腈钠

腈钠是指腈类化合物和钠离子形成的盐，这类盐被认为是反应中存在的中间体。腈钠可由腈和氨基钠、取代氨基钠或金属钠反应得到。但由于腈钠的高度不稳定性，其固体的分离特别困难。^[1]

乙腈钠

乙腈钠（NaCH₂CN，M_r＝63.0）被认为是一种白色固体，可由乙腈和NaN(SiMe₃)₂反应得到：^[2]

CH₃CN + 3 NaN(SiMe₃)₂ —^乙醚→ NaCH₂CN + HN(SiMe₃)₂ + 2 NaN(SiMe₃)₂

该反应中，乙腈只有1个氢原子被钠取代。

由于乙腈的α-H具有一定的酸性，因此与氨基钠在液氨中反应，生成了一种被认为是NaCH₂CN·xNH₃或(CH₂CN)^-Na⁺·xNH₃的产物。但当这种化合物在液氨中结晶时，产生的却是CH₃C(=NH)NHNa（脒的钠盐）。^[3]

乙腈钠可以和卤代烃反应：

NaCH₂CN + RX → NaX + RCH₂CN

苯乙腈钠

苯乙腈钠（C₁₆H₁₃N₂Na，M_r＝256.3）可由苯乙腈和金属钠直接反应得到，其产物为二聚体的钠盐：^[1]

3 C₆H₅CH₂CN + 2 Na → NaCN + C₆H₅CH₃ + C₁₆H₁₃N₂Na

Fred等认为苯乙腈钠的结构应该是(C₆H₅)HC=C=N-Na（M_r＝139.1）^[4]：

2 (C₆H₅)H-C=C=N-H + 2 Na → 2 (C₆H₅)H-C=C=N-Na

(C₆H₅)H-C=C=N-Na + H₂ → C₆H₅CH₃ + NaCN （副反应）

其化学性质活泼，高温下发生分解反应，产生二苯乙烯和氰化钠

2 (C₆H₅)H-C=C=N-Na → NaCN + (C₆H₅)H-C=C-H(C₆H₅)

它和空气中的氧气反应，得到苯甲酸和氰化钠：

2 (C₆H₅)H-C=C=N-Na + O₂ → C₆H₅COOH + NaCN

它和硝酸银在无水乙醇中反应，得到相应的银盐。

腈的其它金属盐

乙腈和叔丁基锂反应，可以得到Li₂CHCN。^[2]

苯乙腈和钾的反应可以得到相应的钾盐，反应按如下方程式发生：^[5]

2 C₆H₅CH₂CN + 2 K → 2 C₆H₅HC=C=NK + H₂

产物C₆H₅HC=C=NK对水蒸气和二氧化碳敏感，酸会将其分解，放出氰化氢。它和(C₆H₅)(CN)HCK有着互变异构，虽然该异构体不占主导，但能够和碘乙烷反应，产生该异构体的取代物：

(C₆H₅)(CN)HCK + C₂H₅I → (C₆H₅)(CN)HC(C₂H₅) + KI

腈的镁、铜^[6]、锌盐^[7]也被制得，它们和钠盐一样，都是很强的亲核试剂。这些腈的金属盐中碳氮键的三键性质之外，通过X射线分析，还有部分碳碳双键的性质。^[8]

