Author Topic: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole... (Read 2846 times)

salat · « **on:** January 01, 2011, 02:58:59 PM »

First phase of a 2 part test comparing Jon's method using ~40% GAA vs Pugsley's DMSO method.

Test of Jon's method: (Jon is going to correct the numbers. These were a beginning chemists first attempt at any kind of synthesis and struggling with math - Aced calculus but can't add worth shit)

75 g NaBr
100 ml GAA
35 ml Sulfuric acid
15 ml brazillian sassafras oil (not cleaned up)

Added 75 g NaBr to 100 ml GAA in 1 liter tall form beaker. Drip 35 ml Sulfuric acid slowly into solution.
<whole bunch of stuff shouldn't have had to do because of inexperienced chemist> Eventually added 80 ml more GAA to get enough to stir, 20 more g NaBr, and 10 ml more sulfuric acid. Filtered off undisolved NaBr (wet cotton rags soaked in water and Bicarb helped keep the fumes under control while dismantling the space alien rig) Had 150 ml tangerine orange solution. Added 15 ml brazillian sassafras oil - instant color - darkish brownish green formed swirls on the top of the orange. In a few minutes it was all very dark green as shown in the pic. Currently in 1 liter flask wrapped in foil. Added another 16 ml for total of 31 ml sassafras - color very dark green and syrupy consistency. More pictures will be taken at 12 hours and 24 hours to monitor the progression.

Hope you get a kick out of space alien Acme Glassware setup. Expected lots of red fumes! Nope!

Salat

akcom · « **Reply #1 on:** January 01, 2011, 09:43:55 PM »

Nice to see some experimental confirmation!
PS love the glassware.

salat · « **Reply #2 on:** January 01, 2011, 10:50:43 PM »

Thanks, don't follow mine though, wait for jon to say what the correct molar should have been.

ebuy odd lots.

It's a 1 liter tall form beaker in a vacuum desiccator bottom with the lid from a massive liquid/liquid extraction apparatus. There's a claisen adapter with a dropping funnel and a teflon valve with a tube into a bucket of water and baking soda. That was in case the thing went nuclear or the pressure built up, the fumes could be vented. Then there's a poor mans powder funnel which was a small funnel attached (precariously) to a teflon tube inside the lid that was just over the top of the 1 liter beaker. Some propylene glycol was in the desiccator and the whole thing inside a water bath so ice could be added as needed. (jon said it wasn't exothermic but xBee wasn't convinced, better safe than sorry the first time a procedure is followed) Also there was a glass tube with a thermocouper so the temperature could be monitored. All of that was because xBee aka SWIMChemGeekHubby has been up in arms re safety and fumes a lot lately. Bromine and GAA are both dangerous to breathe. The whole setup was basically a way to avoid any fumes. The glassware was setup at the end of the table so that fumes would go downwind.

Think it could be simpler next time.

Screw up didn't account for the distance from the bottom of the dropping funnel and the top of the beaker so the glacial acetic went down the insides of the dome instead of into the beaker. So it had to taken off and a tube attached inside. The GAA seeped into the seal on the lid and dissolved the vacuum grease so out comes the electric tape and a roll was sacrificed keeping it all together.

Also there was a deliberately low molar on the sassafras because there seemed to be a possibility that the NaBr had an incipient in it since a lot of it didn't dissolve.

But it was a real fun night!

Salat

Oerlikon · « **Reply #3 on:** January 02, 2011, 04:20:24 AM »

Jon said that some undissolved NaBr is a good thing,that means you didn't used too much sulfuric acid
which destroys safrole. Large excess of chemical that forms other chemical in situ is allmost a norm,
especially if it's cheap and doesn't hurt reaction in any way!
In this case excess of NaBr is very good thing,don't filter it next time!
I got everyting but KI to make iodosafrole,I am glad that someone posted pictures!

Thanks Salat!
Can't wait to see progress!

salat · « **Reply #4 on:** January 02, 2011, 06:23:46 AM »

My test called for checking the color every 12 hours. This thing is like an Easter egg. At 8 today checked it - it was a dark midnight blue. Now it's frozen solid, but it was a very small experiment.

Methylamine has been in progress for a while so it may be sooner than later, although when 2 ADHD people our age live together there's no telling what will happen or when.

Salat

akcom · « **Reply #5 on:** January 02, 2011, 06:54:15 AM »

salat, how are you generating your MeNH2?

salat · « **Reply #6 on:** January 02, 2011, 08:17:09 AM »

xBee has got it down pat using hexamine. Had some problem with the stuff you get from fireworks - excipients.

