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Sodium amide

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Sodium amide, commonly called sodamide (systematic name sodium azanide), is the inorganic compound with the formula NaNH2. 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.[citation needed] NaNH2 conducts electricity in the fused state, its conductance being similar to that of NaOH in a similar state. NaNH2 has been widely employed as a strong base in organic synthesis.

Sodium amide
Ball and stick, unit cell model of sodium amide
Names
IUPAC name
Sodium amide, sodium azanide[1]
Other names
Sodamide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.029.064 Edit this at Wikidata
EC Number
  • 231-971-0
UNII
UN number 1390
  • InChI=1S/H2N.Na/h1H2;/q-1;+1 ☒N
    Key: ODZPKZBBUMBTMG-UHFFFAOYSA-N ☒N
  • [Na]N
  • [NH2-].[Na+]
Properties
NaNH2
Molar mass 39.013 g·mol−1
Appearance Colourless crystals
Odor Ammonia-like
Density 1.39 g/cm3
Melting point 210 °C (410 °F; 483 K)
Boiling point 400 °C (752 °F; 673 K)
Reacts
Solubility 40 mg/L (liquid ammonia), reacts with ethanol
Acidity (pKa) 38 (conjugate acid)[2]
Structure
orthorhombic
Thermochemistry
66.15 J/(mol·K)
76.9 J/(mol·K)
-118.8 kJ/mol
-59 kJ/mol
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g. diesel fuelInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acid
3
2
3
W
Flash point 4.44 °C (39.99 °F; 277.59 K)
450 °C (842 °F; 723 K)
Related compounds
Other anions
 Sodium bis(trimethylsilyl)amide
Other cations
 Lithium amide
Potassium amide
Related compounds
 Ammonia
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Preparation and structure

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Sodium amide can be prepared by the reaction of sodium with ammonia gas,[3] 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, [Na(NH3)6]+e−, is formed as a reaction intermediate.[4]

2 Na + 2 NH3 → 2 NaNH2 + H2

NaNH2 is a salt-like material and as such, crystallizes as an infinite polymer.[5] The geometry about sodium is tetrahedral.[6] In ammonia, NaNH2 forms conductive solutions, consistent with the presence of [Na(NH3)6]+ and NH−2 ions.

Uses

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Sodium amide is mainly used as a strong base in organic chemistry, often suspended (it is insoluble[7]) 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.[8]

 
Pfleger's synthesis of indigo dye.

Dehydrohalogenation

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Sodium amide is a standard base for dehydrohalogenations.[9] 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.[10] 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,[11] as in the preparation of 1-ethoxy-1-butyne.[12]

 

Cyclization reactions

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Where there is no β-hydrogen to be eliminated, cyclic compounds may be formed, as in the preparation of methylenecyclopropane below.[13]

 

Cyclopropenes,[14] aziridines[15] and cyclobutanes[16] may be formed in a similar manner.

Deprotonation of carbon and nitrogen acids

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Carbon acids which can be deprotonated by sodium amide in liquid ammonia include terminal alkynes,[17] methyl ketones,[18] cyclohexanone,[19] phenylacetic acid and its derivatives[20] and diphenylmethane.[21] Acetylacetone loses two protons to form a dianion.[22] Sodium amide will also deprotonate indole[23] and piperidine.[24]

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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

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Safety

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Sodium amide is a common reagent with a long history of laboratory use.[9] It can decompose violently on contact with water, producing ammonia and sodium hydroxide:

NaNH2 + H2O → NH3 + NaOH

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

4 NaNH2 + 5 O2 → 4 NaOH + 4 NO + 2 H2O
4 NaNH2 + 7 O2 → 4 NaOH + 4 NO2 + 2 H2O

In the presence of limited quantities of air and moisture, such as in a poorly closed container, explosive mixtures of peroxides may form.[28] 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.[29]

