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All 13 posts Subject: TMA-2 failure Please login to post Down

POPTART
(Stranger)
11-03-04 02:49
No 539319
      TMA-2 failure

SWIM is totally shit in the head! Here is swim's nightmare:

1. 500ml of calamus oil(from india) is distilled to obtain the asarone (little less than 400ml).
2. buffered performic is done on 211g of asarone + 45.5g sodium bicarbonate + 400ml DCM + (139g H2O2 + 230g formic acid).
3. swim compare the evolution of the reaction as with the usual isosafrole like oil and everything when well.
4. glycol is extracted with dcm and cleaned in the usual manner. DCM is evaporated and glycol concentrated into a brown viscous liquid.
5. For the hydrolysis, SWIM used the HCL method as follows. 270ml MeOH + 450ml H2O + glycol(as is from previous step) and heated to 80 degrees celcius for 2.5 hrs.
6. extracted with DCM and clean in the usual manner.
7. Distilled dcm in water bath then distilled under vacuum the dark brown liquid.
8. Ketone obtained was very viscous (did not solidify in freezer) and golden brown.
9. SWIM was not able to perform a Nabisulfite test to verfy authenticity of ketone, but still continued to the next step.
10. oxime formation using (5.4gNa acetate + 4ml H2O) heated until dissolved. Then added 5g ketone (not verified) + 20ml MeOH. Followed the addition of 2.3g Hydroxylamine HCl. Shaken not stirred and heated to reflux for 1.5 hours.
11. during the whole process, the hydroxylamine HCl never seemed to dissolve.
12. at the end, 10ml H2O was added to the solution and brought to room temperature and finally to the freezer. Upon addition of the water, the dark brown oil reappeared and the previous Hydroxylamine solid dissolved.
Swim's nightmare ends here, the wakeup is terrible, but won't continue onless swim can figure out why this type of dream happened.

That's all fokes, sorry for the disappointment frown

Rhodium
(Chief Bee)
11-03-04 03:55
No 539347
User Picture       Reason for your failure

That is well known, see Post 409525 (Rhodium: "Why asarone cannot be oxidized with peracids", Methods Discourse)

^{The Hive - Clandestine Chemists Without Borders}

POPTART
(Stranger)
11-03-04 13:37
No 539425
      that's not it?

...but the post also mentions that buffered peracetic may work.

There has been reports of people being able to oxidize asarone using buffered peracetic acid, and this is due to the formed epoxide not opening up under the reaction conditions, as the mixture is much closer to neutral than in the unbuffered reaction.

Out of curiousity, I would be curious to know who was able to do it with a buffered solution.
SWIM also performed the buffered oxone and the results contained a lot of red solid polymer.
SWIM's results of the TMP2P is also similar to Post 504222 (otto: "working on asarone", Chemistry Discourse).

Back to square 1.

calcium
(Hive Bee)
11-03-04 14:26
No 539433
      Calamus + Buffered Peracetic

The buffered peracetic, followed by work-up w/ HCl does in fact work.

27 grams of ketone from 41 grams of double distilled calamus oil. Follow Chromic's path.

POPTART
(Stranger)
11-03-04 14:59
No 539439
      But does the performic work as well.

But does the performic work as well. From the descriptions read, everything is similar to the other posts.
Perhaps the dream should be repeated.
What bothers swim the most is the hydroxylamine HCl not dissolving in the solution and the oil coming out of solution after the reflux - obviously nothing happened?
Thanks calcium

hypo
(Balanced Ego)
11-06-04 19:08
No 540049
      the oxime mystery

> Upon addition of the water, the dark brown oil reappeared

don't give up yet. if you search for "oxime oil out", or something like that,
then you'll see that it's a pretty common problem. you can try to extract the
oxime and reduce that. your yields will be low, but that's better than nothing.

MMDA is really nasty in that respect. yields tend to be completely irreproducible.
sometimes you'll get 60% from oiled out oxime, sometimes 10%. it's a bitch.

i really would like to know why this happens and why some substrates are so much
more susceptible to this phenomenon.

HÎ¨=EÎ¨

indole_amine
(Hive Bee)
11-07-04 15:32
No 540205
User Picture       purification?

"yields tend to be completely irreproducible.
sometimes you'll get 60% from oiled out oxime, sometimes 10%. it's a bitch."

Maybe because the oxime is impure, always to a different degree? (that's why one should try and get it to crystallize - or at least distill it..)

And maybe different ketones give rise to different/more impurities upon oximation (or even during their production)?

(Just a thought! wink )

_{indole_amine}

POPTART
(Stranger)
11-08-04 15:31
No 540445
      reading to do

Thanks bees, SWIM did some searching on oximes oiling out and SWIM will carefully read through these.
Adding too much water may make the oxime oil out. Well SWIM is happy to have kept everything. Some cleaning is due.
Will get back with more results.

a la prochaine...

