14C-labeling of a novel fungicide. I. Syntheses of optically active (E)-and (Z)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-[14C]-1-YL)-1-penten-3-OLS

✍ Scribed by Iwao Nakatsuka; Hiroshi Kanamaru; Takeshi Kamada; Kazuo Kawahara; Akira Yoshitake

• Publisher: John Wiley and Sons
• Year: 1986
• Tongue: French
• Weight: 384 KB
• Volume: 23
• Category: Article
• ISSN: 0022-2135
• DOI: 10.1002/jlcr.2580230609

✦ Synopsis

A novel fungicide, (-) (E)-1-( 2,4-di chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-ol (S-3308 L) and i t s three o p t i c a l l y active stereoisaners were labeled w i t h carbon-14 a t the t r i a z o l e r i n g f o r use i n the metabolic and environmental f a t e studies.

1 ,2,4-Triazo1e-l4C

(4) prepared from formamide-14C (3) 1 4 ; was treated w i t h branopi nacolone t o give triazolylpinacolone-(z), which was condensed w i t h 2,4-dichlorobenzaldehyde giving (Z)-ketone-14C (6). (Z)-Ketone-14C (5) was photoisanerized t o (E)-ketone-14C (L), which was reduced t o racemic (E)-S-3308-l4C

(1) i n 20% y i e l d f r a n z. Reduction o f 5 gave racemic (Z)-5-3308-C (2) i n 23% y i e l d from 5. Optical resolution o f both racemates 1 and 2 by a HPLC method w i t h a c h i r a l column gave (-) (E)-, (+) (E)-, (-) (Z)-and (+) (Z) -1 -( 2,4-di chloropheny1)-4,4-dimethy1-2-(1,2,4-triazol-[ C]-l-yl)-l-penten-3-01~ (la, lb, 2a and 2b) i n e s s e n t i a l l y quantitative yields.