亚硝基：修订间差异

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2022年11月28日 (一) 16:13的版本

在有机化学中，亚硝基是指一种由一氧化氮（–N=O ) 基团连接到有机基团而成的官能团。亚硝基化合物可归类为C-亚硝基化合物（例如，亚硝基烷烃；R–N=O ), S -亚硝基化合物 ( nitrosothiols ;RS–N=O ）， N-亚硝基化合物（例如，亚硝胺，RN(–R’)–N=O )和O-亚硝基化合物（亚硝酸烷基酯；RO–N=O ）。

合成

亚硝基化合物可以通过还原硝基化合物^[1]或通过氧化羟胺来制备。 ^[2]邻亚硝基苯酚可通过鲍迪施反应产生。在费歇尔-赫普重排反应中，芳香族 4-亚硝基苯胺由相应的亚硝胺制备。

特性

亚硝基芳烃通常参与单体-二聚体平衡。在固态下通常呈淡黄色的二聚体更常见，而深绿色单体在稀溶液或较高温度下更占优。它们以顺式和反式异构体存在。 ^[4]

由于氮氧自由基的稳定性，亚硝基有机化合物往往具有非常低的 C-N键解离能：亚硝基烷烃的 BDE 约为30—40 kcal/mol（130—170 kJ/mol），而亚硝基芳烃的 BDE 约为50—60 kcal/mol（210—250 kJ/mol）。因此，它们通常对热和光敏感。含有 O-(NO) 或 N-(NO) 键的化合物通常具有更低的键离解能。例如， N-亚硝基二苯胺 Ph₂N–N=O，其 N–N 键解离能仅为23 kcal/mol（96 kJ/mol）。 ^[5]有机亚硝基化合物作为过渡金属的配体。 ^[6]

反应

存在许多利用中间体亚硝基化合物的反应，如Barton反应和Davis-Beirut反应，以及在吲哚的合成中，如： Baeyer-Emmerling吲哚合成， Bartoli吲哚合成。在萨维尔反应中，汞被用来取代硫醇基团中的亚硝酰基。

亚硝化与亚硝基化

亚硝酸盐可以进入两种反应，这取决于物理化学环境。

亚硝基化是添加一个亚硝酰离子NO−
对金属（例如铁）或硫醇，导致亚硝酰铁Fe–NO （例如，在亚硝基化血红素中 = 亚硝基血红素）或S -亚硝基硫醇 (RSNO)。
亚硝化是添加一个亚硝鎓离子NO+
到胺 –NH
2导致亚硝胺。这种转化发生在酸性 pH 值下，特别是在胃中，如N-苯基亚硝胺的形成方程式所示：
<math xmlns="http://www.w3.org/1998/Math/MathML"><semantics><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="true" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><msubsup><mtext> ${\ce {NO2- + H+ <=> HONO}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mn> ${\ce {NO2- + H+ <=> HONO}}$ </mn></mrow><mrow class="MJX-TeXAtom-ORD"><mo> ${\ce {NO2- + H+ <=> HONO}}$ </mo></mrow></msubsup><mo> ${\ce {NO2- + H+ <=> HONO}}$ </mo><msup><mtext> ${\ce {NO2- + H+ <=> HONO}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mo> ${\ce {NO2- + H+ <=> HONO}}$ </mo></mrow></msup><mrow class="MJX-TeXAtom-REL"><mover><mrow class="MJX-TeXAtom-OP MJX-fixedlimits"><mrow class="MJX-TeXAtom-ORD"><mpadded depth="0" height="0"><mrow class="MJX-TeXAtom-ORD"><mo stretchy="false"> ${\ce {NO2- + H+ <=> HONO}}$ </mo></mrow><mrow class="MJX-TeXAtom-ORD"><mo> ${\ce {NO2- + H+ <=> HONO}}$ </mo></mrow></mpadded></mrow></mrow><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="false" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><mrow class="MJX-TeXAtom-ORD"><mo> ${\ce {NO2- + H+ <=> HONO}}$ </mo></mrow><mrow class="MJX-TeXAtom-ORD"><mo stretchy="false"> ${\ce {NO2- + H+ <=> HONO}}$ </mo></mrow></mrow></mstyle></mrow></mover></mrow><mtext> ${\ce {NO2- + H+ <=> HONO}}$ </mtext></mrow></mstyle></mrow><annotation encoding="application/x-tex"> </annotation></semantics></math> ${\ce {NO2- + H+ <=> HONO}}$ </img>

<math xmlns="http://www.w3.org/1998/Math/MathML"><semantics><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="true" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><mtext> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mtext><mo> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mo><msup><mtext> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mo> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mo></mrow></msup><mrow class="MJX-TeXAtom-REL"><mover><mrow class="MJX-TeXAtom-OP MJX-fixedlimits"><mrow class="MJX-TeXAtom-ORD"><mpadded depth="0" height="0"><mrow class="MJX-TeXAtom-ORD"><mo stretchy="false"> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mo></mrow><mrow class="MJX-TeXAtom-ORD"><mo> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mo></mrow></mpadded></mrow></mrow><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="false" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><mrow class="MJX-TeXAtom-ORD"><mo> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mo></mrow><mrow class="MJX-TeXAtom-ORD"><mo stretchy="false"> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mo></mrow></mrow></mstyle></mrow></mover></mrow><msubsup><mtext> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mn> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mn></mrow></msubsup><mtext> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mtext><mo> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mo><msup><mtext> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mo> ${\ce {HONO + H+ <=> H2O + NO+}}$ </mo></mrow></msup></mrow></mstyle></mrow><annotation encoding="application/x-tex"> </annotation></semantics></math> ${\ce {HONO + H+ <=> H2O + NO+}}$ </img>

