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Author: Subject: methylenedioxybenzyl chloride + sommelet?
Douchermann
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[*] posted on 25-9-2008 at 06:53
methylenedioxybenzyl chloride + sommelet?


In this link:

http://www.erowid.org/archive/rhodium/chemistry/piperonal.ni...

a method is given to produce piperonal from methylenedioxy benzene, with the substituted benzyl chloride being an intermediate. My question is, can the sommelet reaction work to produce an aldehyde from this? Why or why not? (I'm more interested in the theory than practicality)

Thanks




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[*] posted on 25-9-2008 at 07:12


I don't see why not.

If you search on 'piperonal sommelet' you will find that several patents refer to the preparation of this compound by this method.
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[*] posted on 25-9-2008 at 07:25


Haha whoops, forgot to search other places than just sciencemadness. Well thank you.



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[*] posted on 25-9-2008 at 08:18


Refluxing in somewhat conc. HCl might damage the methylendioxy bridge though... So better use more dilute acid and lower temps.



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[*] posted on 25-9-2008 at 09:35


GB1538214: What is refrenced in the rhodium article (its always best to track down the primary source)

Journal of Asian Natural Products Research, Vol. 9, No. 1, January–February 2007, 23–28.
Similar procedure; 82% yield on a 50mmol scale.

[Edited on 9-25-2008 by smuv]




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[*] posted on 25-9-2008 at 13:51


Excellent, thank you all.

Klute: In the sommelets I have performed, the HCl is quite dilute in the final mixture, not to mention the concentration would decrease rapidly due to the formation of the methylamine hydrochloride




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[*] posted on 26-9-2008 at 02:31


Good point.

The yields of piperonyl chloride from chloromethylations are very impressive. PainKilla had it right all along :)




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[*] posted on 29-9-2008 at 00:31


The Kornblum oxidation using NaHCO3/DMSO at 100°C works very well on benzyl chlorides. You might consider this as an alternative depending on the substrate nature. The Sommelet reaction is fine but it suffers from poor yield on ortho-substituted benzyl chlorides while the Kornblum oxidation does not have this limitation.



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[*] posted on 30-9-2008 at 15:04


Has anyone have the mp for piperonyl chloride and bromide? I don't have a handbook, and quite surprisingly haven't found anything (bo or mp) by searching the net.

I suppose both are solids?

BTW, I'm considering using them to prepare Cassione, or 4-(3',4'-methylendioxyphenyl)butan-2-one, a derivative of Raspberry ketone that smells like blackcurrant, by alkylating acetoacetate anion. Less trouble than going through the aldehdye IMHO.




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[*] posted on 30-9-2008 at 17:21


I ran a quick beilstein search...

For the bromide: mp range 45-50 the average being about 48c

Bp: 101-103c @ .1 torr; 110c @ 5 torr

For the chloride: mp range 20-23; most being 23

Bp: 78-80C @ .05torr; 89-91 @ 1torr; 134-135 @15 torr

I have not checked primary literature so keep that in mind; these are just straight from a database.

EDIT: Just to clarify the MP range is the min and max melting point recorded in the literature search among all the data collected.

[Edited on 9-30-2008 by smuv]




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[*] posted on 30-9-2008 at 22:06


Thank you very much Smuv. I guess the bromide is more practical to work with (recrystallization), less volatil and (possibly?) irratating?



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[*] posted on 1-10-2008 at 07:39


The conditions required to make the bromide might compromise the dioxol ring. Maybe look into it. After all HBr used to be used to cleave phenol ethers (albeit under harsher conditions).

If it were me...I would make the chloride; even if I could never practically recrystallize it. After distillation I am sure it would be pure enough to move onto the next step (all the side products I can fathom would have much higher bp's and also could be readily detected by TLC).

Whichever route you choose, good luck.




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[*] posted on 1-10-2008 at 07:57


I have stumble don several prearation forming the bromide form the alcohol with aq. HBr at RT or under in good yields:

WO 98/22417:

and J. CHEM. SOC. PERKIN TRANS. 1; 1235-8 (1993)


Quote:

Piperonyl Bromide- Piperonyl alcohol (101.44g, 0.067 mol) was added portionwise to HBr (49% aq. 100 mL), and the resultant suspension was allaowed to stand at room temp for 2h. DCM (1L) was then added, and the organic layer seperated. The aq layer was extracted with DCM (3x 800mL), and the combined organic extract was washed with water (2x500mL) and saturated aq NaHCO3 (3x500mL), dried and concentrated to yield the crude bromide (123.63g, ca. 85%), which was sued without further purification. An analytical sample was prepared by recrystallisation from light petroleum, mp 46-48°C (lit. mp 48°C) [NMR].


Or where you talking about bromomethylation? I think it is done in basicly the same conditions, with even more dilute acid at RT, so the HBr won't be such a problem for the ether bridge I suppose. But the very activated ring might cause di-halomethylation to some extent? Well, again it doesn't seem that problematic considering the high yields obtained in the refs you kindly provided.


