Sodium amide

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.Template:Citation needed 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,<ref>Template:OrgSynth</ref> 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.<ref>Template:Cite book</ref>

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Template:Chem2 is a salt-like material and as such, crystallizes as an infinite polymer.<ref>Template:Cite journal</ref> The geometry about sodium is tetrahedral.<ref>Template:Cite book</ref> 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<ref>Template:Cite book</ref>) 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.<ref>L. Lange, W. Treibel "Sodium Amide" in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim. {{#invoke:doi|main}}</ref>

File:Indigo Synthesis V.1.svg

Pfleger's synthesis of indigo dye.

Dehydrohalogenation

Sodium amide is a standard base for dehydrohalogenations.<ref name=eEROS>Template:Cite book</ref> 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.<ref>Template:OrgSynth</ref> 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.

Hydrogen chloride and ethanol can also be eliminated in this way,<ref>Template:OrgSynth
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Template:OrgSynth</ref> as in the preparation of 1-ethoxy-1-butyne.<ref>Template:OrgSynth</ref>

Cyclization reactions

Where there is no β-hydrogen to be eliminated, cyclic compounds may be formed, as in the preparation of methylenecyclopropane below.<ref>Template:OrgSynth</ref>

Cyclopropenes,<ref>Template:OrgSynth</ref> aziridines<ref>Template:OrgSynth</ref> and cyclobutanes<ref>Template:OrgSynth</ref> 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,<ref>Template:OrgSynth
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Template:OrgSynth</ref> methyl ketones,<ref>Template:OrgSynthTemplate:OrgSynth</ref> cyclohexanone,<ref>Template:OrgSynth</ref> phenylacetic acid and its derivatives<ref>Template:OrgSynth
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Template:OrgSynth</ref> and diphenylmethane.<ref>Template:OrgSynth</ref> Acetylacetone loses two protons to form a dianion.<ref>Template:OrgSynth
Template:OrgSynth</ref> Sodium amide will also deprotonate indole<ref>Template:OrgSynth</ref> and piperidine.<ref>Template:OrgSynth</ref>

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

• Rearrangement with orthodeprotonation<ref>Template:OrgSynth</ref>
• Oxirane synthesis<ref>Template:OrgSynth</ref>
• Indole synthesis<ref>Template:OrgSynth</ref>
• Chichibabin reaction

Safety

Sodium amide is a common reagent with a long history of laboratory use.<ref name=eEROS/> 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.<ref name="Clark2001">Template:Cite journal</ref> 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.<ref>{{#invoke:citation/CS1|citation |CitationClass=web }}</ref>