School Science Lessons
2016-08-22 SP MF
Please send comments to: J.Elfick@uq.edu.au

16a Chemistry of natural products
Table of contents
16.3.1.0 Aliphatic compounds

16.3.4.0 Aromatic compounds

16.3.8.0 Carboxylic acids and fatty acids

16.3.5.0 Terpenoids, isoprenoids

16.3.2.0 Tetrapyrroles, porphyrins, (haem, heme)

16.3.1.0 Aliphatic compounds
Compounds having an open-chain structure.
16.3.2.3 Alditols, polyhydric alcohols, mannitol
16.3.2.2 Carbohydrate acids, D-gluconic acid,
16.3.1.1 Carbohydrates
16.3.8.0 Carboxylic acids and fatty acids
16.3.1.6 Cellulose, hemicellulose
16.3.1.7 Chitin
16.3.2.1 Cyclitols, inositol
16.3.1.4.0 Disaccharides
16.3.2.6.1 Glucosides
16.3.2.4 Glycosaminoglycans, glucosamines
16.3.2.6.0 Glycosides
16.3.3.0.5 Glycerides, esterification of glycerol
16.3.3.0.2 Lecithins
16.3.3.0 Lipids, fats and oils, fatty acids, glycerides
16.3.1.3 Monosaccharides
16.3.1.3.1 Monosaccharides, D and L sugars
16.3.2.8 Nucleosides, nucleic acids, DNA, RNA
16.3.1.8 Pectin, Aspergillus japonicus
16.3.2.5 Phenolic compounds
16.3.6.9 Clove oil, eugenol
16.3.2.7 Polyketides, polyketide antibiotics
16.3.2.9 Polysaccharide gum, phycocolloids
16.3.7.1 Reducing sugars / non-reducing sugars
16.3.3.0.1 Phospholipids, (phosphoglycerides)
16.3.1.4.3 Polysaccharides
16.3.1.5 Starches, amylum, glycogen
16.3.1.2 Sugars
Aldose sugars
Ketose sugars
RuBisCO
Allantoin, C4H6N4O3, in face creams, in Symphytum officinale, comfrey
Glycerol
Glycolic acid, hydroxyacetic acid, HOCH2COOH, α-hydroxy acid
16.3.1.4.1 Trisaccharides
16.3.1.4.2 Tetrasaccharides
16.3.3.1 Waxes

16.3.4.0 Aromatic compounds
Compounds having a benzene ring, and a pleasant smell.
16.3.4.0b Aramids
16.3.4.0.10 Aromatic aldehydes and ketones
16.3.4.0.4 Aromatic amines, anilides
16.3.4.0.9 Aromatic alcohols
16.3.4.0.6 Aromatic halogen compounds
16.3.4.0.1 Aromatic hydrocarbons
16.3.4.0.2 Aromatic nitro compounds
16.3.4.0.7 Aromatic sulfonic acids
16.3.4.0a Aryl groups
16.8.1 Reactions of benzene, C6H6
16.3.4.0.5a Barbiturates (depressants)
16.3.4.0.5b Benzodiazepines (tranquillizers)
16.3.4.1a Benzofuranoids, benzopyranoids
Bergamottin, C21H22O4
Coumarin
16.3.4.0.5 Diazo compounds
16.3.4.5 Five member heterocycles
16.3.4.2.0 Flavonoids, (Bioflavonoids), plant polyphenols
Geosmin, C12H22O, earth smell, muddy fish smell, after rain smell, cut grass smells
16.3.4.0.3 Lactams (-NH(CO-), e.g. caprolactam
16.3.4.4 Lignans, plant phenols
16.3.4.0.12 Parabens
16.3.4.0.13 Pyridine
16.3.4.3 Tannins,  plant polyphenols
Methyl salicylate, C8H8O3
Piperanine
Salicyclic acid
Sodium salicyclate  

16.3.4.2.0 Flavonoids, (Bioflavonoids), plant polyphenols
16.3.4.2.1 Anthoxanthins
16.3.4.2.1a Flavones
16.3.4.2.1b Flavonols, flavan-3-ols
16.3.4.2.2 Flavanones
16.3.4.2.3 Flavanonols
16.3.4.2.4 Flavans, C15H14O
16.3.4.2.5 Anthocyanidins
16.3.4.2.6 Isoflavonoids, phytoestrogens
16.3.4.2.8 Other bioflavonoids

16.3.8.0 Carboxylic acids and fatty acids
16.3.8.0 Carboxylic acids and fatty acids
16.3.8.6 α-hydroxy acids
16.3.4.0.11 Aromatic carboxylic acids, derivatives
16.3.8.2 Dicarboxylic acids
16.3.8.7 Keto acids, acetoacetic acid, pyruvic acid
16.3.8.5 Perfluorooctanoic acid
16.3.8.1 Saturated carboxylic acids
16.3.8.3 Tricarboxylic acids
16.3.8.4 Unsaturated fatty acids

16.3.5.0 Terpenoids, isoprenoids
16.3.5.01 Terpenes, (C5H8)
16.3.5.1.2 Terpinenes, (cyclic terpenes)
16.3.5.02 Isoprene units, (C5H8)
Classification of terpenenes
16.3.5.1.0 Hemiterpenes, C5, (one isoprene unit), e.g. isoprene, C5H8, natural rubber monomer
16.3.5.1.1 Monoterpenes, C10H16, (two isoprene units), e.g. limonene, C10H16,
16.3.5.1.3 Sesquiterpenes, C15H24, (three isoprene units), e.g. selinene, C15H24, in celery seed
16.3.5.1.4 Diterpenes, C20, (four isoprene units), e.g. sclarene, C20H32
16.3.5.1.5 Sesterterpenes, C25, (five isoprene units), e.g. scalarane, C25H44
16.3.5.1.6 Triterpenes C30, (six isoprene units), e.g. gammacerane, C30H52, squalene C30H50
16.3.5.1.8 Tetraterpenes C40, (eight isoprene units), e.g α-carotene, C40H56, β-carotene C40H56
16.3.5.1.9 Polyterpenes, (many isoprene units), e.g. rubber, (C5H8)n

Classification of terpenoids
16.3.5.1, Monoterpenoids,C10
16.3.5.2, Sesquiterpenoids,C15
16.3.5.3, Diterpenoids,C20
16.3.5.4 Triterpenoids, C30
16.3.5.0  Tetraterpenoids, Carotenoids, C40

16.3.2.0 Tetrapyrroles, porphyrins, (haem)
16.3.5.2.1 Tetrapyrroles, related compounds
16.3.5.2.3 Chlorophyll a and chlorophyll b
16.3.5.2.4 Legheamoglobin
16.3.5.2.6 Phycobilin, phycocyanin, phycoerythrin
16.3.5.2.5 Phycobiliproteins, Anabaena azollae
16.3.5.2.7 Phytochromes
16.3.5.2.8 Polyvinyl pyrrolidene, povidone
16.3.5.2.2 Porphyrins

16.3.1.1 Carbohydrates
Carbohydrates were compounds such as aldoses and ketoses, stoichiometric formula Cn(H2O)n, so "hydrates of carbon".
Nowadays, carbohydrates include monosaccharides, oligosaccharides and polysaccharides, and substances from monosaccharides,
1. by reduction of the carbonyl group, >C=O, (alditols),
2. by oxidation of one or more terminal groups to carboxylic acids, e.g. ethanoic acid, CH3COOH,
3. by replacement of hydroxy groups by a hydrogen atom, an amino group, thiol group or other groups, and derivatives of these
compounds.

