Sciencemadness Discussion Board - Adipic acid

Adipic acid

runlabrun - 5-1-2005 at 00:25

Just a quick thought about OTC sourcing of adipic acid, i found cyclohexanone in pvc pipe joiner at 20% v/v some brands vary 10-30% v/v.

Could one distill the cyclohexanone from the 60% MEK, 20% Cyclohexanone, 20% PVC vinyl acetate co-polymer (?) @ 156oC for cyclohexanone after collecting the MEK?
What would happen with the co-polymer? i dont want any crap stuck in my distillation glassware.
Would the best bet to extract the ketones with another solvent to remove this possibility?

Once the cyclohexanone is collected it can easily be oxidised to adipic acid by permangenate and re-crystalised from ice cold water to a decent purity.

-rlr

trilobite - 5-1-2005 at 01:22

Maybe one could invest in a suitable grade of nylon and hydrolyse it... and recover the diamine too.

cyclohexanone from pvc primer

prole - 24-10-2005 at 15:29

I see no one has posted here in a while, but here's my two cents:

I wouldn't use the pvc adhesive for obvious reasons (ever distilled DCM from stripper?). One may find PVC Primer, of the purple variety, in most hardware stores in the cont. US. Listed on the label are in order MEK, cyclohexanone, THF, and acetone. My thoughts are to distill off all the low-boiling solvents, which leaves one with cyclohexanone and purple dye (along with god knows what else). I am afraid of the THF forming explosive peroxides in the process. Should I be worried about this, or would there be a stabilizer included in the mix? At any rate, I'm going to throw some iron filings in the receiving flask.

Once the cyclohexanone and purple dye are isolated, I will add water to form an azeotrope with the cyclo., which I believe boils at 95C. At this point, I would either try salting out the water with the hopes of the dye migrating to the aqueous layer, or distill out the cyclo, dry it, and redistill (maybe under vacuum), and then go on to form adipic acid.

My main concern and cause of anxiety is the THF forming peroxides and ruining my day. Should I be concerned about this?

-prole

Magpie - 24-10-2005 at 18:12

Prole writes:

Quote:

I wouldn't use the pvc adhesive for obvious reasons (ever distilled DCM from stripper?).

What are the problems when distilling DCM from stripper? I was planning on that as a source of DCM. I know some strippers have polymer like garbage in them but IIRC Jabsco brand does not.

prole - 25-10-2005 at 04:59

Sorry Magpie, didn't mean to assume. The best source of DCM - containing stripper in my area has polymer crap in it, and that would be the 'obvious reasons' I was referring to. I did manage to collect two liters of DCM from two gallons of this stuff, although it was messy but not impossible to deal with. Just make sure DCM is first on the list of ingredients.

-prole

prole - 24-2-2006 at 12:06

I have performed the above distillation and salting procedures, and they work. It's alot of work though, but if you like distilling, it's fine. Got a total of 91mL cyclohexanone (bp 155C) from 1169 mL Purple Primer. Yields aren't that great. There's some azeotrope nonsense going on, and there's stuff in there not on the label (really?).

It needed over a litre of dH2O to mix completely with the cyclo. mixture, after all low-boiling solvents were removed. It turns out that the purple dye is insoluble in water. I made some ferrous sulfate and added some to both the distilling and receiving flask while distilling the low bp solvents that contained THF. Probably was unnecessary, but no explosions occurred nevertheless.

In the future, it might be more reasonable to skip the water addition altogether and just distill off the low boiling solvents to like 120C, then add safflower oil (in which cyclohexanone is miscible), and distill off the cyclo. Right now I'm wondering why I bothered with forming the cyclo/water azeotrope in the first place. I think it had something to do with removing the dye.

Now when I get a chance, I'll try to prepare adipic acid. I'm not familiar with the permanganate method. I'm going to use MnO instead.

runlabrun - 24-2-2006 at 22:22

Any rough oxid agent will work, acidified dichromate or permangenate works, MnO will be just fine.
http://orgsyn.org/orgsyn/pdfs/CV1P0018.pdf
This uses ammonium vanadate to convert cyclohexanol to adipic but there is a note on the discussion -->
Adipic acid can be prepared by the oxidation of cyclohexanol and cyclohexanone with nitric acid or potassium permanganate...."

