YES YES and YES!
This is the one and only no bullshit way to purify sassafras, also confirmed already to me by another well respected member, who couldn't believe his eyes reading all the rantings about distilling, refluxing and smoking stillpots after he simply freezed out in 2 subsequent freezings all impurities, and obtained a clear slightly yellow 1-alkene oil (safrole) with a density of 1.0982 at 20C, which is sufficient pure (ideal is 1.1000 density at 20C for Safrole) to proceed with an overnight full vacuum isomerization with 5% 99%KOH to 2-alkene (iso-safrole).
Thanks, MadMax, Roundbottom, Argox. There should be a whole lot more of -- no-bullshit, I wanna see it with my own eyes -- members like MadMax, Roundbottom and Argox.
I must admit I have tried to assist in the endeavours of so many, by describing how to fractionally distill sassafras. However, I never needed to do that, Safrole could be get at bottom prices in my times. MDP2P also, by the way. Nobody even thought about buying sassafras oil, redundant then.
Times have changed, so this is my new stance on Sassafras oil purification:
FORGET DISTILLING SASSAFRAS, FREEZE IT slowly 2 TIMES, decant the unfrozen oil, freeze the melted Safrole slowly again to collect a next crop of impure non frozen oil, and decant the non frozen oil again, this will not freeze at all, especially near the temperatures where the safrole freezes out!
Congealing point of safrole is according to Rhodium table +11.2 C, which was observed as the exact same congealing point for the 1-alkene.
You get rid of Eugenol, alpha and beta-Phellandrenes, various Sesquiterpenes, Pinenes and Camphor and other traces of different oils in a few relaxing hours by the TV set. LT/
PS: see also thread Post 220835 (https://www.thevespiary.org/talk/index.php?topic=9775.msg22083500#msg22083500)
(menthol_man: "Safrole Crystals", Methods Discourse) with beautifull pics of MaDMAx, or his pics at:
http://www.geocities.com/marktsas/saf4.jpg (http://www.geocities.com/marktsas/saf4.jpg)
http://www.geocities.com/marktsas/saf2.jpg (http://www.geocities.com/marktsas/saf2.jpg)
http://www.geocities.com/marktsas/saf3.jpg (http://www.geocities.com/marktsas/saf3.jpg)
See also Baalchemists easy method for freezing Sassafras: Post 253681 (https://www.thevespiary.org/talk/index.php?topic=9775.msg25368100#msg25368100)
(baalchemist: "Re: Safrole Crystals", Methods Discourse),
and Osmium who gives wise advice in Post 223146 (https://www.thevespiary.org/talk/index.php?topic=9775.msg22314600#msg22314600)
(Osmium: "Re: Safrole Crystals", Methods Discourse).
WISDOMwillWIN
Ingredients of sassafras oil with CAS nrs, so you can look data up in Chemfinder, Interactive Physical Properties Database or the Merck Index,
Especially the densities and melting points are interesting for the 2x freezing method:
Usual components 0f Sassafras Oil,
From Guenther, E.,"The Essential Oils", vol II and IV:
pinene.......... 2-10% Bp= 154C at 1 atm
phellandrene. 2-10% Bp= 175C at 1 atm
d-camphor.... 0- 5% Bp= 204C at 1 atm
safrole.......... 80-90% Bp= 234C at 1 atm
eugenol........ 0-10% Bp= 252C at 1 atm
CHEMFINDER data:
( http://chemfinder.cambridgesoft.com/ (http://chemfinder.cambridgesoft.com/)
)
==============================
(1S)-(-)-alpha-PINENE [7785-26-4]
Colorless to pale yellow liquid.
Mp= -64C Density= 0.874 g/cm3 at 20C
Bp= +155 - 156C
==============================
alpha-PHELLANDRENE [99-83-2]
Pale yellow liquid.
Density= 0.843 g/cm3 at 20C
===============================
CAMPHOR [76-22-2] also known as (±)-CAMPHOR, d-CAMPHOR:
But note: is has a different CAS nr than the IPP data! A solid, not the oil!
Colorless, glassy solid with a penetrating, characteristic odor.
Mp= +177C Density= 0.99 g/cm3 at 20C
Bp= 207C Water Solubility= 0.12 g/100mL
IPP data:
CAS Number : 000076-22-2
Chem Name : CAMPHOR
Mol Formula: C10H16O
Mol Weight : 152.24
Melting Pt : +180 deg C
Boiling Pt : 204 deg C
Water Solubility:
Value : 1600 mg/L
Temp : 25 deg C
Type : EXPerimental data
Ref : YALKOWSKY,SH & DANNENFELSER,RM (1992)
=================================
CAMPHOR oil (light) [8008-51-3] :
Colorless liquid.
Density= 0.89 g/cm3 at 20C
No IPP data!
