subskune
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Alternative Synthesis of 2,3-Dichlorosuccinic acid
Hi,
I have been trying to make 2,3-Dichlorosuccinic acid (dcs) for a while now.
I always start from fumaric acid which double bond needs to be chlorinated.
This can be done by bubbling chlorine gas through a boiling suspension of fumaric acid, I know that. My problem is that due to a lack of chemical
equippment all my attempts to bubble it in the suspension ended either in massive leakage or corrosion. Additionally not all of the chlorine was
consumed and i am not able to set up a trap. At the end nothing happended to the fumaric acid and my workplace was flooded in chlorine.
With that limitation I can only create dcs in solution. My first attempt was to add pool chlorinating agent to fumaric acid and let that sit for a
while. The solution became green and smelled horrible but not like chlorine and not much reaction seemed to take place at all. After that I decided to
add hcl in small portions to liberate the chlorine. However the chlorine did not react (fast enough) and bubbled out which again flooded my
workplace...
Finally I had the idea to add h2o2 and hcl together in 1 : 2 mol ration. This quickly became hot and smelled like chlorine. Then I added fumaric acid
and boiled it while massive stirring. A lot of gas was released causing the fumaric acid to foam and it didn't smell. Therefore I assume that gas to
be oxygen. After a while the solution slightly changed color to some transparent wheat like color and it did smell sweet. As I smelled it was
irritating. After a while no more fumaric acid was present and I took the solution of heat. Seconds later white flakes fell out (fumaric acid that was
only dissolved ?). What did happen? I assume the h202 to react with hcl to form chlorine or react directly with the double bond to form an epoxide
which is then hydrolized by the hcl.
How can I get to my dcs without free gas?
Thanks in advance!
[Edited on 27-5-2017 by subskune]
[Edited on 27-5-2017 by subskune]
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Alice
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Quote: Originally posted by subskune  | Hi,
I have been to make 2,3-Dichlorosuccinic acid (dcs) for a while now.
I always start from fumaric acid which double bond needs to be chlorinated.
This can be done by bubbling chlorine gas through a boiling suspension of fumaric acid, I know that. |
So you have a literature source at hand? Would you provide it?
| Quote: | | At the end nothing happended to the fumaric acid and my workplace was flooded in chlorine. |
How do you protect yourself from chlorine? Do you work in a fume hood? It is advisable destroying chlorine by bubbling it through washing bottles
loaded with NaOH or KOH solution.
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subskune
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Thanks for your reply!
| Quote: |
So you have a literature source at hand? Would you provide it?
|
To be honest I asked a chemistry teacher. However I am not 100% sure about that since I indeed found some literature. One is for bromine instead and I
don't know if there is a difference.
You can find it here:
https://www.chemie.uni-hamburg.de/studium/praktika/oc-grund/...
For the dichlorosuccinic acid I found literature which uses different processes. Some use sodium fumarate which I consider to be not important because
it only increases solubility. Other add nacl and increase the cl- ion concentration which is definitely useful because it reduces the formation fo
byproducts significantly.
See here: (end of page)
https://books.google.de/books?id=aTSGAwAAQBAJ&pg=PA549&a...
Sorry but all literature is German...
Unfortunately all of the processes involve handling chlorine gas while I try to produce and consume the chlorine in one pot or work around that as
well using chlorinating agents.
| Quote: |
How do you protect yourself from chlorine? Do you work in a fume hood? It is advisable destroying chlorine by bubbling it through washing bottles
loaded with NaOH or KOH solution.
|
Since I dont have proper equipment like flasks with joints I can't set up a gas trap. I used multiple strong fans to blow the chlorine away
considering wind direction and taking care that no other persons are harmed.
[Edited on 27-5-2017 by subskune]
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Boffis
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I presume that when you say "I have been to make 2,3-Dichlorosuccinic acid (dcs) for a while now" you actually mean you have been attempting to make
it since your efforts don't seem to have been particularly successful. Fumaric acid only reacts quickly with bromine at the temperature of boiling
water so I would suggest that you try this experiment again with a solution of fumaric acid in hot fairly dilute hydrochloric acid and then add the
oxidizing agent dropwise to limit the excess of chlorine developing which is then lost to the atmosphere. You don't give us any idea about the
compound you are trying to prepare so its difficult to judge how successful you may have been. For example, is it a solid or a liquid, what is its
melting point, how soluble in water is etc.? For example what were the white flakes, what makes you think they are not your product? What were you
expecting to see/ to happen? How were you expecting to isolate your product?
From a very brief search on the internet it appears that the target is a solid inspite of the lack of Mp data and is soluble in water.
Incidentally the bromo analogue was discussed recently in another thread and it is much easier to prepare since bromine is a liquid; there is a
reference to its preparation in Organic Syntheses which can be downloaded free. If you are using it as a precursor to acetylene dicarboxylic acid
(Butynedioic acid) then the bromo compound is perfectly serviceable.
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subskune
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| Quote: |
I presume that when you say "I have been to make 2,3-Dichlorosuccinic acid (dcs) for a while now" you actually mean you have been attempting to make
it since your efforts don't seem to have been particularly successful.
