Derivatives of polynitroaliphatic alcohols 47
in the presence of TFAA or PPA as condensing agents;^310 ,^313 ,^314 (4)trans-esterification of the
methyl ester of the acid component with the alcohol in the presence of sulfuric acid or oleum;^310
(5) using the alcohol and acid chloride in the presence of pyridine, trialkylamines or potassium
carbonate;^315 ,^316 (6) reacting the acid chloride and the alcohol without solvent;^298 ,^317 ,^318 and
(7) direct esterification of the alcohol with phosphorous trichloride, chlorosulfonic acid or
anhydrous nitric acid.^311 ,^314
CO 2 CH 2 C(NO 2 ) 2 X
CO 2 CH 2 C(NO 2 ) 2 X
X(O 2 N) 2 CCH 2 O 2 C
X(O 2 N) 2 CCH 2 O 2 C
X(O 2 N) 2 CCH 2 O OCH 2 C(NO 2 ) 2 X
CH 3
NO 2
(O 2 N) 2 FCCH 2 O 2 C CO 2 CH 2 CF(NO 2 ) 2
O 2 N
(O 2 N) 2 FCCH 2 O OCH 2 CF(NO 2 ) 2
O
(O 2 N) 3 CCH 2 O C(CH 3 )
O
CH 2
169, X = F (Ref. 320)
170, X = NO 2 (Ref. 320)
NO 2
168 (Ref. 319)
171, X = CH 3 (Ref. 314)
172, X = F (Ref. 319)
174 (Ref. 321)
173 (Ref. 318)
OO
Figure 1.84
A huge number of ester and carbonate derivatives of polynitroaliphatic alcohol have been
synthesized; driven by the search for new explosives and energetic plasticizers and oxidiz-
ers for propellant and explosive formulations. Most of these are derived from 2-fluoro-2,2-
dinitroethanol^319 −^321 and 2,2,2-trinitroethanol^298 ,^310 ,^311 ,^318 and have excellent oxygen bal-
ances. Some examples are illustrated above (168–174) but more comprehensive lists can be
found in numerous reviews.^37 ,^114 ,^241 ,^242 Direct esterification of polynitroaliphatic alcohols
with nitric acid, mixed acid, or acetic anhydride–nitric acid has been used as a route to mixed
polynitroaliphatic–nitrate ester explosives.^311
H 2 SO 4 (cat)
NO 2
NO 2
C
NO 2
NO 2
X CCCH 2 OCH 2 OCH 2
NO 2
NO 2
2 X CH 2 OH + (CH 2 O)n X
175, X = CH 3 , 70 %
176, X = F, 75–80 %
177, X = NO 2 , 90 %
25, X = CH 3 ,
119, X = F
159, X = NO 2
Figure 1.85
AcOH, O 2 N NO 2
H 2 SO 4 (cat)
178
69 % OO
NO 2
NO 2
19
HOCH 2 CCH 2 OH + (CH 2 O)n
Figure 1.86