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All 8 posts Subject: 10 degree difference? Please login to post Down

humidbeing
(Can't SWIM)
05-25-02 00:14
No 313785
      10 degree difference?

Okay, swim did a iso run on oil not knowing temp at which saf would come over, but water was at 96-97 or so (Saf was freeze purified). The different procedure wa given by a reputable longtime bee who swim can't contact at the moment.

120 gms of saf and 4.5 gms of flake KOH were first boiled at 232C for 20 minutes or so with the whole flask insulated to prevent h2o condencing on wall or neck of flask. Cool down, then dist set up, and temp inside contents slowly brought to 200C with strong mag stirring for 6 hours which were 2.5 hours past the suggested time by elder bee to be safe. Temp was brought up slowly over 45 mns past the 6 hour point, then had forerun of what appeared to be water/oil mix (azeotrope?) of a few MLs, then temp went to 246 and the rest came over at this temp without ever going higher. The distillate was clear and smelled right. A couple of drops were dropped into the saf from which it had came, which resulted in downward "trails" which before getting to the bottom of the glass, assimilated into the saf.

Big question is the temp range at which it came over. The thermometer is located just below the 3-way outlet as it has a 10/30 joint. Swim has been on tfse but this kind of 10 degree difference with that amount of distillate... Either the small amount of water failed the rxn, while creating an intermediary, or it was a good rxn and the ten degree diff isn't abnormal. Thanks bees!

See the problem is that it meets Osmium's test in newbee forum (dumb question) but fails the 20 degree diff in BPS!

CG I miss you sweety, I really do.

Rhodium
(Chief Bee)
05-25-02 02:26
No 313840
User Picture       Cis & Trans Isosafrole

By boiling your isomerization reaction mixture for so long at such a high temperature, the cis-isosafrole (bp 253°C) initially formed by the isomerization of safrole reacted further and was apparently quantitatively converted to trans-isosafrole (bp 246-247°C).

When using the more common isomerization methods with a very short reflux (15 min at 230-250°C with KOH/CaO) or at a low temperature (4-12h with 2% KOH under vacuum at 120-130°C), only a part of the higher boiling cis-isosafrole overcomes the energy barrier to be converted to the lower boiling trans-isosafrole, and thus the observed boiling point for the isosafrole cis/trans mixture usually lies closer to 253°C than 246-247°C.

humidbeing
(Can't SWIM)
05-25-02 05:02
No 313904
      so..

So really, if swim uses hydrolisis with 15% h2so4, it
should make no difference in conversion to ketone, yes?
Thanks rhod, I know the answer already.

CG I miss you sweety, I really do. cool

Rhodium
(Chief Bee)
05-25-02 09:03
No 313955
User Picture       It is the same stuff

Both the cis- and trans-isosafrole react alike, so regardless of which method you use for oxidation (performic, peracetic or oxone) followed by the H₂SO₄ hydrolysis, you will get exactly the same product ketone, our beloved MDP2P.

Osmium
(Stoni's sexual toy)
05-25-02 23:29
No 314189
User Picture       I thought the cis iso has a lower BP, since it is ...

I thought the cis iso has a lower BP, since it is always in the forerun?!
I'm not fat just horizontally disproportionate.

Rhodium
(Chief Bee)
05-26-02 02:37
No 314267
User Picture       bp

I did a websearch, and came up with those numbers (I was also surprised). I'll check again.

Rhodium
(Chief Bee)
05-26-02 17:27
No 314464
      Isosafrole and schizophrenia-like psychosis

This time I checked, the only data I found supporting my earlier claim is in the Safrole FAQ at my page ( https://www.rhodium.ws/chemistry/safrolefaq.txt ), the bp is mentioned more than once, first in the vicinity of its Beilstein reference, (which I can't read, Beilstein is is the most expensive form of steganography ever invented), and once near a ref to an old american chem journal (which I don't have access to). Osmium, could you please check Beilstein "19(3), 273", "19(4), 273" and "19 1, V, p 553" as those are the three beilstein references on isosafrole I've managed to dig up tonight, at least you know the language they have encrypted the encyclopedia with.

