Sodium amide

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Template:Chembox Sodium amide, commonly called sodamide (systematic name sodium azanide), is the inorganic compound with the formula Template:Chem2. It is a salt composed of the sodium cation and the azanide anion. This solid, which is dangerously reactive toward water, is white, but commercial samples are typically gray due to the presence of small quantities of metallic iron from the manufacturing process. Such impurities do not usually affect the utility of the reagent.Script error: No such module "Unsubst". Template:Chem2 conducts electricity in the fused state, its conductance being similar to that of NaOH in a similar state. Template:Chem2 has been widely employed as a strong base in organic synthesis.

Preparation and structure

Sodium amide can be prepared by the reaction of sodium with ammonia gas,[1] but it is usually prepared by the reaction in liquid ammonia using iron(III) nitrate as a catalyst. The reaction is fastest at the boiling point of the ammonia, c. −33 °C. An electride, Template:Chem2, is formed as a reaction intermediate.[2]

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Template:Chem2 is a salt-like material and as such, crystallizes as an infinite polymer.[3] The geometry about sodium is tetrahedral.[4] In ammonia, Template:Chem2 forms conductive solutions, consistent with the presence of Template:Chem2 and Template:Chem2 ions.

Uses

Sodium amide is mainly used as a strong base in organic chemistry, often suspended (it is insoluble[5]) in liquid ammonia solution. One of the main advantages to the use of sodium amide is its relatively low nucleophilicity. In the industrial production of indigo, sodium amide is a component of the highly basic mixture that induces cyclisation of N-phenylglycine. The reaction produces ammonia, which is recycled typically.[6]

File:Indigo Synthesis V.1.svg
Pfleger's synthesis of indigo dye.

Dehydrohalogenation

Sodium amide is a standard base for dehydrohalogenations.[7] It induces the loss of two equivalents of hydrogen bromide from a vicinal dibromoalkane to give a carbon–carbon triple bond, as in a preparation of phenylacetylene.[8] Usually two equivalents of sodium amide yields the desired alkyne. Three equivalents are necessary in the preparation of a terminal alkynes because the terminal CH of the resulting alkyne protonates an equivalent amount of base.

File:Phenylacetylene prepn.png

Hydrogen chloride and ethanol can also be eliminated in this way,[9] as in the preparation of 1-ethoxy-1-butyne.[10]

File:Ethoxybutyne prepn.png

Cyclization reactions

Where there is no β-hydrogen to be eliminated, cyclic compounds may be formed, as in the preparation of methylenecyclopropane below.[11]

File:Methylenecyclopropane prepn.png

Cyclopropenes,[12] aziridines[13] and cyclobutanes[14] may be formed in a similar manner.

Deprotonation of carbon and nitrogen acids

Carbon acids which can be deprotonated by sodium amide in liquid ammonia include terminal alkynes,[15] methyl ketones,[16] cyclohexanone,[17] phenylacetic acid and its derivatives[18] and diphenylmethane.[19] Acetylacetone loses two protons to form a dianion.[20] Sodium amide will also deprotonate indole[21] and piperidine.[22]

Related non-nucleophilic bases

It is however poorly soluble in solvents other than ammonia. Its use has been superseded by the related reagents sodium hydride, sodium bis(trimethylsilyl)amide (NaHMDS), and lithium diisopropylamide (LDA).

Other reactions

Safety

Sodium amide is a common reagent with a long history of laboratory use.[7] It can decompose violently on contact with water, producing ammonia and sodium hydroxide:

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When burned in oxygen, it will give oxides of sodium (which react with the produced water, giving sodium hydroxide) along with nitrogen oxides:

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In the presence of limited quantities of air and moisture, such as in a poorly closed container, explosive mixtures of peroxides may form.[26] This is accompanied by a yellowing or browning of the solid. As such, sodium amide is to be stored in a tightly closed container, under an atmosphere of an inert gas. Sodium amide samples which are yellow or brown in color represent explosion risks.[27]

References

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  1. ↑ Template:OrgSynth
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  6. ↑ L. Lange, W. Treibel "Sodium Amide" in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim. Script error: No such module "doi".
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  8. ↑ Template:OrgSynth
  9. ↑ Template:OrgSynth
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  10. ↑ Template:OrgSynth
  11. ↑ Template:OrgSynth
  12. ↑ Template:OrgSynth
  13. ↑ Template:OrgSynth
  14. ↑ Template:OrgSynth
  15. ↑ Template:OrgSynth
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  16. ↑ Template:OrgSynthTemplate:OrgSynth
  17. ↑ Template:OrgSynth
  18. ↑ Template:OrgSynth
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  19. ↑ Template:OrgSynth
  20. ↑ Template:OrgSynth
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  21. ↑ Template:OrgSynth
  22. ↑ Template:OrgSynth
  23. ↑ Template:OrgSynth
  24. ↑ Template:OrgSynth
  25. ↑ Template:OrgSynth
  26. ↑ Script error: No such module "Citation/CS1".
  27. ↑ Script error: No such module "citation/CS1".
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