Sciencemadness Discussion Board - Experimental Preparation of Chlorobutanol

Experimental Preparation of Chlorobutanol

Madog - 24-1-2004 at 22:32

Chlorobutanol is a seditive, knockout type drug. 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.

First i had to prepare chloroform.
750ml bleech were added to a 1000ml beaker with some crushed ice, it was let to cool and agitated a bit. 15ml of acetone was added to this and it was stirred wit ha stirring rod. I like it sit for about a half hour and it clouded up alot, i stirred it more, let sit, stir, until it had cleared up mostly and there was a bunch of clear non-polar liquid at the bottom. 600ml of the waste was decanted. the rest put into a sep funnel and the chloroform dripped off.
yield: 10ml

the 10ml chloroform, 90ml acetone and 2g NaOH were mixed together in a beaker and set in the freezer for 2h 30 minutes with occasional swirling. the solution clouded up to the point of opacity after the first few minutes. that was filtered to remove the NaOH and most of the excess acetone was distilled off(just a little left). the opaque yellowish liquid left over was poured into cold water and stirred, the liquid at first sank to the bottom then with stiring they formed crystals.

these were filtered and the filter suspended over CaCl2 in a beaker, it looked like the paper got a small rip and some leaked through onto the deciscant, but it may have jsut been water dripping that was forsome reason yellow, or maybe some actualy melted in the warm room. but in the end, the semi-dry yield was 4g. it had some moisture left. 6 capsules were filled with this, each one cointaining 600-800mg of the semi-dry product.

i dont know when i'll get around to testing it on myself, not tonight, and im not especialy keen on doing it on a schll night, and this comming weekend i may not be able to do it. but i will post about it when i do.

[Edited on 1/25/04 by Madog]

[Edited on 1/25/04 by Madog]

Madog - 24-1-2004 at 22:39

nooo! argh! i didnt notice an identical thread half way down the page...

Haggis - 26-1-2004 at 10:12

I too have done experiments with chlorobutanol lately.

My chloroform was prepared from 700ml 6.25% bleach, and 15 ml of acetone. This yeilded 8ml of chloroform.

72 ml of acetone was added to a 250ml beaker and 1.6 g of NaOH was stirred in. There was not a complete dissovation of the hydroxide, and some remained at the bottom after quite a bit of agitation. Then, the 8ml of chloroform was added in three parts and stirred. Almost immediately after addition, the mix turned cloudy. Stirring was done with the end of a zip tie, which is quite convenient.

The mix was placed in the freezer and stirred whenever I thought about it for around two hours. There was still a small amount of NaOH solid on the bottom. I poured this through the filter paper, and as it was going down, it reminded me quite like milk. The filter was discarded and the filtrate put on the lowest setting of a hotplate. I left and came back 30 or so minutes while the acetone heated off. I came back and there was a slightly yellowish liquid sitting in the beaker bubbling slightly, which I predict lost a good amount of product.

The liquid was quickly poured into a beaker of cold water, me not wanting to lost any more product. At first, I was dissappointed due to the lack of crystals or PPT, but after 15 seconds or so of stirring, fluffy crystals started to form. The circular motion of my stirring formed a 'cone' of the crystals in the middle of the beaker, around 2.5 cm high and a a bit wider. Hurray! I probably thought. The crystals were fluffy and reminded me of wax. They were filtered out, washed with cold water, then filtered again.

The odor was something I have not smelt before, so I assume that is what camphor smells like. It is strong, but slightly sweet, with a slight hint of something like licorice. The wet crystals stick together, so I mashed them out on the filter paper so they could dry better.

According to calculations and Madog's results, I should get around 3.2 grams, however it is still wet and I have to wait.

[Edited on 26-1-2004 by Haggis]

Madog - 26-1-2004 at 15:58

mine is reverting back t the liquid in the caps.

a while ago i had made it, and for some reason, i dont remeber, i didnt put it in water, and just put it in a vial. i put this in the freezer to see if it would freeze, it never froze, still have the vial of it, anyone have an explanation for its behavior in changeing states?

