Organic compounds -- part of the class 532-570 series – Organic compounds – Carbohydrates or derivatives
Patent
1996-01-16
1999-09-28
Mullis, Jeffrey C.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carbohydrates or derivatives
536120, 5361231, 536124, C08B 3716
Patent
active
059590890
DESCRIPTION:
BRIEF SUMMARY
This invention relates to methods of synthesis of azido-cyclodextrins, haloalkyl-cyclodextrins, amino-cyclodextrins, amino-alkyl cyclodextrins, substituted amino-cyclodextrins and alkenyl cyclodextrins. Cyclodextrins are widely known as food and drug additives, as catalysts in chemical and industrial processes, and in numerous spectroscopic, analytical and preparative procedures, (see Li and Purdy, Chem. Rev. 1992, 92, 1457-1470, herein incorporated by reference). Their inclusion compounds are similarly widely known (see Saenger, Angew. Chem. Int. Ed. Engl. 1980, 19, 433-362, herein incorporated by reference).
The present invention primarily relates to processes of preparing substituted cyclodextrins. Specific reagents are utilized to produce specific products. The present invention secondarily provides novel compounds prepared by the process. Although the invention will be described and referred to as it relates to processes of preparation of azido-cyclodextrins, haloalkyl-cyclodextrins, amino-cyclodextrins, amino-alkyl cyclodextrins, substituted amino-cyclodextrins and alkenyl cyclodextrins and novel azido-cyclodextrins, haloalkyl-cyclodextrins, amino-cyclodextrins, amino-alkyl cyclodextrins, substituted amino-cyclodextrins and alkenyl cyclodextrins prepared thereby, it will be understood that the principles of this invention are equally applicable to similar processes and products, and accordingly it will be understood that the invention is not limited to such processes and products.
BACKGROUND OF THE INVENTION
Cyclodextrins are cyclic alpha-1,4-oligosaccharide starch derivates. Alpha, beta, gamma, and delta cyclodextrins are known, containing six, seven, eight, and nine glucose units respectively. Their importance lies in their enzymic properties attributed to their hollow truncated cone structure having primary 6-hydroxyls at the narrower end, and secondary 2- and 3-hydroxyls at the wider end, a relatively hydrophobic interior cavity and a relatively hydrophilic exterior.
The cyclodextrins form inclusion complexes and it is believed that these inclusion complexes and similar compounds modify the chemical and physical environment affecting chemical reactions to induce chirality in otherwise achiral reactions. The cyclodextrins are themselves inherently chiral being composed of chiral D-glucose units.
Substituted aminodeoxy cyclodextrins are particularly noted for their chiral catalytic effects (Tagaki et al., Tetrahedron Lett., 1990, 31, 3897-3900, Parrot-Lopez et al., Tetrahedron: Asymmetry, 1990, 1, 367-370, Angew. Chem. Int. Ed. Engl., 1992, 31, 1381-1383, incorporated herein by reference).
Azidodeoxy cyclodextrins are suitable precursors for aminodeoxy cyclodextrins.
It is a principal object of the invention to prepare azidodeoxy cyclodextrins and their amino derivatives.
In accordance with a broadest aspect of an embodiment of the invention there is provided a compound of formula ##STR1## wherein C is cyclodextrin, A is amino, azido or aminocarbonyl aralkoxy, wherein said aralkoxy has 7 to 10 carbon atoms and n is 0, 1, 2 or 3, B is hydroxyl, or one of A and B is azido and the other is aminocarbonyl aralkoxy, R is hydrogen, alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, aminoalkyl of 1 to 6 carbon atoms, azidoalkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkylcarboalkoxy in which the alkyl and alkoxy groups have 1 to 6 carbon atoms each, with the proviso when R is aminoalkyl, azidoalkyl, or haloalkyl n is 0.
In a broadest aspect of another embodiment of the invention there is provided a process of preparation of a compound of formula ##STR2## wherein C is cyclodextrin, A is amino, azido or aminocarbonyl aralkoxy, wherein said aralkoxy has 7 to 10 carbon atoms and n is 0, 1, 2 or 3, B is hydroxyl, or one of A and B is azido and the other is aminocarbonyl aralkoxy, R is hydrogen, alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, amin alkyl of 1 to 6 carbon atoms, azidoalkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkylcarboalkoxy in w
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