参考文献

^ ^1.0 ^1.1 Mary M. Rising, Tsoh-Wu Zee. SODIUM SALTS OF AROMATIC NITRILES. I. J. Am. Chem. Soc., 1928, 50 (6), pp 1699–1707. DOI: 10.1021/ja01393a028
^ ^2.0 ^2.1 Robert West, Gerald A. Gornowicz. Polylithium compounds. IV. Polylithiation of nitriles and the preparations of trisilyl ynamines. J. Am. Chem. Soc., 1971, 93 (7), pp 1714–1720. DOI: 10.1021/ja00736a025
^ F. W. Bergstrom, Robert Agostinho. The Alkylation and Arylation of Aliphatic Nitriles in Liquid Ammonia. J. Am. Chem. Soc., 1945, 67 (12), pp 2152–2154. DOI: 10.1021/ja01228a025
^ Fred W. Upson, Robert T. Maxwell, Howard M. Parmelee. STRUCTURE OF THE SALTS OF AROMATIC NITRILES. J. Am. Chem. Soc., 1930, 52 (5), pp 1971–1975. DOI: 10.1021/ja01368a031
^ Mary M. Rising, Irving E. Muskat, Edmund W. Lowe. SALTS OF AROMATIC NITRILES. II. POTASSIUM PHENYLACETONITRILE. J. Am. Chem. Soc., 1929, 51 (1), pp 262–265. DOI: 10.1021/ja01376a033
^ Matthew Purzycki, Wang Liu, Göran Hilmersson, et al. Metalated nitriles: N- and C-coordination preferences of Li, Mg, and Cu cations. Chem. Commun., 2013,49, 4700-4702. DOI: 10.1039/C3CC41703D
^ Xun Yang, Dinesh Nath, and Fraser F. Fleming. Chemoselective Alkylations with N- and C-Metalated Nitriles. Org. Lett., 2015, 17 (19), pp 4906–4909 DOI: 10.1021/acs.orglett.5b02481
^ Fraser F. Fleming , Zhiyu Zhang , Wang Liu, et al. Metalated Nitriles: Organolithium, -magnesium, and -copper Exchange of α-Halonitriles. J. Org. Chem., 2005, 70 (6), pp 2200–2205. DOI: 10.1021/jo047877r

[Rising-1] 1.0 ^1.1 Mary M. Rising, Tsoh-Wu Zee. SODIUM SALTS OF AROMATIC NITRILES. I. J. Am. Chem. Soc., 1928, 50 (6), pp 1699–1707. DOI: 10.1021/ja01393a028

[West-2] 2.0 ^2.1 Robert West, Gerald A. Gornowicz. Polylithium compounds. IV. Polylithiation of nitriles and the preparations of trisilyl ynamines. J. Am. Chem. Soc., 1971, 93 (7), pp 1714–1720. DOI: 10.1021/ja00736a025

[Berg-3] F. W. Bergstrom, Robert Agostinho. The Alkylation and Arylation of Aliphatic Nitriles in Liquid Ammonia. J. Am. Chem. Soc., 1945, 67 (12), pp 2152–2154. DOI: 10.1021/ja01228a025

[4] Fred W. Upson, Robert T. Maxwell, Howard M. Parmelee. STRUCTURE OF THE SALTS OF AROMATIC NITRILES. J. Am. Chem. Soc., 1930, 52 (5), pp 1971–1975. DOI: 10.1021/ja01368a031

[5] Mary M. Rising, Irving E. Muskat, Edmund W. Lowe. SALTS OF AROMATIC NITRILES. II. POTASSIUM PHENYLACETONITRILE. J. Am. Chem. Soc., 1929, 51 (1), pp 262–265. DOI: 10.1021/ja01376a033

[6] Matthew Purzycki, Wang Liu, Göran Hilmersson, et al. Metalated nitriles: N- and C-coordination preferences of Li, Mg, and Cu cations. Chem. Commun., 2013,49, 4700-4702. DOI: 10.1039/C3CC41703D

[7] Xun Yang, Dinesh Nath, and Fraser F. Fleming. Chemoselective Alkylations with N- and C-Metalated Nitriles. Org. Lett., 2015, 17 (19), pp 4906–4909 DOI: 10.1021/acs.orglett.5b02481

[8] Fraser F. Fleming , Zhiyu Zhang , Wang Liu, et al. Metalated Nitriles: Organolithium, -magnesium, and -copper Exchange of α-Halonitriles. J. Org. Chem., 2005, 70 (6), pp 2200–2205. DOI: 10.1021/jo047877r

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