Hypoxia-selective antitumor agents. 5. Synthesis of water-soluble nitroaniline mustards with selective cytotoxicity for hypoxic mammalian cells

J Med Chem. 1992 Aug 21;35(17):3214-22. doi: 10.1021/jm00095a018.

Abstract

Nitroaniline mustards have potential as hypoxia-selective cytotoxic agents, with reductive metabolism activating the nitrogen mustard by converting the electron-withdrawing nitro group to an electron-donating hydroxylamine or amine. However, the parent compounds have poor aqueous solubility, and their potencies are limited by low reduction potentials (E1/2 ca. -600 mV versus the normal hydrogen electrode) and corresponding slow rates of nitro reduction. To address these limitations, a series of 4-nitroaniline mustards bearing hydrophilic side chains attached via an electron-withdrawing carboxamide group was prepared and evaluated for hypoxia-selective cytotoxicity against Chinese hamster cell lines. The N-[(N,N-dimethylamino)ethyl]carboxamide derivatives proved to have excellent aqueous solubility and improved cytotoxic potency, but their reduction potentials, while higher than the non-carboxamide compounds, were still low and little selectivity for hypoxic cells were observed. A series of carboxamides of 2,4-dinitroaniline mustard was also prepared. These compounds had reduction potentials in the desired range (E1/2 ca. -450 mV by cyclic voltammetry) and were more toxic to hypoxic than aerobic UV4 cells. The most selective compounds were 5-[N,N-bis(2-chloroethyl)amino]-2,4-dinitrobenzamide (20, SN 23862) and its water-soluble N-[(N,N-dimethylamino)ethyl]carboxamide analogue. These showed selectivities of 60- to 70-fold for hypoxic UV4 cells. The selectivity of 20 was much superior to that of its aziridine analogue (23, CB 1954), which was only 3.6-fold more toxic to hypoxic than oxic cells in the same system. Compound 20 is a much less efficient substrate than CB 1954 for the major aerobic nitroreductase from rat Walker tumor cells, NAD(P)H:quinone oxidoreductase (DT diaphorase). Lack of aerobic bioactivation of 20 by DT diaphorases may be responsible for its higher hypoxic selectivity than that of 23.

Publication types

  • Comparative Study
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Aniline Compounds / chemistry*
  • Aniline Mustard / analogs & derivatives*
  • Aniline Mustard / chemical synthesis
  • Aniline Mustard / metabolism
  • Aniline Mustard / pharmacology
  • Animals
  • Antineoplastic Agents / chemical synthesis*
  • Antineoplastic Agents / chemistry
  • Antineoplastic Agents / pharmacology
  • CHO Cells / drug effects
  • Cell Survival / drug effects
  • Chemical Phenomena
  • Chemistry, Physical
  • Cricetinae
  • Humans
  • Molecular Structure
  • Mustard Compounds / chemical synthesis*
  • Mustard Compounds / chemistry
  • Mustard Compounds / pharmacology
  • NAD(P)H Dehydrogenase (Quinone) / metabolism
  • Oxidation-Reduction
  • Oxygen*
  • Rats
  • Solubility
  • Structure-Activity Relationship
  • Tumor Cells, Cultured
  • Water

Substances

  • Aniline Compounds
  • Antineoplastic Agents
  • Mustard Compounds
  • Water
  • 5-(N,N-bis(2-chloroethyl)amino)-2,4-dinitrobenzamide
  • N-((N,N-dimethylamino)ethyl)-5-(N,N-bis(2-chloroethyl)amino)-2,4-dinitrobenzamide
  • 4-nitroaniline
  • Aniline Mustard
  • NAD(P)H Dehydrogenase (Quinone)
  • Oxygen