WordNet

any compound containing the nitrate group (such as a salt or ester of nitric acid)
treat with nitric acid, so as to change an organic compound into a nitrate; "nitroglycerin is obtained by nitrating glycerol"

PrepTutorEJDIC

硝酸塩 / 硝酸塩類化学肥料

Wikipedia preview

出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2015/01/09 15:54:11」(JST)

wiki en

[Wiki en表示]

Nitration is a general class of chemical process for the introduction of a nitro group into an organic chemical compound. More loosely the term also is applied incorrectly to the different process of forming nitrate esters between alcohols and nitric acid, as occurs in the synthesis of nitroglycerin. The difference between the resulting structure of nitro compounds and nitrates is that the nitrogen atom in nitro compounds is directly bonded to a non-oxygen atom, typically carbon or another nitrogen atom, whereas in nitrate esters, also called organic nitrates, the nitrogen is bonded to an oxygen atom that in turn usually is bonded to a carbon atom.

There are many major industrial applications of nitration in the strict sense; the most important by volume are for the production of Nitroaromatic compounds such as nitrobenzene. Nitration reactions are notably used for the production of explosives, for example the conversion of guanidine to nitroguanidine and the conversion of toluene to trinitrotoluene. However, they are of wide importance as chemical intermediates and precursors. Millions of tons of nitroaromatics are produced annually.^[1]

Aromatic nitration

Typical nitration syntheses apply so-called "mixed acid", a mixture of concentrated nitric acid and sulfuric acids.^[2] This mixture produces the nitronium ion (NO₂⁺), which is the active species in aromatic nitration. This active ingredient, which can be isolated in the case of nitronium tetrafluoroborate,^[3] also effects nitration without the need for the mixed acid. In mixed-acid syntheses sulfuric acid is not consumed and hence acts as a catalyst as well as an absorbent for water. In the case of nitration of benzene, the reaction is conducted at 50 °C.^{[citation needed]} The process is one example of electrophilic aromatic substitution, which involves the attack by the electron-rich benzene ring:

Alternative mechanisms have also been proposed, including one involving single electron transfer (SET).^[4]^[5]

Scope

Selectivity can be a challenge in nitrations because as a rule more than one compound may result but only one is desired, so alternative products act as contaminants or are simply wasted. Accordingly, it is desirable to design syntheses with suitable selectivity; for example, by controlling the reaction conditions, fluorenone can be selectively trinitrated^[6] or tetranitrated.^[7]

Another example of selective trinitration is when benzene is symmetrically trinitrated to 1,3,5 trinitrobenzene to produce a precursor for the synthesis of phloroglucinol.

The substituents on aromatic rings affect the rate of this electrophilic aromatic substitution. Deactivating groups such as other nitro groups have an electron-withdrawing effect. Such groups deactivate (slow) the reaction and directs the electrophilic nitronium ion to attack the aromatic meta position. Deactivating meta-directoring substituents include sulfonyl, cyano groups, keto, esters, and carboxylates. Nitration can be accelerated by activating groups such as amino, hydroxy and methyl groups also amides and ethers resulting in para and ortho isomers.

The direct nitration of aniline with nitric acid and sulfuric acid, according to one source ^[8] results in a 50/50 mixture of para and meta nitroaniline. In this reaction the fast-reacting and activating aniline (ArNH₂) exists in equilibrium with the more abundant but less reactive (deactivated) anilinium ion (ArNH₃⁺), which may explain this reaction product distribution. According to another source ^[9] a more controlled nitration of aniline starts with the formation of acetanilide by reaction with acetic anhydride followed by the actual nitration. Because the amide is a regular activating group the products formed are the para and ortho isomers. Heating the reaction mixture is sufficient to hydrolyze the nitroamide back to the nitroamine.

In the Wolfenstein-Boters reaction, benzene reacts with nitric acid and mercury nitrate to give picric acid.

Ipso nitration

With aryl chlorides, triflates and nonaflates ipso substitution can take place as well in so-called ipso nitration.^[10] The phrase was first used by Perrin and Skinner in 1971 in an investigation into chloroanisole nitration ^[11] In one protocol 4-chloro-n-butylbenzene is reacted with sodium nitrite in t-butanol in presence of 0.5 mol% Pd₂(dba)₃, a biarylphosphine ligand and a phase-transfer catalyst to 4-nitro-n-butylbenzene ^[12]

