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Author: Subject: Experimental Preparation of Chlorobutanol
Hermes_Trismegistus
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[*] posted on 27-4-2004 at 15:21
does anyone know the decomposition temperature and products of chlorobutanol?


edit; Internet searches proved fruitless, CRC

[Edited on 27-4-2004 by Hermes_Trismegistus]




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[*] posted on 27-4-2004 at 15:46


Melting point 76*C. Not very good.

It still numbs my tongue though, so it must be chlorobutanol.

I'm going to make a lot now. I bought some SHOCK bleaching powder (65% CaOCl). Oh yeah. I used about 30 grams of it. Will add about 35 ml's acetone, and we'll see what that produces.




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[*] posted on 27-4-2004 at 16:07


Making chloroform with calcium hypochlorite is a real pain in the ass if you dont have a distilling setup. If you are planning on sucking the chloroform out of the reaction mix with an eyedropper like when you use sodium hypochlorite, it is almost impossible because you have a lot of calcium hydroxide precipitate in the same layer as the chloroform. Hydrochloric acid will dissolve the calcium hydroxide leaving a nice layer of chloroform.
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Hermes_Trismegistus
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thumbdown.gif posted on 27-4-2004 at 16:15


Quote:
Originally posted by thunderfvck
It still numbs my tongue though, so it must be chlorobutanol.
.


You're kidding right?




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[*] posted on 27-4-2004 at 18:10


Yes. So that's what that precipitate was...ahh...Truly a pain in the ass indeed. I will have to buy some of this pool bleach stuff. It's like 10.5 NaOCl, looks clear as a whistle, so, until next time.

And if it isn't chlorobutanol, what is it?

I tried recrystallizing it again, it was looking nice, everything was very white. But when all the water was sucked down by my vacuum, it had that wretched orange tint to it once more. Now my yield is pathetic. I must have lost a lot one way or another.




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[*] posted on 27-4-2004 at 19:11


I dont think that Hermes was implying that you do not have chlorobutanol, rather that you should not base the identification of a compound because it makes your tongue numb. A lot of chemicals can make your tongue numb.
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[*] posted on 28-4-2004 at 14:42


Okay, I did it again, this time I made sure everything was kept nice and cool. EXCEPT during one part...when I added the chloroform to the acetone. I was in such a hurry, one of my classes had started and I STILL hadn't left for it...

Anyways, that was in the fridge. I should mention that I used about 12 ml's of chloroform this time.

Afterwards, I just added cold water to it and some precipitate came out. I filtered this but my coffee filters let it all pass through. I noticed I had this oil on the bottom (which was crystal clear, I don't recall it being that clear in previous attempts). So I put it all in my sep. funnel and seperated the oilly layer. Added to this some COLD water and VIGOURSLY shaked it, crystals came out. Filtered and lo and behold, WHITE CRYSTALS! Not a speck of orange. I was quite happy!

Spent a good twenty minutes pat drying it, then recorded a melting point. 75*C. I'm drying it over MgSO4 now, probably not the best salt to use but I don't have any CaCl2, so...

This powder tastes almost identical to the orange one I had made previously, only it has a slightly sweeter taste to it, I find.




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[*] posted on 30-4-2004 at 00:33


I'm fairly certain I have chlorobutanol hemihydrate here. I read that it has a melting point of 78. So my 76 & 75 are fine. I don't understand why my orange yuck product melted at that temperature, though. It's certainly more contaminated than the white. It's probaby because it wasn't dried out enough...I'll take another melting point of the white stuff after it's much drier...

Anyways, I'll be taking some of this next week sometime most likely. Has anyone taken it in a considerably larger dose? Like more than 0.3 g...I know that Haggis had 600mg gel caps, I don't know what he is planning on doing with those, but...

Anyways, I guess I'll stick with 300 mg, see how that works out...I'll take it when I'm awake, and not going to bed. But I have strong feelings that the drug will knock me right out. Anyways, until next week...

Edit: Took another melting point, same thing pretty much. It's pretty sharp. Starts collpasing around 76, melting by 77, by 79 it's fully melted.

