Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
 Pages:  1  ..  3    5  
Author: Subject: Copper(II) Aspirinate Synthesis
bfesser
Resident Wikipedian
*****




Posts: 2114
Registered: 29-1-2008
Member Is Offline

Mood: No Mood

[*] posted on 27-9-2013 at 05:31


Neat. I love seeing photos of copper complexes. What method(s) did you use to verify the identity of your product?



View user's profile View All Posts By User
Oscilllator
International Hazard
*****




Posts: 659
Registered: 8-10-2012
Location: The aqueous layer
Member Is Offline

Mood: No Mood

[*] posted on 27-9-2013 at 20:47


Well Apart from the that its a complex, I don't actually know anything about it. All I can say is that it dissolves in a solution of sodium bicarbonate, and when enough HCl is added to this mixture the deep green colour disappears and a white precipitate (presumably salicylic acid) can be seen floating about.



View user's profile View All Posts By User
sargent1015
National Hazard
****




Posts: 315
Registered: 30-4-2012
Location: WI
Member Is Offline

Mood: Relaxed

[*] posted on 30-9-2013 at 20:58


Quote: Originally posted by Oscilllator  
I also attempted to prepare a nickel analogue, however is seemed that only nickel carbonate formed :(


Did you try dissolving the acetylsalicylic acid in bicarb before adding the metal? Also, with slight excess of the acetyl salicylic acid?



News on my synthesis:
I obtained... a deep blue oil, interestingly enough. I wish we still had our IR setup in my lab, I could check if it was actually coordinated :/




The Home Chemist Book web page and PDF. Help if you want to make Home Chemist history! http://www.bromicacid.com/bookprogress.htm
View user's profile View All Posts By User
Semmelweis
Harmless
*




Posts: 10
Registered: 9-10-2013
Location: Brazil, where we get coconuts from cocopalms
Member Is Offline

Mood: A lack of 5-hydroxytryptamine

[*] posted on 16-10-2013 at 12:16


I guess a more direct approach would be to react the ASA with CuOH.
It's too weak a base to cause hydrolysis.
I make my CuOH from electrolysis. Fun compound to mess with, one easily gets copper chloride to show it's very exothermic reaction with Al.
I think I will be trying this as soon as I get more Aspirin.
View user's profile View All Posts By User
bfesser
Resident Wikipedian
*****




Posts: 2114
Registered: 29-1-2008
Member Is Offline

Mood: No Mood

[*] posted on 16-10-2013 at 13:46


Quote: Originally posted by Semmelweis  
I guess a more direct approach would be to react the ASA with CuOH.
Sometimes I wonder why I even bother.

ASA is quite insoluble in H<sub>2</sub>O at 20&deg;C. If you heat to increase solubility, it will decompose. Also, your "CuOH" is not. It's a complicated aqueous complex precipitated mess. I think you'll be hard-pressed to get them to react, and even if you do, you'll have to wash excess ASA out of your product with an organic solvent and the leftover [CuOH] with a weak acid, such as dil. ethanoic acid (use of a strong acid would turn your product back to ASA and a Cu<sup>2+</sup> salt). In summary, your proposed method would be just as much work, and likely have lower yields and poor purity (inclusion of [CuOH] into precipitate during crystal growth).

A tip: <em>I've found that (in my experience)</em> it's generally a bad plan to react an insoluble species with a solution when you're expected product is itself insoluble&mdash;it's generally slower and affords lower yields of a lower purity product than other means.

[edit] P.S. I see that you're from Brazil; any chance you could U2U me with a city name? I'm looking for someone to collect and ship a mineral specimen.

