Ment2bee (Stranger)
09-16-02 02:38
No 356721
      Sassafras  Bookmark   

Ment2bee was wondering how does safrole form in nature? I know it probably starts off in the tree somewhere as L-tyrosine but from there.....? ethier to L-DOPA or to 4-hydroxycinnamic acid and then to?

[green]

Addon Here....

I have some reason to believe that in nature safrole might be derived directly from eugenol and oxygen, or coniferyl alcohol and oxygen plus some more steps. If this methode is known then the possibilty exists that the sole chemists can go from a 3-methoxy-4-hydroxyphenyl compound to a 3,4-methylenedioxyphenyl compund in one step, instead of two.
 
 
 
 
    Ment2bee
(Stranger)
09-30-02 01:18
No 362101
      Possible step in nature?  Bookmark   

No not familiar, SWIM2Bs intrest lies in applying enzyme mimics to recreate the natural steps. SWIM2B thinks if an electron is withdrawn from the 4-hydroxy in eugenol, say with a copper(II) ion it would create a ring stable radical which might eventually extract a hydrogen from the 3-methoxy group. More likly it would be in equilibrium, but eventually another electron could be withdrawn, this time from the newly created *CH2O- group creating +CH2O- which would in turn bind with the 4-hydroxy givining the 3,4-methylenedioxy group with a proton.

For that same great taste that'll always wire you up and never let you down, make it a dexedrine.
 
 
 
 
    Ment2bee
(Stranger)
10-01-02 17:32
No 362759
      Ezymes are capable of tasks that do not ordinarly ...  Bookmark   

Ezymes are capable of tasks that do not ordinarly happen in the chem lab, like oxidation of aromatics to phenols using O2 or some derivative of O2, deamination of L-phenylalanine acid, ect. It's things like this that lead to me wonderin's about the possible oxidation of eugenol to safrole. I bet it's thermodynamicaly fiesable, O2 oxidations usually are, but is it kineticaly (i.e. with the right enzyme and/or catalyst)?

Anyway I've only had a brief intro to biochemistry through the net, and from my current understanding which is probably wrong, but all aromatics in biology are derived from L-phenylalanine, L-Tyrosine and L-Tryptophan which in turn are derived from shikimic acid.

If this is true, then the way to safrole starts with L-tyrosine. However a quick search using google yields...

http://www.strath.ac.uk/Departments/Chemistry/courseinfo/4thyear/13941.html

"Sigmatropic rearrangement of chorismate to phenylpropanoids."

So I guess that assumption is wrong, but I did find something which kinda of runs parallel to answering my own question. It points at the possible path way to eugenol from coniferyl alcohol or ferulate.

http://www.hort.purdue.edu/rhodcv/hort640c/secprod/se00017.htm

But this is raising more questions for me now, like safrole from caffeic acid?

Second of all, carbon dioxide plus a catechol while biofriendly seems like it would need a ton of pressure and heat, which might lead instead 2-hydroxysalicylic acid derivatives. But getting that ester in mind can be done with phosgene, however reducing esters in general leads to an alcohol and aldehyde. The case with the *catechol carbonic ester*,*benzylene carbonate*? might be different. I still think that reductions would lead to clevage though. Perhaps CS2 could be used instead and a reduction of the resulting (-OC(=S)O-) could be attempted, I don't know.

Wait carbon monoxide, wouldn't that lead to the formate ester? I don't see how the reduction of a catechol formate leads to a methylenedioxybenzene. Reasons?

For that same great taste that'll always wire you up and never let you down, make it a dexedrine.
 
 
 
 
    Ment2bee
(Newbee)
10-11-02 23:36
No 367432
      So much for optimism  Bookmark   

Looks like I'll have to enhance my knowledge in biochemistry before I go on. But it is intresting that no one seems to know about how safrole or eugenol for that matter is created in nature. Probably cause it doesn't have much use outside of recreational pharmacology wink. Anyway I'll continue to look for a miracle enzyme. In the mean time though perhaps there is away to increase the concentrations of safrole in a plant like basil, for example the use of herbovorial insects which are intolerant of safrole to selectivly eliminate basil plants which do not produce enough safrole and rear the suriving plants. Hopefully after enough generations pass, useful concentrations of safrole would prevail. Or a more farfetch but maybe easier in application after invesment would be the genetic engineering of baker yeasts or E. coli to produce safrole. But this is my CO2 methylenation of a catechol speculation, if you will.