16.3.1.2 Sugars
See diagram 16.3.1.3x: Glucose and fructose, straight chain forms
Sugars are simple carbohydrates, one or more monosaccharide units, soluble in water, optically active, sweet to taste and fermentable.
However, the term "sugar" generally refers to monosaccharides and lower oligosaccharides.
"Reducing sugars" reduce copper (II) to copper (I) salts in Fehling's solution or other test solutions, show presence of aldehyde group.
Monosaccharides have a straight chain form or ring form, cannot be split into smaller molecules using dilute acids, cannot be hydrolysed
to simpler compounds.
Polysaccharides have more than ten monosaccharides linked by glycosidic bonds, between C1 on one sugar and C4 on other sugar by
removal of water molecule, i.e. a condensation reaction.
An aldose has aldehyde group, -CHO, i.e. a carbonyl, group, C=O, with a hydrogen atom attached to the carbon atom, e.g. glucose.
Aldose sugars
An aldose sugar is also an aldehyde which contains one aldehyde group per molecule, chemical formula Cn(H2O)n.
Aldose sugars include the following:
1. Glyceraldehyde HO-CH2-CHO
2. Tetrose sugars: erythrose, threose,
3. Pentose sugars:  ribose, arabinose, xylose, lyxose
4. Hexose sugars: allose, altrose, glucose, mannose, gulose, idose, galactose, talose.
Ketose sugars
A ketone group is a carbonyl group, C=O, with two single bonds to other carbon atoms.
A ketose sugar contains one ketone group per molecule, e.g. fructose, CH2OHCHOHCHOHCHOHC=OCH2OH
Ketose sugars include the following:
1. Fructose, C6H12O6, fruit sugar, high fructose corn syrup
Commercial: D-(-)-Fructose, D-Levulose, Fruit sugar
2. Glycerone, C3H6O3, dihydroxyacetone, simplest ketose sugar, triose, stains skin brown but no increase in melanin so used in
sunless tanning, fake sun tan.
Commercial: Dihydroxyacetone, 1,3-Dihydroxy-2-propanone, DHA, Glycerone
3. Ribulose, C5H10O5, pentose, artificial sweetener but not very sweet
Commercial: L-Ribulose, L-Adonose, also D-Ribulose
RuBisCO, C5H12O11P2,  ribulose-1-5 biphosphate carboxylase oxygenase, the most abundant enzyme for first step in carbon
fixation by plants.
Commercial: RuBisCO, powder from spinach
4. Xyulose, C5H10O5, pentose, not used as commercial sweetener
Commercial: D-Xylulose, D-threo-Pentulose, faint yellow syrup

16.3.1.3 Monosaccharides
| See diagram 16.3.1.3a: Aldose: D-glyceraldehyde, L-glyceraldehyde, Ketose: dihydroxyacetone
| See diagram 16.3.1.3b: Aldose sugar: Glucose
| See diagram 16.3.1.3Cch: Aldose sugar: Galactose
| See diagram 16.3.1.3d: Ketose sugar: Fructose
| See diagram 16.3.2.8.2: Aldose sugar: Ribose, deoxyribose, nucleotide
Monosaccharides, Cx(H2O)y, where x = 1 or 2 or 3,. contain a single sugar unit, e.g. glucose, fructose.
So they cannot be hydrolysed to simpler sugars.

Classification: of monosaccharides
1. Classification by number of carbon atoms
Triose, 3 carbon atoms, C3H6O3, dihydroxyacetone, glyceraldehyde
Tetrose, 4 carbon atoms, C4H8O4, e.g. erythrose, threose, erythrulose
Pentose, 5 carbon atoms, C5H10O5, e.g. arabinose, lyxose, ribose, xylulose
Hexose, 6 carbon atoms, C6H12O6, e.g. allose, altrose, glucose, mannose, gulose, idose, galactose, talose

2. Classification by whether aldose or ketose
Aldose contains aldehyde group, (-CHO), at C1, monosaccharide bonded to an aldehyde chain, Cn(H2O)n, e.g. glyceraldehyde,
(CHOCHOHCH2OH), the simplest aldose
Ketose, contains ketone group, (-CO-), at C2, monosaccharide sugar containing a ketone group or compound derived from a ketone,
e.g. dihydroxyacetone, (CH2OHCOCH2OH), the simplest ketose
Table 16.3.1.3 Aldoses and ketoses
C Atoms
Aldose, contains aldehyde group
Ketose, contains ketone group
3 C triose
glyceraldehyde
Dihydroxyacetone
4 C tetrose
erythrose, threose
Erythrulose
5 C pentose
arabinose, lyxose, ribose, xylose ribulose, xylulose
6 C hexose
allose, altrose, galactose, glucose,
gulose, idose, mannose, talose
fructose, psicose, sorbose,
tagatose

16.3.1.3.1 Left-handed and right-handed structural forms, D-sugars and L-sugars
See diagram 16.3.1.3a: Monosaccharides, D-sugar and L-sugar
The Fischer projection formula invented by Emil Fischer, (1852 - 1919), allows the three-dimensional sugar and amino acid molecules
be represented by two-dimensional diagrams on the page.
Horizontal lines show groups projecting above the plane of the page towards you.
Vertical lines show groups projecting below the plane of the page away from you.
So D-glyceraldehyde has the hydroxyl group on C2 on the right and L-glyceraldehyde has the hydroxyl group on C2 on the left,
(Latin: dextro = right, laevo = left).
For all other carbohydrates, if the carbon atom farthest from the aldehyde or ketone group has the same arrangement as
D-glyceraldehyde, hydroxyl on the right of C2, then the compound is a D-sugar.
Similarly, if this "remote carbon atom" has the same arrangement as L-glyceraldehyde, the compound is an L-sugar.
However, monosaccharides exist mainly as cyclic forms, not the aldo-forms or keto-forms.
See diagram 16.3.2.9: Fischer projection and Haworth projection of glucose
The cyclic structure of monosaccharides is shown by a "Haworth projection", invented by W. N. Haworth, 1813-1950, England.
The oxygen atom is at the upper right and the carbon atoms are arranged clockwise with C1 at the far right.
The hydroxyl groups on the right in the Fischer projection are down in the Haworth projection, so the hydroxyl groups on the left in
the Fischer projection are up in the Haworth projection.
The terminal -CH2OH group is up in the Haworth projection for D-sugars, and down for L-sugars.
D-glucose can have α-or β-forms, depending on the position of the hydroxyl group attached to C1, down in the α-form and up in the
β-form.
Most monosaccharides have a ring cycle of six atoms, one oxygen atom and five carbon atoms, called the pyranose form.
A ring cycle of 5 atoms, one oxygen atom and four carbon atoms is called a furanose form.
So D-fructose can exist as α-D-fructofuranose, -OH on C2 is down, and β-D-fructofuranose, -OH on C2 is up.
Glucose, Commercial: "D-(+)-Glucose, dextrose"
Fructose, D form, but laevorotatory, so "L-fructose", Commercial: "D-(-)-Fructose, D-Levulose, Fruit sugar"

16.3.1.4.0 Disaccharides, trisaccharides, tetrasaccharides, polysaccharides
| See diagram 16.3.1.4a: Maltose molecule
| See diagram 16.3.1.4b: Lactose molecule
| See diagram 16.3.1.4c: Sucrose molecule
Disaccharides contain two sugar units:
sucrose = (glucose + fructose),
lactose = (milk sugar, glucose + galactose),
maltose = (malt sugar, glucose + glucose).