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Correct. I'll try out your suggestion, it sounds promising.
| Quote: |
You don't give us any idea about the compound you are trying to prepare so its difficult to judge how successful you may have been. For example, is it
a solid or a liquid, what is its melting point, how soluble in water is etc.?
|
I am sorry for that but I don't have any information about that substance and there is not much around in the internet except calculated boiling
points and melting points. Starting from succinic acid I came to the result that it is likely water soluble (better than fumaric acid) and a solid but
that is not useful at all. I thought someone knows more about 2,3-Dichlorosuccinic acid.
| Quote: |
If you are using it as a precursor to acetylene dicarboxylic acid (Butynedioic acid) then the bromo compound is perfectly serviceable.
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Thats what I want to do but I have no bromine.
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Alice
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| Quote: | | Thanks for your reply! |
You're welcome.
| Quote: | | To be honest I asked a chemistry teacher. However I am not 100% sure about that since I indeed found some literature. One is for bromine instead and I
don't know if there is a difference. |
There is that textbook message "halogens add to alkenes" but in practice this is not always that easy. Bromine will work better as it has a higher
polarizability due to its size. BrCl will work better as well as the bromine atom is already positively polarized.
| Quote: | | For the dichlorosuccinic acid I found literature which uses different processes. Some use sodium fumarate which I consider to be not important because
it only increases solubility. Other add nacl and increase the cl- ion concentration which is definitely useful because it reduces the formation fo
byproducts significantly. |
Maybe solubility, maybe pH, a deprotonated acid is more negatively polarized, which enhances the double bond attacking as a nucleophile. High chloride
concentration may speed up secondary attack of the chloronium ion formed in the first place. What is your solvent btw?
| Quote: | | Sorry but all literature is German... |
I understand many languages. 
Maleic acid is easier to chlorinate as the double bond is cis making it less stable thus more reactive.
| Quote: | Quote:
How do you protect yourself from chlorine? Do you work in a fume hood? It is advisable destroying chlorine by bubbling it through washing bottles
loaded with NaOH or KOH solution.
Since I dont have proper equipment like flasks with joints I can't set up a gas trap. I used multiple strong fans to blow the chlorine away
considering wind direction and taking care that no other persons are harmed. |
Sounds very "experimental". 
Hope you are aware how toxic chlorine is. Chlorine is a very nasty stuff...
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Crowfjord
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Melting point information for 2,3-dichlorosuccinc acid from a scifinder search. The discrepancies in values are probably due to different
stereoisomers. According to the first reference (Kharasch, JOC) the higher melting (214-215 °C) one is for the "meso" isomer, and the lower melting
(174-175 °C) is for the racemic acid.
| Quote: |
Melting Point 214-215 °C (decomp) (2)CAS
Melting Point 214-215 °C Solv: acetic acid (64-19-7) (3)CAS
Melting Point 212 °C (4)CAS
Melting Point 211 °C Solv: water (7732-18-5) (4)CAS
Melting Point 209-213 °C (5)CAS
Melting Point 186 °C (6)CAS
Melting Point 174-175 °C (decomp) (7)CAS
Melting Point 166-167 °C (7)CAS
Melting Point 166-167 °C (decomp) (7)CAS
Melting Point See full text (8)CAS
Notes
(2) Kharasch, M. S.; Journal of Organic Chemistry 1945, V10, P386-93 CAPLUS
(3) Hoshida, Masahiko; JP 45035762 B 1970 CAPLUS
(4) Avram, Margareta; Revue Roumaine de Chimie 1968, V13(8), P1085-95 CAPLUS
(5) Kharasch, Morris S.; US 2426224 1947 CAPLUS
(6) Bertrand, M.; Compt. Rend. 1964, V259(4), P827-9 CAPLUS
(7) Holmberg, Bror; Arkiv. Kemi, Mineral. Geol. 1920, V8(No. 2), P35 pp. CAPLUS
(8) Walther, Horst; Chemische Berichte 1958, V91, P630-6 CAPLUS
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Boffis
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| Quote: | | Quote: | | For the dichlorosuccinic acid I found literature which uses different processes. Some use sodium fumarate which I consider to be not important because
it only increases solubility. Other add nacl and increase the cl- ion concentration which is definitely useful because it reduces the formation fo
byproducts significantly. |
Maybe solubility, maybe pH, a deprotonated acid is more negatively polarized, which enhances the double bond attacking as a nucleophile. High chloride
concentration may speed up secondary attack of the chloronium ion formed in the first place. What is your solvent btw? |
The addition of salt may be to simply reduce the solubility of the dichlorosuccinic acid in an aqueous reaction medium.
@subskune; I would take issue with the claim that Mp and solubility are no help at all, they are very helpful. The solubility because it helps you
predict where your product is at the end of the reaction and Mp helps you assess the likelihood that the material you recover is the product you
wanted or not as the case may be. I this case Crowford's data would suggest that Mp is rather variable and therefore not of great help.
