Author Topic: Why not strait to Iodosafrole? Why always Bromo to Finklestein? (Read 1414 times)

jon · « **Reply #20 on:** October 18, 2012, 08:26:24 AM »

man i shared my noted over and over again look up the halosafrole thread on p-naut.
your using 47% hbr?
no dice man it won't work that dilute in water which is why i make it in situ 40% concentration W/W, insitu in acetic acid. 24-36 hours in the cold check your shit and be certain it's ready for the next step.
it should'nt take 5 hours to bubble in methylamine it took me 15 minutes tops.
usually less than that if you try to heat off any remaining methyl amine you get water and small amounts of water can kill it.
i drip cooled down naoh onto methylamine it is more controllable and generates less heat if any at all this is what you want the opposite order of addition will generate a lot of exotherm and carry water over.
as steam. the devil is in the details.
check your bromo with ice cold h2so4 it should all float if it turns purple extract it and start over until u get it right .
you may only be getting partial yeilds because your bromination is not going all the way always do this test bromo with float not turn purple if the acid is cold.

pbinteger · « **Reply #21 on:** October 18, 2012, 06:09:02 PM »

Welcome back Jon!

Thank you for the response.

What is p-naut? How can I find that thread?

I was attempting to arrive at IodoSafrole using KI, GAA and H2SO4 directly.

I have a bunch extracted and frozen -- next I am going to attempt the HBr to Finklestein.

Here's exactly what I did:
_________________________________________________________________________________________________
IodoSafrole Haloform Reaction

ReAgents:
Glacial Acetic Acid (CH3CO2H)
Sulfuric Acid (H2SO4)
Potassium OR Sodium Iodide (KI / NaI)
Safrole Essential Oil

Ratios:
350G of distilled Safrole (2.16m)
1.9:1 ratio of HBr to Safrole (2.16M(safrole) X1.9(HBr) = 4.5)
4.5M of KI == 748g
4.1M of H2SO4 == 227mL @ 18Molar
The amount of Acetic acid is more of a guess based on the supposed optimal concentration of HBr and GAA. For this scale I will use 250-300mL of GAA (with further experimentation this may be reduced).

Reaction Vessel == Large (2L or 5L Earlenmeyer Flask)
Chill KI -- why? because KI is really heavy it has a lot of thermal mass. If it is not chilled it will heat the RxN too quickly causing excess Iodine production (no bueno)

Also handle your KI quickly -- don't let it be exposed to air for too long as it will pick up moisture.

Freeze down your H2SO4 Damned cold (dry ice & IPA bath)
Then Add GAA (if it freezes you need to warm it up slightly with a salt/ice bath) be careful when pouring because the GAA will freeze to the sides of your vessel

After GAA is thoroughly mixed I'll be warming the reaction up to 0c.

Once RxN is at 0c or GAA && H2SO4 are thoroughly mixed I can add the KI. The idea here is there needs to be a slight excess of KI to H2SO4 to insure there's no leftover H2SO4. Here I want to convert all the H2SO4 into HI within the RxN vessel.

Add KI in small amounts (2 increments) Here I noticed a small color change. Manually Stirring Vigorously (stir bar is insufficient at this temperature -50-60c)

There is some noticeable I2 production here (think about how to avoid this)

1Minute: a lot of undissolved KI -- definitely darkening in color (Iodine)

3Minutes: After adding 2nd bit of KI (~150g) I'm noticing an orange color and some byproduct (likely Sodium Sulfate).

4Minutes: Chilled Safrole in an Ice Bath to bring it closer to RxN temperature as to not heat our RxN too much.

5Minutes: RxN has solidified (very viscous), added the remainder of the KI at this point (300g).
Here I want to give the RxN enough time to react all the H2SO4 (excess can cleave ether from safrole).

8Minutes: Viscosity is like chunky brown mud.
Already I have generated quite a bit of HI Gas. At this point someone I have removed the Safrole from the Salt/ICE bath and placed the RxN vessel in it. someone begins warming it (0c).
(next time through try a bit more GAA)

10Minutes: Vigorous stirring of chunky MUD.

