Author Topic: 1st experience w/ Hydratropic Aldehyde -> P2P  (Read 13533 times)

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xspikehead

  • Guest
1st experience w/ Hydratropic Aldehyde -> P2P
« on: August 28, 2003, 09:16:00 PM »
Swix added 90ml hydratropic aldehyde dropwise over a period of 1 hr to 400ml sulfuric acid chilled to -10-13 C with constant stirring.  Solution quickly turned dark brown when first drops of aldedhyde were added.  After 90ml aldehyde was added, solution was left another 15 min (putting the total time at 75 min). Poured onto 5lbs cracked ice, let resolve to room temp, extracted w/ 300ml toluene, washed organic phase w/ water.  Then performed atmospheric distillation of the toluene - collected 300ml of it.  Was left w/ a thick dark-golden color product in the reaction flask - about 40-50ml worth.  This I THINK is P2P, but it is rather THICK and somewhat DARK... it smells like SOMETHING - kinda aromatic, a little potent... tried performing the sodium bisulfite test but to no avail due to the thickness of the ketone.

Swix understands that this is not the most popular route to P2P, but if anyone had anything to advise - to confirm if this is or isn't P2P, or what to do differently for the future, swix would greatly appreciate it.

xspikehead

  • Guest
SwiX would greatly appreciate a response to...
« Reply #1 on: August 29, 2003, 03:30:00 PM »
SwiX would greatly appreciate a response to this synth SwiX attempted twice, because SwiX fears P2P is not his finished product... but he is hopeful!

90ml hydratropic aldehyde added dropwise to 400ml sulfuric acid for 60 minutes, let react another 15 more minutes.  Stirring was used throughout, temperature was maintained around -16 C.  Poured onto 5lbs cracked ice.  Molten ice was treated w/ 300ml toluene to pull P2P into the toluene.  Washed tol/P2P once w/ water and once w/ dilute sodium bicarbonate solution (to remove sulfuric acid).  Poured mixture into reaction flask, distilled off the 300ml toluene originally added, and SwiX is assuming the 40-50ml residue in the flask (thick oily liquid, golden color) is P2P.

Only problem is, SwiX has heard that P2P is a clear to pale-yellow liquid.... this is MUCH more an oil than it is a liquid.  And secondly, why, when SwiX reads writeups on this process, is the P2P distilled over?  If all SwiX pours in the reaction flask in the first place is the tol/P2P, isn't there just P2P left once SwiX distills off the toluene?  SwiX believes this, especially since he washed the tol/P2P phase w/ water followed by a dilute sodium bicarbonate solution.

A response would be most appreciated.

terbium

  • Guest
Vacuum distill
« Reply #2 on: August 29, 2003, 05:14:00 PM »
If this reaction works, I would expect it likely to give you also a lot of polymerized junk along with the P2P. Your best hope will be to vacuum distill after stripping the toluene from the bicarb washed extract.


java

  • Guest
RE: Hydrotropic Aldehyde....
« Reply #3 on: August 29, 2003, 05:28:00 PM »
Did you happen to read this.......java

https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html



Exerpt
........It is not possible to effectively separate 2-phenylpropanal (bp 222°C/760mmHg) from phenyl-2-propanone (bp 214°C/760mmHg) through simple distillation and certainly not via vacuum distillation as the boiling points are too close. Fractional distillation could theoretically be used to separate them, but the size of the column that would have to be used makes that option impractical. A good idea for separating a mixture of the two is to oxidize the mixture with a mild oxidant which won't affect the P2P, but which will oxidize the aldehyde to 2-phenylpropionic acid. The acid can then be separated from the ketone by dissolving the mixture in a non-polar solvent and washing the solution with dilute sodium hydroxide. The P2P stays in the organic layer, which is then dried over MgSO4, the solvent removed under vacuum and the residue vacuum distilled to give pure P2P.

Also,....


Post 446496 (missing)

(Rhodium: "Phenyl-2-propanal to P2P", Russian HyperLab)


Post 446720 (missing)

(Timmy: "So it is...", Russian HyperLab)


Post 446886 (missing)

(Rhodium: "Thanks for the translation", Russian HyperLab)


there is also much more that can be found on the search engine so dig, dig, and you will find your answers.......java


xspikehead

  • Guest
Did just that, can't tell the difference...
« Reply #4 on: August 29, 2003, 05:33:00 PM »
A vacuum distillation made it into a golden liquid upon entering the receiving flask, only to thicken up to an oily-consistency soon thereafter.  This synthesis has been mentioned a few times on this site, on Rhodium's, and in Uncle Fester's new book, so it MUST work to some degree.  But it makes me wonder why this isn't a more popular route to synthesizing P2P.  Hydratropic aldehyde is easy to obtain from the U.S. suppliers, so that makes me wonder a bit.

