Organic compounds -- part of the class 532-570 series – Organic compounds – Carbohydrates or derivatives
Patent
1994-01-27
1995-08-01
Robinson, Douglas W.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carbohydrates or derivatives
536124, 540450, 540451, 540454, 540460, 540467, 540470, 540474, C08B 3716
Patent
active
054381339
DESCRIPTION:
BRIEF SUMMARY
The invention relates to compounds capable of forming inclusion complexes. More particularly, it relates to modified cyclodextrins.
It is known that cyclodextrins are able to form inclusion complexes with a variety of organic and inorganic compounds. The three most important cyclodextrins are the .alpha.-, .beta.- and .gamma.-cyclodextrins, which respectively consist of six, seven and eight .alpha.-D-glucopyranosyl residues. The ability of a cyclodextrin to form a complex is regulated by the size of the cavity produced by the ring of .alpha.-D-glucopyranosyl residues of which it is composed.
Modified cyclodextrins have been prepared in which the hydroxyl groups have been partially or totally replaced by methyl groups. Such modification is responsible for an extension of the hydrophobic cavity of the cyclodextrin. Other modified cyclodextrins have been reported in which the cavity space has been restricted by the attachment of one or more relatively large chemical groups e.g. naphthyl groups to the cyclodextrin rim. A review of inclusion complexes formed by cyclodextrins which includes a discussion of modified cyclodextrins is presented by R. J. Clarke, J. H. Coates and S. F. Lincoln, Advances in Carbohydrate Chem. and Biochem., 1988, 46, 205.
It is difficult to alter the properties of cyclodextrins by simple and selective modification of the hydroxyl groups and there is a continuing need for alternative modified cyclodextrins. Different methods of adjusting the physical, electronic and receptor properties of cyclodextrins are sought. In particular, different ways of controlling cavity size are required.
The invention provides a modified cyclodextrin in which the cavity size has been altered by the formation of a catenane. The catenane is characterised in that an optionally substituted cyclodextrin is one of the interpenetrating macrocycles. In this way, the properties of the cyclodextrin have been modified without necessitating selective chemical modification of the cyclodextrin's functional groups.
Such modified cyclodextrins may be used for the electrochemical and optical sensing of small organic molecules, especially small aromatic molecules.
The invention provides a cyclodextrin catenane comprising one or two per-2,6-di-O-alkyl-.beta.-cyclodextrin macrocycles and another macrocycle wherein each per-2,6-di-O-alkyl-.beta.-cyclodextrin macrocycle is interpenetrated by the other macrocycle which has the formula ##STR1## wherein D represents --CH.sub.2 -- or --CO--; per-2,6-di-O-alkyl-.beta.-cyclodextrin macrocycles then m is 2.
Suitable R groups include methyl, ethyl and propyl.
Suitable Ar groups include substituted or unsubstituted arylene, bisarylene and arylenealkylenearylene e.g. phenylene, naphthylene, biphenylene and phenylenemethylenephenylene.
Preferred compounds include those in which D represents --CH.sub.2 --, each X represents --O--, y.sup.1 represents --NHCO--, Y.sup.2 represents --CONH--, Ar represents 1,4-phenylene or 4,4'-biphenylene, n is 4 and m is 1.
Other preferred compounds include those in which D represents --CO--, E.sup.1 is --(NHCH.sub.2 CH.sub.2)(OCH.sub.2 CH.sub.2).sub.3 --, E.sup.2 is --(CH.sub.2 CH.sub.2 O).sub.3 (CH.sub.2 CH.sub.2 NH)--, Y.sup.1 represents --NHCO--, y.sup.2 represents --CONH--, Ar represents 1,4-phenylene and m is 1.
Compounds of the invention may be prepared by reaction, in aqueous solution, of (a) per-2,6-di-O-alkyl-.beta.-cyclodextrin, (b) a compound having the formula ##STR2## wherein Q represents --NHR or --SH and D, E.sup.1 and E.sup.2 are as hereinbefore defined; and (c) a compound having the formula Z--Ar--Z wherein Ar is as hereinbefore defined and Z represents --COCl or --SO.sub.2 Cl; the reaction being carried out under conditions which facilitate the ring closure of (b) by reaction with (c).
The reactants (a), (b) and (c) may be employed in substantially equimolar amounts.
For example, when Q is --NH.sub.2 and Z is --COCl, the reaction may be carried out in moderately basic aqueous solution, preferably at pH 10-11, at room temperature.
A mixture o
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Armspach Dominique
Moore Christopher P.
Stoddart James F.
Wear Trevor J.
Eastman Kodak Company
Fonda Kathleen Kahler
Hawley J. Jeffrey
Robinson Douglas W.
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