For that same great taste that'll always wire you up and never let you down, make it a dexedrine.
 
 
 
 
    Ment2bee
(Newbee)
10-25-02 22:58
No 372662
      One Step Safrole (From Eugenol) After All?  Bookmark   

I finally managed to find a webpage demonstrating the ring formation of a methylenedioxy bridge by mother nature herself, bless her!!

http://www.chem.qmul.ac.uk/iubmb/enzyme/reaction/alkaloid/stylopine.html

Now the question is if this way of forming the methylenedioxy bridge is used by the sassafras tree where does this bridge get formed a long the precursor chain? at the very end as in eugenol?laugh one step before the very end as in coniferyl alcohol?smile or even before this,crazy or from isomers of eugenol or coniferyl alcohol, such as 4-methoxy-3-hydroxyallybenzene, and 4-methoxy-3-hydroxycinnamyl alcohol.frown

If safrole did get formed from eugenol this would be great since that means there lies away to oxidize eugenol to safrole without ending up with designer roofing glue. If not vanillic acid and dihydroeugenol could be used for an experiment in ring closer, but it would be more work to get to the final ketone than what it's worth.

As for forced mutations they seem like they would mean work, but would using forced mutation give rise to super safrole producing plants faster than the old growing plants with low safrole concentrations then sniffing out the top ten precent which produce the most, then breeding these only and then repeating? The best thing that could come about all this is a super safrole plant which ends up being a noxious weed taking over continents.laugh

For that same great taste that'll always wire you up and never let you down, make it a dexedrine.
 
 
 
 
    Precursor2112
(Hive Bee)
10-27-02 15:19
No 373217
      A Noxious Weed Indeed!  Bookmark   

The answer..as it did for marijuana 30 years ago...would be breeding.

And Super Breeding.


"Small Minds Have Big Mouths."
 
 
 
 
    GC_MS
(Hive Bee)
11-03-02 13:32
No 376001
      eugenol  Bookmark   

Eugenol is present in sassafras oil.

Ave Hive, synthetisandi te salutant!
 
 
 
 
    Osmium
(Stoni's sexual toy)
11-03-02 17:53
No 376048
      > Eugenol is present in sassafras oil.  Bookmark   

> Eugenol is present in sassafras oil.

I've personally injected several different oils into GC and wasn't able to detect any eugenol.

I'm not fat just horizontally disproportionate.
 
 
 
 
    PolytheneSam
(Master Searcher)
11-03-02 18:50
No 376070
      Post 70974 Post 71023 Post 71162  Bookmark   

Post 70974 (Osmium: "Re: bromosafrole", Novel Discourse) Post 71023 (PolytheneSam: "Re: bromosafrole", Novel Discourse) Post 71162 (Osmium: "Re: bromosafrole", Novel Discourse)

I think the sassafras oil in the Merck Index is from Sassafras albidum.  See also ../rhodium/chemistry /safrolefaq.html

http://www.geocities.com/dritte123/PSPF.html
The hardest thing to explain is the obvious
 
 
 
 
    GC_MS
(Hive Bee)
11-03-02 19:22
No 376087
      sassafras  Bookmark   

I've personally injected several different oils into GC and wasn't able to detect any eugenol

So did I smile. It is present in some sassafras oils in low ppms. Seperate the oil via column chromatography and collect an oil sample in several fractions, e.g. pentane, pentane/ether and ether fractions. Inject all three fractions on your GC and make sure to use splitt injection. I can't remember in which of the three fractions I found some eugenol traces, I'll try to dig up the GC results in one of my maps.

Ave Hive, synthetisandi te salutant!
 
