Organic Chemistry of Explosives

54 Synthetic Routes to AliphaticC-Nitro

salts of polynitroalkanes are exceptionally sensitive to mechanical stimuli and explode readily.

However, these salts are readily converted into the more predictable 1-halo-1,1-dinitro deriva-

tives, which in turn, are reconverted to the originalgem-nitronitronate salts on treatment with

aqueous potassium iodide.

CCH 2 C

NO 2 K

NO 2

KO 2 N

O 2 N

NO 2

C

NO 2

136

O 2 N CH 2 CH 2 NO 2 1. NH^4 OH, EtOH (aq)

2. KCl
   199

Figure 1.96

In Section 1.10.2.3 we observed that a base can react with 1,1,1-trinitromethyl compounds to

either remove an acidic proton or act as a nucleophile to displace a nitro group. Trinitromethyl

compounds can also undergo rearrangement reactions is the presence of a base or nucle-

ophile. 1,1,1,3-Tetranitropropane (136) undergoes an internal redistribution of nitro groups

on treatment with aqueous alkali or ammonium hydroxide to give 1,1,3,3-tetranitropropane,

which is isolated as its sparingly soluble di-potassium salt (199) on adding an aqueous solu-

tion of potassium chloride to the reaction mixture.^253 ,^360 This type of rearrangement occurs

with other trinitromethyl derivatives of structure (198) and in this way, the potassium salt of

1,1,3,3-tetranitrobutane (201) is obtained from 1,1,1,3-tetranitrobutane (200).^361

X = H or alkyl

Y = NO 2

CH 2

NO 2 X

NO 2 Y

198

O 2 NC CH

Figure 1.97

KOAc, EtOH

NO 2

NO 2

C CH 2 CCH 3

KO 2 N

O 2 N

NO 2 NO 2

NO 2

200

2 NCHCO 2 C

H

CH 3

201

Figure 1.98

2,2,2-Trinitrochloroethane (202) and 2,2,2-trinitroethyl acetate (203) also undergo nitro

group rearrangement in the presence of potassium nitrite to give the di-potassium salt of

1,1,2,2-tetranitroethane (74) in both cases.^362

C

NO 2

NO 2

O 2 NCH 2 X

KNO 2 , MeOH (aq) NO^2 K

NO 2

KO 2 N

O 2 N

202, X = Cl^74

203, X = OAc

CC

Figure 1.99