Author Topic: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene  (Read 215 times)

headstrong

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Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« on: April 15, 2010, 06:42:20 AM »
Some difficulties to perform it, more to Eugenol that has an OH group at benzene  ring prone to dimmerization instead of polymerization cause of the double bond. It should be much easier for non phenol substances like 3-ethoxy-4methoxy allylbenzene, plain allylbenzene, or methylenedioxy....
The addition compound is phenylisopropyl hydrogen sulphate (and derivative), that is an acid, say this compound has been successfully isolated, then neutralized with ammonia --> phenylisopropyl ammonium sulphate, a salt.
I'm wondering what will happen if;
1. bring this phenylisopropyl ammonium sulphate at high temperature, is rearrangement will be occured? or
2. mix this salt with solution of ammonia in MeOH, and reflux.
Is it yielding a primary amine?
Any thought?
 
If primary amine is the yield, then worth to discuss this thread title, how to perform the H2SO4/H3PO4 addition  :)

Sedit

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Re: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« Reply #1 on: April 15, 2010, 01:32:26 PM »
H2SO4 is known for direct addition across the Pi bond but its also known to get out of hand cleaving the Ether of benzodioxyl with little effort. There are ways to test for Allyl and propylene benzenes using H2SO4 and looking for some sort of color change but I do not have any references on that right off hand. As far as how to effect the addition it should be nothing more then getting the allylbenzene cold as you possibly can and then slowly add the acid. If the temperature rises even a little two much I would expect a mess. I would also look into weather it adds Primarly Markovnikov or anti-Markovnikov to the Allylbenzene before proceeding. Water in this reaction will case many problems and must be keep out 100% which is more then likely, along with Ether cleavage and stability, the reasons why its not attempted more.

Markovnikov's Rule
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When a compound HX is added to an unsymmetrical alkene, the hydrogen becomes attached to the carbon with the most hydrogens attached to it already.
In this case its exactly what your looking for and will yeild the correct alkyl hydrogensulphate with some minor side product that could be neglected..

As for the formation of the phenylisopropyl ammonium sulphate I would have to think that addition of Ammonia in MeOH would yeild the amine hydrosulfate salt but this seems to conviniant and I'd have to get back to you on that.
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Wizard X

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Re: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« Reply #2 on: April 15, 2010, 11:32:14 PM »
Regioselectivity and the Markovnikov Rule. http://www.cem.msu.edu/~reusch/VirtualText/addene1.htm#add1bb

Look at...

Albert Einstein - "Great ideas often receive violent opposition from mediocre minds."

headstrong

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Re: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« Reply #3 on: April 16, 2010, 02:38:35 PM »
Thanks Sedit & Wizard,
I'm sure H2SO4 and H3PO4 addition are follow Markovnikov rule, same like HX addition. It stating in organic chem book. And yes i'm agree, temperature is maintenance at 0 c to avoid polymerizing and water is avoid since it makes the product hydrolyzed to alcohol.

Quote
As for the formation of the phenylisopropyl ammonium sulphate I would have to think that addition of Ammonia in MeOH would yeild the amine hydrosulfate salt but this seems to conviniant and I'd have to get back to you on that.
Addition 
What's "conviniant" mean, i can't find in some dictionary?
Addition of Ammonia or any other base will yield salt, positively, since this phenylisopropyl hydrogen sulphate is an acid, strong acid the pH may be about 1,7.


Sedit

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Re: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« Reply #4 on: April 16, 2010, 03:39:48 PM »
conĀ·venĀ·ient (kn-vnynt)
adj.
1. Suited or favorable to one's comfort, purpose, or needs: a convenient time to receive guests; a convenient excuse for not going.
2.
a. Easy to reach; accessible: a bank with branches at six convenient locations.
b. Close at hand; near: an apartment that is convenient to shopping and transportation.
3. Obsolete Fitting and proper; suitable.

