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All 11 posts Subject: whats chem behind ketamine thermal rearrangement? Please login to post Down

miss_biggie
(Stranger)
03-09-04 23:24
No 494050
      whats chem behind ketamine thermal rearrangement?

I have heard through grapevine that industrial size batches are performed with ethyl benzoate as solvent and the hcl salt of the hydroxylimine. The examples on rhodiums site use decalin and a long chained alkane (zealot).

Apparenlty it does not work with kerosene..

Performing the rearrang. with the imide salt seems to improve yeilds and decrease black tar.

Does the solvent need to be able to donate anything to assist the rearrangement? Are ethyl benzoate and decalin special in any way that would assist with the rearrangement?   Are they "lewis acids"? (excuse my chem-ignorance)

What might that mean about other solvents that might work for the rearrangement?

Vaaguh
(Hive Bee)
03-11-04 13:46
No 494388
      rearangement

The solvents you mentioned are not special in a way that they facilitate the rearangement. They are simply used because of their high boiling points.

The rearangement of the hydrochloride salt seems to cause less polymerization compared to the freebase, another advantage is that it doesnt tend to stick to the
sides of the flask/vessel as much as the hydrochloride salt during the rearangement.

Hippler

miss_biggie
(Stranger)
03-11-04 16:30
No 494414
      Not true, distilled kerosene does not work.

Not true, distilled kerosene does not work.   It doesn't matter how long it's held at the right temperature. And it does solvate the imine. There seems to be no good reason why it doesn't work, that's why I posted.

Rhodium
(Chief Bee)
03-11-04 18:38
No 494432
User Picture       Unknown mixtures are seldom advantageous

But "kerosene" isn't a pure compound. You never know what inhibiting substances are present in it.

^{The Hive - Clandestine Chemists Without Borders}

Vaaguh
(Hive Bee)
03-11-04 19:47
No 494451
      rearangement

Not true, distilled kerosene does not work.   It doesn't matter how long it's held at the right temperature. And it does solvate the imine.

Altough i do agree with Rhodium, could you clarify how you observe that the rearangement did not work?

Also the compound does not need to bee solvated for it to thermally rearange, in fact the ethyl benzoate does not dissolve the methylketimine.

Hippler

miss_biggie
(Stranger)
03-12-04 23:45
No 494727
      I observe by intravenous injection.

I observe by intravenous injection. Plus the solubility and melting point of the imine easily distingushs it from the amine.

The kerosene, which is distilled for the 180-200+ fraction, does not appear to react with the imine. In the end you have a lot of polymerized imine.

So I would guess that either it hinders the reaction or does not posses some property which would facilitate the reaction. Either way there must be some reason besides just temperature to explain it. Yes, I know, the kerosene is a variable, but please don't let that stop anybody from speculating on what helps the rxn go in a different solvent.

Starting from the free imine results in a lot of tarry imine but it does disolve right from the start. Starting from the imine hcl gives maybe 10-20% if you are lucky and it does not disolve, maybe a little at higher temperatures but I think it's most likely a homogenized solution of melted salt. That's trying it over a range of temperatures, stirring, times and solvent volumes. It simply does not work.

So what other otc oils could be tried? I was thinking synthetic bitter almond oil.   There must be other commonly available non-petro oils out there that have a bp > 180'?

miss_biggie
(Stranger)
03-13-04 00:24
No 494738
      Excuse my chemignorance but wouldn't haven't...

Excuse my chemignorance but wouldn't haven't extra hydrogens around, like with a lewis acid, which decalin and ethyl benzoate are (I think), help the O= loosen up??

http://www.meta-synthesis.com/webbook/13_lab-matrix/LAB_matrix.html

Vaaguh
(Hive Bee)
03-13-04 01:18
No 494746
      I dont think that would make a difference,...

I dont think that would make a difference, kerosene has quite some hydrogens around with those 10-14 carbon molecules.

btw did you inject the brown post mixture ? crazy

Hippler

Rhodium
(Chief Bee)
03-13-04 01:25
No 494751
User Picture       synthetic bitter almond oil = benzaldehyde

I was thinking synthetic bitter almond oil

Don't. It consists of benzaldehyde, and it is not suitable for this reaction. You could however oxidize it to benzoic acid and esterify it with ethanol, and there you have ethyl benzoate, which is.

^{The Hive - Clandestine Chemists Without Borders}

Vaaguh
(Hive Bee)
03-13-04 02:28
No 494761
      ethyl benzoate

the practical workup can be found in this post(also found in vogel):
Post 487721 (Vaaguh: "steps 5 to 10", Methods Discourse)

Hippler

k0dog
(Hive Bee)
03-20-04 00:01
No 496217
      My theory

My intial theory is because both decalin, and ethyl benzoate have pi bond in their rings structures. These electrons could be used as temporary relief for the thermal rearrangement.

Now the use of undecane, dis proves this theory altho does undecane posses anything werid about it?

