Author Topic: Ketone -> Honey w/ NaBH4 + Microwaves! (Page 1) -ReFlux  (Read 1406 times)

0 Members and 1 Guest are viewing this topic.

dormouse

  • Guest
Ketone -> Honey w/ NaBH4 + Microwaves! (Page 1) -ReFlux
« on: April 20, 2000, 08:58:00 PM »

   the Hive BB
  Novel Discourse
  Ketone -> Honey w/ NaBH4 + Microwaves! (Page 1)
  
profile | register | preferences | faq | search
 
This topic is 2 pages long:   1  2  next newest topic | next oldest topic 
Author  Topic:   Ketone -> Honey w/ NaBH4 + Microwaves! 
ReFlux
Hive Bee   posted 06-07-98 05:24 AM          
--------------------------------------------------------------------------------
I was doing a search on reductions w/ NaBH4 for another thread in Novel Discourse section and came up with the following absolutely amazing ref:
Tetrahedron 54,23 pg.6293 (1998), "Sodium borohydride on wet clay; solvent-free reductive amination of carbonyl compounds using microwaves"

I downloaded the abstract of the paper and I was astonished! There it was:

Ketone + Amine (in montmorillonite clay + NaBh4 + MW radiation) ---> Aminated product.

Now I know what your saying, other MW methods involving reflux, or HBP solvents or sealed MW bombs are inherently risky (explosion, fire, MW rad. leaking via reflux hole etc.) But what makes this system so great and relatively safe is that it uses NO SOLVENTS!! Thats right, and except for some H20 in the clay, there are no solvents and therefore none of their attendant risks!

Hypothetically, this could make a fantastic method for MDMA production using easy to aquire chems (except of course for the amine source i,e: methylamine) and your microwave oven: talk about kitchen chemistry! :-)

PS: I decided to post this in a new thread in this forum instead of the thread I found already in progress in the aquisitions forum because it seems that this is a more suitable place for this discussion. No disrespect intended to jimwig, cherie babie et,al!

-ReFlux


Rhodium
Pimp Master   posted 06-07-98 11:14 AM          
--------------------------------------------------------------------------------
This sounds really interesting... But where can you download Tetrahedron abstracts? You have an account somewhere?
 
Rhodium
Pimp Master   posted 06-07-98 11:14 AM          
--------------------------------------------------------------------------------
This sounds really interesting... But where can you download Tetrahedron abstracts? You have an account somewhere?
 
ReFlux
Hive Bee   posted 06-07-98 03:28 PM          
--------------------------------------------------------------------------------
Try this site:

http://oxford.elsevier.com/tis/

 
You can set up a trial account, and then search all Tetrahedran publications online. Most have PDF abstracts that you can download, some even complete articles in PDF!

Happy Hunting!


ReFlux
Hive Bee   posted 06-07-98 03:28 PM          
--------------------------------------------------------------------------------
Try this site:

http://oxford.elsevier.com/tis/

 
You can set up a trial account, and then search all Tetrahedran publications online. Most have PDF abstracts that you can download, some even complete articles in PDF!

Happy Hunting!


007
unregistered   posted 06-07-98 03:52 PM           
--------------------------------------------------------------------------------
sorry homeys but that TIS page doesnt have the issue we need to look at.
any detatils on what ketones were used in the article and what amines? never can be absolutley sure it'll work for ours.
so i am curious who is gonna be the man and be the first to try this? i know i am curious as hell to hear about some trial runs and hypothetical results!
 
007
unregistered   posted 06-07-98 03:52 PM           
--------------------------------------------------------------------------------
sorry homeys but that TIS page doesnt have the issue we need to look at.
any detatils on what ketones were used in the article and what amines? never can be absolutley sure it'll work for ours.
so i am curious who is gonna be the man and be the first to try this? i know i am curious as hell to hear about some trial runs and hypothetical results!
 
007
unregistered   posted 06-07-98 03:58 PM           
--------------------------------------------------------------------------------
better yet, reflux man, why dont you post the abstract or just the experimental from the methods section!
 