[Edited on 16.10.13 by bfesser]




View user's profile View All Posts By User
Semmelweis
Harmless
*




Posts: 10
Registered: 9-10-2013
Location: Brazil, where we get coconuts from cocopalms
Member Is Offline

Mood: A lack of 5-hydroxytryptamine

[*] posted on 16-10-2013 at 15:18


Well, I thought it could be done on ethanol, evaporate, and wash with the weak acid as you said. In fact, I have just done a test with 1 crushed aspirin tablet, some ethanol and a little copper hydroxide, everything eyeballed in a test tube, and after shaking a lot got a color surprisingly near that of the photo. I know, however, that for this to actually work would be against all odds.
View user's profile View All Posts By User
Boffis
International Hazard
*****




Posts: 1642
Registered: 1-5-2011
Member Is Offline

Mood: No Mood

[*] posted on 21-11-2013 at 17:12


I recently repeated my experiment with nickel carbonate but this time I used salicylic acid instead of aspirin. The nickel carbonate dissolves in the suspension of salicylic acid producing a pale greenish liquid that would no crystallise on cooling, on evaporation (a pale green glassy residue was obtained) or on treatment with excess alcohol. I suspended 0.5g of salicylic acid in 10ml of water and heated almost to boiling and added basic nickel carbonate until no further effervescence occurred, filter it while hot through a small hirsh funnel to remove the excess carbonate and cooled it slowly in an open 25cc beaker. By the following morning almost half the liquid had evaporated but no crystals had formed. Evaporation to dryness in a shallow porcelain basin left a glassy residue which dissolved again rapidly in a few cc of water and would not crystallise even when 5ml of ethanol (95%) were added. I conclude that the salicylate complex of Ni2+ is very soluble. It also appears identical to the product that I had obtained from aspirin, which tend to confirm bfessor's contention that the boiling would have hydrolysed the aspirin.
View user's profile View All Posts By User
bfesser
Resident Wikipedian
*****




Posts: 2114
Registered: 29-1-2008
Member Is Offline

Mood: No Mood

[*] posted on 21-11-2013 at 17:36


Interesting. Thanks for sharing your experimental results.



View user's profile View All Posts By User
AlChemicalLife
Harmless
*




Posts: 37
Registered: 18-1-2011
Member Is Offline

Mood: happy and ready for science

[*] posted on 7-12-2013 at 10:36


I was thinking of posting this in a new thread but, Since there is already a thread on this ,i didn't want to annoy people with making another thread of the almost exact same thing , the only thing different is this starts with copper metal. But if you guys would like to take a look that would be great, My synthesis of this compound was using Anon's video on making this Copper Aspirinate, and making it from scratch.

So A few days ago i was asked to write up an experiment which started out with the metal and ended up as a useful compound that could be used as a pharmaceutical or in a way that could help life. So i thought and thought, and experimented with different things , searching YouTube and Google. And i came across a few that i liked but the one that caught my eye was copper aspirinate
, A Copper compound that is used as a treatment for rheumatoid arthritis interested me, than i realized , How am i going to go from copper to the Compound. I kept searching, and found a synthesis that i liked, that used compound's i know how to make from copper , and i went the easiest wrought to do the following Experiment and this experiment is in the processes of being put into my website , but there are a few minor things i will change.

"From Copper metal to Pharmaceutical"
In this experiment I will start with Plain copper metal(And a Few house hold materials) , and end up with Copper aspirinate.
First we need to make a soluble copper compound that will react with Sodium Bicarbonate, usaly we could use copper sulfate, but lets say you dont have that available,Are you out of luck?
Well , luckily for you your not out of luck, We can make another soluble copper compound that will react with Sodium bicarbonate to form Copper carbonate, We will make Copper acetate.Than we will react the copper acetate with sodium carbonate to form copper carbonate , Than we will isolate ASA (Acetylsalicylic acid) From aspirin, and then react the Acetylsalicylic acid with the copper carbonate to form Copper aspirinate

Making the copper acetate: Making this compound could not be easier, you will want to make up a solution with vinegar and hydrogen peroxide, you will want to use double the amount of vinegar that use use from hydrogen peroxide ( Say you use 30mls of hydrogen peroxide , Thank you will want to use 60mls of Vinegar ). After you make this solution you will want to drop in some copper ( About 10grams should be plenty, but if you run out of copper add more ) Now heat the solution To a slight boil and add the copper , you will notice it bubble.( NOTE: you can also just add the copper without heating , this will take longer, but is safer ) As its bubbling you will notice the color change from clear to blue(This is NORMAL) ,the reaction is complete when the solution is a deep blue or when you copper metal stops reacting . The Equation is here - CH3COOH+H2O2+Cu =
Cu(CH3COO)2+H2O+O2.
Now that you have the solution we will move onto making the Copper Carbonate

