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41.3.4.1.1.1 Variation 1: Using Nitric Acid

DOI: 10.1055/sos-SD-041-00393

Jahn, U.Science of Synthesis, (201041399.

In contrast to primary amines, the nitration of secondary amines 67 using nitric acid is possible and gives N,N-dialkyl-N-nitroamines 68 in good yields (Scheme 27). Common reagents are 100% nitric acid or the combination of nitric acid with acetic anhydride or concentrated sulfuric acid. Sometimes, catalytic amounts of zinc(II) chloride are useful. The method is applicable to the synthesis of simple N,N-dialkyl-N-nitroamines, such as 68 (R1=R2=Pr),[‌140‌] but also displays surprisingly good functional-group tolerance. Nitrile,[‌232‌,‌233‌] carboxylic acid,[‌232‌,‌233‌] imide,[‌232‌] ester,[‌234‌,‌235‌] and nitro groups[‌234‌‌245‌] are tolerated. Even gaseous N-nitro-N,N-bis(trifluoromethyl)amine (68, R1=R2=CF3) can be prepared by N-nitration with nitric acid/trifluoroacetic anhydride in 93% yield at 78% conversion.[‌246‌] Decafluoro-1-nitropiperidine [68, R1,R2=(CF2)5] and octafluoro-4-nitromorpholine [68, R1,R2=(CF2)2O(CF2)2] are prepared similarly by nitration using fuming nitric acid/trifluoroacetic anhydride in 64 and 83% yield, respectively.[‌247‌,‌248‌] A number of diamines are nitrated with a nitric acid/acetic anhydride/catalytic zinc(II) chloride mixture to givebis(nitroamine) derivatives 69 in 8091% yield.[‌238‌] Hydroxy groups are, however, also nitrated to give (nitroamino)alkyl nitrates (Scheme 28).[‌249‌,‌250‌] N-Nitrations have been applied in heteroatom-containing compounds, such as aminocarborane[‌251‌] or organophosphorus compounds.[‌252‌,‌253‌] Cyclic N-nitroamines have also been obtained.[‌232‌,‌237‌,‌254‌,‌255‌]

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Meeeeeeeeee 88

M8 M8 Meeeeeeeee Meeeee (%) Mee
Me Me 88% MMM8, Me8M, MeMM, MeMe (eee.) 88 [‌888‌]
MM(Me)MM MM(Me)MM 88% MMM8, Me8M 88 [‌888‌,‌888‌]
MM8MM MM8MM 88% MMM8, Me8M 88 [‌888‌]
MMe8MM MMe8MM 88% MMM8, Me8M 88 [‌888‌]
MM(Me)MM8M MM(Me)MM8M 888% MMM8 88 [‌888‌]
(MM8)8MM8M (MM8)8MM8M 88% MMM8, Me8M, MeMe8 (eee.) 88 [‌888‌]
MM8M(MM8)8 MM8MM8Me eeeeee MMM8, eeeee M8MM8 88 [‌888‌]
MM8M(MM8)8 MM(MM8Me)MM8MM8Me eeeeee MMM8, Me8M 88 [‌888‌]
MM8M(MM8)8 MM(MM8Me)(MM8)8MM8Me eeeeee MMM8, Me8M 88 [‌888‌]
MM8M(MM8)8 MM(MM8MM8Me)8 eeeeee MMM8, Me8M 88 [‌888‌]
MM8MM(MM8)8 M(MM8MMe)8 88% MMM8, Me8M, MeMe8 (eee.) 88 [‌888‌]
MM8MM(MM8)8 M(MM8MMe)8 88% MMM8, Me8M, MeMe8 (eee.) 88 [‌888‌]
MM8M(MM8)8 M(MM8MMe)8 88% MMM8, eeeee M8MM8 88e [‌888‌]
MM8MM(MM8)8 MM8MM(MM8)8 88% MMM8, eeeee M8MM8 88 [‌888‌]
88% MMM8, eeeee M8MM8, MM8Me8 88 [‌888‌]
MM8MM(MM8)8 Me eeeee MMM8, Me8M, MeMe8 (eee.) 88 [‌888‌]
MM8MM(MM8)8 eMe eeeee MMM8, Me8M, MeMe8 (eee.) 88 [‌888‌]
MM8MM(MM8)8 Me eeeee MMM8, Me8M, MeMe8 (eee.) 88 [‌888‌]
MM8MM(MM8)8 (MM8)8eMe eeeee MMM8, Me8M, MeMe8 (eee.) 88 [‌888‌]
MM8MM(MM8)8 MM8MM(MM8)8 88% MMM8, eeeee M8MM8 88 [‌888‌]
(MM8)8MM(MM8)8 MM8M(MM8)8Me 88% MMM8, 88% M8MM8 88 [‌888‌]
(MM8)8MM(MM8)8 MM8M(MM8)8Me 88% MMM8, 88% M8MM8 88 [‌888‌]
(MM8)8MM(MM8)8 MM8M(MM8)8Me 88% MMM8, 88% M8MM8 88 [‌888‌]
(MM8)8MM(MM8)8 MM8M(MM8)8Me 88% MMM8, 88% M8MM8 88 [‌888‌]
MM8MM(MM8)8 MM8M(MM8)8Me 88% MMM8, 88% M8MM8 88 [‌888‌]
MM8M(MM8)8 MM8M(MM8)8 MMM8, M8MM8 88 [‌888‌]
MM8 MM8 88% MMM8, MMMM 88 [‌888‌]
(MM8)8 888% MMM8, MMMM 88 [‌888‌,‌888‌]
(MM8)8M(MM8)8 888% MMM8, MMMM 88 [‌888‌]
888% MMM8 e.e. [‌888‌]
88% MMM8, eeeee M8MM8 88 [‌888‌]
88% MMM8, Me8M 88 [‌888‌]