You also seem to have made very little effort to try and isolate and identify the possible reaction products. Your idea of generating chlorine in situ
is a novel one and I cannot say whether it will work or not but you don't seem to have worked up the aqueous reaction mixture sufficiently to
demonstrate that it didn't work at all.
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subskune
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@Crowfjord
Thanks! Thats a good amount af mps. Do you have any information about solubility in water?
If my synthesis is succesful I'll collect as much data as possible like solubility in different solvents and post it.
@Alice
| Quote: |
What is your solvent btw?
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Water. That does neither mess with hcl and h2o2 nor the pool tablets.
| Quote: |
There is that textbook message "halogens add to alkenes" but in practice this is not always that easy. Bromine will work better as it has a higher
polarizability due to its size. BrCl will work better as well as the bromine atom is already positively polarized.
|
It turns out to be difficult instead. What I considered to be a weekend synthesis is now consuming weeks. I can't access bromine and brcl not even in
my dreams.
| Quote: |
Maleic acid is easier to chlorinate as the double bond is cis making it less stable thus more reactive.
|
If all of my fumaric acid is consumed in my attempts, I will probably buy maleic acid since it is water soluble and as you said less stable.
| Quote: |
Sounds very "experimental".
Hope you are aware how toxic chlorine is. Chlorine is a very nasty stuff...
|
Yeah sometimes I take the experimenting part in chemistry too serious.
My first date with chlorine was better than I expected.
@Boffis
You misunderstood me, my wording was not super precise. I meant that calculated melting points are not useful and my attempt to make a proposition of
the solubility by looking at the succinic acid without chlorine is rather unprofessional.
Finally I did perform the last synthesis yesterday and on the first glance it was a failure because almost the same amount of matter came out of
solution as went in. Assuming that 2,3-Dichlorosuccinic is water soluble (I have no data!) it didn't work. Having no precise mp I can't do analysis
that way. What I'll try later is burning the stuff that fell out of my last experiment and look for hcl vapor with indicator paper.
[Edited on 27-5-2017 by subskune]
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Alice
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| Quote: Originally posted by Boffis |
| Quote: | | Maybe solubility, maybe pH, a deprotonated acid is more negatively polarized, which enhances the double bond attacking as a nucleophile. High chloride
concentration may speed up secondary attack of the chloronium ion formed in the first place. What is your solvent btw? |
The addition of salt may be to simply reduce the solubility of the dichlorosuccinic acid in an aqueous reaction medium. |
Chloronium ions are highly reactive and may be attacked by water leading to the chlorohydrin. The Houben-Weyl source states, without NaCl
3-chloromalic acid is obtained (edit: from maleic acid) which confirms my reasoning. (p. 549-550)
@subskune
| Quote: | | It turns out to be difficult instead. What I considered to be a weekend synthesis is now consuming weeks. I can't access bromine and brcl not even in
my dreams. |
Bromine can be generated in situ, as well as BrCl.
2 NaBr + H2O2 + 2 HCl ---> Br2 + 2 H2O + 2 NaCl
and:
NaBr + Cl2 ---> BrCl + NaCl
The amount of chlorine in the second example is critical as an excess of Cl2 easily leads to BrCl3. But you should aquire better equipement in order
to handle such mixtures properly. If your apparatus isn't really closed you lose unknown amounts of reagents. EDIT: Do not close an apparatus, as this
is dangerous. What I meant is something like a reflux condenser connected to a hose leading to washing bottles....
[Edited on 27-5-2017 by Alice]
[Edited on 28-5-2017 by Alice]
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Crowfjord
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@ subskune:
I couldn't find any proper solubility data, but from a sterochemical/optical rotation study (in Arkiv. Kemi, Mineral. Geol., Volume8, IssueNo. 2, pp
35) they used 1.2264 g of the d-acid in 10.04 mL of aqueous solution. So it is at least soluble in water to 0.122 g/mL.
[Edited on 27-5-2017 by Crowfjord]
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subskune
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@Crowfjord:
That is super useful! Big thanks! Knowing that the solubility in water > 122 g / l I now know that my experiments did not work out. From 400ml
water 37g of unknown stuff crystallized which means that this is almost all the fumaric acid I threw in.
@Alice:
Good news. I will check this out as soon as the nabr arrives (ordered today).
Since the bromine procedure is well known this seems to be a good and controllable way since bromine is a liquid at room temp. and better water
soluble which makes in situ reaction easier.
Maybe I should get some glassware but its pretty expensive. Therefore a dish with icewater on top of a beaker must do the job.
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Alice
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| Quote: Originally posted by subskune | @Alice:
Good news. I will check this out as soon as the nabr arrives (ordered today).
Since the bromine procedure is well known this seems to be a good and controllable way since bromine is a liquid at room temp. and better water
soluble which makes in situ reaction easier. |
Glad to help. I used HCl just as a suggestion to balance the equation so it's neutral. Any acid (e.g. acetic acid) would do the job. Bromine is a
liquid at room temperature but fumes as hell, literally.
Thread about bromine from NaBr: Link
| Quote: | | Maybe I should get some glassware but its pretty expensive. Therefore a dish with icewater on top of a beaker must do the job. |
Expensive but advisable.
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