Making the Copper Carbonate: Making the copper carbonate is easier than make the Copper Acetate. What you want to do now is make up a Saturated solution of Sodium bicarbonate, After you have a solution of Sodium Bicarbonate , take that solution and add it to the copper acetate solution, (You will notice a green/blue precipitate This is our copper carbonate ) Keep adding the solution till no more precipitates out of solution. After you have all of it precipitated out of solution , filter and wash with copious amounts of cold water to remove trace amounts of Bicarbonate that may be in your product. Set the copper carbonate out to dry. While we wait for this to dry we now can make our Acetylsalicylic acid.

Making the Acetylsalicylic acid from aspirin : Making Acetylsalicylic acid, isn't to difficult , its actually pretty fun , So lets get started .
You will first want to start out by placing some water into a freezer to cool it down to a low temp , just above freezing.
As we are waiting for the water to cool, We can prepare our solution we will pour into the cool water.
Start by measuring about 1ml of Isopropyl alcohol per aspirin tablet used, in this experiment i used about 25 Tablets , so i will measure out 25ml's of Isopropyl Alcohol.
Then add the Tablet, and the Isopropyl alcohol to a beaker and lightly heat do dissolve all the aspirin (DO NOT BOIL THE ALCOHOL!, Boiling it may cause the ASA to Turn in to Salicylic acid ) After all the aspirin has dissolved,There may still be a cloudiness do to binders N' such that are not soluble in the IPA.
Take this solution a filter it to make sure no binders are left, Then take you water out of the freezer, now take your solution with the ASA in it and add it to the cold water.
You should see a nice fluffy white precipitate come out of solution, This is you ASA and you can take this and filter this off, while filtering wash with copious amounts of cold water and ice cold Isopropyl alcohol.After This is done you can now dry it or recrystallize it(this isn't necessary, but will improve your product to just make sure no binders are left) . To recrystallize just add just enough Hot Isopropyl alcohol to dissolve all the product , Then set that out to recrystallize, putting a continues air stream helps yield. Dry this and we will move on to the next and final step to our tour of making a pharmaceutical.

Making The Copper Aspirinate: YAY !!FINALLY!! You have survived this long and now its time to make the final product!!, this, like all the other steps isn't to difficult.
First weigh out 9 grams of Acetylsalicylic acid and 3 grams of Copper(II)carbonate.
add the 9 grams of Acetylsalicylic acid to 75ml's of distilled water, Bring this water close to boiling. Now With Lots of stirring (Preferable with a hotplate stirrer ) slowly add the copper carbonate, adding to much at once will result in the reaction overflowing onto the hotplate. You will note a color change from the greenish blue copper carbonate to the Blue Copper Aspirinate. After all the carbonate has been added keep stirring and gentle heating for about 5-10 minutes then shut off the stirring and heat and let the Copper Aspirinate settle. after its settled , if you observe bubbling, turn back on stirring and gentle heating,this means the carbonate and Acetylsalicylic acid haven't fully reacted.
When your ready to proceed, filter the product ( Using a vacuum is highly rec emended ) At this stage your product is impure with left over Un-Reacted Acetylsalicylic acid, add the product to a beaker , and add approximately 100ml's and stir to dissolve impurity's. Now re filter you product, it should look MUCH cleaner , if there are anymore impurity's try and get them out by picking them out . Now Dry your product and your finished!! After this Long experiment you deserve a coke or Pepsi (Or a beer for you fellow beer drinkers) to drink , and a pat on the back, you have made a pharmaceutical from copper metal,aspirin , and a few other house hold products!

any questions of this are welcome !! Hope you enjoyed it.
View user's profile View All Posts By User
bfesser
Resident Wikipedian
*****




Posts: 2114
Registered: 29-1-2008
Member Is Offline

Mood: No Mood

[*] posted on 7-12-2013 at 18:39


Why do people keep insisting on reacting an insoluble copper compound with acetylsalicylic acid? Please read everything written above to understand why this is a bad route. By the way, most of the videos I've seen for copper(II) aspirinate on YouTube have been just plain awful. You should try doing a little proper research before blindly following anything you see on YouTube. You'll find that many of the videos, if not all, were made after this topic was opened. Sadly, none of the authors seem to have read through this or understand what they're actually doing.