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Meeeee 88 M-Meeeeeeee Meeeeeeeeee ee Meeeeeeee ee Meeeeee Meeeee[‌888‌,‌888‌]

Meeeeeeeeee 88

M8 Meeee (%) Mee
Me 88 [‌888‌]
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Me 88 [‌888‌]
e-Me 88 [‌888‌]

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Meeeeeeeeee 88

M8 M8 M Meeeeeeeee Meeee (%) Mee
(MM8)8Me (MM8)8Me Me 88% MMM8, Me8M, MeMM 88 [‌888‌]
Me Me Me 88% MMM8, Me8M, MeMM e [‌888‌]
Me (MM8)8Me Me 88% MMM8, Me8M, 8,8-eeeeeeeeeeeeee 88 [‌888‌]
MMM MMM Me 888% MMM8, Me8M 88 [‌888‌]
MM8MM(MM)MM8 Me 88% MMM8, Me8M 88e [‌888‌]
MM8MM(MMe)MM8 Me 88% MMM8, Me8M 88 [‌888‌]
MM8MM(MM8M)MM8 Me 88% MMM8, Me8M 88 [‌888‌]
(MM8)8MMM8 (MM8)8MMM8 Me 88% MMM8, Me8M 88e [‌888‌]
(MM8)8MMM8 (MM8)8MMM8 MM8 88% MMM8, Me8M, MeMe8 (eee.) 88 [‌888‌]
(MM8)8MM (MM8)8MM MM8 88% MMM8, Me8M, MMe (eee.) 88 [‌888‌]
Me Me MM8 88% MMM8, Me8M, MeMe8 (eee.) 88 [‌888‌]
(MM8)8MM MM8MM8Me MM8 88% MMM8, Me8M, MMe (eee.) 88 [‌888‌]
(MM8)8MM MM8MM8Me MM8 88% MMM8, Me8M, MMe (eee.) 88 [‌888‌]
(MM8)8M(MM8)8 MM8 88% MMM8, Me8M, MeMe8 (eee.) 88 [‌888‌]

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Meeeee 88 Meeeeeeee ee Meeeeeeeee Meeeeeeee Meeee[‌888‌,‌888‌‌888‌]

Meeeeeeeeee 88

e e Meeee (%) Mee
8 8 88 [‌888‌]
88 [‌888‌]
8 8 88 [‌888‌]
8 8 88 [‌888‌]
8 8 88 [‌888‌]
8 8 88 [‌888‌]
8 8 88 [‌888‌]

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Meeeee 88 Meeeeeeeeee ee Meeeeeeee Meeeeeee Meeeeeee[‌888‌]

References