Diethyl sulfate
{{chembox
| Watchedfields = changed
| verifiedrevid = 414421861
| Name = Diethyl sulfate
| ImageFile_Ref = {{chemboximage|correct|??}}
| ImageFile = Diethylsulfate V 2.png
| ImageSize = 200px
| ImageName = Diethyl sulfate
| ImageAlt = Molecular structure of diethyl sulfate.
| ImageFile1 = Diethyl-sulfate-3D-balls-by-AHRLS.png
| ImageSize1 = 200px
| ImageAlt1 = Space filling molecular structure of diethyl sulfate.
| PIN = Diethyl sulfate
| OtherNames = Sulfuric acid diethyl ester
| Section1 = {{Chembox Identifiers
| SMILES = O=S(=O)(OCC)OCC
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 5931
| ChEBI = 34699
| PubChem = 6163
| KEGG_Ref = {{keggcite|correct|kegg}}
| KEGG = C14706
| InChI = 1/C4H10O4S/c1-3-7-9(5,6)8-4-2/h3-4H2,1-2H3
| InChIKey = DENRZWYUOJLTMF-UHFFFAOYAR
| ChEMBL_Ref = {{ebicite|correct|EBI}}
| ChEMBL = 163100
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/C4H10O4S/c1-3-7-9(5,6)8-4-2/h3-4H2,1-2H3
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = DENRZWYUOJLTMF-UHFFFAOYSA-N
| CASNo = 64-67-5
| CASNo_Ref = {{cascite|correct|CAS}}
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = K0FO4VFA7I
| RTECS = WS7875000
}}
| Section2 = {{Chembox Properties
| C=4 | H=10 | O=4 | S=1
| Appearance = Colorless liquid
| Density = 1.2 g/mL
| Solubility = decomposes in water
| MeltingPtC = -25
| BoilingPtC = 209
| BoilingPt_notes = (decomposes)
| Viscosity =
| VaporPressure = 0.29 mm Hg
| MagSus = −86.8·10−6 cm3/mol
}}
| Section3 =
| Section4 =
| Section5 =
| Section6 =
| Section7 = {{Chembox Hazards
| ExternalSDS =
| NFPA-H = 3
| NFPA-R = 1
| NFPA-F = 1
| GHSPictograms = {{GHS05}}{{GHS07}}{{GHS08}}
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|302|312|314|332|340|350}}
| PPhrases = {{P-phrases|201|202|260|261|264|270|271|280|281|301+312|301+330+331|302+352|303+361+353|304+312|304+340|305+351+338|308+313|310|312|321|322|330|363|405|501}}
| FlashPtC = 104
}}
| Section8 = {{Chembox Related
| OtherCompounds = Dimethyl sulfate; diethyl sulfite
}}
}}
Diethyl sulfate (DES) is an organosulfur compound with the formula (C2H5)2SO4.{{Cite web|title=Diethyl Sulfate {{!}} CAMEO Chemicals {{!}} NOAA|url=https://cameochemicals.noaa.gov/chemical/3212|access-date=2021-03-04|website=cameochemicals.noaa.gov}} It occurs as a colorless, oily liquid with a faint peppermint odor. It is toxic, combustible, and likely carcinogenic chemical compound.{{Cite web|title=NCI Thesaurus|url=https://ncit.nci.nih.gov/ncitbrowser/ConceptReport.jsp?dictionary=NCI_Thesaurus&ns=NCI_Thesaurus&code=C44375|access-date=2021-04-02|website=ncit.nci.nih.gov}} Diethyl sulfate is used as an ethylating agent.
Structure and properties
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.
Reactions
Diethyl sulfate is used to an alkylating agent to prepare ethyl ethers, ethyl amines{{ OrgSynth | doi = 10.15227/orgsyn.077.0153 |author1=Buck, J. R.|author2=Park, M.|author3=Wang, Z.|author4=Prudhomme, D. R.|author5=Rizzo, C. J. | title = 9-Ethyl-3,6-Dimethylcarbazole (DMECZ) | year = 2000 | volume = 77 | pages = 153 }} 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:
:{{chem2|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.
Preparation
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:{{cite book |doi=10.1002/14356007.a08_493 |chapter=Dialkyl Sulfates and Alkylsulfuric Acids |title=Ullmann's Encyclopedia of Industrial Chemistry |date=2000 |last1=Weisenberger |first1=Karl |last2=Mayer |first2=Dieter |last3=Sandler |first3=Stanley R. |isbn=978-3-527-30385-4 }}
:{{chem2|ClSO3H + C2H5OH -> C2H5OSO3H + HCl}}
The resulting ethyl sulfate is then heated with sodium sulfate, leading to a redistribution reaction:
:{{chem2|2 C2H5OSO3H + Na2SO4 -> (C2H5O)2SO2 + 2 NaHSO4}}
Safety
Like other strong alkylating agents and especially dimethyl sulfate, diethyl sulfate is toxic and genotoxic.{{Cite web|title=Agents Classified by the IARC Monographs, Volumes 1–129 – IARC Monographs on the Identification of Carcinogenic Hazards to Humans|url=https://monographs.iarc.who.int/agents-classified-by-the-iarc/|access-date=2021-04-02|website=monographs.iarc.who.int}} It is classified as a Group 2A (probably carcinogenic to humans) carcinogen by the IARC.{{Cite web|author=IARC|author-link=International Agency for Research on Cancer|series=Summaries and Evaluations|title=Diethyl Sulfate|year=1999|volume=71|page=1405|publisher=International Agency for Research on Cancer (IARC)|url=http://www.inchem.org/documents/iarc/vol54/04-diethyl-sulfate.html}} Experimentation with animals has suggested this compound is likely carcinogenic to humans as it was implicated in the development of laryngeal cancer.{{Cite web|title=NCI Thesaurus|url=https://ncit.nci.nih.gov/ncitbrowser/ConceptReport.jsp?dictionary=NCI_Thesaurus&ns=NCI_Thesaurus&code=C44375|access-date=2021-02-18|website=ncit.nci.nih.gov}} Evidence of the effects of this chemical compound on reproductive or developmental health is also lacking.{{Cite web|title=Diethyl Sulfate|url=https://www.epa.gov/sites/production/files/2016-09/documents/diethyl-sulfate.pdf|url-status=live|website=United States Environmental Protection Agency|archive-url=https://web.archive.org/web/20161014110318/https://www.epa.gov/sites/production/files/2016-09/documents/diethyl-sulfate.pdf |archive-date=2016-10-14 }}
=Neutralization=
Dialkyl sulfates can be rendered nontoxic by treatment with aqueous ammonia.
Further reading
- {{ cite journal |author1=Theodore, S. |author2=Sai, P. S. T. | title = Esterification of Ethanol with Sulfuric Acid: A Kinetic Study | journal = Canadian Journal of Chemical Engineering | year = 2001 | volume = 79 | issue = 1 | pages = 54–64 | doi = 10.1002/cjce.5450790109 }}
References
{{reflist}}
External links
- {{ cite web | url = http://webbook.nist.gov/cgi/cbook.cgi?ID=C64675 | title = Diethyl sulfate | work = Webbook | publisher = NIST }}
- {{ cite web | url = http://www.inchem.org/documents/icsc/icsc/eics0570.htm | title = DIETHYL SULFATE -- ICSC: 0570 | publisher = Inchem }}
- {{ cite web | url = http://monographs.iarc.fr/ENG/Monographs/vol71/mono71-92.pdf | year = 1992 | volume = 71 | publisher = IARC | series = IARC Monographs | title = Diethyl sulfate }}