Parathion

Parathion
IUPAC name O,O-Diethyl O-(4-nitrophenyl) phosphorothioate
Other names E605
Identifiers
CAS number	56-38-2 Y
ChemSpider	13844817 Y
UNII	61G466064D Y
KEGG	C06604 Y
ChEBI	CHEBI:27928 N
ChEMBL	CHEMBL261919 Y
Jmol-3D images	Image 1
SMILES S=P(Oc1ccc(cc1)[N+]([O-])=O)(OCC)OCC
InChI InChI=1S/C10H14NO5PS/c1-3-14-17(18,15-4-2)16-10-7-5-9(6-8-10)11(12)13/h5-8H,3-4H2,1-2H3 Y Key: LCCNCVORNKJIRZ-UHFFFAOYSA-N Y InChI=1/C10H14NO5PS/c1-3-14-17(18,15-4-2)16-10-7-5-9(6-8-10)11(12)13/h5-8H,3-4H2,1-2H3 Key: LCCNCVORNKJIRZ-UHFFFAOYAR
Properties
Molecular formula	C10H14NO5PS
Molar mass	291.3 g/mol
Appearance	White crystals (pure form)
Melting point	6 °C
Solubility in water	24mg/L in water, high solubility in xylene or butanol
Hazards
MSDS	[1]
R-phrases	R24, R26/28, R48/25, R50/53
S-phrases	S28, S36/37, S45, S60, S61
Flash point	120 °C
N (verify) (what is: Y/N?) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Parathion, also called parathion-ethyl or diethyl parathion, is an organophosphate compound. It is a potent insecticide and acaricide. It was originally developed by IG Farben in the 1940s. It is highly toxic to non-target organisms, including humans. Its use is banned or restricted in many countries, and there are proposals to ban it from all use. Closely related is "methyl parathion" (see below).

Parathion-methyl

"Parathion-methyl" (CAS#298-00-0), also known as methyl parathion or dimethyl parathion, was also developed and is marketed for similar uses. It is a distinct compound with diminished toxicity. Some trade names of parathion-methyl include Bladan M, Metaphos, ME605, and E601.

History

Bottle with E605

Parathion was developed by Dr. Gerhard Schrader for the German trust IG Farben in the 1940s. After the war and the collapse of IG Farben due to the war crime trials, the Western allies seized the patent, and parathion was marketed worldwide by different companies and under different brand names. The most common German brand was E605 (banned in Germany after 2002); this was not a food-additive "E number" as used in the EU today. "E" stands for Entwicklungsnummer (German for "development number").

Handling properties

When pure, parathion is a white crystalline solid, however it is commonly distributed as a brown liquid that smells of rotting eggs or garlic. The insecticide is more or less stable, although it darkens when exposed to sunlight.

Industrial synthesis

Parathion is synthesized from diethyl dithiophosphoric acid (C₂H₅O)₂PS₂H, which is obtained by treatment of P₂S₅ with ethanol (methanol is used to prepare methyl parathion). Diethyl dithiophosphoric acid is chlorinated to generate diethylthiophosphoryl chloride. The diethyl dithiophosphoric acid is then treated with sodium 4-nitrophenolate (the sodium salt of 4-nitrophenol).^[1]

2 (C₂H₅O)₂P(S)SH + 3 Cl₂ → 2 (C₂H₅O)₂P(S)Cl + S₂Cl₂ + 2 HCl

(C2H5O)₂P(S)Cl + NaOC₆H₄NO₂ → (C₂H₅O)₂P(S)OC₆H₄NO₂ + NaCl

Applications

As a pesticide, parathion is generally applied by spraying. It is often applied to cotton, rice and fruit trees. The usual concentrations of ready-to-use solutions are 0.05 to 0.1%. The chemical is banned for use on many food crops.

Insecticidal activity

Parathion acts on the enzyme acetylcholinesterase, but indirectly. After being ingested by insects (and unintentionally, by humans), the parathion becomes oxidized by oxidases to give paraoxon, replacing the double bonded sulfur with oxygen.^[2]

(C₂H₅O)₂P(S)OC₆H₄NO₂ + 1/2 O₂ → (C₂H₅O)₂P(O)OC₆H₄NO₂ + S

The phosphate ester is more reactive in organisms than the phosphorothiolate ester, as the phosphorus atoms become much more electronegative.^[2]

Degradation

Degradation of parathion leads to more water soluble products. Hydrolysis, which deactivates the molecule, occurs at the aryl ester bond resulting in diethyl thiophosphate and 4-nitrophenol.^[2]

(C₂H₅O)₂P(S)OC₆H₄NO₂ + H₂O → HOC₆H₄NO₂ + (C₂H₅O)₂P(S)OH

Degradation proceeds differently under anaerobic conditions: the nitro group on parathion is reduced to the amine.