IMPURE

Hermes_Trismegistus - 26-1-2004 at 19:53

IMPURE

its not pure. One of the concrete definitions of a pure substance is a sharp freezing/melting/boiling point.

Pure chlorobutanol is a dry colourless/white crystal.

Look on page 100/101 of James Zubricks organic lab survival manual. It will give you detailed instructions for recrystillization. Chlorobutanol will probably best be served by a mixed solvent recrys. etoh/h2o.

Then followed by a sublimation (pyrex pot with dry ice in the center of the inverted lid and slow application of heat on the bottom should prompt crystal growth on the glass knob).

I would not skip the recrystillization step though. The mixed solvent system will most likely lead to an oiling out of your chlorobutanol. Don't worry, its common with mixed solvent systems.

There were some instructions on recrystillization on another part ot this site but were somewhat innacurate.

If you don't have James Zubricks little manual, buy one! it is the best 20 bucks you'll ever spend. Buy it before anything else. It is written in plain english for the average first year student.

It's helped me immeasurably.

[Edited on 28-1-2004 by Hermes_Trismegistus]

Darkfire - 26-1-2004 at 20:05

I think madog and all of us who have been here a long time are used to the edit button never working for a year or so.

Haggis - 27-1-2004 at 12:13

Yea, if memory serves correct, it was about a year ago around this time when the edit function kicked on. Oh well.

After washing my chlorobutanol well, I figured it was time for a slight taste test. I was marveling at not worrying about neutralization and how sensitive this white powder I was filtering was, I am used to other compounds.

I took .02 grams of the chlorobutanol. Then I licked my fingers, and found a strong, chemical, astringent taste. It was pasty on my toungue and roof of my mouth as I did the 'tasting' motion. Soon after, that area of my toungue went slightly numb, attributing to the topical anestetic properites. The chemical flavor was persistant and was dispatched with a few swigs of orange Gatorade.

On a usual night for me, I dream throughout the night, waking up often. I went to bed normally, but when I woke up, I found that the beginning portion of the night seemed to be oddly missing. As if I had forgotten about it, it felt empty.

I really should not be consuming such things, and I appologize to my kidneys. This was just preliminary testing, perhaps I shall do more in depth tests sometime soon. I'll see what else of the properties of chlorobutanol I can whip up for my fellow mad scientists.

Update: my chlorobutanol does not produce a change in pH paper. This can mean that it is close to neutral, or it could also mean that somehow my micro sample didn't register enough to produce a change.

[Edited on 28-1-2004 by Haggis]

Wow Haggis. Your crystals were white huh!??

Hermes_Trismegistus - 27-1-2004 at 16:13

You do seem to have gotten a greater purity than others have(see the original chlorobutanol thread for details)

And I am thinking that the reason may be the longer and more vigorous heating of the oil phase while boiling off the excess acetone. Perhaps the contaminants are even more easily sublimated/vapourized than the chlorobutanol.

Only one way to find out. Fractional distillation to decomposition with either a large amount of product or a microscale kit.

Haggis - 29-1-2004 at 19:10

It ended up to be an exact 2 gram yield. The product was powdered with the flat end of a hot melt gluestick and introduced to a plastic vial, which I sealed tightly. Seeing the ease, cheapness, and potential interesting-ness of this chemical, perhaps I shall and try to produce larger batch quantities. Updates ahead.

AAAARRRRRGGGHHHHH!!!!

Hermes_Trismegistus - 29-1-2004 at 22:20

After attempting this synth I suddenly am simultaneously frustrated and enlightened.

The other chlorobutanol thread shows a common occurence. Getting a discoloured and perniciously uncrystalisable substance yellow substance and getting a pure white product using sloppy methodology.

