2-Dipiperonylaminoethanol is tertiary amine derivative classified by the WHO as an antipsychotic and anxiolytic drug. The compound was patented as antispasmodic medication in 1948.

Emepronium bromide (Cetiprina) is a quarternary ammonium compound with anticholinergic effects. It is mainly used in the treatment of urinary frequency, urge and urge incontinence and is usually administered orally and occasionally intramuscularly. Emepronium bromide was introduced into Britain, after having been used in Sweden for a number of years. The drug was advocated especially for elderly patients suffering from nocturia and urgency with incontinence, when these were due to causes other than obstruction. It was also advocated for enuresis and hypertonic bladder states following surgery or radiotherapy.

Vinylbital is a barbiturate derivative. It was introduced into therapy in 1963 and used as a sedative and in the treatment of insomnia.

Niaprazine is a potent and selective antagonist of 5-HT2A and alpha-1 adrenergic receptors. It was used for the treatment of sleep disturbances in children and was investigated for the treatment of sleep disorders in patients with attention-deficit hyperactivity disorder and autistic disorder.

Apronalide is an acyclic analog of barbiturates. It was used under tradename "Sedormid" as a sedative an hypnotic agent. In 1934 it was discovered that the drug causes thrombocytopenic purpura. Apronalide is still marketed in Japan, where it is used in combination with caffeine and ibuprofen for the treatment of headache.

Valnoctamide is a valproic acid derivative associated with a decreased risk for congenital abnormalities and developed by Beersheva Mental Health Center for treatment mania. Valnoctamide has been marketed as an anxiolytic and sedative in several European countries (as Nirvanil), including Italy, Holland, and Switzerland, until the year 2000 but was not actively promoted as an anticonvulsant. It was marketed in the U.S. as Axiquel by McNeil Laboratories in the 1970s. In mice, valnoctamide has been shown to be distinctly less teratogenic than valproic acid. Injection of 3 mkmol ⁄ kg at day 8 of gestation produced only 1% exencephaly (as compared to 0–1% in control mice and 53% in valproate-treated mice). Embryolethality rates showed similar results: 52% with valproate versus 5% in the controls and 2% with valnoctamide. Valnoctamide's patent is expired, and it is not the property of any major pharmaceutical company. Valnoctamide has potential as a therapy in epilepsy including status epilepticus (SE) and neuropathic pain and is currently being developed for the treatment of mania and Schizoaffective Disorder. In clinical trials, Valnoctamide was well tolerated but lacked efficacy in the treatment of symptoms in patients with acute mania.

Chlorhexadol (or Chloralodol), a hypnotic compound which is included in the list of Schedule III drugs of the United States Controlled Substances Act.

Doxefazepam (marketed under brand name Doxans) is a benzodiazepine derivative with putative hypnotic, anxiolytic, anticonvulsant, sedative and skeletal muscle relaxant properties. The potency of action was estimated to be equivalent to diazepam in animal models, and in man, the compound proved to be CNS active in a placebo-controlled study, in which systematic modifications of the background EEG signal were detected after acute administration to awake volunteers. Doxefazepam (10 mg) reduced the number of intermediate awakenings and the shifts between distinct sleep phases; single 20- or 40-mg doses or a 2-week administration of 10 mg doxefazepam increased significantly the total sleep duration and the percent duration of phase 2 and the synchronized sleep and decreased the percent duration of phase 1 and of the intermediate awakenings.

Loprazolam is a hypnotic drug which stimulates GABA-A receptors. Due to its hypnotic activity the drug is used to treat short-term sleep disordes.