reviewer t and s
TRANSCRIPT
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TERPENES
-HC
-plants and animals
-Friedrich Kekul HC of turpentine
-C10H16
-Camphor -> -terpenoids - oxygenated derivatives
-C10H16O
-Otto Wallach -> 5n carbon atoms
-Isoprene units = 2-methylbuta-1,3-diene-Robert Robinson -> Head to tail
-Leopold Ruzicka ->Rule of Ruzicka classify # of C
# of C atoms n Class
10 2 Monoterpenes C10H16
15 3 Sesquiterpenes C15H24
20 4 Diterpenes C20H32
25 5 Sesterpenes C25H4030 6 Triterpenes C30H48
40 8 Tetraterpenes C40H64
>40 >8 Polyterpenes (C5H8)n
Essential Oils
-extracts/steam distillates
-natural flavour additive, fragrance, pharm prop,
pollination, plant adaptation and protection, hormones
Examples
STEROIDS-hormones- chemical
messengers
-tetracyclic triterpenes
-cyclopentahydrophanthrene
backbone
- Me at C10 and C13 -> angular methyl groups -> beta
-non polar
-trans fused
Cholesterol- most common
-squalene
-8 asym C -> 256 stereoisomers
-cholic and chenodeoxyacid, vit D
classes
1. adrenal cortex steroids
-glucocorticoids
-cortisone-mineralcorticoids
-aldosterone
-O at C11
2. androgens
-male sex
hormone, testes, male
2ndary characteristics
-testosterone, 5a-dihydrotestosterone
3. estrogens
-female sex hormone,
ovaries, fem 2nd
char, mens
-estradiol, estriol,estrone
4. progesterogens
-prepare lining of uterus, pregnancy, ovuation during
pregnancy
-progesterone
Synthetic steroid =
norethindrone
Extraction Methods
1. Tapping- incision where resin run through
2. Expression- press till come out
3. Distillation
a. Dry- high T, direct heat
b. Steam- water
c. Hydrodiffusion- steam at top
4. Solvent extraction
a. Ethanolic- not for plant due to high prop of h2o
to oil -> ambergris sperm whales
b. Enfleurage- cover plant in purified fat -> absorb
oil -> ethanol extraction
c. Simple solvent-petroleum ether, acetone,hexane and ethyl acetate
-benzene -> liquid CO2 -> prod =
concrete/resinoids
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5. SPE- diatomaceous inactive earth or
microparticulate silica
6. Immunoaffinity extraction- antibody bound to matrix
-antibody -> analyte -> change [salt]
7. MIP and RAM
Isolation
1. TLC- silica gel plates
2. GC/LC- vapour phase, high T (>200), He carrier(less dense than N), capillary column
3. HPLC- high T not required, further analysis
Tests
1. Bromine water test- Br add to =/triple -> decolorized
2. Leibermann-Burchard- +Ac2O + H2SO4 = pink ->
green
3. Lifschultz- +FeCl3.6H2O +gHOAc +cH2SO4 ->
buish green or +perbenzoic acid + heat + gHOAc +
cH2SO4
4. Phosphomolybdic Acid- dodeca molybdophosphoric
acid or PMA (yellow-green sol in polar) + conj/unsat
-> molybdenum blue -> inc in stains
5. KMnO4 / Baeyer- =/triple -> 2-OH/COOH -> MnO2
ppt -> decolorized
6. Rosenheim- chloroform soln of sterol + TCA ->
blue/pink
7. Salkowski- cholesterol + xs H3PO4 + FeCl3 -> red
purple or + H2SO4 + cholesterol in CHCl3 -> red
upper and green lower layers
8. Zlatkis- cholesterol + gHOAc + FeCl3 + cH2SO4 ->
purple
Elucidation
UV-Vis
IR
NMR- CDCl3
-1D proton NMR spectra have overlapping signalsof CH2 and CH groups that appear as a characteristic
hump in the region 0.52.5 ppm.
MS
XRC- 3D, position and sizes of atoms, length, angle,
types of bonds, chem. funcs
Chemical Synthesis
Marker degredation
Johnson Total progesterone synthesis
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BIOSYNTHESIS
Or
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Then
CHOLESTEROL
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RECENT
Terpenes
-malaria/ dengue -> bunyavirus
-insect repellents
-DEET, picardin, PMD, beautyberry (callicarpa)
Cantrell et al
-Callicarpenal
-Intermedeol
-Spathulenol
Steroids
-drug dev
-vary subs or alter stereochem relationships
-C11 change
-short carbon bridges
-new ring and new function at C11
stereoselective synthesis of pentacyclic steroids w/ NH2
at C11