Phosphamidon

Structural formula
	About 70:30 mixture of ( E ) -isomer (left) and ( Z ) -isomer (right)
General
Surname	Phosphamidon
other names	( E , Z ) -3-chloro-4-diethylamino-4-oxobut-2-en-2-yl-dimethylphosphate ( IUPAC ) ; 2-chloro-2-diethylcarbamoyl-1-methyl vinyl dimethyl phosphate; 2-chloro-3-diethylamino-1-methyl-3-oxo-1-propenyl dimethyl phosphate; Dimethyl phosphate ester-2- chloro- N , N -diethyl-3-hydroxycrotonamide; Trade names: Apamidon ® , Dimecron ® , Dimenox ® , Dixon ® , Phosron ® , Pillarcron ® ;
Molecular formula	C 10 H 19 ClNO 5 P
Brief description	odorless, clear, yellowish liquid
External identifiers / databases
EC number	236-116-5
ECHA InfoCard	100.032.818
PubChem	25750
Wikidata	Q424889
properties
Molar mass	299.69 g mol −1
Physical state	liquid
density	1.2132 g cm −3
Melting point	-45 ° C
boiling point	94 ° C (5.3 Pa )
Vapor pressure	3.39 10 −5 mbar (at 20 ° C)
solubility	miscible with water, polar organic solvents
Refractive index	1.4721
safety instructions
H and P phrases	H: 300-311-341-410
	P: 264-273-280-301 + 310-312-501
Toxicological data	13 mg kg −1 ( LD 50 , mouse , oral ) ; 20 mg kg −1 ( LD 50 , rat , oral ) ;
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

Phosphamidon is a mixture of two ( cis- , trans -isomer ) organic chemical compounds with the empirical formula C ₁₀ H ₁₉ ClNO ₅ P, which was first described in 1960. This mixture is one of the groups of the organophosphate and organophosphate - insecticides .

presentation

The synthesis starts from N , N -diethylacetamide ( 1 ). It is acetylated to diethylacetoacetamide ( 2 ) by self-condensation using phosphorus oxychloride . With sulfuryl chloride is methyl chlorinated. The intermediate product N , N- diethyldichloroacetoacetamide ( 3 ) gives a mixture of 4a and 4b in the reaction with trimethyl phosphite with elimination of chloromethane as the end product .

Cis-trans isomerism

Phosphamidon is subject to the cis - trans isomerism at the oxobutene double bond . An isomer mixture of about 70% ( Z ) - ( cis ) isomer and 30% ( E ) - ( trans ) isomer is used as an insecticide (commercial product ).

Properties and use

Under normal conditions , Phosphamidon is a clear, light yellowish, odorless liquid. It mixes with many polar organic solvents and in all proportions with water. As a commercial product, phosphamidon can contain flammable solvents, the influence of which can completely change the chemical, physical and toxicological properties. When heated or burned, the substance decomposes with the formation of hydrogen chloride , phosphorus oxides and nitrogen oxides . Phosphamidon reacts with bases with hydrolysis . Metals such as aluminum, iron and tin are attacked; it is stable against acids and in neutral solution.

Phosphamidon was first described in 1960 and introduced as a systemic insecticide. Large-scale production as an insecticide was discontinued in 1990 and is still available for scientific purposes.

Admission

For the states of the European Union, phosphamidone is not approved as an active ingredient in plant protection products. In Switzerland, too, as in Austria and Germany, phosphamidone is not an active ingredient in approved plant protection products.

toxicity

As a phosphoric acid ester, phosphamidone is very toxic to humans and animals and therefore highly hazardous to the environment, especially for aquatic fauna. The WHO lists it in hazard class Ia ("extremely dangerous" or "extremely hazardous"). Phosphamidon acts as a cholinesterase inhibitor (acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE)). It has a toxic effect on contact with the skin (contact and nerve toxins), on inhalation and ingestion. Storage in fat and the brain can have a long-term effect, depending on the dose, gene type and additional toxins. The LD ₅₀ p.o. (per os, orally) is 13 mg / kg for mice and 20 mg / kg for rats.

literature

R. Jacques, Hugo J. Bein: Toxicology and pharmacology of a new systemically effective insecticide of the phosphoric acid ester series, phosphamidon (2-chloro-2-diethylcarbamoyl-1-methylvinyl-dimethylphosphate) . In: Archiv für Toxikologie (1960) 18, pp. 316-330.
R. Jacques, Hugo J. Bein: Toxicology and pharmacology of a new systemic phosphoric acid ester insecticide phosphamidon (2-chloro-2-diethylcarbamoyl-1-methylvinyl dimethyl phosphate) . In: Archiv für Toxikologie (1960) 18, pp. 316-330.
Fritz Bachmann: Phosphamidon, a new phosphate ester with systemic action . In: Proc. Intern. Cong. Crop. Protection , 4th Congress, Hamburg 1960; Vol. 2, pp. 1153-1155.
S. Gitelson, JT Davidson, A. Werczberger: Phosphamidon poisoning . In: British Journal of Industrial Medicine (1965) 22, pp. 236-239.

