Synthetic routes to polyols and derivatives 109on nitration with mixed acid. Metriol trinitrate (MTN) is a practical explosive and is attract-
ing renewed interest as a promising alternative to nitroglycerine in propellant and explosive
formulations. Metriol trinitrate, like nitroglycerine, is an excellent plasticizer for nitrocellulose.
O OHOH 2 CHOH 2 C CH^2 OHCH 2 OHHOH 2 CHOH 2 CCH 2 OHCH 2 OHOHOO 2 NOH 2 CO 2 NOH 2 CCH 2 ONO 2CH 2 ONO 2O 2 NOH 2 CO 2 NOH 2 CCH 2 ONO 2CH 2 ONO 24 eq CH 2 OHH 2 SO 4 ,
HNO 3H 2 SO 4 ,
HNO 368 69(^6667)
ONO 2
Figure 3.37
Friederich and Flick^140 synthesized the tetranitrate ester (67) by condensing cyclopentanone
with four equivalents of formaldehyde followed by nitration of the condensation product (66)
with mixed acid. Reduction of the ketone group of (66), followed by nitration, yields the
pentanitrate ester (69). A similar route was used to synthesize analogous nitrate esters from
cyclohexanone.^140
72 73
70
HNO 3
HNO 3
C
CH 2 OCH 2 CH=CH 2
HOCH 2
CH 2 OCH 2 CH=CH 2
O 2 NOCH 2
OsO 4 , H 2 O 2 ,
EtOH
CH 2 OCH 2
CH 2 OCH 2
CH CH 2 ONO 2
ONO 2
CH CH 2 ONO 2
ONO 2
C C
CH 2 OCH 2
HOCH 2
CH 2 OCH 2
OH
CH CH 2 OH
CH CH 2 OH
OH
CH 2 OH
CH 2 OH CH 2 ONO 2
71
O 2 NOCH 2
CH 2 OCH 2 CH=CH 2
CH 2 OCH 2 CH=CH 2
CCH 2 ONO 2
Figure 3.38
The dihydroxylation of alkenes is a useful strategy for the synthesis of polyols and these
can be nitrated to the corresponding nitrate esters. Evans and Gallaghan^141 synthesized both
the mono- (74) and di- (70) allyl ethers of pentaerythritol and used these for the synthesis of
some novel nitrate ester explosives.