Nitryl chloride nitration with

Nitryl chloride reacts with many organics forming their nitro derivatives. Such Friedel-Crafts nitration is catalyzed by a Lewis acid, such as AICI3. An example is nitration of benzene to nitrobenzene ... 

Nitryl chloride reacts with acetic anhydride forming acetyl chloride and acetyl nitrate ... 

It was found by Steinkopf and Kiihnel [106] that the so-called nitryl chloride is an agent that both nitrates and chlorinates aromatic hydrocarbons. However, the reaction could be selective. Thus, only o- nitrophenol was formed when nitryl chloride interacted with phenol below room temperature, but at room temperature 2,4-dichloro-6-nitrophenol was obtained. Naphthalene was chlorinated and nitrated simultaneously to give a- nitro- and a- chloro-naphthalene. 

Nitryl chloride reacts with zinc, mercury, and bismuth to form mixtures of the metal chlorides and nitrates, but does not react with copper, magnesium, iron, aluminum, or tin at 243 K. In the reaction with ammonia, nitryl chloride acts as a source of positive chlorine ... 

With BCI3, Olah and Kuhn obtained a smaller amount of nitrated product and considerable ring chlorination SbFs is also an active catalyst for the nitryl chloride nitration of aromatics BFj was found to be inactive as a catalyst. The following yields were obtained upon nitration of the aromatics using TiCl4 as catalyst benzene, 88% toluene, 81.5% ethylbenzene,... 

A novel, mild system for the direct nitration of calixarenes has been developed using potassium nitrate and aluminum chloride at low temperature. The side products of decomposition formed under conventional conditions are not observed in this system, and the p-nitro-calixarenes are isolated in 75-89% yields.17 Such Friedel-Crafts-type nitration using nitryl chloride and aluminum chloride affords a convenient system for aromatic nitration.18 Nitryl chloride was previously prepared either by the oxidation of nitrosyl chloride or by the reaction of chlorosulfonic acid with nitric acid. However, these procedures are inconvenient and dangerous. Recently, a mixture of sodium nitrate and trimethysilyl chloride (TMSC1) has been developed as a convenient method for the in situ generation of nitryl chloride (Eq. 2.6). 

The nitration reagents (NO2 Y) for electrophilic aromatic nitration span a wide range and contain anions Y such as nitric acid (Y = OH-), acetyl nitrate (Y = OAc-), dinitrogen pentoxide (Y = NO3-), nitryl chloride (Y = Cl-), TV-nitropyridinium (Y = pyridine) and tetranitromethane [Y = C(N02)3-]. All reagents contain electron-deficient species which can serve as effective electron acceptors and form electron donor-acceptor (EDA) complexes with electron-rich donors including aromatic hydrocarbons107 (ArH, equation 86). Excitation of the EDA complexes by irradiation of the charge-transfer (CT) absorption band results in full electron transfer (equation 87) to form radical ion... 

Deville first synthesized dinitrogen pentoxide in 1849 by reacting silver nitrate with chlorine gas. This reaction probably involves the initial formation of nitryl chloride and, accordingly, dinitrogen pentoxide can also be formed from the reaction of nitryl chloride or nitryl fluoride with a metal nitrate. These reactions are more of theoretical interest than of any practical value. 

An older preparation method involves passing dry chlorine gas slowly over dry silver nitrate heated to about 100°C. The gaseous reaction products are allowed to cool to low temperature. After several hours, nitryl chloride condenses to a pale yellowish-brown liquid. Chlorine is removed by purging with CO2. 

Steinkopf and Kuhnel [106] also examined the action of nitryl chloride on ethylene and reported that only 1,2-dichloroethane was formed. Petri [112] however reported the formation of l-chloro-2-nitroethane (with 45% yield) and 2-chloro-ethyl nitrate (35% yield). Ville and DuPont [113] confirmed the formation of l-chloro-2-nitroethane (50% yield) and Goddard [111] confirmed the results of Petri. Price and Sears [107] obtained 2-chloro-l-nitropropane from propane. 

Nitryl chloride, formed from peroxynitrite and HOCl is also capable of nitrating, chlorinating and hydroxylating tyrosine [ 116]. However, the reduction of nitrotyrosine by hypohalous acid has also been demonstrated. Several recent studies indicate that peroxynitrite can lead to generation of both nitrated and hydroxylated phenylalanine residues. The formation of 3-nitrotyrosine and 4-nitrophenylalanine was favoured over the hydroxylation reaction when phenylalanine was treated with peroxy nitrite in vitro [117]. 

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