New Piperonal Synth

[psychokitty]

METHOD FOR THE CONVERSION OF 3- AND 4-METHYLCATECHOL TO BENZALDEHYDE 
Patent Number: WO0006527 
Publication date: 2000-02-10 
Inventor(s): PANSEGRAU PAUL D 
Applicant(s): DAKOTA GASIFICATION CO (US) 
Requested Patent:  WO0006527 
Application Number: WO1999US16272 19990726 
Priority Number(s): US19980126482 19980730 
IPC Classification: C07C45/43; C07C45/27; C07C43/225 
EC Classification: C07C45/43, C07C205/32, C07C213/02 
Equivalents:  EP1102737 (WO0006527) 

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Abstract
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The 3- and 4-methylcatechols are converted to the corresponding benzaldehyde by first alkylating the hydroxyl groups to form an alkylated methylcatechol. The methyl group is then converted to a methyl dibromide group using 1,3-dibromo-5,5-dimethylhydantoin in the presence of a non-polar, non-reactive solvent such as carbon tetrachloride and heptane and a radical initiator having a ten hour half-life temperature in the range of 47 DEG to 55 DEG C. The dibromide is then hydrolyzed to form the aldehyde
 

[psychokitty]

Do I have to spell everything out like everyobee is in kindergarden in order to get a fucking reply to my post?

This is basically a synth for just about any benzaldehyde out there.  I know, I know, phenolic methyl benzenes aren't all that common; however, one could use as a substitute regular old OTC toluene and OTC dibromo dimethylhydantoin (common pool chemical; cheap) plus what seems to be a not-so-OTC peroxide catalyst (but maybe it is; who knows?) to form the intermediate dibromide (like when using calcium hypochlorite and toluene) which would then be hydrolyzed with water to form the oh-so-desired benzaldehyde.  FYI, in the same patent, they use nitromethane to form a nitroalkene which they then reduce using a strange borohydride reagent to the final phenethylamine.

To all bees:  Get your stingers out of the sand and pay more attention.  From here on out, if you fuckers refuse to read between the cracks then I'm going to bail as I seriously can't help but feel that I've outlived my usefulness here.  Really.

[UTFSE]

nice patent    nice find    crazy pussy

lots of big nice molecules floating down the page
lots of related stuff

thanks so much

OTEECEE & meeeee!!!!

[foxy2]

I was going to comment on their procedure to make dimethoxybenzene with dichloromethane cause its most definately a typo or intentional mistake because the procedure to make the methylene dioxy ring is almost identical.  I started writing a post, but figured it was waste since most everyone would see that.

It would bee nice if you used the patent markup to make it linkable.

And i have not seen OTC dibromo dimethylhydantoin (common pool chemical; cheap)  what I have seen is bromo,chloro dimethylhydantoin which I am not so sure works the same?   Plus most meth people who might bee interested probably saw dibromo dimethylhydantoin and figured its only a procedure for chemists, not realizing the chem might bee otc. 

Most of the patent is things that have been covered a bunch, except that oxidation.  Thats probably why there are no comments, and most people probably didn't spend the 10mins it takes to download and look at every page of the patent.

Ok were those enough comments to stroke your ego a bit?
   

To all bees:  Get your stingers out of the sand and pay more attention.  From here on out, if you fuckers refuse to read between the cracks then I'm going to bail as I seriously can't help but feel that I've outlived my usefulness here.  Really.

Awww, Now you know thats not true!!!
I think you must have some depleted neurotransmitters today, better take your medicine.   

Those who give up essential liberties for temporary safety deserve neither liberty nor safety

[UTFSE]

apologies for being so thick here pk

been looking for a way to methoxytoluene and there it is

and referring to the referred patent (US4335263) seems like starting with p-cresol can migrate into all sorts of interesting aromatic configurations

guess by now you done figured that I know less than whaleshit about this organic chemistry - I apologize again but I am trying===== very tiring.
OTEECEE & meeeee!!!!

[Rhodium]

And Kitty, remember that your post instantly got an "excellent" rating for me, so that it is easily found by people looking for good stuff in the search engine. I really appreciate your work!

[hest]

Turning dibromides into aldehydes is one of the 'clasic' ways to make an aldehyde. It is posible to make the dibromide with NBS( more common than 1,3-dibromo-5,5-dimethylhydantoin ) and some radical initiator. This might bee more easy.
Personal I prefer the oxidation of the monobromide with hexamethyltetraamin(boil the bromide with HMTA in alcohol, then hydrolyse in acid wather) or turning the bromide into the acetat (boiling it in AcOH with NaOAc, then hydrolyse, then oxidise the alcohol )

[Antoncho]

.... dear PsychoKitty, i am too sorry for not responding in any way to your post - i know how embarassing it is when you post some really good stuff and no one even bothers to give you a compliment  But please accept one from me, oh my exqusite feline comrade-in-arms!

Personally, i can't say i am particularly interesed in this rxn as i, frankly speaking, heard the very word "hydantoin" for the 1st time in my life in this thread   .

I've got a question for Hest, though. Hest, do you have any experience in performing that Sommelet rxn on any 2,5-substituted aldehyde? i'm asking cause i heard that it worked slower AND/OR w/lower yields on the things w/a substituted ortho-position - and i really want to know if it still could bee used....

i mean , chloromethylation is such an otc procedure, but the consequent usage of KCN is really a bummer... if there was a way to turn a 2,5-diMeO-4-something-benzyl chloride into the corresponding benzaldehyde, that would bee a very appealing route for many non-professional bees. What do you say? Anyone else can help?


Again, please excuse me for offtopic, but since Hest brought it up...


Antoncho

[hest]

Yes It works nicly, I personal alwayes used the bromide, not for making 2,5 dimetoxybenzaldehyde, but some other 2-methoxy-benzaldehydes. I don't have my notes right here, so I can't give you a writeup. I also used some DMSO oxidations to make the aldehyde, DMSO and CaCO₃ at 100°C for a short time (5min??) i think.
My targetMolequle was som (instabel) 2,3-dialdehydes but all the methods was tryet at 2-methoxy-benzylbromide(usual with greath luck).
My notes are not that greath, due to the instability of the targetmolequle.

[little_princess]

Please Antoncho and Hest can you continue your discussion about these other way to make 2,5 dmb in the DMF purfication question and vilsmeyer formylation thread? I'm really interested by your exchange of thoughts. And maybe we can rename the thread 'Other way than vilsmeyer to 2,5 dmb from 1,4 dmb'?

sorry for invading this thread with this silly request...