Ethylsodium

Ethylsodium
Names
Other names
sodium ethanide
Identifiers
3D model (JSmol)
Abbreviations EtNa
ChemSpider
  • InChI=1S/C2H5.Na/c1-2;/h1H2,2H3;/q-1;+1
    Key: IZEUYKFIAWOPOS-UHFFFAOYSA-N
  • C[CH2-].[Na+]
Properties
C2H5Na
Molar mass 52.052 g·mol−1
Related compounds
Other cations
 ethyllithium
Related compounds
 Vinyl sodium; Sodium ethoxide; Methyl sodium
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Ethyl sodium (or ethylsodium) is an organometallic compound containing sodium ions [Na]+ and ethyl anions (ethanide) [CH3CH2]−. It is seldom isolated as a solid product, but can be used as an intermediate in reactions. Ethylsodium is reactive with oxygen, water and most solvents. Only alkanes are inert to ethylsodium, however it does not dissolve in these.[1]

The substance was named by James Alfred Wanklyn in the 1850s.[2][3]

Production

Ethyl iodide reacts with metallic sodium to yield ethyl sodium.[2] Sodium sand also reacts with ethyl chloride to yield ethyl sodium.[4]

CH3CH2I + 2 Na → CH3CH2Na + NaI
CH3CH2Cl + 2 Na → CH3CH2Na + NaCl

Diethyl zinc reacts with sodium metal to yield a double salt: sodium triethylzincate Na[Zn(CH2CH3)3.[3][5] When heated this gives off ethylene to yield sodium di-μ-hydridobis{diethylzincate(II)}.[6]

A similar double salt is sodium tetraethylaluminate.[7]

Diethyl mercury reacts with sodium to yield ethyl sodium.[8]

Reactions

Ethyl sodium reacts with diethyl ether to make sodium ethoxide, ethane and ethylene:[5]

CH3CH2Na + (CH3CH2)2O → C2H6 + C2H4 + CH3CH2ONa

So ether cannot be used a solvent with ethyl sodium.[5]

Ethyl sodium reacts with carbon monoxide to yield diethyl ketone and triethylcarbinol.[5]

Ethyl sodium reacts with (−)2-bromooctane gives 25% racemic 3-methylnonane, also octane, octylene, and some 7.8-dimethyltetradecane.[8] With (+)2-chlorooctane, similar products are produced.[9]

Benzophenone reacts with ethyl sodium to yield diphenylethylcarbinol (C6H5)2(C2H5)COH.[10]

Ethylsodium reacts with aromatic ring compounds to replace a hydrogen atom with sodium. These compounds can be carbonated with carbon dioxide to replace the sodium with a carboxylate group, yielding a sodium carboxylate.

For example benzene forms phenyl sodium:[4]

CH3CH2Na + C6H6 → C6H5Na + C2H6

Further addition of sodium mainly occurs at meta- and para- positions.[4]

Isopropylbenzene mainly forms meta- and para- compounds with ethylsodium.[4]

Toluene reacts to form benzyl sodium. A second sodium will tend to add at the meta position[4] Xylene is metallated on the methyl groups also. Ethylbenzene has a small amount of the alpha hydrogen replaced by sodium in a reaction with ethylsodium.[4]

Cumene also adds sodium at the alpha position. This reaction position differs from that of bulkier organic sodium compounds:[4]

C6H5CH(CH3)2 + NaEt → C6H5CNa(CH3)2
C6H5CNa(CH3)2 + CO2 → C6H5C(CO2Na)(CH3)2(CO2Na) (phenyldimethylacetic acid)

With p-cymene ethylsodium adds sodium to the methyl group.[4]

Mesitylene yields 3,4-dimethylphenlsodium.[4] With diphenylmethane, sodium substitutes on the methylene group.[4]