12Minutes: As it warms the viscosity is thinning.

14Minutes: Viscosity continues to decrease -- stirring becomes possible again.
HI smells gross!

15Minutes: Safrole is added at once. immediate RxN noticed -- significant Hi and color changes Color goes from brown / iodine color to a burgundy. Here
also add a small rinse of the remaining bit of Safrole from flask with GAA and add into RxN.

16Minutes: Stir Safrole Manually into RxN

18Minutes: Add to Freezer and let the RXN sit over night. This reaction will hopefully continue to run to 93% yields. At this moment it is *hopefully at 50-60% yields.
Be sure to keep this cold (freezer cold) and work it up fast (get it away from the acid) to prevent ether cleavage.
__________________________________________________________________________________________________

I did run your ice cold H2SO4 test on what was extracted from this reaction and it passed.
I guess I'm just getting too much water in the IPA or perhaps my IPA is not dry enough to begin with. I distilled it and stored it over anhydrous MGsO4 for days before use... Methinks some 99% stored over 3A mol sieves is going to be the way to go.

I did have to heat the MethylAmine NaOH mixture to get it to continue to react (too cold initially) This was unexpected... KOH seems to work better, but perhaps not because according to you any heat will bring over too much water.

4studiesonly · « **Reply #22 on:** October 18, 2012, 06:24:25 PM »

To pbinteger: He refers to the halosafrole thread on psychonaut, another site....

pbinteger · « **Reply #23 on:** October 18, 2012, 06:36:18 PM »

can anyone provide a link because an advanced search on that site with the keyword "halosafrole." yields zero results.

Thank You ALL!

jon · « **Reply #24 on:** October 18, 2012, 07:42:38 PM »

you should be able to scroll down after a few pages you'll soon learn why HI does'nt work so well.

nigluhS · « **Reply #25 on:** October 18, 2012, 08:33:09 PM »

Thread: Re-visiting Halosafroles

hxxp://www.psychonaut.com/synthetics-extraction-research/36412-re-visiting-halosafroles.html

pbinteger · « **Reply #26 on:** October 19, 2012, 09:51:58 PM »

jon:

do you think distilling 91% IPA and then storing it over anyhdrous mgso4 is sufficient for the amination? or is that too much room for error...

lugh · « **Reply #27 on:** October 19, 2012, 10:29:23 PM »

Quote

do you think distilling 91% IPA and then storing it over anyhdrous mgso4 is sufficient for the amination? or is that too much room for error...

If you would have used the search:

http://127.0.0.1/talk/index.php?action=search

and

http://127.0.0.1/talk/index.php?action=help

you would have found:

http://127.0.0.1/talk/index.php/topic,861.msg13701.html#msg13701

and then there would have been no need of that post

The end results from the effort applied

pbinteger · « **Reply #28 on:** October 19, 2012, 11:04:45 PM »

lugh:

First: Thank you for the useful information.

I'd be very interested to know what search terms you used to get to that link. As a professional programmer I've implemented my own search algorithms. I've seen the power that Apache Solr can deliver with bibliographic algorithms, and of course am a constant user of Google. Not to suck my own dick here, but I know how to use a search engine efficiently. I can say with great confidence, the search functionality on this site is fucking terrible. I have been utterly disappointed with it. I have run every type of search imaginable on this forum and gotten absolutely shite results. I have run keyword searches as an experiment trying to get hits on posts that I knew contained them and gotten empty results. Please admins! for the love of god consider implementing Apache Solr here...

dream0n · « **Reply #29 on:** October 19, 2012, 11:30:18 PM »

The professional doesn't know that the search is Forum subsection based, and not site-wide. Magical. : Depending on what section you're currently viewing.

pbinteger · « **Reply #30 on:** October 19, 2012, 11:56:14 PM »

I did know that.. Did you know you can run a site-wide search under the Advanced search settings?

