Hexaethyl tetraphosphate

{{Chembox | verifiedrevid = | ImageFile =Hexaethyl tetraphosphate.PNG | ImageSize = | IUPACName =diethoxyphosphoryl [diethoxyphosphoryloxy(ethoxy)phosphoryl] ethyl phosphate | OtherNames =HETP; ethyl tetraphosphate; Bladan Base |Section1=! colspan=2 style="background: #f8eaba; text-align: center;" |Identifiers

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| [http://www.commonchemistry.org/ChemicalDetail.aspx?ref=757-58-4 757-58-4] ^Y

|- | 3D model (Jmol) | [http://chemapps.stolaf.edu/jmol/jmol.php?model=%5BO-%5DP%28%5BO-%5D%29%28%3DO%29%5BO-%5D.%5BO-%5DP%28%5BO-%5D%29%28%5BO-%5D%29%3DO.CC.CC.CC.CC.CC.CC.%5BO-%5DP%28%5BO-%5D%29%28%5BO-%5D%29%3DO.%5BO-%5DP%28%5BO-%5D%29%28%5BO-%5D%29%3DO Interactive image]

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| ChemSpider | 12420 ^{[[File:Yes check.svg|7px|alt=Yes|link=]]Y}

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| ECHA InfoCard | 100.010.961 |-

| PubChem | 12960

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|- |Section2=! colspan=2 style="background: #f8eaba; text-align: center;" |Properties

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| C₁₂H₃₀P₄O₁₃

|- | Molar mass

| 506.25 g/mol

|- | Appearance | yellow to brown liquid |-

| Density | 1.331 g/cm³ |- | Melting point | −40 °C (−40 °F; 233 K)

|- | Boiling point | 467.01 °C (872.62 °F; 740.16 K)

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| moderate |-

| Solubility | most organic solvents |-

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| 1.443 |- |Section3={{Chembox Hazards | MainHazards =skin absorption; inhalation | FlashPtC =120.82 | AutoignitionPt = | RPhrases ={{}} | SPhrases ={{}}

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|Section4=!Related compounds |-

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| tetraethyl pyrophosphate
pentaethyl triphosphate |- }}

Hexaethyl tetraphosphate is a chemical compound with the chemical formula (C₂H₅O)₆P₄O₇.^[1] It is a yellow, light amber-colored or brown liquid.^[2][3][4] The chemical is also known as HET.^[2] Its ChemSpider ID is 12420.^[5] It is a constituent of the insecticide Bladan.^[6] In the 1940s, it was about as significant an insecticide as DDT and was referred to as "another of DDT's rivals for fame" in a 1948 book.^[7]

Properties

Hexaethyl tetraphosphate does not readily burn. It is miscible and soluble in water.^[2] It is also soluble in a large number of organic compounds. These include acetone, ether, alcohol, carbon tetrachloride, chloroform, ethyl acetate, glycerol, benzene, diacetone alcohol, alkylated naphthalenes, xylene, and toluene. However, the chemical does not dissolve in kerosene, ligroin, or other paraffin fractions.^[3] When reacting with hydrides and other strong reducing agents, the chemical reacts to form phosphine, a toxic gas.^[2] When hexaethyl tetraphosphate is exposed to moisture, it quickly hydrolyzes. This reaction forms nontoxic products.^[3]

Hexaethyl tetraphosphate has a pH of 5.5. Its index of refraction is 1.443. The chemical boils at 467.01 °C (872.62 °F) at a pressure of 760 millimeters of mercury and its flash point is 249.48 °F (120.82 °C).^[5] Its melting point is −40 °C (−40 °F).^[6] It has a density of 1.331 grams per cubic centimeter. Its enthalpy of vaporization is 70.102 kilojoules per mole. Hexaethyl tetraphosphate has two Rule of 5 violations.^[5]

Hexaethyl tetraphosphate in a pure state does not noticeably corrode metals such as brass and iron. However, when a small amount of water is added to the chemical, it forms a strong acid and quickly corrodes galvanized iron and more slowly corrodes pure iron. Hexaethyl tetraphosphate diluted with 0.1% water has a pH of 2.5.^[6]

