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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
  • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
  • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
  • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
  • B01J20/3268—Macromolecular compounds
  • B01J20/328—Polymers on the carrier being further modified
  • B01J20/3282—Crosslinked polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
  • B01D15/08—Selective adsorption, e.g. chromatography
  • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
  • B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
  • B01D15/3833—Chiral chromatography
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/26—Synthetic macromolecular compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/26—Synthetic macromolecular compounds
  • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
  • B01J20/267—Cross-linked polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
  • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
  • B01J20/29—Chiral phases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
  • B01J20/3204—Inorganic carriers, supports or substrates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
  • B01J20/3206—Organic carriers, supports or substrates
  • B01J20/3208—Polymeric carriers, supports or substrates
  • B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
  • B01J20/3268—Macromolecular compounds
  • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
  • B01J20/3274—Proteins, nucleic acids, polysaccharides, antibodies or antigens
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B3/00—Preparation of cellulose esters of organic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2220/00—Aspects relating to sorbent materials
  • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
  • B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography

Definitions

• the cross-linked three-dimensional polymer network relates to cross-linked three-dimensional polymer networks, their preparation process, as well as optically active support materials containing said three-dimensional polymer networks.
• the invention also relates to the use of these cross-linked three-dimensional polymer networks - as well as the optically active supports for the optical enrichment of chiral molecules and more particularly for the separation of enantiomers by chromatography in liquid, supercritical, gas or gas / liquid.
• the supports of the invention When used in a chromatographic process, the supports of the invention constitute stationary homochiral or "PSC" phases and the technique used is then called chiral or enantioselective chromatography.
• selectors have also been the subject of significant developments on an industrial scale, such as optically active polymers crosslinked in a network and chemically bonded to a support ((PCT / SE 93/01050) or also crosslinked but not necessarily chemically bonded. to a support (FR 98/11376, FR 98/11377, USP 6,042,723, EP 0899272 A1, EP 0864586A2, WO 96/27615, WO 97/04011).
• selectors have also been described in particular in US patent 6,277,782 and patent applications EP985682 and EP656331. These selectors consist of a single type of homochiral units which are monomers or polymers crosslinked using a non-chiral crosslinking agent or a chiral but not optically active crosslinking agent as described in the patent. US 6,011,149.
• the invention therefore relates to a three-dimensional, optically active, crosslinked polymer network, constituted by homochiral units of a first selector and by homochiral units of at least one second selector with a structure different from the first selector, the homochiral units of the first selector comprising at least three functional groups which are polymerizable or capable of crosslinking and the homochiral units of the second selector comprising at least two functional groups which are polymerizable or capable of crosslinking, the homochiral units being chemically linked to each other, excluding three-dimensional polymer networks crosslinked obtained or by reductive amination of chitosan and 2, 3-dialdehyde- ⁇ -cyclodextrin, or by reaction between chitosan and chlorotriazynil- ⁇ -cyclodextrin, or by crosslinking of a polysaccharide and a protein, or by reductive amination of a first polysaccharide whose saccharid cycles ics were opened with an oxidizing agent
• the functional groups which can be polymerized or capable of crosslinking are in particular primary, secondary or tertiary hydroxyl groups, primary or secondary amino groups, sulfhydryl groups, ethylenic double bonds or aldehyde groups.
• the expression “the homochiral units being interconnected” is understood to mean the fact that the various homochiral units are interconnected by bonds resulting from a polymerization
• Crosslinking which allows the formation of a three-dimensional network, is carried out via said functional groups or optionally using a non-chiral crosslinking agent comprising at least two functional groups which can be polymerized or capable of crosslinking.
• a linear sequence is obtained, while by crosslinking, a three-dimensional assembly is obtained.
• the oligomers or polymers are of natural origin (polysaccharides, proteins, DNA, etc.) or are obtained by homopolymerization of the same homochiral monomer. They can also be obtained by copolymerization of two homochiral monomers with different chemical structures. Optically active heteropolymers are then obtained. Optically active homopolymers or heteropolymers consist of at least 11 homochiral units (Nomenclature and Terminology in Organic Chemistry, September 1996, Engineering Techniques, 249, rue de Crimée, 75019 PARIS) and their related oligomers are consisting of 1 to 10 homochiral units, identical for homopolymers and homooligomers and different for heteropolymers and heterooligomers.
• a ⁇ -cyclodextrin or cyclomaltoheptaose is a cyclic oligosaccharide (Chemical Reviews, 1998, vol. 98, n ° 5, pl745) and therefore a homooligomer.
