氨三乙腈

氨三乙腈
	IUPAC名; 2,2′,2′′-Nitrilotriacetonitrile
别名	三(氰甲基)胺; 2,2',2''-氮川三乙腈
识别
CAS号	7327-60-8
PubChem	81762
ChemSpider	73778
SMILES	C(C#N)N(CC#N)CC#N;
InChI	1S/C6H6N4/c7-1-4-10(5-2-8)6-3-9/h4-6H2;
InChIKey	LJAIDEYQVIJERM-UHFFFAOYSA-N
性质
化学式	C6H6N4
摩尔质量	134.14 g·mol−1
熔点	125 °C（398 K）
结构
空间群	Pnma
晶格常数	a = 7.1085, b = 9.9320, c = 9.3869
危险性
	GHS危险性符号;
GHS提示词	危险
H-术语	H301, H302, H312, H315, H319, H335, H373
P-术语	P260, P261, P264, P270, P271, P280, P301+310, P301+312, P302+352, P304+340, P305+351+338, P312, P314, P321
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

氨三乙腈（NTAN）是一种有机化合物，化学式为C₆H₆N₄，它是氨三乙酸、三(氨乙基)胺（英语：Tris(2-aminoethyl)amine）和胺乙基哌嗪的前驱体。

合成

氨三乙腈可由甲醛、氨和氰化氢在酸性水溶液中通过氨的氰甲基化反应得到。^[2]^[3]

氨气进入反应体系，以六亚甲基四胺^[4]或硫酸铵的形式和甲醛水溶液（通常为37wt%）在pH<2的调节下与氰化氢在100 °C反应得到。^[5]在生产过程中，尤其是连续反应的情况下，低于90 °C时，氨三乙腈会沉淀出来，堵塞反应器管路，导致热失控。 ^[6]

应用

在碱性催化剂（如甲醇钠）存在下，氨三乙腈可与亚氨基二乙腈在熔体中均聚或共聚，形成深色的固体聚合物，它在1000°C以上可碳化形成含氮导电聚合物。^[7]

氨三乙腈在氢化时，其中一个氰基会转化为亚氨基，相比于亚氨基的进一步氢化，它倾向于进攻另一个相邻的氰基以形成稳定的六元环。催化氢化的最终产物是胺乙基哌嗪。

在雷尼镍等催化剂存在下、氨过量时进行氢化，氨三乙腈会转化为三(氨乙基)胺（英语：Tris(2-aminoethyl)amine）^[8]。

三(氨乙基)胺（tren）的合成。

得到的这种化合物（简写tren）可用作四齿配体和过渡金属离子形成稳定的螯合物。^[9]

氨三乙腈和甲醛在pH 9.5下反应，得到2,2-二羟甲基氨三乙腈，它在氢氧化钠溶液中于100 °C水解，得到2,2-二羟甲基氨三乙酸三钠，酸化后得到2,2-二羟甲基氨三乙酸。^[10]

该化合物可作为重金属离子或碱土金属离子的络合剂，如作为漂白剂（过硼酸钠等）的稳定剂和作为洗涤助洗剂，用于抑制纺织品在洗涤过程中产生水垢。

氨三乙腈在硫酸中水解，可以定量产生氨三乙酰胺，它可用作金属配位的中性四齿配体。^[11]升高温度，通过闭环反应可以得到3,5-二氧代哌嗪-1-乙酰胺，中和后在过量氨水中加热，也可以定量转化为氨三乙酰胺。^[12]^[13]

氨三乙腈在酸性或碱性条件下水解，可以得到氨三乙酸及其钠盐。^[14]^[2]反应中可能产生的CN⁻可以通过氧化后处理（如在pH 8下使用次氯酸钠氧化）去除。^[15]

Alkaline hydrolysis of NTAN to NTA trisodium salt

它和盐酸羟胺、氢氧化钠在乙醇水溶液中反应，可以得到四齿配体氮三乙酰胺肟，它可以螯合Cu²⁺。^[16]

