Pempidine Explained

Pempidine is a ganglion-blocking drug, first reported in 1958 by two research groups working independently, and introduced as an oral treatment for hypertension.[1]

Pharmacology

Reports on the "classical" pharmacology of pempidine have been published.[2] [3] The Spinks group, at ICI, compared pempidine, its N-ethyl analogue, and mecamylamine in considerable detail, with additional data related to several structurally simpler compounds.[2]

Toxicology

LD50 for the HCl salt of pempidine in mice: 74 mg/kg (intravenous); 125 mg/kg (intraperitoneal); 413 mg/kg (oral).[2]

Chemistry

Pempidine is an aliphatic, sterically hindered, cyclic, tertiary amine, which is a weak base: in its protonated form it has a pKa of 11.25.[4]

Pempidine is a liquid with a boiling point of 187–188 °C and a density of 0.858 g/cm3.[2]

Two early syntheses of this compound are those of Leonard and Hauck,[5] and Hall.[4] These are very similar in principle: Leonard and Hauck reacted phorone with ammonia, to produce 2,2,6,6-tetramethyl-4-piperidone, which was then reduced by means of the Wolff–Kishner reduction to 2,2,6,6-tetramethylpiperidine. This secondary amine was then N-methylated using methyl iodide and potassium carbonate.[6]

Hall's method involved reacting acetone with ammonia in the presence of calcium chloride to give 2,2,6,6-tetramethyl-4-piperidone, which was then reduced under Wolff–Kishner conditions, followed by N-methylation of the resulting 2,2,6,6-tetramethylpiperidine with methyl p-toluenesulfonate.

Notes and References

  1. Spinks A, Young EH . Polyalkylpiperidines: a new series of ganglion-blocking agents. . Nature . May 1958 . 181 . 4620 . 1397–1398 . 10.1038/1811397a0 . 1958Natur.181.1397S . 4196802 .
  2. Spinks A, Young EH, Farrington JA, Dunlop D . The pharmacological actions of pempidine and its ethyl homologue . British Journal of Pharmacology and Chemotherapy . 13 . 4 . 501–20 . December 1958 . 13618559 . 1481871 . 10.1111/j.1476-5381.1958.tb00246.x .
  3. Muggleton DF, Reading HW . Absorption, metabolism and elimination of pempidine in the rat . British Journal of Pharmacology and Chemotherapy . 14 . 2 . 202–208 . June 1959 . 13662574 . 1481796 . 10.1111/j.1476-5381.1959.tb01384.x .
  4. Hall HK . Steric Effects on the Base Strengths of Cyclic Amines . Journal of the American Chemical Society . 1957 . 79 . 20 . 5444–5447 . 10.1021/ja01577a031 .
  5. Leonard NJ, Hauck Jr FP . Unsaturated amines. X. The mercuric acetate route to substituted piperidines, Δ2-tetrahydropyridines and Δ2-tetrahydroanabasines. . Journal of the American Chemical Society . October 1957 . 79 . 19 . 5279–5292 . 10.1021/ja01576a056 .
  6. The boiling point of 147 °C given by these authors for their 1,2,2,6,6-pentamethylpiperidine is significantly below the range of approximately 182–188 °C reported by other chemists.