Author Topic: cant get safrole? FREEZE IT!  (Read 31842 times)

0 Members and 1 Guest are viewing this topic.

PrimoPyro

  • Guest
Go To Bed
« Reply #40 on: April 09, 2002, 08:23:00 AM »
LaBTop: You are far too cranky. Go to bed, or at least lay off the stimulants for a few days; might want to take a handful of downers while you're at it...

You guys are setting up a fucking government here with all these checks and balances and watching everyone and rating. Fucking calm down. No wonder so many bees only read the couch.

(I bet I could hold my breathe and count until this post gets rated, and I wouldn't even hit 100. So be it.)

                                                  PrimoPyro

EDIT After Rating:  ;D  Who's doing that!?  ;D  That's just to "prove" to me that I can't predict everything you do, isn't it? I say I expect a negative rating, so I get a positive one as an "oh yeah?" instead? That is hilarious.  ;D  Who did that??


Vivent Longtemps La Ruche!

greeter

  • Guest
(empty)
« Reply #41 on: April 09, 2002, 11:04:00 AM »

foxy2

  • Guest
Arrogant
« Reply #42 on: April 09, 2002, 11:56:00 AM »
Quick to judge.

How many types of sassafras essential oil are there?
At least 3 common ones and others
Chinese, American, brazillian.

How many people make sassafras essential oil?
Hundreds of companies most likely.

How can you say one method works the same for all the oils?
YOU CAN'T

If you have 70% oil it sure in the hell is going to behave much differently than 95% oil.  So all this talk of foolproof one and only methods is a bit arrogant IMHO.  We are dealing with natural products from many different sources and even different plants.  I'm sure that 10-20% eugenol would have a huge affect on any crystallization, what about water content, ect ect ect.

Don't say somethings foolproof until you do GC analysis of your oil so everyone knows exactly what is in the oil your using.

Hey LabTop
"I will not allow any posts anymore which claim sincerity, who are not doublechecked first by at least 2 known exact
operating Hivers, any other posts must contain a disclaimer:"

LOL, thats funny.
Your starting to worry me here.  Anyone would have to bee an idiot to take what one person posts as a "tried and true" method.  The disclaimer is INHERANT in every post I read, IMHO.  Shit you have to look at patents and journal articles the same way!!!  See the recent information on nitroethane for your example.  Anyone who really cares will take the time and search for someone who verified a procedure.  I do admire your catologing and attempting to do this for everyone, however I think reading many different accounts of the same procedure is much more valuable than one "tried and true" method.  Maybe this is because I am always looking to optimize what I do and reading multiple experiences is the best way to get a jump start on innovation.

Thoughts and ramblings
Foxy

Those who give up essential liberties for temporary safety deserve neither liberty nor safety

scram

  • Guest
Freeze method
« Reply #43 on: April 09, 2002, 07:37:00 PM »
I can tell you from lots of experience only using this method with no distillation apparatus has worked well to get mdmx mdex and mdx.  

BTW, when I saw the voluem 5 Guenther it stated safrole had a density of 1.70 to 1.09. Maybe it mean sassafras oil. not sure
Re: "Baalchemist, for example. What was he thinking, what was his possible motive, when he posted that BULLSHIT about 1 gallon jugs and seed crystals and turning the jugs upside down overnight in freezer.  I tell you he NEVER actually did what he posted, because it is PHYSICALLY IMPOSSIBLE."

I think baalchemist meant to do it the same way I have which is the best method I've found to date, pretty much what is already discussed here:

Place in jars, make sure you got at least 1/2 volume of air in the container in the fridge at the coldest setting (use coldest setting first for practicing). place seed in there if it doesn't already spontaniously crystalize. Full crystallization can be complete in anywhere from 2 minutes to 6 days depending on temp. Slowest is the only way to go. But first practice on getting the shit to crystalize a few times before tweaking it to a warmer temp.

Best length for crystalizing is at least 3 to 6 days. The crystals form from bottom up pushing the impurities away from the lattice in a slow gradual manner. Once about 66% has crystlized, YOU THEN TURN THE JAR UPSIDE DOWN and let it drain off at ~12c for 1 day to get a opaque clear liquid. Melt it and Repeat once more. Works very simply and on the second run you'll get fat crystals that have virtually no yellow impurities locked into the crystal lattice. Check the old hive for information I posted about this method nearly 2 years ago when I still tweaking this method.  PEACE OUT!

