., 595 (1992) 63), are suspended in a mixture of 100 milliliters of methanol and 400 milliliters of water, and they shake. The suspension is irradiated for 20 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The suspension is filtered, and the filter cake is washed with methanol and dried. The solid material is then extracted with methylene chloride in a Soxhlet apparatus for 16 hours. The insoluble residue is suspended in about 30 milliliters of methylene chloride, and stirred for about 30 minutes. Then add 300 milliliters of hexapo (addition rate: 1 milliliter / minute). The product is isolated by filtration, and washed with hexane.

Example 4 In a manner analogous to Example 1, 4.0 grams of aminosilapped silica is coated with 1.53 grams of cellulose tris (benzoate 3-methyl) (prepared according to the known procedures: J. Chromatogr., 595 (1992) 63) . The photochemical immobilization of the cellulose derivative is carried out in a manner analogous to Example 1, in a mixture of 150 milliliters of methanol and 300 milliliters of water. The removal of non-immobilized material by extraction with methylene chloride, and the reconditioning by its treatment with hexane, are also carried out analogously. Elemental analysis: C 15.83%.

Example 5 In a manner analogous to Example 1, 4.0 grams of aminosilanized silica is coated with 1.53 grams of cellulose tris (benzoate-2-methyl) (prepared according to the known procedures: J. Chromatogr., 595 (1992) 63) . The photochemical immobilization of the cellulose derivative is carried out in a manner analogous to Example 1, in a mixture of 100 milliliters of methanol and 400 milliliters of water. The removal of non-immobilized material by extraction with methylene chloride, and the reconditioning by its treatment with hexane, are also carried out analogously. Elemental analysis: C 11.66%.

Example 6 In a manner analogous to Example 1, 4.0 grams of aminosilanized silica are coated with 1.53 grams of cellulose tris (benzoate 4-ethyl) (prepared according to the known procedures: J. Chromatogr., 595 (1992) 63) . The photochemical immobilization of the cellulose derivative is carried out in a manner analogous to Example 1, in a mixture of 200 milliliters of methanol and 300 milliliters of water. The removal of non-immobilized material by extraction with methylene chloride, and the reconditioning by its treatment with hexane, are also carried out analogously. Elemental analysis: C 19.24%.

Example 7 In a manner analogous to Example 1, 4.0 grams of amino-silanized silica is coated with 1.53 grams of tris (tertiary 4-butyl benzoate) of cellulose (prepared according to the known procedures: J. Chromatogr., 595 (1992) 63 ). The photochemical immobilization of the cellulose derivative is carried out in a manner analogous to Example 1, in a mixture of 100 milliliters of methanol and 400 milliliters of water. The removal of non-immobilized material by extraction with methylene chloride, and the reconditioning by its treatment with hexane, are also carried out analogously. Elementary analysis: C 4.41%.

Example 8 In a manner analogous to Example 1, 4.0 grams of aminosilanized silica is coated with 1.53 grams of cellulose tris (4-fluorobenzoate) (prepared according to the known procedures: J. Chromatogr., 595 (1992) 63). The photochemical immobilization of the cellulose derivative is carried out in a manner analogous to Example 1, in a mixture of 150 milliliters of methanol and 250 milliliters of water. The removal of non-immobilized material by extraction with methylene chloride, and the reconditioning by its treatment with hexane, are also carried out analogously.

Example 9 In a manner analogous to Example 1, 4.0 grams of aminosilanized silica is coated with 1.53 grams of cellulose tris (2,5-dichlorobenzoate) (prepared according to the known procedures: J. Chromatogr., 595 (1992) 63 ). The photochemical immobilization of the cellulose derivative is carried out in a manner analogous to Example 1, in a mixture of 150 milliliters of methanol and 250 milliliters of water. The removal of non-immobilized material by extraction with methylene chloride, and the reconditioning by its treatment with hexane, are also carried out analogously. Elemental analysis: C 12.38%; Cl 7.73%.