16.3.1.4.1 Trisaccharides
Raffinose, (triose: fructose + galactose + glucose), (C18H32O16),
Also, melezitose, maltotriose, (amylotriose)

16.3.1.4.2 Tetrasaccharides
See diagram 16.3.1.4: Stachyose, acarbose
Acarbose, (C25H43NO18), anti-diabetic drug
Stachyose, (tetrose: fructose + galactose + glucose + galactose, i.e. raffinose + galactose), (C24H42O21), in green beans

16.3.1.4.3 Polysaccharides, glycans
Polysaccharides are long carbohydrate molecules consisting of repeated monomer units joined together in a chain by glycosidic bonds
and contain linked monosaccharide units, (C6H10O5)n
1. Homopolysaccharides, homoglycans, contain the same type of monomer unit
2. Glucosans, (from glucose)
Starch, amylopectin glucosan + amylose sugar
Glycogen, glucose residues
Cellulose, D-glucose units
2. Fructans, (from fructose)
Inulin, D-fructose, in artichokes
2. Galactans, (from galactose)
Agar
1. Heteropolysaccharides, heteroglycans, contain different type of monomer r units
Acidic, mucopolysaccharides, glycosaminoglycans long unbranched polysaccharides, repeating disaccharide units
Chitin
Heparin
Chondroitin sulfate
Keratan sulfate
Pectin
Hyaluronic acid
Dextran, Modified polysaccharide
Chitin
Chitin, (C8H13O5N)n, is a polymer of the monosaccharide derivative of glucose, N-acetylglucosamine, in fungi cell walls, arthropod
exoskeletons, e.g. crabs, insect exoskeleton, mollusc radula, cephalopod beak, e.g. squid.
Similar structure to cellulose and keratin
Used as a binder in dyes, adhesives, fabrics and dissolving surgical thread.
Pectin
Pectin is a polysaccharide that forms the primary cell walls of many terrestrial plants.
Pectin has various uses in the food industry as it acts as a gelling agent for jams and jellies.
It is also used as a food thickening agent and stabilizer in juices, milk.
Arabinoxylans
Arabinoxylans is a polysaccharide found in the primary and secondary cell wall of plants i.e. wood and also in the cereal grains.
It is a combination of arabinose and xylose.
β-glucan, (cellotriose, β-D-glucan, glucan, C18H32O16),  D-(+)-cellotriose, glucopyranosyl
Oligosaccharides raffinose, stachyose and verbascose are present in significant quantities in legume seeds

16.3.1.5 Starches, amylum, glycogen
See diagram 16.3.1.5a: Starch, amylose,
(amylum), (amylose, soluble starch, many glucose units), (amylopectin, insoluble starch, 40 to 60 branched glucose units).
(Starch, amylum = amylose + amylopectin)
Glycogen in animals.,
Glycogen, α-1,4- and α-1,6-glucan, unbranched glucose polymer similar to amylopectin
Inulin = D-fructose units, from Helianthus
Boil cut potato in water then let cool.
Filter the solution to separate the soluble amylase from the insoluble amylopectin of the starch grains.
Add tincture of iodine to the filtered starch solution.
An intense blue colour occurs.
The solution contains β-amylase, C6H10O5 that forms a complex with iodine: (β-amylase)p, (I-), (I2)r(H2O)s [where r < p < s].

16.3.1.6 Cellulose, hemicellulose
See diagram 16.3.1.6a: Cellulose, three glucose molecules linked to form cellulose
See diagram 16.3.1.7a: Cellulose
See diagram 16.3.1.7C: Linamarin
See diagram 16.3.1.7d: Cyanohydrin
Cellulose is a long unbranched glucose polymer.
Cellulose in plant cell walls, hemicellulose in some plant endosperm to form vegetable ivory.
Gun-cotton was prepared by saturating cotton or cellulose material in nitric acid and sulfuric acid to produce a highly explosive material.

16.3.1.7 Chitin
See diagram 16.3.1.7a: Chitin
Chitin, (C8H33O5N)n, is an insoluble nitrogenous polysaccharide, contains chains of N-acetylglucosamine in support structure of
invertebrates and fungi, e.g. shells of arthropods.

16.3.1.8 Pectin, Aspergillus japonicus
Pectin, poly-D-galacturonic acid methyl ester, from apple and citrus peel, is a heterosaccharide component of terrestrial plant cell walls.
It is used as a substrate to identify, differentiate and characterized pectinases.
Pectin is used to study its degradation by pectinolytic bacteria.
Pectin has high molecular weight, cements adjacent plant cells, and is dissolved by pectinase in ripening fruit.
It is sold as a white-brown powder and is used to form gels and as thickening agents.
Galactouronic acid, C6H10O7, is a component of pectin.
Pectinase, polygalacturonase, catalyzes hydrolysis in pectin
Pectinesterase, pectin methylesterase, catalyzes hydrolysis of methyl esters of pectin --> pectate + methanol
Pectolyase from Aspergillus japonicus plant cell culture, catalyzes breakdown of methyl esters --> oligosaccharides

16.3.2.1 Cyclitols, inositol
Cyclitols are cycloalkanes containing one hydroxyl group on each of three or more ring atoms, e.g. Inositol, cyclohexane,
cyclohexane-1,2,3,4,5,6-hexol, C6H12O6,  prescribed for some medical conditions, but should not be taken as a "vitamin supplement"
to the diet.
Inositol is in eggs:  22.15
Commercial: myo-Inositol, 1,2,3,4,5,6-Hexahydroxycyclohexane, meso-Inositol, C6H12O6

16.3.2.2 Carbohydrate acids
D-gluconic acid, CH2(OH)(CHOH)4COOH, produced by fungi
D-glucuronic acid, C6H10O7, in gums, forms glucuronides
d-gluconic acid, d-glucuronic acid, food additive E574, anti-caking agent, sequestrant
Commercial: D-Glucuronic acid, Glucodiuronic acid, C6H10O7

16.3.2.3 Alditols, polyhydric alcohols, mannitol
General formula: HOCH2[CH(OH)]nCH2OH,
Mannitol CH2OH(CHOH)4CH2OH, from mannose or fructose, sugar in fungi and brown algae, food sweetener.
Commercial: D-Mannitol, Mannite, C6H14O6