• the homochiral units comprising at least two or at least three functional groups which can be polymerized or capable of crosslinking are chosen from the group comprising in particular (R, R) - dithiothreitol (DTT), tartaric acid or its derivatives, such as N, N '-diallyltartramide (DAT), ditertio-butylbenzoyldiallyltartramide (DBBDAT), diacetyldiallyltartramide (DADAT), cyclodextrin, in particular ⁇ -cyclodextrin, or its derivatives such as tetrakis-6-O - (4-allyloxyphenylcarbamate) tris-6-0- (3,5- dimethylphenyl carbamate) -heptakis- 2, 3-O-di- (3, 5-dimethylphenyl carbamate) - ⁇ -cyclodextrin (T (AOPC-DMPC) , cellulose or its derivatives such as
• the three-dimensional polymer network, optically active, - crosslinked is constituted by homochiral units of a first selector and by homochiral units of a second selector of structure different from the first selector and by homochiral units of a third selector with a structure different from the first and the second selector, the homochiral units of the first selector comprising at least three functional groups polymerizable or capable of crosslinking and the homochiral units of the second selector as well as the homochiral units of the third selector comprising at least two functional groups which are polymerizable or capable of crosslinking, the homochiral units being chemically linked together.
• an agent is attached to at least part of the homochiral units of a selector chosen from the group comprising the first selector, the second selector and possibly the third selector of non-chiral crosslinking comprising at least two functional groups which can be polymerized or capable of crosslinking.
• the crosslinking agent comprising at least two functional groups which can be polymerized or capable of crosslinking is chosen from the group comprising in particular ethane dithiol, trithiocyanuric acid, 1,6-hexanedithiol, 1, 2, 6-hexanetriol -trithioglycolate, 2, 5-dimercapto-1, 3, 4-thiadiazole.
• the homochiral units of at least one of the selectors are not derivatives of ⁇ -cyclodextrin.
• the polymer network can comprise either units of a bifunctional derivative of ⁇ -cyclodextrin, that is to say a derivative of ⁇ -cyclodextrin of which at least 2 -OH groups have been each replaced by a functional group which can be polymerized or capable of crosslinking, or else units of a trifunctional derivative of ⁇ -cyclodextrin, that is to say a derivative of ⁇ -cyclodextrin in which at least 3 -OH groups have each been replaced by a functional group which can be polymerized or capable of crosslinking.
• This polymer network therefore does not comprise both units of a bifunctional derivative and units of a trifunctional derivative of ⁇ -cyclodextrin.
• the invention also relates to a process for the preparation of the optically active crosslinked polymer network and which is characterized in that: a) at least one first selector consisting of at least one homochiral unit comprising at least three functional groups which can be polymerized or capable of being selected is selected crosslink, at least a second selector consisting of at least one homochiral unit comprising at least two functional groups which can be polymerized or capable of crosslinking, and optionally at least a third selector consisting of at least one homochiral unit comprising at least two functional groups which can be polymerized or capable to crosslink b) optionally, at least one non-chiral crosslinking agent is selected comprising at least two functional groups which are polymerizable or capable of crosslinking, c) optionally, at least part of the homochiral units of at least one selector are reacted chosen from group c including a first selector, a second selector and possibly a third selector, with the non-chiral crosslinking agent, d) either, the homo
• steps b) and c) in steps d) and e), at least certain homochiral units of the first selector and / or of the second selector and / or possibly of the third selector on which is used are used. fixed the crosslinking agent.
• the invention also relates to an optically active support material, the optical activity properties of which are due to the fact that it consists in part of the polymer network described above.
• the optically active support material according to the invention consists for at least 0.1 to 100.0% by said optically active three-dimensional polymer network.
• the 100% supplement is generally in the form of silica gels, solid particles of mineral origin, such as oxides of silicon, titanium, aluminum, clays or of organic origin, such as polystyrenes, polyvinyl alcohols, etc.
• Silica gels are the preferred supports when it is desired to use the final support material as PSC for enantioselective chromatography.
• the polymer network is either chemically bonded to the mineral or organic support, or else physically deposited in the pores of the support, as described in the patents cited in the prior art.
• the support undergoes a prior chemical transformation allowing the introduction of functions capable of reacting and of creating covalent bonds with the selectors of the polymer network.
• the invention also relates to the use of an optically active support material comprising the cross-linked three-dimensional polymer network described above, for removing from a mixture of at least two constituents, chosen from the group comprising organic, mineral or organo-minerals, at least most of any of these constituents.
• the support materials can also be used as a stationary phase to separate said constituents by a chromatographic method. Chromatographic processes use a simple column or a multi-column system using the so-called simulated moving bed technique.
• the invention also relates to the use of an optically active support material comprising the cross-linked three-dimensional polymer network described above, for removing from a mixture of at least two enantiomers, chosen from the group comprising chiral organic molecules or organo - chiral minerals, at least part of one of these constituents, to enrich the mixture with one of the optically active homochiral molecules and thus obtain one of the enantiomers enriched.
• the method used can be a simple contacting of said optically active support material with the mixture of enantiomers, one of the enantiomers being preferably adsorbed.