<math xmlns="http://www.w3.org/1998/Math/MathML"><semantics><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="true" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><msubsup><mtext> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mn> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mn></mrow></msubsup><msubsup><mtext> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mn> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mn></mrow></msubsup><msubsup><mtext> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mn> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mn></mrow></msubsup><mo> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mo><msup><mtext> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mo> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mo></mrow></msup><mo stretchy="false"> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mo><msubsup><mtext> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mn> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mn></mrow></msubsup><msubsup><mtext> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mn> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mn></mrow></msubsup><mtext> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mo stretchy="false"> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mo><mtext> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mtext><mo stretchy="false"> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mo></mrow><mtext> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mtext><mo> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mo><msup><mtext> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mtext><mrow class="MJX-TeXAtom-ORD"><mo> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </mo></mrow></msup></mrow></mstyle></mrow><annotation encoding="application/x-tex"> </annotation></semantics></math> ${\ce {C6H5NH2 + NO+ -> C6H5N(H)NO + H+}}$ </img>

许多伯烷基N -亚硝基化合物，例如CH
3N(H)NO ，在水解成醇方面往往不稳定。那些衍生自仲胺（例如，(CH
3)
2NNO衍生自二甲胺）更稳健。正是这些N-亚硝胺是啮齿动物的致癌物。

无机化学中的亚硝基

亚硝酰基是含有 NO 基团的非有机化合物，例如通过 N 原子直接与金属结合，形成金属-NO 部分。或者，非金属的例子是常见的试剂亚硝酰氯（Cl–N=O ）。一氧化氮是一个稳定的自由基，有一个不成对的电子。一氧化氮的还原产生亚硝酰阴离子，NO−
：

{\ce {NO + e- -> NO-}}

</mtext><mo>

{\ce {NO + e- -> NO-}}

</mo><msup><mtext>

{\ce {NO + e- -> NO-}}

</mtext><mrow class="MJX-TeXAtom-ORD"><mo>

{\ce {NO + e- -> NO-}}

</mo></mrow></msup><mo stretchy="false">

{\ce {NO + e- -> NO-}}

</mo><msup><mtext>

{\ce {NO + e- -> NO-}}

</mtext><mrow class="MJX-TeXAtom-ORD"><mo>

{\ce {NO + e- -> NO-}}

</mo></mrow></msup></mrow></mstyle></mrow><annotation encoding="application/x-tex"> </annotation></semantics></math>

{\ce {NO + e- -> NO-}}

</img>

NO 的氧化产生亚硝鎓阳离子，NO+
:

{\ce {NO -> NO+ + e-}}

</mtext><mo stretchy="false">

{\ce {NO -> NO+ + e-}}

</mo><msup><mtext>

{\ce {NO -> NO+ + e-}}

</mtext><mrow class="MJX-TeXAtom-ORD"><mo>

{\ce {NO -> NO+ + e-}}

</mo></mrow></msup><mo>

{\ce {NO -> NO+ + e-}}

</mo><msup><mtext>

{\ce {NO -> NO+ + e-}}

</mtext><mrow class="MJX-TeXAtom-ORD"><mo>

{\ce {NO -> NO+ + e-}}

</mo></mrow></msup></mrow></mstyle></mrow><annotation encoding="application/x-tex"> </annotation></semantics></math>

{\ce {NO -> NO+ + e-}}

</img>

一氧化氮可以作为配体形成金属亚硝酰络合物或只是金属亚硝酰。这些配合物可以被视为加合物NO+
,NO−
，或一些中间情况。

在食物中

在食品和胃肠道中，亚硝化和亚硝基化对消费者健康的影响不同。

在腌肉中：经过腌制的肉类含有亚硝酸盐，pH 值约为 5，其中几乎所有亚硝酸盐都以NO−
2 (99%)。腌肉还添加了抗坏血酸钠（或异抗坏血酸或维生素C）。正如 S. Mirvish 所证明的，抗坏血酸盐抑制胺亚硝化为亚硝胺，因为抗坏血酸盐与NO−
2形成 NO。 ^[7] ^[8]抗坏血酸和 pH 值 5 的状况有利于血红素铁的亚硝基化，形成亚硝基血红素，当包含在肌红蛋白中时是红色素，当它通过烹饪释放时是粉红色素。它参与了腌肉的“熏肉味”。据欧洲加工肉类游说团顾问 KO Honikel 称，因此，亚硝基血红素被认为对肉类行业和消费者有益。 ^[9]据加工肉类行业以外的科学家称，亚硝基血红素被认为是一种致癌化合物。 ^[10] ^[11] ^[12]
在胃中：分泌的氯化氢形成酸性环境（pH=2) 和摄入的亚硝酸盐（与食物或唾液一起）会导致胺亚硝化，从而产生亚硝胺（潜在致癌物）。如果胺浓度低（例如，低蛋白饮食，无发酵食品）或维生素 C 浓度高（例如，高水果饮食）。然后形成S -nitrosothiols，在 pH 值下稳定维持在2左右。
在结肠中：中性 pH 值不利于亚硝化。即使在添加仲胺或亚硝酸盐后，粪便中也不会形成亚硝胺。 ^[13]中性 pH 值有利于NO−
从S -亚硝基硫醇中释放，以及铁的亚硝基化。根据 Bingham 和 Kuhnle 的说法，Bingham 团队在吃红肉的志愿者^[14]的粪便中测量的先前称为 NOC（ N-亚硝基化合物）的物质主要是非N-亚硝基 ATNC（表观总亚硝基化合物），例如S -nitrosothiols 和亚硝酰铁（如亚硝酰血红素）。 ^[15]

