Ethylene glycol --> chloroacetic acid

[ning]

Well, here's another wild one for ye'all out there. Continuing on the same dream-thread of ethylene glycol as versatile precursor, here is ning's idea for chloroacetic acid, useful for making exotic poisons and modafinil, as well as malonic acid and its esters.

No documentation yet, hope to have some soon.

Ethylene glycol --> ethylene chlorohydrin
ethylene chlorohydrin --> chloroacetic acid

First, hydrochlorination of ethylene glycol, by use of NaCl and H2SO4, with catalytic acetic acid.

Second, oxidation of ethylene chlorohydrin with a suitable oxidizing agent to carboxylic acid.

Ning suspects the usual suspects would remove the -Cl group. This is bad. The oxidation should probably bee done in acid conditions. Perhaps acidic KMnO4 or better, nitric acid.

Would this work?

[Mountain_Girl]

Another use for chloroacetic acid is the synth of nitromethane.
Can I extend homologuously [ ] and suggest that propylene glycol may give nitroethane by this route [from chloropropionic acid] ?

That is assuming the oxidation details can be sorted satisfactorily [for which I can contribute nothing unfortunately].

Nice posts
you've been
posting ning.

[Rhodium]

Post 469021

(roger2003: "Nitroethane from chloropropionic acid", Chemistry Discourse)

[ning]

Why thank you, Mountain Girl ^^

Here they are, people--a few refs to chew. Unfortunately, only a few, but enough to show it's possible.

Ning searched for HO.CH2CH(X).(ALH)2 --> HOOCCH(X).(ALH)2

The results are divided into three main types:
- K2Cr2O7 / H2SO4
- KMnO4 / NaOH
- HNO3

Most of the refs are for chromic acid, but since we here at the hive are environmentally conscious, I'll neglect those unless requested.

I. KMnO4 reactions
2-fluoroethanol --> fluoroacetic acid: Zh. Obshch.Khim 19, 111. Chem. Abstr. 1949, 6164 ; Kogyo Kagaku Zasshi 1955, 335. Chem. Abstr. 1956, 4063

several fluoroalcohols: Mol. Cryst. Liq. Cryst. 1991, 129

II. Nitric acid

Bull. Soc. Chim. Fr. 1876(!), 24
JACS 1950, 4353
USPT 2455405
Eur. J. Org. Chem. 2003, 526

III. Other

DMDO: Russ. Chem. Bl. 2000, 1332. Izv. Akad. Nauk Ser. Khim. 200, 1338.

They also used NaIO4/RuCl3, but I doubt y'all care about that.

Ning wonders whether KMnO4 under acidic conditions would work, or sodium persulfate + dilute sulfuric acid.
Hell, probably acidic bleach would work.

Polverone would be happy to know that HOEtF was one of the substrates oxidized.

[ning]

I knew I'd find some little bugger floating around here somewhere! Look:

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0166

Organic Syntheses, CV 1, 166 : beta-CHLOROPROPIONIC ACID, from  Trimethylene Chlorohydrin via Nitric Acid oxidation.

75% yield.

I'm sure this process could bee adapted to our needs....

[Rhodium]

Note that the Org. Syn. procedure above is for turning 3-chloropropanol to 3-chloropropionic acid^*, not 2-chloropropionic acid (which is the isomer which can be used as a nitroethane precursor - only alpha-nitro acids decarboxylate easily to nitroalkanes).


* The GHB receptor agonist codenamed 'UMB66', recently mentioned in

Post 506013 (missing)

(7is: "More GHB ligands", General Discourse)

[ning]

I just wanted to find a procedure that oxidized a chloroalcohol to a chloroacid with nitric acid  

Nonetheless, interesting to realize that...