16.3.2.4 Glycosaminoglycans, (mucopolysaccharides), glucosamines
16.3.0 Amines and alkaloids
Glycosaminoglycans, (mucopolysaccharides), glucosamines, dermatan sulfate, chondroitin, hyaluronic acid, heparin, keratin sulfate.
Glucosamine is converted to glycosamineglycans.
Glucosamine hydrochloride and glucosamine sulfate may repair cartilage and alleviate osteoarthritis.
Commercial: D-(+)-Glucosamine hydrochloride, C6H13NO5. HCl
Heparin, Chondroitin sulfate, Hyaluronan, Heparan sulfate, Dermatan sulfate, Keratan sulfate
Commercial: Heparin sodium salt from porcine intestinal mucosa, anticoagulant

16.3.2.5 Phenolic compounds
Phenolic compounds occur in seeds, grape skins and and are extracted from oak barrels.,
Phenolic compounds: citronella, clove oil, dicoumarin, eucalyptol, ubiquinone, urushiol, vanillin
Catechol, C6H4(OH)2, 1,2-dihydroxybenzene, colourless crystalline phenol, harmful, irritant, pyrocatechol, powder, C6H4-1,2-(OH)2
Urushiol, mixture of catechol molecules substituted with different alkyl chains, in poison ivy, used in lacquer ware, causes allergic
reactions in people handling mango leaves and stems
Citronella grass, Cymbopogon citratus, Poaceae
Phenolic polymers: tannins, lignin
Flavours: eugenol, (olive, cinnamon), cinnamaldehyde, (cinnamon, cassia), anethole, (anise), thymol, (thyme), carvacuol, (oregano),
estragola, (tarragon), vanillin, (vanilla)
Polyphenols, e.g. hydrolysable tannins
16.3.2.5a Catecholamines
Catecholamines have a benzene ring with two adjacent hydroxyl groups and a side chain of ethylamine to function as psychoactive
compounds, hormones or neurotransmitters
Catecholaminergic substances release a catcholamine as a neurotransmitter.
Catecholamines are catechol derivatives [CH4(OH)2 = catechol ring], e.g.
Dopamine, (3-hydroxy tyramine, 3,4-dihydroxy-phenylethylamine, C8H11NO2)
Adrenaline, epinephrine, (C9H13NO3): 9.241
Noradrenaline, (norepinephrine), [(HO)2C6H3.CHOH.CH2.NH2]
16.3.2.7 Polyketides, polyketide antibiotics
16.1.5.2: Lactones
Molecules having more than two carbonyl groups connected by single carbon atoms.
Occur in some bacteria and fungi, e.g. Aspergillus.
They have antibiotic, anticancer, cholesterol-lowering, immunosuppressive effects, e.g. erythromycin, lovastatin.
They include polyketide antibiotics, streptomyces metabolites, erythromycin, linear tetracyclines, macrolides and lactones,
erythromycin polyenes, nystatin, polyether antibiotics, β-lactams, aflatoxins.
Commercial: Erythromycin, E-Mycin, Erythrocin, C37H67NO13, white powder
Lactones are components of coconut aroma and peach aroma, e.g. octalactone.
Commercial: Y-Octalactone, 4-Hydroxy octanoic acid, C8H14O2

16.3.2.8 Nucleosides, nucleic acids, DNA, RNA
| See diagram 16.3.2.8: Nucleic acid
| See diagram 16.21.10: Purines
| See diagram 16.21.13: Pyrimidines
1. Nucleic acids are macromolecules from the nuclei of cells, composed of nucleotide units, and can be hydrolysed into pyrimidine or
purine bases, adenine, cytosine, guanine, thymine, uracil, D-ribose or 2-deoxy-D-ribose, and phosphoric acid.
2. Nucleic acids do several functions in living cells, e.g., the storage of genetic information and its transfer from one generation to the
next
3. DNA, (deoxyribonucleic acid), the expression of this information in protein synthesis, (mRNA, tRNA), and may act as functional
components of subcellular units such as ribosomes, (rRNA).
4. RNA, (ribonucleic acid), contains D-ribose, whereas DNA contains 2-deoxy-D-ribose as the sugar component.
5. A nucleoside is a compound in which a purine or pyrimidine base is bound via a N-atom to C-1 replacing the hydroxy group of
either 2-deoxy-D-ribose or of D-ribose, but without any phosphate groups.
Nucleosides include adenosine, guanosine, cytidine, and uridine, (which contain ribose), and deoxyadenosine, deoxyguanosine,
deoxycytidine and thymidine, (which contain deoxyribose).
6. A nucleotide is a nucleoside in which the primary hydroxy group of either 2-deoxy-D-ribose or of D-ribose is esterified by
orthophosphoric acid.
7. An oligonucleotide is a long linear sequences of nucleotides.

16.3.2.9 Polysaccharide gums, gums, phycocolloids
Food stabilizers and thickeners:
1. Gums: (guar gum from Cyamopsis), (gum tragacanth from Astragalus, locoweed), (locust bean gum from carob, Certonia),
(gum arabic from Acacia senegal), (gum karyaya from Sterculia), (gum ghatti from Anogeissus), (xanthan gum from fermented corn
sugar).
2. Phycocolloids: (alginates, algin, from kelp, Laminaria and Macrocystis), (carrageenan from red algae, Irish moss, Chondrus
crispus
), (agar from red algae, Gelidium and Gracilaria).

16.3.3.0 Lipids, fats and oils, fatty acids, glycerides
Fatty acids are aliphatic monocarboxylic acids.
See diagram 16.3.3.1: Esterification of glycerol to form fatty acids, fats
See diagram 16.3.3: Lipids, cephalins, glycerides, (triglycerides), glycolipids, lecithins, (choline), phosphoglycerides, prostaglandins
See diagram 19.2.1: Oleic acid, stearic acid, linoleic acid, (cis and trans)
See diagram 16.3.3.2: Fat molecules
See diagram 16.3.3.3: Tristearin
See diagram 16.3.3.4: Human fat molecule

16.3.3.0.1 Phospholipids, (phosphoglycerides)
Phospholipids form when hydroxyl groups form esters with phosphate groups.
They occur as two groups:
1. Phosphoglycerides, e.g. lecithin in cell membranes and in bile.
Phosphatidyl choline, (formerly lecithin), phosphatide with organic base choline, in biological membranes, e.g. egg yolk, is used as a
natural emulsifier.
Egg yolk phospholipids (EYPL) are used as carriers for lipophilic drugs and are a major ingredient of lipid microspheres.
2. Sphingolipids in plant and animal cell membranes.
It is a fat molecule with a phosphate group, replacing the third fatty acid.
glycerol-3-phosphate + 2-monacyl glycerol --> triacyl glycerol + phospholipids.
Sphingolipids: sphingenine, cerebrosides, sphingomyelin.

16.3.3.0.2 Lecithins
Lecithins, diacylphosphatidylcholine, esters of glycerol and choline with fatty acids and H3PO4, in cell membranes.
The lecithin group, (phosphatidylcholine group) are yellow-brown fatty phospholipids in egg yolks and plasma membranes of plant
and animal cells.
They are used as emulsifiers in commercial foods, and cosmetics.

16.3.3.0.4 Lipids
Lipids are biological substances that are soluble in nonpolar solvents:
1. saponification lipids, e.g. glycerides, (fats and oils), and phospholipids,
2. non-saponification lipids, e.g. steroids.
Lipids refers to the oils, fats and waxes found in living organisms.
Lipids are insoluble in water but soluble in inorganic solvents, e.g. chloroform.
The simple lipids do not contain fatty acids, e.g. steroids, terpenes.
The complex lipids are esters of long chain fatty acids, e.g. glycerides, glycolipids, phospholipids, waxes.