参考文献

^ Dubsky, J. V.; Wensink, W. D. Direct nitration of aliphatic imino compounds. II. Action of absolute nitric acid on 3,5-diketo-1-acetamidohexahydro-1,4-diazine. Berichte der Deutschen Chemischen Gesellschaft. 1916, 49: 1041–1044. ISSN 0365-9496. CODEN BDCGAS
^ ^2.0 ^2.1 US 3337607,J.C. Wollensak,“Process for preparation of an amine nitrile”,发表于1967-08-22
^ US 3840581,H. Neumaier, W. Vogt, K. Sennewald, R. Schuller, G. Lenz,“Process for the manufacture of nitrilotriacetonitrile”,发表于1974-10-08
^ US 3061628,J.J. Singer Jr., M. Weisberg,“Process and preparation of amino nitriles and acetic acids”,发表于1962-10-30
^ EP 0102343,C.Y. Shen,“Process for producing nitrilotriacetonitrile”,发表于1986-02-26
^ E. Fiedler, Emergency Runaway Reaction – What Precedes? What Follows?, Chem. Engineer. Transactions (CET) 48, 2016, 48: 361–366, ISBN 978-88-95608-39-6, doi:10.3303/CET1648061
^ US 3578643,L.L. Wood, R.A. Hamilton,“New polymers from nitrilotriacetonitrile and iminodiacetonitrile”,发表于1971-05-11
^ US 3565957,S.B. Mirviss, D.J. Martin, E.D. Weil,“Hydrogenation of nitrilotriacetonitrile”,发表于1971-02-23
^ G. Anderegg; V. Gramlich, 1:1 Metal Complexes of Bivalent Cobalt, Nickel, Copper, Zink, and Cadmium with the Tripodal Ligand tris[2-(dimethylamino)ethyl]amine: Their stabilities and the X-ray crystal structure of its copper(II) complex sulfate, Helv. Chim. Acta 77 (3), 1994, 77 (3): 685–690, doi:10.1002/hlca.19940770312
^ EP 0396999,A. Oftring, S. Birnbach, R. Bauer, C. Gousetis, W. Trieselt,“2-Methyl- und 2-Hydroxymethyl-serin-N,N-diessigsäure und ihre Derivate”,发表于1990-11-14
^ D.A. Smith; S. Sucheck; S. Cramer; D. Baker, Nitrilotriacetamide: Synthesis in concentrated sulfuric acid and stability in water, Synth. Commun. 25 (24), 1995, 25 (24): 4123–4132, doi:10.1080/00397919508011491
^ GB 1170399,“A process for preparing 3,5-dioxo-1-piperazineacetamide and nitrilotriacetic acid triamide”,发表于1969-11-12
^ D.A. Smith; S. Cramer; S. Sucheck; E. Skrzypzak-Jankun, Facile synthesis of substituted nitrilotriacetamides, Tetrahedron Lett. 33 (50), 1992, 33 (50): 7765–7768, doi:10.1016/0040-4039(93)88040-P
^ US 4547589,C.Y. Shen,“Hydrolysis of nitrilotriacetonitrile”,发表于1985-10-15
^ US 8362298,O.M. Falana, A. Hikem, S.R. Kakadjian, F. Zamora,“Hydrolyzed nitrilotriacetonitrile compositions, nitrilotriacetonitrile hydrolysis formulations and methods for making and using same”,发表于2013-01-29
^ Pearse, George A.; Raithby, Paul R.; Maughan, Maria M.J. Synthesis and x-ray crystal structure of 2,2′,2″-iminotris(acetamidoxime) copper(II) sulphate monohydrate, [CuN(CH₂CNH₂:NOH)₃(SO₄)]·H₂O. Polyhedron. 1994-01, 13 (4): 553–558 [2022-08-02]. ISSN 0277-5387. doi:10.1016/S0277-5387(00)84731-2. （原始内容存档于2018-06-26）.

