dormouse (Member)
04-23-00 06:07
No 108781
      Aliquat 336 chlorosafrole -gyrogearloose  Bookmark   


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Author  Topic:   Aliquat 336 chlorosafrole 
gyrogearloose
Member   posted 08-22-99 07:50 AM          
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Hi gaang,
The elves started something new last night at the behest of another hive member.....
They got hold of 16.2 grams of alkene of choice and added it to 150 ml of hexane, then added that to 150 ml of 38% HCL with vigerous stirring added 4 gms of aliquat 336, the phases combined now and got pink.
Let it stir until start product smell went away.( about five hours, Used slight heat less than 50 degrees C.
Cooled to RT. Washed with sodium bicarb solution twice, then H20 twice, got a light brown oil.
Added this to 30 grams if NaI in acetone and refulxed for 45 min. will finish tonight and report on the morrow. so far so good tho.....
Gyro


Rhodium
Administrator   posted 08-22-99 08:12 AM          
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Ehm, the NaI will make a complex with your acetone, and the chlorosafrole won't react with anything. You must distill your reaction mixture to isolate the pure chlorosafrole. It distills at about 140-150C at aspirator vacuum.
 
gyrogearloose
Member   posted 08-23-99 10:25 PM          
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Well you are right sir,
Nothing was produced except some few needles
nothing to speak of. Can you enlighten the elves on this proceedure? They are ready to try again.....Should they use some other solvent?
also how to proceed from there?
Thanking you in advance.....
gyro
 
Rhodium
Administrator   posted 08-24-99 04:20 PM          
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NaI can be used to purify ketones (like MDP2P) just like bisulfite, as they both make crystalline complexes with them.
The only good way of purifying chlorosafrole is by distillation.


r2d3
Member   posted 08-24-99 05:59 PM          
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Rho: Would these crystals be a good way to store MDP2P, or is there too much loss in the formation and regeneration or other problems?
 
Penis Seinfeld
Member   posted 08-24-99 08:15 PM          
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Rhod, he is not using NaI for purification, but rather for a halide swap.
Cloro-->iodo.

What solvent would dissolve both NaI and the chloro compund in question and allow this swap to take place?

PS


Osmium
Member   posted 08-25-99 04:04 AM          
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Acetone?
 
Penis Seinfeld
Member   posted 08-25-99 12:25 PM          
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Osmium:
Yes, acetone, but NaI, according to Hellman, will complex with acetone, so that won't do any good.

PS


Osmium
Member   posted 08-25-99 01:26 PM          
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No, don't think so. The complex is not that stable, it will decompose during the reaction, forming the organic iodide and NaCl.
 
Rhodium
Administrator   posted 08-25-99 03:50 PM          
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r2d2: I don't know.
penis: AHA! Then the problem is how to separate iodosafrole from chlorosafrole from other gunk. Sorry, I can't be of any help here, other than to reccommend fractional vacuum distillation.


gyrogearloose
Member   posted 08-25-99 11:32 PM          
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The elves got some 33% HBr. In GAA yesterday and
there was 500 ML so slowly they dumped in 250 ML of clean new saf.
All was cooled to 0.C. Still it heated up considerablely, and meqsures were taken.
the 1000 ML flask with the HBr was put on to stir and then the 250 ml was added over many hours.
(6 to be exact.) On changing the stirrer,(the first one failed 14 hrs into it) it was noted by the elves
that the flask weighed mush more than i the first place. Like a lead bar was placed in it. The stirring was continued
up til today. They will put it over Ice chips later unless you know of a better way.
after they will extract with DCE. QUestion is how to proceed with bromo product for amination, have read that reflux with MeOH and sodium azide does the job, also have your info on the suggested ways with the IDO, I assume they would work as well with the Bromo.
If this is true tell me. I hope this works out because the HBr is available to me here cheap. Still all the other items are as well. The chlorosaf smelled like minty is it correct?
Let us carry on....


CHEM GUY
Member   posted 08-26-99 05:04 PM          
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Fact: NaI is soluble in acetone. (So is NaF)
Fact 2: NaCl is NOT soluble in acetone. (neither is NaBr)
Spectulation 1: Chloro-safrole is soluble in acetone.

Procedure:
Add chloro safrole to a molar excess of NaI to anhydrous (or close) acetone. Heat to 50C for more than 6 minutes.

If the chloro-safrole dissolves in the acetone NaCl WILL preciptate out.
Order of reactivity is:
primary > secondary > tetrary


Rhodium
Administrator   posted 08-26-99 05:13 PM          
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Chlorosafrole is soluble in acetone, yes. But I still think that the chlorosafrole should be purified by distillation before this halo exchange rather than after, to minimize side reactions.
 
