Pages: 1

Author Topic: Separation of piperonal and 3-phenyl propyl alcohol  (Read 325 times)

AoicVH

  • Larvae
  • *
  • Posts: 5
Separation of piperonal and 3-phenyl propyl alcohol
« on: December 02, 2011, 05:36:00 PM »
I was wondering, if someone had a solution of about 15% piperonal in 3-phenyl propyl alcohol how one would separate the two of them. 

The boiling points of both chemicals are apart 28°C from each other (3-phenyl propyl alcohol boils at 235°C and piperonal at 263°C).

Is there a chance that the piperonal could decompose when heated in a distillation even under vacuum?

If a pump pulls about 15mm Hg the estimated boiling point of 3-phenyl propyl alcohol is 110°C.

Upon tests the mixture when heated (atmospheric pressure, 200°C) turned from pale yellow to yellow/orange, if put in the freezer at -22°C (3-phenyl propyl alcohol melting point is -19°C)

over night, some of it will freeze into crystals, when the remaining liquid is removed and the crystals are allowed to warm up again they melt, therefore it (the frozen compund) must be somewhat pure 3-phenyl propyl alcohol.

So fellow readers what would you do, is there a better way to separate those two compounds than through their melting and boiling points?

Maybe there is a method like the addition product from ketones and NaI only for aldehydes?

-Edited to match forum rules-
« Last Edit: December 02, 2011, 06:11:44 PM by AoicVH »

Sedit

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 2,099
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #1 on: December 02, 2011, 05:58:24 PM »
Quote from: AoicVH on December 02, 2011, 05:36:00 PM
Maybe there is a method like the addition product from ketones and NaI only for aldehydes that SWIM is not aware of?

The use of SWIM is irritating please stop and read the rules.

The addition produces you speak of work like shit on Ketones, they are made for Aldehydes. Use it as it would be your best bet.
There once were some bees and you took all there stuff!
You pissed off the wasp now enough is enough!!!

AoicVH

  • Larvae
  • *
  • Posts: 5
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #2 on: December 02, 2011, 06:21:42 PM »
Quote from: Sedit on December 02, 2011, 05:58:24 PM
Quote from: AoicVH on December 02, 2011, 05:36:00 PM
Maybe there is a method like the addition product from ketones and NaI only for aldehydes that SWIM is not aware of?

The use of SWIM is irritating please stop and read the rules.

The addition produces you speak of work like shit on Ketones, they are made for Aldehydes. Use it as it would be your best bet.

I am sorry, i edited my post to match the forum rules

Hm, i thought the sodium bisulfite and sodium iodide addition products are especially suitable for ketones like acetone but now i see at least bisulfite is used for aldehydes too.

Maybe i misunderstood your reply because i am no native speaker, but do you imply to use the solution as it is for example the formation of a nitropropene ?

Even if it would go as planed, there still would be the problem of removing the nitropropene from the finished reaction, as 3-phenyl propyl alcohol is not miscible in water

Edited
« Last Edit: December 02, 2011, 06:51:50 PM by AoicVH »

Sedit

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 2,099
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #3 on: December 02, 2011, 09:50:56 PM »
A Sodium Bisulfite solutions will remove the Aldehyde if that is your desired goal. Sodium Bisulfite does not complex well with Ketones, the process was made for the purification of aldehydes.
There once were some bees and you took all there stuff!
You pissed off the wasp now enough is enough!!!

AoicVH

  • Larvae
  • *
  • Posts: 5
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #4 on: December 03, 2011, 08:47:13 AM »
thank you for your replies  :)

i had a dream tonight, i tried to separate the two compounds with sodium iodide because i had no bisulfite.

To 5 ml of the solution, 0.4g of NaI where added and the mixture was heated on a water bath to 100°C and swirled from time to time.

No change was observed, the NaI seemed like it would not dissolve or react with the solution, upon rapid cooling there was no crystallization

So it seems that at least with NaI it does not work, therefore i will try to dream next time of some bisulfite

I was wondering if i may had something wrong in my dream, and should have heated the solution to a higher temperature ?

smellslikeindole

  • Larvae
  • *
  • Posts: 10
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #5 on: December 03, 2011, 11:12:20 AM »
Sodium-iodide is a neutral salt, good for a lot things, like making iodides, iodine, hydrioidic acid ect, but it has limited uses in organic chemistry and the main point is: it will not react with ketones with a neutral water solution.