SWIM used to make herbal extracts when he was alot younger. Alot of herbal extracts and thus had ample opportunity to explore different OTC solvents.

A bane of his existance was this one type of rust inhibitor that he couldn't seem to separate from the various solvents he used, Even by distillation.

but for some reason when he finished his oily herbal extracts instead of boiling off with the sovent as it had done in prior solvent purification attempts, this damned rust inhibitor would remain in the oily emulsion that was so precious to SWIM's employers.

No-one ever knew about this damn rust inhibitor except SWIM. SWIM knew but since the customers loved the resinous extract and didn't seem to notice it, and the employers seemed to love the wonderful texture and smell the rust inhibitor gave to the oily product (as well as increased yeilds). SWIM never told anyone.

But the damn thing still pisses him off to this day.

and then SWIM synths "chlorobutanol" and while the excess of acetone is boiling off he smells something.

A chemically smell with definite earthy undertones. Normally no-one would identify it. But SWIM does. CUZ SWIM has smelled it before.

Its that damn rust inhibitor. THey put it into the metal cans of acetone, and when madscientists use the acetone to make chloroform it seperates into the chloroform and when those madscientists use an excess of acetone with the chloroform to make the chlorobutanol the damn inhibitor in the acetone gets sucked into the damn chloroform before it reacts and then just sits around in solution waiting to be concentrated by evaporation.

I can smell the camphorus odor of the expected chlorobutanol. But behind it I can also smell that damned earthy rust inhibitor.

PISS ME OFF :mad:

to be continued..........

Haggis - 31-1-2004 at 10:27

At 12:00 midnight one evening I weighed out .3g of chlorobutanol into a film canister. Lime gatorade was poured into the canister and the 'shot' was taken. A bit of chlorobutanol was left on the bottom, so I took another one till it was gone.

The flavor was strong and slightly unpleasant, so I drank some more gatorade to dispatch the flavor. Then I sat down and read. After 25 minutes I started feeling 'slow'. I put down my book and layed down.

Then I don't remember much untill waking up around 5 am from a dream. I assume that the minimal amount of CB wore off from my system after around 4 hours, and I started dreaming, then woke up from it after it was no longer holding me asleep.

I then fell easily back to sleep till 12:00. This makes me assume that the amount I took was not sufficient, for my metabolism, to keep me asleep for the entire night, but the remenants of it in my system were strong enough to encourage me to sleep after the full effects wore off.

I won't have a good opportunity to test it's effects again for a while, unless I do it tonight. Note to self: find some empty gel capsules and fill them, the flavor isn't cool.

The_Davster - 21-2-2004 at 17:39

I recently tried this reaction and I got...uh..interesting results. The first time I tried this I used exactly Haggis' procedure, and I got a yellowish product which reverted to the liquid within a week. the second time I tried the reaction I got a pure white precipitate. :cool:

I used exactly haggis' numbers-but not the same procedure. After it was sitting in the ice bath for 2h I filtered it and after the filtering, the filtrate went from milky to yellowish( I dont know why this happened). I put the filtrate into a 125mL erlenmeyer flask, stoppered it, and put it back into the ice bath overnight because I was too tired to finish the procedure that night. The next day the yellow color was mostly gone, it was just very pale yellow. I did not bother with heating off the excess acetone, I just dumped the mix into cold distilled water. After filtering it was pure white. :cool:

. And when I touched a very small ammount of it, my finger felt like it fell asleep.

No results on yield yet as it is still drying.

Madog - 29-3-2004 at 18:53

thats interesting. I'm going to probaly try this again sometime, i'll have to try waht you did.

my capsules with the material half reverted to the oil but styed at that. i still have them. never got around to performing a bioassay.

The_Davster - 29-3-2004 at 20:40

Note: dont air dry it, most of mine evaporated, and dont dry it over drano, turns green. I really got to get a desicator.

