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Diethyl sulfate - Wikipedia

From Wikipedia, the free encyclopedia

Diethyl sulfate Diethyl sulfate Names Preferred IUPAC name

Diethyl sulfate

Other names

Sulfuric acid diethyl ester

Identifiers CAS Number

3D model (

JSmol

)

ChEBI ChEMBL ChemSpider ECHA InfoCard 100.000.536 KEGG PubChem CID RTECS number UNII CompTox Dashboard (EPA) InChI SMILES Properties Chemical formula C4H10O4S Molar mass 154.18 g·mol−1 Appearance Colorless liquid Density 1.2 g/mL Melting point −25 °C (−13 °F; 248 K) Boiling point 209 °C (408 °F; 482 K) (decomposes) Solubility in water decomposes in water Vapor pressure 0.29 mm Hg Magnetic susceptibility

(χ)

−86.8·10−6 cm3/mol Hazards GHS labelling: Pictograms Signal word Danger Hazard statements H302, H312, H314, H332, H340, H350 Precautionary statements P201, P202, P260, P261, P264, P270, P271, P280, P281, P301+P312, P301+P330+P331, P302+P352, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P308+P313, P310, P312, P321, P322, P330, P363, P405, P501 NFPA 704 (fire diamond) 3 1 1 Flash point 104 °C (219 °F; 377 K) Related compounds

Related compounds

Dimethyl sulfate; diethyl sulfite

Except where otherwise noted, data are given for materials in their

standard state

(at 25 °C [77 °F], 100 kPa).

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Infobox references

Chemical compound

Diethyl sulfate (DES) is an organosulfur compound with the formula (C2H5)2SO4.[1][2] It occurs as a colorless, oily liquid with a faint peppermint odor. It is toxic, combustible, and likely carcinogenic chemical compound.[3][2] Diethyl sulfate is used as an ethylating agent.

Structure and properties[edit]

Although the formula for diethyl sulfate is typically written (C2H5)2SO4, a more descriptive formula would be (C2H5O)2SO2. It is a diester of sulfuric acid. Sulfur is tetrahedral.

Diethyl sulfate hydrolyzes readily, forming ethanol and ethyl sulfate. Eventually sulfuric acid is formed with excess water.

Diethyl sulfate is used to an alkylating agent to prepare ethyl ethers, ethyl amines[4] and ammonium salts, and ethyl thioethers. In preparing ethyl esters of fatty acids, both equivalents of the ethyl electrophile are transferred, unlike the usual alkylation of phenoxides:[1]

2 RCO2Na + (C2H5O)2SO2 → 2 RCO2C2H5 + Na2SO4

Both dimethyl sulfate and diethyl sulfate react with inorganic nucleophiles as well. For example, potassium iodide gives ethyl iodide.

Diethyl sulfate cannot be prepared efficiently analogously to the method used for dimethyl sulfate. The reaction of oleum with diethyl ether results in excessive oxidation of the ethyl groups. Instead, diethyl sulfate is prepared in two steps starting from chlorosulfuric acid:[1]

ClSO3H + C2H5OH → C2H5OSO3H + HCl

The resulting ethyl sulfate is then heated with sodium sulfate, leading to a redistribution reaction:

2 C2H5OSO3H + Na2SO4 → (C2H5O)2SO2 + 2 NaHSO4

Like other strong alkylating agents and especially dimethyl sulfate, diethyl sulfate is toxic[2] and genotoxic.[5] It is classified as a Group 2A (probably carcinogenic to humans) carcinogen by the IARC.[6] Experimentation with animals has suggested this compound is likely carcinogenic to humans as it was implicated in the development of laryngeal cancer.[7] Evidence of the effects of this chemical compound on reproductive or developmental health is also lacking.[8]

Dialkyl sulfates can be rendered nontoxic by treatment with aqueous ammonia.[1]

  1. ^ a b c d Weisenberger, Karl; Mayer, Dieter; Sandler, Stanley R. (2000). "Dialkyl Sulfates and Alkylsulfuric Acids". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a08_493. ISBN 978-3-527-30385-4.
  2. ^ a b c "Diethyl Sulfate | CAMEO Chemicals | NOAA". cameochemicals.noaa.gov. Retrieved 2021-03-04.
  3. ^ "NCI Thesaurus". ncit.nci.nih.gov. Retrieved 2021-04-02.
  4. ^ Buck, J. R.; Park, M.; Wang, Z.; Prudhomme, D. R.; Rizzo, C. J. (2000). "9-Ethyl-3,6-Dimethylcarbazole (DMECZ)". Organic Syntheses. 77: 153. doi:10.15227/orgsyn.077.0153.
  5. ^ "Agents Classified by the IARC Monographs, Volumes 1–129 – IARC Monographs on the Identification of Carcinogenic Hazards to Humans". monographs.iarc.who.int. Retrieved 2021-04-02.
  6. ^ IARC (1999). "Diethyl Sulfate". Summaries and Evaluations. International Agency for Research on Cancer (IARC). p. 1405.
  7. ^ "NCI Thesaurus". ncit.nci.nih.gov. Retrieved 2021-02-18.
  8. ^ "Diethyl Sulfate" (PDF). United States Environmental Protection Agency. Archived (PDF) from the original on 2016-10-14.

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