There is a few pages on the internet giving details of the permangenate proceedure...
http://members.aol.com/profchm/chap22-6.html
http://www.slcc.edu/schools/hum_sci/chemistry/labs/chem1140/...

-rlr

Magpie - 1-3-2006 at 19:54

I need cyclohexanone to make adipic acid so took a crack at distilling Oatey purple primer for PVC & CPVC pipe today. I understand that this is also available in clear but I couldn't find any locally. At any rate this dye really wasn't too much of a problem.

Being concerned about peroxides I added some FeSO4 to the pot. I used a fractionation column for the first 3 cuts (acetone, THF, MEK) then a simple distillation on the last cut (cyclohexanone). I also added some cut-up copper wire to the THF condensate to prevent peroxide formation. I used a steam bath for the first 2 cuts then an electric mantle for the last 2. Steam just wasn't hot enough for the MEK and cyclohexanone cuts.

Although laborius, this seemed to work out OK. The purple dye just stayed in the pot and was thrown out with the final residue (~ 2 mL). I used the acetone that came off first to wash out the little dye left in the flasks as I went along.

Here's some estimates of the relative volumes obtained:

Acetone 17%
THF 31%
MEK 17%
Cyclohexanone 15%

I am planning redistill the THF to purify it.

1st edit: I need to add a caveat here: The boiling point breaks were not real clean even though I was using a fractionating column. I very well may have collected some azeotropes. I have not yet checked the literature for them.

2nd edit: I checked Gmehling's Azeotropic Data for binary, tertiary, and quaternary azeotropes. I found none.

[Edited on 2-3-2006 by Magpie]

[Edited on 2-3-2006 by Magpie]

[Edited on 2-3-2006 by Magpie]

runlabrun - 2-3-2006 at 19:54

ah great, was it % by volume or weight?
Yeah, the methods i have linked are similar to that i used in the past, very simple oxidation proceedure then wash with ICE cold water as adipic acid is only sparingly soluble in ice water, but it needs to be ICE water, ie near enough to freezing over in the freezer before use, this will remove alot of your residue from permangenate or dichromate whatever you choose to use.

-rlr

Magpie - 2-3-2006 at 20:29

Those are by volume. The cyclohexanone has such a much higher bp that it comes off quite cleanly.

I will be using a procedure from my 1960 organic lab manual to make the adipic acid. It specifies KMnO4.

Fom the adipic acid I plan to make cyclopentanone. Cyclic compounds like this fascinate me. I guess it is like a dog reaching around and grabbing its tail.

Magpie - 17-3-2006 at 12:03

I made 3g of adipic acid by oxidation of 5g of cyclohexanone that I obtained by distillation of Oatey PVC/CPVC pipe primer. This is the expected yield according to my old school procedure. Actual yield is only 40% based on theoretical. Purity was good as my melting point was 152-154C vs handbook value of 151-3C.

My procedure uses KMnO4 in water with a mL of 10%KOH. I had to heat the reactants to 45C to get it going (contrary to my procedure) but once going it had to be periodically cooled it to keep it under 50C per procedure.

Here is a picture of the acid crystals:

[Edited on 26-1-2007 by chemoleo]

adipic.jpg - 79kB

garage chemist - 14-9-2006 at 01:47

I made adipic acid yesterday. It worked very good.
I plan to do it again, and this time with double amounts, as adipic acid is useful for several other syntheses. I will also make pictures.

I used nitric acid as the oxidiser and proceeded according to Vogel. It works beautifully, the reaction is very exothermic but can be held under control. Enormous amounts of brown NOx gases are produced, a fume hood is an absolute must.
I used cyclohexanol bought from a chemical supplier as the starting material (cyclohexanone can be used without change in the procedure).