另见

亚硝胺，NO 连接到胺上的官能团，例如 R₂N–NO
亚硝基苯
一氧化氮
硝酰

参考资料

^ G. H. Coleman; C. M. McCloskey; F. A. Stuart. Nitrosobenzene. Org. Synth. 1945, 25: 80. doi:10.15227/orgsyn.025.0080.
^ "2-Methyl-2-nitrosopropane and Its Dimer". Org. Synth. 52.
^ E.Bosch. Structural Analysis of Methyl-Substituted Nitrosobenzenes and Nitrosoanisoles. J. Chem. Cryst. 2014, 98 (2): 44. S2CID 95291018. doi:10.1007/s10870-013-0489-8.
^ Beaudoin, D.; Wuest, J. D. Dimerization of Aromatic C-Nitroso Compounds. Chemical Reviews. 2016, 116 (1): 258–286. PMID 26730505. doi:10.1021/cr500520s.
^ Luo, Yu-Ran. Comprehensive Handbook of Chemical Bond Energies. Boca Raton, FL: Taylor and Francis. 2007. ISBN 9781420007282.
^ Pilato, R. S.; McGettigan, C.; Geoffroy, G. L.; Rheingold, A. L.; Geib, S. J. tert-Butylnitroso complexes. Structural characterization of W(CO)₅(N(O)Bu-tert) and [CpFe(CO)(PPh₃)(N(O)Bu-tert)]⁺. Organometallics. 1990, 9 (2): 312–17. doi:10.1021/om00116a004.
^ Mirvish, SS; Wallcave, L; Eagen, M; Shubik, P. Ascorbate–nitrite reaction: possible means of blocking the formation of carcinogenic N-nitroso compounds. Science. July 1972, 177 (4043): 65–8. Bibcode:1972Sci...177...65M. PMID 5041776. S2CID 26275960. doi:10.1126/science.177.4043.65.
^ Mirvish, SS. Effects of vitamins C and E on N-nitroso compound formation, carcinogenesis, and cancer. Cancer. October 1986, 58 (8 Suppl): 1842–50. PMID 3756808. S2CID 196379002. doi:10.1002/1097-0142(19861015)58:8+<1842::aid-cncr2820581410>3.0.co;2-#.
^ Honikel, K. O. The use an control of nitrate and nitrite for the processing of meat products. Meat Science. 2008, 78 (1–2): 68–76. PMID 22062097. doi:10.1016/j.meatsci.2007.05.030.
^ Lunn, J.C.; Kuhnle, G.; Mai, V.; Frankenfeld, C.; Shuker, D.E.G.; Glen, R. C.; Goodman, J.M.; Pollock, J.R.A.; Bingham, S.A. The effect of haem in red and processed meat on the endogenous formation of N-nitroso compounds in the upper gastrointestinal tract. Carcinogenesis. 2006, 28 (3): 685–690. PMID 17052997. doi:10.1093/carcin/bgl192.
^ Bastide, Nadia M.; Pierre, Fabrice H.F.; Corpet, Denis E. Heme Iron from Meat and Risk of Colorectal Cancer: A Meta-analysis and a Review of the Mechanisms Involved. Cancer Prevention Research. 2011, 4 (2): 177–184. PMID 21209396. S2CID 4951579. doi:10.1158/1940-6207.CAPR-10-0113.
^ Bastide, Nadia M.; Chenni, Fatima; Audebert, Marc; Santarelli, Raphaelle L.; Taché, Sylviane; Naud, Nathalie; Baradat, Maryse; Jouanin, Isabelle; Surya, Reggie; Hobbs, Ditte A.; Kuhnle, Gunter G. A Central Role for Heme Iron in Colon Carcinogenesis Associated with Red Meat Intake. Cancer Research. 2015, 75 (5): 870–879. PMID 25592152. S2CID 13274953. doi:10.1158/0008-5472.CAN-14-2554.
^ Lee, L; Archer, MC; Bruce, WR. Absence of volatile nitrosamines in human feces. Cancer Res. October 1981, 41 (10): 3992–4. PMID 7285009.
^ Bingham, SA; Pignatelli, B; Pollock, JR; et al. Does increased endogenous formation of N-nitroso compounds in the human colon explain the association between red meat and colon cancer?. Carcinogenesis. March 1996, 17 (3): 515–23. PMID 8631138. doi:10.1093/carcin/17.3.515 .
^ Kuhnle, GG; Story, GW; Reda, T; et al. Diet-induced endogenous formation of nitroso compounds in the GI tract. Free Radic. Biol. Med. October 2007, 43 (7): 1040–7. PMID 17761300. doi:10.1016/j.freeradbiomed.2007.03.011.

