N nitration with

Amines and amides can be N-nitrated with nitric acid, or and... 

Amination at an azole ring nitrogen is known for N-unsubstituted azoles. Thus, 1,2,3-triazole and 4,5-diphenyl-l,2,3-triazole with hydroxylamine-O-sulfonic acid give 1-amino 145 and 2-amino 146 derivatives in a ratio of 4 1 and 1 3, respectively. 3-Amino-5-/isy/-butylpyrazole affords 147 and indazole and tetrazole give comparable amounts of the 1- and 2-amino derivatives, and ethyl benzothiazol-2-ylcarboxylate reacts at room temperature <2001JOC8528>. Pyrazole is easily N-nitrated with nitrogen dioxide in the presence of ozone <1996JCR(S)388>. 

More recently there has been some interest in the structures of the iV-nitration products of 4-nitroimidazoles. Both 4-nitro- (81UP40600) and 2-isopropyl-4-nitro-imidazole (72aC3472) have been shown to N-nitrate with such an orientation that the 1,4-dinitro compound results (see Figure 2). 

Fig. 5.1. Zeroth-order rates of nitration with acetyl nitrate compared with those for other systems, (a) HNOa/ sulpholan, (i) HNO3/CCI4, (c) AcONOj/AcjO/O % AcOH, (d) AcONOj/AcaO/O % AcOH/[mesitylene] = o-8 mol l-i,n (e) AcONOj/AcaO/ [AcOH] = 2-2moll-i,ii >(/)AcONOa/AcaO/[AcOH] = 1-96 mol l-i and (g) AcONOa/ AcaO/[AcOH] 3 9i mol l-i/[mesitylene] = o-8 mol 1-i H.

Acetic anhydride and acetic acid increase the solubiUty of the two phases in each other, and they are employed for the commercial N-nitration of hexamethylenetetramine [100-97-0] (11) to form cyclotrimethylenetrinitramine [121-82-4] (RDX), (CH2)3(NN02)3. Renewed consideration has been given to replacing H2SO4 with an improved soHd catalyst to reduce the environmental problems of disposal or reconcentration of the waste acid and to increase production of desired nitrated isomers. For example, a catalyst with suitable pore size might increase the production of 4-MNT and reduce that of 3-MNT when toluene is nitrated. 

TABLE 20.7 Conformational Coefficients for Water-Soluble Polymers in 0.05 N Sodium Nitrate with TSK-PW Columns... 

Bromo-7-methyl-6-methylaminoquinoline was nitrated with ACONO2 to give the 6-N(N02)Me derivative, which rearranged in diluted sulfuric acid to the 5-nitro derivative. Reduction of the latter compound, followed by condensation with BrCN and final hydrogenolysis using H2, led to a product of >99% radiochemical purity (85MI1). 

N,N -dimethyloxaldiamide is reacted with PCI5 to give 4-chloro-1-methyl imidazole. This is nitrated with HNO3 to give 5-nitro-1-methyl-4-chloroimidazole. Then, a mixture of 4.6 grams of anhydrous 6-mercaptopurine, 5 grams of 1-methyl-4-chloro-5-nitroimidazole and 2.5 grams of anhydrous sodium acetate in 100 ml of dry dimethyl sulfoxide was heated at 100°C for 7 hours. 

O- and N-containing heterocyclics Aliphatic nitrates with an a-methyl group (CH3CHONOz)... 

It is prepd by the action of methylamine on 4-chloro-l-nitrobenzene (Ref 5) by the action of methyl iodide (Ref 6), or methyl sulfate on 4-nit roaniline (Ref 7) or by the hydrolysis of 4-nitro-N-methylformanilide with hot coned aq HC1 (Ref 8). In a study of the effect of nitric acid concn on the prods of the nitration of N,N-dimethylaniline to form Tetryl, it was isolated in low yield by the action of nitric acid, d 1.046g/cc, plus Na nitrite on N,N-dimethylaniline (Ref 10). A eutectic mixt with N-ethyl-4-nitroaniline has been patented as a stabilizer for NC (Ref 12). Studies at NPF indicate that 4-nitro-N-methyl-aniline is superior to Centralite, 2-nitrodiphenyl-amine, or Acardite in stabilizing. NC Refs 1) Beil 12, 586, (295) 1125 ... 

Nitroisobutylglycol dinitrate). CH3.C.N02(CH20N02)2, mw 225.14, N 18.67%, OB to C02 —24.87%, mp 38°, ignites above 240°. Prepd from the glycol by nitration with mixed acid, with 90% yield. Brisance, crushes 53g sand, equivalent to Tetryl. Qc is 531.4cal/mole. Impact sensitivity, FI 86% relative to PA, with Bruceton No 5 machine,... 