LMAO sorry man im a scientist not an english major. I forget some such as yourself are not native to the English languages so I will do my best to spell works correctly but I assure you this is a struggle for me. When I was expelled from highschool the first time wen I was 16 they gave me an IQ test in various areas and I topped them all with my lowest scores being in things like history ect, but everything else I was scoring in the top 1 or 2% in the IQ test.... However when they wanted me to write an essay for the english portion of the test I scored in the 3d grade level  ;D. Yes I could have done better but they said it was my last test(out of 9 straight hours of the shit) and when I was done I could go home. But either way I hate writting and spelling so Iv never been good at it. I always just spell things as they sound and if anything I mistype confuses you feel free to ask and I will gladly clearify for you,
Sorry for the Inconvenience I may have caused you ;D <--- see I used its opposite in a sentance A++ for me :P


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Addition of Ammonia or any other base will yield salt, positively, since this phenylisopropyl hydrogen sulphate is an acid, strong acid the pH may be about 1,7.
Yes you are right it will form a salt just like when Alcoholic NH3 is added to Bromosafrole but the NH3 replaces the HBr on the double bound and forms an amine. The HBr now attacks the Amine yeilding the Hyrogen bromide salt of the amine. In the cases your discribing you would yeild the hydrogen sulfate salt of MDA. I would still stay away from H2SO4 for this reaction and use H3PO4 instead because Sulfuric acid always contains water and In this case I do not believe you will avoid forming the alcohol no matter how much you try to avoid it. As a side note there was discussion back at the hive a while back that I remember where people wher trying to form the Alcohol using H2SO4 The problem was no matter how hard people tryed they always got the OH on the #1 carbon and not the #2 carbon. I forget who it was but I will give credit where its due when I can locate the thread but someone there ran NMR and found that as soon as the Alcohol formed for some reason unknown to me, and them it appears, it would rearrange to the #1 Alcohol.
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headstrong

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Re: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« Reply #5 on: April 17, 2010, 06:59:03 AM »
Ah it's same with convenient, when i google "conviniant" many people use it so may be it's a native English language. No problem dude, i and any other can ask if find something like this, thanks.

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The HBr now attacks the Amine yeilding the Hyrogen bromide salt of the amine. In the cases your discribing you would yeild the hydrogen sulfate salt of MDA.
That's the point, what's exactly i asked, and from your answer it's theortically possible: alkyl hydrogen sulphate + ammonia in alcohol ----heat----> primary amine
I'll do my homework, thanks.

Quote
I would still stay away from H2SO4 for this reaction and use H3PO4 instead because Sulfuric acid always contains water
This also a hot topic in my mind: secondary alkyl halide + NH3 ----> primary amine, alkyl hydrogen phosphate may be comparable with alkyl chloride that is not reactive, and alkyl hydrogen sulphate with alkyl iodide.
I think the best way is; just dump and see what happen  lol.

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I do not believe you will avoid forming the alcohol no matter how much you try to avoid it.
Yes I'm agree, since it's impossible to make absolutely anhydrous reagents.

 
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As a side note there was discussion back at the hive a while back that I remember where people wher trying to form the Alcohol using H2SO4 The problem was no matter how hard people tryed they always got the OH on the #1 carbon and not the #2 carbon.
I think it's practically yielding about 80% product that's follow Markovnikov rule and 20 %the otherwise, so when hydrolysis is performed then 20 % OH on #1 carbon. But if it's really 100% anti markovnikov, the H at #2 carbon, and sulphate at #1 carbon, means trouble. Below a data from Hive about MDP2Pol by H2SO4 addition, stating that it's follow markovnikov rule, but this data is so old (1998-2000), may be what you mean is the newer.

SOMA

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Re: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« Reply #6 on: April 17, 2010, 11:35:46 AM »
AFAIK H2SO4 addition to the double bond follows markovnikov's rule 100% but after hydrolysis to the alcohol it rearranges by it self from the 2-propanol to the 1-propanol.

Wizard X

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Re: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« Reply #7 on: April 18, 2010, 12:46:44 AM »
AFAIK H2SO4 addition to the double bond follows markovnikov's rule 100% but after hydrolysis to the alcohol it rearranges by it self from the 2-propanol to the 1-propanol.