[1] G. H. Coleman; C. M. McCloskey; F. A. Stuart. Nitrosobenzene. Org. Synth. 1945, 25: 80. doi:10.15227/orgsyn.025.0080.

[2] "2-Methyl-2-nitrosopropane and Its Dimer". Org. Synth. 52.

[3] E.Bosch. Structural Analysis of Methyl-Substituted Nitrosobenzenes and Nitrosoanisoles. J. Chem. Cryst. 2014, 98 (2): 44. S2CID 95291018. doi:10.1007/s10870-013-0489-8.

[4] Beaudoin, D.; Wuest, J. D. Dimerization of Aromatic C-Nitroso Compounds. Chemical Reviews. 2016, 116 (1): 258–286. PMID 26730505. doi:10.1021/cr500520s.

[5] Luo, Yu-Ran. Comprehensive Handbook of Chemical Bond Energies. Boca Raton, FL: Taylor and Francis. 2007. ISBN 9781420007282.

[6] Pilato, R. S.; McGettigan, C.; Geoffroy, G. L.; Rheingold, A. L.; Geib, S. J. tert-Butylnitroso complexes. Structural characterization of W(CO)₅(N(O)Bu-tert) and [CpFe(CO)(PPh₃)(N(O)Bu-tert)]⁺. Organometallics. 1990, 9 (2): 312–17. doi:10.1021/om00116a004.

[7] Mirvish, SS; Wallcave, L; Eagen, M; Shubik, P. Ascorbate–nitrite reaction: possible means of blocking the formation of carcinogenic N-nitroso compounds. Science. July 1972, 177 (4043): 65–8. Bibcode:1972Sci...177...65M. PMID 5041776. S2CID 26275960. doi:10.1126/science.177.4043.65.

[8] Mirvish, SS. Effects of vitamins C and E on N-nitroso compound formation, carcinogenesis, and cancer. Cancer. October 1986, 58 (8 Suppl): 1842–50. PMID 3756808. S2CID 196379002. doi:10.1002/1097-0142(19861015)58:8+<1842::aid-cncr2820581410>3.0.co;2-#.

[9] Honikel, K. O. The use an control of nitrate and nitrite for the processing of meat products. Meat Science. 2008, 78 (1–2): 68–76. PMID 22062097. doi:10.1016/j.meatsci.2007.05.030.

[10] Lunn, J.C.; Kuhnle, G.; Mai, V.; Frankenfeld, C.; Shuker, D.E.G.; Glen, R. C.; Goodman, J.M.; Pollock, J.R.A.; Bingham, S.A. The effect of haem in red and processed meat on the endogenous formation of N-nitroso compounds in the upper gastrointestinal tract. Carcinogenesis. 2006, 28 (3): 685–690. PMID 17052997. doi:10.1093/carcin/bgl192.

[11] Bastide, Nadia M.; Pierre, Fabrice H.F.; Corpet, Denis E. Heme Iron from Meat and Risk of Colorectal Cancer: A Meta-analysis and a Review of the Mechanisms Involved. Cancer Prevention Research. 2011, 4 (2): 177–184. PMID 21209396. S2CID 4951579. doi:10.1158/1940-6207.CAPR-10-0113.

[12] Bastide, Nadia M.; Chenni, Fatima; Audebert, Marc; Santarelli, Raphaelle L.; Taché, Sylviane; Naud, Nathalie; Baradat, Maryse; Jouanin, Isabelle; Surya, Reggie; Hobbs, Ditte A.; Kuhnle, Gunter G. A Central Role for Heme Iron in Colon Carcinogenesis Associated with Red Meat Intake. Cancer Research. 2015, 75 (5): 870–879. PMID 25592152. S2CID 13274953. doi:10.1158/0008-5472.CAN-14-2554.

[13] Lee, L; Archer, MC; Bruce, WR. Absence of volatile nitrosamines in human feces. Cancer Res. October 1981, 41 (10): 3992–4. PMID 7285009.

[14] Bingham, SA; Pignatelli, B; Pollock, JR; et al. Does increased endogenous formation of N-nitroso compounds in the human colon explain the association between red meat and colon cancer?. Carcinogenesis. March 1996, 17 (3): 515–23. PMID 8631138. doi:10.1093/carcin/17.3.515 .

[15] Kuhnle, GG; Story, GW; Reda, T; et al. Diet-induced endogenous formation of nitroso compounds in the GI tract. Free Radic. Biol. Med. October 2007, 43 (7): 1040–7. PMID 17761300. doi:10.1016/j.freeradbiomed.2007.03.011.