Furan reacts with NaEt to yield 2-furyl sodium and similarly thiophene reacts to yield 2-thienyl sodium. If one side of the furan is blocked, sodium will add to the other side of the oxygen, so 2-methylfuran produces 5-methyl-2-furyl sodium. In the same way 2-methylthiophene yields 5-methyl-2-thienyl sodium and 2-tert-butylthiophene yields 5-tert-butyl-2-thienyl sodium. 3-Methylthiophene produces 4-methyl-2-thienyl sodium.[4]

References

  1. ↑ Kondo, Keisuke; Lowe, Matthew; Davison, Nathan; Waddell, Paul G.; Armstrong, Roly J.; Lu, Erli; Kubota, Koji; Ito, Hajime (8 December 2025). "Mechanochemical synthesis of organosodium compounds through direct sodiation of organic halides". Nature Synthesis. 5 (5): 669–679. doi:10.1038/s44160-025-00949-7.
  2. 1 2 Anderson, David E.; Malaspina, Lorraine A.; Grabowsky, Simon; Hevia, Eva (8 September 2025). "Synthesis and Structure of Neopentyl Sodium: A Hydrocarbon-Soluble Reagent for Controlled Sodiation of Non-Activated Substrates". Angewandte Chemie International Edition. 64 (37) e202511492. Bibcode:2025ACIE...6411492A. doi:10.1002/anie.202511492. PMC 12416459. PMID 40728144.
  3. 1 2 Wanklyn, J. Alfred (31 December 1859). "XXII. On some new ethyl-compounds containing the alkalimetals". Proceedings of the Royal Society of London (9): 341–345. doi:10.1098/rspl.1857.0084.
  4. 1 2 3 4 5 6 7 8 9 10 11 Bryce-Smith, D. (1963). "1136. Organometallic compounds of the alkali metals. Part VII. Orientation in protophilic aromatic metallation by ethylsodium and ethyl-lithium–potassium reagents: factors influencing the reactivity of metallating reagents". J. Chem. Soc. 0: 5983–5991. doi:10.1039/JR9630005983.
  5. 1 2 3 4 Seyferth, Dietmar (1 January 2006). "Alkyl and Aryl Derivatives of the Alkali Metals: Useful Synthetic Reagents as Strong Bases and Potent Nucleophiles. 1. Conversion of Organic Halides to Organoalkali-Metal Compounds". Organometallics. 25 (1): 2–24. doi:10.1021/om058054a.
  6. ↑ Lennartson, Anders; Håkansson, Mikael; Jagner, Susan (3 September 2007). "Facile Synthesis of Well-Defined Sodium Hydridoalkylzincates(II)". Angewandte Chemie International Edition. 46 (35): 6678–6680. Bibcode:2007ACIE...46.6678L. doi:10.1002/anie.200701477. PMID 17665387.
  7. ↑ Schlosser, M. (1964). "Organosodium and Organopotassium Compounds" (PDF). The Vespiary. Retrieved 2026-05-16.
  8. 1 2 Brink, Norman G.; Lane, John F.; Wallis, Everett S. (May 1943). "Reactions of Organometallic Compounds with Alkyl Halides. I. The Action of Sodium Ethyl on (—)2-Bromoöctane". Journal of the American Chemical Society. 65 (5): 943–949. Bibcode:1943JAChS..65..943B. doi:10.1021/ja01245a048.
  9. ↑ Ulrich, Stephen E.; Gentes, Franklin H.; Lane, John F.; Wallis, Everett S. (November 1950). "Reactions of Organometallic Compounds with Alkyl Halides. II. On Sodium Ethyl and (+)2-Chloroöctane". Journal of the American Chemical Society. 72 (11): 5127–5130. doi:10.1021/ja01167a087.
  10. ↑ Schorigin, Paul (May 1908). "Synthesen mittels Natrium und Halogenalkylen". Berichte der Deutschen Chemischen Gesellschaft. 41 (2): 2711–2717. doi:10.1002/cber.190804102208.
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