Ok so since swid finally spelt the shit right he comes upon a post discussing the us of ethanolamine to hydrolyze. Swid is ever hesitant to go charging ahead without a layed out synthesis. Vibrating lights posted this workup in Post 404393 (https://www.thevespiary.org/talk/index.php?topic=7353.msg40439300#msg40439300)
(Vibrating_Lights: "Will the ring of the phlactamide group also...", Chemistry Discourse)
15 gms(.048m) of N-(2-(2,5 Dimethoxyphenyl)ethyl)phthalimide is placed into 50ml MEOH with 1.02gms(.01m)KBr. Then the solution is stirred while .01m of Oxone(aq) is added. The solution is stirred till completeion. 2ml of (aq)Sodiumbisulfite is added then the rxn is basified with 25%NaOH and extracted 3x50ml of DCM. Dcm extracts are washed with Bisulfate again then once with NaHCO2. The Dcm is removed under vaccume to give N-(2-(4
bromo-2,5-Dimethoxyphenyl)ethyl)phthalimide. (.048m) 15 gms N-(2-(4 Bromo-2,5-Dimethoxyphenyl)ethyl)phthalimide Is refluxed in ethanolamine for 20 mins. Then the rxn is flooded with water. The amine is extractred with 3x50ml of dcm and the residue distilled under N2 to give 2CB. 2CB freebase is then treated with .045m of 20% HCL.
Ok well this is a somewhat experimental workup. If the above indeed sounds good, what amount of ethanolamine would you bees suggest? Does the above sound good to more experienced bee's? Also does anybody that has tried making 2CH or halogenated phenethylamine using this route(with ethanolamine) have any suggestions for a less experienced bee?
Swids friend has few hundred g's of the N-(2-(2,5 Dimethoxyphenyl)ethyl)phthalimide coming next week. There is no turning back now without losing money out the ass. If swid can post a success with this project then ANYBODY who is semi competant will be assured success. Will post results, when results are known.
Many thanks
The patent listed by PolytheneSam at the top of that thread does indeed give suggested amounts of ethanolamine to use. I have posted the relevant parts of that patent in Post 444604 (https://www.thevespiary.org/talk/index.php?topic=7353.msg44460400#msg44460400)
(Rhodium: "Cleavage of phthalimides to amines w/ Ethanolamine", Chemistry Discourse) - but to get all the details you should read the patent itself (link available in my post)
Ethanolamine has been used in phthalimide cleavage with yields from 82 to 90% for 2 h at 60°C in:
Cleavage of Phtalimide protection groups to primary amines
J. Med. Chem. 42(9), 1648-1660 (1999) (https://www.thevespiary.org/rhodium/Rhodium/pdf/phtalimide.removal.ethanolamine.pdf)
(https://www.thevespiary.org/rhodium/Rhodium/pdf/phtalimide.removal.ethanolamine.pdf)
An Exceptionally Mild Phtalimide Deprotection of Amines
J. O. Osby, M. G. Martin & B. Ganem
Tet. Lett. 25(20) 2093-96 (1984) (https://www.thevespiary.org/rhodium/Rhodium/chemistry/phtalimide.deprotection.nabh4.html)
(https://www.thevespiary.org/rhodium/Rhodium/chemistry/phtalimide.deprotection.nabh4.html)
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000444411-file_3zgk.gif)
Summary
Phthalimides are converted to primary amines in an efficient, two-stage, one-flask operation using NaBH4/2-propanol, then acetic acid.
yes, i think to remember something like that...
wouldn´t it be possible with a very mild lewis acid as catalysator?
Edit:
Here is the post i´ve been searching for:
Post 414539 (https://www.thevespiary.org/talk/index.php?topic=11616.msg41453900#msg41453900)
(ChemisTris: "Abstract", Novel Discourse)
But they use substituted phenoles as substrate. It may be possible with plain 1,4-Dimethoxybenzene too.
Well, take a look at the comments made in Post 414798 (https://www.thevespiary.org/talk/index.php?topic=11616.msg41479800#msg41479800)
(Antoncho: "Some useful additions to the posted above....", Novel Discourse)
As a side note, .... It is obvious that the low yield in the 1st amino alkylation is due to the low reactivity of the starting phenol, not to its sensitivity..... Bad news.....(that is, we can't use fully methylated precursors).
I don't think you would be able to exceed 50% yield even by using 4-Methoxyphenol - but then again, why not alkylate hydroquinone with N-(2-Bromoethyl)-Phtalimide? Methylation followed by removal of the phtalimide group could very well give high yields of 2C-H.