Esplosivo - 30-3-2004 at 11:35

Yea, air drying results in loss of the product in substantial amounts. Rogue chemist you don't need to buy a dessicator. Just make one, it is extremely cheap and useful. If you want some info on building one just open a thread or U2U me.

The_Davster - 30-3-2004 at 11:54

Explosivo, first result when I googled "improvised desicator" was on this site, one question though, is road salt(CaCl2 and NaCl) fine to use as is as a desiccant or should it be heated to drive off the moisture?

Esplosivo - 30-3-2004 at 11:57

I personally use home-made CaCl2 mixed with CuSO4. The mixture is heated strongly to remove the water of hydration. I guess this should also work for road salt.

[Edited on 30-3-2004 by Esplosivo]

Geomancer - 30-3-2004 at 12:40

I bought a big jug of CaCl<sub>2</sub> sold for deicing ("Driveway Heat"

. Should work fine, but to ensure freshness you can heat it on the stove. When heated in a metal pan, mine gives off very little water, unlike the masses given off by epsom salts. I used it to dry some Iodine crystals; it worked well (takes some time, though), but I think that was the stuff that I had processed on the stove.

Mumbles - 30-3-2004 at 13:27

The CaCl2 sold around here for icemelting is covered in a layer of something. I think it may be CaCO3. If this is the same stuff others can procure, it's helpful to crush the prills a bit. The desication time is greatly reduced for me.

In the pursuit of anhydrous chlorobutanol.

Hermes_Trismegistus - 26-4-2004 at 11:26

After reading the msds of chlorobutanol (1,1,1 trichloro 2 methyl 2 propanol) It was noticed that most pharmacopeia's list the hemi-hydrate form and only one or two list the anhydrous form.

so.......of course......monkey read.....

The recrystyllization of chlorobutanol has been difficult, the two solvents thats seemed logical to use acetone and xylene don't seem to work real well.

During evaporation of the chosen solvent the vast majority of the product seems to disappear. The scientist is not particularly proficient at chemistry and it took awhile for him to consider the possibility of the chlorobutanol forming an azetrope with the solvent and evaporating away together.

To Be continued....

thunderfvck - 26-4-2004 at 19:53

Interesting thread. I'm in the process of doing this as we speak! MUAHAHAH.

I found a good link:

http://www.monoxyde.org/chemistry/chlorobutanol.txt

Author recommends recrystallizing in ethanol, as it gives clean white crystals. Water can also be used, but from this guy's experience, he recommends ethanol.

thunderfvck - 27-4-2004 at 00:07

Well I'm finished...almost.

750 ml bleach (lemon scented - I had nothing else) with 15 ml acetone. I got about 4.5 ml (very shitty) of chloroform.

45 ml's of acetone was measured, added to a beaker. 1.00 g of NaOH added. Had a great difficulty dissolving it. It wouldn't all dissolve so I proceeded to add the chloroform. Turned milky instantly. Tried to get the NaOH to dissolve, a lot of trouble with this...Put it in the freezer for about two hours, stirring every 10-20 minutes (FINALLY got all the NaOH to dissolve after about 1.5 hours). After the two hours I removed it from the freezer, place it on a hot plate and let it boil.

When it was settling out, I noticed that the milkiness seemed to drop to the bottom while the acetone remained on top. I decanted the acetone/goods and placed it in a beaker. I then proceeded to boil both of them down (one had the milky stuff, the other had the decanted acetone/goods). The decanted one started to turn yellow after awhile. When I felt it was time, I removed both from the heat and added cold water to both. The milky one acted oddly, it became oilish in its structure and white stuff floated to the top. The decanted one dropped out crystals.

I filtered the decanted one and got some yellowish/orange crystals. Dried them up then decided to add more cold water to the milky one. What appeared to be the same crystals popped out from the oilly milk liquid. Filtered these crystals. This must be chlorobutanol, no?

