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Novel Discourse | Thread: Previous Bookmark Forum index Next | ![]() |
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Posts 1 - 15 of 29 | Subject: Another easy route to P-2-Pīs | Page: All Last Next | Down | ![]() |
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Barium (Newbee) 06-13-02 15:09 No 320730 |
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Another easy route to P-2-Pīs (Rated as: excellent) |
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18,1g (100mmol) 1-(2-fluorophenyl)-2-nitropropene was added dry in portions to 49,5g (220mmol) SnCl2x2H2O suspended in 75ml EtOAc while the reaction temperature was kept between 20-40 deg C by a cold water bath. When all nitropropene was added and the color had changed to white (5 min) the EtOAc solution was transferred to a rb flask containing 250ml water and 50 ml hydrochloric acid. The EtOAc was removed by distillation under diminished pressure and the aqueous suspension of oxime and tin salts was allowed to stir at 80 deg C for 1 hour. The water phase was now steam distilled to remove the ketone. When no more oily drops came over the distillate was extracted with DCM. The DCM extracts was dried over MgSO4 and the DCM removed by distillation leaving a quite pure ketone as a colorless oil. Yield: 13,5g (89%) 1-(2-fluorophenyl)-2-propanone Purity: 98% (HPLC) Tin(II)chloride is quite non-toxic and generally very nice. ![]() |
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Rhodium (Chief Bee) 06-13-02 15:30 No 320732 ![]() |
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Varma & Kabalka? | Bookmark Reply | |||||
Is this the procedure from Varma & Kabalka's paper, which I wrote about in TSII? There have been reports of it not working so good in larger batches - but apparatly you've managed to do that. What are the physical properties of 2-Fluoro-P2P, and have you made the corresponding amphetamine or methamphetamine? |
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Barium (Newbee) 06-13-02 16:08 No 320736 |
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Itīs a variation of the Varma and Kabalka method, ... | Bookmark Reply | |||||
Itīs a variation of the Varma and Kabalka method, but they stopped at the oxime stage and said that it was just to extract the oxime with ether. Well the extraction of the oxime from the tin crap/sludge is a NIGHTMARE. So I thought way not render the whole thing acidic and hydrolyse the oxime to the ketone. At the same time the problem with the tin is no more, since Sn(II)chloride and Sn(IV)chloride will stay in the water phase. I just did this two hours ago. First trial. Great success!! The physical properties: bp 47 deg C @ 0,05mmHg, d 1,077g/ml according to Aldrich. Clear oily liquid with a aromatic smell, quite nice. I have not distilled it yet. I rarely do so with the ketones since I get them pure enough anyway. The amphetamine, N-methyl and N-ethyl will be made in a short while. |
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Barium (Newbee) 06-13-02 18:02 No 320761 |
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It just hit me | Bookmark Reply | |||||
This is another way of getting phenylacetones from nitropropenes without affecting aromatic halogens. So if someone starts with 2,5-dimethoxy-4-iodobenzaldehyde it seems easy enough to get the nitropropene-----phenylacetone----and get DOI without doing it the shulgin way. Why does it seem like I am talking to myself the last days. Not many replies to my posts. Donīt you guys and girls like them? ![]() |
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Rhodium (Chief Bee) 06-13-02 18:14 No 320769 ![]() |
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I love them! Haven't you noticed that I have ... | Bookmark Reply | |||||
I love them! Haven't you noticed that I have rated a large part of them as "excellent", and archived several of them at my site? If you want some further discussion on the various topics you've brought up, then I'll try to do that - because encouraging you to post more of your ground-breaking stuff is definitely worth it. How did the analysis go of the compound that wasn't 2C-H? |
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Barium (Newbee) 06-13-02 18:37 No 320780 |
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Ooops didnīt see that | Bookmark Reply | |||||
Sorry about that Rhodim! I havenīt visited your webpage for a couple of days now so I havenīt seen the updates youīve made until now. Iīm glad you liked them enough to archive them. I have not had time to send the mysterious compound for a NMR yet. But it will be done. According to the authors of the article I posted yesterday (nickel/hypophosphite), their method will reduce nitroparffins to amines. Letīs see if it reduces 1-(2,5-dimethoxyphenyl)-2-nitroethane to 2C-H as well.... It would also be nice to hear if someone else actually tries my methods. |
