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Anthranilic acid from phthalimide using OTC sodiumhypochlorite solution
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Author Topic: Anthranilic acid from phthalimide using OTC sodiumhypochlorite solution
Methaco(s)mic
Hive Bee posted 10-21-1999 06:00 PM
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When it comes to Quaalude chemistry we still have one major victory left: An useful/simple/OTC anthranilic acid from naphthalene synthesis. Rhodium has a long time ago pointed out that phthalimide could probably be converted to anthranilic acid using a commercial NaOCl solution such as "Clorox". So I called my friend Dr Dream, authorized researcher in Europe.
He told me he had not used "Clorox" but a product called "Alclorite", this is pretty much the same as I understand it. But "Alclorite" is preferred (perhaps essential!) because "Clorox" contains tensides (sp?) that we don't need for our purposes. BTW Alclorite is supposed to contain 3.5% (w/w) NaOCl.
In great detail Dr Dream told me about three more or less successful tests:
Test #1
225ml Alclorite and 10.0g NaOH were mixed in a 500ml Erlenmeyer. 8.0g NaOH and 80ml H2O were mixed in another 250ml Erlenmeyer. 15.0g phthalimide was grinded to a very fine powder. The Alcorite solution was cooled to about 0°C, perhaps a bit cooler. Half of the phthalimide was added in portions, the solution was again cooled in the freezer before the rest was added, in portions. When it was all dissolved the solution was a bit yellow-orange.
The 80ml NaOH solution from above was added and the temperature was raised to 80°C and held there for two minutes. Brought it back to room temperature using cold water.
Transferred the mixture to a 1000ml beaker and neutralized it with about 110ml of 10% hydrochloric acid. The pH was 7.0-7.5. A precipitate formed and it was removed by filtration. (After drying in an oven the amount was 1.93g). Now glacial acetic acid was added to the solution, a total of 22ml was used. A lot of CO2 was formed. A mess precipitated and the solution was filtered. Rather dirty but not hopelessly dirty "crystals" were collected. They were dried in an oven at 100°C (darkened a little bit) and before further purification the yield was 8.48g (60,6%).
Test #2
260ml Alclorite (15-2/15 = 225/260, just a thought) and 12.0g NaOH were mixed as above and cooled to -10°C.
A NaOH solution in water was prepared just as above and cooled to +4°C. 15.0g Phthalimid was grinded into a very fine powder and added in portions, while stirring fast, to the Alclorite solution. When it had all dissolved the solution was not more (Alclorite is slightly yellow) colored at all, quite the opposite in fact. The temperature of the solution was now +5°C. Added the 80mls of NaOH solution and begun to heat the mixture. At 30°C it quickly turned rather deep orange/red/brown. Heated it up to 90°C let it cool to 80°C over 5 minutes and then cooled it actively. The solution was much more colored then in Test #1. Neutralized the solution in a 1000ml beaker with a little less then 50ml 30% hydrochloric acid. A precipitate was formed, proceed as above and got 2.34g dirty phthalimide back (It "must" be phthalimide, it will not dissolve in water, has no taste at all (slightly salty but that is because of the NaCl solution it came from), and it look like phthalimide).
Now GAA was added as above, 20ml, which was more than enough. Filtered, dried, and ended up with 11.83g of very, very dirty crystals. 11.83g was more then possible if we consider the >2g phtalimide we got back, and the fact that the solution was colored as hell. Well, the yield of PURE crystals from this will be much lower.