When I put the oil in the sep. funnel, and yaddah yaddah, seperated it, well there was a bit left over, so I let it sit in there, thinking I'd collect another day or soemthing. Anyways, I go downstairs today, notice that the oil layer is gone. Hmmph, I wondered, what the hell. Anyways, it was only after about 5-10 minutes, while I was setting up for the melting point, that I noticed something strange coming out of the sep. funnel tube, my crystals! haha. It was beautiful. I had like, 0.5 g worth of crystals just sticking out from the bottom of the funnel. There was one big chunk with a bunch of smaller ones. And crystals were lined all through the tube. I had to go in there to scrape them out! haha, I thought that was amusing. The stopcock was closed, obviously (I had like 450 ml's of water, and 5 ml's worth of oil). The oil crawled out and crystallized!

[Edited on 30-4-2004 by thunderfvck]




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[*] posted on 3-5-2004 at 07:29


Well, I took 0.28 g last night with no affects. I have a lot of trouble sleeping at night, especially on Sunday nights when I have to wake up so freaking earliy on Monday morning. I dosed at 4:15...Went to bed an hour later. Took me until 6:30 to fall asleep which is typical. So the drug didn't do a thing for me! Anyway, next week I'll increase it to 0.5 g and see how that works out on me.

I have a question concerning the emchanism of reaction between the chloroform and acetone. It is base catalysed, and often when it is base catalysed the base remove a hydrogen from the nucleophile which in this case is chloroform. So is this what happens? The OH removes a proton from the chloroform, which then forms an anion (CCl3 -)...Is this right? It would seem to be a very strong base, stronger than hydroxide which would prevent its formation. But perhaps the chlorines have a significant inductive effect which removes much of the negative charge from the carbon. Anyways, help is appreciated.

I'm also having trouble understanding the mechanism for the formation of chloroform - but that's another story. I must first read about chlorates and hypochlorates and read about how they react, etc. I'll know where to come if help is needed..Thanks!




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[*] posted on 3-5-2004 at 17:54


Looks good to me. A brief search indicates chloroform has a pKa of about 25. As for the haloform thing, the reaction appears at least equivalent to having free chlorine and base around. If you find a mechanism involving hypochlorite per se, though, let us know.
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[*] posted on 9-5-2004 at 18:18


Good to see that people are still researching this synthesis. I still have the small vial of product I got from the original attempt, and the subliminated crystals just keep growing all the time. Vacuum distillation or sublimition may be an effective method of purification. In any case I'd still be rather leery about purity of this substance since I am rather sure that there are plenty of side reactions that are going on besides the one that produces the chlorobutanol. IIRC someone at the hive attempted to synthesize this and taste tested it, he claimed that all it did was give him gas and camphor burps! As a sleep aid I'm still unconvinced about its effectiveness, though I never tasted the product because of purity issues.

Keep up the good work, I'll be curious to see where this thread goes.
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[*] posted on 9-5-2004 at 19:36


I'm fairly certain about the purity. The melting point was a couple of degrees below the literature value, it's white, it smells like it, numbs the tongue...I don't know. It seems that what I got is chlorobutanol. As for it being a good sleep aid, I don't know. I have to take more. Maybe tonight. After my homework. 0.5 g. We'll see. Maybe a little salvia to kick it up a notch. HA. :o



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[*] posted on 10-5-2004 at 07:51


Okay. Took 0.5 g. Didn't knock me out. Made me feel pretty strange though...

I think I'm not getting tired because I'm not TRYING to sleep. I'm just sitting on the computer, playing games or whatnot, waiting for the chlorobutanol to knock me out. It would probably work better if I was in bed, reading or something...

Agh.

I'm not going to do this anymore.




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[*] posted on 20-10-2004 at 12:20


I may have made some bromobutanol today. I prepared a large amount of bromine and decided I wasn't in the mood to have terrible eye pain later and it was getting cold outside so I decided to neutralize it.

I took a 500 ml beaker and added roughly 40 g of NaOH to it and added about 100 ml of water and then started pouring in my strong bromine solution with free bromine in it. It all reacted quickly and I was left with an off-yellow solution. But just as I was ready to throw it out I thought, "Well, I'm working on my book project, maybe I could do a quick haloform reaction and take some pictures."

So I added about 15 ml of acetone and let the flask sit for a bit. It went cloudy and started heating up. I lifted it up to see if any bromoform had settled, and indeed some had, but I also noticed solid sodium hydroxide in the bottom of the beaker. Not wanting to affect my haloform reaction I dumped out the contents of the beaker into another. But some of the created bromoform had settled all around the sodium hydroxide which was stuck to the bottom. I set this off to the side and watched the haloform reaction continue.

