5-[(Aminoalkyl)amino]-substituted anthra[1,9-cd]pyrazol-6(2H)-ones as novel anticancer agents. Synthesis and biological evaluation

Journal of Medicinal Chemistry
1984.0

Abstract

The anthracycline antitumor antibiotics daunorubicin and doxorubicin have a well-established place in the clinical treatment of various malignant diseases but possess serious cardiotoxicity. We now report the synthesis and initial biological evaluation of two representatives (compounds 8 and 10) of a novel class of highly active anticancer DNA-complexing agents, namely, 5-[(aminoalkyl)amino]anthra[1,9-cd]pyrazol-6(2H)-ones (anthrapyrazoles), which were anticipated to have diminished or absent cardiotoxicity due to a reduced tendency to semiquinone free radical formation. The synthetic pathway (Scheme I) involved alkylation of 1,4-dichloro-5-hydroxy-9,10-anthracenedione (3) to form benzyl ether 4, condensation with 2-[(2-hydrazinoethyl)amino]ethanol to yield regioisomers 5 and 6, reaction of 5 to form "two-armed" compound 7, and hydrogenolysis to obtain target compound 8; similar transformations on 6 afforded 10. Biological activity (Table I) showed compound 8 was essentially equipotent with mitoxantrone in the in vitro L1210 lymphocytic leukemia assay, had excellent activity against P388 leukemia (with cures at 12.5-25 mg/kg) and strong activity against mammary adenocarcinoma 16C (surpassing mitoxantrone by 2-3 logs of tumor cell kill), while compound 10 was 100-fold less active in vitro and approximately 4-fold less potent in vivo. Future reports will detail the synthesis of a large series of anthrapyrazoles and their broad-spectrum anticancer activity, as well as preclinical toxicology studies. Additionally, insulin therapy effectively controls glucose levels in diabetes but does not prevent chronic complications (e.g., neuropathy, nephropathy, retinopathy, cataracts) linked to aldose reductase-catalyzed glucose conversion to sorbitol. We developed a potent, orally active aldose reductase inhibitor, N-[[5-(trifluoromethyl)-6-methoxy-1-naphthalenyl]thioxomethyl]-N-methylglycine (tolrestat, 1). Its synthesis involved treatment of 6-methoxy-5-(trifluoromethyl)naphthalene-1-carboxylic acid (2) acid chloride with methyl sarcosinate, reaction with phosphorus pentasulfide, and hydrolysis; key intermediate 2 was obtained via iodination, trifluoromethylation, and hydrolysis (or oxidation of 6). Biochemical and pharmacological properties of tolrestat were investigated and compared with existing inhibitors like alrestatin and sorbinil.

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