He's been threatening to write up what he's learned, I'll ask. He said the reaction is really taking place at a lower temp. I don't know if any of the writeups out there for hexamine are 100% correct. Things like leaving it sitting stirring overnight before heating are important.
I've been thinking of attempting the acetamide reaction mainly as an excuse to use the 3 liter jacketed reaction vessel!

I'm a glassware slut!

Salat

jon · « **Reply #7 on:** January 02, 2011, 10:07:53 PM »

weigh your sulfuric acid, don't count on volumetric measurements i still can't figure out why you made that so overcomplicated.
everything is done on the basis of weight and mole numbers.

salat · « **Reply #8 on:** January 03, 2011, 12:26:23 AM »

Quote

i still can't figure out why you made that so overcomplicated.

I'm a tweaker? We both do it. And am a computer/database whiz, often wonder why even software companies that should know better can't design a decent database.

Never had a chemistry class - only physics in college and biology in high school. In one year of home study have learned to distill (fractionate, vacuum, steam, and solvent recovery), soxhlet, use sep funnel. Most of my work has been in plant extraction. Only recently began using NaOH, HCl, etc. Used weaker bases and acids to start with. Spill too much. Butyl gloves are my friend. Mole numbers are not something I have ever had to deal with and it's been over 20 years since my last college math class.

This is first attempt at a reaction of any kind.

Next time will be simpler. (for one thing have the more detailled directions you sent me) Researched a lot and it is important to keep it very cool because you get Br mixed in if the temp gets high. If it's turning orange fumes you got Br with your HBr.

Stuff in the freezer is a dark blue with purplish tones to it - frozen solid, probably because of the small scale. Moved it into Fridge (it's protected from light). Don't think it's done yet.

Will do on weighing the sulfuric. xBee has been drumming the need to keep the ratio of sulfuric to NaBr low. Went back over some old threads and pulled your instructions. Going to try to translate them into beginner chemistry instructions.
Thanks
Salat

Oerlikon · « **Reply #9 on:** January 03, 2011, 01:16:33 AM »

Salat,just give me mass of safrole and exact concetration of your acid when you
want to brominate it next time and I will calculate
molar to mass ratios of all chemicals you need...
It is most borning and most important aspect of chemistry,apart from healthy logic...

If you are computer whiz you probably know math well,
those are just darn fractions and multiplications,so when you
understand it,try to make program or something

salat · « **Reply #10 on:** January 03, 2011, 01:52:10 AM »

Thanks, I appreciate the offer, but it's one of those things I need to learn. Had very advanced math (calculus, diff equations etc 20 years ago - don't use it balance the checkbook).

For me there is no substitute for trying and screwing up. Once I get it internally, it will be my friend forever. It isn't all that different from cooking conversions. Just have to remembering that a solution percentage is of the entire solution weight not the solvent weight. Jon's suggestion to use weights instead of volume is easy to do also.

Salat

Oerlikon · « **Reply #11 on:** January 03, 2011, 02:23:47 AM »

I am math moron but I learned stoichiometry pretty quick.
It's like riding a bike,it is pain in the ass at first but if you practice it for a while it becomes natural!

jon · « **Reply #12 on:** January 04, 2011, 02:08:54 AM »

don't let it run for more than a day you can go over a bit but too long and it turns to tar.
go ahead and extract it.
to test it get some sulfuric acid freezing cold then add a drop of the extracted bromosafrole to it.
it should sit on top if it has any alkene the acid will turn purple.

salat · « **Reply #13 on:** January 04, 2011, 04:30:06 AM »

It's drying now.

I think I understand your methods a lot better. If you stick with weights you don't have to worry as much about conversions or math.

Salat

Oerlikon · « **Reply #14 on:** January 04, 2011, 05:29:39 PM »

What is most dominant color of clean bromosafrole!?

I don't understand Salat,you said you stick with weight you mentioned but than you added
non proportional amounts of solvent and reactants (in relation to those you listed first)
in other part of experiment!?

Hope you didnt end up with tar!

salat · « **Reply #15 on:** January 04, 2011, 09:58:28 PM »

No, I intend to stick with weight next time based on further explanation from jon on how he does things.

I have a small crystal dish of a dark reddish brown liquid in the fridge which I assume is bromosafrole. I don't know what color it should be, not having access to university resources is a problem. As soon as I figure out where Mr Merck's book went to, I'll try looking for properties now that I have located the correct name for it.