Test #3
210ml cold Alclorite and 8.0g was mixed in a 500ml Erlenmeyer and we cooled it to -10°C. 80ml ~10% NaOH solution was prepared as before and cooled to +5°C. 15.0g Phthalimide as a very, very fine powder was added, all at once, and the flask was plugged and stirred at 1600rpm. The solution became as above not more colored then before, rather less colored. Cooled it again to +3°C. Added the NaOH solution and put the solution in the cold fridge (+3°C). I stood there overnight (yes, even Dr Dream sleeps). Now it was placed in room temperature and left there for 3.5 hours. At ~20°C it was just as achromatic as before. Heated it to 85°C and kept it there for 5 minutes, the solution hardly darkened at all! (2 minutes at 80°C would possibly not be noticeable!). Cooled fast to room temperature, then further to +5°C. Neutralized with 31.5ml 30% hydrochloric acid (this made the solution yet a bit more colored, but not much compared to Test #1). Solution got cloudy, filtered, 2.07g when dry. Now GAA was added (solution in 1000ml beaker!), 15ml was probably enough, but we added 20ml. Nice crystals formed! filtered and dried. Only very slightly yellow/brown, maybe pure enough for whatever uses. The yield was a fair 9.42g (67.4%). When we subtracted for the 2g phthalimide we got back, the effective yield of almost pure crystals was 77.7%!
So if you do just as Dr Dream did, everything should be just fine, but the nice doctor also e-mailed me this step by step method:
1: In a 250ml Erlenmeyer mix 80ml H2O and 8.0g NaOH, cool to about +5°C and don't mess with it until later. To another 500ml Erlenmeyer add 210ml Alclorite (or other ~3.5% NaOCl solution, 215ml is 0.1mol) and cool this to +5°C or cooler. Then add 8.0g (0.2mol) NaOH to the now cold Alclorite solution, by precooling it we prevent the temperature from getting too high. Cool the NaOH/Alclorite solution to -10°C in the freezer (If you check the pH of the Alclorite you will find it to be 12-13, but this doesn't mean that I contains much NaOH from the beginning, a 0.05% solution has pH 12).
2: Grind 15.0g (0.1mol) phthalimide to a very, very fine powder. Now add this to the cold (-10°C) Alclorite solution, plug the flask and mix with magstirrer on fastest setting (or shake). The phthalimide will dissolve within 5 min and the solution will not be more colored than before. Place in the freezer again for at least 30 minutes.
3: Now add the cold NaOH solution prepared above to the cold (not over +5°C) Alclorite solution, nothing happens.
Let stand in room temperature until it reaches 20°C. Now heat to 80-85°C over 10 minutes and hold there for at least two minutes but not more then five. The solution will be a little less achromatic now, but only slightly. Cool in water to room temperature or preferable below so the awaiting hydrochloric acid addition will not heat it up to much.
4: Transfer the solution to a 1000ml beaker, keep some (~20-30ml) in the Erlenmeyer flask. Stir at medium speed on a magstirrer. Now begin to add hydrochloric acid, the ~30% OTC version will do more then fine. You can probably add the first 25ml rather careless. But now you must measure pH, by adding acid drop by drop and using the saved solution (the 20-30ml above) as backup you should eventually have a nice pH 7.0 solution (if you mess this up, a pH above 7.0 is MUCH better then getting it below 7.0). The solution will become a little more colored when you add the hydrochloride acid.
5: At this point your solution has probably become cloudy because of a precipitate, this must be unreacted phthalimide (about 2g) so filter (suction!) and save it. Now you will have a clear solution again.
6: Again add your solution to a 1000ml beaker, make sure the temperature is about +20°C or below. Strirr at medium speed and begin to slowly add glacial acetic acid. If foaming has not begun after the two first milliliters, you probably should have neutralized better above, but just keep adding acid. A lot of CO2 is formed so add it slowly.
15ml will probably be enough, but some extra milliliters will do no harm. The antharanilic acid will precipitate, as you add the GAA.
7: Filter (Buchner, plastic cover to such away solution) and dry the crystals in an oven at +50°C (higher temperature might darken the crystals) for several hours. The resulting powder should be slightly yellow/brown but NOT much. The yield at this point would probably be over 9g. Recrystallisation from water with some decolorizing carbon present will give nice clean crystals.
8: After some runs you can grind up the saved phthalimide and reflux it in water (10-15ml/g, it will not dissolve) for half an hour, then cool and filter to get pure phthalimide ready to be reused.