007
unregistered   posted 06-07-98 03:58 PM           
--------------------------------------------------------------------------------
better yet, reflux man, why dont you post the abstract or just the experimental from the methods section!
 
quirks
Hive Bee   posted 06-07-98 04:06 PM          
--------------------------------------------------------------------------------
Damn! My library doesn't have it yet... That's the most recent issue eh? Next week!
 
quirks
Hive Bee   posted 06-07-98 04:06 PM          
--------------------------------------------------------------------------------
Damn! My library doesn't have it yet... That's the most recent issue eh? Next week!
 
quirks
Hive Bee   posted 06-09-98 07:52 AM          
--------------------------------------------------------------------------------
"The process in it's entirety involves simple mixing of in situ generated imines with 10% NaBH4-wet clay and irradiating the rxn in an unmodified household microwave..."
Benzadehyde -> analine 5min 97% yeild


"Typical procedure: a mixture of p-chlorbenzadyhyde (5 mmol), analine (5 mmol) and montmorilonite K10 clay (0.1g) contained in a 25ml beaker was placed in an alumina bath inside a microwave and irradiated for 2min. The insitu schiffs base was mixed thourougly with freshly prepared NaHB4 clay (5 mmol on 1.72 g reagant) and water (1 ml). The rxn was again irradiated for 2 minutes..." that's it, followed by extraction and purification...

I'll scan the whole thing in and send it uuencoded to whoever would like it. (maybe Rd. can ocr?)


quirks
Hive Bee   posted 06-09-98 07:52 AM          
--------------------------------------------------------------------------------
"The process in it's entirety involves simple mixing of in situ generated imines with 10% NaBH4-wet clay and irradiating the rxn in an unmodified household microwave..."
Benzadehyde -> analine 5min 97% yeild


"Typical procedure: a mixture of p-chlorbenzadyhyde (5 mmol), analine (5 mmol) and montmorilonite K10 clay (0.1g) contained in a 25ml beaker was placed in an alumina bath inside a microwave and irradiated for 2min. The insitu schiffs base was mixed thourougly with freshly prepared NaHB4 clay (5 mmol on 1.72 g reagant) and water (1 ml). The rxn was again irradiated for 2 minutes..." that's it, followed by extraction and purification...

I'll scan the whole thing in and send it uuencoded to whoever would like it. (maybe Rd. can ocr?)


quirks
Hive Bee   posted 06-09-98 08:19 AM          
--------------------------------------------------------------------------------
Whoops! That's supposed to be benzadehyde + analine -> pheneyhlamnie (sp) (I think)
In general:

R1
\
C=O + H2N-R3 ----> (K10 clay, MW) --->
/
R2

R2
\
C=N-R3 ----> (NaBH4 - K10 clay, MW) ---->
/
R1

Da good stuff.


They note: 95%+ yeilds, all less then 5 minute rxn times, and no side products whatsoever. (they say NaCNBH3 can leave residual CN stuff)

Will NaCNBH4 be obsoleted?? what is K10 clay?


 
quirks
Hive Bee   posted 06-09-98 08:19 AM          
--------------------------------------------------------------------------------
Whoops! That's supposed to be benzadehyde + analine -> pheneyhlamnie (sp) (I think)
In general:

R1
\
C=O + H2N-R3 ----> (K10 clay, MW) --->
/
R2

R2
\
C=N-R3 ----> (NaBH4 - K10 clay, MW) ---->
/
R1

Da good stuff.


They note: 95%+ yeilds, all less then 5 minute rxn times, and no side products whatsoever. (they say NaCNBH3 can leave residual CN stuff)

Will NaCNBH4 be obsoleted?? what is K10 clay?


 
quirks
Hive Bee   posted 06-09-98 09:26 AM          
--------------------------------------------------------------------------------
Wouldn't that just make a cool way to get 2-cb too?? 2,5 dimethoxybenzadehyde + phenethlyamine ----> (5 minutes on high, pun intended) ----> 2c-H
The microwave was a sears kenmore 100 watt model.


quirks
Hive Bee   posted 06-09-98 09:26 AM          
--------------------------------------------------------------------------------
Wouldn't that just make a cool way to get 2-cb too?? 2,5 dimethoxybenzadehyde + phenethlyamine ----> (5 minutes on high, pun intended) ----> 2c-H
The microwave was a sears kenmore 100 watt model.


