Author Topic: hey guys what about this? (Read 596 times)

jon · « **on:** November 13, 2009, 02:17:35 AM »

hi demethylation of eugenol simaltaneous additionn of hi to the doublbe bond.
then methylenation with ch2i2.
would the iodoalkane stand up to the base in the williamson ether synth?
i'll bet it would since it's run at room temp.
after methylenation the iodosafrole would react just as good as i said in the previious post.
what do you think???

Vesp · « **Reply #1 on:** November 13, 2009, 04:52:47 AM »

Improve your quality as a forum member, and your posts. Seriously, not even giving the proper symbols for the elements?

Spell better, be more understandable, etc...

If you don't respect the forum, don't expect the forum to respect you back.

...Vesp

heisenberg · « **Reply #2 on:** November 18, 2009, 12:50:07 PM »

Quote from: jon on November 13, 2009, 02:17:35 AM

hi demethylation of eugenol simaltaneous additionn of hi to the doublbe bond.
then methylenation with ch2i2.
would the iodoalkane stand up to the base in the williamson ether synth?
i'll bet it would since it's run at room temp.
after methylenation the iodosafrole would react just as good as i said in the previious post.
what do you think???

I would imagine that the first reaction would probably work. If there's any experimentation, please let us know how it goes, as well as the reaction conditions.

The ether synthesis might be more tricky. Too much base (or too hot) could hydrolyze off your iodine, and the ether synthesis itself could yield a polymer.

jon · « **Reply #3 on:** November 18, 2009, 01:45:19 PM »

that's why the use of potssium fluoride.
if stochiometric amounts of base are employed and allowed to react to form the phenolate it might be alright.
the rxn is done in a polar aprotic solvent (ether synth)
this might hinder e2 side rxns?
maybe no?
i'm just a dumb chemist help me out here.

heisenberg · « **Reply #4 on:** November 18, 2009, 05:12:46 PM »

A polar aprotic solvent would still allow E2 reactions.

jon · « **Reply #5 on:** November 19, 2009, 03:02:37 PM »

my bad, need to crak sum books u know what though i'm not hard up for safrole anyhoo.
xxxxxxxxxx looks a lot easier for the sassafras challanged.
heisenburg as in his uncertainty priciple?

or just heisenburg? excuse the grammar, punctuation, and capitalization omminsions.
sorry....

zzhuchila_clocker · « **Reply #6 on:** November 21, 2009, 08:22:15 PM »

Quote

that's why the use of potssium fluoride.
if stochiometric amounts of base are employed and allowed to react to form the phenolate it might be alright.

hey! not only e2 reaction can be problem, but sn2 as well. i mean, if F- as a base is strong enough to form a phenolate in equilibrium(needed for alkylation with CH2I2), this phenolate can be alkylated by iodopropane moiety as well(of another molecule). But due to sterical hindrance that would be not so favorable as e2 elimination.. As for fluoride, it is reputedly (can try to find a refference) used as a mild base for E2 eliminations. Not sure about that though, but i've probably seen one example with alkyl tosylate.

ps: Next time, try to attach pictures, diagrams, as for your idea - it is promising(just needed to find a good methylenation route - and not obligatory it should use CH2I2 rather then CH2Cl2). As for your level in organcs - don't worry - not a single dumb thing from you yet concerning mechanisms (strange, till you can't type a word without mistake, right?). Just be more comprehensive, attach diagrams, dont forget about courtesy and everything will be fine! (or, quit using that particular substance)

vajrakana · « **Reply #7 on:** December 03, 2009, 12:23:58 AM »

This idea has been around for a long time, and on the Hive was reported to yield less than good results. It was a WizardX process, and again, is NOT reported as working well. Here is the text:

Quote

Synthesis of IsoSafrole from eugenol

Look at RP_XF8.jpg

I will give you this procedure, however there are other synthetic methods which require chemical reagents difficult to obtain, or autoclave equipment.

