Organic Chemistry of Explosives

10 Synthetic Routes to AliphaticC-Nitro

CH 3 CH 2 CH 2 CH 2 SO 2 CH 3

CH 3 CHBrCO 2 Et

Br

DMF

DMF

DMF

DMSO

DMF

DMF

H 3 CCH 2 CH 2 Cl

O

PhCH 2 Br

(CH 3 ) 2 C

CN

Br

DMF

O

ICH 2 CH 3

46

57

47

66

55

52

70

Table 1.3

Synthesis of nitroalkanes and their derivatives from the reaction of alkyl halides

with sodium nitrite under the modified Victor Meyer conditions

84

84

91

89

84

87

74

Substrate Solvent Yield (%) of

nitroalkane Ref.

The reaction ofα-halocarboxylic acids with sodium nitrite has been used to synthesize ni-

tromethane, nitroethane and nitropropane, although the reaction fails for higher nitroalkanes.^94

A number of other reactions have been reported which use nitrite anion as a nucleophile,

including: (1) reaction of alkyl halides with potassium nitrite in the presence of 18-crown-6,^95

(2) reaction of alkyl halides with nitrite anion bound to amberlite resins,^96 (3) synthesis of 2-

nitroethanol from the acid-catalyzed ring opening of ethylene oxide with sodium nitrite,^97 and

(4) reaction of primary alkyl chlorides with sodium nitrite in the presence of sodium iodide.^98

1.5.3 Ter Meer reaction

Br

R

O 2 N

R

O 2 N

NO 2 R

NO 2

NO 2 −

NO 2 −

−H+

H+

11 12

15

HCR

R

CHNO 2

Br 13

14

C NO 2 H NO 2 H + Br−

C

C

Figure 1.9

The Ter Meer reaction^99 provides a convenient route to terminalgem-dinitroaliphatic (15) com-

pounds via the displacement of halogen from terminalα-halonitroalkanes (11) with nitrite anion