I am attempting to perform a Schmidt reaction (RCOOH ----NaN3/H2SO4----> RNH2) for a project at school. All of the literature I've found on this
reaction suggests to dissolve the substrate in chloroform, add concentrated H2SO4, and then add the NaN3 slowly and later.
The problem is, every time I add the H2SO4, my CHCl3 solution starts to darken and a tar begins to form immediately. I've tried cooling the H2SO4 and
CHCl3, as well as making the addition extremely slow. I've also tried extensive drying of the chloroform before use.
Any suggestions to make this run smoothly?
Thanks!mario840 - 1-1-2011 at 11:23
chloroform and H2SO4 is a method of purifying of CHCl3, just use ether or dichloromethanequerjek - 1-1-2011 at 11:28
Tried it in DCM and got the same tarry results. Also, lots of literature has said not to use DCM because of its explosion risk with the HN3 formed in
situ. Ether I'm not entirely sure about, but I haven't seen that used a solvent in my research, and given its latent explosion risk, adding HN3
doesn't sound like a good idea to me...
[Edited on 1-1-2011 by querjek]rrkss - 1-1-2011 at 11:31
Distill the the darkened CHCl3 and try again with the more pure distilled product. Usually H2SO4 is added to CHCl3 to destroy organics.mario840 - 1-1-2011 at 11:32
why not ?? just generate it from NaN3 and H2SO4 etc. and condensate or not and introduce into solution with rubber hose this is so simple , calculate
how many grams do you need and make it from x g of NaN3 , maybe your chemical are bad qualityrrkss - 1-1-2011 at 11:37
why not ?? just generate it from NaN3 and H2SO4 etc. and condensate or not and introduce into solution with rubber hose this is so simple , calculate
how many grams do you need and make it from x g of NaN3 , maybe your chemical are bad quality
Look up HN3, not a good idea what you are proposing, highly toxic and explosive.smuv - 1-1-2011 at 11:50
I used to have a reference that pretty meticulously described how to preform the schmidt reaction and prepare the hydrazoic acid
solution...unfortunately I cannot find it. I believe this is the citation: Wolff, H. Org. React. 1946, 3.
While hydrazoic acid solutions are dangerous, they may be prepared in a safe manner if proper protocols are followed.
Edit: I found the reference, I can't upload it though because I only have the raw scanned pages, I don't have time to convert to pdf. It sounds like
you are doing everything right, although you are generating the HN3 in situ. Maybe you should try an ex situ preparation of an HN3 solution and then
add this to your substrate. Ref attached. You could also use benzene as a solvent.
There is a good possibility the compound you are doing the reaction on is not very acid stable causing the strongly acidic reaction conditions to
destroy it. I can provide more help if you tell me specifically what compound you are performing the schmidt on.
[Edited on 1-1-2011 by smuv]mario840 - 1-1-2011 at 12:22
when you working with HN3 soon or later you will be exposed to this chemical beacuse of low boiling point , withouth experience and most important
PROPER LAB GLASS , you will fail , like myfan64 who died probably from phosgene, for me easiest way is bubbling HN3 through ChCl3 or beznzene or ether
(of course with a little phenidone), everything is toxic try some 250 g NaCl and good luck to your kidneysquerjek - 1-1-2011 at 12:26
Thanks for that reference! I've give it a shot later. Any ideas whether toluene would function as a solvent?
The substrate is methylenedioxyphenylpentanoic acid--I gather that the methylenedioxy bridge isn't too acid-stable?smuv - 1-1-2011 at 12:48
Yeah, definitely prepare the Hydrazoic acid first, it is a way weaker acid than sulfuric. If that doesn't work you can do the hoffmann reaction and
avoid acidic conditions, use dioxan as a co solvent (might be able to get away with methanol).
OK must stop procrastinating...I will post that full ref later. My gut about toluene is it won't be a good solvent but I can't really think of any
reasonable reaction it would undergo with HN3 that benzene wouldn't, but I really haven't given it much thought.The WiZard is In - 1-1-2011 at 14:50
I used to have a reference that pretty meticulously described how to preform the schmidt reaction and prepare the hydrazoic acid
solution...unfortunately I cannot find it. I believe this is the citation: Wolff, H. Org. React. 1946, 3.
Me the analogue guy again. The ever useful Merck Index has
a chapter on Named Reactions — Under Schmidt they list your
Wolff ref. and among others -
Thomas Laue, Andreas Plagens - 2005 - 310 pages - Preview
Schmidt Reaction Reaction of carboxylic acids, aldehydes or ketones with hydrazoic acid ORC + HN3 ... aldehydes or ketones with hydrazoic acid in the
presence of a strong acid is known as the Schmidt reaction.1,2 A common application is ...Ozone - 1-1-2011 at 22:31
There must be crap in your chloroform. Concentrated sulfuric acid is routinely used as a clean-up method for halogenated organics--frequently yielding
red-tar-stuff.
Acid chould be OK.
Do *not*, however, mix with a strong alkali such as NaOH--You will make carbene and the risks of explosion, etc. increase rapidly.
