dormouse (Member)
04-19-00 06:47
No 122781
      Yet one more use of Dronian PTC technology: a kinder, gentler MDMA synthesis -drone  Bookmark   


   the Hive BB
  Serious Chemistry Forum
  Yet one more use of Dronian PTC technology: a kinder, gentler MDMA synthesis
  
profile | register | preferences | faq | search
 
 next newest topic | next oldest topic 
Author  Topic:   Yet one more use of Dronian PTC technology: a kinder, gentler MDMA synthesis 
drone 342
Member   posted 12-30-98 12:40 PM          
--------------------------------------------------------------------------------
By using a 10X molar excess of methylamine to halosafrole in DCM with a PTC, one has a peachy-keen way of making MDMA at room temperature! Think about it!!!
 
drone 342
Member   posted 12-30-98 12:44 PM          
--------------------------------------------------------------------------------
BTW, of course, the beauty of it is that the methyledioxyphenylisopropyl ligand acts as a steric barrier to further alkylation; true, some tertiary amine will be made, but not much, especially with plenty of excess methylamine floating around.
I posted this idea months go (when I was still new and not taken as seriously), but there were no takers. Again, I post this, and maybe someone will give it a closer look. Enjoy.

-drone #342


Cherrie Baby
Member   posted 12-30-98 03:27 PM          
--------------------------------------------------------------------------------
Try it? - that would involve making halosafrole. Will Chlorosafrole be OK?
Have you any references for this or for a analogous reaction.

Sometimes these PTC reactions don't go as planned. [Eg they work with a crown ether but not with a quat.] Sometimes they give miserable yields. What precise conditions and yields can be expected? Suggest an actual quat for us?

Sorry if I sound like the state prosecutor but us chemists must be thorough.


 
drone 342
Member   posted 12-30-98 05:29 PM          
--------------------------------------------------------------------------------
This is ambient temperature, using benzyltriethylammonium chloride as the PTC. This is analogous to the same reaction I gave to make DiPT, following my directions, but with an excess of the amine rather than the alkyl halide. There are several citations for this method I based this on in the literature, but I am not at liberty to cite them. Sorry, but that's how it is.
I know its unscientific not to give ref's, but we're living under circumstances that make scientific research into these thing tenuous.


drone 342
Member   posted 12-30-98 06:19 PM          
--------------------------------------------------------------------------------
Chlorosafrole won't work as well. Chlorine isn't as good of a leaving group. Converting chlorosafrole into bromosafrole isn't the hardest thing in the world to do, though.
I'll write up something more detailed later.

-drone #342


Rhodium
Administrator   posted 01-01-99 01:29 PM          
--------------------------------------------------------------------------------
To bromosafrole? How? To iodosafrole with NaI/Acetone I can imagine, but bromosafrole?
 
drone 342
Member   posted 01-01-99 01:45 PM          
--------------------------------------------------------------------------------
iodo would be better yet from the standpoint of reactivity, but for price and amount fo material needed, bromo is better. chloro's are placed quite easily and commonly to bromo's by HBr, sometimes with the little help of a catalyst like AlCl3. Still, I really think comming up with a facile, standerdized means of making bromosafrole isn't that hard of a task. There are really is an enormous amount of literature on these kind of reactions. The only trick is to dig through it all to find the best examples.
 
drone 342
Member   posted 01-02-99 11:45 AM          
--------------------------------------------------------------------------------
To 235 ml of 10% methylamine in MeNH2 is added 0.89 g benzyltriethylammonium chloride and 18.6 g of crushed NaOH. The mixture is stirred magnetically at rt for 1 h. 24.5 g bromosafrole is added, and is allowed to react overnight at room temperature with stirring. The next day, the solution is check ed via TLC to determine completion of the reaction. Once completion is determined, the inorganic material is filtered out, and the solution is washed with H2O. The solution is dried over MgSO4, and stripped in vacuo. The final product is subsequently distilled in vacuo.
 
