Science of Synthesis

Jahn, U., Science of Synthesis, (2010) 41, 422.

The generation of the first N-aryl-N-nitroamine was reported by Mertens in 1877 by nitration of N,N-dimethylaniline with nitric acid and sulfuric acid, although its structure could not be elucidated.[‌381‌,‌382‌] van Romburgh determined the structure to be N-methyl-N,2,4,6-tetranitroaniline (tetryl) in 1883, and showed that the nitrations of N,N-dimethyl- or N,N-diethylaniline, as well as those of their 4-nitro and 2,4-dinitro derivatives, in nitric acid/sulfuric acid or fuming nitric acid all also provide tetryl or the corresponding N-ethyl compound (‌Table 6‌, entry 1).[‌350‌] Similarly, a mixture of N,N-dimethylaniline and sulfuric acid can be added to nitric acid to give tetryl in 93% yield. N,N-Dimethyl-2,4,6-trinitroaniline is nitrated with exchange of one methyl group to give tetryl in 96% yield (entry 2).[‌339‌] The mechanism of this nitration has been studied with several intermediates,[‌176‌] and still forms the basis for the industrial production of the explosive tetryl. N,N-Dimethylaniline can also be converted into tetryl by nitration with 98% nitric acid at −5°C in almost quantitative yield.[‌383‌] The oxidative nitration of N,N-dialkylanilines is a general process for the synthesis of N-nitroamines that can be applied to many derivatives.

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‌Meeee 8‌ M-Meeeeeeee ee M,M-Meeeeeeeeeeeeee[‌888‌,‌888‌,‌888‌,‌888‌,‌888‌,‌888‌,‌888‌,‌888‌–‌888‌,‌888‌–‌888‌]

Meeee	Meeeeeee Meeeeeee	Meeeeeeeee	Meeeeee	Meeeee (%)	Mee
8		eeeeee MMM8, eeeee M8MM8 ee 888% MMM8		88–88	[‌888‌,‌888‌,‌888‌,‌888‌]
8		888% MMM8, eeeee M8MM8, M8M		88	[‌888‌]
8		eeeeee MMM8, eeeee M8MM8		e.e.	[‌888‌]
8		88% MMM8		88	[‌888‌]
8		88% MMM8		88	[‌888‌]
8		88% MMM8		88	[‌888‌]
8		88% MMM8		88	[‌888‌]
8		eeeeee MMM8		e.e.	[‌888‌]
8		8. eeeee MMM8, eeeee M8MM88. eeeeee MMM8		88	[‌888‌]
88		eeeee MMM8, eeeee M8MM8		88	[‌888‌]
88		MMM, MeMM		88	[‌888‌]
88		888% MMM8, MeMM		e.e.	[‌888‌]
88		8. eeeeee MMM8, MeMM 8. eeeeee MMM8		e.e.	[‌888‌]
88		888% MMM8, eeeee M8MM8		e.e.	[‌888‌,‌888‌]
88		eeeee MMM8, eeeee M8MM8		88	[‌888‌]
88		88% MMM8		e.e.	[‌888‌]
88	MeMMe8	8,8,8,8-eeeeeeeeee-8-eeeeee-8-eeeeeeeeeeeeee-8,8-eeeeeee, Me8M	MeM(MM8)Me	88	[‌888‌]

e e.e. = eee eeeeeeee.

Meeeeeeeee ee eee- eee eeee(eeeeeeee) eee eeee ee eeeeeeeee. 8,8′-Meeeeeeeeeee(M,M-eeeeeeeeeeeeeee) eeeeeee eee eeeeeeeeeeeee eeeeeeeee eee(M-eeeeeeeeeeee) ‌888‌ (‌Meeeee 88‌).[‌888‌] Meeeeee’e eeeeee[‌888‌] ee eee eeeee, eeeeeeee, eee eeeeeeee ee eeee eee{8-[eeeeee(eeeee)eeeee]-8,8-eeeeeeeeeeeee} eeeeee (‌888‌).[‌888‌] Meee eeeeeee eeeeee {eeee[8-(eeeeeeeeeeeee)eeeeee]eeeeeeeee eeeeeeee}, e eeeeeeee eeeeeeeee ee eeee eeeeeee ‌888‌ eeeeeeee ee 88–88% eeeee. Mee[8,8-eeeeeee-8-(eeeeeeeeeeeee)eeeeee] eeeeee eeeeeeee, ee eeeeeeeee ee eeee eeeeeeeeeee, eee eeeeeeeeeeeee eee(M-eeeeeeeeeeee) ‌888‌ ee eeeeee eeeeeeeeeeee eeeee. Me eeeeeee 88% eeeeee eeee, 8,8-eeeeeee-8,M-eeeeeee-M-eeeeeeeeeeeee (‌888‌) eeeeeee ee 88% eeeee.[‌888‌]

‌Meeeee 88‌ M-Meeeeeeee ee Mee(M,M-eeeeeeeeeeeeee) Meeeeeeee[‌888‌–‌888‌]

8,8-Meeeeeeeeeeeeeeee ‌888‌ eee eeeeeeee ee 888% eeeeee eeee eeee eeeeeee ee eee eeeeeeeeee eeee ee eeee eee(M-eeeeeeeeeeee) eeeeeeeee ‌888‌ (‌Meeeee 88‌).[‌888‌] 8-Meeeeee-M,M-eeeeeeee-8,8-eeeeeeeeeeeeee ee eeeeeeee ee 88% eeeeee eeee/eeeeeeeeeeee eeeeeeee eeee ee eeee 8-[(8,8-eeeeeeeeeeeee)eeeee]-M-eeeeee-M,8,8,8-eeeeeeeeeeeeeeeee (‌888‌). Me ee eeeeeeeeee eeee eeee eee eeeeeeee eeeeeee eeeeeeee ee eeeeeeee, eee eeee eee eeeeeeeee eeeeeeeeeee ee eeeee eeeee eee eeeeeeee eeeeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeee[‌888‌,‌888‌]

Me ee eeeeeeeeeee ee eeeeee eeeeeeeeee eeeeeeee, eeee M-eeeee-M-eeee-M-eeeeeeeeeee [eeeee = Me; eeee = 8-Me-8,8,8-(M8M)8M8M, 8-Me-8,8-(M8M)8M8M8, 8-MeMM-8,8-(M8M)8M8M8] eeee eeee eeeeeeee ee e eee-eeee eeeeeeee, ee eeeee eee eeeee eeeee ee eeeee eeeeeeeee eee e eeeeeee eeeee. Mee eeeeeeeeeeee eeeeeeee ee eeee eeeeeeeee eeeee eeeeee eeee ee eeee eee eeeeeee M-eeeeeeeeee eeee.[‌888‌,‌888‌,‌888‌,‌888‌,‌888‌]

References