Sodium phenoxide

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Sodium phenoxide
Structural formula of sodium phenoxide.svg
Names
Preferred IUPAC name
Sodium phenoxide[1]
Other names
Sodium phenolate
Identifiers
  • 139-02-6 checkY
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.004.862 Edit this at Wikidata
UNII
  • InChI=1S/C6H6O.Na/c7-6-4-2-1-3-5-6;/h1-5,7H;/q;+1/p-1
    Key: NESLWCLHZZISNB-UHFFFAOYSA-M
  • InChI=1/C6H6O.Na/c7-6-4-2-1-3-5-6;/h1-5,7H;/q;+1/p-1
    Key: NESLWCLHZZISNB-REWHXWOFAP
  • [Na+].[O-]c1ccccc1
Properties
C6H5NaO
Molar mass 116.09 g/mol
Appearance White solid
Hazards
Main hazards Harmful, Corrosive
Flash point Nonflammable
Nonflammable
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Sodium phenoxide (sodium phenolate) is an organic compound with the formula NaOC6H5. It is a white crystalline solid. Its anion, phenoxide, also known as phenolate, is the conjugate base of phenol. It is used as a precursor to many other organic compounds, such as aryl ethers.

Synthesis and structure[]

Most commonly, solutions of sodium phenoxide are produced by treating phenol with sodium hydroxide.[2] Anhydrous derivatives can be prepared by combining phenol and sodium. A related, updated procedure uses sodium methoxide instead of sodium hydroxide:[3]

NaOCH3 + HOC6H5 → NaOC6H5 + HOCH3

Structure[]

Like other sodium alkoxides, solid sodium phenolate adopts a complex structure involving multiple Na-O bonds. Solvent-free material is polymeric, each Na center being bound to three oxygen ligands as well as the phenyl ring. Adducts of sodium phenoxide are molecular, such as the cubane-type cluster [NaOPh]4(HMPA)4.[4]

Sodium phenoxide can be produced by the "alkaline fusion" of benzenesulfonic acid, whereby the sulfonate groups are displaced by hydroxide:

C6H5SO3Na + 2 NaOH → C6H5ONa + Na2SO3

This route once was the principal industrial route to phenol.

Subunit of the structure of solvent-free sodium phenoxide, illustrating the binding of phenoxide to sodium through both the arene and the oxygen.

Reactions[]

Sodium phenoxide is a moderately strong base. Acidification gives phenol:[5]

PhOH ⇌ PhO− + H+          (K = 10−10)

The acid-base behavior is complicated by homoassociation, reflecting the association of phenol and phenoxide.[6]

Sodium phenoxide reacts with alkylating agents to afford alkyl phenyl ethers:[2]

NaOC6H5 + RBr → ROC6H5 + NaBr

The conversion is an extension of the Williamson ether synthesis. With acylating agents, one obtains phenyl esters:

NaOC6H5 + RC(O)Cl → RCO2C6H5 + NaCl

Sodium phenoxide is susceptible to certain types of electrophilic aromatic substitutions. For example, it reacts with carbon dioxide to form 2-hydroxybenzoate, the conjugate base of salicylic acid. In general however, electrophiles irreversibly attack the oxygen center in phenoxide.

The Kolbe–Schmitt reaction.

References[]

  1. ^ International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. pp. 1071, 1129. doi:10.1039/9781849733069. ISBN 978-0-85404-182-4.
  2. ^ a b C. S. Marvel, A. L. Tanenbaum (1929). "γ-Phenoxypropyl Bromide". Org. Synth. 9: 72. doi:10.15227/orgsyn.009.0072.CS1 maint: uses authors parameter (link)
  3. ^ Kornblum, Nathan; Lurie, Arnold P. (1959). "Heterogeneity as a Factor in the Alkylation of Ambident Anions: Phenoxide Ions1,2". Journal of the American Chemical Society. 81 (11): 2705–2715. doi:10.1021/ja01520a030.
  4. ^ Michael Kunert, Eckhard Dinjus, Maria Nauck, Joachim Sieler "Structure and Reactivity of Sodium Phenoxide - Following the Course of the Kolbe-Schmitt Reaction" Chemische Berichte 1997 Volume 130, Issue 10, pages 1461–1465. doi:10.1002/cber.19971301017
  5. ^ Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, ISBN 978-0-471-72091-1
  6. ^ K. Izutsu (1990). Acid-Base Dissociation Constants in Dipolar Aprotic Solvents. 35. Blackwell Scientific Publications.

External links[]

Media related to Sodium phenoxide at Wikimedia Commons

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