Organic Chemistry of Explosives

254 Synthetic Routes toN-Nitro

CH 2

N

NN

N

H 2 C CH 2

H 2 C CH 2

O 2 N NO 2

HO OH

NO 2

252

N

NN

N

H 2 C CH 2

H 2 C CH 2

O 2 N NO 2

CH 2

CH 2

O 2 NO N ONO 2

NO 2

256

AcO N OAc

NO 2

257

MeNH 2

NH 2

CH 2

NH 2

CH 2 NH 2

CH 2 NH 2

Ac 2 O

(CH 2 ) 6 N 4

Hale

nitrolysis

255

100 °C

• 2H 2 O, 16 %

HNO 3 , 0 °C

254

44 %

78 %

45 %

HNO 3

38 %

AcOH,

NaOAc

69 %

239

(DPT)

CH 3

253

N

NN

N

H 2 C

H 2 C

CH 2

CH 2

O 2 N NO 2

CH 3

O

NN

O

258

H 2 C

H 2 C

CH 2

CH 2

O 2 N NO 2

N

Figure 5.112 The chemistry of dimethylolnitramine (252)

converted to the more stable diacetate ester (257) on reaction with sodium acetate in acetic

anhydride.^188 1,3-Dinitroxydimethylnitramine (256) is present in the aqueous filtrate from both

the KA-process and E-process (Section 5.15.1).

5.15.4.3 The chemistry of linear nitramines

ONO 2

MeOH

60 %

(2 steps)

EtOH

15 %

(2 steps)

(CH 2 ) 6 N 4

104

247

(BSX)

HNO 3 , N 2 O 5

HNO 3 , Ac 2 O,

20 °C, 51 %

HNO 3 , Ac 2 O,

70 °C, 88 %

AcOH,

NaOAc

76 %

HNO 3

54 %

1. Ac 2 O


2. 97 % HNO 3 ,
   25 °C

OAc

NO 2 NO 2 NO 2

O 2 NO

259

NNN

NO 2 NO 2 NO 2

O 2 NO

260

NNN

OAc

NO 2 NO 2 NO 2

AcO NNN

EtO

261

OAc

NO 2 NO 2 NO 2

NNN

MeO

262

OMe

NO 2 NO 2 NO 2

NNN

Figure 5.113 Linear nitramines from the nitrolysis of hexamine

The nitrolysis of hexamine can be used to obtain the linear nitramines (247), (259) and (260)

depending on the conditions and reagents used. Thus, the nitrolysis of hexamine with a mixture