Development of new synthetic routes to bile pigments and synthesis of deuterated porphyrins

Thesis/Dissertation · Tue Jan 01 04:00:00 UTC 1985

OSTI ID:5942071

Shim, Y K

New synthetic routes to pyrromethanones using hydrogen peroxide/pyridine upon alpha-free pyrromethanes and a synthesis of mesobiliverdin are described. The pyrromethanones were applied to the synthesis of mesobiliverdin using 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) oxidation of mesourbilin, to give a high yield of the desired mesobiliverdin. New synthetic methodology to pyrrolinones using various oxidizing reagents were also described. Treatment of alpha-free pyrrole with thallium(III) trifluoroacetate (TTFA) gave a mixture of a pyrrolinone and a dimeric compound. The yield and the ratio of the two products were variable depending upon the solvents and the mole ratio of the TTFA used. Pyrrolinone syntheses using the other oxidizing reagents are also described. Syntheses of carbon-14 labelled biliverdins are also described. In addition, the preparation of biliverdin IX-BETA using b-bilene route is described. The second part of this study contains an introduction to porphyrins and syntheses of 6,7-bis(2-methoxycarbonyl-1,1-dideuteroethyl)-1,3,5,8-tetramethyl-2,4-divinylporphyrin. The latter is important in the study of heme protein reconstitution experiments. As a result of numerous synthetic approaches the desired product was obtained from the appropriately deuterated formylpyrrole using the a,c-biladiene route.

• Research Organization: California Univ., Davis (USA)
• OSTI ID: 5942071
• Country of Publication: United States
• Language: English

Related Subjects

550201* -- Biochemistry-- Tracer Techniques
59 BASIC BIOLOGICAL SCIENCES
AROMATICS
AZINES
AZOLES
BILE
BILIVERDIN
BIOLOGICAL MATERIALS
BODY FLUIDS
CARBON 14 COMPOUNDS
CARBOXYLIC ACIDS
CHEMICAL PREPARATION
DEUTERIUM COMPOUNDS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN PEROXIDE
ISOTOPE APPLICATIONS
LABELLED COMPOUNDS
MATERIALS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
PIGMENTS
PORPHYRINS
PYRIDINE
PYRIDINES
PYRROLES
QUINONES
SYNTHESIS
TRACER TECHNIQUES