I recrystallized the product from water (instead of HNO3, like in the procedure- I don't want to use my HNO3 as a solvent, it's too valuable for that). I will weigh my yield today, determine the melting point, and do the second batch.

Nitric acid is used in considerable excess- for getting 13,3g of adipic acid, 63,3ml 65% HNO3 are needed. It is highly advisable to collect the filtrate from the first crystallization of the adipic acid and recover and concentrate the unreacted HNO3 by fractional distillation through a column. The reconcentrated HNO3 can be used again for the same process (it contains some pentanoic acid and other organic byproducts that codistill with the HNO3, so it shouldn't be returned into the HNO3 bottle).

[Edited on 14-9-2006 by garage chemist]

not_important - 15-9-2006 at 21:34

Quote:

Originally posted by runlabrun
...
Could one distill the cyclohexanone from the 60% MEK, 20% Cyclohexanone, 20% PVC vinyl acetate co-polymer (?) @ 156oC for cyclohexanone after collecting the MEK?
What would happen with the co-polymer? i dont want any crap stuck in my distillation glassware.
...
-rlr

A trick is to use a 'chaser', something with a higher boiling point than that of the highest boiling desired product. In this case you could distill the lower boiling fractions out of kerosene or lamp oil, leaving only those boiling above 200 C. Add at least 5% by volume of this to the mix you want to distill, and then take out the fractions you want. The high boiling chaser keeps the flask from going dry, and if you are using a fractionating column chases the last of the product from it.

Hot kerosene is a decent solvent for many organics, hot meaning 150 C and higher. So after you finish the distallation you can pour off the still hot kerosene chaser containing any gorp. Sometimes a short reflux of a fresh batch of kerosene, paint thinner, or tech xylene is needed to finish cleaning the flask.

Mason_Grand_ANNdrews - 21-9-2006 at 10:55

I have a idea to the adipic acid symthesis. Maybe it can manufactured from 1,4-butanediol by oxidation. I think it is a little waste, 1,4-butanediol is somewhat expensive and it is no aromatic system. Adipic acid is easy to get from a chem supplier. Add 10 g of 1,4-butanediol to 240 ml of 96% H2SO4 in a 500 ml beaker and 35 g of powdered sodium dichromate is stirred in. Some crystals should be precipate during the reaction. Cool the beaker when necessary and the temperature will rise above 40 °C. After that the baeker is stirred for 2 hours at 50 °C and the crude crystals of Adipic acid can filtered and purifyed by boiling the crystal in water.
Magpie, i have never heared you can make adipic acid by oxidation of 5g of cyclohexanone ?
There are no infos to a make cyclic compound from this. Seems easy to use a oxidizer. When you can found in what n-octanol is soluble, i would think a oxidation with 5% sodium hypochlorite/NaOH is right and cyclohexane can removed by distillation. (bp ~81 °C) I guess it`s easy theory.

Nicodem - 21-9-2006 at 11:36

Madandcrazy* you are a fascinating source of entertainment. It is unbelievable how much misinformation, misunderstanding, misspelling and nonsense you are able to concentrate in so little text. By the way, adipic acid is 1,6-hexanedioic acid and not 1,4-butanedioic acid (succinic acid) as you imply. Correcting the rest would be a hopeless task.

* Sorry, but I used to found your old nickname much more apropriate so I can't help still using it.

Mason_Grand_ANNdrews - 28-9-2006 at 08:55

What you think about much misinformation and a know process, you think a little lazy. Excuse me about my issues to
my last post but i guess it's no nonsense. Guy, you want tempt or lure me.

Quote:

* Sorry, but I used to found your old nickname much more
apropriate so I can't help still using it.

The Friedel-Crafts process gives very interested informations
to a `cycloaddition´ and energetic materials. I have
something choosen for you but i dont know the reaction will
work without the blocked hydrogen atom on the amino
group. (When it not work, maybe the hydrogen is blocked
with a chemical which you can break by oxidation after the
reaction is complete).
The mentioned process starts with n-phenyl-2,6-
dichloroaniline and ends with n-(2,6-dichlorophenyl)-2-
indolinone or rather diclofenac sodium salt.

