Chemistry Forums for Students > Organic Chemistry Forum for Graduate Students and Professionals

Explosive decomposition of 1,5-Hexadiene-3,4-di-O-mesylate

(1/3) > >>

MOTOBALL:
Many years ago I prepared 1,5-hexadiene-3,4-diol (mixture of the erythro and threo isomers) as a syrup by the action of a Zn/Cu couple on acrolein.

The product was purified by distillation under reduced pressure to give a syrup; b.p. 92 Deg/10 mm Hg; refractive index Na D line @ 21 deg =  1.4745
Lit. b.p 55 deg/0.02 mm Hg; Na D line @ 25 deg = 1.4739.

A solution of this syrup in pyridine was treated with CH3SO2Cl (3% xs); extraction with CHCl3 and the usual workup gave a yellow syrup; TLC showed 1 minor (fast-moving) component, and 1 major (slower-moving) component. The IR spectrum showed no -OH absorption.

On attempted distillation under reduced pressure (7 mm Hg) the product decomposed explosively at ca. 120 deg (oil bath temp.).
My recollection is that a nasty black residue and some shattered glassware was the result.

I had previously recrystallized mesylates of carbohydrates without mishap.

I have subsequently encountered, via the internet, the occasional comment regarding the explosivity of mesylates.

Any comments and literature references would be appreciated.

Regards,
MOTOBALL

rolnor:
Its strange, there is no red-ox possible really, maybe elimination?

clarkstill:
Elimination-electrocyclization-elimination to give benzene?

Honestly no idea, but a fun thought experiment.

rolnor:
Interesting idea, I think of a similar case, if you mix acetone with conc. sulphuric acid you get mesitylene.

Babcock_Hall:
I wonder whether it would be helpful to calculate the oxygen balance of this molecule.  Explosives are sometimes formulated so that their combined oxygen balance is close to zero, although this is far from being always true.  Suzanne Bell's book Forensic Chemistry talks about this a little on pp. 371-372.  It is also discussed in Chapter 5 of a forensic chemistry book (Jay Siegel, ed.; Wiley Blackwell) by John Goodpaster, starting at p. 189.  The oxygen balance = (mass of oxygen released or consumed)/(mass of explosive).

Navigation

[0] Message Index

[#] Next page