Eugenol , M.W = 164.20 gr/mol; density @ 20 degC = 1.067 gr/cm3

Procedure

Obtain pure eugenol from clove oil which has a boiling point of 255 degC at 760mmHg. With vacuum distillation the boiling point is 123 degC at 12-13mmHg, and 110-111 degC at 5mmHg.

In a 500ml round bottom flask, cool in ice to 0-2 degC, 100mls of 57% HI SOLUTION (HYDRIODIC ACID, M.W = 127.93) = 99 grams of HI = 0.774 moles of HI. (B.p 125.5-126.5 deg C/760mm Hg ; Density 1.70 gr/ml ; 55-57% w/w HI is 0.936 to 0.99 grams of HI per ml).

Add 32.8 grams, ~ 35.0 mls (0.2 moles) of Eugenol to the 100mls of 57% HI, while the flask is still in the ice. Swirl gently, stopper, place back in the ice and insulate the container holding the ice and place in the fridge compartment for a period of 12 hours. Every 2 hours swirl gently again.

After the 12 hours period, add 1.0 grams of hydroquinone (a polyerisation inhibitor) [NOTE1] and swirl, stopper, remove from the ice to allow it to obtain room tempeture. Attach a long reflux condenser and reflux for 2 1/2 hours between 120-130degC, perfect tempature is 128 degC. After refluxing for the time period allow to cool to room tempature. Dilute with 1 liter of ice cold distilled water and solvent extract with 3 X 100mls of diethyl ether or petroleum ether and wash once with minimum distilled water 50 mls. Distill the solvent off and the methyl iodide, CH3I, Bp 42.4 degC. [NOTE2] Crystals will form, however some oily residue may or will persist.

In a 1 liter round bottom, reflux reaction flask, add the following.
A volume of 300 mls of ethanol is added to the crystal residue of 3,4-dihydroxy-1-propenylbenzene, 3,4(HO-)C6H3-CH=CH-CH3 and the 3,4-dihydroxy-1-(1-iodo)phenylpropane, 3,4-dihydroxy-1-(1-iodo)phenylpropane, 3,4(HO-)C6H3-CHI-CH2-CH3 and hydroquinone.
Another 1.0 grams of hydroquinone is added and mixed together. [NOTE1] A solution of 22.44 grams (0.4 moles)of potassium hydroxide, KOH, in 200 mls of 50/50 distilled water/ethanol is made. The potassium hydroxide solution is then added with stirring to the above 3,4-dihydroxy-1-propenylbenzene, 3,4(HO-)C6H3-CHI-CH2-CH3 residue-ethanol solution. The combined mixture is then gently refluxed with stirring on a hot water bath or steam bath for 1 hour. [NOTE3]

Add a solution of 53.58 grams (0.2 moles) of diiodmethane, ICH2I (M.W = 267.9 gr/mol), in 150 mls of ethanol and continue refluxing for 2 hours. [NOTE4] Strip all ethanol solvent under vacuum distillation, and add 400 mls of distilled water. Solvent extract with ether 2 X 100 mls. Keep the water layer as it contains unreacted 3,4-dipotassiumoxy-1-propenylbenzene, 3,4(KO-)C6H3-CH=CH-CH3. [NOTE5]
The ether/isosafrole solution mixture is washed once with distilled water, and under careful vacuum distillation the isosafrole is distilled at 179.5 degC at 100 mmHg or 135.6 degC at 20 mmHg.
[NOTE6]

Page 1

[NOTE1] hydroquinone oxidizes in air and in solutions exposed to air rapidly.
Keep the flask well closed and protected from light.

[NOTE2] the solution contains a mixture of methyl iodide, CH3I ; 3,4-dihydroxy-1-propenylbenzene, 3,4(HO-)C6H3-CH=CH-CH3 and the 3,4-didydroxy-1-(1-iodo)phenylpropane, 3,4(HO-)C6H3-CHI-CH2-CH3 and hydroquinone.