LaBTop

  • Guest
Got some sleep.
« Reply #44 on: April 10, 2002, 02:49:00 AM »

Post 294426

(LaBTop: "Sassafras components data", Methods Discourse)
, and look at all the densities from the sassafras constituents according to Guenther, then you see not ONE which nears 1.1000, only safrole. So there is nothing mentioned more dense than safrole, which could interfere with the reported 1.0992 density of the purified frozen safrole from Argox, and lifting it's density above the Merck ref of 1.096 . (Merck=most reliable imho)
Ofcourse there could be something dense there at forehand which we don't know.
But the sassafras was FIRST distilled with a very good fractionating column, so the freezing was tested with already quite pure "sassafras"/safrole.
How can someone who has calibrated exactly a one liter erlenmeyer with 20C water, and uses a calibrated official one liter vessel, and a precise digital balance, leveled with a waterbubble, checked with calibrated weights, come then to a density at 20C of 1.0992 , for the frozen part (safrole), after 3 x freezing?
You see also that 3 different companies give 3 different densities for safrole.

Scram, I think I found the confusion, found 2 posts from Baalchemist,
1. "could" be interpreted wrong, because it doesn't state that the liquid is ALREADY frozen before turning it upside down, (btw, he states also a d20 of ~ 1.1)
2. is more clear:

1. =========================
baalchemist (Chef d'Equippe)
01-07-02 15:13
No 253681 
Re: Safrole Crystals

Baal takes 1 gallon jugs of Chinese sassy and tosses them in the freezer for about 30-40 mins. Then a seed crystal is tossed in and the jug is put back into the freezer, but this time turn it upside down and leave it overnight. The next day the jug will be completely crystallized and the residual crap has found its way to the bottom(which is actually the jug top) and can be removed easily. Baal will let this 'drain' upside down over a beaker for a few mins and is left with clear white safrole w/S.D.~1.1 . This is then vac. isomerized with KOH 'as is'. Been doing it that way for a couple years now without a problem, of course Baal has been fortunate enough to have only acquired that 95%+ stuff in recent years.

2. =========================
baalchemist (Hive Bee / Eraser)
04-15-01 03:16
No 184267 
Re: Sassafras oil --> Safrole??

Freezing is the easiest if you got the good chinese shit, that 60-70% shit needs a seed crystal most of the time. Once its frozen, turn the bottle upside down in the freezer for a day or two. All your crap will settle away from the goods for easy disposal.
============================

In 2. he also states to wait for 2 days before draining.

Argox prolly didn't wait that long, and/or his sassafras was purer. And he stated that he fractional distilled the sassafras first, so got a MUCH cleaner product to freeze! That can explain the observed anomaly, that the impure oil constituents where located UNDER the crystals at the bottom of the pail, even after turning the pail upside down, and were NOT leaked through the crystal matrix, and therefore he had to puncture the bottom of the pail to drain it away. And he prolly did not wait 2 days to see if it leak through.
 
Still I can see his reasoning: whatever you do, if you have to wait a long time before freezing proceeds, the impure oils will form in a "hole" on top of the crystals. That means if you turn your pail upside down, your impure oil will still form in the same hole, but NOW facing the bottom.
And he saw NO oil leaking through the crystal mass at all. So unscrewing a lid or removing a lid will show you ONLY a dry mass of crystals, while the impure oil is locked between the bottom and the crystalmass.

I would like to ask MadMax and Roundbottom if they ever found impure oil leaked through the crystal mass, at the BOTTOM. Because when it leaks through from bottom to top if upside down, it should also leak through from top to bottom prolly when used in normal position.
If they never found any bottom sludge, then "leaking through" seems strange.
Or if they ever used that upside down method long enough (2 days) and can confirm it too.
And don't mind anyones reputations when the truth is at risk, look at my sticky threads where I proposed fractional distillation of sassafras for so long, and it turns out that a simple test done for a few days proofs that it is totally redundant and a waste of time prolly in most cases.
However, the fanatical purist should fractionally distill the sassafras first, and THEN freeze it 3x, to get near quantitative amounts of pure safrole oil!
But that's for real scientists who seek reliable data of ONE component, and cooks can skip that step. LT/

PS: Primo Pyro, as stated in my later post, I saw no practical possibility to implement such a basic scientific standard of contra expertising here.

PSII: My opinion is that the rating system should be used with care, so we don't wreck it's potential value to indicate real good posts, and the bad ratings should be used to dam the sinflood of unnescessary multiple posts about one test, which could be posted after the tester has tried everything possible, and searched extensively for answers while in the process of testing, and THEN, when all his tests went wrong, he comes here to ask for help.