Labrat
Hive Bee   posted 06-09-98 09:47 AM          
--------------------------------------------------------------------------------
This is the future! Just mixing some clay (K10, can be bought from chem outlet for cheap and no suspicion attached!) with a ketone and an amine, then beam it in, voila an imine. Then mix some clay with sodium borohydride, make it wet, then mix it with the imine/clay mixture, beam it once more: voila, very good yields of secondary amines in a few minutes with a household microwave. I've seen some good articles coming from the same author (Rajender) as this article. I'll keep an eye on him! Lr/
 
Labrat
Hive Bee   posted 06-09-98 09:47 AM          
--------------------------------------------------------------------------------
This is the future! Just mixing some clay (K10, can be bought from chem outlet for cheap and no suspicion attached!) with a ketone and an amine, then beam it in, voila an imine. Then mix some clay with sodium borohydride, make it wet, then mix it with the imine/clay mixture, beam it once more: voila, very good yields of secondary amines in a few minutes with a household microwave. I've seen some good articles coming from the same author (Rajender) as this article. I'll keep an eye on him! Lr/
 
quirks
Hive Bee   posted 06-09-98 11:18 AM          
--------------------------------------------------------------------------------
(ignore that 2c-h stuff above, I was confused...)
Would md-p2p + formadide or acetamide (otc) -> n-formyl-amphetamine or n-acetylamp?? Or is that extra oxygen going to make problems?? N= is weaker then the O= right??

What about md-p2p + MeNH3? When they made the schiff's base from propylamine they had to irradiate in bursts of 2 minutes on 20% power in order to keep the temp below 60 degrees to keep from losing too much propylamine from evaporation. Would extra water or solvent screw things up?

How else does one make an imine?


quirks
Hive Bee   posted 06-09-98 11:18 AM          
--------------------------------------------------------------------------------
(ignore that 2c-h stuff above, I was confused...)
Would md-p2p + formadide or acetamide (otc) -> n-formyl-amphetamine or n-acetylamp?? Or is that extra oxygen going to make problems?? N= is weaker then the O= right??

What about md-p2p + MeNH3? When they made the schiff's base from propylamine they had to irradiate in bursts of 2 minutes on 20% power in order to keep the temp below 60 degrees to keep from losing too much propylamine from evaporation. Would extra water or solvent screw things up?

How else does one make an imine?


ReFlux
Hive Bee   posted 06-09-98 11:19 AM          
--------------------------------------------------------------------------------
quriks - Good work! Could you please "beam" me a copy of that article. My library is about a month out from having that ref!
As for Montmorillonite K 10 clay, it is an extremely cheap, abuntant mineral with broad uses in industry and agriculture as well as health food! Just try doing a search for it in Yahoo or something and you'll see what I mean!


 
ReFlux
Hive Bee   posted 06-09-98 11:19 AM          
--------------------------------------------------------------------------------
quriks - Good work! Could you please "beam" me a copy of that article. My library is about a month out from having that ref!
As for Montmorillonite K 10 clay, it is an extremely cheap, abuntant mineral with broad uses in industry and agriculture as well as health food! Just try doing a search for it in Yahoo or something and you'll see what I mean!


 
ReFlux
Hive Bee   posted 06-09-98 11:30 AM          
--------------------------------------------------------------------------------
quirks- The problem with using and extra solvent is that it will be vaporized (unless it hass a very HBP) and the resulting vapor can be an extreme hazard (fire, explosion, toxin etc.) As for using H20 in initial phase of rxn...hmmm. Hypothetically, perhaps a 40% aq. MeNH3 would work since the amine is still in its nucleophilic state here. Will have to do further research.
 
ReFlux
Hive Bee   posted 06-09-98 11:30 AM          
--------------------------------------------------------------------------------
quirks- The problem with using and extra solvent is that it will be vaporized (unless it hass a very HBP) and the resulting vapor can be an extreme hazard (fire, explosion, toxin etc.) As for using H20 in initial phase of rxn...hmmm. Hypothetically, perhaps a 40% aq. MeNH3 would work since the amine is still in its nucleophilic state here. Will have to do further research.
 