Read up on carbocation. When an unsymmetrically substituted double bond is protonated, we expect the more stable carbocation intermediate to be formed faster than the less stable alternative.

http://www.cem.msu.edu/~reusch/VirtualText/addene1.htm#add1bc

Example. The Ritter Reaction.

http://www.organic-chemistry.org/namedreactions/ritter-reaction.shtm
http://en.wikipedia.org/wiki/Ritter_reaction
http://www.erowid.org/archive/rhodium/chemistry/p2p.phenylpropenes.html



« Last Edit: April 18, 2010, 01:39:20 AM by Wizard X »
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headstrong

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Re: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« Reply #8 on: May 06, 2010, 09:14:32 AM »
So, what's the conclusion between Soma and Wizard post ??? ?

I have an interesting experiment to share, H3PO4 addition into alkene of Betel leaf oil. But i don't know what alkene it is, the supplier stating that it's an artificial oil and they know nothing else, never mind since they let me bought 20 ml. Betel leaf essential oil usually contains ~40 % Safrole and ~58% Eugenol. Here it went;
1. NaOH solution wash to remove Eugenol
2. collect the oil layer (~10ml), wash by dilute HCl solution
3. add 2 ml hexane into the oil that is in a 50 ml beaker glass, stir well. (dunno this step is really necessary or not)
4. drop wise addition of 100% H3PO4, 4 ml, by continuous stirring/swirling, occasionally i put this beaker glass into water bath to keep the temperature ~ room temperature. This time some oil is migrate into H3PO4 layer, finally they become 1 slurry layer, and the color is change to red. 100% H3PO4 can be easily prepared by heating 85% one at temperature above 139 c.
5. pour 12 ml hexane, stir/swirl well, then it was separated to two layer, discard hexane layer
6. add 20 ml water, stir well, some oil was separated, float on the surface, and the color is change to faint yellow. I got ~4 ml oil, i think it's an alcohol.




Sydenhams chorea

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Re: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« Reply #9 on: May 28, 2010, 06:28:50 PM »
Do you think the artificial betel leaf oil contains that much safrole? I know that the natural oil contains only around 6%.
see: http://www.thegoodscentscompany.com/gca/gc1068341.html

Quote
AFAIK H2SO4 addition to the double bond follows markovnikov's rule 100% but after hydrolysis to the alcohol it rearranges by it self from the 2-propanol to the 1-propanol.

The only source of that rearrangement was a purported analysis done by a Korean lab and paid for by Strike IIRC. This rearrangement was said to happen over hours at room temperature.

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I got ~4 ml oil, i think it's an alcohol.

Can this be confirmed in any way? eg. Jones oxidation or Lucas test?
It is perhaps the narcotic. Hyoscine affects certain people very oddly. One cannot be sure. Sometimes, these cases take strange forms. The victim becomes in a sense, 'mediumistic', a vehicle for all the intangible forces in operation around her.

headstrong

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Re: Sulfuric acid/Phosphoric acid addition into terminal double bond of allylbenzene
« Reply #10 on: June 02, 2010, 12:15:45 PM »
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Do you think the artificial betel leaf oil contains that much safrole? I know that the natural oil contains only around 6%.
Some sources stating about 40% Safrole, so it should be depend on the origin of the oil. Below is GC analysis of Betel leaf oil.

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The only source of that rearrangement was a purported analysis done by a Korean lab and paid for by Strike IIRC. This rearrangement was said to happen over hours at room temperature.
Thanks.

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Can this be confirmed in any way? eg. Jones oxidation or Lucas test?
I did oxidize it with ca(ClO)2-acetic acid system, after few first drops Ca(ClO)2-water solution it become exothermic, but no reaction at all after that, possibility that oil contains a little safrole. And the 4 ml oil is alcohol among many other impurities. I need oil that the ingredient is known for this experiment. I'll back to Eugenol.

« Last Edit: June 02, 2010, 12:24:11 PM by headstrong »