Did a mixed solvent recrystalization with H2O/EtOH. I'm still waiting for crystals to come out, and it's not looking good. It didn't take much hot ethanol to dissolve all the crystals, about 5-10 ml's, and this was the minimum amount. Added some hot water until cloudy (about 1-2 ml's), then added more ethanol to clear it up. Let it sit at ambient temperature. Went out for a smoke, feeling pretty good. Came back inside, still no crystals. The solution is a yellowish/orange color, very camphory smelling (I love this smell...). I placed the flask in the fridge and still nothing. I guess I'll put it in the freezer but I doubt that will help. Hmmm. I guess the stuff is quite soluble in ethanol at room temperature then. But why would this author dude suggest to use ethanol to recrystallize? At the end of the article, someone else mentioned that they used 50% ethanol. I guess I may have to try that one...

Anyways, fun experiment. I finally have basically all my equipment, except my ohaus which I am patiently awaiting...I have a shitty digital that I used to mass everything..ugh. I got my stands today and this opened a whole new dimension. Very exciting.

Hermes_Trismegistus - 27-4-2004 at 09:58

Quote:

Originally posted by thunderfvckAfter the two hours I removed it from the freezer, place it on a hot plate and let it boil.

I then proceeded to boil both of them down (one had the milky stuff, the other had the decanted acetone/goods). no?

Perhaps not, you applied alot of heat to a delicate reaction. Perhaps next time try to keep the reaction cold throughout. Use a vacuum to dessicate or just dry normally while maintaining cold temperatures.

thunderfvck - 27-4-2004 at 11:03

The reaction was kept cold until the boiling of acetone began. Even when I started heating it (at the lowest heat possible) the precipitate fell to the bottom. I think it was just a matter of letting it sit.

Anyways, after putting it in the freezer for like, 5 minutes, MASSIVE precipitate

I added some cold water to get it moving, filtered, pat-dried...Yield was 2.17 g. Slightly orange in color. I haven't taken a melting point yet (I will as soon as I get home...)...But I tried some on my tongue, NUMBNESS!! I'm so excited (and I just can't hide it! Oh no no no, I know I know I know I know I know I want you, I want you).

I think I'll recrystallize it again from cold ethanol (to hell with the mixed solvent), and see how that turns out.

I'll take some in time, in time...

Oh I get it!

Hermes_Trismegistus - 27-4-2004 at 15:07

When you read the literature, you must have assumed that the "distillation" occured at above room temperature and at normal pressure.

And that's why everyone is boiling it.

I have a vacuum pump so I distil acetone at quite a low temperature.

When I didn't have a vacuum pump I did the reaction in the freezer and then used a whole bunch of plates to evaporate off the acetone.

I poured about two or three ml's onto a cool plate, swirled it around and put it to the side, then I would repeat with several more plates.

By the time I went back to the first plate, almost all the acetone would be evaporated.

The pure white crystalline slurry would then be recrystallized and washed with water.

Perhaps your boiling of the chlorobutanol/acetone mix was decomposing it into something else.

That would account for it becoming orange and oiling out.

does anyone know the decomposition temperature and products of chlorobutanol?

Hermes_Trismegistus - 27-4-2004 at 15:21

edit; Internet searches proved fruitless, CRC

[Edited on 27-4-2004 by Hermes_Trismegistus]

thunderfvck - 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.

The_Davster - 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.

Hermes_Trismegistus - 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?

thunderfvck - 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.

The_Davster - 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.

thunderfvck - 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.

thunderfvck - 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]

thunderfvck - 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!

Geomancer - 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.

blazter - 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.

thunderfvck - 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.

thunderfvck - 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.

BromicAcid - 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.)

Ingestion

chloric1 - 6-2-2005 at 08:35

I know this self testing is of scientific nature but what are the possible side effects?

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.

vulture - 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?

Sandmeyer - 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]

tom haggen - 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?

tom haggen - 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]

sparkgap - 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.

sparky (^_^)

[Edited on 5-5-2005 by sparkgap]

woelen - 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

. 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

).