There might be even better ways to perform this, don't lock your thinking bees. Always assume that every synthesis you find can be improved!
-Methaco(s)mic
methaco_s_mic@hotmail.com (send PGP key or no replay)
The Alchemist
Hive Bee posted 10-21-1999 07:03 PM
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You beat me. I was going to post the synth located in Vogel's for anthranillic acid.
Congrats and happy 'luding!!!
The Alchemist
Hive Bee posted 10-21-1999 07:03 PM
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You beat me. I was going to post the synth located in Vogel's for anthranillic acid.
Congrats and happy 'luding!!!
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"The Godfather of Soul is in the belly of the beast for smokin' that dust at St. Anthony's feast."
Cheapskate
Hive Bee posted 10-21-1999 10:32 PM
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Now if you guys would just find a better way of making the damn o-toluidine! I hate that dissolving metal (iron) reduction.
Rhodium
Pimp Master posted 10-22-1999 10:02 AM
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Thank you methacosmic! I never really liked the literature synths of Anthranilic acid from phtalimide, because they all use BROMINE for the preparation of hypobromite - which I thought was unnecessary when we have OTC hypochlorite in the store just around the corner - and now you proved it was correct!
And remember that phtalimide can be made by heating phtalic anhydride and ammonia, phtalic anhydride by heating phtalic acid, and phtalic acid by oxidizing naphtalene with H2SO4!
Sky
Hive Bee posted 10-22-1999 09:58 PM
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I Tried Oxydizeing Naphthalene to phthalic acid its not as easy as it sound. the Distillation is at higher Temperatures than I like to deal with. You can't beat the O-Toluidine method I'm like Cheapskate if there were an easier way to make O-Toluidine that would help a lot.
Slappy
PimpBee posted 10-23-1999 04:43 AM
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Just buy it. Sure, it's watched, but I can still buy it by the 200 L drum without too much suspicion. Kind of expensive though.
Sky
Hive Bee posted 10-27-1999 06:06 AM
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Could O-Xylene be Oxidized with Premagnate to give COOH in the ortho position then reduced to phthalic acid?
Rhodium
Pimp Master posted 10-27-1999 08:35 AM
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It should be possible to directly oxidize o-Xylene to phtalic acid with potassium permanganate.
Phtalic acid is a benzene ring with two adjacent COOH groups.
Sky
Hive Bee posted 10-27-1999 02:06 PM
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Is O-Xylene Watched or hard to purchase? I know Xyol can be bought OTC as a solvant but it mainly contians the meta Isomer.
Cheapskate
Hive Bee posted 01-18-2000 07:09 PM
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I'm bringing this thread back to life to verify Methaco(s)mic's synthesis. It works.
Now a question, Given that anthranillic is relatively easy, can it be turned into o-toluene? Maybe drag out the old iron reduction and try it?
CS
Rhodium
Pimp Master posted 01-19-2000 10:50 AM
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Unfortunately, I don't think so. Carboxylic acids aren't readily reduced, and especially not all the way to the hydrocarbon (i.e. a methyl group).
Cheapskate
Hive Bee posted 01-19-2000 09:32 PM
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Crap! Well, how much o-xylene is in OTC xylene?? I can get about a ton of this stuff anytime I want. Is this worth a try?
By the way, I tried the reaction above with mail ordered phthalimide. But a question remains.
One of the local suppliers has phtalimide for around US$5.00 a pound. But it's listed differently in their various catalogs. In one place they have phtalamide in the other they have phtalimide. These are different. If I go for a quantity batch, I want phtalImide right? It seems to be easy to convert PhtalAmide to PhtalImide even if I can only get the wrong one. I even noticed this kind of mistake in the write ups on Rhodium's site.
Am I making any sense?
Cheapskate
Hive Bee posted 01-19-2000 09:34 PM
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Also, If I walk in and ask for it...how the hell do you pronounce phtalimide??
is it tal i mid
or f tal i mid
or p tal i mid
or something else?