My suggestions are easy and i have selected any examples.
("theory only")

2-indolinone (oxindole), C8H7NO:
You starts with aniline in chloroacetyl chloride, the salt is
neutralized with dilute HCl, the reaction is continued with
AlCl3 and than treated again with dilute HCl. 2-indolinone
(oxindole) should form a insoluble salt in the mixture.

sodium anthranilate, NH2C6H4COONa:
The crude filtrate from the previous synthesis is dissolved in
dilute EtOH, a concentrated NaOH solution is stirred to this
and than the mixture is neutralized with 5% sodium
bicarbonate solution, you can get crude sodium anthranilate. (Anthrafenac Sodium

)
I belive when it is neutralized with HCl,it gives crude anthranilic acid.

4-methyl-2-pyrrolodinone (gamma-butyrolactam), C5H9NO:
A good idea is when you start with allylamin/chloroacetyl
chloride and the same conditions, may be you can get 4-
methyl-2-pyrrolodinone which is removed by distillation
above 250 °C.

4-amino-3-methylbutanoic acid sodium salt:
The crude 4-methyl-2-pyrrolodinone from the previous
synthesis is stirred to dilute EtOH, treated with a concentrated NaOH solution and neutralized with 5% sodium
bicarbonate solution. After neutralisation of the salt with
dilute (10%) HCl you can get 4-amino-3-methylbutanoic acid.
No chemical informations to found.

4-amino-butanoic acid, C4H9NO2:
If you will start with 2-pyrrolidinone in EtOH and
concentrated NaOH solution, after the 4-amino-butanoic acid
sodium salt is neutralized with 5% sodium bicarbonate
solution and the salt is braked with dilute HCl, you can get
crude 4-amino-butanoic acid.

piperidine, C5H11N:
Maybe it is possible piperidine is obtained by the synthesis
of 2-indolinone when you will start with propylamin (C3H9N)
and the crude piperidine is removed by distillation above 106
°C from the solution.

2-piperidinone (delta-valerolactam), C5H9NO:
Maybe you can get 2-piperidinone by propylamin (C3H9N)
and the synthesis of 2-indolinone and the crude 2-
piperidinone is removed from the mixture by distillation
above 260 °C.

5-aminopentanoic acid, C5H11NO2:
2-piperidinone is treated in dilute EtOH/concentrated NaOH solution, the 1-aminopentanoic acid sodium salt is than
neutralized with 5% sodium bicarbonate solution and dilute
HCl. I can not found any chemical informations for this
chemical, may be the crude is distilled out from the mixture.

hexanoic acid (Caproic acid), C6H12O2:
Cycohexanone is stirred to dilute EtHO, a concentrated
NaOH solution is added to this, the mixture is stirred and
than heated for a while to 50 °C, than the mixture is chilled
to 5 °C, the hexanoic acid sodium salt is neutralized with 5%
sodium bicarbonate solution and treated with dilute HCl and
the crude hexanoic acid is removed by distillation above 206
°C.

I hope it is somewhat helpful, exuse me for some errors, some login problems

.

[Edited on 28-9-2006 by Mason_Grand_ANNdrews]

Mason_Grand_ANNdrews - 2-10-2006 at 11:00

Some correcting to the last issues.
Piperidine Synthesis:
2-piperidinone is stirred to dilute EtOH, a concentrated NaOH
solution is stirred in, the mixture is neutralized with 5%
sodium bicarbonate solution and the salt is breaked with
dilute HCl. Than the water is removed by distillation and
calcium carbonate in H2O is stirred to the mix, the solution is
gradualy heated to 60 °C, stirred for a while and than
washed with dilute HCl. The water is vaporized and the
crude piperidine is removed by distillation above 106 °C.
You can also make it from from 4-amino-pentanoic acid
(sodium salt).
I hope it is somewhat helpful. I`ve some ideas to the real
anthranilc acid synthesis, maybe some days later.

[Edited on 2-10-2006 by Mason_Grand_ANNdrews]