38 F. C. STEWARD AND J. K. POLLARD 
Identification of ’ Hydroxyvaline 
Nomenclature No 75 No 78 
5 ene THC LC CHOH 
y ue — 
HB Be “H'8 crycn > CH3CH 3b 
z ce plete “ CHNH> HCNH»5 SNe 
COOH COOH CO 
erie Valine natural s Hydroxyvaline ¥ Hydroxyvaline 
(chromatographically spore lactone 
from all other hydroxyvalin 
Synthesis 
CH5 CH5 CH CH H H 
cach” reduction cH3cH? 4 CH3 ener os Tare a CHEK 
thiony! eels 1 NH, CHIN | CHNH>5 ~*=  CHNH 
cae chloride COOH” COOH" 
aketo-8CH3- achloro -@CH3 C4550,H825:.N964 4CH3aspartic 
sbutyrolactone 8 hutyrolactone C4111, H832:N105 acid found 
8870 |= threo- 
methy!laspartic 
after Barker ) 
Configuration 
COOH COOH COOH COOH 
Amethy! aspartase _. NHoCH HCNHo NHoCH HCNH9 
mesaconic acid  s— HCCH3 CH3CH CH3CH HCCH3 
COOH COOH COOH COOH 
L-threo- D-threo- _—_Lerythrofmethy! D-erythro4 
£ methylaspartic Amethylaspartic aspartic methylaspartic 
Fig. 13. The structure and synthesis of natural y-hydroxyvaline and its lactone and certain criteria 
used to prove its identity. 
related as a free hydroxyamino acid (hydroxyvaline) and its lactone. The synthesis 
of y-hydroxyvaline by SONDHEIMER (working with the authors, see Fig. 13) esta- 
blished the identity of the natural compound as the y-hydroxy compound by chroma- 
tographic comparison of the natural products, both free base and lactone, with the 
synthetic material (POLLARD, SONDHEIMER AND STEWARD”). When further evidence 


ures te 
r ney #8) saree Lanne TH i 
japeetec i cn a 
pei te a “unit : #8 Ha | iF fn . 
“ * j UG Teaeere 
Fig. 14. Resolution of synthetic y-hydroxyvaline into y- and allo-y-hydroxyvaline on ion-exchange 
resin. (Reference amino acids were inserted in the sample at low concentration.) 
EFFLUENT (mi) 

References p. 42 