Rhodium
Pimp Master posted 01-19-2000 09:48 PM
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Ftal-IM-id (according to Websters dictionary)
Actually, in the course of the reaction, phtalimide is converted to phtalamide (phtalic acid monoamide), so the two can be used interchangeably. It's just that phtalimide is cheaper and more common than phtalamide.
Sky
Hive Bee posted 01-19-2000 10:27 PM
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Nitro toluene is easy to make all that has to be done is to remove the O from the NO and replace it with an H. There is at least 4 synthesis to make Meth By removing the OH there has to be a less laboring way to make Methyl Aniline. Does anyone Know how it Done industrially? Could it be possible too acetylate Nitro toluene to form Crystals then hydrogenate it?
Cheapskate
Hive Bee posted 01-19-2000 10:57 PM
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Thanks Rhodium. I'm going to the store on Friday and try not to make a fool of myself. By the way, did the folks have fun with the package I sent a while back?
Sky, I don't follow your thought pattern. What are you suggesting?
Rhodium
Pimp Master posted 01-20-2000 10:52 AM
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Unfortunately, I have not heard from him since then... I'll try to contact him again.
Sky
Hive Bee posted 01-20-2000 11:04 PM
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350,000 tons of aniline is produced in the USA annually, the reduction is carried out through catalytic hydrogenation using H2,Ni.
Cheapskate
Hive Bee posted 01-21-2000 06:04 PM
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Rhodium, MY GOD!! I HOPE I DIDN'T KILL HIM!!
Sky, any idea of the industrial process?? I wonder if a balloon full of H2 with the raney nickel process could do something? I've also looked into disposable glassware for doing this with iron and a quart canning jar seems to work well. Stink disposal can be done with a vacuum pump. Got any suggestions for a stirring device? The overhead drill is noisy and hard to set up. Actually one could keep it stirred up by pumping in air to stir it around.
Hey! Suppose one were to run a tube to the bottom of a quart jar and pump air in, then exhaust it through a tube into the sewer system? I wonder if this kind of bubbling would be enough mixing. The addition of HCl could be done quickly through a cork in the lid.
Any other suggestions? other than to shut up and quit rambling?
Sky
Hive Bee posted 01-21-2000 08:07 PM
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Thats what I was thinking a container that could stand 100psi put in your Nitro Toluene add your Ni pump in 50psi of H2. how does that sound? Filter out Ni purify that should do it. no steam distillation. What do you think?
Cheapskate
Hive Bee posted 01-22-2000 01:54 AM
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I gotta find a source of H2. The Nickel I can get. The container is a pressure cooker.
Teonanacatl
Hive Bee posted 01-22-2000 02:09 AM
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What about Drone's H2 generator?
Sky
Hive Bee posted 01-23-2000 12:01 PM
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Cheapskate if you try this let me know how it work! Give me details or give me death.
Cheapskate
Hive Bee posted 01-24-2000 08:35 PM
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Hold the horses. All of my initial trys for Anthranilic after the first one have failed. I haven't completely tested the first try to see if it was actually anthranilic acid either, this will be done soon.
The problem is control of the temperature. The mix will turn black and create a horrible tar if one is not incredibly careful. I encountered this the first time, but not to the degree all subsequent trys have failed. If the temperature rises above 40C the reaction mixture turns dark and recovery of anything is impossible. This presents a problem if one is to raise the mix to 80C as stated in the write up.
On examination of the reaction details there seems to be a mistake. The reaction was taken from the bromine reaction on Rhodium's page with substitution of sodium hypochlorite for the bromine. The first part of Rhodium's reaction calls for the creation of sodium hypobromite with NaOH and Bromine. In Metacosmic's the same thing is directed. But the Sodium Hypochlorite is already in solution. This would make the amount of NaOH way too high. It could still be neutralized as instructed, but there would be a heck of a lot of lye in there eating away at the phthalimide. In my tries, control of temperature is almost impossible. Only with the addition of ice directly to the reactants and constantly holding the flasks in ice water was the mix possible. Raising the temperature to 80C destroyed the reaction.
