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Author: Subject: Nitrogen adds to Double Bond
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[*] posted on 6-1-2017 at 11:34
Nitrogen adds to Double Bond


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.

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morsagh
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[*] posted on 6-1-2017 at 14:37


This is conjugated alkene bond with aldehyde, so i guess that mechanism is 1,4 addition of nucleophille.
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[*] posted on 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.
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[*] posted on 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.
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[*] posted on 7-1-2017 at 07:02


Quote: Originally posted by Crowfjord  
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.




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[*] posted on 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
...




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[*] posted on 7-1-2017 at 07:42


Quote: Originally posted by Eddygp  


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 Addition
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[*] posted on 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.



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[*] posted on 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/cr0306788



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[*] posted on 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?
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[*] posted on 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]
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[*] posted on 10-1-2017 at 15:35


No. Why don't you just tell the guys what you are trying to do?

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