Bright Star
Hive Bee   posted 06-09-98 12:27 PM          
--------------------------------------------------------------------------------
Me too quirks! This is lovely! Nice research!
 
Bright Star
Hive Bee   posted 06-09-98 12:27 PM          
--------------------------------------------------------------------------------
Me too quirks! This is lovely! Nice research!
 
Semtex Enigma
Hive Bee   posted 06-09-98 01:17 PM          
--------------------------------------------------------------------------------
How would one seperate what one wants from the clay post rxn?
 
Semtex Enigma
Hive Bee   posted 06-09-98 01:17 PM          
--------------------------------------------------------------------------------
How would one seperate what one wants from the clay post rxn?
 
quirks
Hive Bee   posted 06-09-98 01:43 PM          
--------------------------------------------------------------------------------
They extracted with DCM.
Anybody want to comment on wether the NaBH4 will fuck with the =O if one were to try to make formyl-MDA or acetyl-MDA??


quirks
Hive Bee   posted 06-09-98 01:43 PM          
--------------------------------------------------------------------------------
They extracted with DCM.
Anybody want to comment on wether the NaBH4 will fuck with the =O if one were to try to make formyl-MDA or acetyl-MDA??


sunlight
Hive Bee   posted 06-11-98 07:24 AM          
--------------------------------------------------------------------------------
Please, I need more explanations about what is K10 clay and about waht means alumina bath. Anyone ?
 
sunlight
Hive Bee   posted 06-11-98 07:24 AM          
--------------------------------------------------------------------------------
Please, I need more explanations about what is K10 clay and about waht means alumina bath. Anyone ?
 
horrendous
unregistered   posted 06-11-98 07:52 AM           
--------------------------------------------------------------------------------
What the heck, please include me on the mailing list .Hope this wont interfere with nuking my popcorn.
 
horrendous
unregistered   posted 06-11-98 07:52 AM           
--------------------------------------------------------------------------------
What the heck, please include me on the mailing list .Hope this wont interfere with nuking my popcorn.
 
Sonson
NewBee   posted 06-11-98 08:07 AM          
--------------------------------------------------------------------------------
The aluminabath is some kind of cooling device. I don't know where to get one...maybe someone else an fill in?
 
Sonson
NewBee   posted 06-11-98 08:07 AM          
--------------------------------------------------------------------------------
The aluminabath is some kind of cooling device. I don't know where to get one...maybe someone else an fill in?
 
007
unregistered   posted 06-11-98 08:47 AM           
--------------------------------------------------------------------------------
well i know where one could get clays for medicinal uses such as Montmorillonite, Bentonite, Illite and Kaolinite, but the people dont know what the K10 means so any info would be greatly apppreciated.
is alumina bath just a vessel filled with alumina (same shit used in a column?) ? -just an idea, -like a sand bath(used for heating to high temps when water will not do)?
 
007
unregistered   posted 06-11-98 08:47 AM           
--------------------------------------------------------------------------------
well i know where one could get clays for medicinal uses such as Montmorillonite, Bentonite, Illite and Kaolinite, but the people dont know what the K10 means so any info would be greatly apppreciated.
is alumina bath just a vessel filled with alumina (same shit used in a column?) ? -just an idea, -like a sand bath(used for heating to high temps when water will not do)?
 
007
unregistered   posted 06-11-98 09:00 AM           
--------------------------------------------------------------------------------
also, would this need to be done under pressure so mmethylamine is not lost when heated/nuked?
and anyone with the article, sometimes at the end the researchers add notes of where the chems/materials came from, which company, grades, or notes about how reagents might hagve been prepared between opening from chem supplier and before the experiment. Does the article have any notes like that concerning the clay or other materials?
 