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PrimoPyro (Hive Prodigy) 06-13-02 18:37 No 320781 |
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rest assured I like reading your posts as well, I ... | Bookmark Reply | |||||
rest assured I like reading your posts as well, I just haven't been able to comment on any of them with anything significant. But just to let you know, I am also reading them and liking what I read. ![]() |
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Barium (Newbee) 06-13-02 18:39 No 320782 |
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Thanks PP!!.. :-) | Bookmark Reply | |||||
Thanks PP!!.. ![]() |
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Antoncho (Official Hive Translator) 06-13-02 19:47 No 320801 |
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Questions | Bookmark Reply | |||||
Don't worry, Barium, it happens all the time ![]() Actually, i have two things to note: 1) In the known (Ritter's i think, no?) experiments the reduction was attempted on a nitrostyrene. As seen from those two articles posted by Yellium, they are more picky/less stable to the conditions. Maybee, that's the cause. Or maybee it's still the matter of ring-activation, or maybee both - i personally don't have a clue ![]() ![]() 2) Barium, you used SnCl2 dihydrate - and in the original articles they said 'monohydrate'. I never heard of SnCl2*H2O - only the dihydrate, but maybee i'm just uninformed - what do you think? Once again - your posts are a true pleasure to read, i'm glad you joyned us ![]() Antoncho |
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Barium (Newbee) 06-14-02 17:34 No 321226 |
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This nitroalkene --> ketoxime --> ketone ... | Bookmark Reply | |||||
This nitroalkene --> ketoxime --> ketone was tried with two other phenyl-2-nitropropenes. 40,75g (250mmol) 1-phenyl-2-nitropropene 115g (512mmol, 2,05 eq.) SnCl2x2H2O 150ml EtOAc 140ml conc HCl 500mml water yield; 30,82g (230mmol, 92%) 1-phenyl-2-propanone 51,75g (250mmol) 1-(3,4-methylenedioxyphenyl)-2-nitroprop 115g (512mmol, 2,05 eq.) SnCl2x2H2O 150ml EtOAC 140ml conc HCl 500ml water yield; 41,83g (235mmol, 94%) 1-(3,4-methylenedioxyphenyl)-2-propanone |
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Barium (Newbee) 06-14-02 17:50 No 321230 |
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Hi Antoncho! Varma and Kabalka said that SnCl 2 ... | Bookmark Reply | |||||
Hi Antoncho! Varma and Kabalka said that SnCl2/EtOAc doesnīt work with nitroethenes but does so with nitropropenes. I belive that the aldoxime doesnīt survive the enviroment but is hydrolysed to the acetaldehyde, which readily polymerises. No I used SnCl2 not SnCl4. I have also only heard of either the anhydrous salt or the dihydrate of SnCl2. Thank you for those kind words... ![]() |
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Rhodium (Chief Bee) 06-14-02 18:27 No 321251 ![]() |
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Varma & Kabalka made a followup to that paper, ... | Bookmark Reply | |||||
Varma & Kabalka made a followup to that paper, using basic SnCl2, and then it worked on both nitrostyrenes and nitropropenes. |
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Antoncho (Official Hive Translator) 06-14-02 20:29 No 321288 |
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Actually,.... | Bookmark Reply | |||||
Rhodium, i'm not sure if we're talking of the same articles, but in Post 70459 (yellium: "Syn. Comm 18(7), 693-697 (1988)", Novel Discourse) the aldoximes were made under neutral conditions, while w/sodium stannite only Ph-nitropropenes were successfully reduced. It's not like i'm picking at you ![]() So, anyway....... It's definitely a great news to hear that the same method works on, seemingly, ANY phenylnitropropene - SWIM would absolutely prefer this proc to electrolytic iron in GAA [yuck]. Saved it on my HD right away. Antoncho |
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Rhodium (Chief Bee) 06-14-02 20:48 No 321293 ![]() |
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You are correct, I mixed the papers up in my head ... | Bookmark Reply | |||||
You are correct, I mixed the papers up in my head (Dave, my mind's going!). Reading the actual papers, I now saw that sodium stannite reduced phenylnitropropenes, while tin(II)chloride reduced both them and nitrostyrenes. But I don't remember which method Ritter had problems with (getting polymers when scaling up over 2g). |
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goiterjoe (Title on BackOrder) 06-15-02 02:20 No 321410 ![]() |
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huh? | Bookmark Reply | |||||
In reply to: Is this the procedure from Varma & Kabalka's paper, which I wrote about in TSII? Did you write articles for Srike? Or did you just slip up? |
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