java

  • Guest
RE: Hydrotropic Aldehyde....
« Reply #5 on: August 29, 2003, 07:21:00 PM »
Well it works as you know , but then let's just fine tune it and not worry about why more bee's don't go this route.......we don't want it to go the way of ephedrine in it's prohibition.  So get your methylamine and finish it up and do a write up so other bee's can keep refining the technique....java


java

  • Guest
RE: 1st experience w/ Hydratropic ...
« Reply #6 on: August 30, 2003, 10:04:00 AM »
As stated in the rhodium article , fractional distillation will not work because of the proximity of both temp of products hence it is recommended  .........anyway read the post's included.....also stuff about the creamy stuff you got in Jan's thread.....java

Post 319753 (missing)

(Jan1983: "Succsess story: 85ml H2SO4 96% 18ml Hydratropic ...", Stimulants)


Post 409033 (missing)

(Rhodium: "Separating 2-phenylpropanal and phenyl-2-propanone", Stimulants)


Post 409076 (missing)

(Rhodium: "Read up some more first, you are confusing a...", Stimulants)


Post 319331 (missing)

(Jan1983: "P2P from 2-Phenylpropanal > 2-PHENYLPROPANAL ...", Stimulants)


Edit: try to post the references you've found in support of your method......all the stuff I've  mentioned could have been found in the hive  search  option....try.... 2-phenyl  propanal, Hydrotropic aldehyde, 2-phenylpropanal


java

  • Guest
RE: Hydratropic aldehyde.;.....
« Reply #7 on: December 12, 2003, 02:47:00 PM »
Here is some stuff Lugh posted on the synthesis of 2-phenylpropanal (hydratropic aldehyde)......

Post 427944 (missing)

(lugh: "Hydratropaldehyde", Stimulants)


and more recently azole worked hard to provide the article were P2P is converted from 2-phenlpropanal under reflux with dilute H2SO4 in good yields....

Post 476441 (missing)

(azole: "as requested by java", Russian HyperLab)


just updating the info on this process for all the bee's interested ........java

Note..there is a reference that would be appreciated ......

Preparation of 2-phenylpropanal by catalytic addition of Hydrogen and Carbon Monoxide
Adkins and Krack
JACS 70 383 (1948)


Rhodium

  • Guest
Catalytic Hydratropic Aldehyde
« Reply #8 on: December 12, 2003, 03:20:00 PM »
Preparation of Aldehydes from Alkenes by the Addition of Carbon Monoxide and Hydrogen with Cobalt Carbonyls as Intermediates
Homer Adkins, George Krsek

J. Am. Chem. Soc. 70, 383-386 (1948)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/p2pal.pdf)


roger2003

  • Guest
Hydratropaldehyde
« Reply #9 on: December 13, 2003, 08:48:00 AM »
The JACS procedure was not successfull (yield and poisen pp) an there was found a better way:

Patent GB1255537



Abstract:

Phenylpropanals. RUHRCHE- MIE A.G: 27 June, 1969 [24 July, 1968], No. 30083/69. Heading C2C. Phenylpropanals are obtained by hydro- formylating styrene with CO and H 2 at 80- 200 C. and 50-500 atmospheres pressure in the presence of a rhodium catalyst containing 0À05-0À000125% by weight of rhodium based on the styrene. The phenylpropanals can be hydrogenated to phenylpropanols, either with CO and H 2 without the separation of the rho- dium catalyst or the addition of another catalyst, or in the presence of a copper chromite catalyst.

See also german patents:

Patent DE1793017


Patent DE1939322




roger2003

  • Guest
Isomerisation, Polymerisation
« Reply #10 on: December 14, 2003, 03:23:00 AM »
In Ber 60, 1050 (1927)the converting-procedure from a-Phenylpropanal to P2P is discussed.

The yield is 62% of isomerisation-product (with H2SO4 at -16°) and the rest is a polymerisation product.

The combined products (7,2 g from 9 g a-Phenylpropanal) are distilled at 11 mm (Hg):

91-92° =  1   g
92-94° =  2   g
94-96° =  2,6 g

and there was a (polymerisation) residue from 1,6 g


java

  • Guest
Re: 2-phenylpropanal conversion to P2P
« Reply #11 on: December 14, 2003, 03:57:00 PM »
Well so far it's been proven that the conversion works both in the literature , In Ber 60, 1050 (1927, and the article provided by azole...and in the most recent past , actual hands on experiments posted by Jan1983 not only provided his results as well as a now missing post Post 331698 (not existing) ...."largescale P2P" in which he describes and gives his result on a large scale run. As  far as the synthesis the stating material , 2-phenylpropanal , all the procedures seem a bit difficult and involve some nasty chemicals.