Example 10 2.4 grams of cellulose tris (carbamate phenyl) (prepared according to the known procedures: J. Chromatogr., 363 (1986) 173), are dissolved in 36 milliliters of tetrahydrofuran. The resulting solution is divided into three portions. 5.5 grams of aminosilanized silica (Nucleosil-4000, particle size of 10 micras, Macherey-Nagel) are mixed in succession with the three portions, and then concentrated in a rotary evaporator. After drying under vacuum, 7.5 grams of the product are isolated.

Immobilization: 5.0 grams of this material are suspended in 300 milliliters of hexane (isomeric mixture), and stirred. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The precipitate is filtered, washed with hexane, and dried. Yield: 4.9 grams. This product is extracted with tetrahydrofuran in a Soxhlet apparatus for 17 hours. The insoluble residue is suspended in about 30 milliliters of tetrahydrofurape, and 300 milliliters of hexane are added (addition rate: 1.2 milliliters / minute). The product is isolated by filtration, and washed with hexapo (3.4 grams).

Example 11 1.2 grams of cellulose tris (carbamate phenyl) (prepared according to the known procedures: J. Chromatogr., 363 (1986) 173), are dissolved in 18 milliliters of tetrahydrofuran. The resulting solution is divided into three portions. 2.75 grams of aminosilanized silica (Nucleosil-4000, 10 micron particle size, Macherey-Nagel) are mixed in succession with the three portions, and then concentrated in a rotary evaporator. After drying under vacuum, 3.7 grams of the product are isolated.

Immobilization: 3.7 grams of this material are suspended, along with 37 milligrams of thioxanthone, in 300 milliliters of hexane (isomeric mixture), and shaken. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The precipitate is filtered, washed with hexane, and dried. Yield: 3.62 grams. This product is extracted with tetrahydrofuran in a Soxhlet apparatus for 17 hours. The insoluble residue is suspended in about 30 milliliters of tetrahydrofuran, and 300 milliliters of hexane are added (addition rate: 1.2 milliliters / minute). The product is isolated by filtration, and washed with hexane. Yield: 3.2 grams. Elemental analysis: C 15.53%; H 1.26%; N 1.89%.

Example 12 1 gram of tris (3,5-dimethylphenyl carbamate), of cellulose (prepared according to the known procedures: J. Chromatogr., 363 (1986) 173), is dissolved in 13.9 milliliters of tetrahydrofuran. The resulting solution is divided into three portions. 2.3 grams of aminosilanized silica (Nucleosil-4000, particle size of 7 micras, Macherey-Nagel) are mixed in succession with the three portions, and then concentrated in a rotary evaporator. After drying under vacuum, 3.1 grams of the product are isolated.

Invention: 3.1 grams of this material are suspended in 250 milliliters of hexane (isomeric mixture), and stirred. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The precipitate is filtered, washed with hexane, and dried. Yield: 3.03 grams. This product is extracted with tetrahydrofurapo in a Soxhlet apparatus for 17 hours. The insoluble residue is suspended in about 30 milliliters of tetrahydrofuran, and 300 milliliters of hexane are added (addition rate: 1.2 milliliters / minute). The product is isolated by filtration, and washed with hexane (2.6 grams). Elemental analysis: C 13.64%; H 1.27%; N 1.43%.

EXAMPLE 13 7.5 grams of cellulose tris (carbamate 3,5-di ethylphenyl) granules (prepared according to a known procedure) are suspended, together with 150 milligrams of thioxanthone, in 300 milliliters of hexane (isomeric mixture), and they stir. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The suspension is filtered, and the filter cake is washed with isopropanol and hexane, and dried. The solid material is then extracted with tetrahydrofuran in a Soxhlet apparatus for 16 hours. The insoluble residue is suspended in about 70 milliliters of tetrahydrofuran, and stirred for about 30 minutes. Then add 500 milliliters of hexane (addition rate: 1 milliliter / minute). The product is isolated by filtration, and washed with hexane.