• the optical enrichment operation is carried out by filtration of the complex [optically active support material / adsorbed enantiomer].
• the complex is then destroyed by contacting with a liquid which is a solvent for said enantiomer and which has the property of suppressing the specific interaction of said enantiomer with the optically active support material.
• the desorbed enantiomer is either unused because it is not of interest and in this case it is the first filtrate which is optically enriched in the desired enantiomer, or used as the optically enriched enantiomer.
• the invention also relates to the use of an optically active support material as an enantioselective stationary phase for separating optically active molecules by a chromatographic method. This technique is also interesting as a method of producing optically or enantiomerically pure or enriched homochiral molecules.
• microcrystalline cellulose (average degree of polymerization n of 100), 75 ml of pyridine and 38 ml of heptane are placed in a reactor. Agitation and heating at reflux make it possible to dehydrate the cellulose by azeotropic entrainment.
• 6.8 g of 3,5-dimethylphenylisocyanate (3,5-DMPC) are added and the medium is again brought to reflux for 24 hours.
• the solution is cooled and then poured onto 100 ml of methanol. The precipitate is washed with 300 ml of methanol and then dried under vacuum at 50 ° C.
• microcrystalline cellulose (average degree of polymerization n of 100), 75 ml of pyridine and 38 ml of heptane are placed in a reactor. Agitation and heating at reflux make it possible to dehydrate the cellulose by azeotropic entrainment. 9.31 g of 4-allyloxyphenylisocyanate (AOPC) are added and the medium is brought to reflux for 24 hours in the presence of 0.05 g of 4-dimethylaminopyridine. The solution is cooled and then poured onto 100 ml of methanol. The precipitate is washed with 300 ml of methanol and then dried under vacuum at 50 ° C.
• AOPC 4-allyloxyphenylisocyanate
• ⁇ -cyclodextrin 75 ml of pyridine and 38 ml of heptane are placed in a reactor. Agitation and heating at reflux make it possible to dehydrate the cellulose by azeotropic entrainment.
• 1.35 g of 4-allyloxyphenylisocyanate (AOPC) are added and the medium is brought to reflux for 24 hours in the presence of 0.05 g of 4-dimethylaminopyridine.
• 6.8 g of 3,5-dimethylphenylisocyanate (3,5-DMPC) are added and the medium is again brought to reflux for 24 hours.
• the solution is cooled and then poured onto 100 ml of methanol. The precipitate is washed with 300 ml of methanol and then dried under vacuum at 50 ° C.
• DBBDAT is synthesized from commercial (-) - N, N'-diallyltartramide (DAT): 1 g of DAT is dissolved in 25 ml of methylene chloride. 1.72 g of tert-butylbenzoyl chloride are added with 1.2 ml of triethylamine and the medium is maintained for 24 hours at 20 to 30 ° C. The chloromethylenic phase is washed with 3 times 20 ml of water and is then evaporated to dryness. The solid is dried at 50 ° C under vacuum.
• DAT commercial (-) - N, N'-diallyltartramide
• a purity control by elution in a 90/10 chloroform / methanol eluent on a thin layer chromatography plate indicates a total transformation of the raw material and the formation of a single product.
• the mass recovered is 2.47 g.
• selector L crosslinked with DDT 0.82 g of selector from Example 1 or L (AOPC-DMPC) are dissolved with 12 ml of tetrahydrofuran and 50 mg of (R, R) -1,4-dithiothreitol or DDT. 4 g of silica 1000 ⁇ (pore diameter), 5 ⁇ m (particle diameter) are suspended in the preceding solution. 100 ml of heptane and 0.05 g of AIBN (azo-bis isobutyronitrile) are added slowly over 1 hour. The suspension is filtered after being brought to reflux for 24 hours. The solid is washed with 100 ml of ethanol and then dried at 50 ° C. Dry weight: 4.6 g.
• AIBN azo-bis isobutyronitrile
• N, N '-diallyl-L-tartramide or DAT which corresponds to 1 mole of DAT involved for 1 cellobiose unit of Example 2 (6 terminal double bonds), hence the ratio
• the chromatographic conditions are as follows: mobile phase flow rate: 1 ml / min; UV detection at 254 nm; optical density scale: 0.1; injection of a solution comprising 1 mg of the racemic product to be separated given below in 1 ml of eluent also given below.
• the retention times t of each of the enantiomers recovered are indicated, as well as the capacity factor k ′ 2 and the selectivity factor ⁇ .
• EDT Ethanedithiol DDT: (R, R) -dithiothreitol DAT: N, N'-diallyltartramide
• DADAT Diacétyldiallyltartramide T (APOC-DMPC). tetrakis-6-O- (4-allyloxy ⁇ henylcarbamate) tris-6-O- (3,5- dimethylp enyl carbamate) heptakis 2,3-O-di- (3,5-dimethylphenyl carbamate) - ⁇ -cyclodextrin

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