[NOTE3] at this stage the 3,4-dihydroxy-1-(1-iodo)phenylpropane,
3,4(HO-)C6H3-CHI-CH2-CH3 will be converted to 3,4-dihydroxy-1-propenylbenzene,
3,4(HO-)C6H3-CH=CH-CH3 and 3,4-dipotassiumoxy-1-propenylbenzene, 3,4(KO-)C6H3-CH=CH-CH3.

[NOTE4] methanol can be used in all cases, instead of ethanol. At this stage the main product is isosafrole. Dibromomethane, BrCH3Br can also be used.

[NOTE5] add dilute HCL untill slightly acidic and solvent extract to obtain the 3,4-dihydroxy-1-propenylbenzene, 3,4(HO-)C6H3-CH=CH-Ch3.

[NOTE6] propenylbenzene, C6H5-CH=CH-CH3, are susceptible to polyerisation, influenced by acids. Both isosafrole and safrole can be steam distilled.

TESTS

3,4-dihydroxy-1-propenylbenzene; 3,4(HO-)C6H3-CH=CH-CH3, in an alcoholic solution develops a deep green-blue colour on treatment with 2% alcoholic ferric chloride solution.

Eugenol : In a cold saturated aqueous solution of ferric chloride, gives a turbid grayish-yellow colour. With 2% alcoholic ferric chloride solution, a blue colour, which fades to grey-yellow colour in 15 minutes. An intense purple-black colour develops when reacted with 48% hydrobromic acid at 2 degC.

Safrole and Isosafrole : an intense red to scarlet red colour develops when dissolved in concentrated sulphuric acid.

page 2
< finishes here

I hope thats all it, I have spelt everything the same & tried to get the layout the same too.

I notice Colour is spelt 'colour', which is how we English/kiwis spell it.
Not like the 'color' the Americans use

Other than figuring out the Hydrogen sulphide gas its all pretty easy.
And its been said to work too!

quetzalcoatl · « **Reply #8 on:** December 06, 2009, 04:34:00 AM »

hey vajrakana, or anyone else -
do you think that eugenol could be dental eugenol,
which contains traces of zinc oxide?

jon · « **Reply #9 on:** December 06, 2009, 04:56:40 AM »

no way around that base catylized e2 then?

MRS · « **Reply #10 on:** January 06, 2010, 02:25:44 PM »

Would the methylenation also proceed with 3,4-dihydroxyphenyl-2-propanone as substrate, or would the basic conditions give rise to excessive condensations? Phenolic OH's are more acidic (10 magnitudes larger) but I'm wondering if the phenoxylate would attach the carbonyl as well as the dihalomethane.

SOMA · « **Reply #11 on:** January 06, 2010, 05:01:49 PM »

Demethylation of eugenol — Eugenol was demethylated by the following methods:
(i) Eugenol (10 ml.) petroleum ether (bp 100-20°C; 100 ml.) and aluminium chloride (15 g.) were refluxed for 3 hr and the reaction product worked up as usual. A colourless solid (mp 104-5°C) and a liquid (bp 108-15°C/0.3 mm.); n27.5D1.5300) were obtained.

What about this?

Edit: The source: http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/allylcatechol.html sorry if there was any misinterpretation I havent tried this.

java · « **Reply #12 on:** January 06, 2010, 05:17:02 PM »

SOMA that quote comes from.....

Synthesis of 4-Allylcatechol &
Mechanism of Claisen Rearrangement in Catechols
Sethi Rao & Subba Rao
Ind. J. Chem. 2, 323 (1964)

......http://www.erowid.org/archive/rhodium/chemistry/allylcatechol.html

......it would be proper to give the source of the material you post ....as otherwise it would sound like it's something you came up with ...........java

SOMA · « **Reply #13 on:** January 06, 2010, 08:10:45 PM »

Quote from: SOMA on January 06, 2010, 05:01:49 PM

Demethylation of eugenol — Eugenol was demethylated by the following methods:
(i) Eugenol (10 ml.) petroleum ether (bp 100-20°C; 100 ml.) and aluminium chloride (15 g.) were refluxed for 3 hr and the reaction product worked up as usual. A colourless solid (mp 104-5°C) and a liquid (bp 108-15°C/0.3 mm.); n27.5D1.5300) were obtained.