A few minutes later I looked back into the beaker it had originally been in. The bottom was very hot, much hotter then it had been and it was giving off a very preculiar smell, a series of crystals had formed in the empty spaces at the bottom, small needles jumped out.

I decided to toss it, but I think it could have well been bromobutanol, it was interesting nonetheless. (I also got a small amount of bromoform, it does not appear to be noticeably pure at all, I could not get it to freeze in ice, after an hour in the freezer it got a little slushy, that's all. Maybe it was the small amount.)




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[*] posted on 6-2-2005 at 08:35
Ingestion


I know this self testing is of scientific nature but what are the possible side effects?:o You are talking about halogenated organics that may or may not be pure. I can't help to imagine what affect this has on the liver. Do these materials accumulate? You should start asking these questions before you dose up again. I don't want to be a wet blanket but I see little cautionary measure in this topic.



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[*] posted on 11-2-2005 at 13:50


Quote:

I have a question concerning the emchanism of reaction between the chloroform and acetone. It is base catalysed, and often when it is base catalysed the base remove a hydrogen from the nucleophile which in this case is chloroform. So is this what happens? The OH removes a proton from the chloroform, which then forms an anion (CCl3 -)...Is this right? It would seem to be a very strong base, stronger than hydroxide which would prevent its formation. But perhaps the chlorines have a significant inductive effect which removes much of the negative charge from the carbon. Anyways, help is appreciated.


I've been wondering about the mechanism too. The most plausible to me is that the OH- attacks the chloroform, as the carbanion of chloroform seems to be quite stable, it can be used to prepare carbenes apparently. But this very first step already collides with reaction conditions. In order to have any appreciable OH- concentration, water should be initially present.

Now the CCl3- attacks the acetone forming the alkoxide. Now we are one step away from forming chlorobutanol (which is actually a terribly wrong name for this compound) and that is protonation. And again reaction conditions are unfavorable because we are working in basic environment.

Is there anyone who can shed some more light on this?




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[*] posted on 11-2-2005 at 14:28


Quote:
The OH removes a proton from the chloroform, which then forms an anion (CCl3 -)...Is this right? It would seem to be a very strong base, stronger than hydroxide which would prevent its formation. But perhaps the chlorines have a significant inductive effect which removes much of the negative charge from the carbon. Anyways, help is appreciated.


It is not really surprising. I don't know the actual pKa of chloroform, but a weak base can deprotonate a weak acid to generate a stronger base. This is of course reversible and happens fast, even thou the deprotonation is apparantly thermodynamically unfavorable.

A god example of this is the first step in the synthesis of this "chlorobutanol" - a haloform reaction. The same scenario is seen there, -OH deprotonates (enolizes) the acetone, but pKb of OH- is 5 units less than pKa of acetone, it still works and you can make chloroform...

[Edited on 11-2-2005 by Sandmeyer]




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[*] posted on 1-5-2005 at 19:20


I just think that it would be dangerous to do self testing here. For one, you’re using NaOH, and if it isn't reagent grade than you have probably contaminated your product with heavy metals. How exactly could you set up an apparatus to do a controlled sublimation of chlorobutanol under a vacuum?



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[*] posted on 4-5-2005 at 15:32


Another thing that has been bothering me. I know this is a stupid question, but how is chloroform non-polar? You have a carbon atom surrounded by 3 Chlorine atoms and 1 hydrogen atoms. It seems like this molecule would have a dipole moment.

[Edited on 4-5-2005 by tom haggen]




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[*] posted on 4-5-2005 at 20:09


Chloroform is very slightly polar, tom. The reason it's traditionally classed as a nonpolar solvent is that its dielectric constant is so low (4.8 @ ambient temperatures; by comparison water's dielectric constant is ~ 80), it acts as if it was a nonpolar solvent.

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[Edited on 5-5-2005 by sparkgap]




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[*] posted on 13-1-2006 at 13:56


In personal communication with one of the members of this forum I was told about this thread about chlorbutol and I was asked to post here about my method of preparing this. Several months ago I did some experimenting with this as well, but in quite a different way as described up to now in this thread.

I used an alcoholic solution of NaOH/KOH for the reaction, such that there is much better contact between the reactants and catalyst. Using KOH or NaOH in an ethanol solution makes the reaction quite violent. At that time I also added it to my database of experiments (all the experiment I do and did, I put in a database, which is accessible from the Internet, since I have my website).

http://woelen.scheikunde.net/science/chem/exps/expshow.cgi?i...