I can't understand why the first try worked at all. I must have screwed something up.
Of course this is only a pretend thing, I would never actually do any of this.
Rhodium
Pimp Master posted 01-25-2000 03:04 AM
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It should be a lot of lye, as the pthalimide is supposed to be hydrolyzed to pthalamide.
I don't know about your american brands, but "Alclorite" hasn't got much excess NaOH in it.
Cheapskate
Hive Bee posted 01-25-2000 08:11 PM
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I've tried as little as 1g of NaOH and it still fails. No NaOH at all gives a reaction that performs similarly to the on on your page, but how does one neutralize bleach? It turns the litmus paper white. Then addition of GAA doesn't do anything except bubble away.
I haven't given up yet.
Rhodium
Pimp Master posted 01-27-2000 09:16 AM
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If you neutralize bleach too far, chlorine gas will be given off. Be careful.
Cheapskate
Hive Bee posted 01-31-2000 12:10 AM
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I don't think this synthesis works. I've tried over 50 times now varying the amount of all ingredients over a wide range and all I've gotten out of it is a black mess.
Even at 0C the reaction will eventually fail. I've tried various concentrations of sodium hypochlorite from .5 to 5. Various concentrations of NaOH (including none at all) and didn't even come close to getting a yield of anthranilic. The first try that gave me some hope turned out to be some kind of salt, high boiling point.
I even got some sodium hypochlorite and mixed it myself in dH2O to be sure it wasn't something strange from the OTC liquid (not Chlorox).
Could someone in Europe that has access to Alclorite try this and post the results?
Rhodium
Pimp Master posted 01-31-2000 07:04 AM
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Make a 3.5% Ca(OCl)2 solution out of pool shock and try that instead if your sodium hypochlorite solution is flawed.
I belive in Methacosmic. I know him.
ChemHack
Hive Bee posted 01-31-2000 01:27 PM
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Are you using the Amide or the Imide 
quote:
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"Actually, in the course of the reaction, phtalimide is converted to phtalamide (phtalic acid monoamide)[..]" -PimpMaster
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The Merck lists the Amide as the diamide and the Imide as the monoamide. Perhaps this is the source of the problem ?
ChemHack
Hive Bee posted 01-31-2000 01:30 PM
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Also about the Amide, the Merck says that boiling of the aqueous or alcoholic solution results in decomp into the Imide and Ammonia gas and that the decomp is hastened by the prescense of acid.
It also says that the Imide is "fairly" soluable in boiling acetic acid.
Methaco(s)mic
Hive Bee posted 02-01-2000 03:23 PM
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Cheap - It *DID* work fine for me, I swear.
When I added phthalimide to plain "Alclorite"
it refused to dissolve and slowly turned darker, and darker. I have to add minimum
one mol eq. NaOH to dissolve the phthalimide.
I failed you lude synth several times at first but I didn't question your success, only my own skill.
Rhodium - Thanks, I'm not the kind that would lie for "fame".
Rhodium
Pimp Master posted 02-01-2000 06:06 PM
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Chemhack: My nomenclature may be wrong, but what I meant to say was that the NaOH converts the imide to pthtalic acid monoamide. I just thought it was called phtalamide, but apparently it is wrong.
The phtalic acid monoamide is then converted to anthranilic acid with the hypochlorite through the hofmann rearrangement.
Cheapskate
Hive Bee posted 02-02-2000 01:19 AM
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I guess I was pretty disgusted by black tar! Sorry methacosmic.
When I put phtal I (damnit) mide in the sodium hypochlorite (5%) and stir it, it dissolves. Then a reaction starts and the solution rises to 70-80C with a heavy release of some gas or other. It dissolved just fine. Let this set with stirring and a red sticky crystaline substance precipitates out in about 24 hours. Same thing happens when I try it with 2.5% hypochlorite.