Example 14 2.83 grams of cellulose tris (carbamate 4-methylphenyl) (prepared according to the known procedures: J. Chromatogr., 363 (1986) 173), are dissolved in 50 milliliters of tetrahydrofuran. The resulting solution is divided into three portions. 8.5 grams of aminosilanised silica (Nucleosil-4000, 10 micron particle size, Macherey-Nagel) are mixed in succession with the three portions, and then concentrated in a rotary evaporator. After drying under vacuum, 1.1 grams of the product are isolated.

Immobilization A: 4.0 grams of this material are suspended in 300 milliliters of hexane (isomeric mixture), and stirred. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The precipitate is filtered, washed with hexane, and dried. Yield: 3.93 grams. This product is extracted with tetrahydrofuran in a Soxhlet apparatus for 22 hours. The insoluble residue is suspended in about 30 milliliters of tetrahydrofuran, and 300 milliliters of hexane are added (adding rreth: 1.2 milliliters / minute). The product is isolated by filtration, and washed with hexane (3.50 grams).

Immobilization B: 4.0 grams of this material are suspended, along with 40 milligrams of thioxanthone, in 300 milliliters of hexapo (isomeric mixture), and shaken. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The precipitate is filtered, washed with hexane, and dried. Yield: 3.9 grams. This product is extracted with tetrahydrofuran in a Soxhlet apparatus for 24 hours. The insoluble residue is suspended in about 30 milliliters of tetrahydrofuran, and 300 milliliters of hexane are added (addition rate: 1.2 milliliters / minute). The product is isolated by filtration, and washed with hexane. Performance: 3.8 grams. Elemental analysis: C 14.75%; H. 1.31%; N 1.56%.

Example 15 3.3 grams of cellulose tris (carbamate 4-clarophenyl) (prepared according to the known procedures: J. Chromatogr., 363 (1986) 173), are dissolved in 50 milliliters of tetrahydrofuran. The resulting solution is divided into three portions. 7.7 grams of aminosilanized silica (Nucleosil-4000, 10 micron particle size, Macherey-Nagel) are mixed in succession with the three portions, and then concentrated in a rotary evaporator. After drying under vacuum, 10.6 grams of the product are isolated.

Immobilization A: 4.0 grams of this material are suspended in 300 milliliters of hexane (isomeric mixture), and stirred. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The precipitate is filtered, washed with hexane, and dried. Yield: 3.89 grams. This product is extracted with tetrahydrofuran in a Soxhlet apparatus for 18 hours. The ipsoluble residue is suspended in about 30 milliliters of tetrahydrofuran, and 300 milliliters of hexane are added (addition rate: 1.2 milliliters / minute). The product is isolated by filtration, and washed with hexane (3.6 grams).

Immobilization B: 4.0 grams of this material are suspended, along with 40 milligrams of thioxanthone, in 300 milliliters of hexane (isomeric mixture), and shaken. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The precipitate is filtered, washed with hexane, and dried. Performance: 3.8 grams. This product is extracted with tetrahydrofuran in a Soxhlet apparatus for 20 hours. The insoluble residue is suspended in about 30 milliliters of tetrahydrofuran, and 300 milliliters of hexane are added (addition rate: 1.2 milliliters / minute). The product is isolated by filtration, and washed with hexane. Yield: 3.2 grams. Elemental analysis: C 9.88%; N 1.18%, Cl 2.90%.

Example 16 2.3 grams of cellulose tris (carbamate 3-chloro-4-methylphenyl) (prepared according to the known procedures: J. Chromatogr., 363 (1986) 173), are dissolved in 48 milliliters of tetrahydrofuran. The resulting solution is divided into three portions. 8.1 grams of aminosilanized silica (Nucleosil-4000, particle size of 10 micras, Macherey-Nagel) are mixed in succession with the three portions, and then concentrated in a rotary evaporator. After drying under vacuum, 10.1 grams of the product are isolated.

