Sciencemadness Discussion Board - Chloral from Chloroacetaldehyde

Chloral from Chloroacetaldehyde

Daffodile - 10-4-2016 at 08:52

Alright so yesterday I made some Chloroacetaldehyde from Ethanol, and today I hope to Chlorinate it to Chloral, Trichloroacetaldehyde. However, some water got into it, and I don't know if that will effect the final Chlorination (I've heard different things about it.) Should I distill the Chloroacetaldehyde to dry it, or is it fine as is?

Photos are only included to show that this is legit.

[Edited on 10-4-2016 by Daffodile]

blogfast25 - 10-4-2016 at 09:43

Quote: Originally posted by Daffodile

Alright so yesterday I made some Chloroacetaldehyde from Ethanol, [...]

Some information about that part of your process would be welcome.

Daffodile - 10-4-2016 at 12:06

Okay so I took apart some heavy duty batteries, and got two cylinders of Manganese Dioxide, each about 10 centimeters long. I put one in a 500ml filter flask, added 300ml of 31.45% Hydrochloric Acid, stoppered and heated it to 70 degrees Celcius. The side arm tube led into a 250ml RBF attached to a leibig condenser circulating icewater. There was 25ml of Ethanol in the RBF that the Chlorine gas was bubbled through. The setup did its stuff for about two hours, when shut it down and distilled the product. A lot of gas was released as well as some Acetaldehyde at lower temperatures, the remaining liquid distilling between 83 and 87 degrees. The product was Chloroacetaldehyde.

Daffodile - 10-4-2016 at 12:13

Today I chlorinated the product the same way to try and make Chloral. To test the final product, distilled between 90 and 100 degrees C, I added some Sodium Hydroxide. It turned brown, boiled (dissolving the rest of the Hydroxide), precipitated and redissolved a white salt, and precipitated a brown liquid. The brown liquid seemed to be dichloromethane with some chloroform, meaning that the chlorination was not complete. At least I now know how to make DCM.

aga - 10-4-2016 at 12:56

Whether this is all bullshit or not, i quite like the pipe down the centre of the reflux condenser idea, although for other reactions that do not produce a solid.

Edit:

Does MnO + HCl produce any Cl₂ at all ?

I'd have thought it'd just go MnO + 2 HCl => MnCl₂ + H₂O

More edit:

Ah. DIOXIDE. ok.

MnO₂ + 4 HCl = Cl₂ + 2 H₂O + MnCl₂

Edit some more ...

The reaction for EtOH + Cl₂ requires about a 1:3 weight ratio to 'fully' convert to chloroacetaldehyde, giving a max 80% efficiency.

(from J.B. Cohen, Practical Organic Chemistry, 1900 page 99, referencing Liebig, Annalen, 1832 and Dumas, Aim. Chim. Phys. 1834).

Your 25g of EtOH would require a minimum of 75g Chlorine gas to achieve that.

From your figures, a max of 53 grammes of chlorine gas would be produced.

So yes, definitely under-chlorinated.

(especially as the MnO₂ reaction produces ~27g of water in the generator reaction).

[Edited on 10-4-2016 by aga]

gdflp - 10-4-2016 at 13:14

Quote: Originally posted by aga

Does MnO + HCl produce any Cl₂ at all ?

I'd have thought it'd just go MnO + 2 HCl => MnCl₂ + H₂O

It's manganese dioxide. MnO2 + 4HCl --> MnCl2 + 2H2O + Cl2. It only works on some forms of manganese dioxide, some more unreactive forms seem to be unreactive towards HCl.

battoussai114 - 10-4-2016 at 14:17

Battery MnO2 does react with HCl, but it's sort of slow and I never actually bothered going forward with it since there are better ways to generate chlorine and it's inefficient in cleaning MnO2 from glassware.

Daffodile - 10-4-2016 at 15:52

Yeah I really should use TCCA or Calcium Hypochlorite, but I use all my Hypochlorite to make Hydrazine, and TCCA is expensive.

The most interesting part, for me, was that I can make DCM this way, and I havent been able to find it otherwise.

By the way, the rubber tube was attached to a glass tube, or pipet thing, which bubbled the Chlorine. You can sorta see it in the picture.

[Edited on 10-4-2016 by Daffodile]

blogfast25 - 10-4-2016 at 16:24

Quote: Originally posted by Daffodile

The most interesting part, for me, was that I can make DCM this way, and I havent been able to find it otherwise.

How do you know you have DCM?

chemrox - 10-4-2016 at 18:49

for Cl2 generation see prepchem I like the H2SO4 method to avoid the dehydration step (it's a little messy) The H2SO4 will capture the water.

Daffodile - 10-4-2016 at 19:25

Quote: Originally posted by blogfast25

Quote: Originally posted by Daffodile

The most interesting part, for me, was that I can make DCM this way, and I havent been able to find it otherwise.

How do you know you have DCM?

Mostly because of smell, also because of boiling point of the Dichloroacetaldehyde. I checked, and it seems that was most of the distilled product. Also, DCM is insoluble and sinks just like what I separated.

aga - 11-4-2016 at 10:24

Quote: Originally posted by Daffodile

DCM is insoluble and sinks just like what I separated.

Pb behaves similarly

Daffodile - 11-4-2016 at 10:56

Very funny. I'm pretty sure its DCM, because additional to the evidence I got, I also have a strong feeling about it, the sort you get from being around the stuff for awhile. After all, if I left you alone in a room with a bottle of Acetone or Ethanol, it certainly wouldn't take you too long to identify it.

chemrox - 11-4-2016 at 12:35

Quote: Originally posted by gdflp

Quote: Originally posted by aga

Does MnO + HCl produce any Cl₂ at all ?

I'd have thought it'd just go MnO + 2 HCl => MnCl₂ + H₂O

See Prepchem for methods of making Cl2. I may have reponded before-lost track of a "quote" anyway H2SO4 picks up the water so no need for inline desiccators using MgO2/H2SO4 and I tried it and it works

aga - 11-4-2016 at 13:34

Quote: Originally posted by Daffodile

After all, if I left you alone in a room with a bottle of Acetone or Ethanol, it certainly wouldn't take you too long to identify it.

If some half-wit had half-chlorinated my Beer i'd know immediately !

The 95% water would have screwed it right up.

Still, never tried that particular random mix, so perhaps worth a Sip to see if it's any good.

I suspect the Hop flavour would be gone altogether.

Daffodile - 11-4-2016 at 20:31

Quote: Originally posted by aga

Quote: Originally posted by Daffodile

After all, if I left you alone in a room with a bottle of Acetone or Ethanol, it certainly wouldn't take you too long to identify it.

If some half-wit had half-chlorinated my Beer i'd know immediately !

Hey I'm not that much of a half wit, the U2Us were only slightly serious.