Unfortunately, at that time I did not precisely measure the quantities, the only thing I was thinking about was using a large excess amount of acetone, to be sure that most (or all) of the toxic chloroform is destroyed in the reaction.

I only sniffed the stuff, I never taste chemicals :P. I really like its smell and it attracted me :). I had the feeling to sniff over and over again. However, I started to feel funny/light/dull quickly after smelling some of the stuff and at that point I stopped. I think it is not good if your sense of consciousness changes because of some chemical stuff, beit drugs, alcohol or whatever (but that is another discussion, maybe something for whimsy :P).

The crystals I obtained were purely white. All reagents were commercially obtained, so no yellowish CHCl3 from bleach was used, but a nice colorless liquid.




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[*] posted on 13-1-2006 at 15:01


I too used an alcoholic solution of NaOH for the synthesis of chlorobutanol some time ago (I didn't keep any records of the quantities I used). The solutions/liquids were precooled in a freezer for some time. This probably helped 'dampen' the rxn. After mixing the reactants the mixture was again placed in the freezer, with periodical mixing. Product seemed to form much faster (comparable yields in a shorter time I mean) than the 'conventional' procedure (i.e. without ethanol). The product didn't seem affected - should one worry about hemiacetal/acetal formation here due to mixing of an alcohol and ketone under basic conditions?

I too used lab grade chemicals for the synthesis and got pure white crystals which sublimate to give beautiful-looking crystals along the sides of the tube. Love the smell too. I think that, as already mentioned a long time ago (by Hermes IIRC), the acetone might be the cause of the 'yellowish' impurity, due to some rust inhibitor. I once also tried a small batch using homemade chloroform (acetone + NaOCl) which was not distilled or 'purified' by conc. H2SO4 and the chlorobutanol product was still white (acetone used was lab grade).

[Edited on 13-1-2006 by Esplosivo]




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[*] posted on 13-1-2006 at 15:04


Chlorobutanol isn't all that toxic... it seem widely used as a preservative etc.
Check this.
Quote:
Although chlorobutanol is available in a large number of preparations, the incidence of toxicity appears to be low. However, with continued exposure to high-dose chlorobutanol, significant toxicity may occur.



Fishburn & Watson
(J. Amer. Pharmaceut. Assoc., 28, 491-3, 1939)

Quote:
We recommend the following procedure for the preparation of chlorobutanol.

One hundred grams acetone (5 mols) and 40 Gm. Chloroform (1 mol) are mixed, and
7 Gm. potassium hydroxide (5%) dissolved in the minimum quantity of alcohol, are
added. The addition occupies fifteen minutes; cooling is usually unnecessary.

The precipitated potassium chloride is filtered off and washed with a little
acetone.

The filtrate is distilled on the [boiling] water-bath and when no further liquid
distils, about 200 ml. of [distilled] water are added.

The chlorobutanol is filtered off as a white solid.

Yield (calc on CHCl3), 25% theoretical.

The acetone distilled off [can be] used in a subsequent preparation."

Chlorobutanol is slightly soluble in cold water, more soluble in hot water, and
readily soluble in ethanol (acetone, chloroform and numerous other organic
solvents).



Taken from http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/c...


[Edited on 13-1-2006 by chemoleo]




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[*] posted on 13-1-2006 at 18:36


Quote:
Originally posted by Madog
In the body it yields the same chemical that causes the effects of chloral hydrate, a comercial sleep aid. So their effects are identical. Today i made some chlorobutanol, for no reason specificaly.



In the above post(first in this thread) it claims that chloral hydrate and chlorobutanol give the same product in the body, however I have read some info sheets on both stating that chloral hydrate is carcinogenic, whereas chlorobutanol is unknown. So seeing as they both give the same product in the body I would be inclined to think that chlorobutanol would be carcinogenic as well? Or is there a flaw in my logic somewhere?




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[*] posted on 13-1-2006 at 23:25


This depends a lot on intermediates and products in the metabolic conversion of the chloral hydrate to some active form which might not be the same as those for chlorobutanol (especially in the initial stages), together with the fact that unmodified chloral hydrate has a different structure which 'might' interact with pre-oncogenes (genes which might become 'carcinogenic') whereas due to a different structure chlorobutanol might not (assuming the conversion to the active product is not that fast). These are just hypothesis and I might be wrong.



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