The Sodium-bisulfite is an awesome reagent, because it will make an adduct with a ketone or an aldehyde and this sulfonic acid could be easily separated from other compounds and after succesfull separation it could be regenerated to an aldehyde or ketone with a weak base (e.g.:NaHCO3).

Here is an example for forming the bisulfite adduct of an aromatic aldehyde:
hxxp://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv5p0437

Sydenhams chorea

  • Pupae
  • **
  • Posts: 97
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #6 on: April 20, 2012, 10:36:18 AM »
A similar solution (but I thought of a higher % piperonal) has been used as is in the Henry condensation with 1-nitropropane by yours truly, with moderate succes (got product but yield wasn't stellar). Either the nitrobutene precipitated after freezing or I diluted it with methanol first, I don't remember from head as this was years ago.

The hydrocinnamyl alcohol can probably be recovered from the post-rxn solution.
« Last Edit: April 20, 2012, 10:40:45 AM by Sydenhams chorea »
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.

carl_nnabis

  • Subordinate Wasp
  • ***
  • Posts: 245
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #7 on: July 07, 2012, 02:49:18 AM »
nice experimentation! since were talking about similiar mixtures, i have always thought of the hydrocinnamic alcohol wont hurt in the reaction, but was too frightened to actually do it without the separation using bisulfite ::)
"It's like the drug trip I saw when I was on that drug trip!"

Electro´S

  • Pupae
  • **
  • Posts: 95
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #8 on: December 10, 2012, 05:27:42 PM »
The 3-phenyl propyl alcohol/ piperonal mixture was mixed with a sodium bisulfite solution. The bisulfite adduct of piperonal is isolated and "dried".
Now the bisulfite is added to a baker with water and is heated with stirring and diluted HCl is added drop by drop until bisulfite is gone. Them the solution at room temperature is decanted and the botton layer is recovered. After a lot of fails, a small amount of the botton layer was mixed with cold ethanol and a little of cold water. After scratching the walls with a rod, piperonal crystals precipitate and is isolated by filtration.
Beautiful crystals was recovered, but in the second attempt precipitation was fail.
How you would precipitate the aldehyde???
Any idea is welcome.

T-cowboy

  • Pupae
  • **
  • Posts: 57
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #9 on: December 10, 2012, 09:18:33 PM »
yes same here,  every time it fails. maybe NAOH next time

lugh

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 876
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #10 on: December 11, 2012, 12:56:46 AM »
A strong base such as sodium hydroxide might cause problems:

http://127.0.0.1/talk/index.php/topic,2962.msg34167.html#msg34167

there's some useful information attached to:

https://the-collective.ws/forum/index.php?topic=23230.msg163682#msg163682

The end results from the effort applied  8)
Chemistry is our Covalent Bond

Electro´S

  • Pupae
  • **
  • Posts: 95
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #11 on: December 11, 2012, 01:15:39 AM »
Yep!!! looks like piperonal crystalize in contact with frezze ethanol in small batches. Just 2 or 3 drops, and the crystals start growing.
Them, bisulfite extraction, Dilute Warm HCl and isolate de heavy oil. A little of cold ethanol and... A good starting point!!!

T-cowboy

  • Pupae
  • **
  • Posts: 57
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #12 on: December 11, 2012, 02:40:07 AM »
Quote from: Electro´S on December 11, 2012, 01:15:39 AM
Yep!!! looks like piperonal crystalize in contact with frezze ethanol in small batches. Just 2 or 3 drops, and the crystals start growing.
Them, bisulfite extraction, Dilute Warm HCl and isolate de heavy oil. A little of cold ethanol and... A good starting point!!!

i sure did not understand that one. please explain in details my good friend. after bisulfite, then warm 30% hcl? then 2-3 drops ethanol?

Electro´S

  • Pupae
  • **
  • Posts: 95
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #13 on: December 11, 2012, 04:24:22 AM »
Yes, Bisulfite => filtration => warm HCl 5-10% => isolation de botton layer and 2 3 drops cold ethanol. Try it with one or two ml of piperonal.

Electro´S

  • Pupae
  • **
  • Posts: 95
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #14 on: January 03, 2013, 10:02:26 AM »
Yep!!!
OTC MDP2NP is obtained directly from the bottom liquid layer (After liberating aldehyde from the bisulfite) with cyclohexylamine catalyst.

T-cowboy

  • Pupae
  • **
  • Posts: 57
Re: Separation of piperonal and 3-phenyl propyl alcohol
« Reply #15 on: January 06, 2013, 08:51:59 PM »
Still cannot convey this extraction of piperonal. damn. must have lost lakes of piperonal!!
Pages: 1