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Otto Wallach
5n carbon atoms Isoprene units = 2methylbuta-1,3diene
Leopold Ruzicka
Rule of Ruzicka classification by number of C
Robert Robinson
Head to tail
Value of n
Class
10 15 20 25 30 40 >40
2 3 4 5 6 8 >8
Citral Camphor
Limonene
Menthol
Terpineol
-pinene
Artemisinin
Hormones Tetracyclic triterpenes Cyclopentaperhydrophanthrene backbone Me at C10 and C13- angular methyl groups
Above plane
Source
Phtyosterol Zoosterol Ergosterol Ecdysteroid
Most common and abundant Precursor of other steroids Cell membrane component Squalene 8 asym C and 256 stereoisomer
Cortisone
Aldosterone
Testosterone
5-dihydrotestosterone
Female sex hormones Ovaries Female secondary characteristics Regulate menstrual cycle
Estradiol Estrone
Prepare lining of uterus for implantation of an ovum Maintenance of pregnancy Prevent ovulation during pregnancy Progesterone
Synthetic steroid
Deliberate damage of plant to collect the resin. Use of incision into the tree where the resin runs through. Used in collecting latex for rubber and gum turpentine.
Oil extraction where physical pressure is applied The sample is pressed until the oil comes out of it. Used for citrus oil due to abundance of raw materials.
Involves high temperature The vessel containing the plant sample is directly heated Used for oils derived from wood to vaporize chemical components
Water is added to the plant sample Limits the temperature to 100C Lessens degradation of hydrocarbons
Essentially is steam distillation. Difference is the introduction of steam at the top of the vessel while water and oils are collected at the bottom. Plan materials carried down by the condensate. Saves energy because it is not necessary to vaporize the oil.
Use of suitable solvent to dissolve desired sample Comes in different type of solvents Inlcudes:
Ethanolic Extraction Enfleurage Simple Solvent Extraction
Use of ethanol to extract desired sample Not useful for extraction from plant sample because of high proportion of water to oil More useful with products like ambergris.
Ambergris comes from sperm whales; used in perfumes.
Ancient method of extraction Plant material is covered in purified fat Purified fat absorbs oil Oil can be extracted from fat using ethanolic extraction Similar to maceration; difference is the presence of heat in maceration
Use of petroleum ether, acetone, hexane and ethyl acetate and combinations to extract desired oil. Previously benzene was used but due to health concerns was stopped. Use of liquid carbon dioxide as solvent very effective but expensive. Products are called concrete or resinoids
Same as simple solvent extraction Polarity of sample is taken into consideration May include more purification steps to separate steroids from lipoproteins to increase yield. Glasswares must be properly silanise using dimethyldichlorosilane to prevent steroids from binding
Analyte is eluted by passing through the solid matrix with organic solvent. Water is absorbed by the matrix.
Uses an antibody bound to a matrix Analyte is percolated through the antibody Eluted by changing the concentration of salt May use highly selective antibodies or low specific antibodies.
Large number of sample in one run If steroid is UV absorbing the use of UV light and fluorescent adsorptive material could be used. Usually uses silica gel plates Solvent: combination of chloroform, benzene, ethyl acetate, hexane, etc.
Partition system where the steroid solute is in the vapor phase. Due relatively high molecular weight of steroids and their derivatives, GLC has to be carried out at high temperatures, usually in excess of 200C. The sample is carried through the system by a gas, usually helium, because it is less dense than nitrogen. Originally carried out using packed columns but today capillary columns of glass or fused silica are more popular.
High temperatures are not required. Material can be recovered from the column eluates for further analytical procedures. The resolution achieved by HPLC is superior to TLC and paper chromatography, Methods of linking HPLC to mass spectrometers have greatly improved, allowing the routine use of LC-MS and LCMS-MS Typically, columns are 100300 mm in length and around 45 mm internal diameter.
Bromine adds to unsaturated double and triple bonds to form dibromoalkanes and tetrabromoalkanes Gets decolorized until reaction is complete
Uses acetic anhydride and sulfuric acid Color changes from pink to green Happens because of the hydroxyl group of cholesterol increases conjugation in the ring
Sample + FeCl36H20 + glacial acetic acid + concentrated sulfuric acid = bluish green color Alternatively :
Sample + perbenzoic acid + glacial acetic acid Heat + sulfuric acid = bluish green color
Is also known as dodeca molybdophosphoric acid or PMA It is a yellow-green compound, freely soluble in water and polar organic solvents such as ethanol. Conjugated, unsaturated compounds reduce PMA to molybdenum blue. Increase in intensity means increase in double bonds stained
Oxidize the carbon-carbon double bond to give alkanediols or the carbon-carbon triple bond to give carboxylic acids. A brown precipitate of MnO2 is produced. Disappearance of the characteristic color of permanganate ion is a positive test for unsaturation. Compounds containing certain other types of functional groups may also decolorize permanganate ion.
A chloroform solution of sterol with 90% tricholoracetic acid which gives a blue or pink color.
Cholesterol + excess phosphoric acid + ferric ions (FeCl3) = reddish purple color Alternative:
sulfuric acid + cholesterol in chloroform = twophase system red upper layer and green lower layer
Cholesterol + glacial acetic acid + ferric chloride + concentrated sulfuric acid = purple color
Elucidation is done by spectral comparison Chromophores and structural environment detected for unknown samples
OH single bonds vibrate with 3600 cm-1, carbonyl double bonds with 1700 cm-1, and carbon-oxygen single bonds with 1200 cm-1
NMR spectra of steroids measured in CDCl3. 1D proton NMR spectra have overlapping signals of CH2 and CH groups that appear as a characteristic hump in the region 0.52.5 ppm. 13C NMR eliminates this problem
Detects the molecular mass of a compound with a precision of 10-4 mass units. Due to the isotope mass defect of elements the molecular formula of a terpene can be determined by high-resolution mass spectrometry of the molecular ion. For example, the molecular formula C17H22O4 of acanthifolin from Senecio acanthifolius (Asteraceae) is calculated from the molecular mass of 290.1525 determined by high-resolution mass spectrometry of the molecular ion.
This determines the arrangement of atoms within a crystal and provides information about:
1) 3D picture of the density of electrons within a crystal, 2) mean positions and sizes of the atoms in the crystal, 3) lengths, angles, and types of chemical bonds and 4) chemical functions, interactions, and processes.
Chemical Synthesis
Chemical Synthesis
Biosynthesis
Step 2: Decarboxylation
Step 4: Cleavage
Biosynthesis
Malaria and dengue fever Blood-feeding arthropods Bunyavirus DEET Picardin PMD Beautyberry = Callicarpa
d. O3, THF PPh3 NaBH4 e. CH2Cl2 TIPSOTf 2,6-lutidine f. TPAP NMO CH2Cl2
i. TBAF THF
j. HCl THF
m. RuCl3.H2O EtOH
C11 change -> change in biological effect 11-amino-12-hydroxy/keto steroids potential HIV-1 protease (Salunke et.al.) Short carbon bridges span characteristic portion of steroid backbone
New ring New function at C11 Cholic acid -> stereoselective synthesis of pentacyclic steroids w/ NH2 at C11
cholate
a. Methanol PTSA
methyl-3,7-diacetoxycholate
methyl 3,7-diacetylchol-11-enate
e. m-CPBA in CH2Cl2