Good smell, but makes you numb

[woelen]

This is a funny experiment, I want to share here. This is not because of beautiful colors, but of a very pleasant smell. There is some aftereffect, which can be described as being numb, somewhat floating feeling. It has no adverse effects, if not done too often.

 

First chloroform is made, through the so-called haloform reaction:

Take some chlorine bleach and add acetone. Add 3 ml of acetone to 50 ml of 10% active chlorine bleach. Use the bleach without perfumes or other additives. This will make chloroform. This step may take some time. Just let the chloroform settle at the bottom, until a few blobs are obtained. Collect them with a pipette. No need to purify them, their main impurities are acetone and water. These blobs are used in another reaction, requiring more acetone.

 

The net reaction is as follows, the mechanism behind the reaction is more complex:

CH3COCH3 + 3ClO(-) ---> CH3COO(-) + CHCl3 + 2OH(-)

 

 

Next, dissolve some NaOH (or easier, some KOH) in a few ml of ethanol (96%, not denatured). Set this aside.

Mix your chloroform with four times its volume of acetone and then add a small amount of the ethanol with NaOH or KOH to this mix of acetone and chloroform. Shake very well and cool the mix. Shake well. You will notice a strong rise of temperature, the chloroform and acetone react exothermically, producing a compound, called chlorobutanol, a.k.a. chlorbutol.

 

 

Pour the liquid into 20 ml of ice cold water. You will see formation of an oily liquid and needle like long crystals on top of the water. Take away as much of the water as possible with a pipette, without taking away the oil and crystals (if they are there) and add new water again. Some of the oil may float on the water, some of it may form a blob at the bottom.

 

The net reaction is:

 

CHCl3 + CH3COCH3 ---> CH3C(CCl3)(OH)CH3

 

The mechanism behind the reaction is that the OH(-) ion in alcohol takes away the H from the CHCl3:

 

CHCl3 + OH(-) ---> H2O + CCl3(-)

 

The latter ion is extremely reactive. It attacks the acetone, it attaches to the middle C, where the O is connected and charge shifts towards the more electronegave O-atom:

 

CH3COCH3 + CCl3(-) --> CH3C(CCl3)(O(-))CH3

 

The middle negative charge is compensated by picking a H(+) from water:

 

CH3C(CCl3)(O(-))CH3 + H2O ---> CH3C(CCl3)(OH)CH3 + OH(-)

 

The net effect is that no hydroxide is consumed, it hence is a catalyst.

 

 

What you now have has a really strong and very good smell. It gives a strong cooling sensation and seems to open up your throat and makes you breathe more easily. This is quite a pleasant sensation. If you inhale too much of the compound, then you start to feel numb, and you get a "floating" feeling. So, don't breathe too much, unless you want to sleep.

 

This compound is used in medicine, as a travelling aid for people, who get sick on car or boat trips. They eat the compound in the form of an encapsulated pill. PLEASE DO NOT DO THAT WITH THE MATERIAL YOU MAKE. IT STILL CONTAINS NaOH OR KOH AND ACETONE, WHICH ARE NOT GOOD AT ALL! Sniffing the stuff is fine, and quite pleasant, but DON'T EAT IT. Also don't drive a car or use heavy machines after sniffing this material too much! This is a funny experiment, but don't do foolish things with it.

[YT2095]

I don`t have access to 10% NaOCl, only 5%.

Soooo, do I double the quantity, or can I use some Ca(ClO)2 in with it instead and stick to the 100ml?

 

also you state no detat EtOH, would MEK denat cause a problem if it`s the only denat agent?

[woelen]

With 5% NaOCl you can double the quantity, but I'm afraid that the yield of chloroform will be much less. Chloroform is quite soluble in water, and with such dilute solutions, you may find that most of it dissolves in the aqueous solution. Of course you could distill off the chloroform, but that takes away the nice simplicity of this experiment.

 

First try if working with 5% NaOCl gives sufficient chloroform. If not, you could try making a 5% solution of NaOH, and add Ca(ClO)2 to it. The trouble with that solution, however, is the turbidity of all the calcium in it.

A better alternative may be the following:

- Take some of your 5% solution of NaOCl

- Dissolve some additional NaOH in it (add 5% or so).

- Bubble chlorine gas through this solution, until hardly any chlorine is absorbed anymore

- Finally, dissolve another 2% of NaOH in order to make it alkaline again.

The chlorine you can make with HCl and MnO2, or HCl and TCCA. Only a few hundreds of mg is needed.