16.3.3.0.5 Glycerides, esterification of glycerol
Glycerides are common biological substances made from esters of glycerol, (propane-1,2,3-triol), with fatty acids:
1. triglycerides,
2. 1,2-diglycerides or 1,3-diglycerides,
3. 1-monoglycerides or 2-monoglycerides.
The fats and oils found in living organisms are mainly triglycerides:
1. Monoglycerols, (monoglycerides), e.g. 1-monoacyl glycerol, 2-monoacyl glycerol,
2. Diglycerols, (diglycerides), e.g. 1,2-diacyl glycerol, 1,3-diacyl glycerol,
3. Triglycerols, (triglycerides), (fats, main storage lipids), e.g. triacyl glycerol.
Glycerides, glycerine esters, are fatty acid esters of glycerol, (HOCH2CH(OH)CH2OH).
Esters can form at one, two or three of the hydroxyl groups to form monoglycerides, diglycerides and triglycerides.
Esterification of glycerol
Plant oils are usually triglyceride molecules, esters, composed of a 3C alcohol, glycerol, + 18C or 16C fatty acids containing 12C to
24C.
The number of carbon atoms is counted from the end of the molecule with the carboxylic acid group, COOH.
The position of the first double bond is counted from the other end, the methyl or ω end.
Whether the fatty acid is an ω-6 fatty acid or an ω-3 fatty acid depends on the position of the first double bond.

16.3.8.0 Carboxylic acids and fatty acids
Carboxylic acids contain the carboxyl group, carbonyl: -COOH, e.g. ethanoic acid (acetic acid) CH3COOH, so the general formula
is RCOOH.
The carbonyl group, (carboxy) is -COOH.
The group of saturated and unsaturated aliphatic carboxylic acids are called fatty acids and are found as esters in fats and oils.
Lower carbon fatty acids are corrosive liquids with strong odour and are soluble in water.
Higher carbon fatty acids are oily liquids with unpleasant smell and are only slightly soluble in water.
Fatty acids from C10 onwards are usually solids and are insoluble in water.
The poly unsaturated fatty acids linoleic acid, linolenic acid and arachidonic acids are essential fatty acids in the diet to prevent
atheroma ("hardening of the arteries"), and synthesize prostaglandins.
Saturate fatty acids with no double bonds are linked to the development of atheroma.
Fatty acids in plants occur as esters of glycerol or other hydroxy compound, or amides of long chain amines, e.g. sphingenine.
Fatty acids have trivial and systemic names and the molecule may be saturated, (no double bonds), or unsaturated, (one or more
double bonds).
The products called "natural oils" are not necessarily unsaturated fats.

16.3.8.1 Saturated carboxylic acids
Arachidic acid, (icosanoic acid), CH3(CH2)18COOH, (in peanut oil)
Benzoic acid, C6H5COOH, benzenecarboxylic acid, phenylformic acid, harmful if ingested
Butyric acid, butanoic acid, C3H7COOH, CH3(CH2)2COOH, in rancid butter
Capric acid, decanoic acid, CH3(CH2)8COOH, (in coconut oil, palm oil, mammal milk)
Caproic acid, (hexanoic acid), CH3(CH2)4COOH, (in goat fat)
Caprylic acid, octanoic acid, CH3(CH2)6COOH, (coconuts, breast milk, in sting of whip scorpions!)
Chloroacetic acid, CH2ClCOOH, (used in chemical reactions)
Decanedioic acid, HOOC(CH2)8COOH, sebacic acid, from castor oil
Dichloroacetic acid, DCA, CHCl2COOH, (in chlorinated drinking water)
Ethanoic acid, CH3COOH, acetic acid, vinegar
Formic acid, CH2O2, HCOOH, methanoic acid, (in insect stings, ants)
Lauric acid, dodecanoic acid, CH3(CH3)10COOH, (in coconut oil, soaps)
Myrstic acid, tetradecanoic acid, CH3(CH3)12COOH, (in nutmeg)
Oxalic acid, C2H2O4.2H2O, HO2CCOOH, ethanedioic acid, (in rhubarb, Oxalis)
Palmitic acid, CH3(CH2)14CO2H, hexadecanoic acid, (palm oil, coconut oil, most animals / plants)
Proprionic acid, propanoic acid, CH3CH2COOH, (stored grains preservative)
Stearic acid, octadecanoic acid, CH3(CH2)16COOH, (in fats, soaps, waxes)
Trichloroacetic acid, C2HCl3O2,CCl3COOH, Highly toxic, (used in chemical reactions)
Trifluoroacetic acid, CF3COOH, corrosive, (used in chemical reactions)
Valeric acid, (pentanoic acid), CH3(CH2)3COOH, (valerian herb)

16.3.8.2 Dicarboxylic Acids
Adipic acid, hexanedioic acid, HOOC(CH2)4COOH
Aldaric acid, HOOC-(CHOH)n-COOH
Fumaric acid, butenedioic acid, HCOOHC:CHCOOH } isomers
Maleic acid, butenedioic acid, HCOOHC:CHCOOH } isomers
Malic acid, 2-hydroxybutanedioic acid, HOOCCH(OH)CH2.COOH
Malonic acid, propanedioic acid, HOOCCH2COOH
Oxalic acid, ethanedioic acid, (COOH)2
Oxaloacetic acid, HO2CCH2COCO2H (in Kreb's cycle)
Succinic acid, butanedioic acid, (CH2)2(COOH)2
Tartaric acid, 2,3-dihydroxybutanedioic acid, (CHOH)2(COOH)2

16.3.8.3 Tricarboxylic acids
16.9.5 Citric acid cycle, Krebs cycle
Citric acid, HOOCCH2C(OH)(COOH)CH2COOH (in Kreb's cycle, plant and animal cells)
Isocitric acid, C6H8O7

16.3.8.4 Unsaturated fatty acids ,(have double bond =)
Acrylic acid, (2-propenoic acid), CH2=CHCOOH
α-linoleic acid, CH3(CH2)CH=CH(CH2)CH=CH(CH2)CH=CH(CH2)7COOH, polyunsaturated fatty acid
Linoleic acid, CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH, polyunsaturated fatty acid
Linolenic acid CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH
Oleic acid, cis-octadec-9-enoic acid, cis-09-octodecanoic acid, CH3(CH2)7CH=CH(CH2)7COOH, mono-unsaturated fatty acid
See: Models, biochemistry, Oleic acid, C18H34O2, 1 molecule, (photograph), "Scientrific", (commercial website)
Oleic acid, C17H33COOH, CH3(CH2)7CHCH(CH2)7COOH, octadec-8-enoic acid, colourless viscous liquid, red oil, m.p. 14oC
Palmitoleic CH3(CH2)5CH=CH(CH2)7COOH

16.3.8.5 Perfluorooctanoic acid
Perfluorooctanoic acid, (PFOA), C8HF15O2, a surfactant, is used to make non-stick cookware, e.g. PTFE, ("Teflon"), and
stain-resistant footwear and clothing.
It persists in the environment and is toxic to animals may be a carcinogen.

