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Ephoton
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thanx ill give that one a go 
sorry for the short replies im on pda at the moment
im sure some here would like this as it checks my spelling better than my nix box
[Edited on 3-10-2008 by Ephoton]
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Klute
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With what benzyl halide? Piperonyl?
Did you make i by halomethylation or from the alcohol?
I'm planning on trying this reaction this weekend. Hopefully i will have some black currant to add to the ginger, raspberry and coconut. Should try
adding them to tea one day 
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
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Ephoton
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hehe yep I think its well time I made some more inocent compounds too ill just
use the product from a loomins for now.
what about putting the product through a beayer villager. this way you can get the alcohol after hydrolisis with an extra carbon.
ie phenethyl alcohol.
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Klute
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Well, there would be more simple ways of doing this, like aldol with formaldehyde and reduction of the vinyl ketone, or even grignard from the benzyl
halide with paraformaldehyde. I guess it depends on how well the BV proceeds (oxidation of the alcohol?)
[Edited on 3-10-2008 by Klute]
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
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Ephoton
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I am interested in the flavor as well its just nice to find new ways to compounds I can make already.
bv ends in an ester you don't get the alcohol till the hydrolisis to my knowlage and experience. yes formaldehyde aldol another nice idea.
thanx.
anyway this is getting way off topic
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smuv
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| Quote: | Originally posted by Klute
Well, there would be more simple ways of doing this, like aldol with formaldehyde and reduction of the vinyl ketone, or even grignard from the benzyl
halide with paraformaldehyde. I guess it depends on how well the BV proceeds (oxidation of the alcohol?)
[Edited on 3-10-2008 by Klute] |
I hope I am not mistaken but, do you mean an aldol between the benzaldehyde and formaldehyde? They are both non enolizable.
Also the grignard of benzyl halides with formaldehyde can be irregular for some substrates. For example the major products of the reaction of
formaldehyde and benzyl magnesium chloride are o-Methylbenzyl alcohol and 2-hydroxymethylphenylethanol. I think this occurs because the charge of
the 'benzyl anion' gets conjugated with the ring making it super electron rich, allowing it to undergo electrophilic aromatic substitution under these
conditions. This is just my theory I could be dead wrong on why but I know it happens, Less so with acetaldehyde.
"Titanium tetrachloride…You sly temptress." --Walter Bishop
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Klute
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My bad on the aldol, I don't know know what I was thinking
That unconventional grignard seems pretty interesting. How is that o-methyl group formed? Dehalogeantion? I can understand the nucleophilic
substitution with formaldehyde to the benzylic alcohol, but how can there be two reactions with the anion (Aromatic nucleophilic substituion, and
addition on formaldehyde) to 2-hydroxyphenethylethanol? Or is this considering excess Mg?
Is the yield of these products high enough to be a preparative procedure, or is this only a complex mixture in low yields?
Well, terribly sorry for the bad suggestions, even though I would have placed my bets on the grignard.. Too bad then.
I guess Ephoton idea stands then. Although a smooth peracid would be needed to avoid any hydrolysis (using caro acid or even performic usually causes
aprtial or total hydrolysis of the ester during the oxidation). Hopefully peracetic should be kind enough with the ester?
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
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smuv
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| Quote: | | Well, terribly sorry for the bad suggestions, even though I would have placed my bets on the grignard.. Too bad then. |
Completely understandable. I have come to discover the grignard reaction is more complex than it seems on the surface. I find its reactivity with
unconventional substrates extremely interesting (non carbonyl compounds). Who knows though, maybe for methylenedioxybenzene things work out.
Are these alcohols supposed to smell nice?
Mechanism of the Reaction between Benzylmagnesium Chloride and
Carbonyl Compounds. A Detailed Study with Formaldehyde
Journal of Organic Chemistry, 47(7), 1243-9; 1982
[Edited on 10-5-2008 by smuv]
[Edited on 10-5-2008 by smuv]
Attachment: Irregular_grignard.pdf (897kB)
This file has been downloaded 1048 times
"Titanium tetrachloride…You sly temptress." --Walter Bishop
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Ephoton
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ammonium persulfate is the go for hydrolisis I would think.
butan - 2 - ones can then be made after nitric oxidation too PAA then any p2p synth from this compound if modified for the extra carbon will work.
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Klute
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Yes, I beleive the corresponding 2-phenyethanols posses pleasants smells too.
I think you must have attached the wrong article: this one is on the Hofman decomposition of N-bromo amides...
Ephoton, do you mean basic/neutral ammonium persulfate would be ok for the BV? I think this would majorily SEM, and oxidation to the acid and other
complex reactions.... Peroxodisulfates are suually used with H2SO4 (optionally in AcOH) for BV oxidations, and would surely cause at leasts ome
hydrolysis, although in 75% AcOH and stoechiometric amount of H2SO4 at 0-10°C it seems the ester is largely present.
I would go with a traditional peracetic, or perborate in GAA. Possibly the ester itself will smell very nice!
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
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smuv
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I fixed the link...woops!
If I were in your situation, I would seriously consider friedel crafts with ethylene oxide or grignard with ethylene oxide (starting from
methylenedioxybenzene or the para halide). I am fairly sure the friedel crafts can be done at low temperatures, so ether clevage should be minimal;
of note grignards on this substrate conceivably and to some extent do react with the methylenedioxy ring.
I guess ethylene oxide isn't the nicest stuff to work with though.
[Edited on 10-5-2008 by smuv]
"Titanium tetrachloride…You sly temptress." --Walter Bishop
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Klute
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Good point, but making ethylen and ethylen oxyde isn't evry practical, well not quite the chemistry I like. The BV oxidation does sound like a good
option now. I might give a try on microscale with some of the butanones.
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
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stoichiometric_steve
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Just to bring this up: in chloromethylations, usually bis(chloromethyl)ether is formed, a pretty potent carcinogen.
I hope all of you that want to follow this route keep that in mind...
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