(C₂H₅O)₂P(S)OC₆H₄NO₂ + 6 H → (C₂H₅O)₂P(S)OC₆H₄NH₂ + 2 H₂O

Safety

Parathion is a cholinesterase inhibitor. It generally disrupts the nervous system by inhibiting the acetylcholinesterase. It is absorbed via skin, mucous membranes, and orally. Absorbed parathion is rapidly metabolized to paraoxon, as described above. Paraoxon exposure can result in headaches, convulsions, poor vision, vomiting, abdominal pain, severe diarrhea, unconsciousness, tremor, dyspnea, and finally lung-edema as well as respiratory arrest. Symptoms of poisoning are known to last for extended periods of time, sometimes months. The most common and very specific antidote is atropine in doses of up to 100 mg daily. Because atropine may also be toxic, it is recommended that small frequently repeated doses be used in treatment. If human poisoning is detected early and the treatment is prompt (atropine and artificial respiration), fatalities are infrequent. Insufficient oxygen will lead to cerebral hypoxia and permanent brain damage. Peripheral neuropathy including paralysis is noticed as late sequelae after recovery from acute intoxication. Parathion has been used for committing suicide and deliberately poisoning other persons. It is known as "Schwiegermuttergift" (mother-in-law poison) in Germany. For this reason most formulations contain a blue dye providing warning.

Parathion has been used as a chemical weapon, most notably by the Selous Scouts during the Rhodesian Bush War.^[3]

Based on animal studies, parathion is considered by the U.S. Environmental Protection Agency‎ to be a possible human carcinogen.^[4] Studies show that parathion is toxic to fetuses, but does not cause birth defects.^[5]

It is classified as a UNEP Persistent Organic Pollutant and WHO Toxicity Class, "Ia, Extremely Hazardous".

Parathion is very toxic to bees, fish, birds, and other forms of wildlife.^[5] Parathion can be replaced by many safer and less toxic alternatives (less toxic organophosphates, carbamates, or synthetic pyrethroids).

Protection against poisoning

To assure human protection the end user must wear protective gloves, clothing, and a respirator of the organic-vapour. Industrial safety during the production process requires special ventilation and continuous measurement of air contamination in order not to exceed PEL levels as well as keeping personal hygiene. Frequent determination of workers' serum acetylcholinesterase activity is also helpful in regards of occupational safety, because the action of parathion is cumulative. If an area of the body is contaminated with parathion, if possible, it should be removed immediately. Also, atropine has been used as a specific antidote.

Proposals to ban

According to the non-governmental organisation Pesticide Action Network or PAN, parathion is one of the most dangerous pesticides. This organization lists parathion also as a 'bad actor chemical'.^[6] In the US alone more than 650 agricultural workers have been poisoned since 1966, of which 100 died. In underdeveloped countries many more people have suffered fatal and nonfatal intoxications. The World Health Organization, PAN and numerous environmental organisations propose a general and global ban. Its use is banned or restricted in 23 countries and its import is illegal in a total of 50 countries.^[6]

See also

• Pesticide toxicity to bees

References

1. ^ Fee, D. C.; Gard, D. R.; Yang, C. “Phosphorus Compounds” Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons: New York, 2005. doi:10.1002/0471238961.16081519060505.a01.pub2.
2. ^ ^{a b c} Metcalf, R. L. “Insect Control” Ullman’s Encyclopedia of Industrial Chemistry. Wiley-VCH Verlag GmbH & Co. KGaA: New York, 2002. doi: 10.1002/14356007.a14_263.
3. ^ Moorcraft, Paul and McLaughlin, Peter. The Rhodesian War: A Military History. Yorkshire: Pen & Sword, 2008, p. 106
4. ^ "Parathion". Integrated Risk Information System. U. S. Environmental Protection Agency. 26 January 2007. http://www.epa.gov/iris/subst/0327.htm. 
5. ^ ^{a b} "Pesticide Information Profiles - Parathion". Extension Toxicology Network. Oregon State University. September 1993. http://extoxnet.orst.edu/pips/parathio.htm. 
6. ^ ^{a b} S. Kegley, B. Hill, S. Orme. "Parathion - Identification, toxicity, use, water pollution potential, ecological toxicity and regulatory information". Pesticide Action Network. http://pesticideinfo.org/Detail_Chemical.jsp?Rec_Id=PC35122. 

External links

• ATSDR - Methyl Parathion Expert Panel Report U.S. Department of Health and Human Services (public domain)
• Ethyl parathion: International Chemical Safety Card 0006
• Methyl parathion: International Chemical Safety Card 0626