The Merck monograph says the trans isomer has bp760 253°C, bp100 179.5°C, bp20 135.6°C, bp3.4 85-86°C, and the cis isomer bp3.5 77-79°C.

Now I wonder which one is correct. Merck has been wrong before (I spotted 11 errors in the 12th edition, not counting spelling mistakes), and probably not too many chemists write to Merck and complain about their List I substance "boils 6-7°C too low".

I couldn't find any bp data in the TCI, Acros or Sigma-Aldrich catalogs either, as all of the companies which actually stock isosafrole only have an unspecified mixture of both isomers. An interesting thing to note is that TCI of Japan list isosafrole's flash point as 92°C, while Acros of Belgium list it at 110°C and Sigma-Aldrich (US) lists it as >230°F (>110°C). If it were only the latter two measurements I would buy the reasoning, but a 20°C difference between the hemispheres is a bit too much in my opinion to be trustworthy. Who burns isosafrole on purpose by the way, just to be able to jot down its flash point? At least Sigma-Aldrich has sense enough to write boiling range 77-86°C/3.5mmHg for their 97% pure cis/trans mixture, as that is the boiling point extremes for a mixture of the isomers.

I found something amusing while on the net too. Don't try this at home! "Schizophrenia-like psychosis" is not synonymous with tripping your ass off!

Isosafrole and schizophrenia-like psychosis
American Journal of Psychiatry, 141(8), pp 997-998 (1984)

Abstract A 19-year-old man developed a schizophrenia-like psychosis after ingesting isosafrole. His use of amphetamines and LSD failed to produce a similar syndrome. Isosafrole may provide another biochemical model for schizophrenia.

http://ajp.psychiatryonline.org/cgi/content/abstract/141/8/997

Rhodium
(Chief Bee)
03-26-04 08:26
No 497471
User Picture       About the boiling points

I just felt a link to the following post would be pertinent in this open-ended thread: Post 385627 (Rhodium: "Isosafrole Physical data", Newbee Forum)

^{The Hive - Clandestine Chemists Without Borders}

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	All 8 posts		Subject: 10 degree difference?		Please login to post		Down


		humidbeing (Can't SWIM) 05-25-02 00:14 No 313785				10 degree difference?
						Okay, swim did a iso run on oil not knowing temp at which saf would come over, but water was at 96-97 or so (Saf was freeze purified). The different procedure wa given by a reputable longtime bee who swim can't contact at the moment. 120 gms of saf and 4.5 gms of flake KOH were first boiled at 232C for 20 minutes or so with the whole flask insulated to prevent h2o condencing on wall or neck of flask. Cool down, then dist set up, and temp inside contents slowly brought to 200C with strong mag stirring for 6 hours which were 2.5 hours past the suggested time by elder bee to be safe. Temp was brought up slowly over 45 mns past the 6 hour point, then had forerun of what appeared to be water/oil mix (azeotrope?) of a few MLs, then temp went to 246 and the rest came over at this temp without ever going higher. The distillate was clear and smelled right. A couple of drops were dropped into the saf from which it had came, which resulted in downward "trails" which before getting to the bottom of the glass, assimilated into the saf. Big question is the temp range at which it came over. The thermometer is located just below the 3-way outlet as it has a 10/30 joint. Swim has been on tfse but this kind of 10 degree difference with that amount of distillate... Either the small amount of water failed the rxn, while creating an intermediary, or it was a good rxn and the ten degree diff isn't abnormal. Thanks bees! See the problem is that it meets Osmium's test in newbee forum (dumb question) but fails the 20 degree diff in BPS! CG I miss you sweety, I really do.