[edit] If you put this on your website, a link to Science Madness would be appreciated.

[Edited on 8.12.13 by bfesser]




View user's profile View All Posts By User
AlChemicalLife
Harmless
*




Posts: 37
Registered: 18-1-2011
Member Is Offline

Mood: happy and ready for science

[*] posted on 8-12-2013 at 08:43


I just wrote that experiment up for fun, weather or not it was effective or efficient wasn't on my mind. And when i get done with proofing and taking picture ill post it on my website and put a link to this thread , and it will be noted this is not the most efficient or effective way to make it, but it is fun and i enjoyed it :) .
View user's profile View All Posts By User
sargent1015
National Hazard
****




Posts: 315
Registered: 30-4-2012
Location: WI
Member Is Offline

Mood: Relaxed

[*] posted on 28-12-2013 at 11:22


First off, feels good to be done with the semester and back on ScienceMadness! Back to my aspirinate fun!

Second,
Quote: Originally posted by AlChemicalLife  

Bring this water close to boiling. Now With Lots of stirring (Preferable with a hotplate stirrer ) slowly add the copper carbonate, adding to much at once will result in the reaction overflowing onto the hotplate...


If you heat it, you run the risk of decomposition, likely forming some salicylic acid. Why not skip the carbonate synthesis step and make it directly from copper acetate??




The Home Chemist Book web page and PDF. Help if you want to make Home Chemist history! http://www.bromicacid.com/bookprogress.htm
View user's profile View All Posts By User
bfesser
Resident Wikipedian
*****




Posts: 2114
Registered: 29-1-2008
Member Is Offline

Mood: No Mood

[*] posted on 4-1-2014 at 12:05


Just found this gem:

<strong>Hybrid (Electrochemical-Chemical) Single Crystal Synthesis of Copper Aspirinate Starting from an Aspirin Tablet: an Undergraduate Bioinorganic Experiment.</strong>
A. Pérez-Benítez, M.A. Méndez-Rojas, S. Bernès, E. González-Vergara
<em>Chemical Education Journal (CEJ)</em>, Vol. 11, No. 2 /Registration No. 11-8 /Received January 23, 2008
<a href="http://chem.sci.utsunomiya-u.ac.jp/v11n2/PerezBenitez/PEREZ_BODY.html" target="_blank">http://chem.sci.utsunomiya-u.ac.jp/v11n2/PerezBenitez/PEREZ_BODY.html</a> <img src="../scipics/_ext.png" />




View user's profile View All Posts By User
sargent1015
National Hazard
****




Posts: 315
Registered: 30-4-2012
Location: WI
Member Is Offline

Mood: Relaxed

[*] posted on 22-1-2014 at 13:09


That is awesome! ! ! Anyone try it yet?




The Home Chemist Book web page and PDF. Help if you want to make Home Chemist history! http://www.bromicacid.com/bookprogress.htm
View user's profile View All Posts By User
bfesser
Resident Wikipedian
*****




Posts: 2114
Registered: 29-1-2008
Member Is Offline

Mood: No Mood

[*] posted on 22-1-2014 at 15:31


I replicated the experiment shortly after that post, substituting 0.9 mm pencil lead, and got very poor results. I did get some product, but the crystals are much smaller than claimed by the original authors&mdash;I didn't bother to recover them.



View user's profile View All Posts By User
TheChemiKid
National Hazard
****




Posts: 493
Registered: 5-8-2013
Location: ̿̿ ̿̿ ̿'̿'̵͇̿̿з=༼ ▀̿̿Ĺ̯̿̿▀̿ ̿ ༽
Member Is Offline

Mood: No Mood

[*] posted on 4-2-2014 at 15:04


Here is a video I made on the synthesis of copper aspirinate. Hope you enjoy it.



When the police come


\( * O * )/ ̿̿ ̿̿ ̿'̿'̵͇̿̿з=༼ ▀̿̿Ĺ̯̿̿▀̿ ̿ ༽
View user's profile View All Posts By User
DraconicAcid
International Hazard
*****




Posts: 3801
Registered: 1-2-2013
Location: The tiniest college campus ever....
Member Is Offline

Mood: Semi-victorious.

