Methacrolin is added dropwise to Pthalimide in alcohol with some NaOEt and warmed at 40 - 50°C for 2 hrs to form
a-methyl-B-pthalimidopropionaldehyde. Y ca: 80% (F. e. s. O. A. Moe and D. T. Warner, Am. Soc. 71, 1251 (1949)).
I wanted to post this reference so I could ask if this reaction might be general to all alkenes.
I can´t be certain since the aldehyde group is electron withdrawing, but the nitrogen adds to the second carbon away from the aldehyde, maybe
because it is less hindered.
morsagh - 6-1-2017 at 14:37
This is conjugated alkene bond with aldehyde, so i guess that mechanism is 1,4 addition of nucleophille.zed - 6-1-2017 at 17:40
No, not all Alkenes. It is a special case.
A similar reaction is found in the reaction of Phenethylamine with EthylAcrylate.Crowfjord - 6-1-2017 at 18:02
It's definitely a 1,4 addition and it works due to the electronic withdrawing nature of the carbonyl. Also known as a Michael addition or Micheal
reaction. Eddygp - 7-1-2017 at 07:02
It's definitely a 1,4 addition and it works due to the electronic withdrawing nature of the carbonyl. Also known as a Michael addition or Micheal
reaction.
I thought Michael was reserved exclusively for enolate (1,4-)conjugate addition, other Nu are just referred to as conjugate addition or 1,4-addition.
I can be wrong.PHILOU Zrealone - 7-1-2017 at 07:06
N adds to double bond...and so what...
It happens in a lot of examples into chemistry: C=O bond addition
-imine formation from R-NH2
-amine formation from R-NH-R'
-oxyme formation from H2N-OH
-hydrazone and azine formation from H2N-NH2
-nitrimide formation from H2N-NO2
... C=NH bond addition
-hydrazine, hydrazone and azine formation from H2N-NH2
... C=C bond addition
-very common into aromatic serie like NO2(+) nitration, diazo coupling
-direct addition of HNO3, NxOy or Cl-NO or Cl-NO2 onto alkenes --> nitroso, nitro, nitrosonitro, dinitro, nitritonitro
...Crowfjord - 7-1-2017 at 07:42
I thought Michael was reserved exclusively for enolate (1,4-)conjugate addition, other Nu are just referred to as conjugate addition or 1,4-addition.
I can be wrong.
Whoops, yeah you're right. Michael reaction doesn't include nitrogen or oxygen nucleophiles. The mechanism of addition is pretty much the same though.
Michael Additionxxxxx - 7-1-2017 at 15:34
Here is another paper describing the addition of nitrogen to a double bond. I'm not certain it would be general to all alkenes because of the ether
linkage.
DDTea - 7-1-2017 at 16:57
Searching for terms like "carboamination" and "hydroamination" will turn up a lot of methodology, with varying scopes and utility. Anti-Markovnikov
hydroamination of alkenes remains an important research goal. This review is probably a good starting point: http://pubs.acs.org/doi/abs/10.1021/cr0306788xxxxx - 8-1-2017 at 11:53
So the process might work with ethylene or propylene on a benzene ring with an electron-withdrawing subsituent or just a benzene ring if a base of
suffiencient strength is used?Maroboduus - 8-1-2017 at 12:18
Methacrolein in that first diagram seems to have five bonds on the central carbon and an extra hydrogen atom.
WTF?
BTW: You should read some of this guy's other posts.
[Edited on 8-1-2017 by Maroboduus]zed - 10-1-2017 at 15:35
No. Why don't you just tell the guys what you are trying to do?