Now hundreds of posts are dumped here every half hour into the process of the testing ITSELF.
Stupid, you can see clearly that the dumfuck has his IP connection beside his workbench!
When I can conclude this, LawEnforcement can see that clearly too.

WISDOMwillWIN

humid

  • Guest
freezing adulterated oil
« Reply #45 on: April 10, 2002, 06:17:00 AM »
Just to put to rest (somewhat) the question that Foxy
brought up about oils with a higher % of crap in them,
swim placed the eugenol etc, extracted from 1 liter of
natural Albidium into about 800 ML of the same unexstracted
oil and used an amount of this adulterated oil in a
simple freezing technique using a seed crystal.
  The safrole crystalized out with the expected additional
 amount of crap oil floating on top.
 So it seems that safrole will crystalize despite being
 present in an excess of the other natural constituents
of sassafras oil.

flipper

  • Guest
yep
« Reply #46 on: April 10, 2002, 10:24:00 AM »
Ok now I think there are some comunication disturbences. Well What I make of it is this:

1:Too succesfully purify your safrole you need a sassafras oil that already has been vacuüm distilled ones so you have a somewhat cleaner oil.

2:you need seed crystalls

3:It's good to do the procedure three times.

4:Unfrozen liquid forms above the frozen safrole crystalls.

5:You will get 99% pure safrole with a density of 1,1 g/cm³

questions

Ok is this correct or not?
How do I get seed crystalls??

You've gotta love me.

RoundBottom

  • Guest
glad to see you're rested [smile]
« Reply #47 on: April 10, 2002, 12:59:00 PM »
> if they ever found impure oil leaked through the crystal mass, at the BOTTOM

in my unscientific, anecdotal experience, i have not seen any impurities resting at the bottom below the crystals.  they do seem to be 'pushed' up and i always seem to have a little 'well' at the top where the impurities sit.  it's noticable in max's pix, too.

my thought is, the crystals are pure safrole.  if you start the freezing process and then stop while there is still safrole to be frozen, your crystals should be pretty pure.  unless the impurities are trapped in the crystals.  this is beyond my expertise, maybe i'm just talking out the side of my mouth.

i learned a thing or two from charlie dontcha know.

LaBTop

  • Guest
Parrotting.
« Reply #48 on: April 10, 2002, 02:34:00 PM »
Flipper:
Ok now I think there are some comunication disturbences. Well What I make of it is this:

1:Too succesfully purify your safrole you need a sassafras oil that already has been vacuüm distilled ones so you have a somewhat cleaner oil.
LT: I just explained it is NOT needed! Only if the institution where you would ever work as a research analytical chemist wants to be sure and let's you check about the compounds EXACT data!

2:you need seed crystalls
I doubt it, if a deep freezer is used first.LT/

3:It's good to do the procedure three times.
You'r good in repeating. LT/

4:Unfrozen liquid forms above the frozen safrole crystalls.
Dito. LT/

5:You will get 99% pure safrole with a density of 1,1 g/cm³
Dito! Btw, you will only be sure when you have access to complicated analytical instruments, so "probably ~99%" and "nearly 1.100 g/cm3". And that's no nitpicking, that's everydays logic for "cooks", who have to live with certain insecurities, due to oppression. LT/


questions

Ok is this correct or not?
How do I get seed crystalls??
"You've gotta love me."

Where do you see communication disturbances? I think I made it perfectly clear that I doubt you will see any impure oils filter or leak through the main bulk of safrole crystals, if performed like Argox says. And his data empirically found indicate that the whole "upside-down" thingy is redundant, if not at all impossible when you want to reach his data results.
"1. Ok is this correct or not? 2. How do I get seed crystalls??"
Now here (1.) you start really annoying me, THAT's the whole basic principle we are looking for, you don't need to pop in and repeat everything.
And (2.) how to get seed crystals is made perfectly clear by a few people already. UTFSE! or reread this thread. LT/



WISDOMwillWIN

humid

  • Guest
freezing
« Reply #49 on: April 10, 2002, 03:17:00 PM »
LT, just to clairify, you can get it to freeze w/o a
seed crystal, but when it does it'll all go at once,
trapping unwanted gunk in the matrix.
  By using seed and chilled (not supercooled) oil, the
 lattice grows slowly, pushing the impurities away,
just like recrystalization does with bisolvent solutions
at the right temp
 And as gump says "that's all I'm gonna say about that.

