Organic Chemistry of Explosives

108 Synthetic Routes to Nitrate Esters

3.9 Synthetic routes to some polyols and their nitrate ester derivatives

CH 3 NO 2 + 3 CH 2 O C

CH 2 OH CH 2 ONO 2

CH 2 ONO 2

CH 2 ONO 2

CH 2 OH

O 2 N CH 2 OH O 2 N C

100 % HNO 3

or

H 2 SO 4 , HNO 3

(^5859)
KHCO 3 (aq)
Figure 3.33
CH 3 CH 2 NO 2 + 2 CH 2 O
CH 2 OH CH 2 ONO 2
CH 2 ONO 2
NO 2
CH 2 OH
CH 3 C NO 2 CH 3 C
100 % HNO 3
or
H 2 SO 4 , HNO 3
(^6061)
KHCO 3 (aq)
Figure 3.34
The reaction between formaldehyde and compounds containing acidic protons is probably
the most important route to polyols. Some of these polyols have beenO-nitrated and used as
practical explosives. The condensation of nitromethane and nitroethane with excess formalde-
hyde in the presence of potassium hydrogen carbonate yields tris(hydroxymethyl)nitromethane
(58)^133 and 1,1-bis(hydroxymethyl)nitroethane (60)^134 respectively. The nitration of (58) and
(60) with either absolute nitric acid or mixed acid gives the secondary high explosives, (59)^135
and (61)^136 respectively.
CH 2 ONO 2
CH 2 ONO 2
CH 2 ONO 2
C O 2 NOCH 2 C
CH 2 OH
CH 2 OH
HOCH 2 CH 2 OH
HNO 3 , 0 °C
95 %
362
Figure 3.35
The condensation of acetaldehyde with excess formaldehyde in the presence of aqueous
calcium hydroxide yields pentaerythritol (62);^137 esterification of the latter with absolute nitric
acid yields the powerful explosive, pentaerythritol tetranitrate (PETN) (3).^11
63 4
C
CH 2 OH
CH 2 OH
CH 2 OH
CH 3
64
C
CH 2 OH
CH 2 OH
CH 2 OH
C CH 3 CH 2
CH 2 ONO 2
CH 2 ONO 2
CH 2 ONO 2
CH 3
65
C
CH 2 ONO 2
CH 2 ONO 2
CH 2 ONO 2
CH 3 CH 2
Figure 3.36
1,1,1-Tris(hydroxymethyl)ethane (metriol) (63) and 1,1,1-tris(hydroxymethyl)propane (64)
are commercially available and yield the trinitrate esters (4)^138 (metriol trinitrate) and (65)^139