007
unregistered   posted 06-11-98 09:00 AM           
--------------------------------------------------------------------------------
also, would this need to be done under pressure so mmethylamine is not lost when heated/nuked?
and anyone with the article, sometimes at the end the researchers add notes of where the chems/materials came from, which company, grades, or notes about how reagents might hagve been prepared between opening from chem supplier and before the experiment. Does the article have any notes like that concerning the clay or other materials?
 
jimwig
Hive Bee   posted 06-11-98 03:43 PM          
--------------------------------------------------------------------------------
where have I been all this time. Not here obviously. great posts guys gals
 
jimwig
Hive Bee   posted 06-11-98 03:43 PM          
--------------------------------------------------------------------------------
where have I been all this time. Not here obviously. great posts guys gals
 
Trentway
unregistered   posted 06-11-98 04:09 PM           
--------------------------------------------------------------------------------
Excuse the dumb question, but what is the clay doing in this situation, and how does it interact with the microwaves? I mean, I guess the clay will have a huge surface area, and that sounds very nice for various catalytic stuff and so on, but then where do the µwaves come in? Also, this sounds like *very* small scale stuff that I guess wouldn't scale up easily.
There's a guy in Scotland who wrote a book claiming that clay is the secret to the origin of life. Um, here we are: Graham Cairns-Smith, Seven Clues to the Origin of Life, Cambridge University Press, 1985. His model includes self replicating clays, and talks about the various crystal structures, and how they might form reaction vessels for organic synthesis. He doesn't suggest there were µwaves in the primordial earth though!


Trentway
unregistered   posted 06-11-98 04:09 PM           
--------------------------------------------------------------------------------
Excuse the dumb question, but what is the clay doing in this situation, and how does it interact with the microwaves? I mean, I guess the clay will have a huge surface area, and that sounds very nice for various catalytic stuff and so on, but then where do the µwaves come in? Also, this sounds like *very* small scale stuff that I guess wouldn't scale up easily.
There's a guy in Scotland who wrote a book claiming that clay is the secret to the origin of life. Um, here we are: Graham Cairns-Smith, Seven Clues to the Origin of Life, Cambridge University Press, 1985. His model includes self replicating clays, and talks about the various crystal structures, and how they might form reaction vessels for organic synthesis. He doesn't suggest there were µwaves in the primordial earth though!


jimwig
Hive Bee   posted 06-11-98 04:39 PM          
--------------------------------------------------------------------------------
Now if you were a sitting there in the oooze itsveryself and the cosmic rays were a zooming around to and thru ya then you would've been gigahertzed. And since you was clay then. . . . !
+++++++++++++++++++++++++++++++++++++++++++

Dr Reflux, et.al. thanks for picking up this topic and posting it where it should have been. Go "and remember the may the force be with you".


jimwig
Hive Bee   posted 06-11-98 04:39 PM          
--------------------------------------------------------------------------------
Now if you were a sitting there in the oooze itsveryself and the cosmic rays were a zooming around to and thru ya then you would've been gigahertzed. And since you was clay then. . . . !
+++++++++++++++++++++++++++++++++++++++++++

Dr Reflux, et.al. thanks for picking up this topic and posting it where it should have been. Go "and remember the may the force be with you".


Cherrie Baby
Hive Bee   posted 06-11-98 05:11 PM          
--------------------------------------------------------------------------------
"Clay not only behaves as an acid but also provides water from its interlayers that is responsible for the acceleration of the reducing ability of NaBH4".
Without clay only 10% yield is obtained.

Only polar substances absorb microwaves - so you won't get good heating without a polar substance such as clay present.


 
Cherrie Baby
Hive Bee   posted 06-11-98 05:11 PM          
--------------------------------------------------------------------------------
"Clay not only behaves as an acid but also provides water from its interlayers that is responsible for the acceleration of the reducing ability of NaBH4".
Without clay only 10% yield is obtained.

Only polar substances absorb microwaves - so you won't get good heating without a polar substance such as clay present.


 
Rhodium
Pimp Master   posted 06-11-98 08:17 PM          
--------------------------------------------------------------------------------
But hey - wasn't someone supposed to scan that article for me so I could OCR it and put it on my page?
 
This topic is 2 pages long:   1  2
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 DiscussionNewbie ForumAcquisition DiscourseChemistry DiscourseMethods DiscourseNovel DiscourseCrystal MethSerious Chemistry ForumThe Hive CouchAdmin 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.