Organic Chemistry of Explosives

5-Membered rings – 2N 295

NOH

2

NN

N

H

NO

CH 3

H 3 CH 3 C

N

H

NH 2

CH 3

N

N

H

N 2

CH 3

H 3 C

N

H

N

H

N

N

CH 3

N

H

N

H

N

N

O 2 N

CH 3

N

H

N

H

N

N

O 2 N O 2 N

COOH

N

H

N

H

N

N

NO 2

N

N

N

N

O 2 N

NO 2

NH 2

H 2 N

NaOAc

H 2 NOSO 3 H

EtOH

N 2 H 4

1

OO

OO

34

7 6 5

89

(DNPP)

10

(LLM-119)

NaNO 2 ,

HCl (aq) N 2 H 4 , EtOH

heat

HNO 3 , TFA

H 2 SO 4 ,

Na 2 Cr 2 O 7

100 % HNO 3

45 °C, 70 % base (aq)

NaNO 2 ,

EtOH,

TFA

Figure 7.1

(9) with hydroxylamine-O-sulfonic acid^8 in aqueous base yields LLM-119 (10);^7 the latter

exhibits higher performance than DNPP and a lower sensitivity to impact.

N

N

H

H 2 N NO 2

O 2 N

N

N

H

NO 2

O 2 N

H 2 NNMe 3 I

11 12

(LLM-116)

DMSO, KOtBu

70 %

Figure 7.2

The increase in thermal stability and reduction in impact sensitivity observed on introduc-

ing amino groups adjacent to nitro groups in aromatic systems is known to result from in-

tramolecular hydrogen bonding interactions (Section 4.8.1.4). This effect is also illustrated in

4-amino-3,5-dinitropyrazole (LLM-116) (12), an energetic material showing a lower sensitiv-

ity to impact than 3,5-dinitropyrazole (11). LLM-116 (12) is synthesized from theC-amination

of 3,5-dinitropyrazole (11) with 1,1,1-trimethylhydrazinium iodide (TMHI) in the presence of

potassiumtert-butoxide base.^9

N

N

NMe 2

Cl

O 2 N

N

N

H

NH 2

H 2 N

O 2 N

(^1314)
heat, 80 %
EtOH, N 2 H4.H 2 O
Figure 7.3