Synthetic routes to some polyols and their nitrate ester derivatives

9 SYNTHETIC ROUTES TO SOME POLYOLS AND THEIR NITRATE ESTER DERIVATIVES 

The reaction between formaldehyde and compounds containing acidic protons is probably the most important route to polyols. Some of these polyols have been 0-nitrated and used as practical explosives. The condensation of nitromethane and nitroethane with excess formaldehyde in the presence of potassium hydrogen carbonate yields tris(hydroxymethyl)nitromethane (58) and l,l-bis(hydroxymethyl)nitroethane (60) respectively. The nitration of (58) and (60) with either absolute nitric acid or mixed acid gives the secondary high explosives, (59) and (61) respectively. 

The condensation of acetaldehyde with excess formaldehyde in the presence of aqueous calcium hydroxide yields pentaerythritol (62) esterification of the latter with absolute nitric acid yields the powerful explosive, pentaerythritol tetranitrate (PETN) (3).  

CH3—C-CH2OH CH3—C-CH2ONO2 CH3CH2—C-CH2OH CH3CH2—C-CH2ONO2 

1 -Tris(hydroxymethyl)ethane (metriol) (63) and 1,1,1 -tris(hydroxymethyl)propane (64) are commercially available and yield the trinitrate esters (4) (metriol trinitrate) and (65)  

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