"Vanity is defintely my favourite sin"
-Devil's advocate

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	All 11 posts		Subject: whats chem behind ketamine thermal rearrangement?		Please login to post		Down


		miss_biggie (Stranger) 03-09-04 23:24 No 494050				whats chem behind ketamine thermal rearrangement?
						I have heard through grapevine that industrial size batches are performed with ethyl benzoate as solvent and the hcl salt of the hydroxylimine. The examples on rhodiums site use decalin and a long chained alkane (zealot). Apparenlty it does not work with kerosene.. Performing the rearrang. with the imide salt seems to improve yeilds and decrease black tar. Does the solvent need to be able to donate anything to assist the rearrangement? Are ethyl benzoate and decalin special in any way that would assist with the rearrangement? Are they "lewis acids"? (excuse my chem-ignorance) What might that mean about other solvents that might work for the rearrangement?



		Vaaguh (Hive Bee) 03-11-04 13:46 No 494388				rearangement
						The solvents you mentioned are not special in a way that they facilitate the rearangement. They are simply used because of their high boiling points. The rearangement of the hydrochloride salt seems to cause less polymerization compared to the freebase, another advantage is that it doesnt tend to stick to the sides of the flask/vessel as much as the hydrochloride salt during the rearangement. Hippler



		miss_biggie (Stranger) 03-11-04 16:30 No 494414				Not true, distilled kerosene does not work.
						Not true, distilled kerosene does not work. It doesn't matter how long it's held at the right temperature. And it does solvate the imine. There seems to be no good reason why it doesn't work, that's why I posted.



		Rhodium (Chief Bee) 03-11-04 18:38 No 494432				Unknown mixtures are seldom advantageous
						But "kerosene" isn't a pure compound. You never know what inhibiting substances are present in it. ^{The Hive - Clandestine Chemists Without Borders}



		Vaaguh (Hive Bee) 03-11-04 19:47 No 494451				rearangement
						Not true, distilled kerosene does not work. It doesn't matter how long it's held at the right temperature. And it does solvate the imine. Altough i do agree with Rhodium, could you clarify how you observe that the rearangement did not work? Also the compound does not need to bee solvated for it to thermally rearange, in fact the ethyl benzoate does not dissolve the methylketimine. Hippler



		miss_biggie (Stranger) 03-12-04 23:45 No 494727				I observe by intravenous injection.
						I observe by intravenous injection. Plus the solubility and melting point of the imine easily distingushs it from the amine. The kerosene, which is distilled for the 180-200+ fraction, does not appear to react with the imine. In the end you have a lot of polymerized imine. So I would guess that either it hinders the reaction or does not posses some property which would facilitate the reaction. Either way there must be some reason besides just temperature to explain it. Yes, I know, the kerosene is a variable, but please don't let that stop anybody from speculating on what helps the rxn go in a different solvent. Starting from the free imine results in a lot of tarry imine but it does disolve right from the start. Starting from the imine hcl gives maybe 10-20% if you are lucky and it does not disolve, maybe a little at higher temperatures but I think it's most likely a homogenized solution of melted salt. That's trying it over a range of temperatures, stirring, times and solvent volumes. It simply does not work. So what other otc oils could be tried? I was thinking synthetic bitter almond oil. There must be other commonly available non-petro oils out there that have a bp > 180'?



		miss_biggie (Stranger) 03-13-04 00:24 No 494738				Excuse my chemignorance but wouldn't haven't...
						Excuse my chemignorance but wouldn't haven't extra hydrogens around, like with a lewis acid, which decalin and ethyl benzoate are (I think), help the O= loosen up?? http://www.meta-synthesis.com/webbook/13_lab-matrix/LAB_matrix.html



		Vaaguh (Hive Bee) 03-13-04 01:18 No 494746				I dont think that would make a difference,...
						I dont think that would make a difference, kerosene has quite some hydrogens around with those 10-14 carbon molecules. btw did you inject the brown post mixture ? Hippler



		Rhodium (Chief Bee) 03-13-04 01:25 No 494751				synthetic bitter almond oil = benzaldehyde
						I was thinking synthetic bitter almond oil Don't. It consists of benzaldehyde, and it is not suitable for this reaction. You could however oxidize it to benzoic acid and esterify it with ethanol, and there you have ethyl benzoate, which is. ^{The Hive - Clandestine Chemists Without Borders}



		Vaaguh (Hive Bee) 03-13-04 02:28 No 494761				ethyl benzoate
						the practical workup can be found in this post(also found in vogel): Post 487721 (Vaaguh: "steps 5 to 10", Methods Discourse) Hippler



		k0dog (Hive Bee) 03-20-04 00:01 No 496217				My theory
						My intial theory is because both decalin, and ethyl benzoate have pi bond in their rings structures. These electrons could be used as temporary relief for the thermal rearrangement. Now the use of undecane, dis proves this theory altho does undecane posses anything werid about it? "Vanity is defintely my favourite sin" -Devil's advocate

All 11 posts	End of thread	Top