POPTART
(Stranger)
11-10-04 14:29
No 540828
      Found some interesting information while using

Found some interesting information while using TFASE.
Post 356265 (Barium: "Oxime formation", Methods Discourse) and
Post 356287 (Chromic: "Clarifications on Sonson's method", Methods Discourse)

Will be tested out and come back with results.

hypo
(Balanced Ego)
11-10-04 15:01
No 540831
      clarification of the clarification ;)

i don't know what barium's problem was, but it definitely works with
the usual ketones. maybe 2,5-DMP2P is different.

there's one minor point where i have to disagree with chromic:

> If the oxime doesn't crystallize overnight, it ain't gunna...

full crystallisation can take 1-2 weeks, starting at day 2-3!

ps: you should note success by smell: the oxime, even when oiled out, has
that characteristic amine/oxime smell as opposed to the flowery ketone smell.
you can't mistake the two.

indole_amine: what are the boiling points of our oximes? distilling solids
can be quite annoying (if you don't have a short-path distillation thingie).

HÎ¨=EÎ¨

indole_amine
(Hive Bee)
11-11-04 15:45
No 541028
User Picture       purification clarification... ;^)

Many things solidify/crystallize in the freezer, but can be distilled without any difficulties. Think of GAA!

I would guess that the oxime bp lies somewhere between the boiling points of the ketone and the amine... tongue

(I don't remember the bp anymore; but I once vac distilled P2P oxime, years ago)

_{indole_amine}

hypo
(Balanced Ego)
11-12-04 10:50
No 541206
      so...

...did anybody ever distill substituted P2P-oximes? was it worth the hassle/losses?
(i don't care about P2P-oxime since it's probably more or less indestructible, just like P2P)

HÎ¨=EÎ¨

indole_amine
(Hive Bee)
11-13-04 18:08
No 541398
User Picture       substituents *should* be distillable too

Yes, substituents at the wanted positions (especially 2,4,6 substituted methoxy derivatives?) generally make for a higher sensibility towards polymerization.

But I think as long as something oils out at rt, it should be possible to distill it somehow, without great losses (maybe with steam, short-path dist. or just plain high vacuum fractionated rectification? smile ) - at least if the corresponding amine and ketone can be distilled, or don't you think that similar structures do posess similar properties in this case?

_{indole_amine}

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	All 13 posts		Subject: TMA-2 failure		Please login to post		Down


		POPTART (Stranger) 11-03-04 02:49 No 539319				TMA-2 failure
						SWIM is totally shit in the head! Here is swim's nightmare: 1. 500ml of calamus oil(from india) is distilled to obtain the asarone (little less than 400ml). 2. buffered performic is done on 211g of asarone + 45.5g sodium bicarbonate + 400ml DCM + (139g H2O2 + 230g formic acid). 3. swim compare the evolution of the reaction as with the usual isosafrole like oil and everything when well. 4. glycol is extracted with dcm and cleaned in the usual manner. DCM is evaporated and glycol concentrated into a brown viscous liquid. 5. For the hydrolysis, SWIM used the HCL method as follows. 270ml MeOH + 450ml H2O + glycol(as is from previous step) and heated to 80 degrees celcius for 2.5 hrs. 6. extracted with DCM and clean in the usual manner. 7. Distilled dcm in water bath then distilled under vacuum the dark brown liquid. 8. Ketone obtained was very viscous (did not solidify in freezer) and golden brown. 9. SWIM was not able to perform a Nabisulfite test to verfy authenticity of ketone, but still continued to the next step. 10. oxime formation using (5.4gNa acetate + 4ml H2O) heated until dissolved. Then added 5g ketone (not verified) + 20ml MeOH. Followed the addition of 2.3g Hydroxylamine HCl. Shaken not stirred and heated to reflux for 1.5 hours. 11. during the whole process, the hydroxylamine HCl never seemed to dissolve. 12. at the end, 10ml H2O was added to the solution and brought to room temperature and finally to the freezer. Upon addition of the water, the dark brown oil reappeared and the previous Hydroxylamine solid dissolved. Swim's nightmare ends here, the wakeup is terrible, but won't continue onless swim can figure out why this type of dream happened. That's all fokes, sorry for the disappointment



		Rhodium (Chief Bee) 11-03-04 03:55 No 539347				Reason for your failure
						That is well known, see Post 409525 (Rhodium: "Why asarone cannot be oxidized with peracids", Methods Discourse) ^{The Hive - Clandestine Chemists Without Borders}



