氨基钠

氨基钠是一种无机化合物，化学式为。室温下纯品为白色固体，试剂常带金属铁而呈灰色。氨基钠与水强烈反应，是有机合成中常用的强碱。

 制备及结构 

氨基钠可由钠与氨气反应，Bergstrom, F. W. (1955). "Sodium amide ". Org. Synth. Coll. Vol. 3:778. 或硝酸铁催化下钠与液氨的反应来制备。后者反应在氨沸点（约-33°C）时反应最快，也更常用：Greenlee, K. W.; Henne, A. L. (1946). "Sodium Amide". Inorganic Syntheses 2:128–35.

 2 Na  +  2 NH3  →  2 NaNH2  +  H2

NaNH2为类盐固体，晶格中Zalkin, A.; Templeton, D. H. "The Crystal Structure Of Sodium Amide" Journal of Physical Chemistry 1956, Volume  60, pp 821 - 823. DOI: 10.1021/j150540a042 钠原子为四面体结构。Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN 0-19-855370-6. 溶于氨时，NaNH2溶液存在Na(NH3)6+和NH2−离子，可导电。

 用途 

工业上，氨基钠是制取靛蓝染料、肼和氰化钠等工业品的原料。Merck Index (12th Edn.) 可用于干燥液氨或氨气，其液氨溶液也是有机化学中常用的强碱。氨基钠碱性很强而且亲核性很弱，但不易溶于大多数溶剂中，因而已被氢化钠、双(三甲硅基)氨基钠（NaHMDS）以及二异丙基氨基锂（LDA）等类似试剂所取代。

 制备炔烃 

氨基钠可使邻二溴代烷失去两分子溴化氢，生成炔烃。如下图制备苯乙炔的反应所示：Campbell, Kenneth N.; Campbell, Barbara K. (1950). "Phenylacetylene ". Org. Synth. 30:72; Coll. Vol. 4:763.

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也可使分子脱去氯化氢和/或乙醇，Jones, E. R. H.; Eglinton, Geoffrey; Whiting, M. C.; Shaw, B. L. (1954). "Ethoxyacetylene ". Org. Synth. 34:46; Coll. Vol. 4:404.
Bou, Anna; Pericàs, Miquel A.; Riera, Antoni; Serratosa, Fèlix (1987). "Dialkoxyacetylenes: di-tert-butoxyethyne, a valuable synthetic intermediate ". Org. Synth. 65:68; Coll. Vol. 8:161.
Magriotis, Plato A.; Brown, John T. (1995). "Phenylthioacetylene ". Org. Synth. 72:252; Coll. Vol. 9:656.
Ashworth, P. J.; Mansfield, G. H.; Whiting, M. C. (1955). "2-Butyn-1-ol ". Org. Synth. 35:20; Coll. Vol. 4:128. 如下图中制备1-乙氧基-1-丁炔的反应：Newman, Melvin S.; Stalick, W. M. (1977). "1-Ethoxy-1-butyne ". Org. Synth. 57:65; 6:564.

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 成环反应 

无β-氢可消除时，则可发生成环反应，见下面合成亚甲基环丙烷的反应：Salaun, J. R.; Champion, J.; Conia, J. M. (1977). "Cyclobutanone from methylenecyclopropane via oxaspiropentane ". Org. Synth. 57:36; Coll. Vol. 6:320.

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环丙烯、Nakamura, Masuharu; Wang, Xio Qun; Isaka, Masahiko; Yamago, Shigeru; Nakamura, Eiichi (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 ". Org. Synth. 80:144. 吖丙啶Bottini, Albert T.; Olsen, Robert E. (1964). "N-Ethylallenimine ". Org. Synth. 44:53; Coll. Vol. 5:541.
和环丁烷Skorcz, J. A.; Kaminski, F. E. (1968). "1-Cyanobenzocyclobutene ". Org. Synth. 48:55; Coll. Vol. 5:263. 环系都可通过此法制取。