 

If you use ethanol, denatured with MEK, then you'll end up with a compound, very similar to chlorobutanol. I also did the experiment with MEK instead of ethanol, and the result is very similar (similar smell, similar appearance), but I'm not sure about the toxicity of the MEK-derived compound.

 

MEK is close to acetone, it is CH3COCH2CH3 instead of CH3COCH3, and the product formed will be CH3C(CCl3)(OH)CH2CH3, instead of CH3C(CCl3)(OH)CH3. I would be careful sniffing the stuff when it contains CH3C(CCl3)(OH)CH2CH3. That single added -CH2- group can make a lot of difference in toxicity.

[YT2095]

yup, it seems I`m going to have to distill it off.

However, Chloroform actually smells quite nice on its own

it`s the 1`st time I`ve tried making it and it`s Worked, all my other attempts made Phosgene, and that Doesn`t smell nice!

 

edit: Bingo! I now recognise the smell a little, it`s Methylene Chloride (Paint stripper) the wife agrees too.

[YT2095]

I`m having to make my own Bleach here now, But... there`s some pics of it to share with you all, so that`s not so bad

 

http://myweb.tiscali.co.uk/yt2095/experiments/aparatus.jpg

 

the jar on the Right is the Cl2 generator and the Silver unit with silicone tube to it is the Air pump to force the Cl2 through into the Next vessel on the left that contains the 5% NaOCl with dissolved NaOH in it.

 

http://myweb.tiscali.co.uk/yt2095/experiments/chlorine.jpg

 

this is what a Liter of chlorine gas looks likes in one go, I`ve put some white paper behind it to show it`s true color more effectively.

[woelen]

It is better not to smell the chloroform too much. Chloroform is a carcinogen. Chlorobutanol is safe, and acetone also is only slightly toxic. That is the reason, why I suggest to use such a large excess amount of acetone, such that the end product certainly will not contain left-over chloroform (otherwise I would not instruct you to sniff the chlorobutanol).

But yes, I agree that chloroform has a fairly pleasant odour.

 

I, btw, also found a synth for chloroform, based on calcium hypochlorite:

 

Synth of chloroform with Ca(ClO)2

 

I must admin, I have NOT tested this myself, I just found this, searching the net for chloroform calcium hypochlorite synthesis.

[John Cuthber]

You show me a safe drug and I will show you a placebo.

 

Anyway, just a handy hint for those looking for details of syntheses on the net. Put the word "flask" in the search string. That will get most of the sites with practical detail and lose a lot of less directly useful stuff.

[YT2095]

well my chloroform turned out quite nicely, although the yield was not quite what I expected (somewhat less), I didn`t think it was going to do Anything at 1`st, then it went cloudy and turbid and started to get quite warm! after about 4 mins, a cold water bath kept the temp nicely cool though, I certainly did NOT expect That! 1`st thought was "Runnaway Nitration" type of events.

 

and it smelled a little more "pleasant" than my original attempt (I think that was methylene chloride).

 

I didn`t know what to do with the excess Cl2 so I bubbled it through some EtOH, it`s changed the smell some what, and I have no idea what to use it for yet as plenty side reactions probably occurred too, it may come in handy as a crude de-greasing agent eventually.

 

John, as Neither Woelen OR I are into drugs of ANY sort (except beer and cigs for me) and are in Extreme opposition to it, I doubt very much this was the motive behind this thread, you are Quite Wrong!

[woelen]

Indeed, I agree with YT. I regard this just as a nice curiousity, and it has nothing to do with drugs (chlorobutanol is not even classified as a drug, and it can be purchased without prescription for relieving people from travelling illness).

 

 

and it smelled a little more "pleasant" than my original attempt (I think that was methylene chloride).

Your initial product also was chloroform, but the smell probably was mixed with an acrid chlorine/hypochlorite smell. The so-called haloform reaction is unique in its property, that only CHCl3 can be formed (or CHBr3 or CHI3 if hypobromite/hypoiodite is used) and not any other halogenated hydrocarbon. So, formation of CH2Cl2 cannot be the case. Search the net for "haloform reaction" and a lot of information pops up. This is quite an interesting reaction on its own.

 

 

I didn`t know what to do with the excess Cl2 so I bubbled it through some EtOH

That makes chloral, CH3C(=O)Cl. When you add some water to this, you get chloral hydrate. Chloral has properties, similar to chlorobutanol, it also makes you numb. But it does not have that nice smell. You will also have side reactions, but the main product will be chloral.

[fattyjwoods]

looks like fun, I can’t wait to make my older brother sniff it!