Antiparasitic agents

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...

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514 30, 549264, 536 71, A61K 31335

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active

057234884

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BRIEF SUMMARY
This invention relates to antiparasitic agents and in particular to compounds related to the avermectins and milbemycins but having substituents at the 3-position.
The avermectins are a group of broad-spectrum antiparasitic agents referred to previously as the C-076 compounds. They are produced by fermenting a certain strain of microorganism Streptomyces avermitilis in an aqueous nutrient medium. The preparation and structure of these compounds obtained by fermentation are described in British Patent Specification 1573955. The milbemycins are structurally related macrolide antibiotics lacking the sugar residues at the 13-position. They may be produced by fermentation, for example as described in British Patent Specification No. 1390336 and European Patent Specification No. 0170006.
In addition to these fermentation-derived products, a large number of publications describe compounds derived semisynthetically from these products, many of which possess useful antiparasitic properties. Some of this chemistry is reviewed in Macrolide Antibiotics, Omura S., Ed., Academic Press, New York (1984) and by Davies, H. G. and Green, R. H. in Natural Product Reports (1986), 3, 87-121 and in Chem. Soc. Rev. (1991), 20, 211-269 and 271-239.
Compounds related to the original C-076 avermectins have also been prepared by fermentation of avermectin-producing micro-organism: For example European Patent Specifications 021473 and 0317148 describe production of compounds related to the C-076 avermectins but having a different substituent at the 25-position by fermentation in the present, in the fermentation medium, of certain acids.
Other publications mentioning different combinations of substituents at various positions on the avermectin or milbemycin nucleus are EP-A-317148, 340932, 350187, 410165, 259779 and 254583; DE-A-2329486 and GB-A-2166436.
B. J. Banks, in International Patent Application WO-A-9318041, describes the 3-substituted avermectin and milbemycin derivatives, where there is a 3,4-double bond and no 5-substituent.
The avermectins and milbemycins and their derivatives have the structure: ##STR2## wherein the broken lines represent independently optional bonds, R.sup.1 and R.sup.2 being absent when the C22-C23 bond is present, R.sup.1, R.sup.2, R.sup.6 and R.sup.12 are independently H, OH, halo, oxo, oximino or an organic radical, R.sup.4 and R.sup.5 are organic radicals, and R.sup.3 is H or an organic radical.
These compounds include the avermectins themselves and their substituted derivatives in which R.sup.6 is a 4'-(a-L-oleandrosyl)-a-L-oleandrosyloxy group, optionally substituted at the 4" position; the avermectin monosaccharides and their derivatives in which R.sup.6 is a-L-oleandrosyloxy, optionally substituted at the 4' position; the avermectin aglycones and their derivatives in which R.sup.6 is OH or a substituent other than oleandrosyl replacing this group, and the milbemycins and their derivatives in which R.sup.6 is H.
All the avermectins and structurally related milbemycins and their derivatives hitherto reported do not have a substituent at the 3-position when the double bond is in the C3-C4 position and with a 5-substituent, neither has any process capable of producing such compounds been reported.
It has now been discovered that avermectin and milbemycin derivatives having a wide range of substituents at the 3-position may be prepared and that some of these compounds have outstanding antiparasitic properties.
Compounds of the invention are of formula (I): ##STR3## wherein the broken lines represent independently optional bonds, R.sup.1 and R.sup.2 being absent when the C22-C23 double bond is present, R.sup.1, R.sup.2, R.sub.6 are independently H, OH, halo, oxo, oximino, or an organic radical, R.sup.4 and R.sup.5 are organic radicals, R.sup.1 is H or an organic radical, or oximino optionally substituted by a C.sub.1 -C.sub.8 alkyl, alkenyl, alkynyl, aryl, trialkylsilyl, aralkyl, C.sub.1 -C.sub.9 alkanoyl group or other group capable of being hydrolysed in vivo to the oxime, or hydrazono optionally sub

REFERENCES:
patent: 4423209 (1983-12-01), Mrozik
patent: 5073567 (1991-12-01), Kojima
patent: 5240915 (1993-08-01), Rosegay

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