LaBTop

  • Guest
Foxy2,
« Reply #50 on: April 10, 2002, 03:48:00 PM »
Both Humid and Roundbottom indicate already also that the impurities in different "species" of sassafras don't make a flying fart difference, as I expected.
Especially Humids method of re-introducing a big amount of Eugenol + other impurities, into his original sassafras oil, to check if that would interfere with the freezing, proofs it right, it doesn't! I like prompt returns on insecurities that way. Thanks, Humid.
And Roundbottoms observations indicate the same as we already heard, the impurities form in in hole on TOP of the freezing crystal mass. Just like you could see in MadMax pics, as I did also already.
Any water can be removed in a preliminary step first, however as you can see in the water solubility data I handed over on a silver platter, these eventual water contents are neglectible for all compounds of sassafras oil, and btw, if you unfreeze purified safrole, the next isomerization step asks FIRST for a water removal, to not interfere with the KOH complex while isomerizing.
If unsure what to do, throw in your new sassafras oil, a buttload of dried silicagel first, and decant after a night standing.

That thought of many different percentages in sassafras oil ofcourse came directly to my mind also, that's why I searched 6 hours on the Net to dig up those data from the main constituents of Sassafras oil. And that's why I gave the Guenther list of those VARIABLE percentages.
And gave you all the MAIN constituents data for sassafras oil, from the bible of Essential oils, Guenther again. And I am SURE the ranges he found in percentages for every constituent found, reflected the bulk of available sassafras species and suppliers.
He's a German scientist, FAMOUS for their precise and reliable data mining. (Proof: PolytheneSam, only partly German, but mainly PRECISE :) , you Foxy, however, have never indicated your roots, so I can't give you credit on that, but there must have been some german precursor in your family too ;) )
And again, review those main data, there's not one except Eugenol, which could propose a threat while freezing.

The intention of posting that list, was mainly to make clear to the investigative mind, that Eugenol has a Mp of -7.5C, and Safrole a Mp of + 11.2 which means there is such an immens difference in melting points, that you can forget the possibility of Eugenol interfering with the freezing process.
Btw, I indicated in red already that the data from the Chemfinder website is UNRELIABLE, at least for this compound. But there are many more flaws in other compound data from them also. They should get a burning message to review their whole online data asap.

Eugenol is the only impurity I would even worry about, caused by its close relation chemically spoken, to Safrole, and we know that it, if carried along into the next isomerization annex next steps, will respond to these treatments in the same manner as Safrole, thus severely wrecking the posted YIELD results of far too many members.

All the other impurities form no serious threat to interfere in the freezing technique, they all stay liquid within the set freezing range of your deep freezer (-5).
Why a deep freezer? Because those work much faster, and fast freezing is a wellknown technique in many procedures.

Now, to conclude, may I say that your (reasonable, but not deeply thought over) reply:
""If you have 70% oil it sure in the hell is going to behave much differently than 95% oil. So all this talk of foolproof one and only methods is a bit arrogant IMHO. We are dealing with natural products from many different sources and even different plants. I'm sure that 10-20% eugenol would have a huge affect on any crystallization, what about water content, ect ect ect.
Don't say somethings foolproof until you do GC analysis of your oil so everyone knows exactly what is in the oil your using."",

is reasonably profen to be not appliable for as good as all cases of members, buying industrial sassafras oils.
Do not feel offended, this is an ongoing discussion and in the process everybody introduces new bits of  theory and/or knowledge, and so it should be, always. LT/

PS: Foxy, let's not call it arrogant, but Wonder, wonder why such a simple method was overshadowed for so long by much too complicated theory and practice, while a simple check of the densities after a fractional distillation could have indicated that there was something terribly wrong with all those posters who believed truely they had pure safrole in hand, but in fact had their sassafras nearly unchanged back. Just lately freezing came back to this board again, before it was just shortly mentioned now and then, but never really propogated as the one and only reliable fast and clean method.
And THAT's why I get so upset, not having access to a lab for so long already, and having to rely on postings from amateurs, who don't CHECK their products data after each conversion step. You will understand that too, being in the same situation.
Non lab owners should be very carefull with what they post, leave always room for cooks to proof you wrong. See myself, I really never expected such a bad result from sassafras fractional distillation, a technique what comes to mind as the first option in most purifying procedures.

WISDOMwillWIN

RoundBottom

  • Guest
isomerization
« Reply #51 on: April 10, 2002, 04:22:00 PM »
also of note, i previously posted about an isomerization attempt using crystalized safrole,

Post 278285

(RoundBottom: "Re: vacuum refluxing", Chemistry Discourse)
.  labtop mentioned it was the best result he had seen (which still surpises the heck outta me, SWIMs lab technique is nothing if not amaturish, and leans more to comical  :-[ ).