=================================
SAFROLE [94-59-7]
Colorless or slightly yellow liquid
Mp= +11.2C Density= 1.095 g/cm3 at 20C
Bp= +232 Water Solubility= Insoluble. <0.1 g/100 mL at 18 C
=================================
EUGENOL [97-53-0]
Clear, colorless or pale yellow liquid. AIR SENSITIVE.
Mp= +15.44C Density= 1.066 g/cm3 at 20C
Bp= +487 at 0 mm Water Solubility= <0.1 g/100 mL at 20 C
These data are totally different from the IPP data!
=================================
+ + + + + + + + + + + + + + + + + + + + + + + + + + + +
Interactive Physical Properties Database:
( http://esc.syrres.com/interkow/physdemo.htm (http://esc.syrres.com/interkow/physdemo.htm)
):
==================================
CAS Number : 001330-16-1
Chem Name : PINENE
Mol Formula: C22H32
Mol Weight : 296.50
Melting Pt : not given
Boiling Pt : not given
Water Solubility:
Value : 7.36 mg/L
Temp : 25 deg C
Type : EST
Ref : MEYLAN,WM ET AL. (1996)
==================================
CAS Number : 000099-83-2
Chem Name : alpha-PHELLANDRENE
Mol Formula: C10H16
Mol Weight : 136.24
Melting Pt : < +25 deg C (that's vague, we need a more precise value!)
Boiling Pt : 172 deg C
Water Solubility:
Value : 2.86 mg/L
Temp : 25 deg C
Type : ESTimated data
Ref : MEYLAN,WM ET AL. (1996)
==================================
CAS Number : 000464-49-3
Chem Name : (1R,4R)-(+)-CAMPHOR, d-CAMPHOR
Mol Formula: C10H16O
Mol Weight : 152.24
Melting Pt : +178.8 deg C
Boiling Pt : 207.4 deg C
Water Solubility:
Value : 100 mg/L
Temp : 25 deg C
Type : EXPerimental data
Ref : RIDDICK,JA ET AL. (1986)
===================================
CAS Number : 000094-59-7
Chem Name : SAFROLE
Mol Formula: C10H10O2
Mol Weight : 162.19
Melting Pt : +11.2 deg C
Boiling Pt : 234.5 deg C
Water Solubility:
Value : 121 mg/L
Temp : 25 deg C
Type : ESTimated data
Ref : MEYLAN,WM ET AL. (1996)
===================================
CAS Number : 000097-53-0
Chem Name : EUGENOL
Mol Formula: C10H12O2
Mol Weight : 164.21
Melting Pt : -7.5 deg C
Boiling Pt : 253.2 deg C
Water Solubility:
Value : 2460 mg/L
Temp : 25 deg C
Type : EXPerimental data
Ref : YALKOWSKY,SH & DANNENFELSER,RM (1992)
===================================
What do we learn by this? You can not TRUST BLINDLY any online data, check always the BOOKS! LT/
WISDOMwillWIN
As Strike already outlined in TSII, page 33, Brazilian Sassafras or Brown Camphor contains normally no Eugenol.
Thus a 3-5% NaOH solution wash before freezing the oil is redundant in most cases.
Let's look at what he had to say about purifying by freezing of Sassafras oil, page 34 :
It will be a little tricky, but one can also try to purify by freezing!
The sassafras oil is thrown into the freezer to chill. Safrole itself freezes at -14C, so anything that starts to freeze before that can be cold filtered in a prechilled vacuum setup. Thefiltrate goes back in the freezer until -14C is reached and the motherload of safrole freezes up. This again is filtered cold but this time the frozen mass of safrole crystals are washed with some icecold methanol or ethanol (preferably beeing -14C also), to wash away the unfrozen high-boiling constituents.
As you can see in the above posts, there are much better procedures described now, to purify by freezing.
= = = = =
LT/: Editted 08May2002.
Proceed with your now mainly pure 1-alkene (safrole) to a:
5% weight/weight (99%pure) KOH + Safrole overnight vacuum reflux:
Setup:
1.---Highly adviced: (when you have one!) an air cooled 20 or 40 cm vigreux column vertically set on your distillationflask,
2.---(flask placed in an aluminum oilbath, [filled with peanut oil or silicone oil and a STIRBAR], which stands on a stirrer/hotplate, flask for 3/4 or nearly totally submerged in the oil, just the neck free),
this will keep the refluxtemp of the MANY constantly condensing and falling back safrole/isosafrole drops much higher than by using just simply a watercooled condenser, thus avoiding a too fast cooling down of the main safrole/isosafrole/KOH body in your distillationflask at full vacuum reflux all those hours overnight and perhaps slow down the reflux rate and lower flask-temperature,
3.--- PLUS on top of that a vertical set watercooled-condenser setup,
(which will trap and forcefully cool all eventual vapours which eventually still escaped the vigreux column).
4.---On top of the condenser you place a vacuum adapter and vacuum tubing to your vacuum pump.
This gives conversion from 1-alkene (safrole) to 2-alkene (isosafrole), under full vacuum, OVERNIGHT, while first removing all traces of water which would wreck your isomerization results.