 
 
 
    Aurelius
(Hive Bee)
11-05-02 18:22
No 376739
      GC  Bookmark   

Osmium, what kind of GC do you have available? (what did you use that is)
 
 
 
 
    GC_MS
(Hive Bee)
11-05-02 19:01
No 376754
      oops  Bookmark   

Didn't write down what fraction I found the eugenol in. I used a split ratio of 60; run took 90 minutes (with temperature programming, though I don't have the exact details anymore).

Ave Hive, synthetisandi te salutant!
 
 
 
 
    GC_MS
(Hive Bee)
11-07-02 22:20
No 377383
      eugenol  Bookmark   

F T Noggle Jr, C R Clark, J DeRuiter
Gas chromatographic and mass spectrometric analysis of N-methyl-1-aryl-2-propanamines synthesized from the substituted allylbenzenes present in sassafras oil
J Chromatogr Sci 29 (1991)267-271

...In addition to safrole, sassafras oil contains other allylbenzenes such as eugenol and 4-allyl-1,2-dimethoxybenzene.

Ave Hive, synthetisandi te salutant!
 
 
 
 
    Osmium
(Stoni's sexual toy)
11-07-02 22:45
No 377389
      > Osmium, what kind of GC do you have ...  Bookmark   

> Osmium, what kind of GC do you have available?

Don't remember the model etc, all I do remember is that it had a 30m long capillary column.

> ...In addition to safrole, sassafras oil contains other
> allylbenzenes such as eugenol and 4-allyl-1,2-dimethoxybenzene.

Well, maybe theirs did. Those that I tested did not. Not even traces.


I'm not fat just horizontally disproportionate.
 
 
 
 
    Rhodium
(Chief Bee)
11-08-02 00:03
No 377404
      J Chrom Sci  Bookmark   

GC_MS: The above paper references J. Chrom. Sci. 29, 168-173 (1991) for a more in-detail discussion of the presence of eugenol in sassafras oil. Do you think you get that article for us?
 
 
 
 
    Jackhammer
(Hive Bee)
11-08-02 02:05
No 377473
      split?  Bookmark   

I would go for splitless injection, or even better a PTV or some other large volume injection system....

Manīs main task in life is to give birth to himself.
 
 
 
 
    Jackhammer
(Hive Bee)
11-08-02 02:14
No 377477
      Old article  Bookmark   

I have one article dealing with GC techniques for the analysis of essential oils. It is a recent review that appeared in J. Chrom. A, 936(2001)1-22 They give a lot of examples, unfortunately nothing about sassafras

Manīs main task in life is to give birth to himself.
 
 
 
 
    GC_MS
(Hive Bee)
11-08-02 08:05
No 377590
      GC  Bookmark   

Osmium: it might depend on what is defined as 'sassafras oil'. The genuine oil is derived from the Sassafras tree, but there are other plants that deliver essential oils with a high safrole content as well. These oils are referred to as sassafras oil as well. Don't think I have to explain you the details (you'll know them yourself), but one plant might give you essential oils with eugenol traces while the other does not. I also have an mdma impurity article somewhere (can't find it right now) where the most important impurities to prove the use of the bromination route (a la Merck) are the brominated analogues of eugenol and alikes.
Rh: I'll try asap
Jackhammer: I won't use splitless injection for essential oils, unless I like to clean my quad every day, unless I want my boss to buy me new fillaments every month, and unless I like peaks eluting for 10 minutes.

EDiT - ... and I usually use capillary columns, no packed ones. Packed columns are close to extinction wink.

Ave Hive, synthetisandi te salutant!
 
 
 
 
    Osmium
(Stoni's sexual toy)
11-08-02 09:46
No 377612
      > Don't think I have to explain you the ...  Bookmark   

> Don't think I have to explain you the details (you'll know them yourself),

Yes I know. Just found it strange that I didn't find any in several different oils.
One of the oils I had, the cheap and shitty smelling one, had the highest safrol content (95% or so). It was obvious that this was some sort of brown camphor, since there was almost nothing with a lower boiling point than safrole present, while the other oils had several lower boiling components.

I'm not fat just horizontally disproportionate.