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.

Esplosivo - 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]

chemoleo - 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]

The_Davster - 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?

Esplosivo - 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.

jon - 19-1-2006 at 20:49

has anyone messed around with clomethiazole I hear it's a superb hypnotic it's made from vitamin b-1 thiamine.
you split off the thiamine with sodium hydrosulfite to yeild the pyrimidine portion which crystalizes. seperate that. then you you perform acid base work up on the sulfurol 4-methyl-5-hydroxyethyl-thiazole this you chlorinate to yeild clomethiazole not scheduled not an analouge of any controlled substance so no way to schedule it.
you can chlorinate with thionyl chloride or by heating in a sealed tube with conc. HCl at 140 celcius for three hours and then workup.
very potent stuff.
very tricky to crystalize though it only forms salts with ethylene disulfonic acid.
though there are some literature reports of it forming crystalizable salts with HCl.

[Edited on 20-1-2006 by jon]

Mechaton - 21-5-2006 at 13:09

Hey, I actually have something useful to add! I know a fairly easy way to purify the nasty orange crud generally obtained from making chorobutanol with readily available reagents.

First, get a baby medicine syringe with the bottle adapter and some standard glass capillary tubing. The tubing should fit inside the bottle adapter so you can use the syringe to pull liquid into the tube. You'll need this later.

To purify the orange crystals place them in a round bottom flask and swirl it a bit to cover the bottom. It's fine if the crystals are a little moist. Sit the flask about a quarter way into a sand bath, so there is a good bit of flask left in the cooling air. Stopper the flask and apply a decent bit of heat. The chlorobutanol will start to sublimate. With continuous moderate heat the vapors will form fluffy white crystals all over the upper part of the flask. Keep the heat up until a dark orange liquid forms in the bottom, though you'll probably need to peek through the stopper to see it given how many crystals you'll get on the flask.

This liquid is partially molten chlorobutanol but if you fiddle with the heat right and wait for maximum crystal growth it'll be mostly waxy impurities. Now it's time to use your syringe doohickey. Unstopper the flask and stick the capillary tubing down into the liquid. Be careful of crystals blowing out of the hot flask, but it won't be under too much pressure. Use the syringe to draw the liquid out of the flask and into the tubing. Try to avoid getting it in your syringe, because its going to harden and you're going to have to dip the tubing in boiling water to get it out later on.

When you have as much liquid as you can get very carefully take the flask out of the hot sand and let it cool. The remaining impurities will cool and stick to the bottom of the flask. The pure crystals will be stuck to the sides of the flask above the line of the sand bath. When the flask is cool you can flip it over and smack it lightly to get most of the chlorobutanol crystals out. For the rest just wash the inside of the flask with water. Neither waxy impurities nor chlorobutanol dissolve well in water, but the crystals wash off whereas the wax sticks to the glass. The wax can be removed from your flask by pouring in a handful of BBs with a little water and swirling it Vigorously.

I hope that technique is helpful and not hidden somewhere else on this forum. It produces beautiful white crystals with asharp melting point from the home-made chloroform, department store acetone, and lye catalyst method.

[Edited on 21-5-2006 by Mechaton]

Renaissance Man - 30-1-2011 at 11:25

Quote: Originally posted by Hermes_Trismegistus

STABILITY: the half-life at 25 for chlorobutol(chloretone) in a solution buffered at pH 3 was calculated to be 90 years, whereas at pH7.5 it was 0.23 year.

Similarily for the decomposition in aqueous sol'n when heated for 30 min at 115 degrees was calculated to be 13% at pH 5 and 58% at pH 6.
--- A.D. Nair and J. L. Lach, Journal of the American Pharmaceutical Association, scient. Edn., 1959, 48, 390.

