Sciencemadness Discussion Board

Cyclobutanone

runlabrun - 24-2-2005 at 05:03

Hi all,

Im looking for a way to produce cyclobutanone, all ive found so far is the synth on orgsyn which i dont like... Sorry!
The one thing i did find however is by searching for cycloketone formation i found one of rhodium mirrors pages which listed cyclopentanone synthesis as:
Quote:
100g adipic acid and 10g Ba(OH)2 is intimately mixed and placed into a flask with a thermometer. The rxn is heated to 280°C, the mixture initially melts and then the distillation takes place, which lasts about 1-2 hrs. The hot distillate is saturated with NaCl, the upper layer is decanted and distilled, collecting the fraction boiling at 128-130°C. Dry with MgSO4.
Yield: 51g (89% of theory).
Notes:
- Ca(OH)2 may bee substituted for Ba(OH)2 without much loss in the yield.
- if one is to use pre-made Ca or Ba adipinate, no temp control is necessary.

Could this be possible starting from glutaric acid? the same mechanism might apply?
I can find references to this reaction or the apparent yeilds... anyone got an idea where this came from? i searched to no avail...

If this could work, distillation of cyclobutanone from glutaric acid / calcium hydroxide would be very nice....
Where would you get glutaric acid from? glutamic is in health stores so is there a way to remove the amine? or is glutaric acid availible aswell?

Thanks.
-rlr

sparkgap - 24-2-2005 at 05:40

rlr,

I regret to inform you that, although your idea of synthesizing cyclobutanone from glutaric acid is logical, it suffers from the fatal flaw in that kinetic and thermodynamic considerations are bound to make your synthesis difficult. The synthesis described by Rhodium is known to work well only on adipic and pimelic acids (corresponding to cyclopentanone and cyclohexanone), not very well on the higher dicarboxylic acids, and almost not at all for succinic and glutaric acid.

Come to think of it, constructing four-membered rings were almost always difficult in organic synthesis, unless some special factors intervened.

BTW, mechanism wise, it looks like Dieckmann cyclicization, except that diacids are used instead of diesters.

sparky (^_^)

runlabrun - 24-2-2005 at 15:02

Crap... Thanks sparkgap.
About 5min after i posted that i found some info in vogel.
Thats what i have thus far figured out, 4 member rings are terrible to make...
Well if anyone can think of a way apart from the method on orgsyn to make cyclobutanone.... share.... im stumpped...

Thanks
-rlr