[*] posted on 4-2-2014 at 15:25


Nice video, but it's incorrect to refer to the copper aspirinate as a ligand. The aspirinate ion acts as a ligand to the copper, but the whole thing isn't a ligand.



Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
View user's profile View All Posts By User
bfesser
Resident Wikipedian
*****




Posts: 2114
Registered: 29-1-2008
Member Is Offline

Mood: No Mood

[*] posted on 4-2-2014 at 15:37


Nice work, kid. You've made the only decent video I've seen of copper(II) aspirinate, so far! I'd recommend correcting the narration to refer to it as a "copper chelate" (<a href="https://ssl.gstatic.com/dictionary/static/sounds/de/0/chelate.mp3" target="_blank">/ˈkēˌlāt/</a> <img src="../scipics/_ext.png" />;) or "copper coordination complex" (<a href="https://ssl.gstatic.com/dictionary/static/sounds/de/0/coordination.mp3" target="_blank">/kōˌôrdnˈāSHən/</a> <img src="../scipics/_ext.png" />;), and putting a visual in the black screen part near the end.



View user's profile View All Posts By User
sargent1015
National Hazard
****




Posts: 315
Registered: 30-4-2012
Location: WI
Member Is Offline

Mood: Relaxed

[*] posted on 6-2-2014 at 19:43
Copper imidazole complex


Nice video man! Since we are giving pointers (and this is what I tell my students), you should give molar quantities rather than grams of this plus grams of that. It is much more scientific and less "cooking" style.

Anyways, back to the fun of copper complexes since I will have free time this weekend!
First things first, my imidazole complex of copper seemed to work (seemed since I have a waxy, dark blue product now, and no access to an FTIR). I guess if you guys want to try and confirm this little experiment I ran, I'll write up a little blurb. I don't have any idea for purifying so far, maybe you guys will have ideas.

0.232 g (3.4 mmol) of imidazole was dissolved in ~100% ethanol. To this solution, 0.72 g (0.85 mmol) of copper (II) aspirinate was added. The cloudy blue solution was stirred for an hour.

And this is where my notes went to crap and it has been awhile since I actually performed the experiment, so I am not positive if I did anything after that step. All I know is that I let it air dry for several days and got a waxy, blue solid.
Ideas/comments/etc. are encouraged here. I am in the process of remaking some copper aspirinate to redo it.




The Home Chemist Book web page and PDF. Help if you want to make Home Chemist history! http://www.bromicacid.com/bookprogress.htm
View user's profile View All Posts By User
sargent1015
National Hazard
****




Posts: 315
Registered: 30-4-2012
Location: WI
Member Is Offline

Mood: Relaxed

thumbup.gif posted on 6-2-2014 at 20:51
Copper (II) Benzoate Synthesis


Also, I noticed that no one has a write up for copper (II) benzoate. I like my method which uses both organic and inorganic routes to the product. Not really scientific writing, but eh, I've been grading papers all day.

1) Benzoic acid from toluene. I love this reaction way more than I should, plus it is a great beginner organic reaction. No write up here (Someone really should put one in the "Pre-Pub" section though), just a nice video of the synthesis: benzoic acid

benzoic acid.gif - 2kB

2) Next, we can take our fresh benzoic acid and deprotonate it with sodium hydroxide in water. The important part for this step is to make sure that the benzoic acid is in excess and can be filtered away before the next step. This ensures that there is no leftover sodium hydroxide in the solution, which will inadvertently react with copper sulfate.

sodium benzoate.gif - 2kB

3) Lastly, to your filtrate from step 2, add half an equivalence of copper (II) sulfate pentahydrate. Immediately, the product, copper (II) benzoate, will crash out of the solution and can be obtained by filtration and rinsed thoroughly with water. This yields fine, pale blue crystals.

copper benzoate.gif - 3kB

Simple synthesis, really, and emphasizes a lot of good chemistry and techniques.