What about this?

Edit: The source: http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/allylcatechol.html sorry if there was any misinterpretation I havent tried this.

Answering myself:

- The colourless solid they obtain has a melting point 50ºC over the melting point of allyl catechol, so it might be contaminated allyl catechol with some unknown crap that makes the MP so high, or it's just pure crap it all.

- The liquid can't be allyl catechol, I think unless the reported vacuum pressure is wrong, because it's theoretical boiling point at atmosferic pressure is much higher than the theoretical boiling point of allyl catechol.

Might work for the demethylation of vanillin or VMK and it's easy to try, with anhydrous AlCl3 from a chemical supply house, vanillin and pet ether (properly dried zippo lighter fluid naphta might substitute) once you've got your suspected di-hydroxy benzaldehyde, it should be fairly water soluble and unsoluble in dichloromethane for example (Vanillin is unsoluble in water and soluble in DCM)

shroomedalice · « **Reply #14 on:** January 07, 2010, 01:23:00 AM »

It is the demthylation that is going to give you hell. as you have a phenyl group next to a methoxy group you are
going to find that you need to use something a little more tailored to the reaction.

this has been looked at so many times with very little joy.

nitrobenzene and AlI is a good one

pyridine HCl

AlCl and pyridine

there are a few others that I can think of but can not realy remeber there iupac names properly.

you will find the same problem with vanillia as eugenol just not to the same degree.

jon · « **Reply #15 on:** January 07, 2010, 03:47:10 AM »

there are sordid tales of many a chemist who have tried to master this on psychonaut i'm not so sure what is happeneing but the demethylation is the achilles heel i can't recall why that catechol is so unstable under some of the proscribed demethylation conditions just know it's a real bitch.

MRS · « **Reply #16 on:** January 07, 2010, 08:07:46 AM »

Maybe I'm missing something, but my question was about the methylenation of the 3,4-dihydroxy group to 3,4-methylenedioxy. I have read Sciencemadness on that matter and http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/methylenation.html with the references but nowhere is spoken of the viability of the methylenation of 3,4-dihydroxyphenyl-2-propanone.

jon · « **Reply #17 on:** January 07, 2010, 09:09:11 AM »

from what i glean KF is a good base diiodomethane gives reproducable results and the addition of the catechol to the diiodide in dmso or whatever has to be done at a rate to avoid the formation of dimers.
an there are other problems like phenolates being prone to polymerizations and unstable.
ie. the whole idea looks easy on paper but in practice it's a bitch but i'm not going to discourage you.

MRS · « **Reply #18 on:** January 07, 2010, 09:42:40 AM »

The trick is to employ a high temperature (either to employ a high boiling solvent, e.g. DMSO/DMF/ethylene glycol, or a pressurized water/dihalomethane system) and low concentrations of substrate. The DMF/KF/CH2Br2 method employed here http://www.erowid.org/archive/rhodium/chemistry/methylenation-kf-ch2x2.html gives a 90% yield of piperonal. The benzaldehyde proton is more acidic then the phenyl-2-propanone protons, so I see no reason why it shouldn't work with 3,4-dihydroxyphenyl-2-propanone. Now just to decide on the most viable methylenation method..

jon · « **Reply #19 on:** January 07, 2010, 05:39:14 PM »

kind of figured KF is the optimal base read a lot about it that was one of the main sticking points

Author Topic: hey guys what about this? (Read 596 times)

jon

hey guys what about this?

Vesp

Re: hey guys what about this?

heisenberg

Re: hey guys what about this?

jon

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heisenberg

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jon

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zzhuchila_clocker

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vajrakana

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quetzalcoatl

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jon

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MRS

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SOMA

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java

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SOMA

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shroomedalice

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jon

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MRS

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jon

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MRS

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jon

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