EDIT: Considering that I want to use the benzyl halides for AcAcoEt alkylations in acetone and a weak base (carbonate), I prefer betting on the bromide which might be more reactive in these conditions, considering the preparation of the chloride or the bromide are very simialr and I suppose pretty much as efficent. But, if I had to go via halomethylation, I would do a first try with chloromethylation accoridng to the article you posted, and eventually try bromomethylation as the conditions are more practical and the bromomethyl methyl ether less volatil that it's counterpart (not like I was going to prepare before hand, be reassured :) ).

I will report back when i get time to start this.


[Edited on 1-10-2008 by Klute]




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[*] posted on 1-10-2008 at 09:34


I was worried about ether cleavage during bromomethylation. Of course the procedure you posted shows that my concerns were not warranted.

With these reactions there is always some dihalomethylation additionally the formation of derivatives where the halomethylated product is attacked by some uncreated substrate (like a Friedel-Crafts between product and substrate).

I have seen a few examples of bromomethylation of activated substrates in literature, they all seem to use HBr in AcOH along with paraformaldehyde. I am not sure why these conditions were used instead of aqueous HBr, then again this is just what I have stumbled upon, I have never extensively researched this subject.

PS I never knew acetoacetic ester synthesis could be preformed under such mild conditions.




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[*] posted on 1-10-2008 at 12:36


See patent US 1 094 417 for an example, where AcAcOEt is alkylated with p-MeOBnCl in ~50% isolated yield. I guess conventional RONa/ROH conditions would be prefered.

Do you still ahve the bromomethylation refs at hand? I remeber reading one or two myself, the reaction looked very practical and pretty high yielding.




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[*] posted on 1-10-2008 at 18:34


So here is what I have on the subject:

Eur. J. Org. Chem. 2002, 3162-3170
Bis-bromomethylation of p-dimethoxybenzene

J. Org. Chem. 1993,58, 1262-1263
General bromomethylation procedure for activated aromatics; every modern bromomethylation paper seems to reference this one.

Fuson, R. C.; McKeever, C. H. Org. React. 1942, 1, 63.
Review of chloromethylation; covers some bromomethylation and chloroethylation, propylation etc...

Organic Process Research & Development 2005, 9, 1013-1014.
Observation of Bromomethyl Ethers during the Bromomethylation of Aromatic Compounds.

P.S. its a GB patent no US; interesting though.




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[*] posted on 1-10-2008 at 22:22


Thank you very much!

What's the problem with british patent, heh? :mad: :P




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[*] posted on 2-10-2008 at 02:17


Attached.

Attachment: Aqueous bromomethylation utilizing PTC.pdf (96kB)
This file has been downloaded 1501 times

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[*] posted on 2-10-2008 at 02:18


Attached.

Attachment: Chloromethylation of Alkoxybenzenes and conversion to benzaldehyde via sommelet.pdf (205kB)
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[*] posted on 2-10-2008 at 02:21


Attached.

Attachment: WO2005042512 - Piperonal - chloromethylation benzyl acetate alcohol oxidation to aldehyde.pdf (620kB)
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[*] posted on 2-10-2008 at 02:23


One more, can post more on chloro/bromomethylation if it's needed, but this covers a lot.

Attachment: Bromomethylation with paraformaldehyde and HBr.pdf (249kB)
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[*] posted on 2-10-2008 at 05:52


Wonderfull! thanks alot PainKilla!



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[*] posted on 2-10-2008 at 20:01


klute I tried that us patent at espace and got a patent on folding gocarts any chance on some more info on this condensation as I would love to know about it.

thanx




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[*] posted on 2-10-2008 at 22:49


Sorry, I thought you were refering to the WIPO patent at first..

I was pretty stunned, as I had the paper version in front of my eyes, and fell onto the bloody folding go-cart at espacent or pat2pdf.org!

I've just realized that it's a british aptent actually! Sorry for the mistake! (see, british patents kick ass :P
:D )

Here is the link:

Method of producing 1-(4-methoxyphenyl)butanone and 1-(4-methoxyphenyl)butanone

and the WIPO patent:

[Edited on 3-10-2008 by Klute]

Attachment: 98022417.pdf (893kB)
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[*] posted on 2-10-2008 at 22:52


And the quoted J. Chem. Soc., Perkin Trans. article

I haev found more info on the acetoacetate condensation, and will post the article as soon as i gather them. I have found a patent where a michael addition very similar to a claisen, except that a Mannich base is used instead of a alkyl halide (forming the alkene in-situ), using sodium isopropoxide in IPA.
There also a seemingly very interesting article on Claisen via ptc in aprotic solvents. I will post all this in a related thread, as I'm deviating from the thread subject here..


[Edited on 3-10-2008 by Klute]

Attachment: Perkin1_1993p1235.pdf (520kB)
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