The reflux method ,as noted in the article Azole provided, it seems the process with dilute H2SO4 works with better yields and avoids the large amount of acid and low temp. However the finish product still needs to be oxidised to remove the unprocessed 2-phenylpropanal  and washed with a dil. NaOH solution, hence the end solution will be w/o and removed with Toluene to get cleaned P2P.

I think there is a way to re arrange styrene in the presence solvent X such that 2-phenylpropanal is  the result product......ofcourse this is just a suspicion based on no facts , maybe wishful thinking .If that was the case we would have a very easy OTC method to P2P .. so the search continues......java

Edited Just as I posted this Roger2003 posted this.....

Post 476771

(roger2003: "Hydratropaldehyde", Chemistry Discourse)


so it seems that the process Xis starting to show it's face ....got to go read it now...java


roger2003

  • Guest
Hydratropaldehyde
« Reply #12 on: December 15, 2003, 03:17:00 AM »
The from Azole provided article has the same authors like Ber. 60, 1050 (1927) - Danilov - Danilova

In Ber. 60, 1050 is also described a process with HgCl2 and higher yields (80%), but they have a mixture of P2P and a-phenylpropanal.

The oxo-process, starting from styrene, needs CO and H2 with a catalyst.

If you want to work without pressue (CO and H2) you have to start from a-methylstyrene and convert this to the corresponding Oxide (epoxide)

This epoxide you can convert directly to P2P (with H2SO4 at -16° -low yield) or to a-phenylpropanal by distilling (high yield).

There is another way directly from a-methylstyren to P2P (with Thalliumsalts) The references you will find in my posted artice (in your thread)

This method needs only a-methylstyrene and thallium(III)salts and no other chemicals, but you have to convert the thallium(I) salts to thallium(III) salts. This is possible in differnt ways.


CheshireHouse

  • Guest
swim's attempt
« Reply #13 on: June 23, 2004, 12:57:00 AM »
720ml H2SO4 chilled to -20C.  Added 162ml 2-phenylpropanal dropwise, at rate so as to keep temp below -16C, with good stirring.  Allowed to remain chilled & stirred for unknown amount of time (fell asleep) but probably about a couple of hours.

Resultant mixture was dark brown.  Poured onto some ice (but not nearly as much as recommended, as had only a small amount of distilled ice & didn't want to use non-distilled ice).   Seemed to turn a little white at first but remained mostly dark brown.  Contained a large, lumpy, polymerized mass.

Added equal volume toluene, stirred well.  Toluene picked up dark brown color, dissolved polymerized mass. 

Distilled toluene at atmospheric pressure.  Distilled remainder at 24mmHg, got no fraction close to proper temp.  Did not continue to distill, gave up when realized temp was far too high for it to be p2p.  What was left, after return to atmospheric pressure & turning off of temp, was black and formed a solid brick in the bottom of the flask.

Anybody have any tips for SWIM on where she went wrong?  Not using enough ice significant?  Would appreciate thoughts.

Thanks! :)


amalgum

  • Guest
Cheshirehouse: You didn't say anything about...
« Reply #14 on: June 23, 2004, 11:55:00 AM »
Cheshirehouse:
You didn't say anything about washing the toluene with carbonate first before distilling.  SWIM thinks since you didn't do that traces of sulfuric is what fucked it all up (polymerization).
Plus you people are just not listening.  Your gonna have to use a mild oxidant before distillation.  Your not gonna separate the unreacted aldehyde by distillation dammit.  There are plenty of very cheap otc oxidising reagents you could use for this.  Then extract back into toluene and wash again with a carbonate to convert all the hydratropic acid you just made from the left over aldehyde to a water soluable sodium salt.  Then it's ready for distillation.

Come-on.  SWIM has been reading about this route for a long time.  It seems to be well documented.  Just how much research do you all actually do before trying something?

CheshireHouse

  • Guest
OK about washing with the carbonate.
« Reply #15 on: June 23, 2004, 02:25:00 PM »
OK about washing with the carbonate.

As for making sure the P2P was able to be separated from any unreacted aldehyde, I first wanted to see whether I was getting anything at all.  Despite not being able to separate the close fractions, I figured I'd see whether I was getting any fractions in that range at all.  Since I didn't, I'm glad I didn't waste the time.

Another question I had was, does anyone know what (if anything) happens to 2-phenylpropanal when reacted with methylamine?  If nothing, then why not just leave it mixed?  Or, if it does, is it easier to separate whatever the reaction product is from methamphetamine than it is to separate the aldehyde from P2P?