Scooby Doo
Member   posted 08-26-99 08:31 PM          
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Hey there Gyro, please be careful with the azide. If you can smell your solvent during or after the reaction its a good chance your getting hydrazoic (sp?) acid fumes. Also if you have a partner look at each others eyes early symptoms are very blood shot eyes. Next your face will feel hot and puffy, if this occurs get out and take lots of fresh air for about 30 mins. It doesn't take long after the puffy feeling to faint. This stuff can really creep up on ya.
Good luck


gyrogearloose
Member   posted 08-26-99 11:15 PM          
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Thanks scooby do, I did not know this info and it may be good to know. The real question is still does that way wrok> As for the chloro way The elves have completed another batch of that and distilled it. Will now try DMF as solvent for ido part and report back. On the other hand when the elves poured the Bromo? product out of the chipped ice there was a very heavy viscous large quanity of what at first looked like purple oil, after washing it with sodium Bi carb solution twice
it turned out to be very Green and very heavy
and has increased in volumn as well. It smells like fresh flowres, saf smell all gone. Any advice from someone who has been successful before with amination of this product. The 33% HBr in Gaa appears to have worked. Green is the color of interest....
Green, green, its green thay say on the other side of the hill.
gyro
 
gyrogearloose
Member   posted 08-26-99 11:18 PM          
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ps CHem guy thankyou for proceedure.The elves will have a go tonight.....
 
Penis Seinfeld
Member   posted 08-26-99 11:18 PM          
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CHEM GUY:
gyro already tried to do the swap in acetone. It didn't work. Probably because NaI forms a complex with acetone. Another solvent is needed. Can anyone make a couple of suggestions?

Think about how important this will be if it works. Heat alkene w/ conc HCl and an OTC PTC w/ your DIY stirrer. Do the halide swap. Stir you iodo compund with methanolic ammonia or MeAm, or just use aq. and an OTC PTC. Does it get any simpler or more OTC?


I would love to help gyro by doing a little of my own experimentation, but that is just not possible fo rme right now. Help guys.

PS


CHEM GUY
Member   posted 08-27-99 05:55 PM          
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If you use acetone it will work if you don't heavily saturate the solution with NaI.
The photocopy in front of me says:
"Reagent: Dissolve 15 g of NaI in 100 mL of pure acetone. The reagent should be stored in a dark."

Also if it didn't work it was probably because there was water in the acetone which prevented the NaCl from preciptating out because NaCl is soluble in H2O. The acetone must be VERY dry.


CHEM GUY
Member   posted 08-27-99 05:58 PM          
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A second thought, if you are unsure of the anhydrous nature of the acetone, just saturate it with NaCl so that any NaCl formaed by the reaction will be forced to precipate out. I don't have any references on that thought but it sounds logical, doesn't it?
 
LaBTop
Member   posted 08-28-99 04:35 AM          
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Chemguy, I have some experience with the reading ability of Gyro's elfes. Give them an extensive, !NON! chem-professional write up, and they will do any job, but still a bit sloppy in the beginning, but they will improve during the process. They do not understand high or medium level chemistry, so you have to instruct them as if it is a first class high school chemistry practicum.
Then they will do any job you ask for, with lots of enthousiasm and good results.
Gyro, nice to see you whipped the elfes again into trying a new method.
Perhaps look at my last post in "Grab your seats(HBr+Safrole)" and look if chloroform , ether or DCM or DCE can be used as a solvent.
But acetone should work also. Amination like the polish guy's should work, but there are many more possible, Chemguy will know.
Use MgSO4.7H2O and dry that at 250 C 2 hours in oven, then use 10 or 20 % w/w in the acetone,stirr 30 min and decant the acetone into the reaction flask, close that one properly, then it's surely dry, water in the reaction will spoil things terribly.
Wood like you and Chemguy get this to work, is a big surprise for us.  LT/
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EMOTIONSwill always beFREE!


 
LaBTop
Member   posted 08-28-99 06:11 AM          
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Well,Strike was allready very interested in this method, together with some others: Post 122771 (dormouse: "Synthetic challenge: Pseudo 2C-B  -Rhodium", Serious Chemistry) 
Labrat gave some good advice and Rhodium, you allready did the first part, why did'nt you proceed?
Some interesting theoretical discussion in this thread.
At last someone is working it out to the end.  LT/
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EMOTIONSwill always beFREE!


