Marcfortine/paraherquamide derivatives useful as antiparasitic a

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Heterocyclic carbon compounds containing a hetero ring...

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544229, 544230, 435118, C07D49122, A01N 4390, C12P 1718, A61K 31495

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active

057769362

DESCRIPTION:

BRIEF SUMMARY
BACKGROUND OF THE INVENTION

The marcfortines are known compounds and are disclosed by Polonsky et al. in Journal of the Chemical Society Chemical Communications 1980 601-602 (Marcfortine A) and Tetrahedron Letters 1981 22 1977-1980 (Marcfortines B and C). The compounds are fungal metabolites of Penicillium roqueforti. The marcfortines are structurally related to the paraherquamides which are also known compounds. The paraherquamides are disclosed by Yamazaki et al. in Tetrahedron Letters 1981 22 135-136, and by Blanchflower et al., Journal of Antibioties, 1991, 44, 492-497. U.S. Pat. Nos. 4,866,060 and 4,923,867 disclose the use of the marcfortines A, B, and C, and certain derivatives thereof as useful for the treatment and prevention of parasitic diseases in animals.
Paraherquamide has the following structure: ##STR1##
Marcfortine A has the following structure: ##STR2##
Marcfortine B has the following structure: ##STR3##
Marfortine C has the following structure: ##STR4##
WO 91/09961 (published 11, Jul. 1991) discloses various derivatives of marcfortine and paraherquamide, and N(12) oxides thereof, well as the production the production of VM 29919 (paraherquamide) and VM 55596 (the N(12)oxide of paraherquamide) inter alia from Penicillium Sp. IMI 332995.
U.S. Pat. No. 4,873,247 discloses derivatives of paraherquamide and a strain of Penicillium charlessi MF 5123 (ATCC 20841) for the production of paraherquamide. U.S. Pat. No. 4,978,656 (as well as EP 390532-A, EP-301742-A) discloses various synthetic derivatives of paraherquamide as well as the production of paraherquamide from Penicillium chariessi MF 5123 (ATCC 20841).
Paraherquamide is a compound produced under certain conditions by the fungal organism Penicllium paraherquei. WO 92/00300 (published 9 Jan. 1992) discloses the synthesis paraherquamide related compounds produced from Penicillium paraherquei, deposited at the C.A.B. International Mycological Institute, Ferry Lane, Kew, London, under deposit number CMI 68220.


SUMMARY OF THE INVENTION

This invention is concerned with the synthesis of C-18 thiomarcfortine A, B, and C and derivatives thereof, C-18 thioparaherquamide and derivatives thereof, novel N-1 marcfortines A, B, and C and derivatives thereof, novel N-1 paraherquamide and derivatives thereof, and the use of these compounds as antiparasitic agents. Thus it is an object of this invention to describe these thiomarcfortine, thioparaherquamide, marcfortine and paraherquamide derivatives. A further objective of this invention is to describe processes for the preparation of these compounds. A still further objective is to describe the use of the instant compounds as antiparasitic agents in the treatment and prevention of parasitic diseases. A still further object is to describe compositions for the treatment of parasitic diseases which contain the novel compounds of this invention as the active ingredient thereof. Further objectives will become apparent from a reading of the following description.


DESCRIPTION OF THE INVENTION

The compounds of the instant invention are represented by Formula I: ##STR5## wherein:
n is 0 or 1;
R.sub.14a and R.sub.14b, being the same or different, are selected from hydrogen, hydroxy, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.6 alkenyl, C.sub.1 -C.sub.6 alkenyl-C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.6 alkynyl-C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.6 alkylsilyloxy, diphenylphosphoryloxy and halogen, or R.sub.14a and R.sub.14b together form the epoxide or .dbd.CH.sub.2, with the provisio that when n is 1, then R.sub.14a and R.sub.14b are both hydrogen;
m is 0 or 1 (preferably 0);
W is O or S;
when W is S, R.sub.1 is hydrogen, C.sub.1 -C.sub.7 alkyl, cyclo C.sub.3 -C.sub.8 alkyl, benzyl, C.sub.2 -C.sub.7 alkanoyl (--C(O)C.sub.1 -C.sub.6 alkyl) {optionally substituted with carboxy (--COOH), C.sub.1 -C.sub.7 alkanoyl, carbo C.sub.1 -C.sub.7 alkoxy (--C(O)OC.sub.1 -C.sub.7 alkyl), --NR.sub.4 R.sub.5, aminocarbonyl (--C(O)NR.sub.4 R.sub.5)}, C.sub.10 -C.sub.24 alkanoyl (--C(O)C.sub.9 -C.sub.23

REFERENCES:
Blizzard, Timothy A; Margiano, Gaye; Mrozik, Helmut; Schaeffer, James M; Fisher, Michael H; Chemical Modification of Paraherquamide. 4. 1-N-Substituted Analogs, Tetrahedron Letters, vol. 32, No. 22, pp. 2441-2444, 1991.
Blizzard, Timothy A; Marino, Gaye; Mrozik, Helmut; Fisher, Michael H; Hoogsteen, Karst; Springer, James P; Chemical Modification of Paraherquamide. 1. Unusual Reactions and Absolute Stereochemistry, Journal Org. Chem. 1989, 54, 2657-2663.

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