Sciencemadness Discussion Board

nitropropene via nitromethane?

wertfun - 4-12-2005 at 11:57

Any body has info about nitropropene synth. below?

The method is the aldol condensation, using NaOH to condense the aldahyde and nitromethane and then HCL to dehydrate it to the nitropropene

As I know nitropropene with nitromethane gives inactive product.

[Edited on 4-12-2005 by wertfun]

[Edited on 4-12-2005 by wertfun]

Axt - 4-12-2005 at 14:25

General nitroalkane-aldehyde condensation is below. Know nothing on dehydrating it.
Quote:
To a stirred mixture of 3 moles of nitroalkane (note 1) and 120 ml. of water was added dropwise (note 2) a solution of 3 moles of aldehyde (CH3CHO, C2H6CHO) and 155 ml. of water during 90 minutes. Small portions of solid sodium carbonate were added from time to time to keep the mixture basic to litmus (note 3). Stirring was maintained for 2 hours after aldehyde was all added, then the mixture was let stand for 3 hours, ether extracted, and the ether extract was washed and dried (Na2SO4). The ether was removed and the nitro alcohol was twice vacuum distilled.

Note 1. Three-molar quantities were taken with nitromethane but only one-molar with nitroethane. Note 2. The aldehyde could be added all at once except in the preparation of 1-nitro-2-propanol. Note 9. The temperature rise was greatest in the preparation of I-nitro-2-propanol, gradually reaching 60° even with the incremental addition of aldehyde. This reaction mixture alone of the four nitro alcohols prepared became homogeneous as the reaction progressed.

J. Org. Chem.; 1955; 20(7); 927-936


Yield was 70% for nitromethane-acetaldehyde.

wertfun - 4-12-2005 at 17:50

I think we have to wait Darkfire to learn how to dehydrate it.

sparkgap - 4-12-2005 at 19:17

Uh, which of the three nitropropenes did you want? 1- and 2-nitropropene can't be prepared via a condensation reaction.

IIRC, just heating the nitromethane-acetaldehyde would cause spontaneous dehydration to 3-nitropropene, but I'm not really certain...

sparky (~_~)

wertfun - 5-12-2005 at 00:52

I wanted the the one in the second post( darkfire ) told about it shortly.

http://www.sciencemadness.org/talk/viewthread.php?tid=2908

The first post asked about P2NP. And darkfire answers.

CherrieBaby - 5-12-2005 at 10:23

You can't use this method (or any condensation) to get P2NP with nitromethane, it will give P3NP with nitromethane + phenyl acetaldehyde. Bezaldehyde + nitroethane give P2NP.

On the bonus side, if you want the nitrostyrene, you can use MeNO2 with Bezaldehyde to give Nitrostyrene, and that can then be reduced with just Fe/HCl to phenethylamine, as per: Synthetic Communications, 35, #7, 2005, pp 913-922 - kindly posted by acetate here: http://rapidshare.de/files/8566503/Synthetic.rar.html

wertfun - 6-12-2005 at 08:10

Thanks for PDF information.
Is it possible to use nitromethane in Urushiraba Method?

[Edited on 6-12-2005 by wertfun]

[Edited on 7-12-2005 by wertfun]

enima - 7-12-2005 at 09:13

why don't you _try_ reading before asking stupid questions.

enima - 7-12-2005 at 10:11

nitromethane in urushibara will result in methylamine being produced.

What would be interesting is urushibara and formic acid.


[Edited on 7-12-2005 by enima]

[Edited on 7-12-2005 by enima]

wertfun - 7-12-2005 at 10:56

thanks:P

Ephoton - 3-2-2006 at 07:14

I have read this thread a few times and an idea has been growing becouse of it.
3 nitro propene could be used to make one of thouse butyl couterparts for amph
that drone was talking about.
would not the alkene on the end of the chain reduce with the alkene on the nitro carbon.