Enantiomerically enriched 1-phenylethylamines

1 . Process for preparing enantiomerically enriched compounds of the formula (I)

in which

* marks a stereogenic carbon atom,

n is 1, 2 or 3,

m is an integer in the range from 0 to (5-n) and

R 1 is in each case independently selected from the radicals: C 1 -C 12 -alkyl, C 1 -C 12 -alkoxy, C 1 -C 1-2 -alkylthio, C 5 -C 14 -aryl, C 5 -C 14 -aryloxy, C 6 -C 15 -arylalkyl, C 6 -C 15 -arylalkoxy, chlorine, fluorine, cyano, free or protected formyl, free or protected hydroxyl, free or protected mercapto, C 1 -C 12 -haloalkyl, C 1 -C 12 -haloalkylthio, C 1 -C 12 -haloalkoxy and radicals of the formulae (IIa) and (IIb)

A-B-D-E (IIa)

A-E (IIb)

in which

A is absent or is a C 1 -C 8 -alkylene, C 1 -C 8 -alkenylene or C 1 -C 8 -haloalkylene radical and

B is absent or oxygen, sulphur or NR 2 where

R 2 is hydrogen, C 1 -C 8 -alkyl, C 6 -C 15 -arylalkyl or C 5 -C 14 -aryl and

D is a carbonyl group and

E is OR 3 or N(R 4 ) 2

where

R 3 is C 1 -C 8 -alkyl, C 6 -C 15 -arylalkyl or C 5 -C 14 -aryl and

R 4 is in each case independently hydrogen, C 1 -C 8 -alkyl, C 6 -C 15 -arylalkyl or C 6 -C 14 -aryl, or N(R 4 ) 2 together is a cyclic amino radical having 4 to 12 carbon atoms,

comprising,

* in a step A), reacting

compounds of the formula (III)

with compounds of the formula (IVa) or (IVb)

R 5 O—NH 2   (IVa)

R 5 O—NH 2 .HX  (IVb)

in which

R 5 is hydrogen or C 1 -C 12 -alkyl and

X is an anion

to initially give compounds of the formula (V)

and,

in a step B), reducing

the compounds of the formula (V)

in an organic solvent

with a complex borohydride and

an acid

to racemic compounds of the formula (Ia)

and,

in a step C), enriching

the racemic compounds of the formula (Ia) enantiomerically with the aid of enantiomerically enriched acids.

2 . Process according to claim 1 , further comprising step D), of converting the enantiomerically enriched compounds of the formula (I) to enantiomerically enriched ammonium salts of the formula (Ib)

in which X is a halide or a sulphonate.

3 . Process according to claim 1 , wherein

n is 1,

m is 0 or 1 and

R 1 is in each case independently selected from the radicals: C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 5 -C 14 -aryl, C 5 -C 14 -aryloxy, C 6 -C 15 -arylalkyl, C 6 -C 15 -arylalkoxy, chlorine, fluorine, cyano, free or protected formyl, free or protected hydroxyl, free or protected mercapto and C 1 -C 4 -haloalkyl.

4 . Process according to claim 1 , wherein 1-(3-nitrophenyl)ethylamine or 1-(3-nitrophenyl)ethylamine hydrochloride are prepared.

5 . Process according to claim 1 , wherein the complex borohydrides used in step B) are those of the formula (VI)

Met[BH q R 6 (4-q) ] p   (VI)

in which

Met is a mono- or divalent metal such as preferably zinc, lithium, sodium or potassium and

R 6 is C 1 -C 8 -alkyl and

q is 1, 2, 3 or 4, preferably 4 or 1 and

p is the valency of Met.

6 . Process according to claim 1 , wherein the acids used in step B) are Lewis acids, Brönsted acids and compounds which form Lewis or Brönsted acids on reaction with complex borohydrides.

7 . Process according to claim 1 , wherein camphorsulphonic acid is used in step C).

8 . Diastereomerically enriched compounds of the formula (Ic)

in which n, m and R 1 are each as defined in claim 1 and R* is the anion of an enantiomerically enriched organic acid.

9 . (S)-1-(3-Nitrophenyl)ethylammonium camphorsulphonate.

10 . Enantiomerically enriched compounds of the formula (Ib)

in which n, m and R 1 are each as defined in claim 1 and X is a halide.

11 . (S)-1-(3-Nitrophenyl)ethylammonium chloride.

12 . A process for preparing pharmaceutical ingredients comprising incorporating compounds according to claim 8 .

13 . A process for preparing pharmaceutical ingredients comprising incorporating compounds according to claim 9 .

14 . A process for preparing pharmaceutical ingredients comprising incorporating compounds according to claim 10 .

15 . A process for preparing pharmaceutical ingredients comprising incorporating compounds according to claim 11.