If I follow your instructions to the letter the phtalimide won't dissolve in the NaOH hypochlorite solution until the temperature rises to +5C or so. If I keep it below 0C it just swirls around. I actually waited 30 minutes to see if this would happen. Took a lot of salt and ice. I've actually frozen the NaOH solution and chunked the ice? into the solution to try and keep it cold. If ever the temperature rises to around 40C, it's black tar time. If I keep the reaction around +10C it turns black, just takes longer. What the heck is in this alcorite??
I actually believe you did this, but I sure as hell can't. It's not the money for reactants, that's cheap. It's trying time after time with no sign of success that's wearing me down. That and cleaning glassware!!
Is there some clue someone somewhere can toss me?
Cheapskate
Hive Bee posted 02-02-2000 01:26 AM
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Another thing. I tried this in two steps. First with the NaOH alone to get the mono Amide. And then the hypochlorite. Black tar. Maybe if I could separate out the monoamide somehow. Couldn't come up with a way though.
What kind of pool shock?? I've seen about 23 different brands of this stuff with varying amounts of stuff in them.
Cheapskate
Hive Bee posted 02-02-2000 01:31 AM
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Just to make myself a complete and total pest. I finally managed to do the dissolving iron reduction without the fumes driving me out of the state. It seem as that if one puts the HCl and water and nitrotoluene in a flask and then adds the iron a little at a time, the reaction is much more easily controlled. One can wait until the iron dissolves and add some more using the temperature as an indicator. This keeps the fumes down and you don't wind up with as big a mess. Still have to steam distill it though.
Yes, I had time to try this while cooling beakers full of bleach!!
Cheapskate
Hive Bee posted 02-04-2000 01:15 AM
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Success....maybe.
I took about 150 5% sodium hypochlorite solution and dumped in a table spoon of phthalimide. Nothing unusual about this. Stirred rapidly...waited...waited and the reaction took off as I described above. The solution had darkened, it started to boil and lots of gas was given off it lightened to yellow and gas subsided. Turned on the heat and kept it hot for several minutes, it started to turn red. It got darker so I removed it from the heat and cooled under runing water. There was a red solid floating around. I filtered the sticky stuff. There wasn't much of it, maybe a gram or two. Put this in a test tube added water and tried to dissolve, it wouldn't dissolve, even when held boiling for several minutes.
Waited while I started a couple of unrelated reactions. As the water in the tube started to cool nice clear needle crystals started to form in the water! They grew from the top and bottom toward the middle almost filling the volume of water.
Now, this hasn't been tested yet and I haven't figured how to get the red sticky stuff that was left over, but it certainly looks different and isn't the black tar I've been getting.
If everybody isn't totally pissed at me could they explain what the glacial acetic acid is for in the hoffmanesque reaction methacosmic described? I didn't use it in this at all and can't really see any need.
CS
Methaco(s)mic
Hive Bee posted 02-07-2000 02:28 PM
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CS - Yes you can add more hydrochloric acid and skip the GAA. I got the idéa for this last part of the synth from Vogel V and found it good. Using GAA after the pH is neutral is probable considered better chemistry by most proffessional chemists. The risk of getting the pH waaay to high also diappers.
About the other problems: Tell me in e-mail
exactly where your experience differ from my writeup, we'll figure it out.
-Methaco(s)mic
Rhodium
Pimp Master posted 02-07-2000 05:19 PM
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You surely mean "...the pH way to LOW..."?
Cheapskate
Hive Bee posted 02-09-2000 07:49 PM
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Ok, mail with details sent. I'm actually getting really close.....I hope.
Methaco(s)mic
Hive Bee posted 02-12-2000 10:54 AM
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Rhod: Yes, LOW!!
CS: Thanks, I'll answer soon.
Cheapskate
Hive Bee posted 02-14-2000 07:02 PM
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OK, I did it!! Completely different procedure though. I'm writing it up now and I'll post it in a new thread since this one is getting too long. Sure would have been less work if I could get alcorite. But the method I wound up with can be done in the US by most anyone.
CS
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