References

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  1. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "amides". doi:10.1351/goldbook.A00266
  2. ^ Buncel, E.; Menon, B. (1977). "Carbanion mechanisms: VII. Metallation of hydrocarbon acids by potassium amide and potassium methylamide in tetrahydrofuran and the relative hydride acidities". Journal of Organometallic Chemistry. 141 (1): 1–7. doi:10.1016/S0022-328X(00)90661-2.
  3. ^ Bergstrom, F. W. (1955). "Sodium amide". Organic Syntheses; Collected Volumes, vol. 3, p. 778.
  4. ^ Greenlee, K. W.; Henne, A. L. (1946). "Sodium Amide". Inorganic Syntheses. Vol. 2. pp. 128–135. doi:10.1002/9780470132333.ch38. ISBN 9780470132333.
  5. ^ Zalkin, A.; Templeton, D. H. (1956). "The Crystal Structure Of Sodium Amide". Journal of Physical Chemistry. 60 (6): 821–823. doi:10.1021/j150540a042. hdl:2027/mdp.39015086484659.
  6. ^ Wells, A. F. (1984). Structural Inorganic Chemistry. Oxford: Clarendon Press. ISBN 0-19-855370-6.
  7. ^ Audrieth, Ludwig F.; Kleinberg, Jacob (1953). Non-aqueous solvents. New York: John Wiley & Sons. p. 79. LCCN 52-12057.
  8. ^ L. Lange, W. Treibel "Sodium Amide" in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a24_267
  9. ^ a b Belletire, John L.; Rauh, R. Jeffery (2001). "Sodium Amide". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rs041. ISBN 0-471-93623-5.
  10. ^ Campbell, K. N.; Campbell, B. K. (1950). "Phenylacetylene". Organic Syntheses. 30: 72{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 4, p. 763.
  11. ^ Jones, E. R. H.; Eglinton, G.; Whiting, M. C.; Shaw, B. L. (1954). "Ethoxyacetylene". Organic Syntheses. 34: 46{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 4, p. 404.
    Bou, A.; Pericàs, M. A.; Riera, A.; Serratosa, F. (1987). "Dialkoxyacetylenes: di-tert-butoxyethyne, a valuable synthetic intermediate". Organic Syntheses. 65: 58{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 8, p. 161.
    Magriotis, P. A.; Brown, J. T. (1995). "Phenylthioacetylene". Organic Syntheses. 72: 252{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 9, p. 656.
    Ashworth, P. J.; Mansfield, G. H.; Whiting, M. C. (1955). "2-Butyn-1-ol". Organic Syntheses. 35: 20{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 4, p. 128.
  12. ^ Newman, M. S.; Stalick, W. M. (1977). "1-Ethoxy-1-butyne". Organic Syntheses. 57: 65{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 564.
  13. ^ Salaun, J. R.; Champion, J.; Conia, J. M. (1977). "Cyclobutanone from methylenecyclopropane via oxaspiropentane". Organic Syntheses. 57: 36{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 320.
  14. ^ Nakamura, M.; Wang, X. Q.; Isaka, M.; Yamago, S.; Nakamura, E. (2003). "Synthesis and (3+2)-cycloaddition of a 2,2-dialkoxy-1-methylenecyclopropane: 6,6-dimethyl-1-methylene-4,8-dioxaspiro(2.5)octane and cis-5-(5,5-dimethyl-1,3-dioxan-2-ylidene)hexahydro-1(2H)-pentalen-2-one". Organic Syntheses. 80: 144{{cite journal}}: CS1 maint: multiple names: authors list (link).
  15. ^ Bottini, A. T.; Olsen, R. E. (1964). "N-Ethylallenimine". Organic Syntheses. 44: 53{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 541.
  16. ^ Skorcz, J. A.; Kaminski, F. E. (1968). "1-Cyanobenzocyclobutene". Organic Syntheses. 48: 55{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 263.
  17. ^ Saunders, J. H. (1949). "1-Ethynylcyclohexanol". Organic Syntheses. 29: 47; Collected Volumes, vol. 3, p. 416.
    Peterson, P. E.; Dunham, M. (1977). "(Z)-4-Chloro-4-hexenyl trifluoroacetate". Organic Syntheses. 57: 26{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 273.
    Kauer, J. C.; Brown, M. (1962). "Tetrolic acid". Organic Syntheses. 42: 97{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 1043.
  18. ^ Coffman, D. D. (1940). "Dimethylethynylcarbinol". Organic Syntheses. 20: 40; Collected Volumes, vol. 3, p. 320.Hauser, C. R.; Adams, J. T.; Levine, R. (1948). "Diisovalerylmethane". Organic Syntheses. 28: 44{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 3, p. 291.
  19. ^ Vanderwerf, C. A.; Lemmerman, L. V. (1948). "2-Allylcyclohexanone". Organic Syntheses. 28: 8{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 3, p. 44.
  20. ^ Hauser, C. R.; Dunnavant, W. R. (1960). "α,β-Diphenylpropionic acid". Organic Syntheses. 40: 38{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 526.
    Kaiser, E. M.; Kenyon, W. G.; Hauser, C. R. (1967). "Ethyl 2,4-diphenylbutanoate". Organic Syntheses. 47: 72{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 559.
    Wawzonek, S.; Smolin, E. M. (1951). "α,β-Diphenylcinnamonitrile". Organic Syntheses. 31: 52{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 4, p. 387.
  21. ^ Murphy, W. S.; Hamrick, P. J.; Hauser, C. R. (1968). "1,1-Diphenylpentane". Organic Syntheses. 48: 80{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 523.
  22. ^ Hampton, K. G.; Harris, T. M.; Hauser, C. R. (1971). "Phenylation of diphenyliodonium chloride: 1-phenyl-2,4-pentanedione". Organic Syntheses. 51: 128{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 928.
    Hampton, K. G.; Harris, T. M.; Hauser, C. R. (1967). "2,4-Nonanedione". Organic Syntheses. 47: 92{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 848.
  23. ^ Potts, K. T.; Saxton, J. E. (1960). "1-Methylindole". Organic Syntheses. 40: 68{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 769.
  24. ^ Bunnett, J. F.; Brotherton, T. K.; Williamson, S. M. (1960). "N-β-Naphthylpiperidine". Organic Syntheses. 40: 74{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 5, p. 816.
  25. ^ Brazen, W. R.; Hauser, C. R. (1954). "2-Methylbenzyldimethylamine". Organic Syntheses. 34: 61{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 4, p. 585.
  26. ^ Allen, C. F. H.; VanAllan, J. (1944). "Phenylmethylglycidic ester". Organic Syntheses. 24: 82{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 3, p. 727.
  27. ^ Allen, C. F. H.; VanAllan, J. (1942). "2-Methylindole". Organic Syntheses. 22: 94{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 3, p. 597.
  28. ^ Clark, Donald E (2001). "Peroxides and peroxide-forming compounds". Chemical Health and Safety. 8 (5): 12–22. doi:10.1016/S1074-9098(01)00247-7. ISSN 1074-9098.
  29. ^ "Sodium amide SOP". Princeton.
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