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Klute
International Hazard
Posts: 1378
Registered: 18-10-2006
Location: France
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Well, I have news.
The CTH methylation, basicly the freifelder procedure but adding potassium formate as H2 uptake had ceased, provided some secondary amine free from
any primary and apparently any tertiary, after a quick (1H) reflux of the crude freebase in ethyl formate.
I tried the nitrous test at first, but there was still some bubbling, with some nitrosoamine (orange oil), so I tried a Hinsberg test, which was
textbook perfect: Some yellow/orange solid sulfonamide was formed, and not precipitate appeared when the supernatant was acidified, compared to a
reference test (primary amine). But the yile d was a little on the low side, , 5.3g of the oxalate, from 12.2g of the freebase (21.8% yield..).
I also finished the TMP methylation of the benzaldehdye-imine: the freebase priamry amine was refluxed in toluene with 20% excess benzaldehyde for
1H in a Dean Stark until the calculated amount of water had been seperated, then the toluene was stipped off, and 1 equivalent of TMP added and heated
to over 100°C for 36H.
The dark mixture was then acidified with dilute AcOH, refluxed for 20min to hydrolyze the imine, acidified with conc . HCl, washed with toluene to
remove alot of black tarish material, the orange aq. was then basified and th eamine layer that seperated extarcted with toluene, washed with brine,
and dried. The freebase solution was then dripped into 10% excess anhydrous oxalic solution in IPA, left to stir for 15min, rets 15min at 5°C,
vacuum filtered, washed with IPA:acetone 1:1, pet ether, dried by suction and in a dessicator over night.
The rockhard granular solid obtained didn't dissolve neatly in dil. HCl, giving an opaque solution with some insoluble material. Upon adding NaNO2,
a cloudy white solid formed (??), and there was some bubbling.
When added to 10% NaoH, some yellow amine-smelling oil seperated, but so did a fluffy white solid. Adding some TsCl formed some sulfonamide, but
didn't affect the white solid. Acidifying the supernatant caused precipitation identical to the priamry amine reference test...
So I guess the TMP methylation is incomplete, and forms some unindentified impurites along with a little amount of secondary amine.
I'm going to try out the methylation of the n-formyl derivative with TMP or methyl tosylate in presence of NaH, as I'm not totally satisfied by the
CTH.
I'm unable to join any photos, as my camera refuses to turn on... I hope I can get it changed or fixed quickly...
[Edited on 6-8-2008 by Klute]
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
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ayashee4
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Registered: 18-2-2011
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Quote: Originally posted by solo  | 
The result of methylating a primary amino alcohol by using formaldehyde and zinc with some NaH2PO4 with a stirred for 20 hours , then it was Ph to
11 and allowed to sit overnight........, however I need to find out the solubility of this compound.............N-methyl phynylalaninol phosphate, so
far not sol.in H2O, etOH, chloroform, ehtylacetate, toluene, .... but soluble in hypophosphorous acid, I .will check the MP it seem high there might
be a mixture of N-methyl-phenylalaninol phosphate and and NaH2PO4 salts mixed so I will soak it in H2O overnight and then dry and weight the
remaining material see if it's close to the molar amount that is expected. .....however I think the method works on primary amino alcohols will check
on amino acids........solo
[Edited on 9-11-2007 by solo] |
Hey Solo,
I am going to be investigating the reaction "Reductive methylation by aqueous formaldehyde and zinc" with proline.
I was wondering whether it has worked with amino acids for you??
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