The Home Chemist Book web page and PDF. Help if you want to make Home Chemist history! http://www.bromicacid.com/bookprogress.htm
View user's profile View All Posts By User
DraconicAcid
International Hazard
*****




Posts: 3801
Registered: 1-2-2013
Location: The tiniest college campus ever....
Member Is Offline

Mood: Semi-victorious.

[*] posted on 6-2-2014 at 21:06


I suspect your structure for copper(II) benzoate is inaccurate. Isn't it similar to the acetate, actually being dimeric?



Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
View user's profile View All Posts By User
sargent1015
National Hazard
****




Posts: 315
Registered: 30-4-2012
Location: WI
Member Is Offline

Mood: Relaxed

[*] posted on 6-2-2014 at 21:10


Didn't think about it, but here is the wiki answer:
http://en.wikipedia.org/wiki/Copper_benzoate

"Copper(II) benzoates exists in at least two structural forms, depending on the degree of hydration."




The Home Chemist Book web page and PDF. Help if you want to make Home Chemist history! http://www.bromicacid.com/bookprogress.htm
View user's profile View All Posts By User
HeYBrO
National Hazard
****




Posts: 289
Registered: 6-12-2013
Location: 'straya
Member Is Offline

Mood: :)

[*] posted on 7-2-2014 at 03:50


Quote: Originally posted by sargent1015  


2) Next, we can take our fresh benzoic acid and deprotonate it with sodium hydroxide in water.



Nice route but, the deprotination seems unnecessary IMO, as you form potassium benzoate in the first step, which then you acidify and then deprotinate... The solubility between the two is negliable too (sodium benzoate 62.9 g/100 ml water, potassium benzoate 65 g/100 mL- wiki) I am I missing something or..?




View user's profile View All Posts By User
Nicodem
Super Moderator
*******




Posts: 4230
Registered: 28-12-2004
Member Is Offline

Mood: No Mood

[*] posted on 7-2-2014 at 04:45


Quote: Originally posted by sargent1015  
Didn't think about it, but here is the wiki answer:
http://en.wikipedia.org/wiki/Copper_benzoate

"Copper(II) benzoates exists in at least two structural forms, depending on the degree of hydration."

The structure depicted on the Wikipedia page is most certainly completely wrong. Interestingly, the wiki article itself claims a different structure in its Structure section. Anyway, if you follow the references it gives, you can see that the various copper(II) benzoates all are coordination compounds, just like the copper carboxylates generally are. The benzoate ligand acts as bridging ligands between two copper atoms. See Acta Cryst. 1992, B48, 253-261 (DOI:10.1107/S0108768191012697, attached) for the structure of some Cu2(BzO)4L2 compounds.
I don't have the access to DOI: 10.1143/JPSJ.18.117 where the structure of copper benzoate trihydrate is reported, but then again neither do you seem to know which copper(II) benzoate did you obtain.

Attachment: ActCryst_B48_253_261.pdf (278kB)
This file has been downloaded 428 times





…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)

Read the The ScienceMadness Guidelines!
View user's profile View All Posts By User
sargent1015
National Hazard
****




Posts: 315
Registered: 30-4-2012
Location: WI
Member Is Offline

Mood: Relaxed

[*] posted on 7-2-2014 at 10:08


Quote: Originally posted by HeYBrO  

Nice route but, the deprotination seems unnecessary IMO, as you form potassium benzoate in the first step, which then you acidify and then deprotinate... The solubility between the two is negliable too (sodium benzoate 62.9 g/100 ml water, potassium benzoate 65 g/100 mL- wiki) I am I missing something or..?


I should have clarified, while it is cool and dandy to make copper benzoate, I do not need a huge surplus of it. So I made the benzoic acid, isolated it, and used only the amount I wanted for the copper benzoate synthesis.


Thanks Nicodem for the correct structure, it's been quite some time since I've played with inorganic. Just goes to show you how "reliable" wiki is.

Quote:

but then again neither do you seem to know which copper(II) benzoate did you obtain.

Not even the slightest clue :D

-Sarge




The Home Chemist Book web page and PDF. Help if you want to make Home Chemist history! http://www.bromicacid.com/bookprogress.htm
View user's profile View All Posts By User
 Pages:  1  ..  3    5  

  Go To Top