		Rhodium (Chief Bee) 05-25-02 02:26 No 313840				Cis & Trans Isosafrole
						By boiling your isomerization reaction mixture for so long at such a high temperature, the cis-isosafrole (bp 253°C) initially formed by the isomerization of safrole reacted further and was apparently quantitatively converted to trans-isosafrole (bp 246-247°C). When using the more common isomerization methods with a very short reflux (15 min at 230-250°C with KOH/CaO) or at a low temperature (4-12h with 2% KOH under vacuum at 120-130°C), only a part of the higher boiling cis-isosafrole overcomes the energy barrier to be converted to the lower boiling trans-isosafrole, and thus the observed boiling point for the isosafrole cis/trans mixture usually lies closer to 253°C than 246-247°C.



		humidbeing (Can't SWIM) 05-25-02 05:02 No 313904				so..
						So really, if swim uses hydrolisis with 15% h2so4, it should make no difference in conversion to ketone, yes? Thanks rhod, I know the answer already. CG I miss you sweety, I really do.



		Rhodium (Chief Bee) 05-25-02 09:03 No 313955				It is the same stuff
						Both the cis- and trans-isosafrole react alike, so regardless of which method you use for oxidation (performic, peracetic or oxone) followed by the H₂SO₄ hydrolysis, you will get exactly the same product ketone, our beloved MDP2P.



		Osmium (Stoni's sexual toy) 05-25-02 23:29 No 314189				I thought the cis iso has a lower BP, since it is ...
						I thought the cis iso has a lower BP, since it is always in the forerun?! I'm not fat just horizontally disproportionate.



		Rhodium (Chief Bee) 05-26-02 02:37 No 314267				bp
						I did a websearch, and came up with those numbers (I was also surprised). I'll check again.



		Rhodium (Chief Bee) 05-26-02 17:27 No 314464				Isosafrole and schizophrenia-like psychosis
						This time I checked, the only data I found supporting my earlier claim is in the Safrole FAQ at my page ( https://www.rhodium.ws/chemistry/safrolefaq.txt ), the bp is mentioned more than once, first in the vicinity of its Beilstein reference, (which I can't read, Beilstein is is the most expensive form of steganography ever invented), and once near a ref to an old american chem journal (which I don't have access to). Osmium, could you please check Beilstein "19(3), 273", "19(4), 273" and "19 1, V, p 553" as those are the three beilstein references on isosafrole I've managed to dig up tonight, at least you know the language they have encrypted the encyclopedia with. The Merck monograph says the *trans* isomer has bp760 253°C, bp100 179.5°C, bp20 135.6°C, bp3.4 85-86°C, and the *cis* isomer bp3.5 77-79°C. Now I wonder which one is correct. Merck has been wrong before (I spotted 11 errors in the 12th edition, not counting spelling mistakes), and probably not too many chemists write to Merck and complain about their List I substance "boils 6-7°C too low". I couldn't find any bp data in the TCI, Acros or Sigma-Aldrich catalogs either, as all of the companies which actually stock isosafrole only have an unspecified mixture of both isomers. An interesting thing to note is that TCI of Japan list isosafrole's flash point as 92°C, while Acros of Belgium list it at 110°C and Sigma-Aldrich (US) lists it as >230°F (>110°C). If it were only the latter two measurements I would buy the reasoning, but a 20°C difference between the hemispheres is a bit too much in my opinion to be trustworthy. Who burns isosafrole on purpose by the way, just to be able to jot down its flash point? At least Sigma-Aldrich has sense enough to write boiling range 77-86°C/3.5mmHg for their 97% pure cis/trans mixture, as that is the boiling point extremes for a mixture of the isomers. I found something amusing while on the net too. Don't try this at home! "Schizophrenia-like psychosis" is not synonymous with tripping your ass off! Isosafrole and schizophrenia-like psychosis American Journal of Psychiatry, 141(8), pp 997-998 (1984) Abstract A 19-year-old man developed a schizophrenia-like psychosis after ingesting isosafrole. His use of amphetamines and LSD failed to produce a similar syndrome. Isosafrole may provide another biochemical model for schizophrenia. http://ajp.psychiatryonline.org/cgi/content/abstract/141/8/997



		Rhodium (Chief Bee) 03-26-04 08:26 No 497471				About the boiling points
						I just felt a link to the following post would be pertinent in this open-ended thread: Post 385627 (Rhodium: "Isosafrole Physical data", Newbee Forum) ^{The Hive - Clandestine Chemists Without Borders}

All 8 posts	End of thread	Top