 
Rhodium
Administrator   posted 08-28-99 06:23 AM          
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Why? Because I wasn't interested in getting any honey out of it, I just wanted to see if the PTC hydrohalogenation reaction worked, which it did, using HCl. I'm a researcher, not a manufacturer
 
gyrogearloose
Member   posted 08-29-99 08:10 AM          
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Well the bromanation with the 33% worked as per bioassey, more later..
 
gyrogearloose
Member   posted 08-29-99 11:22 PM          
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Yes, yes....
The 33% HBr In GAA works fine. After the elves jsut put some 28% ammonium solution with it and heated it to reflux for 24 hrs and Voila, MDA clean and pure easy as pie, (messy as per LaBtop)but easy.
Good yeild as well. Crystals from HCL with the freebase oil then cold acetone for the white ones.....
 
ReFlux
Member   posted 09-03-99 04:26 PM          
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Gyro-Could you tell me the reaction conditions and molar reactants for the 33% HBR in GAA?
Thanks

-ReFlux


Acme
Member   posted 09-03-99 11:25 PM          
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Gyro-
Just curious, if you would be so kind to clarify, when one has freebase oil, after clean reductive amination or distillation of product from another route, and you say to use an equal volume of 38% HCl, is that made from conc Hcl + water or are you assuming conc HCl is 38% already. And, if you would be so kind, as to the acetone, whatall volume compared to the mixture acid/amine is used, and is cooling in a dry ice bath at ~ -10 C OK. Never a problem with condensing water into the acetone? I mean, are you talking labgrade 99+% acetone are we talking whatthefuckathomeOTCdriedw/baked epsomsaltsandedcanted?
 
gyrogearloose
Member   posted 09-06-99 01:52 AM          
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Yeah I am talking about 99.9 lab grade acetone. The HCL says on the bottle 38.8%
These items are available here to the elves down at elf chemical supply.
the elves like to make the free\base neutral and then add cold as hell from the ice cream freezer acetone from new bottle to this and bang crystals.
Reflux:
The elves did not know about moles yet so they used 250 ml of cold not safrole with 500 ml of factory fresh 33% in GAA and kept it cold with ice bath over night. so about 14 hours were burnt up then poured it over ice chips and waited for seperation of heavy priple stuff, washed it with sodium bi carb twice then washed it by letting it sit overnight in h20, all the green color went into h20 layer and was left with a brown heavy viscous flower smelling oil that increased in volumn and weight.
hope this helps
gyro


city_of_ice
Junior Member   posted 09-06-99 03:06 AM          
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gyro- 4 questions will help some newbees
because this recipe has got to be the all-time simplest.
250 ml not-safrole dripped into 500ml of 33%HBr in GAA in ice bath for 14 hr.
-extracted the bromoproduct I assume with DCM-
(How much bromoproduct was there?)
then you refluxed with 28% ammonium solution for 24 hours.
(How much ammonium solution?)
Then you extracted MDA.(How?-
3N HCl, then basify to pH9?)
Then you added a bit of 38% HCl to pH7, then
cold from freezer acetone for crystals.
(How much acetone?)
Excellent work, gyro, this beats all.


samoza
Junior Member   posted 09-06-99 03:09 AM          
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Can you really make MDA just by brominating not-safrole then refluxing with 28%ammonia?
Just 2 steps?
Holy Mother of God.
 
Acme
Member   posted 09-07-99 01:09 AM          
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Gyro-
The elves and your kindness and efforts are appreciated by all at the hive and oft not recognnized despite emminent merit.
Do you use a dry-ice cold finger or some other low temp condensation system when you reflux the aq ammonia solution (which notme imagines is fairly biphasic)? Ammonia gas is very noxious, even in a hood.
 
gyrogearloose
Member   posted 09-08-99 05:49 AM          
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The Elves work on the roof top after sunset when the wind is blowing like hell. No neighbors to speak of, and yes the amm. stinks like hell and if you get downwind it burns the eyes like hell. the elves put it in a pipe and seal it with a stir bar inside at bottom, the bottom is thin enough to stir through.
So I imangine some pressure is there as well.
after stopping the thing they cool to RT then add to 5% HCL water, after shaking like mad then seperate off junk throw aside, take water portion then add NaOH solution until oil comes out, Basic, cool to room temp( I can't imply strong enough to wait for seperation to be complete here)
Extract with DCM for oil, the elves put a fan on it rather than a vac here, its hot here, then they neutralize the oil and pour in cold acetone for the job finish....
By the way both 28% water solution worked and methanolic amm worked and methylamine HCL worked, and amm. acetate worked.
so have at it.....
gyro
 
ReFlux
Member   posted 09-08-99 08:23 PM          
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Gyro- Just a couple of questions: How did you know what temperature of heating is right since the contents of the bomb are essentially invisible? Also, what kind of yields did you achieve?
Thanks!