A 0.5% sol'n of chlorobutol with a pH of 5 to 6 lost 10% of its potency when stored for six weeks at between 25 and 30 degrees. Neutral or alkaline sol'n's were less stable.
--- N.V. Patwa and C.L. Huyck Journal of the American Pharmaceutical Association, 1966, NS6, 372.

[Edited on 14-1-2004 by Hermes_Trismegistus]

Given this I think it is probably a bad idea to be heating it to distill the acetone as many of us are doing, unless the non-hydrate is much more stable, I think (correct me if I am wrong) these figures are all on the hydrate as it is listed as being in aqueous solution.

I used 50 ml of acetone, .6 grams of lab grade NaOH (just bit more mols catalyst per mol chloroform than the 1 gram of KOH which was reported to be the ideal quantity for 5 ml of chloroform) and 5 grams chloroform. I used mass so it is a bit less than 3.5 ml equivalence. I added a bit of methanol to help dissolve the sodium hydroxide in the mixture. Everything was damned near dry, the acetone and chloroform was dried with anhydrous Magnesium sulfate overnight. Reaction temperature was always between -4 to -8 C.

During the reaction the liquid became cloudy as expected, a bit like coconut milk. I put this in the freezer to let it settle out a bit. The vast majority fell out quickly as a fine white powder, but there was still a bit of cloudiness after 30 minutes. Decanting once or twice is diffidently the way to go unless you have some kind of small scale vacuum filtration device like a Gooch crucible setup, after the first decantation 2 coffee filters work pretty fast and then a piece of folded lab filter paper to get the last bit out.

I was a bit foolish and added cold water with a bit of HCl to the acetone mixture right after filtering in hopes of improving stability before distillation; it was at a pK of 2-3 afterwords. I noticed when It was heated there was a small amount of oil on the bottom, but when stirred it disappeared. In the end this procedure yielded nothing after an attempt to crystallize anything cooling, adding ice water did not help.

I then tried to recover anything I could from the filtered precipitate. I added near freezing water, nearly all of the precipitate (which is what I think was almost all sodium hydroxide) went into solution. However I noticed that floating in solution were these small flake-like crystals beautify glittering as they floated around. I filtered this once and washed the crystals with a bit of ice water. I was left with a small off white pile of amorphously packed crystals, and as the filter paper dried all the way I noticed that it sparkled as I turned it in the light, as if there was clear sequence or glitter powder on it. I scraped off what I thought looked like 2-3 mg and put it on the tip of my tongue. A strong astringent taste which was mostly what I think to have been residual NaOH, but after 5 seconds an unmistakable numbing of the tip of my tongue was noticed. Not the kind from chemical astringency, more like having a menthol cough drop but without the flavor, maybe something like a phenol based product like chloraseptic.

I strongly suspect that this was chlorobutanol. I am just wondering if anyone knows why the NaOH percipitated like it did, it was in solution prior to this, did it undergo reaction to NaCl or something? I would doubt it but besides the possibility of the chlorobutanol displacing it from solution that is all I can think of.

atomicfire - 7-2-2011 at 09:38

I've been browsing these forums for awhile now, and just recently decided to test some things out I saw on here, this synthesis being one of them.

I took ~90ml acetone and about 0.5g NaOH and placed them into a 150ml beaker. I added 10ml chloroform(acs not stuff I made) and let this stir on a stirplate for a while. After a few minutes it went 'milky' and I could see a precipitate. I let this stir for about 30min.

Having done this on a friday and having more things to do, I let this sit in a fume hood with a watchglass over it so the leftover acetone/chloroform or whatever was left could evaporate. Monday I found a small mass of white(not snow white, but not off white) precipitate still very wet. I let this sit in a dessicator for a few hours to try to dry it some more, but the mass still had some liquid in it. I tried a melting point test on it and it seems to be around 75C.

This looks like I got something similiar to a previous poster. Any thoughts on what to do to 'purify' it or what exactly do we have here?

