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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