References

^ Gerald Booth "Nitro Compounds, Aromatic" Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a17_411
^ John McMurry Organic Chemistry 2nd Ed.
^ George A. Olah and Stephen J. Kuhn, "Benzonitrile, 2-methyl-3,5-dinitro-", Org. Synth. ; Coll. Vol. 5: 480
^ Esteves, P. M.; Carneiro, J. W. M.; Cardoso, S. P.; Barbosa, A. G. H.; Laali, K. K.; Rasul, G.; Prakash, G. K. S.; e Olah, G. A. (2003). "Unified Mechanism Concept of Electrophilic Aromatic Nitration Revisited: Convergence of Computational Results and Experimental Data". J. Am. Chem. Soc. 125 (16): 4836–49. doi:10.1021/ja021307w. PMID 12696903.
^ Queiroz, J. F.; Carneiro, J. W. M.; Sabino A. A.; Sparapan, R.; Eberlin, M. N.; Esteves, P. M. (2006). "Electrophilic Aromatic Nitration: Understanding Its Mechanism and Substituent Effects". J. Org. Chem. 71 (16): 6192–203. doi:10.1021/jo0609475. PMID 16872205.
^ E. O. Woolfolk and Milton Orchin, "2,4,7-Trinitrofluorenone", Org. Synth. ; Coll. Vol. 3: 837
^ Melvin S. Newman and H. Boden, "2,4,5,7-Tetranitrofluorenone", Org. Synth. ; Coll. Vol. 5: 1029
^ Web resource: warren-wilson.edu
^ Mechanism and synthesis Peter Taylor,Royal Society of Chemistry (Great Britain),Open University
^ Prakash, G.; Mathew, T. (2010). "Ipso-Nitration of Arenes". Angewandte Chemie (International ed. in English) 49 (10): 1726–1728. doi:10.1002/anie.200906940. PMID 20146295. edit
^ Perrin, C. L.; Skinner, G. A. (1971). "Directive effects in electrophilic aromatic substitution ("ipso factors"). Nitration of haloanisoles". Journal of the American Chemical Society 93 (14): 3389. doi:10.1021/ja00743a015. edit
^ Fors, B.; Buchwald, S. (2009). "The Pd-Catalyzed Conversion of Aryl Chlorides, Triflates, and Nonaflates to Nitroaromatics". Journal of the American Chemical Society 131 (36): 12898–12899. doi:10.1021/ja905768k. PMC 2773681. PMID 19737014. edit

UpToDate Contents

全文を閲覧するには購読必要です。 To read the full text you will need to subscribe.

1. 安定狭心症のマネージメントにおける硝酸塩 nitrates in the management of stable angina pectoris
2. 急性冠症候群のマネージメントにおける硝酸剤 nitrates in the management of acute coronary syndrome
3. 収縮能障害による心不全患者におけるヒドララジンおよび硝酸塩による治療 hydralazine plus nitrate therapy in patients with heart failure due to systolic dysfunction
4. 裂肛：内科的および外科的マネージメント anal fissure medical and surgical management
5. 高血圧緊急症の薬物治療 drug treatment of hypertensive emergencies

English Journal

Coumarins from Angelica decursiva inhibit α-glucosidase activity and protein tyrosine phosphatase 1B.

Ali MY1, Jannat S1, Jung HA2, Jeong HO3, Chung HY3, Choi JS4.
Chemico-biological interactions.Chem Biol Interact.2016 May 25;252:93-101. doi: 10.1016/j.cbi.2016.04.020. Epub 2016 Apr 13.
In the present study, we investigated the anti-diabetic potential of six natural coumarins, 4-hydroxy Pd-C-III (1), 4'-methoxy Pd-C-I (2), decursinol (3), decursidin (4), umbelliferone 6-carboxylic acid (5), and 2'-isopropyl psoralene (6) isolated from Angelica decursiva and evaluated their inhibito
PMID 27085377

Investigating the formation and toxicity of nitrogen transformation products of diclofenac and sulfamethoxazole in wastewater treatment plants.

Osorio V1, Sanchís J1, Abad JL2, Ginebreda A1, Farré M1, Pérez S3, Barceló D4.
Journal of hazardous materials.J Hazard Mater.2016 May 15;309:157-64. doi: 10.1016/j.jhazmat.2016.02.013. Epub 2016 Feb 8.
Diclofenac (DCF) and sulfamethoxazole (SMX) are highly consumed pharmaceuticals and concentrated in effluents from conventional wastewater treatment plants (WWTPs) since they are not completely eliminated. Under microbial mediated nitrification/denitrification processes occurring in nitrifying activ
PMID 26894288

Methotrexate administration induces differential and selective protein tyrosine nitration and cysteine nitrosylation in the subcellular organelles of the small intestinal mucosa of rats.

Natarajan K1, Abraham P2.
Chemico-biological interactions.Chem Biol Interact.2016 May 5;251:45-59. doi: 10.1016/j.cbi.2016.03.032. Epub 2016 Mar 30.
Gastrointestinal toxicity is one of the most frequent dose limiting side effects of methotrexate (MTX), a commonly used chemotherapeutic drug. Peroxynitrite (PON) overproduction is reported to contribute to MTX induced gastrointestinal mucositis. However, the consequence of PON overproduction i.e. p
PMID 27038877

Japanese Journal

ガザミの種苗生産技術と栽培漁業の現状 (特集有用水産生物の種苗をつくる(2))

小畑泰弘
海洋と生物 37(2), 151-157, 2015-04
NAID 40020445034

高温高圧水-マクロリアクターによる有機材料合成法の開発

川波肇
有機合成化学協会誌 73(5), 475-482, 2015
High-pressure and high-temperature water including supercritical water with its unique properties is considered as a green solvent; a suitable replacement of conventional organic solvents. Until to th …
NAID 130005077688

酸素制御による部分的亜硝酸化の実現と維持

劉媛,北條俊昌,何士龍,甄広印,李玉友
土木学会論文集G（環境） 70(7), III_233-III_241, 2014
　省エネルギー型の新たな窒素除去方法として嫌気性アンモニア酸化(アナモックス)反応を利用した技術が注目されている．アナッモクスの幅広い応用を促進するために，本研究では約57%の部分的亜硝酸化の実現および維持方法について検討した．部分的亜硝酸化処理は完全混合型反応槽を用い，流入水のNH4+-N濃度を250mg/L，窒素負荷を0.5kgN/m3・dとし，リアクターの温度を25℃前後に設定して運転を行っ …
NAID 130004962643