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US 6,528,642 B1Granted
Mono-and di-derivatives of cyclodextrins, synthesis thereof and purification and use thereof in support
AssigneesInstitut Francais du Petrole, Chiralsep S.A.R.L.
InventorsRaphaël Duval, Hubert Lévêque
Life of this patent
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Abstract
Mono- and di-derivatives of cyclodextrins are completely defined, also a method for their synthesis and purification, functionalised cyclodextrins obtained from these derivatives, and the synthesis of supports comprising these cyclodextrin derivatives. Use of the supports for the preparation or separation of enantiomers, for asymmetric synthesis, for catalysis, for the preparation or separation of geometrical isomers or positional isomers, or for the preparation or separation of organic molecules with a hydrophobic nature is also described.
Claims6
A composition comprising at least two alkenyl-derivatized cyclodextrins selected from the group consisting of the formulae (XIa), (XIb), (XIc), (XId), (XIe), (XIf) (XIg), (XIh), (XIi), (XIj), (XIk) and (XIl),
- in which
- R4 represents a C1 to C20 alkylene group, or an arylene group, optionally substituted by a C1 to C20 alkyl group,
- Z1 represents —Y1W1
- Z2 represents —Y2W2
- Z3 represents —Y3W3
- Y1, Y2 and Y3, which maybe identical or different, represent an oxygen atom, a sulphur atom, an amino group, or a sulphoxide or sulphone group;
- W1, W2 and W3, which may be identical or different, represent:
- a group A2—A1—A0—, where:
- A0 represents —CO— or —CS—;
- A1 represents a bond or a secondary amino group;
- A2 represents a linear or branched alkyl group (C1-C24), optionally substituted by an aryl group, or an aryl group itself optionally substituted by a linear or branched (C1-C24) alkyl group, where the aryl groups are optionally substituted by one or more identical or different halogen atoms(s), or linear or branched (C1-C6) alkyl groups(s), or hydroxyl groups, or linear or branched (C1-C6) trihalogenoalkyl groups;
- a linear or branched (C1-C24) alkyl group;
- or
- a (C3-C8) cycloalkyl group;
- Z1, Z2 or Z3 each represent a carboxylic acid or ester function, a sulphinamide or sulphimide function, a hydroxyl function, a sulphonic acid function, a sodium, potassium or ammonium sulphate function, an ethyl-, propyl- or butylsulphonic function, a phosphoric acid function or a sodium, lithium, potassium or ammonium phosphate function;
- or
- Z1 and Z3 together represent a 3,6-anhydro function;
- or
- Z2 and Z3 together represent a 2,3-anhydro function;
- and
- n is 6, 7 or 8.
18 more elements
A homopolymer or copolymer selected from the group consisting of:
- (a) a homopolymer of formula (XIII):
- formed by homopolymerization of at least one native or modified cyclodextrin of the formula (XI)
- where
- R4 represents a C1 to C20 alkylene group or an arylene optionally substituted by a C1 to C20 alkyl group, and CDz represents the divalent residue (IIz), (IIIz), (IVz), (IIzz), (IIIzz) or (IVzz)
- of said native cyclodextrin or the divalent residue (Vz), (VIz), (VIIz), (Vzz), (VIzz) or (VIIZZ)
- of said modified cyclodextrin;
- and wherein
- Z1 represents —Y1W1
- Z2 represents —Y2W2
- Z3 represents —Y3W3 and
- Y1, Y2 and Y3, which may be identical or different, represent an oxygen atom, a sulphur atom, an amino group, or a sulphoxide or sulphone group;
- W1, W2 and W3, which may be identical or different, represent:
- a group A2—A1—A0:, where:
- A0 represents —CO— or —CS—;
- A1 represents a bond or a secondary amino group;
- A2 represents a linear or branched alkyl group (C1-C24), optionally substituted by an aryl group, or an aryl group itself optionally substituted by a linear or branched (C1-C24) alkyl group, the aryl groups also optionally substituted by one or more identical or different halogen atoms(s), or linear or branched (C1-C6) alkyl group(s), or hydroxyl groups, or linear or branched (C1-C6) trihalogenoalkyl groups;
- a linear or branched (C1-C24) alkyl group;
- or
- a (C3-C8) cycloalkyl group;
- Z1, Z2 or Z3 each represents a carboxylic acid or ester function, a sulphinamide or sulphimide function, a hydroxyl function, a sulphonic acid function, a sodium, potassium or ammonium sulphate function, an ethyl-, propyl- or butylsulphonic function, a phosphoric acid function or a sodium, lithium, potassium or ammonium phosphate function;
- or
- Z1 and Z3 together represent a 3,6-anhydro function;
- or
- Z2 and Z3 together represent a 2,3-anhydro function;
- and
- n is 6, 7 or 8;
- (b) a homopolymer of formula (XII):
- formed by homopolymerization of at least one native or modified monosubstituted cyclodextrin of formula (X):
- CH2═CH—R4—CDy (X)
- where R4 represents a C1 to C20 alkylene group or an arylene group optionally substituted by a C1 to C20 alkyl group, and CDy represents the monovalent residue (IIy), (IIIy) or (IVy)
- of said native cyclodextrin or the monovalent residue (Vy) (VIy) or (VIIy);
