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Syntheses, resolution optique et radiolyse d' Acides Amines Trities a Haute Activite Specifique. I ‐ D,L‐Lysine ( 3 H‐4,5,6,6); L‐lysine ( 3 H‐4,4,5,5); L‐Leucine ( 3 H‐4,5,5,5); Acide D‐α‐amino Adipique ( 3 H‐4,4,5,5); Acide γ‐Amino Butyrique ( 3 H‐2,2,3,3)
Author(s) -
Ego Dominique,
Beaucourt JeanPierre,
Pichat Louis
Publication year - 1986
Publication title -
journal of labelled compounds and radiopharmaceuticals
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.432
H-Index - 47
eISSN - 1099-1344
pISSN - 0362-4803
DOI - 10.1002/jlcr.2580230302
Subject(s) - chemistry , hydrolysis , catalysis , enantiomeric excess , medicinal chemistry , tritium , lysine , enantiomer , stereochemistry , amino acid , organic chemistry , enantioselective synthesis , biochemistry , physics , nuclear physics
2,6‐Diamino‐4‐hexynoic acid 5 was prepared from 1,4‐dichloro‐2‐butyne and diethyl acetamidomalonate. The catalytic reduction of 5 with tritium led to (4,5,6,6‐ 3 H) DL‐lysine 6 ′ spec. act. 113 Ci/mM. The catalytic reduction With tritium of L‐2‐amino‐6‐t‐butoxycarbonylamino‐4‐hexynoic acid 7 followed by hydrolysis gave [4,4,5,5‐ 3 H] L‐lysine 6 spec. act. : 120 Ci/mM. DL‐2‐amino‐5,5‐dichloro‐4‐methyl‐4‐pentenoic acid 11 was prepared from 2‐methyl‐1,1,3‐trichloro‐1‐propene and diethyl acetamidomalonate. The optical isomers Were separated by preparative HPLC. The catalytic reduction of the L enantiomer gave [4,5,5,5‐ 3 H] L‐leucine 13 spec. act. 140 Ci/mM. Ethoxycarbonylation of ethyl 2‐acetylamino‐2‐ethoxycarbonyl 4‐pentynoate : 15 in presence of palladium gave triethyl 4‐acetylamino‐1‐butyne‐1,4,4‐tri‐carboxylate 16 . Reduction of 16 with tritium followed by hydrolysis gave DL‐[4,4,5,5‐ 3 H]α‐aminoadipia acid 18 ′ spea. act. 130 Ci/mM. The oxidation of 18 ′ with L‐aminoxidase led to D‐α‐aminoadipia acid 18 with the same specific activity. Methoxycarbonylation of 3‐phthalimido‐1‐propyne 19 in presence of Pd gave methyl 4‐phthalimido‐2‐butynoate 20 which tritiation followed by hydrolysis led to [2,2,3,3‐ 3 H] GABA 22 spec. act. 109 Ci/mM. 3 H NMR analyses Were carried out in each case. Studies on the self radiolysis of these aminoacids during storage are reported.