16.3.8.6 α-hydroxy acids
Naturally occurring carboxylic acid, hydroxyl group on the carbon adjacent to the carboxyl group.
Use in skin care.
See diagram 16.3.8.6: Alpha hydroxy acids
Citric acid, HOOCCH2C(OH)(COOH)CH2COOH, citric fruits
Glyceric acid, C3H6O4, 2,3-Dihydroxypropanoic acid
Glycolic acid, Hydroxyacetic acid, HOCH2COOH, sugar cane, sugar beet
Lactic acid, L-(+)-Lactic acid , 2-Hydroxypropionic acid, Sarcolactic acid, C3H6O3, sour milk
Malic acid, HOOCCH(OH)CH2.COOH, green apple sour taste, grapes
Mandelic acid, C6H5CH(OH)CO2H, bitter almond
Tartaric acid, L-(+)-Tartaric acid, L-Threaric acid, C4H6O6, HO2CCH(OH)CH(OH)CO2H, leavening agent

16.3.8.7 Keto acids
Acetoacetic acid, diacetic acid, C4H6O3, CH3COCH2COOH
Pyruvic acid, C3H4O3, CH3COCOOH, metabolism of proteins and carbohydrates, release of energy

16.3.3.1 Waxes
Waxes are fatty acid esters of high molecular weight alcohols, i.e. lipids with a long chain alcohol + more than 3 fatty acids.
Solid at room temperature, harder, more brittle and less greasy than fats at the same temperature.
Waxes are found in skin, fur feathers, and outer layers of leaves and fruits as follows:
Fats and oils that are fatty acid esters of the trialcohol glycerol.
Waxes are esters of long chain C16 and above alcohols, (with one hydroxyl group), and long chain C18 and above fatty acids.
Natural waxes are mixtures of esters and some hydrocarbons.
Beeswax [C30H61(C=O)OC15H31, C25-27H51-55(C=O)OC30-32H61-65] comes from the cells of the honeycomb and contains esters
of C16 and C28 acids with C30 and C32 alcohols + mainly C31 hydrocarbons.
Beeswax is used in furniture polishes.

Candelilla wax, food additive E902, glazing agent, emollient
Candelilla, (Euphorbia antisyphilitica), and  (E. cerifera), Euphorbiaceae
Candelilla wax is yellow-brown, hard, brittle, aromatic, and opaque to translucent, glazing agent E902, in chewing gum.

Carnauba wax comes from the leaves of the Brazilian wax palm, Coperniciaprunifera, (C. cerifera), Arecaceae.
It contains esters of the C32 and C34 alcohols and C24 and C28 fatty acids.
This wax is harder and more impervious than beeswax.
Carnauba wax, glazing agent, E903, used to wax fruit, in cosmetics.

Cetyl palmitate [(CH3(CH2)13CH2(C=O)O(CH2)15CH3)] [C15H31COO-C16H33] is a component of spermaceti wax in sperm
whale oil.

Jojoba oil, Simmondsia chinensis, Simmondsiaceae, mainly wax esters, in cosmetics, seed is toxic and indigestible
 Meadow foam oil, (Limnanthes alba), Family Geometridea

Wool wax, wool grease, degras, from the scouring of wool contains fatty acid esters of cholesterol, lanosterol and fatty alcohols.
It forms as semi-solid emulsion in water that is purified to make lanolin.

16.3.4.0 Aromatics, aromatic compounds
Aromatics, aromatic compounds, benzene derivatives, ring systems, arenes: benzene, toluene, naphthalene
See diagram 16.3.4.0: Acridine, anthracene, anthroquinone, cinnoline, naphthalene, naphthol, quinoline
See diagram 16.8.0: Acetylsalicyclic acid, (aspirin), benzene, benzoic acid, naphthalene
See diagram 16.3.4.1: Single substitution, more than single substitution
See diagram 16.3.4.4: Heterocyclic compounds: pyridine, (2-aminopyridine, 3-bromopyridine, 3-nitropyridine, nicotinic acid ),
(azines: piperidine, pyridinium chloride), pyrylium ion, (quinoline, isoquinoline, 5-nitroquinoline), (pyrimidines: cytisine, thymine, uracil),
(diazines: pyrazine, pyridazine, pyrimidine)
Aromatics have planar ring-type groups usually composed of carbon atoms, at least one benzene ring in the molecule, e.g. benzene,
naphthalene, with alternating double and single bonds.
Extensive localization occurs because some electrons in the molecule are free to move from one atom to another.
The term "aromatic" was used to describe the smell of some compounds later were found to contain benzene or fused benzene rings in
the structure.
It includes arenes and their substitution products, e.g. benzene, naphthalene, toluene, and aromatic heterocyclic structures, e.g. thiophene.

16.3.4.0a Aryl groups
Groups derived from arenes by removal of a hydrogen atom from a ring carbon atom.
Usually, groups having hydrogen removed from an aromatic compound,
e.g. benzene, C6H6 - hydrogen atom, H --> phenyl group, C6H5.

16.3.4.0b Aramids
Aramids are aromatic polyamides, e.g. "Kevlar", "Nomex".
Aramid fibres are made by spinning liquid crystal aramid polymers to long chain polymer molecules with remarkable strength.
The polymer chains are linked laterally by hydrogen bonds, used in rope and textile high performance fibres.
"Kevlar", a synthetic fibre with of high-tensile strength, is used as a reinforcing material for the rubber in motor vehicle tyres.

16.3.4.0.1 Aromatic hydrocarbons, arenes
See diagram 16.8.1: Benzene compounds, anthracene
Aromatic hydrocarbons, e.g. Benzene, (C6H6), also in some countries: petrol, pentane-hexane mixture, petroleum spirit.
Benzene is the simplest aromatic compound. As it is toxic and carcinogenic, it should not be used in schools.
Aromatic hydrocarbons, arenes, alkylbenzenes, e.g. benzene C6H6, toluene C6H5CH3, [xylene (dimethylbenzene) (CH3)2C6H4],
[styrene, (phenylethene), (C6H5CH=CH2)], naphthalene C10H8, anthracenen C14H10, cyclohexane C6H12.
Anthracene, C14H10, paranaphthalene, anthracin, anthracene oil, Irritant, harmful if ingested, Very Hazardous, Toxic

16.3.4.0.2 Aromatic nitro compounds
Aromatic nitro compounds, e.g. Nitrobenzene, oil of mirhan, (C6H5NO2)
16.3.4.0.3 Lactams
Lactams, (-NH(CO-), e.g. caprolactam, (6-hexanelactam), (C6H11NO)
See diagram 16.3.4.3: Lactams, penicillin G, amoxicillin
Lactams in part of a ring, cyclic amides, amino group + carboxylic acid group --> amide linkage, e.g. caprolactam, (6-hexanelactam),
(C6H11NO), to make nylon, 4-aminobutanoic acid lactam, (β lactam 4C ring, γ-lactam 5C ring, δ-lactam 6C ring), e.g. the pyrimidine
base uracil, β-lactam antibiotics, e.g. penicillin, also: caprolactam, (C6H11NO), also: lactones, (cyclic esters), e.g. 4-hydroxybutanoic
acid lactone CH2CH2CH2OC=O, γ-butyrolactone, GBL, C4H6O2.