- of said modified cyclodextrin, where Z1, Z2, Z3 and n are as defined above;
- (c) a copolymer of formula (XIV):
- formed by copolymerization of at least one native or modified monosubstituted cyclodextrin of formula (X), defined above, and at least one native or modified disubstituted cyclodextrin of formula (XI), defined above;
- (d) a copolymer of formula (XV):
- formed by copolymerization of at least one native or modified monosubstituted cyclodextrin of formula (X), defined above, and a bifunctional comonomer A where A is of the formula:
- where B′ represents an aryl or polyaryl group containing 5 to 30 carbon atoms, or an alkyl group containing 2 to 30 carbon atoms, optionally substituted by a halogen atom;
- or A is of the formula —X—L—X—
- where X represents
- a sulphur atom (thioether function) or a sulphoxide function or a sulphone function;
- L represents (CH2)n or an alkylene group, an alkylene substituted by an alcohol or acid function, or an arylene group;
- (e) a copolymer of the formulae (XVI):
- —(A—CH2—CH2—R4—CDz—R4—CH2—CH2)n′5
- formed by copolymerization of at least one native or modified disubstituted cyclodextrin of formula (XI), defined above, and a bifunctional comonomer A, defined above;
- and
- (f) a copolymer of the formula (XVII):
- formed by copolymerization of at least one native or modified monosubstituted cyclodextrin of formula (X), defined above, at least one native or modified cyclodextrin of formula (XI), defined above, and a bifunctional comonomer A, defined above;
- where for each of (a) through (f), n0 to n10, n′5, m and p is from 1 to 10,000.
45 more elements
A method for synthesizing a monosubstituted derivative of native cyclodextrin of formula (X):
- CH2═CH—R4—CDy (X)
- where R4 represents a C1 to C20 alkylene group or an arylene group, optionally substituted by a C1 to C20 alkyl group, and CDy represents the residue (IIy) (IIIy) or (IVy)
- of said native cyclodextrin;
- or a disubstituted derivative of native cyclodextrin of formula (XI):
- where R4 represents a C1 to C20 alkylene group, or an arylene group, optionally substituted by a C1 to C20 alkyl group, and CDz represents the divalent residue (IIz), (IIIz), (IVz), (IIzz), (IIIzz) or (IVzz)
- of said native cyclodextrin;
- comprising reacting a native cyclodextrin with the formula:
- with a compound with formula T—R4—CH═CH2, in which R4 has the same meaning as that given above and T represents a halogen atom, or tosyl or a mesyl radical, said compound T—R4—CH═CH2 being used in a proportion of 1 to 24 moles per mole of a native cyclodextrin.
5 more elements
A method for synthesizing a monosubstituted derivative of modified cyclodextrin of formula (X)
- CH2═CH—R4—CDy (X)
- where R4 represents a C1 to C20 alkylene group or an arylene group, optionally substituted by a C1 to C20 alkyl group;
- CDy represents the monovalent residue (Vy), (VIy) or (VIIy) of said modified cyclodextrin;
- or a disubstituted derivative of modified cyclodextrin of formula (XI):
- where
- R4 represents a C1 to C20 alkylene group or arylene group, optionally substituted by a C1 to C20 alkyl group;
- CDz represents the divalent residue (Vz), (VIz), (VIIz), (Vzz), (VIzz) or (VIIzz) of said modified cyclodextrin;
- and where
- Z1 represents —Y1W1
- Z2 represents —Y2W2
- Z3 represents —Y3W3 and
- Y1, Y2 and Y3, which may be identical or different, represent an oxygen atom, a sulphur atom, an amino group, or a sulphoxide or sulphone group;
- W1, W2 and W3, which may be identical or different, represent:
- a group A2—A1—A0—, where:
- A0 represents —CO— or —CS—;
- A1 represents a bond or a secondary amino group;
- A2 represents a linear or branched alkyl group (C1-C24), optionally substituted by an aryl group, or an aryl group itself optionally substituted by a linear or branched (C1-C24) alkyl group, the aryl groups also optionally substituted by one or more identical or different halogen atoms(s), or linear or branched (C1-C6) alkyl group(s), or hydroxyl groups, or linear or branched (C1-C6) trihalogenoalkyl groups;
- a linear or branched (C1-C24) alkyl group;
- or
- a (C3-C8) cycloalkyl group;
- Z1, Z2 or Z3 each represents a carboxylic acid or ester function, a sulphinamide or sulphimide function, a hydroxyl function, a sulphonic acid function, a sodium, potassium or ammonium sulphate function, an ethyl-, propyl- or butylsulphonic function, a phosphoric acid function or a sodium, lithium, potassium or ammonium phosphate function;
- or
- Z1 and Z3 together represent a 3,6-anhydro function;
- or
- Z2 and Z3 together represent a 2,3-anhydro function;
- and
- n is 6, 7 or 8;
- comprising reacting a modified cyclodextrin with the formula:
- with a compound with formula T—R4—CH═CH2, in which R4 has the same meaning as that given above and T represents a halogen atom, or a mesyl radical, said compound T—R4—CH═CH2 being used in a proportion of 1 to 24 moles per mole of modified cyclodextrin.
26 more elements
Dependencies are inferred from the claim text.