		POPTART (Stranger) 11-03-04 13:37 No 539425				that's not it?
						...but the post also mentions that buffered peracetic may work. There has been reports of people being able to oxidize asarone using buffered peracetic acid, and this is due to the formed epoxide not opening up under the reaction conditions, as the mixture is much closer to neutral than in the unbuffered reaction. Out of curiousity, I would be curious to know who was able to do it with a buffered solution. SWIM also performed the buffered oxone and the results contained a lot of red solid polymer. SWIM's results of the TMP2P is also similar to Post 504222 (otto: "working on asarone", Chemistry Discourse). Back to square 1.



		calcium (Hive Bee) 11-03-04 14:26 No 539433				Calamus + Buffered Peracetic
						The buffered peracetic, followed by work-up w/ HCl does in fact work. 27 grams of ketone from 41 grams of double distilled calamus oil. Follow Chromic's path.



		POPTART (Stranger) 11-03-04 14:59 No 539439				But does the performic work as well.
						But does the performic work as well. From the descriptions read, everything is similar to the other posts. Perhaps the dream should be repeated. What bothers swim the most is the hydroxylamine HCl not dissolving in the solution and the oil coming out of solution after the reflux - obviously nothing happened? Thanks calcium



		hypo (Balanced Ego) 11-06-04 19:08 No 540049				the oxime mystery
						> Upon addition of the water, the dark brown oil reappeared don't give up yet. if you search for "oxime oil out", or something like that, then you'll see that it's a pretty common problem. you can try to extract the oxime and reduce that. your yields will be low, but that's better than nothing. MMDA is really nasty in that respect. yields tend to be completely irreproducible. sometimes you'll get 60% from oiled out oxime, sometimes 10%. it's a bitch. i really would like to know why this happens and why some substrates are so much more susceptible to this phenomenon. HÎ¨=EÎ¨



		indole_amine (Hive Bee) 11-07-04 15:32 No 540205				purification?
						"yields tend to be completely irreproducible. sometimes you'll get 60% from oiled out oxime, sometimes 10%. it's a bitch." Maybe because the oxime is impure, always to a different degree? (that's why one should try and get it to crystallize - or at least distill it..) And maybe different ketones give rise to different/more impurities upon oximation (or even during their production)? (Just a thought! ) _{indole_amine}



		POPTART (Stranger) 11-08-04 15:31 No 540445				reading to do
						Thanks bees, SWIM did some searching on oximes oiling out and SWIM will carefully read through these. Adding too much water may make the oxime oil out. Well SWIM is happy to have kept everything. Some cleaning is due. Will get back with more results. a la prochaine...



		POPTART (Stranger) 11-10-04 14:29 No 540828				Found some interesting information while using
						Found some interesting information while using TFASE. Post 356265 (Barium: "Oxime formation", Methods Discourse) and Post 356287 (Chromic: "Clarifications on Sonson's method", Methods Discourse) Will be tested out and come back with results.



		hypo (Balanced Ego) 11-10-04 15:01 No 540831				clarification of the clarification ;)
						i don't know what barium's problem was, but it definitely works with the usual ketones. maybe 2,5-DMP2P is different. there's one minor point where i have to disagree with chromic: > If the oxime doesn't crystallize overnight, it ain't gunna... full crystallisation can take 1-2 weeks, starting at day 2-3! ps: you should note success by smell: the oxime, even when oiled out, has that characteristic amine/oxime smell as opposed to the flowery ketone smell. you can't mistake the two. indole_amine: what are the boiling points of our oximes? distilling solids can be quite annoying (if you don't have a short-path distillation thingie). HÎ¨=EÎ¨



		indole_amine (Hive Bee) 11-11-04 15:45 No 541028				purification clarification... ;^)
						Many things solidify/crystallize in the freezer, but can be distilled without any difficulties. Think of GAA! I would guess that the oxime bp lies somewhere between the boiling points of the ketone and the amine... (I don't remember the bp anymore; but I once vac distilled P2P oxime, years ago) _{indole_amine}



		hypo (Balanced Ego) 11-12-04 10:50 No 541206				so...
						...did anybody ever distill substituted P2P-oximes? was it worth the hassle/losses? (i don't care about P2P-oxime since it's probably more or less indestructible, just like P2P) HÎ¨=EÎ¨



		indole_amine (Hive Bee) 11-13-04 18:08 No 541398				*substituents should* be distillable too**
						Yes, substituents at the wanted positions (especially 2,4,6 substituted methoxy derivatives?) generally make for a higher sensibility towards polymerization. But I think as long as something oils out at rt, it should be possible to distill it somehow, without great losses (maybe with steam, short-path dist. or just plain high vacuum fractionated rectification? ) - at least if the corresponding amine and ketone can be distilled, or don't you think that similar structures do posess similar properties in this case? _{indole_amine}

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