It's pretty douchy to assume that someone hasn't tried to search for something before posting a question regarding it. It's one of my pet peeves on these forums. I understand the origin of people's frustration, but there are ways to delineate between the lazy and those who have not typed the correct search terms, or are not intimately aware of the running topics across multiple sub-sections.

the search still sucks ass. How could any of you defend it?

I just ran a site-wide search for 'prepare dry IPA', 'preparation dry Isopropanol, and 'very dry isopropyl,' which is the fucking title of the link that lugh provided, and NONE Of these searches yielded that link. You can see where the algorithm is picking pieces of the search term rather than the entire term. It's not a smart search... period...

If I run a search against the selected sub section of 'Drug Synthesis and Extraction,' with keywords known to be in posts I've already located through constant clicking (not search efficiency), I've gotten empty results or less relevant results than ones that *SHOULD be higher if the Simple Machine's search algorithm was worth a shit.

My point is -- the information archived here is genius and invaluable -- it deserves a better search.

lugh · « **Reply #31 on:** October 20, 2012, 12:20:42 AM »

Quote

I'd be very interested to know what search terms you used to get to that link.

Inputting the word isopropyl in the search field and by restricting the search to topic subjects you will get five hits

Number three is iknowjt's thread titled very dry isopropyl alcohol

Alternatively one could input "absolute isopropanol" in the search field and get one hit

Quote

My point is -- the information archived here is genius and invaluable -- it deserves a better search.

Those of us that were on the Hive are well aware of the various deficiencies of Simple Machnes Forum

The end results from the effort applied

pbinteger · « **Reply #32 on:** October 20, 2012, 01:03:15 AM »

Thank You Lugh

So anyway back to Chemistry:

Here is a picture of the theoretical rig for generating the gas for the amination attempt....

I could see some problems with it 1.) back gassing 2.) upward column (gravity)
I would simplify it next time....

fractal · « **Reply #33 on:** October 21, 2012, 03:13:07 AM »

You could put a one way valve on to stop back flow.

pbinteger · « **Reply #34 on:** October 21, 2012, 04:49:29 AM »

good idea

can you guys check my math? -- i'm going to do a smaller scale Bromo attempt:

50 g safrole / 162.19 = .308 moles * 1.9 = .586 moles HBr
.586 moles of NaBr / 1.1 = .53 moles of H2SO4 required
.53 m/ 18 m/L (18molar) = .0294 l = 29.4 mL
so...i would use 10% more NaBr .586 X 1.1 = .645 m
.645 m X 102.894 g/mol = 66.4 g of NaBr
.586 m of HBr 80.91 g/m = 47.4 g HBr
if I used 52.6 g of GAA it would be 47.4% so not much GAA looks like...
would be nice to compare all these weights to something someone else that has been reported.
60 g of GAA would give me 44% in solution
sounds reasonable.

ImAMANGUYS · « **Reply #35 on:** October 21, 2012, 11:49:35 PM »

Quote from: pbinteger on October 21, 2012, 04:49:29 AM

good idea

can you guys check my math? -- i'm going to do a smaller scale Bromo attempt:

50 g safrole / 162.19 = .308 moles * 1.9 = .586 moles HBr
.586 moles of NaBr / 1.1 = .53 moles of H2SO4 required
.53 m/ 18 m/L (18molar) = .0294 l = 29.4 mL
so...i would use 10% more NaBr .586 X 1.1 = .645 m
.645 m X 102.894 g/mol = 66.4 g of NaBr
.586 m of HBr 80.91 g/m = 47.4 g HBr
if I used 52.6 g of GAA it would be 47.4% so not much GAA looks like...
would be nice to compare all these weights to something someone else that has been reported.
60 g of GAA would give me 44% in solution
sounds reasonable.

If you're working off the equation:

NaBr + H2SO4 = NaHSO4 + HBr

which i believe is correct, then it looks like you've got yourself some good calculations.

