Antoncho (Stranger)
12-19-00 11:29
No 76498
      chloroacetic. any suggestions?     

hi its me again asking stupid questions

there are places where they don't sell racing fuel, y'know, ergo a question: what's the easiest way to make chloroacetic acid in big quantities? The FAQ on the Rhod's page says it takes like 50(?) g of it to make 10 g of nitromethane, so...

I remember having seen chlacetic being made by cold chlorination of GAA, but can recapitulate nothing more. And it's of course a major pain in the ass - having to gas such a huge quantity of acid.

The question is:

- anyone can post a viable synth of chloroacetic with all the temps/conditions, please?

- what about Ca(OCl)2? at least theoretically, possible?
(Hive Bee)
12-19-00 13:12
No 76510
      Re: chloroacetic. any suggestions?     

Hi Antocho,

1] Uemura checked the Merck, it refers to Gattermann Wieland, 'Die Praxis der org. Chemikers'.  They produce chloracetic acid indeed via chloration of GAA. Uemura doesn't have the book with him, but as far he remembers, chlorine was bubbled thru boiling GAA under sunlight (oder mercury light) up a certain increase in weight was reached. Further some iodine is needed to make effective use of the chlorine! Thats why commercial products of chloroactic acid are pink! BTW: chloroactic acid is a bit nasty!

2] Nitromethane from chloroacetic acid via Kolbe degradation has bad yields. Gattermann-Wieland give 39% only.

It's not your question, but nitroethan can be made more OTC via the Namethylsulfate and NaNO2. This works reasonable. See the FAQ you mentioned.

Cave Canem! Latin.
(Hive Bee)
12-23-00 06:26
No 77382
      Re: chloroacetic. any suggestions?     


First, let me thank you for the translation you gave us for that patent. I'd seen the reference to that procedure before, but since I don't speak Russian, I pretty much gave up on having that information.

Secondly, I wanted to thank you for asking this question. Essentially what you're looking for isn't really chloroacetic acid, but rather nitromethane. Since that's true, I did a little general search for nitroalkane preparations, and I found some very good stuff. By finding things for you, I found a great deal of things for myself.

Perhaps the most interesting thing I found was the syntheses of nitroalkanes from alcohols. Yes, it looks like, methanol and ethanol can be used as starting material for nitromethane and nitroethane! Thereís even an article in Russian that you could translate (if you donít mind, puzhalyista.)wink

Chem.Ber., 54, 412, (1921)
J.Amer.Chem.Soc., 104, 8, 2296-2300, (1982)
J.Phys.Chem. 87, 9, 1622-1625, (1983)
Pol.J.Chem., 69, 10, 1437-1446, (1995)
Russ.J.Phys.Chem.(Engl.Transl.), 62, 5, 612-615, (1988)
Zh.Fiz.Khim., 62, 1209-1214 (1988)

Take care, and once again, thanks

12-23-00 15:16
No 77438
      Re: chloroacetic. any suggestions?     

wow man i'm flattered, most sincereously so!
As for the article - i'm sorry but i am currently living in a place where there's no such libraries within like a 700 km rangefrownSo... If there is a way to get those articles online, or some bee find it and post a copy of it. In which case i will certainly be glad to have it translated. BTW, i've looked around Hive and found a route with phenylalanine, which brings me to wonder if it is possible to oxidize MeNH2 to MeNO2 with smth like permanganate/chromic salts.
Thank you much for the information you've posted. Keep in touch!
10-17-04 02:17
No 536131
      Chloroacetic Acid To Nitromethane
(Rated as: good read)

An electrolytic chlorination of acetic acid, JACS 46 545-54 (1924):

An improvement over Whitemore's synthesis of nitromethane from chloroacetic acid, JACS 53 234-7 (1931):


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