[Edited on 7-2-2011 by atomicfire]

Paddywhacker - 24-2-2011 at 01:29

Hey, what does the acetate ester of chlorobutanol smell like?

Eclectic - 24-2-2011 at 15:14

Seems it might be advantageous to neutralize the alkali with HCl before workup.

I Like Dots - 5-7-2013 at 17:25

Hey guys,

I had a go at this synthesis, and like most was left with slightly yellow, watery crystals. I noticed a lot of argument about what chlorobutanol should look like, so here you go!

I recrystallized in pure MeOH and had this in a few days after sitting in the fridge.

I dissolved 4gm of wet crystals in ~20ml methanol. enough to completely dissolve and then some.

Then I placed it in the refrigerator and "forgot" about it for a few days.

This is what it looked like after 2 days:

Final yield was 1.5 grams, I will try to purify the top layer that started forming and creeping up the sides.

[Edited on 6-7-2013 by I Like Dots]

sargent1015 - 12-7-2013 at 09:23

That is simply beautiful! Reviving an old thread to finally show us what the compound looks like was a good idea. I wonder if some of those 2006 posters are still on the forum.

Now I am tempted to try this... Just for the pretty crystals

bfesser - 12-7-2013 at 09:39

<strong>I Like Dots</strong>, thanks for the contribution. Photos of pretty crystalline products are always appreciated. Those remind me of the jar of basement <a href="http://www.magusbooks.com/category/Herbs" target="_blank">'new-age' bookstore</a> <img src="../scipics/_ext.png" /> grade <a href="http://en.wikipedia.org/wiki/Menthol" target="_blank">menthol</a> <img src="../scipics/_wiki.png" /> crystals I have stored away in my closet awaiting purification.

By the way, for anyone in the Twin Cities, MN area; that shop is a source for small amber Polyseal® bottles and some basic reagents (menthol, sulfur, camphor, etc.)—if you don't mind the pagans and incense.

[Edited on 7/12/13 by bfesser]

softbeard - 23-7-2013 at 18:41

Through my own experimentation, I found a good way to get most of chlorobutanol to crystallize out of water is to salt it out with magnesium sulfate. Following the standard preparation using excess acetone [basis: ~ 75 ml acetone] (3-4 parts acetone/ 1 chloroform, by volume), small quantities of NaOH, and was allowed to reflux for ~ 30 min. Further, small portions, of NaOH were added until there was no more refluxing. The resulting yellowish milky product was heated until most acetone was distilled off. To this, about 100ml tap water was added, enough to dissolve all the NaCl/sodium formate. This resulted in a two-phase system. The organic phase (deep red) was separated and further heated to evaporate residual acetone/chloroform. A semi-crystalline mass resulted with a strong odor of chlorobutanol.
The aqueous phase was saturated with magnesium sulphate. After ~10 minutes, it precipitated copious amounts of chlorobutanol hemi-hydrate, which was filtered and washed with water.
I realize this is a very qualitative description, but thought it might be useful. Frankly, for chlorobutanol preps, there is probably little reason for quantitative descriptions.
For purification, I think recrystallization from aqueous magnesium sulfate might be one of the more efficient routes.

softbeard - 25-7-2013 at 11:56

I forgot to add; pH control is, of course crucial here. Make sure we're on the neutral-acidic side with HCl, or your favourite acid, prior to adding magnesium sulfate.

I Like Dots - 20-8-2013 at 13:45

Now im thinking about other this reaction with other halogens.. I saw bromic acid possibly produced bromobutanol ( Chemspider calls it brometone) id like to try that as well.

From PubChem
"PREPD FROM ACETONE & BROMOFORM IN THE PRESENCE OF SODIUM OR POTASSIUM HYDROXIDE."
So basically same process.

Interestingly i could only find sparse info on the iodine version. (iodobutanol?) but im assuming it would be the same again.

edited for formatting.

[Edited on 20-8-2013 by I Like Dots]