Immobilization A: 3.9 grams of this material are suspended in 300 milliliters of hexane (isomeric mixture), and stirred. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HP -125 Watts, quartz housing). The precipitate is filtered, washed with hexane, and dried. Yield: 3.65 grams. This product is extracted with tetrahydrofuran in a Soxhlet apparatus for 17 hours. The insoluble residue is suspended in about 30 milliliters of tetrahydrofuran, and 300 milliliters of hexane are added (addition rate: 1.2 milliliters / minute). The product is isolated by filtration, and washed with hexane (3.4 grams).

Immobilization B: 3.6 grams of this material are suspended, together with 36 milligrams of thioxanthone, in 300 milliliters of hexane (isomeric mixture), and shaken. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The precipitate is filtered, washed with hexane, and dried. Yield: 3.41 grams. This product is extracted with tetrahydrofuran in a Soxhlet apparatus for 17 hours. The insoluble residue is suspended in about 30 milliliters of tetrahydrofuran, and 300 milliliters of hexane are added (addition rate: 1.2 milliliters / minute). The product is isolated by filtration, and washed with hexane. Yield: 3.3 grams. Elemental analysis: C 11.95%; N 1.26%, Cl 3.12%.

Example 17 1.2 grams of amylose tris (carbamate 3,5-dimethyl-phenyl) (prepared according to the known procedures: Chem. Lett., 1987, 1857), are dissolved in a mixture of 15 milliliters of tetrahydrofuran and 15 milliliters of sodium chloride. methylene. The resulting solution is divided into three portions. 3.6 grams of aminosilanized silica (Nucleosil-4000, 10 micron particle size, Macherey-Nagel) are mixed in succession with the three portions, and then concentrated in a rotary evaporator. After drying under vacuum, 4.4 grams of the product are isolated.

In oví 1 izad ón: 4.1 grams of this material are suspended, along with 41 milligrams of thioxanthone, in 300 milliliters of hexane (isomeric mixture), and shaken. The suspension is irradiated for 24 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The precipitate is filtered, washed with hexane, and dried. Yield: 4.1 grams. This product is extracted in a Soxhlet apparatus with methylene chloride for 17 hours, and then with tetrahydrofuran for 22 hours. The insoluble residue is suspended in about 30 milliliters of tetrahydrofuran, and 300 milliliters of hexane are added (addition rate: 1.2 milliliters / minute). The product is isolated by filtration, and washed with hexapo. Performance: 3.8 grams. Elemental analysis: C 13.01; H 1.26; N 1.34.

Column packing: 2.5 grams of the material obtained, are formed into a paste in 25 milliliters of hexane / 2-propanol (90:10 percent by volume), or in chloroform / heptane (50:50 percent by volume), and Using the paste formation method, it is introduced into a steel column (25 centimeters x 0.4 centimeters) at a pressure of 100 bar.

Example 18 2 grams of amyl (molar mass of about 150,000, Serva) is dried at 130 ° C for 6 hours in a round bottom flask, while being flooded with nitrogen. Then, in the order given, they are added at room temperature: 25 milliliters of pyridyb, 0.1 milliliters of dibutyl tin laurate, and 10 milliliters of (S) -l-phenylethyl isocyanate. The suspension is boiled under reflux (bath temperature at 130 ° C) for 72 hours. After the solution is cooled to 60 ° C, 50 milliliters of metapol are added, and the resulting suspension is poured into 300 milliliters of methanol. The suspension is filtered and washed with methanol. The solid residue is dissolved in 120 milliliters of methylene chloride. The resulting solution is filtered and precipitated in 500 milliliters of methanol. The precipitate is filtered and washed with methanol. The filter cake is again dissolved in 120 milliliters of methylene chloride, and precipitated with 500 milliliters of ethanol. The precipitate is filtered, washed with ethanol, and dried under a high vacuum at 60 ° C. Yield: 4 grams. Elemental analysis: calculated: C 65.66; H, 6.18; N 6.96; found: C 64.74; H 6.28; N 6.77. 2 grams of amylose tris ((S) -carbamate-1-phenyl) are dissolved in a mixture of 30 milliliters of tetrahydrofuran and 30 milliliters of methylene chloride. The resulting solution is divided into three portions. 6.6 grams of aminosilanized silica (Nucleosil-4000, 7-millimeter particle size, Macherey-Nagel) is mixed in succession with the three portions, and then concentrated in a rotary evaporator. After drying under vacuum, 8.3 grams of the product are isolated.