[1] Dubsky, J. V.; Wensink, W. D. Direct nitration of aliphatic imino compounds. II. Action of absolute nitric acid on 3,5-diketo-1-acetamidohexahydro-1,4-diazine. Berichte der Deutschen Chemischen Gesellschaft. 1916, 49: 1041–1044. ISSN 0365-9496. CODEN BDCGAS

[Ethyl-2] 2.0 ^2.1 US 3337607,J.C. Wollensak,“Process for preparation of an amine nitrile”,发表于1967-08-22

[Knapsack-3] US 3840581,H. Neumaier, W. Vogt, K. Sennewald, R. Schuller, G. Lenz,“Process for the manufacture of nitrilotriacetonitrile”,发表于1974-10-08

[4] US 3061628,J.J. Singer Jr., M. Weisberg,“Process and preparation of amino nitriles and acetic acids”,发表于1962-10-30

[5] EP 0102343,C.Y. Shen,“Process for producing nitrilotriacetonitrile”,发表于1986-02-26

[6] E. Fiedler, Emergency Runaway Reaction – What Precedes? What Follows?, Chem. Engineer. Transactions (CET) 48, 2016, 48: 361–366, ISBN 978-88-95608-39-6, doi:10.3303/CET1648061

[7] US 3578643,L.L. Wood, R.A. Hamilton,“New polymers from nitrilotriacetonitrile and iminodiacetonitrile”,发表于1971-05-11

[8] US 3565957,S.B. Mirviss, D.J. Martin, E.D. Weil,“Hydrogenation of nitrilotriacetonitrile”,发表于1971-02-23

[9] G. Anderegg; V. Gramlich, 1:1 Metal Complexes of Bivalent Cobalt, Nickel, Copper, Zink, and Cadmium with the Tripodal Ligand tris[2-(dimethylamino)ethyl]amine: Their stabilities and the X-ray crystal structure of its copper(II) complex sulfate, Helv. Chim. Acta 77 (3), 1994, 77 (3): 685–690, doi:10.1002/hlca.19940770312

[10] EP 0396999,A. Oftring, S. Birnbach, R. Bauer, C. Gousetis, W. Trieselt,“2-Methyl- und 2-Hydroxymethyl-serin-N,N-diessigsäure und ihre Derivate”,发表于1990-11-14

[11] D.A. Smith; S. Sucheck; S. Cramer; D. Baker, Nitrilotriacetamide: Synthesis in concentrated sulfuric acid and stability in water, Synth. Commun. 25 (24), 1995, 25 (24): 4123–4132, doi:10.1080/00397919508011491

[12] GB 1170399,“A process for preparing 3,5-dioxo-1-piperazineacetamide and nitrilotriacetic acid triamide”,发表于1969-11-12

[13] D.A. Smith; S. Cramer; S. Sucheck; E. Skrzypzak-Jankun, Facile synthesis of substituted nitrilotriacetamides, Tetrahedron Lett. 33 (50), 1992, 33 (50): 7765–7768, doi:10.1016/0040-4039(93)88040-P

[14] US 4547589,C.Y. Shen,“Hydrolysis of nitrilotriacetonitrile”,发表于1985-10-15

[Falana-15] US 8362298,O.M. Falana, A. Hikem, S.R. Kakadjian, F. Zamora,“Hydrolyzed nitrilotriacetonitrile compositions, nitrilotriacetonitrile hydrolysis formulations and methods for making and using same”,发表于2013-01-29

[16] Pearse, George A.; Raithby, Paul R.; Maughan, Maria M.J. Synthesis and x-ray crystal structure of 2,2′,2″-iminotris(acetamidoxime) copper(II) sulphate monohydrate, [CuN(CH₂CNH₂:NOH)₃(SO₄)]·H₂O. Polyhedron. 1994-01, 13 (4): 553–558 [2022-08-02]. ISSN 0277-5387. doi:10.1016/S0277-5387(00)84731-2. （原始内容存档于2018-06-26）.

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