Organic compounds -- part of the class 532-570 series – Organic compounds – Carbohydrates or derivatives
Patent
1994-07-26
1996-01-30
Nutter, Nathan M.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carbohydrates or derivatives
536 58, 536 59, 536 63, 536 64, 536 65, 536 66, 536 68, 536 69, 536115, 536116, 536118, 536119, C08B 300, C08B 500, C08B 700, C08B 1300
Patent
active
054881021
DESCRIPTION:
BRIEF SUMMARY
This application is a continuation of International Application Ser. No. PCT/EP93/03236, filed Nov. 19, 1993.
The invention relates to polymerisable esters of carbohydrates and dicarboxylic acids having an ester group containing radically polymerisable radicals, to homopolymers and copolymers therefrom, to processes for their preparation and to their use.
The introduction of polymerisable groups into carbohydrates such as, for example, cyclodextrins is desirable owing to their properties, especially their high degree of hydrophilicity, their specific complex-forming behaviour and their bioactivity. Acrylate-containing, methacrylate-containing and cinnamoyl-containing cyclodextrins and polymers therefrom have been described, for example, by A. P. Croft et al. in Tetrahedron, Vol. 39, No. 9, pages 1425 to 1427 (1983). The polymerisable groups are regiospecifically bonded in the 2- or 3-positions. They are obtained by the reaction of suitable activated esters, namely nitrophenylcarboxylic acid esters, with a cyclodextrin. It is generally very difficult completely to remove the resulting nitrophenol, since cyclodextrins form inclusion compounds with those organic compounds. Owing to the fact that nitrophenols are not physiologically acceptable, have a polymerisation-inhibiting action and are also very expensive to purify, polymers from such polymerisable cyclodextrins can be used only to a limited extent.
It is also known to prepare homopolymers or copolymers from acrylate or methacrylate esters of sugars. The acylation of sugars is less regioselective, however, and always results in non-uniform compound mixtures which also comprise compounds having more than one polymerisable acyl group. Polymers from those mixtures therefore always comprise undesired and cross-linked or branched products having a tendency to precipitate out of solutions. In addition, the natural properties of the sugar radicals that are desirable for many applications are lost as a result of multiple substitution. Furthermore, the ester bond of those acrylates and methacrylates is relatively rigid. The areas of application are considerably limited by those disadvantages. In order to obtain regioselectively substituted polymers of an acrylate ester of galactose, it has been proposed to acryloylate the diacetonide of galactose, followed by polymerisation and subsequent unblocking (CA 70:29704p). That complex process is uneconomical, however.
WO 91/17255 describes the enzyme-catalysed preparation of polymers from sugars and dicarboxylic acid esters by means of a regioselective diacylation, wherein the sugar radicals are bonded as comonomers in the polymer backbone and, as a consequence, bioactive properties are virtually lost.
It has now been found that cyclosaccharides can be monoacylated regioselectively in the 2- or 3-positions or the primary hydroxy group of monomeric, dimeric or linear oligomeric saccharides can be monoacylated regioselectively, by carrying out the acylation with monovinyl or divinyl esters of dicarboxylic acids. Surprisingly, despite the presence of two ester groups of equal reactivity no dimers or polysubstituted products are obtained. Vinyl ester groups can be transesterified with unsaturated alkanols to form other radically polymerisable monomers or can be amidated with unsaturated amines. Those monomers and the monovinyl esters of sugars are especially suitable for the preparation of linear polymers, the saccharide group being bonded to a flexible spacer. As a consequence of the specific monoacylation and the flexible bonding to a polymer backbone, the properties of the saccharide radicals are largely retained also in the polymers.
The invention relates to compounds of formulae I and Ia C.sub.3 -C.sub.8 cycloalkylene or C.sub.6 -C.sub.14 arylene, cyclic-oligomeric carbohydrate or of a derivative of such a carbohydrate, linear or branched oligomeric carbohydrate or of a derivative of such a carbohydrate, and especially from 2 to 8, carbon atoms. The radical R can contain ethene or ethyne groups as radically polymerisab
REFERENCES:
patent: 3565887 (1971-02-01), Parmerter et al.
"Cyclodextrin-Containing Polymers 1 Prep. of Polymers", Harada, Akira, et al., Macromolecules, vol. 9, No. 5, Sep.-Oct. 1976.
"Synthesis of Chemically Modified Cyclodextrins", Croft, Alan, et al. Tetrahedron Report No. 147, Pergamon Press Ltd. 1425-1427.
Ciba Geigy Corporation
McC. Roberts Edward
Meece R. Scott
Nutter Nathan M.
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