Individual evidence

↑ ^a ^b ^c ^d Entry on phosphamidone in the Pesticide Properties DataBase (PPDB) of the University of Hertfordshire , accessed on July 31, 2013.
↑ ^a ^b ^c ^d ^e R. Jacques, Hugo J. Bein: Toxicology and pharmacology of a new systemically effective insecticide of the phosphoric acid ester series, Phosphamidon (2-chloro-2-diethylcarbamoyl-1-methylvinyl-dimethylphosphate), Archives for Toxicology (1960 ) 18, pp. 316-330.
↑ ^a ^b ^c WHO / FAO Data Sheet on Pesticides (PDS) for Phosphamidon ( Memento of July 2, 2014 in the Internet Archive )
↑ Entry on Phosphamidon. In: Römpp Online . Georg Thieme Verlag, accessed on February 17, 2015.
↑ ^a ^b Entry on phosphamidon in the GESTIS substance database of the IFA , accessed on July 23, 2016(JavaScript required) .
↑ Entry on phosphamidone in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on February 1, 2016. Manufacturers or distributors can expand the harmonized classification and labeling .
↑ R. Anliker, E. Beriger and K. Schmid: The synthesis of ¹⁴ C-labeled phosphamidon, a new systemic insecticide . In: Cellular and Molecular Life Sciences (1961) , Vol. 17, Number 11, pp. 492-493.
↑ Regulation (EC) No. 2076/2002 of the Commission of November 20, 2002 extending the deadline in accordance with Article 8 paragraph 2 of Council Directive 91/414 / EEC and on the non-inclusion of certain active substances in Annex I of this directive and the revocation of Approvals of plant protection products with these active ingredients (PDF) .
↑ General Directorate Health and Food Safety of the European Commission: Entry on phosphamidone in the EU pesticide database; Entry in the national registers of plant protection products in Switzerland , Austria and Germany ; accessed on March 8, 2016.

Web links

Phosphamidon EC data sheet
WHO / FAO Data Sheet on Pesticides (PDS) for Phosphamidon ( Memento of July 2, 2014 in the Internet Archive )

[Datchem-1] Entry on phosphamidone in the Pesticide Properties DataBase (PPDB) of the University of Hertfordshire , accessed on July 31, 2013.

[TOX1960-2] R. Jacques, Hugo J. Bein: Toxicology and pharmacology of a new systemically effective insecticide of the phosphoric acid ester series, Phosphamidon (2-chloro-2-diethylcarbamoyl-1-methylvinyl-dimethylphosphate), Archives for Toxicology (1960 ) 18, pp. 316-330.

[inchem-3] WHO / FAO Data Sheet on Pesticides (PDS) for Phosphamidon ( Memento of July 2, 2014 in the Internet Archive )

[roempp-4] Entry on Phosphamidon. In: Römpp Online . Georg Thieme Verlag, accessed on February 17, 2015.

[GESTIS-5] Entry on phosphamidon in the GESTIS substance database of the IFA , accessed on July 23, 2016(JavaScript required) .

[CLP_100.032.818-6] Entry on phosphamidone in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on February 1, 2016. Manufacturers or distributors can expand the harmonized classification and labeling .

[7] R. Anliker, E. Beriger and K. Schmid: The synthesis of ¹⁴ C-labeled phosphamidon, a new systemic insecticide . In: Cellular and Molecular Life Sciences (1961) , Vol. 17, Number 11, pp. 492-493.

[8] Regulation (EC) No. 2076/2002 of the Commission of November 20, 2002 extending the deadline in accordance with Article 8 paragraph 2 of Council Directive 91/414 / EEC and on the non-inclusion of certain active substances in Annex I of this directive and the revocation of Approvals of plant protection products with these active ingredients (PDF) .

[PSM-9] General Directorate Health and Food Safety of the European Commission: Entry on phosphamidone in the EU pesticide database; Entry in the national registers of plant protection products in Switzerland , Austria and Germany ; accessed on March 8, 2016.