ChemHack
Member   posted 01-02-99 02:35 PM          
--------------------------------------------------------------------------------
"To 235 ml of 10% methylamine in MeNH2 is added..."
Hmmmmm.... You still hung over from yesterday?


 
rev drone
Member   posted 01-05-99 02:43 PM          
--------------------------------------------------------------------------------
Sorry about that. Of course, that should read "10% methylamine in DCM".
-drone #342


rev drone
Member   posted 01-14-99 09:34 AM          
--------------------------------------------------------------------------------
I did a search on catalyzed addition of cyclic bromo compounds to amines, figuring that whatever is good for the goose is good for the gander. Here is a gleening of Beilstein goodness on some PTC-catalyzed and non-PTC-catalyzed nucleohpilic additions of amines to cyclic alkyl halides. I just thought some fresh ideas and approaches to this might be a good idea.
Reactant BRN 1209256 bromocyclopentane
2804184 2-amino-fluoren-9-one
Product BRN 2731843 2-cyclopentylamino-fluoren-9-one
-------------------------

Reaction Details

Reaction Classification Preparation
Reagent triethyl phosphate
Ref. 1 2338520; Journal; Pan; Fletcher; JOCEAH; J.Org.Chem.; 27; 1962; 3639, 3641; JOCEAH; J.Org.Chem.; 23; 1958; 799, 800;

Reaction

Reaction ID 938269
Reactant BRN 1209256 bromocyclopentane
Product BRN 635706 cyclopentylamine
1362103 dicyclopentyl-amine
-------------------------

Reaction Details 1 of 2

Reaction Classification Preparation
Reagent NCl3, AlCl3
Solvent CH2Cl2
Ref. 1 183547; Journal; Kovacic,P.; Lowery,M.K.; JOCEAH; J.Org.Chem.; EN; 34; 1969; 911-917;
-------------------------

Reaction Details 2 of 2

Reaction Classification Preparation
Reagent NCl3, AlCl3
Solvent CH2Cl2
Ref. 1 183547; Journal; Kovacic,P.; Lowery,M.K.; JOCEAH; J.Org.Chem.; EN; 34; 1969; 911-917;

Reaction

Reaction ID 1225661
Reactant BRN 505944 2-amino-ethanol
1901417 bromo-cyclooctane
Product BRN 2648699 C10H21NO3S2
-------------------------

Reaction Details

Reaction Classification Preparation
Other conditions (i) xylene, (ii) aq. HBr, (iii) aq. Na2S2O3, EtOH
Note 1 Multistep reaction
Ref. 1 80156; Journal; Klayman,D.L.; Gilmore,W.F.; JMCMAR; J.Med.Chem.; EN; 7; 1964; 823-824;

Reaction ID 3731217
Reactant BRN 741851 methylamine
1919846 2-bromo-cyclohexanol
Product BRN 3194023 trans-2-methylamino-cyclohexanol
-------------------------

Reaction Details

Reaction Classification Preparation
Solvent H2O
Yield 71. (BRN=3194023)
Ref. 1 5769601; Journal; Pracejus, H.; Pracejus, G.; Costisella, B.; JPCEAO; J.Prakt.Chem.; EN; 329; 2; 1987; 235-245;

------------------
-the good reverend drone


Cherrie Baby
Member   posted 01-15-99 01:49 PM          
--------------------------------------------------------------------------------
Bromosafrole might not be needed !
There's a possibility that this could go with just chlorosafrole !

How ??

If a small amount of iodine or iodide is added as an initiator - iodosafrole is then produced via a halide swap. The iodosafrole reacts with methylamine to give product-X. The HI released then reacts with more chlorosafrole to give the iodosafrole back etc etc.

Care is needed - too much iodine behaves as a PTC poison. I think that much less than 1 mole atom of iodine per mole of PTC is OK. I would start with mole I per mole of PTC and do another run with mole of I per mole of PTC.


 
Cherrie Baby
Member   posted 01-19-99 11:30 AM          
--------------------------------------------------------------------------------
By PTC poison - I mean that I<sub>2</sub> can stop the PTC working - not that it is poisonous to people.
Has no one tried this ? - it is the simplest, easiest method of all.

Sorry I can't do so myself - I would if I had the safrole. I'll try it with something else - ASAP.


rev drone
Member   posted 01-20-99 12:43 PM          
--------------------------------------------------------------------------------
Cherrie,
Of course, KI or NaI could also be used in a similar fashion to do the same sort of halide-exchange catalysis thing, and you wouldn't have to worry about poisoning

------------------
-the good reverend drone


All times are CT (US)
 next newest topic | next oldest topic


Administrative Options: Close Topic | Archive/Move | Delete Topic
    Hop to: Select a Forum or ArchiveList of Forums:General DiscussionAcquisition DiscourseChemistry DiscourseMethods DiscourseNovel DiscourseCrystal MethSerious Chemistry ForumThe Hive CouchSerious Tryptamine DiscourseAdmin Chill-out TentList of Archives:Couch ArchivesClassics!Law and OrderThe litter box.misc. PEAs  

Contact Us | the Hive

Powered by: Ultimate Bulletin Board, Version 5.39a
Infopop Corporation (formerly Madrona Park, Inc.), 1998 - 1999.