Thanks for your reply!  :)


CheshireHouse

  • Guest
Also, the polymerization [UPDATED]
« Reply #16 on: June 23, 2004, 02:33:00 PM »
Also, the polymerization appeared to occur long before I attempted to distill the mixture... as I noted above, there was a huge, gummy mass that formed after having poured the reaction product over ice & having let it melt.  It did dissolve into the toluene when I added it, but I would think that it was too late at that point to wash out excess sulfuric with hopes of avoiding polymerization... unless I'm completely wrong about what that gummy mass was, which is entirely possible.

Has anyone else observed this formation of a large, gummy mass at the point when the reaction product was added to ice?

//edit:  from what I remember, Rhodium originally mentioned having to separate the p2p from the aldehyde in connection with the alpha-methyl styrene synth, which gave a 45% yield of p2p & 55% hydratropic aldehyde (or vice versa).  In fact, he mentioned the synth under discussion here as a possible way to convert the remaining aldehyde.  So does anyone have any evidence that there's even any unreacted aldehyde left after reacting the aldehyde with the H2SO4 in this synth, that would need to be dealt with?  Or did everyone just take Rhodium's comment regarding the other synth & run with it?

In fact, one of the translated articles says "In the case of concentrated sulfuric acid the yields were sometimes reduced because of formation of condensation products; the reaction products didn't contain the starting aldehyde. The experiment is carried out as follows: to sulfuric acid (sp. grav. 1.84) cooled to -20° or to -10° an aldehyde is added with stirring...".  This would seem to confirm that in the case of using concentrated sulfuric at -20, there's no need to worry about any unconverted aldehyde.


java

  • Guest
References please
« Reply #17 on: June 23, 2004, 07:26:00 PM »
CheshireHouse  Could you please list the references you keep quoting so I can understand where you are coming from with your analysis of the reaction....java


amalgum

  • Guest
This is from: https://www.the-hive.ws/forum/sho...
« Reply #18 on: June 23, 2004, 09:15:00 PM »
This is from:

Post 319139 (missing)

(Jan1983: "P2P / Hydratropic Acid", Stimulants)


(Sorry, very limited html knowledge, so somebody could please fix that link.  I beleive it was posted earlier anyway in this thread.  It took only five minutes to look it up with TFSE)




Rhodium
(Chief Bee)
06-10-02 03:13
No 319315
         Purification is a MUST!   Bookmark  Reply    

If you subject hydratropic aldehyde to an Al/Hg reductive amination with methylamine, you will get N-methyl-2-phenylpropylamine, which to my knowledge is not tested in humans and is possibly toxic.

You must certainly remove all the aldehyde from your P2P before continuing. Ask Osmium about what OTC oxidant you should use, he must know what would work best for that.

It is not possible to effectively separate 2-phenylpropanal (bp 222°C/760mmHg) from phenyl-2-propanone (bp 214°C/760mmHg) through simple distillation, and certainly not via vacuum distillation as the boiling points are too close. Fractional distillation could theoretically be used to separate them, but the size of the column that would have to be used makes that option impractical. 




(Never mind, the link fixed itself, hell yeah 8) )


CheshireHouse

  • Guest
Sorry about that.
« Reply #19 on: June 23, 2004, 11:39:00 PM »
I brought up the synthesis from alpha-methyl styrene a few years ago, in this thread:

Post 43910

(CheshireHouse: "alpha-methyl styrene", Serious Chemistry)
.  A year or so later, Rhodium made the comment I was referring to about the inseparability of the aldehyde & p2p, in this one:

Post 314878 (missing)

(Rhodium: "Method choice", Chemistry Discourse)
.

The quote I made comes from here:

Post 476441 (missing)

(azole: "as requested by java", Russian HyperLab)
. He also says, even more to the point,

The transformation of aldehydes to ketones occurs easily under some heating in the presence of mercuric salts and especially easily, one may say, immediately, under the action of concentrated sulfuric acid with cooling. In this process, mercuric salts and concentrated sulfuric acid form loose complexes with the reactants and the reaction products. The end-products of the reaction (ketones) form more stable complexes than aldehydes do. This accounts for the fact that only ketone can be found in these complexes, especially in the case of concentrated sulfuric acid.



So it seems to me that in the particular reaction under discussion, i.e., reaction of 2-phenylpropanal with conc. H2SO4 at low temp, there should be none of the original aldehyde present -- and therefore no reason to worry about how to separate it from the p2p.

Hope that covers everything I quoted from, if not let me know.  :)

p.s. sorry if the links point to a post instead of a thread, I can't get them to work the way I want them to :/