There seems to be some differing information and opinions on the forum though about this as I've seen it posted that the equation is:

2NaBr + H2SO4 = Na2So4 + 2HBr

If so you have some errors.

I do know how to do the calculations and math but i don't know enough about the reaction.

Best of luck.

pbinteger · « **Reply #36 on:** October 22, 2012, 02:17:24 AM »

I just finished the reaction.

What's so confusing about it is the sheer amount of undissolved salts... why is that necessary? to reduce the risk of side reactions?

It did proceed exactly as what has been written here.

The cold acid solution turned a fairly bright orange after the addition of the NaBr.
I decided to warm the reaction to 10c and let it stir vigorously for 2 hours before adding the safrole.
After 2 hours stopped all stirring. I chilled the rxn back down to 0c and added the safrole all at once.
The color changed immediately to a deep red burgundy and the red oil seems to be sitting nicely above the unreacted solids (looks like it'll be easy to decant).
It's in the freezer
workup tomorrow.

ImAMANGUYS · « **Reply #37 on:** October 22, 2012, 02:43:00 AM »

Quote from: pbinteger on October 22, 2012, 02:17:24 AM

What's so confusing about it is the sheer amount of undissolved salts... why is that necessary? to reduce the risk of side reactions?

The reason you add a molar excess of NaBr salts is because sulfuric is diprotic, meaning it donates more than one Hydrogen atom. The reason most salts are undissolved BEFORE the reaction is because you are creating between 40-50 percent of the final solution with it, and the solubility of NaBr in GAA is not that high. The reason some salts are undissolved AFTER the reaction is because it is the reagent in excess as its best to proceed with H2SO4 as limiting. Not one hundred percent certain, but this is evident from viewing the measurements and write-ups.

It did proceed exactly as what has been written here.

Quote from: pbinteger

It's in the freezer
workup tomorrow.

Keep us updated! What temp is your freezer at?

Best of luck.

pbinteger · « **Reply #38 on:** October 24, 2012, 02:53:46 AM »

The freezer holds steady at -10c on it's lowest setting (highest temp)

I'm in the process of working this up -- I've attached some pictures.

I'm afraid I might have a bunch of unreacted safrole -- the color of the workup is nothing like I would expect.

Jon has described dark green in solvent and dark burgundy in concentrated form.

As I work this up the oil / solvent layer just gets more and more yellow and smells more of safrole. I just based it out with bicarb and yellow oil is dropping out and separating.

Now I'm fairly confused because this rxn proceeded as described, and when the oil went into the sep funnel it was a dark burgundy reddish color......

I just finished the final brine wash and it is separating back out, but the oil layer is still just milky on the top or yellow on the bottom.

I've attached some pictures.

pbinteger · « **Reply #39 on:** October 24, 2012, 03:37:25 AM »

I just washed the rxn vessel out with DCM. What came out into a smaller sep funnel was a bichromatic dark red -- green if you shine light directly on it -- solution.

As soon as you wash it with water -- it lightens up to pinkish.

Then as soon as that seps out -- and you basify it -- it turns to yellow.

So I added that small amount of yellow DCM extraction to my bigger jar of yellow DCM extraction and put it in the fridge.

sigh...

What could have gone wrong?

Perhaps this is just an emulsion ?

I remember seeing that happen when I was attempting the iodosafrole directly -- some of what I would separate would turn into a milky yellow and then change color drastically over a 24 hour period -- to dark red or green.

Thank YOU!

Author Topic: Why not strait to Iodosafrole? Why always Bromo to Finklestein? (Read 1414 times)

jon

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

pbinteger

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

4studiesonly

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

pbinteger

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

jon

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

nigluhS

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

pbinteger

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

lugh

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

pbinteger

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

dream0n

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

pbinteger

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

lugh

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

pbinteger

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

fractal

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

pbinteger

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

ImAMANGUYS

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

pbinteger

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

ImAMANGUYS

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

pbinteger

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?

pbinteger

Re: Why not strait to Iodosafrole? Why always Bromo to Finklestein?