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@@ 第1行： / 第1行： @@
-#REDIRECT [[亚硝基化合物]]
+[[File:Nitroso-compound-2D.svg|right|thumb|亚硝基[[结构式]]]]
+在[[有机化学|有机化学中]][[官能团|，]]'''亚硝基'''是指一种由[[一氧化氮]]（{{Chem2|\sN\dO}} ) 基团连接到有机基团而成的官能团。亚硝基化合物可归类为''C-''亚硝基化合物（例如，亚硝基[[烷烃]]；{{Chem2|R\sN\dO}} ), ''S'' -亚硝基化合物 ( nitrosothiols ;{{Chem2|RS\sN\dO}} ）， ''N-''亚硝基化合物（例如，[[亚硝胺]]，{{Chem2|RN(\sR’)\sN\dO}} )和''O-''亚硝基化合物（[[亚硝酸酯|亚硝酸烷基酯]]；{{Chem2|RO\sN\dO}} ）。
+== 合成 ==
+亚硝基化合物可以通过还原[[硝基化合物]]<ref>{{Cite journal |last=G. H. Coleman |last2=C. M. McCloskey |last3=F. A. Stuart |year=1945 |title=Nitrosobenzene |journal=Org. Synth. |volume=25 |page=80 |doi=10.15227/orgsyn.025.0080}}</ref>或通过氧化[[羟胺]]来制备。 <ref>{{OrgSynth|title=2-Methyl-2-nitrosopropane and Its Dimer|volume=52}}</ref>邻亚硝基苯酚可通过[[鲍迪施反应]]产生。在[[费歇尔-赫普重排反应]]中，芳香族 4-亚硝基苯胺由相应的[[亚硝胺]]制备。
+== 特性 ==
+[[File:VIYMEX.png|right|thumb|140x140px| 2-亚硝基甲苯二聚体的结构<ref>{{Cite journal |last=E.Bosch |year=2014 |title=Structural Analysis of Methyl-Substituted Nitrosobenzenes and Nitrosoanisoles |url=https://www.semanticscholar.org/paper/28b949da39094f54fd27e3289970e027971aef0e |journal=J. Chem. Cryst. |volume=98 |issue=2 |page=44 |doi=10.1007/s10870-013-0489-8 |s2cid=95291018}}</ref>]]
+亚硝基芳烃通常参与[[二聚體|单体-二聚体平衡]]。在固态下通常呈淡黄色的二聚体更常见，而深绿色单体在稀溶液或较高温度下更占优。它们以[[顺反异构|''顺式''和''反式''异构体]]存在。 <ref>{{Cite journal |last=Beaudoin, D. |last2=Wuest, J. D. |year=2016 |title=Dimerization of Aromatic ''C''-Nitroso Compounds |journal=Chemical Reviews |volume=116 |issue=1 |page=258–286 |doi=10.1021/cr500520s |pmid=26730505}}</ref>
+由于氮氧[[自由基]]的稳定性，亚硝基有机化合物往往具有非常低的 C-N[[键离解能|键解离能]]：亚硝基烷烃的 BDE 约为{{Cvt|30|-|40|kcal/mol|kJ/mol|-1}} ，而亚硝基芳烃的 BDE 约为{{Cvt|50|-|60|kcal/mol|kJ/mol|-1}} 。因此，它们通常对热和光敏感。含有 O-(NO) 或 N-(NO) 键的化合物通常具有更低的键离解能。例如， ''N-''亚硝基二苯胺 Ph<sub>2</sub>N–N=O，其 N–N 键解离能仅为{{Cvt|23|kcal/mol|kJ/mol|0}} 。 <ref>{{Cite book|title=Comprehensive Handbook of Chemical Bond Energies|last=Luo|first=Yu-Ran|publisher=Taylor and Francis|year=2007|isbn=9781420007282|location=Boca Raton, FL}}</ref>有机亚硝基化合物作为[[过渡金属]]的[[配體|配体]]。 <ref>{{Cite journal |last=Pilato |first=R. S. |last2=McGettigan |first2=C. |last3=Geoffroy |first3=G. L. |last4=Rheingold |first4=A. L. |last5=Geib |first5=S. J. |date=1990 |title=''tert''-Butylnitroso complexes. Structural characterization of W(CO)<sub>5</sub>(N(O)Bu-''tert'') and [CpFe(CO)(PPh<sub>3</sub>)(N(O)Bu-''tert'')]<sup>+</sup> |journal=Organometallics |volume=9 |issue=2 |page=312–17 |doi=10.1021/om00116a004}}</ref>
+== 反应 ==
+存在许多利用中间体亚硝基化合物的反应，如[[巴顿反应|Barton反应]]和[[戴维斯-贝鲁特反应|Davis-Beirut反应]]，以及在[[吲哚]]的合成中，如： [[拜爾-艾默林吲哚合成|Baeyer-Emmerling吲哚合成]]， [[巴尔托利吲哚合成|Bartoli吲哚合成]]。在[[萨维尔反应]]中，汞被用来取代硫醇基团中的亚硝酰基。
+== 亚硝化与亚硝基化 ==
+[[亚硝酸盐]]可以进入两种反应，这取决于物理化学环境。
+* 亚硝基化是添加一个[[一氧化氮|亚硝酰离子]]{{Chem2|NO-}}对金属（例如铁）或硫醇，导致亚硝酰铁{{Chem2|Fe\sNO}} （例如，在亚硝基化血红素中 = 亚硝基血红素）或''S'' -亚硝基硫醇 (RSNO)。
+* 亚硝化是添加一个[[亚硝𬭩离子|亚硝鎓离子]]{{Chem2|NO+}}到胺 –{{Chem2|NH2}}导致[[亚硝胺]]。这种转化发生在酸性 pH 值下，特别是在胃中，如''N-''苯基亚硝胺的形成方程式所示：
+*: &lt;math xmlns="http://www.w3.org/1998/Math/MathML"&gt;<semantics><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="true" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><msubsup><mtext><chem>NO2- + H+ <=> HONO</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mn><chem>NO2- + H+ <=> HONO</chem></mn></mrow><mrow class="MJX-TeXAtom-ORD"><mo><chem>NO2- + H+ <=> HONO</chem></mo></mrow></msubsup><mo> <chem>NO2- + H+ <=> HONO</chem></mo><msup><mtext> <chem>NO2- + H+ <=> HONO</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mo> <chem>NO2- + H+ <=> HONO</chem> </mo></mrow></msup><mrow class="MJX-TeXAtom-REL"><mover><mrow class="MJX-TeXAtom-OP MJX-fixedlimits"><mrow class="MJX-TeXAtom-ORD"><mpadded