16.3.4.0.4 Aromatic amines
Aromatic amines, anilides, e.g. phenylamine, (aniline, amino benzene), (C6H5NH2)
(phenylammonium ion, anilinium ion C6H5NH3+), benzylamine, diphenylamine, methylaniline, triphenylamine, dimethylaniline, acetanilide,
quinoline, (C9H7N).

16.3.4.0.5 Diazo compounds
Diazo compounds, (2 linked nitrogen compounds), e.g. methyl orange, (dimethyl-aminoazobenzene sulfonic acid),
(diazonium ion: C6H5N2+, C6H5N+N), diazonium salts [(RNN+)Cl-], e.g., methyl orange, (dimethyl-aminoazobenzene sulfonic acid),
[(CH2)2NC6H4N=NC6H4SO2O-Na+] benzene diazonium chloride, chrysoidine azo compounds, (-N-N-), (diazonium ion + benzene
ring)

16.3.4.0.5a Barbiturates (central nervous system depressants)
See diagram 16.3.4.05a: Amylobarbital, barbital, pentobarbital, phenobarbital, quinalbarbital, sodium phenytoin, thiopental
barbiturates were formerly used as sedatives and hypnotics.
Barbituric acid is formed by condensing urea with diethyl malonate, an ester from apples.
Barbituric acid derivatives include the following:
1. Barbital (US), barbitone, C8H12N2O3, "Veronal", formerly used or attempted used by would-be suicides
2. Phenobarbital (US), phenobarbitone, C12H12N2O3, "Luminal", sedative and hypnotic, an anticonvulsant drug used to treat epilepsy.
Phenobarbital causes side effects, e.g. sedation, depression and agitation,  so it may be replaced by phenytoin, C15H12N2O2, in the
anti-epileptic drug sodium phenytoin, "Dilantin".
3. Sodium thiopental, C11H17N2NaO2S,  ("Sodium Pentathol", thiopentone sodium, "Trapanal"), "truth drug", is a short acting
barbiturate general anaesthetic, used to start anaesthesia, e.g. for caesarian section operation.
It causes unconsciousness in seconds.

16.3.4.0.5b Benzodiazepines (tranquillizers, sedatives, hypnotics)
See diagram 16.3.4.0.5b: Diazepam (Valium), oxazepam (Serax), nitrazepam (Mogadon), chlordiazepoxide (Librium), flunitrazepam
(Rohypnol).
Benzodiazepines assist the neurotransmitter γ-aminobutyric acid to treat anxiety, insomnia, seizures, and preparation for medical
procedures.

16.3.4.0.6 Aromatic halogen compounds
Aromatic halogen compounds, aryl halide, halogenarenes, e.g. benzyl chloride, (C6H5COCl)
See diagram 16.3.4.0.6: DDT, methoxychlor, Synergists: piperonyl butoxide
See diagram 16.13.3: Benzene hexachloride, chlorothalanil, DCPA, dalapon
See diagram 16.13.4: Aldrin, chlordane, dieldrin, endosulfan, heptachlor
16.7.2 Dalapon
Bromobenzene, iodobenzene, chlorobenzene, (BHC, benzene hexachloride, lindane), chlorothanil
Cyclodienes: chlordane, aldrin, dieldrin, heptachlor, endosulfan
DDT insecticide: (ClC6H4Cl)2CH(CCl3), (Former name: dichlorodiphenyltrichloroethane), ( New IUPAC name:
1,1,1-trichloro-2,2-bis, (4-chlorophenyl)ethane.)!

16.3.4.0.7 Aromatic sulfonic acids
Aromatic sulfonic acids, e.g. benzene sulfonic acid, (C6H5SO2OH), sodium benzene sulfonate

16.3.4.0.9 Aromatic alcohols
Aromatic alcohols, e.g. phenyl methanol, (benzyl alcohol), (C6H5CH2OH),

16.3.4.0.10 Aromatic aldehydes and ketones
Benison, C14H12O2, 2-Hydroxy-2-phenylacetophenone, 2-Hydroxy-1,2-Diphenylethanone, desyl alcohol, bitter almond oil
Benzaldehyde, benzenecarbaldehyde, benzene aldehyde, C6H5CHO, almond kernel flavouring, camphor is synthesized from
benzaldehyde in a condensation reaction.
See diagram 16.8.1

16.3.4.0.11 Aromatic acids
Aromatic acids and their derivatives, e.g. benzoic acid, (C6H5COOH)
See diagram 16.3.4.11: Acetyl salicyclic acid, (aspirin), | See diagram 16.3.4.12: Benzoic acid, caffeine, paracetamol, phenacetin
e.g. benzoic acid, (C6H5COOH), benzoyl chloride, (C6H5COCl), salicyclic acid, (1-hydroxybenzoic acid), (HOC6H4COOH),
aspirin, acetyl salicyclic acid, (2-acetoxy benzoic acid), [C6H4(OCOCH3)COOH] alcohol detergent, aromatic detergent, weed killer
2:4-dichlorophenoxyacetic acid, shikimic acid [C6H6(OH)3COOH]
Acetyl salicyclic acid is hydrolysed with hydrochloric acid to salicylic acid and acetic acid.
Sometimes old bottles of aspirin have a vinegar (acetic acid) smell because of this reaction.

16.3.4.0.12 Parabens
Parabens get their name from their origin as esters of parahydroxybenzoic acid., Parabens, HO.C6H4.CO.O-R, where R = alkyl group
See diagram 16.3.4.12: Parabens
See 19.4.4.23 Preservatives, food additives: E214 to E219
Parabens are esters of para-hydroxybenzoic acid and are used commonly as preservatives in cosmetics and food.
However, some parabens may cause allergic reactions in some people and affect DNA.
Some parabens are said to imitate oestrogen and are suspected of causing cancer, but there is no evidence that they are carcinogenic.
However, in Australia, some skin care products are labelled "Paraben free" because of this suspicion.
Propyl paraben, propyl 4-hydroxybenzoate, "Nipagin A", E216, is a natural subsonic but is usually manufactured for use as a food
preservative against fungi and as a cosmetics industry preservative.
Methyl paraben, methyl 4-hydroxybenzoate, "Nipagin B", E218, CH3(C6H4(OH)COO, is used as anti-fungal agent in hair gels and
similar products, it occurs in blueberries
Ethyl paraben, ethyl 4-hydroxybenzoate, E214, is used as a food preservative.

16.3.4.0.13 Pyridine
Pyridine, (pyridino), C5H5N, monodentate ligand
Pyridine, C5H5N, has a penetrating offensive odour and in some countries it is added to methylated spirit to deter ingestion.