Went through the wash procedure as described in one of jon's post. Every cook has their own methods of preparing a given recipe - its more complicated with chemistry, but there is a learning process to be gone through the first few times you do any reaction. When an experienced chef shares their techniques it shortcuts things a bit, but you still have to learn what the words on the paper mean in real experience.

I intend to process this into iodo today and then do the whole thing again from start to finish.

The was Post reaction process in shorthand (my checklist) was
1.   Decant into Sep funnel
2.   Add H20 1-2 volumes
3.   Remove water Layer
4.   Extract with DCM or TCM
5.   Wash with water
6.   Add sodium bicarb unit no more fizzing - to neutralize the GAA
7.   Wash with water
8.   Wash with brine
9.   Dry under vacuum

A weird thing happened during the first wash - see attached pic. The oil formed a pattern of dots at the top and fell down one by one with new ones rising to take it's place. Eventually it all settled out and was separated. Changed flourescent bulbs for old ones and covered the funnels with towels while working.

I deviated a bit and setup a vacuum distillation with almost NO heat. This only works if you have a really strong vacuum source. Like the Savant GP100 gel pump. You can get really fine control if you put a needle valve on your manifold that is open to a filter or drying tube. That way you can selectively add air and get very fine control. The setup is shown below. It consists of a flask with room temperature water bath and teflon stirbar, bump trap, condensor, receiving flask and cold trap to prevent the DCM fumes from going to the pump and into the air. To evap off the DCM, start the stirring and condensor water, then opened up the needle valve all the way before turning on the pump. Then slowing close the valve until the liquid starts boiling (NO HEAT at all). Keep an eye on the drip rate from the condensor when it starts to slow down you turn the knob on the needle valve just a pinch until the bubbles start to pool again. Keep the stirring strong. At the end you need to be prepared to stop before the mixture freezes. I had to heat the water a bit to take off the cold at the end so it wouldn't freeze. (xBee taught me these techniques)

After that I gave it to xBee to put in the desiccator and get the water off it. Using 3A mol sieve in the desiccator and he has a very nice leybold that gets ridiculous amounts of vacuum so the whole thing was done overnight. Made a lot of mistakes but learning a lot also.

Have attached is a word doc encapsulating a post jon wrote on the post workup. He may have modifications and refinements to add since then.

Salat

jon · « **Reply #16 on:** January 04, 2011, 10:37:41 PM »

bee careful bromosafrole is quite volitile and will go off into thin air i would'nt leave it in the dessicator very long.
btw bromosafrole is bichromatic concetrated it has a burgandy color diluted in solution like that it will bee green or brown
i have to say nice technique and nice glass i'm green with envy.
in short
throw the shit in a sep funnel
add 1-2 volumes water
let the bromosafrole crash
sep it out
extract the water layer a few times (gauge by color)
combine the solvent with the bromosafrole
discard the acid/water
wash the solvent/bromosafrole with water adding bicarb and swirling until fizzing stops
dump this wash
wash with water
then brine
and instead of losing product to volitization in the dessicator
try drying the solvent/ bromosafrole and filtering using a drying agent like mgso4

Oerlikon · « **Reply #17 on:** January 04, 2011, 10:52:37 PM »

Jon,I suspected you will say she is overcomplicating things,but you love her setup

You said nothing about distillation but mentioned that bromosafrole
is volatile,and now salat is using vacuum distillation!?

No strong vacuum pump is needed to boil lower halogenalkanes like
DCM or TCM at room temp.,any water aspirator will do it!
Even water and acetic acid will boil with lukewarm water bath under these conditions.

I am confused salat,why are you using vacuum at all!?
(Apart from drying that can be done in regular desiccator...)
What and why will "freeze" if you don't do something right!?

jon · « **Reply #18 on:** January 04, 2011, 11:03:19 PM »

i used an ass pirate myself to remove the solvent
i dunno but the setup looks nice it is a bit overkill
under a hard vacum the molecules get spaced out and it has a cooling effect.

Oerlikon · « **Reply #19 on:** January 04, 2011, 11:18:34 PM »

ass pirate...LOL
Sounds same but has oppsoite effect of but pirate!

That freezing effect is interesting to know!

What do you mean under "bichromatic concetrated" ?!
You mean that pure bromosafrole has color of concetrated
bicromate solution or...!?

I would leave DCM+bromosafrole in glass of
dry MgSO4 for a while,decant it and wash MgSO4 with some more DCM,
combine that,strip off DCM with normal distilation
and leave remaining in normal dessicator for few days.

Author Topic: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole... (Read 2846 times)

salat

Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

akcom

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