N-Methyl-N-f2-Nitroxy propyl) Nitramine. (Me2NENA N-(2-NitroxypropyI) methyl nitramine. (02N)N(CH3).(CH2CH(0N02).CH3, mw 179.16, N 23.46%, OB to C02 -66.80%, pale yellow oil, mp 22—23°, d 1.320g/cc at 25/4°, RI 1.478 at 25°. Prepn from 2-hydroxy-propylamine after nitration with 98% nitric acid at 10° by reaction of the amine-nitric acid mixt with acetic anhydride acetyl chloride at 35°. Reaction mixt poured on ice. Yield is 74%. No expl properties listed Reft 1) Beil - not found 2) Blomquist, OSRD 4134, 45 119 (1944)... 

Nitro-1 -Naphthol (8-Nitro-l-oxy-naphthalene). (O2N)C10H6.OH,mw 189.18, N 7.41%, OB to C02 —173.38%, mp 212° (decompn). Prepn from 1-naphthy 1-m-nitrobenzene sulfonate by nitration with nitric acid in AcOH, then hydrolysis with piperidine... 

Dinitro-1-Naphthol (2,4-Dinitro-l-oxy-naphthalene). Yellow crysts, mp 139.5°. Sol in ale chlf. Prepn from naphthalene as a byproduct during nitration with dil nitric acid Hg(II) nitrate. The Lead Salt of the above can be shown as Pb[O.C loHs(N02)2]2, mw 729.57, N 7.68%, OB to C02 -76.75%. The explosive sensitivity of this salt compared to PA is 49%... 

Which of these options is the best Lewis structure Actually, no single Lewis structure by itself is an accurate representation of NO3. Any single structure of the anion shows nitrate with one NDO double bond and two N— O single bonds. In Section 9 1, we show that single and double bonds between the same types of atoms have different lengths and different energies. In contrast, experiments show that the three nitrate N—O bonds are identical. To show that the nitrate N—O bonds are all alike, we use a composite of the three equivalent Lewis structures. These are traditionally called resonance structures. Resonance stmctures are connected by double-headed arrows to emphasize that a complete depiction requires all of them. 

Figure 12. Isotherms of M-n compared with in various binary nitrates as a function of molar volume. (Reprinted from I. Okada and P.-H. Chou, Anomalous Behavior of Internal Mobilities for Ag(I) and T1(I) Ions in Molten Nitrates, J. Electrochem. Soc. 144(4) 1333, 1997, Fig. 13. Reproduced by permission of the Electrochemical Society, Inc.)...

At the reaction conditions the rather loosely bound N02 can migrate and react with remaining [CuO Z centers, producing surface nitrates (with T72(0,0) CuN03 n being the most stable one). 

The reaction is complete when the clear supernatant solution in the reaction vessel no longer contains chlorine as detected by the addition of dilute nitric acid and silver nitrate solution to ca. 1-ml. of the clear solution withdrawn from the reaction flask. After the reaction is complete, the ice bath is removed, and stirring is continued for 2 hours at room temperature. After standing overnight, the dimethylammonium chloride is filtered and washed with n-hexane, with careful exclusion of the moisture of the atmosphere. The combined filtrates are distilled at atmospheric pressure to remove the solvent. The tris(dimethylamino)arsine distills at 36°/2 mm. (55 to 57°/10 mm.). The yield is 402 g. (78%). 

A similar complex 80 is also produced in a reaction of cobalt(ll) nitrate with potassium tricyanomethanide (Ktcm) and benzotriazole (BtH). According to the X-ray data for this complex, the CoN6 octahedron is only slightly distorted, having the N-Co-N angles in the range of 88.37-91.16°. The equatorial Co-N(tcm) distances (2.106 and 2.110 A) are... 

In this development of a flow injection method for the determination of nitrate andnitrite, Anderson [168] chose the Shinn [155] method to reduce nitrate and nitrite because of its high sensitivity and relative freedom from interferences. Anderson [168] used flow injection in the photometric determination of nitrite and nitrate with sulfanilamide and N-( 1-naphthyl) ethylenediamine as reagents, as discussed next. The detection limit is 0.05 xm for nitrite and 0.1 xm for nitrate at a total sample volume of 200 iL. Up to 30 samples can be analysed per hour with relative precision of about 1%. 

Fung, H-L., Chong, S., Kowaluk, E., Hough, K., Kakemi, M., Mechanisms for the pharmacological interaction of organic nitrates with thiols. Existence of an extracellular pathway for the reversal of nitrate vascular tolerance by N-acetylcytseine. J. Pharmacol. Exp. Ther. 245 (1988), 524-530... 

Procedure Weigh accurately about 0.2 g of chlorobutol in a flask and dissolve in 5 ml of alcohol. Add to it 5 ml of sodium hydroxide solution, and boil under a reflux condenser for 15 minutes. Cool, dilute with 20 ml of DW, add 5 ml of nitric acid, 1 ml of nitrobenzene and 50 ml of 0.1 N silver nitrate solution. Shake the contents vigorously for 1 minute, add 4 ml of ferric ammonium sulphate solution and titrate the excess of silver nitrate with 0.1 N ammonium thiocyanate solution. Each ml of 0.1N silver nitrate is equivalent to 0.005917 g of C4H7C130. 

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