Immobilization: 3.2 grams of this material are suspended, along with 32 milligrams of thioxanthone, in a mixture of metapol / water (175 milliliters of each), and shaken (400 revolutions per minute). The suspension is irradiated for 21 hours with a submersible mercury discharge lamp (Philips, HPK-125 Watts, quartz housing). The precipitate is filtered, washed with 100 milliliters of ethanol, and dried. Yield: 3.28 grams. This product is extracted with tetrahydrofuran in a Soxhlet apparatus for 15 hours. The insoluble residue is suspended in about 30 milliliters of tetrahydrofuran, and 300 milliliters of hexane are added (addition rate: 1.6 milliliters / minute). The product is isolated by filtration, and washed with hexane. Yield: 3.1 grams (immobilization of 76.9 percent).

Test of chiral stationary phases: The phases of Examples 2, 4, 6, 11, 12, 14-17, are tested with different racemic structures, and with different mobile phases (see Tables). High performance liquid chromatography is performed using a Shimadzu LC-6A system, with a flow rate of 0.7 milliliters / minute, and at room temperature.

The detection is carried out by means of ultraviolet spectroscopy and polarimetry (Perkin Elmer 241 LC). The separation factor a is determined as the value of the measurement, 'i - t0 ce = = where k'2 and k'i are the factors k'i t, - te of respective capacity of the second and first eluted enantiomers, and t, and t | they are the retention times of the same, tj is the tertiary tributyl benzene elution time (compound not retained).

Separation factor in chromatographic separations using the product of Example 2.

Separation factor in chromatographic separations using the product of Example 4. Separation factor in chromatographic separations using the product of Example 6.

Separation factor in chromatographic separations using the product of Example 9.

Separation factor in chromatographic separations using the product of Example 11.

Separation factor in chromatographic separations using the product of Example 12.

Separation factor in chromatographic separations using the product of Example 14.

Separation factor in chromatographic separations using the product of Example 15.

Separation factor in chromatographic separations using the product of Example 16.

Separation factor in chromatographic separations using the product of Example 17.

Separation factor in chromatographic separations using the product of Example 18.

Claims (18)

1. A photochemically crosslinked polysaccharide derivative, wherein the OH groups as OR groups have been esterified or converted to carbamate (urethane) or mixtures thereof, with the proviso that the OR groups do not contain polymerizable double bonds before crosslinking.

2. A photochemically crosslinked polysaccharide derivative, wherein the OH groups as OR groups have been converted to an unsubstituted or substituted aryl, arylalkyl, hetaryl, or heteroaryl alkyl ester, or to an unsubstituted aryl, arylalkyl, hetaryl, or hetarylalkyl carbamate or substituted (urethane), or mixtures thereof, with the proviso that the OR groups do not contain polymerizable double bonds before crosslinking.

3. A photochemically cross-linked polysaccharide derivative, wherein the OH groups as OR groups have been converted to an unsubstituted or substituted aryl or arylalkyl ester, or an unsubstituted or substituted aryl or arylalkyl carbamate, or mixtures thereof, with the condition that the OR groups do not contain polymerizable double bonds before crosslinking.

4. A photochemically cross-linked cellulose or amylose derivative, wherein the OH groups as OR groups have been converted to an aryl or arylalkyl ester, or an aryl or arylalkyl carbamate, the ester or carbamate being unsubstituted or mono- or poly-substituted by lower alkyl and / or by halogen, or mixtures thereof, with the proviso that the OR groups do not contain polymerizable double bonds before crosslinking.

