| 摘要 |
Prepn. of polyamines of formula (I) comprises: (i) reacting an aminopropanol with di-t-butyl dicarbonate and a base at room temp. for 30 mins. to 5 hrs. to form 1,1-dimethylethyl ester of (2-hydroxy-1(R)-methylethyl)carbamic acid (II); (ii) esterifying (II) with methanesulphonyl chloride in presence of a base at -20 to 20 deg C for 5-20 hrs. to form 1,1-dimethylethyl ester of (2-(methylsulphonyloxy)- 1(R)-methyl-ethyl) carbamic acid (III); (iii) reacting (III) with an alkali metal cyanide at 20-75 deg C for 5-20 hrs. to form the 1,1-dimethylethyl ester of (2-cyano-1(R)-methylethyl)carbamic acid (IV); (iv) hydrogenating (IV) with Raney nickel at 3-3 x 10<6> Pa and room temp. for 3-72 hrs. to form the 1,1-dimethylethyl ester of (3-amino-1(R)-methylpropyl)carbamic acid (V).; (v) reacting (V) with benzaldehyde and a dehydrating agent at room temp. for 8-30 hrs. to form an imine, which is reduced by sodium or potassium borohydride at 5-15 deg C for 2-12 hrs. to form the 1,1-dimethylethyl ester of (3-(phenylmethylamino)-1(R)-methylpropyl)carbamic acid (VI); (vi) refluxing (VI) with 4-chlorobutyronitrile and a base for 6-48 hrs. to form the 1,1-dimethylethyl ester of 9-cyano-3(R)-methyl-6-phenylmethyl-2,6-diazanonanoic acid (VII); and (vii) hydrogenating (VII) with Raney nickel in the presence of a base at 2-15x10<5> Pa, at room temp. for 2-20 hrs. to form (I). C* = asymmetric carbon of R or S configuration .
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