-ReFlux


Jiggs
Member   posted 09-08-99 10:32 PM          
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How much methylamine HCl do you use for a given amount of bromoproduct?
 
gyrogearloose
Member   posted 09-09-99 08:09 AM          
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Reflux:
Dude The elves have a tempature well made into the side of the pipe. Stick in the ole digital temp controler and dial up your favorite temp and bang within+- 1 degree it goes there for the time you tell it......
Jiggs:
ten times molar amount..
Gyro
 
ReFlux
Member   posted 09-09-99 01:39 PM          
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Gyro- Thanks bro! I think I know a couple of dwarfs that will be interested in this info! PS: Any idea on yields? Also, did you use some kind of co-solvent? Methanol or something?
Thanks.

-ReFlux


Dirk Diggler
Junior Member   posted 09-09-99 07:31 PM          
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Aliquat 336 is tricaprylammonium chloride, for those interested, not trioctyl, as cited by strike (unless the formula has changed since the last time i looked in an oc book this afternoon), no flame, just professional criticism. ill check aldrich and report back. waterbed ptcs higher-alkyl than 5C or 8C, could it make a difference?
 
Penis Seinfeld
Member   posted 09-09-99 07:38 PM          
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Uhh, capryl- and octyl- are the same thing. And it is actually Trioctyl(or capryl)methylammonium chloride. Why even bring something so insignif. up?
Gyro, please mail me if you see this.

PS


gyrogearloose
Member   posted 09-10-99 03:43 AM          
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Your point?
It isn't the same the world over, althought I think some americans beleive the standard is set there. Anyway we have both so there.
Na NA na Na na.......gyro


gyrogearloose
Member   posted 09-10-99 11:51 PM          
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this is fir Dirk digger:
aliquat 336 is tricaprylylmethylammonium chloride as per label on the Bottle.
also have Benzyl triethyl ammonium chloride.

Both seem effacatious. what say ye now knave?


 
FMAN
Member   posted 09-15-99 08:36 PM          
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GO CHEM GUY  Are you lose in the head?
 
FMAN
Member   posted 09-15-99 08:56 PM          
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Thsi sounds good
so when shall we expect the completed researcher report then, with all the exacts?
you do want to share this information with the public? Or do you allready have the public in awe of your tallent? Are you afraid that the fuzz is gona step in and mess with your regent? Maybe your more pussy than I thought, maybe not, I wait the complete write up a a truelly stupendious write up, this will result in some respect and critism and also some merit in my opinion are you ready to make this discovery real or will it be lost again into some closet hidding session??? Help ? or Hurt?
---Amethystium---
 
gyrogearloose
Member   posted 09-16-99 02:35 AM          
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Are you talking to me?, are you talking to me????
 
Rhodium
Administrator   posted 09-16-99 07:34 AM          
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FMAN! This is your first warning for posting off topic stuff. Two more times and your username is removed - sorry...
 
newbee boy
Member   posted 09-16-1999 09:05 PM          
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Rhodium I think that was a bit harsh(sorry to butt in)FMAN was just saying what some bees are feeling. There are a lot of bees following this thread and are just waiting for a writeup instead of scattered facts. Some of us realise that it is still very much in experimantal stage and not ready yet. But others are getting impatient(sorry FMAN)It wasn't off-topic just a little demanding!!Again please excuse my off-topic interuption!
NB>out
 
Jiggs
Member   posted 09-18-1999 06:21 PM          
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What happened to page 2 of this thread?
When I click for page 2 there are no
posts on it.
Anyway, I have looked at the halo-olefin
page on Rhodium's site... http://rhodium/lycaeum.org/chemistry/halosafrole.txt 
and it's very interesting to note that
you get a higher yield of bromosafrole
if you start with crude sassy oil than
if you start with pure safrole.
I imagine this would also be true
of crude parsley oil vs. myristicin.
 
spitball
Administrator   posted 09-19-1999 04:21 AM          
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test?
 
gyrogearloose
Member   posted 09-24-1999 06:55 AM          
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Calm down, I ain't on you payroll ya know.
Its not like all I have to do is sit in the lab all day finding out ways for people who have no drive to get ahead, The elves are a hard lot to control, when something doesn't go right they get dejected and go on to something else, anyway hang on more info soon as its conclusive, OK?
The elves hate theory posted here and insist on experence instead.
They folllowed many a theory up a blind path.
What they post is at least their findings.
gyro
 
Synthia
Junior Member   posted 10-23-1999 08:00 PM          
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Gyro: will the elves be posting some more info to conclude this method?
We appreciate the elves are a hard working team and they are very fruitful.Evidently, their efforts and knowlege is required at this time ,as this ghost is not sure if there is 2 different methods in this thread.This ghost is sure there is one with the aliquate (which failed) and one with out and additionally, appears to be similar to the Hbr>Saf method posted elseware.

So please,if the elves manage to take a break from work,this ghost wonders if u could request the elves to take some time out to comply.

This ghost would truely be greatful.


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