depth="0" height="0"><mrow class="MJX-TeXAtom-ORD"><mo stretchy="false"> <chem>NO2- + H+ <=> HONO</chem></mo></mrow><mrow class="MJX-TeXAtom-ORD"><mo> <chem>NO2- + H+ <=> HONO</chem></mo></mrow></mpadded></mrow></mrow><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="false" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><mrow class="MJX-TeXAtom-ORD"><mo> <chem>NO2- + H+ <=> HONO</chem></mo></mrow><mrow class="MJX-TeXAtom-ORD"><mo stretchy="false"> <chem>NO2- + H+ <=> HONO</chem></mo></mrow></mrow></mstyle></mrow></mover></mrow><mtext> <chem>NO2- + H+ <=> HONO</chem></mtext></mrow></mstyle></mrow><annotation encoding="application/x-tex"> </annotation></semantics>&lt;/math&gt;<chem>NO2- + H+ <=> HONO</chem> </img>
+*: &lt;math xmlns="http://www.w3.org/1998/Math/MathML"&gt;<semantics><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="true" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><mtext> <chem>HONO + H+ <=> H2O + NO+</chem></mtext><mo> <chem>HONO + H+ <=> H2O + NO+</chem></mo><msup><mtext> <chem>HONO + H+ <=> H2O + NO+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mo> <chem>HONO + H+ <=> H2O + NO+</chem> </mo></mrow></msup><mrow class="MJX-TeXAtom-REL"><mover><mrow class="MJX-TeXAtom-OP MJX-fixedlimits"><mrow class="MJX-TeXAtom-ORD"><mpadded depth="0" height="0"><mrow class="MJX-TeXAtom-ORD"><mo stretchy="false"> <chem>HONO + H+ <=> H2O + NO+</chem></mo></mrow><mrow class="MJX-TeXAtom-ORD"><mo> <chem>HONO + H+ <=> H2O + NO+</chem></mo></mrow></mpadded></mrow></mrow><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="false" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><mrow class="MJX-TeXAtom-ORD"><mo> <chem>HONO + H+ <=> H2O + NO+</chem></mo></mrow><mrow class="MJX-TeXAtom-ORD"><mo stretchy="false"> <chem>HONO + H+ <=> H2O + NO+</chem></mo></mrow></mrow></mstyle></mrow></mover></mrow><msubsup><mtext> <chem>HONO + H+ <=> H2O + NO+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mn> <chem>HONO + H+ <=> H2O + NO+</chem></mn></mrow></msubsup><mtext><chem>HONO + H+ <=> H2O + NO+</chem></mtext><mo><chem>HONO + H+ <=> H2O + NO+</chem></mo><msup><mtext><chem>HONO + H+ <=> H2O + NO+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mo><chem>HONO + H+ <=> H2O + NO+</chem></mo></mrow></msup></mrow></mstyle></mrow><annotation encoding="application/x-tex"> </annotation></semantics>&lt;/math&gt;<chem>HONO + H+ <=> H2O + NO+</chem> </img>
+*: &lt;math xmlns="http://www.w3.org/1998/Math/MathML"&gt;<semantics><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="true" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><msubsup><mtext> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mn> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mn></mrow></msubsup><msubsup><mtext><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mn> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mn></mrow></msubsup><msubsup><mtext><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mn><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mn></mrow></msubsup><mo><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mo><msup><mtext><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mo><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mo></mrow></msup><mo stretchy="false"> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mo><msubsup><mtext> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mn> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mn></mrow></msubsup><msubsup><mtext><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mn> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mn></mrow></msubsup><mtext><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mo