http://slashdot.org/articles/01/12/12/2227205.shtml (http://slashdot.org/articles/01/12/12/2227205.shtml)
Patent US3689504 (http://l2.espacenet.com/dips/viewer?PN=US3689504&CY=gb&LG=en&DB=EPD)
EXAMPLE 1
p-Chloro-N-(cyclopropylmethyl)-.alpha.-methyl-phenethylamine
To 600 ml. of benzene is added 50.0 grams of p-chlorophenyl-acetone and 22.8 grams of cyclopropylmethylamine. The mixture is heated to reflux employing a Dean-Stark water separator and refluxed until no more water separates. The reaction mixture is then concentrated and the crude ketimine isolated.This is the imine forming, done totally different as me, but IT WORKS ALSO! The crude ketimine is dissolved in 600 ml. methanol and the solution is cooled in an ice bath. To this cooled solution is added 22.4 grams of sodium borohydride portionwise with stirring, Exactly the same as me! and the reaction mixture is refluxed for 4 hours. This is NEW and much faster then 36 hrs waiting! The solution is concentrated and 400 ml. of water is added.Same as me, except the concentrating, that's Sunlights and Argox way!
The mixture is rendered alkaline with 60 ml. of 45 percent aqueous potassium hydroxide and 60 grams potassium hydroxide pellets and the resulting oily mixture is extracted three times with ether. The combined ether solutions are washed once with water and dried over anhydrous magnesium sulfate. The solution is then filtered, concentrated and distilled yielding 47.3 grams of p-chloro-N-(cyclopropylmethyl)-.alpha.-methyl-phenethylamine having a boiling point of 107.5 DEG-109 DEG C, at 1.3 mm, nD@25 1.5233.
The acid-addition salts of these compounds are prepared by dissolving the base obtained in accordance with the procedure outlined above, in anhydrous ether and adding the acid corresponding to the salt desired. For example, the hydrochloride salt of the compound prepared according to Example 1 is prepared by dissolving the 47.3 grams of p-chloro-N-(cyclopropylmethyl)-.alpha.-methyl-phenethylamine in 700 ml. of anhydrous ether and the mixture is cooled in an ice bath. To this solution is added ethereal hydrochloric acid dropwise with stirring precipitating the hydrochloride salt out of solution. The acid is added until no more precipitate forms. In like manner, other acid-addition salts may be prepared such as the phosphate, sulfate, fumerate and oxalate, among others.
The procedure of Example 1 may be followed to prepare other phenethylamine derivatives by reacting the appropriately substituted phenylacetone with the desired amine derivative and reducing the product of this reaction to yield the desired compound. Following below in Table 1 is a list of compounds prepared in accordance with this invention showing the respective definitions of R, R1, R2, R3, R4 and X, with reference to Formula I, and the identifying physical constants. ##SPC2## ##SPC3## ##SPC4## ##SPC5##
The compounds of Examples 37 through 40 are prepared according to the method of Example 1 by substituting the correspondingly substituted phenylacetone as the starting material. For example, to prepare the compound of Example 37, the para-chlorophenylacetone is replaced with 3,4-methylene dioxy phenylacetone
So Sam, can you, or anybody else, post the whole Example 37 procedure here, I'm VERY VERY curious about that one! Thanks for finding this.
I'm hoping that this could work for the MDA boro/ammonium acetate one pot, the only problem will be that the NH3 gas formed will be escaping the reflux column, but this could be mastered by a special reflux column with a fine screen in the bottom, and then filled up with chunks of dry ice !!! That way the NH3 can't escape. You could also slowly bubble small amounts of extra NH3 gas into the imine forming step, thus keeping NH3 gas, and ammonium ions as concentrated as can be. LT/
SWIM has seen 500g NaBH4 for $200USD... but how to get it.
Lucky you!! Here's $150/100g, BUT OTOH, it's 100% OTC :)
http://www.geocities.com/dritte123/phenpat.html (http://www.geocities.com/dritte123/phenpat.html)
http://www.geocities.com/dritte123/PSPF.html (http://www.geocities.com/dritte123/PSPF.html)