26 Synthetic Routes to AliphaticC-Nitro
Homologuen =1
2
3
4
50
0
10
84
890
49
25
70
---via the dinitroalkane (83) via the bis-methylol (84)Yield (%) of tetranitroalkane (86)Source: Reprinted with permission from C. E. Colwell, H. Feuer, G. Leston and A. T.
Nielsen, J. Org. Chem., 1962, 27 , 3598; Copyright 1962 American Chemical Society.Table 1.8
Synthesis of tetranitroalkanes (86) via the oxidative nitration of
dinitroalkanes (83) and their bis-methylol derivatives (84)
(NO 2 ) 2 CH(CH 2 )nCH(NO 2 ) 2Oxidative nitration is not effective for the synthesis ofgem-dinitroaliphatic compounds
containing an electron-withdrawing groupαto the carbon bearing the nitro groups. Oxidative
nitration is not successful for the conversion of terminalgem-dinitro compounds into 1,1,1-
trinitromethyl derivatives.
A major drawback of the Kaplan–Shechter reaction is the use of expensive silver nitrate
as one of the reagents, which prevents scale up to an industrial capacity. Urba ́nski and co-
workers^201 modified the process by showing that the silver nitrate component can be replaced
with an inorganic one-electron transfer agent like ferricyanide anion. In a standard procedure
the nitroalkane or the corresponding nitronate salt is treated in alkaline media with potassium
HHNO 2NO 2NO 2NO 2NO 2NO 2NO 2HHO 2 NO 2 NNO 2NO 2NO 2NO 2NO 2NO 2NO 2NO 2NO 2O 2 NO 2 NO 2 NO 2 NO 2 NO 2 NHHHHNaOH, NaNO 2 ,
K 3 Fe(CN) 6 ,
MeOH (aq), 65 %NaOH, NaNO 2 ,
K 3 Fe(CN) 6 ,
CH 2 Cl 2 , H 2 O, MeOH
83–91%NaOH, NaNO 2 ,
K 3 Fe(CN) 6 ,
CH 2 Cl 2 , H 2 O, 76 %NaOH, NaNO 2 ,
K 3 Fe(CN) 6 , Na 2 S 2 O 8 ,
dioxane (aq), 64 %150151141, 126141Table 1.9
Synthesis of energetic polynitropolycycloalkanes via oxidative nitrationSubstrate Conditions/reagents Product Ref.