stretchy="false"><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mo><mtext> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mtext><mo stretchy="false"> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mo></mrow><mtext><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mtext><mo><chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mo><msup><mtext> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mo> <chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></mo></mrow></msup></mrow></mstyle></mrow><annotation encoding="application/x-tex"> </annotation></semantics>&lt;/math&gt;<chem>C6H5NH2 + NO+ -> C6H5N(H)NO + H+</chem></img>
+许多伯烷基''N'' -亚硝基化合物，例如{{Chem2|CH3N(H)NO}} ，在水解成醇方面往往不稳定。那些衍生自[[仲胺]]（例如，{{Chem2|(CH3)2NNO}}衍生自[[二甲胺]]）更稳健。正是这些''N-''亚硝胺是啮齿动物的致癌物。
+== 无机化学中的亚硝基 ==
+[[File:Metal-nitrosyl-coordination-modes-2D.png|right|thumb|100x100px|线性和弯曲的金属亚硝基]]
+亚硝酰基是含有 NO 基团的非有机化合物，例如通过 N 原子直接与金属结合，形成金属-NO 部分。或者，[[非金属元素|非金属]]的例子是常见的试剂[[亚硝酰氯]]（{{Chem2|Cl\sN\dO}} ）。一氧化氮是一个稳定的[[自由基]]，有一个不成对的电子。一氧化氮的还原产生[[亚硝酰]]阴离子，{{Chem2|NO-}} ：
+: &lt;math xmlns="http://www.w3.org/1998/Math/MathML"&gt;<semantics><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="true" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><mtext><chem>NO + e- -> NO-</chem></mtext><mo><chem>NO + e- -> NO-</chem></mo><msup><mtext><chem>NO + e- -> NO-</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mo><chem>NO + e- -> NO-</chem></mo></mrow></msup><mo stretchy="false"> <chem>NO + e- -> NO-</chem></mo><msup><mtext><chem>NO + e- -> NO-</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mo><chem>NO + e- -> NO-</chem></mo></mrow></msup></mrow></mstyle></mrow><annotation encoding="application/x-tex"> </annotation></semantics>&lt;/math&gt;<chem>NO + e- -> NO-</chem></img>
+NO 的氧化产生[[亚硝𬭩离子|亚硝鎓]]阳离子，{{Chem2|NO+}} :
+: &lt;math xmlns="http://www.w3.org/1998/Math/MathML"&gt;<semantics><mrow class="MJX-TeXAtom-ORD"><mstyle displaystyle="true" scriptlevel="0"><mrow class="MJX-TeXAtom-ORD"><mtext><chem>NO -> NO+ + e-</chem></mtext><mo stretchy="false"><chem>NO -> NO+ + e-</chem></mo><msup><mtext><chem>NO -> NO+ + e-</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mo><chem>NO -> NO+ + e-</chem></mo></mrow></msup><mo> <chem>NO -> NO+ + e-</chem></mo><msup><mtext><chem>NO -> NO+ + e-</chem></mtext><mrow class="MJX-TeXAtom-ORD"><mo><chem>NO -> NO+ + e-</chem></mo></mrow></msup></mrow></mstyle></mrow><annotation encoding="application/x-tex"> </annotation></semantics>&lt;/math&gt;<chem>NO -> NO+ + e-</chem></img>
+一氧化氮可以作为[[配體|配体]]形成[[亚硝酰配合物|金属亚硝酰络合物]]或只是金属亚硝酰。这些配合物可以被视为加合物{{Chem2|NO+}} ,{{Chem2|NO-}} ，或一些中间情况。
+=== 在食物中 ===
+[[File:Nitrosyl-Heme.png|right|thumb|350x350px|亚硝酰血红素]]
+在食品和胃肠道中，亚硝化和亚硝基化对消费者健康的影响不同。
+* 在腌肉中：经过腌制的肉类含有亚硝酸盐，pH 值约为 5，其中几乎所有亚硝酸盐都以{{Chem2|NO2-}} (99%)。腌肉还添加了[[抗壞血酸鈉|抗坏血酸钠]]（或异抗坏血酸或维生素C）。正如 S. Mirvish 所证明的，抗坏血酸盐抑制胺亚硝化为亚硝胺，因为抗坏血酸盐与{{Chem2|NO2-}}形成 NO。 <ref>{{Cite journal |last=Mirvish |first=SS |last2=Wallcave |first2=L |last3=Eagen |first3=M |last4=Shubik |first4=P |date=July 1972 |title=Ascorbate–nitrite reaction: possible means of blocking the formation of carcinogenic ''N''-nitroso compounds |journal=Science |volume=177 |issue=4043 |page=65–8 |bibcode=1972Sci...177...65M |doi=10.1126/science.177.4043.65 |pmid=5041776 |s2cid=26275960}}</ref> <ref>{{Cite journal |last=Mirvish |first=SS |date=October 1986 |title=Effects of vitamins C and E on ''N''-nitroso compound formation, carcinogenesis, and cancer |journal=Cancer |volume=58 |issue=8 Suppl |page=1842–50 |doi=10.1002/1097-0142(19861015)58:8+<1842::aid-cncr2820581410>3.0.co;2-# |pmid=3756808 |s2cid=196379002}}</ref>抗坏血酸和 pH 值 5 的状况有利于血红素铁的亚硝基化，形成亚硝基血红素，当包含在肌红蛋白中时是红色素，当它通过烹饪释放时是粉红色素。