 去质子化 

氢碳酸，包括末端炔烃、Saunders, J. H. (1949). "1-Ethynylcyclohexanol ". Org. Synth. 29:47; Coll. Vol. 3:416.
Peterson, P. E.; Dunham, M. (1977). "(Z)-4-Chloro-4-hexenyl trifluoroacetate ". Org. Synth. 57:26; Coll. Vol. 6:273.
Kauer, J. C.; Brown, M. (1962). "Tetrolic acid ". Org. Synth. 42:97; Coll. Vol. 5:1043.
甲基酮、Coffman, Donald D. (1940). "Dimethylethynylcarbinol ". Org. Synth. 20:40; Coll. Vol. 3:320.
Hauser, C. R.; Adams, J. T.; Levine, R. (1948). "Diisovalerylmethane ". Org. Synth. 28:44; Coll. Vol. 3:291.
环己酮、Vanderwerf, Calvin A.; Lemmerman, Leo V. (1948). "2-Allylcyclohexanone ". Org. Synth. 28:8; Coll. Vol. 3:44.
苯乙酸及衍生物Hauser, Charles R.; Dunnavant, W. R. (1960). "α,β-Diphenylpropionic acid ". Org. Synth. 40:38; Coll. Vol. 5:526.
Kaiser, Edwin M.; Kenyon, William G.; Hauser, Charles R. (1967). "Ethyl 2,4-diphenylbutanoate ". Org. Synth. 47:72; Coll. Vol. 5:559.
Wawzonek, Stanley; Smolin, Edwin M. (1951). "α,β-Diphenylcinnamonitrile ". Org. Synth. 31:52; Coll. Vol. 4:387.
和二苯甲烷Murphy, William S.; Hamrick, Phillip J.; Hauser, Charles R. (1968). "1,1-Diphenylpentane ". Org. Synth. 48:80; Coll. Vol. 5:523. 等，都可被液氨中的氨基钠脱去质子。用两分子胺基钠时，乙酰丙酮失去两个质子生成双负离子：Hampton, K. Gerald; Harris, Thomas M.; Hauser, Charles R. (1971). "Phenylation of diphenyliodonium chloride: 1-phenyl-2,4-pentanedione ". Org. Synth. 51:128; Coll. Vol. 6:928.
Hampton, K. Gerald; Harris, Thomas M.; Hauser, Charles R. (1967).

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吲哚Potts, K. T.; Saxton, J. E. (1960). "1-Methylindole ". Org. Synth. 40:68; Coll. Vol. 5:769. 和哌啶Bunnett, J. F.; Brotherton, T. K.; Williamson, S. M. (1960). "N-β-Naphthylpiperidine ". Org. Synth. 40:74; Coll. Vol. 5:816. 也可发生类似反应。

 其他反应 

 邻位去质子化重排Brazen, W. R.; Hauser, C. R. (1954). "2-Methylbenzyldimethylamine ". Org. Synth. 34:61; Coll. Vol. 4:585.
 达参反应（Darzen反应）合成氧杂环丙烷环系Allen, C. F. H.; VanAllen, J. (1944). "Phenylmethylglycidic ester ". Org. Synth. 24:82; Coll. Vol. 3:727.

 合成吲哚Allen, C. F. H.; VanAllen, James (1942). "2-Methylindole ". Org. Synth. 22:94; Coll. Vol. 3:597.
 齐齐巴宾反应（Chichibabin反应），吡啶氨化合成2-氨基吡啶

 安全 

氨基钠会与水猛烈反应生成氢氧化钠和氨，且在空气中可燃烧生成钠氧化物及二氧化氮：

 NaNH2 + H2O → NH3 + NaOH
 2NaNH2 + 4O2 → Na2O2 + 2NO2 + 2H2O

氨基钠应当储存在密闭容器中，最好以氮气保护。当放置于密闭性不好的容器中时，氧气和水不充足，有可能生成爆炸性的氧化产物从而使固体泛黄棕色。此类试剂应当尽快销毁，方法为向氨基钠的烃类溶剂悬浮液中小心加入乙醇。

氨基钠可能会对皮肤、眼部及黏膜有強腐蚀性，应当留心空气中悬浮的氨基钠粉末。

 参见 
 氨基锂
 氨基鉀
 氨基銣
 氨基銫
 双(三甲基硅基)氨基钠

 参考文献 

 外部链接 
 氨基钠的反应 —Organic Syntheses

Category:钠化合物
Category:氨基化物