> - measured 2400mL of safrole double crystalized from sassy oil (brazillian)

this safrole was not 'dried' in any way before use. 

SWIM is having a heck of a time with the Os AlHg, though; the learning process never ends.  babybees, keep at it, you can get it.  SWIM knew zip about chemistry before ariving on the HIVEs doorstep.


i learned a thing or two from charlie dontcha know.

humid

  • Guest
freezing
« Reply #52 on: April 10, 2002, 04:41:00 PM »
Cool, RB, and let swim say that upon observing the rest
of the adulterated oil (should be around 40% bad, 60% good)
which was placed in the fridge and seeded with crystals
 from batch number one, that time seems to be factor.
  Way more crystals should be present than are.
 Cold sinks, and as the safrole becomes cold it also
becomes more dense (unlike water), and swims thinks it's
just the fact that the denser safrole is just held up
a little, by the increased shit it has to go through
before reaching the lattice where it can bond.
 Usually goes MUCH quicker than this.
 (swim just left the first sit in overnight with no
observation)
So the only difference between safrole content where
freezing is concerned is rate.
  (or so it looks)
EDIT So it seems that a weird side effect of using
adulterated oil, is that the slowing of the rate at which
the lattice grows may actually create purer crystals!
  (chemical irony, i'm stoned) ;)

Shambhala

  • Guest
Freeze The Sassafras
« Reply #53 on: April 10, 2002, 08:10:00 PM »

RoundBottom

  • Guest
insignificant, yes, but i like it, too...
« Reply #54 on: April 11, 2002, 12:14:00 AM »
shammy, i thought it was a cute post.  i wonder if someone could make a rap record out of that or something.

i learned a thing or two from charlie dontcha know.

PrimoPyro

  • Guest
Shambala --> Thumbs Up
« Reply #55 on: April 11, 2002, 12:21:00 AM »
I liked that post, too.  :)

You got my vote.  :P

Vivent Longtemps La Ruche!

foxy2

  • Guest
Found Out!!
« Reply #56 on: April 11, 2002, 04:46:00 AM »
Damn LT
Your good!
you Foxy, however, have never indicated your roots, so I can't give you credit on that, but there must have been some german precursor in your family too

Well I can tell ya this much
I am 1/4 Nazi, got a tiny bit of Napolean and a small slice a Sven, and the rest on me likes a good Sauna,
I really like Saunas
Now your Hypothesis is verified and ego inflated  :P
:)  :)  :)  
Foxy

FUCK!!!!!!!!!!!!!
I had like 10 different journal articles open(not saved) and fucking Dr Watson happened when I open google, aarrrrrrrrrrrr fukin

Those who give up essential liberties for temporary safety deserve neither liberty nor safety

foxy2

  • Guest
Something else
« Reply #57 on: April 11, 2002, 04:57:00 AM »
Ok arrogant was overstated
But being so critical of baalchemist seemed a bit rediculous.  Especially after reading his posts on the subject.  He didn't exaclty post a step by step guide, just some bs from memory. 
I just tought getting all hot and bothered when something posted here doesn't work was rather stupid and I didn't like the bitching attitude.  That colored my reply a bit.

But I guess I can understand the bitching if you just spilled a bunch of sassy all over.  :)
That might smell a LITTLE  :o
Foxy

Those who give up essential liberties for temporary safety deserve neither liberty nor safety

LaBTop

  • Guest
Conclusion:
« Reply #58 on: April 11, 2002, 10:01:00 AM »
The main purpose of this thread will be reached when everybody starts getting the basic idea:
Be as PRECISE as possible, don't take shortcuts, and especially when you report your findings in our forums, be VERY exact, controll as many different data from your supposed product as you can, and include them in your reports.
There are too many, if not nearly all, reports, where a very messy report is quickly delivered, and no confirmation is given at all if the product obtained was bio assayed by anybody, and confirmed to be the desired product.
But everybody hops on that bandwagon, starts experimenting, and then 2 month later we find out that the originator never made the desired product, and was too embarressed or just lazy, or deliberately did not report back to tell us he/she failed in the most important conclusion:
Did it work or not!
LT/

PS: this thread will be moved in a week to the Methods forum, so don't panic when it's gone here. :)

WISDOMwillWIN

humidbeing

  • Guest
freezing adulterated oil
« Reply #59 on: April 11, 2002, 01:09:00 PM »
You should see the SIZE of the crystals that resulted
from the slow freezing in the adulterated oil.
 Great big ones about an inch square. Sorry can't
eyeball too well in metric. :P

CG I miss you sweety, I really do.