Precautions and toxicity

Hexaethyl tetraphosphate can give off fumes that are toxic or corrosive if it is heated. Runoff containing the chemical can also lead to the pollution of waterways. Containers of it can also explode at high temperatures. If inhaled, swallowed, or absorbed via the skin, it can cause death.^[2] Mites, aphids, thrips, leafhoppers, and some types of caterpillars are highly susceptible to being poisoned by hexaethyl tetraphosphate.^[3][8] The chemical's toxicity to insects is not affected by whether it is made by the Scrader process or the Woodstock process.^[9] It is also very toxic to humans.^[6]

Out of 133 plant species that were tested for a reaction to hexaethyl tetraphosphate, only two types of plants were negatively affected. These were chrysanthemums and tomatoes.^[6]

The LD50 of hexaethyl tetraphosphate for thrips is 0.01%. 99% of aphids can be killed by a concentration of 1 to 2.5 grams of a 10% solution of the chemical in a 1000 cubic foot area. In one experiment, 100% of melon aphids were killed after exposure to an aqueous solution containing 0.025% hexaethyl tetraphosphate and 0.025% sodium lauryl sulfate. 99% of aphids can be killed by 0.3 grams of a 10% solution of the chemical in methyl chloride in 1000 cubic feet, and 100% of aphids can be killed by twice the amount of solution. 96% of apple aphids can be killed be exposure to an aqueous solution of 0.1% hexaethyl tetraphosphate and 0.05% sodium lauryl sulfate. Dust containing 3% hexaethyl tetraphosphate at a concentration of 40 pounds per acre can kill some bean aphids.^[9] 100% of cabbage aphids can be killed by an aqueous solution of 0.1% of the chemical and 0.05% sodium lauryl sulfate. Cabbage aphids can be quickly killed by a spray containing one pint of the chemical per 100 gallons of water.^[10]

100% of chrysanthemum aphids can be killed by an aqueous solution of 0.1% hexaethyl tetraphosphate and 0.05% sodium lauryl sulfate. 97% of chrysanthemum aphids can be killed by 3 grams of a 10% solution of the chemical in 1000 cubic feet. 100% of helianthus aphids can be killed by an aqueous solution containing 0.05% each of hexaethyl tetraphosphate and sodium lauryl sulfate. 94% of pea aphids can be killed by exposure for 24 hours to an emulsion containing a concentration of 2.4% of the chemical. 90% of potato aphids can be killed by exposure for 42 hours to a one pint of a 50% solution of the chemical in 100 gallons of water.^[10]

The effects of hexaethyl tetraphosphate on the cholinesterase of rat and cockroach tissue have been tested.^[11]

Production

Hexaethyl tetraphosphate was first synthesised by the German chemist Gerhard Schrader, who reacted phosphorus oxychloride and triethyl orthophosphate at approximately 150 °C. This reaction is known as the Schrader process. The Germans also made hexaethyl tetraphosphate by phosphorus oxychloride and ethyl alcohol. This reaction requires slightly lower pressure than the Schrader process.^[3] The reaction has a chemical equation of POCl₃ + 3(C₂H₅)₃PO₄ → (C₂H₅)₆P₄O₁₃ + 3C₂H₅Cl.^[8]

By 1947, hexaethyl tetraphosphate was being produced on a commercial scale. It cost US$1.10 per pound in the form of drums and $2.00 per pound in the form of carboys.^[8] In the 1940s, the chemical was commercially produced at concentrations of 50%.^[9]

Hexaethyl tetraphosphate's U.N. Shipping Number is 1611.^[12]

Applications

Hexaethyl tetraphosphate is used as an insecticide, in particular, the insecticide Bladan.^[1][3] The Germans commonly used this chemical as an insecticide during World War II, when nicotine-based insecticides were not available.^[3]

History

The term 'hexaethyl tetraphosphate' originated between 1945 and 1950.^[1] The chemical was first described by a person named Schrader, who patented a process for making the chemical in 1938.^[3][8] It was discovered during research on chemical warfare agents.^[3] Americans first heard of the chemical after 1945, from two people named Hall and Kilgore. The United States began to produce the chemical in 1946.^[8]

References