Vinylogous Acyl Compounds. XX. Reactivity and Toxicity of Aryl‐substituted β‐Chlorovinyl Ketones, β‐Chlorovinyl Aldehydes, and β‐Chlorovinyl Methyleniminium Salts Based on kinetic measurements, the nucleophilic replaceability of the chlorine in aromatic β‐chlorovinyl ketones ArCO‐CH  CH‐Cl (1), isomeric β‐chlorovinyl aldehydes OCHCHC(Cl)Ar(2), and corresponding β‐chlorovinyl methyleniminium salts Me2N⊕;CHCHC(Cl)Ar X⊖ (3) is compared and related to toxicological findings. The chemical reactivity of these important synthetic building blocks increases in the order 2<1<3, the acute toxicity (24 h LD50 i. p. in the mouse) shows the graduation 2<3<1. Compounds of type 1 prove to be relatively toxic (LD50 24–42 mg/kg) and display a marked necrotic action after percutaneous absorption, whereas the aldehydes 2 have not only a minor acute toxicity (LD50 158–298 mg/kg) but also a somewhat less marked skin damaging activity. In addition, the LD50 values of selected β‐chlorovinyl carbonyl compounds are compared with those of corresponding halogen‐free compounds as well as of vinylogous carbonamidium salts ArCOCHCHN⊕R3X⊖. The latter, which can be used as synthetic equivalents of 1, differ in both the reduced acute toxicity and missing skin damaging properties.

Zur Einschätzung des Alkylierungsvermögens der cyclischen Schwefelsäureester 1,2‐Äthylensulfat 1, 1,3‐Propylensulfat 2 und 1,3‐Butylensulfat 3 wurden die Geschwindigkeiten ihrer Umsetzungen mit 4‐(4‐Nitrobenzyl)‐pyridin (NPB) in Acetophenon bei 20–50°C gemessen und analog ermittelten Parametern des Dimethylsulfats 4, Diäthylsulfats 5, 1,3‐Propansultons 6, 1,4‐Butansultons 7 und p‐Toluolsulfonsäuremethylesters 8 gegenübergestellt. Die resultierende Reaktivitätsabstufung unterscheidet sich z. T. von der, die man bei der Hydrolyse in Wasser erhält, doch erweist sich in beiden Fällen 1,2‐Äthylensulfat 1 als jeweils reaktivstes Agens. Aus LD50‐Bestimmungen (Maus, i. p.) geht hervor, daß 1,2‐Äthylensulfat auch die höchste akute Toxizität der untersuchten Verbindungen besitzt.

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Dimethoate, bromophos, naled or trichlorophon were applied i.p. or p.o. to rats in 3 doses each differing by the factor 10. In the urine of 24 h gas chromatographic determination of dimethylphosphate (DM), O.O-dimethylthiophosphate (TP), and/or O.O-dimethyldithiophosphate (DT) were carried out. After i.p. application of dimethoate the excretion rate of DT calculated from the dates found with the lowest dosage differed significantly from those found with the two other doses (t-test; p = 0.01). The excretion rates of DM and TP, in the same way, or those of DM, TP, and DT after oral intake of dimethoate did not show any significant differences. The excretion rates of TP after bromophos and of DM after naled or trichlorophon did not differ significantly after the same way of application. The findings make evident that under the given test conditions the excretion rate of DM, TP, or DT is practically independent on the dose.

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