A.---To remove all water traces FIRST, you begin the procedure with a different simple setup, with the vacuum adapter connected directly to the distillation flask, put on the full vacuum for 30 minutes, while the hotplate is switched on for the first time. In that time the mix will not heat up very much, thus avoiding sucking off too much volatile oils, but the high vacuum will remove all water traces at that temperature.
After those 30 minutes you put the vigreux column + watercooled condenser back on the distillation flask, put the vacuum adapter back on top of the watercooled condenser, and switch the vacuum on again.
(Already in the first 15 minutes after switching on the vacuum pump and the stirrer/hotplate and adding a egg-shaped stirrbar to the contents of your distillation flask, before your safrole/KOH even reaches near its boiling point under your specific vacuum, depending on what pump you use, you will -perhaps, when traces of water are present- see some light boiling in your flask, that is the eventual water boiling and evaporating to your pump, after that time all that water will be gone into your pump; leave the GAS BALLAST of your pump full open!, in case of an oil-filled vacuumpump, this will allow the watertraces to be washed out of the pump by the air washed through the vacuum oil when that gasballast is full open. You should leave that one always fully screwed open, it will influence your maximum vacuum very minimal, no more than half a mbar, but will keep your vacuumoil as clean as possible).
B.---After those first 30 minutes, you replace the whole setup as in 1-2-3-4 above, and continue the heating and stirring under full vacuum again.
Then when your safrole + KOH starts steadily boiling and full refluxing back from the vigreux column, fix your temperature setting at that specific temperature scale point of your hotplate,
(I can't give a precise temperature, because it will differ for everyones specific vacuum obtained by different pumps and setups),
and leave it OVERNIGHT full refluxing. No need to crank up the heat further, don't do it.
C.---The next morning you switch off the vacuum temporarily, to insert a T-piece with thermometer sticked in, on top of the (ev., but highly adviced) vigreux column, attach your watercooled condenser now on the T-piece's sidearm under a ~30° downward angle, put a vacuum alonge on the other end of the condenser, and hang a receiving flask on the vacuum alonge, put the vacuumtube on the alonge outlet, switch the vacuumpump and mixer on again, and just increase the heating untill the vapours of your boiling --now 95-98% isosafrole/3-5% safrole mix-- reaches the top of the (ev.) vigreux and the sidearm of the still head (it still refluxes back partially, that's good, you now have the purests vapours at that temp reaching the top of your vigreux and still head side arm) and starts condensing in the condenser and drips in the receiving flask.
C2.---The first small portion coming over will be the 5 to 2% safrole+?impurities? -left after the isomerization process.
When at that temp setting and vacuum nothing more comes over, remove the receiving flask and discard this portion in a "Fore-run Safrole" labeled glass bottle for use in the next isomerization batch again! Check its DENSITY (and total weight of this fraction compared to the starting weight of your safrole!) and compare it to my density data in Post 294426 (https://www.thevespiary.org/talk/index.php?topic=9414.msg29442600#msg29442600)
(LaBTop: "Sassafras components data", Methods Discourse) in this thread.
Note this fore-run temp setting and density and total fraction weight in your labnotes (handy for your next batch).
C3.---Hang your receiving flask on the alonge again, switch the vacuum on again, and proceed to heat further untill you reach a new higher temp where as good as all fluid (isosafrole) at that temperature will come over. Inbetween you will have to check at intervals your (now) isosafrole vapour temperature in the still head (T-piece), if that goes up suddenly FAST more than 5-10°C, your done, all what comes next is not isosafrole and should be thrown away. Better don't use the leftovers from your distilling flask (KOH + Whatever carbonized shit?) in a next batch, just use then fresh KOH in your distilled and freezed-out safrole again!
Check the density of your obtained isosafrole against the density data in my Post 294426 (https://www.thevespiary.org/talk/index.php?topic=9414.msg29442600#msg29442600)
(LaBTop: "Sassafras components data", Methods Discourse) in this thread.
If not sufficient precise, repeat the whole procedure again, until you got it RIGHT.
A PURE isosafrole will give you the highests REAL KETONE yields in a performic, peracetic or other method, ALWAYS! LT/
WISDOMwillWIN
Post 294426 (https://www.thevespiary.org/talk/index.php?topic=9414.msg29442600#msg29442600)
(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
also of note, i previously posted about an isomerization attempt using crystalized safrole, Post 278285 (https://www.thevespiary.org/talk/index.php?topic=7071.msg27828500#msg27828500)
(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.
Here are a couple pics of slow grown safrole crystals,
that were obtained from an adulterated soultion of
non safrole components, from natural oil.
http://WWW.rhodium.ws/archive/picture108.jpg (http://WWW.rhodium.ws/archive/picture108.jpg)
http://WWW.rhodium.ws/archive/picture110.jpg (http://WWW.rhodium.ws/archive/picture110.jpg)
Those are rods are half inch thick and 3/4 inch long.
CG I miss you sweety, I really do.