它参与了腌肉的“熏肉味”。据欧洲加工肉类游说团顾问 KO Honikel 称， 因此，亚硝基血红素被认为对[[肉类行业]]和消费者有益。 <ref>{{Cite journal |last=Honikel |first=K. O. |year=2008 |title=The use an control of nitrate and nitrite for the processing of meat products |journal=Meat Science |volume=78 |issue=1–2 |page=68–76 |doi=10.1016/j.meatsci.2007.05.030 |pmid=22062097}}</ref>据加工肉类行业以外的科学家称，亚硝基血红素被认为是一种致癌化合物。 <ref>{{Cite journal |last=Lunn |first=J.C. |last2=Kuhnle |first2=G. |last3=Mai |first3=V. |last4=Frankenfeld |first4=C. |last5=Shuker |first5=D.E.G. |last6=Glen |first6=R. C. |last7=Goodman |first7=J.M. |last8=Pollock |first8=J.R.A. |last9=Bingham |first9=S.A. |year=2006 |title=The effect of haem in red and processed meat on the endogenous formation of N-nitroso compounds in the upper gastrointestinal tract |url=https://academic.oup.com/carcin/article/28/3/685/2476497 |journal=Carcinogenesis |volume=28 |issue=3 |page=685–690 |doi=10.1093/carcin/bgl192 |pmid=17052997}}</ref> <ref>{{Cite journal |last=Bastide |first=Nadia M. |last2=Pierre |first2=Fabrice H.F. |last3=Corpet |first3=Denis E. |year=2011 |title=Heme Iron from Meat and Risk of Colorectal Cancer: A Meta-analysis and a Review of the Mechanisms Involved |url=https://cancerpreventionresearch.aacrjournals.org/content/4/2/177 |journal=Cancer Prevention Research |volume=4 |issue=2 |page=177–184 |doi=10.1158/1940-6207.CAPR-10-0113 |pmid=21209396 |s2cid=4951579}}</ref> <ref>{{Cite journal |last=Bastide |first=Nadia M. |last2=Chenni |first2=Fatima |last3=Audebert |first3=Marc |last4=Santarelli |first4=Raphaelle L. |last5=Taché |first5=Sylviane |last6=Naud |first6=Nathalie |last7=Baradat |first7=Maryse |last8=Jouanin |first8=Isabelle |last9=Surya |first9=Reggie |last10=Hobbs |first10=Ditte A. |last11=Kuhnle |first11=Gunter G. |year=2015 |title=A Central Role for Heme Iron in Colon Carcinogenesis Associated with Red Meat Intake |url=https://cancerres.aacrjournals.org/content/75/5/870 |journal=Cancer Research |volume=75 |issue=5 |page=870–879 |doi=10.1158/0008-5472.CAN-14-2554 |pmid=25592152 |s2cid=13274953}}</ref>
+* 在[[胃|胃中]]：分泌的[[氯化氢]]形成酸性环境（pH=2) 和摄入的亚硝酸盐（与食物或唾液一起）会导致胺亚硝化，从而产生[[亚硝胺]]（潜在致癌物）。如果胺浓度低（例如，低蛋白饮食，无发酵食品）或维生素&nbsp;C 浓度高（例如，高水果饮食）。然后形成''S'' -nitrosothiols，在 pH 值下稳定维持在2左右。
+* 在[[大肠|结肠]]中：中性 pH 值不利于亚硝化。即使在添加仲胺或亚硝酸盐后，粪便中也不会形成亚硝胺。 <ref>{{Cite journal |last=Lee |first=L |last2=Archer |first2=MC |last3=Bruce |first3=WR |date=October 1981 |title=Absence of volatile nitrosamines in human feces |journal=Cancer Res. |volume=41 |issue=10 |page=3992–4 |pmid=7285009}}</ref>中性 pH 值有利于{{Chem2|NO-}}从''S'' -亚硝基硫醇中释放，以及铁的亚硝基化。根据 Bingham 和 Kuhnle 的说法，Bingham 团队在吃红肉的志愿者<ref>{{Cite journal |last=Bingham |first=SA |last2=Pignatelli |first2=B |last3=Pollock |first3=JR |display-authors=etal |date=March 1996 |title=Does increased endogenous formation of ''N''-nitroso compounds in the human colon explain the association between red meat and colon cancer? |journal=Carcinogenesis |volume=17 |issue=3 |page=515–23 |doi=10.1093/carcin/17.3.515 |pmid=8631138 |doi-access=free}}</ref>的粪便中测量的先前称为 NOC（ ''N-''亚硝基化合物）的物质主要是非''N-''亚硝基 ATNC（表观总亚硝基化合物），例如''S'' -nitrosothiols 和亚硝酰铁（如亚硝酰血红素）。 <ref>{{Cite journal |last=Kuhnle |first=GG |last2=Story |first2=GW |last3=Reda |first3=T |display-authors=etal |date=October 2007 |title=Diet-induced endogenous formation of nitroso compounds in the GI tract |journal=Free Radic. Biol. Med. |volume=43 |issue=7 |page=1040–7 |doi=10.1016/j.freeradbiomed.2007.03.011 |pmid=17761300}}</ref>
+== 另见 ==
+* [[亚硝胺]]，NO 连接到胺上的官能团，例如 R<sub>2</sub>N–NO
+* [[亚硝基苯]]
+* [[一氧化氮]]
+* [[次硝酸|硝酰]]
+== 参考资料 ==
+{{Reflist}}
+[[Category:亚硝基化合物]]
+[[Category:官能团]]