5. A photochemically cross-linked cellulose or amylose derivative, wherein the OH groups as OR groups have been converted to a phenyl or benzyl ester, or to a phenyl or benzyl carbamate, the ester or carbamate being unsubstituted or mono- or poly-substituted by lower alkyl and / or by halogen, or mixtures thereof, with the proviso that the OR groups do not contain polymerizable double bonds before crosslinking.

6. A process for the preparation of a photochemically crosslinked polysaccharide derivative according to claim 1, wherein a polysaccharide derivative in which the OH groups as OR groups have been esterified or converted to carbamate (urethane), after being coated previously on a carrier, or after preconditioning as a pure material using an emulsion, it is crosslinked by means of irradiation (hv), to form a compound according to claim 1.

7. A process according to claim 6 , wherein a polysaccharide derivative in which the OH groups as OR groups have been converted to an aryl, arylalkyl, hertylic U3, or unsubstituted or substituted hetarylalkyl ester, or an aryl, arylalkyl, hetaryl, or unsubstituted hetarylalkyl carbamate or replaced, after pre-coating on a carrier, or after pre-conditioning as a pure material using an emulsion It is crosslinked by irradiation (hv) to form a compound of claim 2.

8. A process according to claim 6, wherein a polysaccharide derivative wherein the OH groups as OR groups have been converted into a unsubstituted or substituted aryl or arylalkyl ester, or an unsubstituted or substituted aryl or arylalkyl carbamate, after being previously coated on a carrier, or after preconditioning as a pure material using an emulsion, is crosslinked by irradiation ( hv) to form a compound of claim 3.

9. A process according to claim 6, wherein a derivative of cellulose or amylose, wherein the OH groups as OR groups have been converted to an aryl or arylalkyl ester which is unsubstituted or mono- or poly-substituted by lower alkyl and / or by halogen, or in an aryl or arylalkyl carbamate which is unsubstituted or mono- or poly-substituted r lower alkyl and / or halogen, after being previously coated on a carrier, or after preconditioning as a pure material using an emulsion, it is crosslinked by means of irradiation (hv) to form a compound of claim 4.

10. A process according to the claim 6, wherein a derivative of cellulose or amylose, wherein the OH groups as OR groups have been converted to a phenyl or benzyl ester which is unsubstituted or mono- or poly-substituted by lower alkyl and / or by halogen, or a phenyl or benzyl carbamate which is unsubstituted or mono- or poly-substituted by lower alkyl and / or by halogen, after being precoated on a carrier, or after preconditioning as a pure material using an emulsion, is crosslinked by irradiation medium (hv) to form a compound of claim 5.

11. A process according to any of claims 6 to 10, wherein the crosslinking is effected me. by irradiation, by means of a submersible mercury discharge lamp.

12. A process according to any of claims 6 to 10, wherein the crosslinking is effected by irradiation by means of a laser lamp.

13. A process according to any of claims 6 to 10, wherein the cross-linking is carried out in the presence of a photosepsibilizer. A process according to any of claims 6 to 10, wherein the carrier used for the coating is silica gel, modified silica gel, aluminum oxide (alumina), glass, graphite, or zirconium oxide. 15. A process according to any of claims 6 to 10, wherein an inert solvent is used for the preparation of a suspension. 16. The use of a photochemically crosslinked polysaccharide derivative according to any of claims 1 to 5, as a stationary phase in chromatographic processes, especially for the separation of enantiomers. 17. The use of a photochemically crosslinked polysaccharide derivative according to any of claims 1 to 5, as a material for the preparation of membranes for various types of application. 18. The use of a photochemically crosslinked polysaccharide derivative according to any of claims 1 to 5, in the preparation of coatings on different materials, for example wood, paper, plastic, and metals.