16.3.4.1a Benzofuranoids, benzopyranoids
See diagram 16.3.4.12: Coumarin, furan, bergamottin | See diagram 16.3.4.13: Bergamottin, lovastatin, atorvastatin
Atorvastatin calcium salt trihydrate, C33H34FN2O5.0.5Ca.1.5H2O
Benzofuranoids: (furan C4H4O), (benzofuran, coumarone, C8H6O, 2,3-benzofuran), (benzodifuran), (isobenzofuran)
Benzofuranoid derivatives used as anti-inflammatory constituents from Eupatorium cannabinum.
Benzopyranoids: (pyran, C5H6O, oxime, 2H pyran, 4H pyran), (1-benzopyrans), (3,4-dihydro-2H-1-benzopyran, chroman),
4-chromanone, C9H8O2), (chromone, C9H6O2), (2-chromeme), (3-chromeme), (flavone, C15H10O2), (flavanone C15H12O2),
(fisetin flovanol C15H10O6.nH2O), (coumarin, C9H6O2)
Benzopyrans, chromenes, have a benzene ring + heterocyclic pyran ring, C5H6O.
Coumarin, warfarin, (C9H6O2, 1,2-benzopyrone, 1-benzopyran-2-one), in perfumes, (tonka bean Dipterix odorata, Aloe vera,
Artemisia vulgaris), (used to make warfarin, C19H16O4, a medical anticoagulant and rat poison, e.g. "Ratsac".)

16.3.4.2.8 Other bioflavonoids
Proanthocyanidin, rotenone, pisatin, isoflavan, pisatin, proanthocyanidins, orcein, vulpinic acid, taxol, urushiol, (pentadecyl-catechol),
(phytoalexins: resveratrol, psoralen), (flavone alkaloids: ficine, vochysine).
Brazilin, red pigment, (C16H14O5), from Caesalpinia echinata, "Brazil wood" originally "bresel wood", Natural Red 24
Haematoxylin, log wood, (C16H14O6), from Haematoxylum campechianum, logwood tree, Natural Black

16.3.4.3 Tannins
Tannins, (kinotannic acid), plant polyphenols, phenolic polymers: polyphenols, galloyl ester, vescalagins
Tannin, i.e. tannic acid, a polyphenol, is a yellow-brown compound in coffee beans, oak galls, mahogany, tea leaves, tree bark, walnuts.
Reacts with proteins in skins to form leather.
Used as a mordant, inks and dyeing. Tannic acid is not an acid.
Tannins are any group of yellow-brown astringent compounds derived from gallic acid, found in bark and galls, used to convert animal
hide to leather.
Tannins from hemlock, (Tsuga), oak, (Quercus), mangrove, (Rhizophora), wattle, (Acacia), babul, (Acacia sp) chestnut, (Castanea),
quebracho, (Schinopsis), sumacs, (Rhus), canaigre from tanner's dock, (Rumex), E181 Tannic acid, tannins, (from oak trees, tea),
(clarifying agent).

16.3.4.4 Lignans, plant phenols
Lignans: (from degradation of lignin), plant phenols, dihydroguaiaretic acid, hinokinin, podophyllotaxin

16.3.4.5 Five member heterocycles
See diagram 16.3.4.5: 5-member heterocycles | See diagram 14.05: Histamine, major tranquillizers, tricyclic anti-depressants
Heterocyclic molecules have different atoms in the ring: furan C4H4O, thiephene C4H4S, pyrrole, (CH)4NH, thiazole C3SNH3,
saccharin C7H5NO3S,
Histamine, C5H9N3, immidazole C3N2H4
Indole, C8H7N, [amino acid proline (CH2)3NHCHCOOH]

16.3.5.01 Terpenes, (C10H16)
See diagram 16.1.1.2.2: Isoprene | See 16.1.1.2.2: Dienes, isoprene units
Terpenes, any terpenoid,   volatile, aromatic, in essential oils, usually conifers, citrus
Terpenes may be removed from essential oils to prevent oxidation spoilage.
Terpenes are unsaturated hydrocarbons with of two or more isoprene, (C5H8) units, joined together.
Terpenes are unsaturated hydrocarbons formed by polymerization of two or more 5-carbon isoprene units, CH2:C(CH3)CH:CH2,
C5H8.
An isoprene unit has a four carbon chain and a one carbon branch at C2.
Terpenes, (isoprenoids), occur mostly in plant essential oils and may be isolated as a water-insoluble oil through distillation.
Terpenes contain functional groups, e.g. C=C, OH, C=O and may be acyclic or cyclic.
Terpenes are volatile organic compounds, (VOCs), and are flammable or combustible.
Terpenes may be poisonous and can cause painful rashes, e.g. Manchineel tree, (Hippomane mancinella),  Cicutoxin water hemlock,
(Cicuta douglasii).
Phenolic compounds, often associated with terpenes, contain benzene rings with attached hydroxyl groups, (C-OH).
Terpenes may be organic solvents and cleaning agents with strong characteristic odours derived from pine trees or citrus fruit,
e.g.  d-limonene, and turpentine, (a mixture of terpenes).

1. List of terpenes, molecular formula
Bisabolol C15H26O (-)-α-Bisabolol, from leaves of Hymenocrater yazdianus, Lamiaceae
Camphor, D-Camphor, C10H16O, original source was camphor tree, camphor laurel, Cinnamomum camphora, Lauraceae
Trans-caryophyllene, C15H24, cloves Syzygium aromaticum, hemp Cannabis sativa, rosemary Rosmarinus officinalis, hops, black
pepper.
Camphene, Cadinene, Caryophyllene, Cedrene,
1,4-Cineole, C10H18O, in eucalyptus oil, natural monoterpene that inhibits plant growth, monoterpenoid
Citral, C10H16O, from Cymbopogon citratus, lemongrass, monoterpenoid
Citronellal, C10H18O, from Citrus depressa, Taiwan mandarin
Citronellol, C10H20O, monoterpenoid, in citronella oils, Cymbopogon nardus, oils of rose, Pelargonium geraniums
Cymene, C10H14, 4-Isopropyltoluene
Dimethyl-3-octanol, C10H22O, Tetrahydrolinalool
Geraniol, C10H18O, monoterpenoid, rose oil, palmarosa oil, citronella oil, geranium, lemon, rose-like scent
Lavandulol, C10H18O, monoterpenoid alcohol, lavendar oil, , weak floral, herby odor, with lemon-like cirus fruity nuance, insect
pheromone
Limonene, C10H16, dipentene, cyclie terpene, Chinese medicinal herb, used in synthesis of carvone, dissolve polystyrene, insect repellant
Linalool, C10H18O, monoterpenoid, Ocium canum, many flowers and spic plants, pleasant odour
Menthone, C10H18O
Mercaptomenthone, 8-Mercaptomenthone, C10H18OS
Myrcene, C10H16
Myrtenal, C10H14O, in cumin seed, juniper berry, pepper, peppermint, scotch spearmint.
Phellandrene, C10H16, cyclic monoterpene, Eucalyptus radiata. beta-phellandrene in Canada balsam oil, Foeniculum vulgare
Pinene, C10H16, from stem of Canarium tramdenanum, α-pinene, main component of turpentine
Pulegone, C10H16O, in Schizonepeta tenuifalia
Rose oxide, C10H18O, monoterpenoid, fragrance chemical, roses oil, lychee, Gewurztraminer wines
Sabinene hydrate, 4-Thujanol, C10H18O
Terpinene, cyclic terpene, C10H16,
alpha-Terpinene, oil with lemon smell, cardomum, coriander, marjoram
beta-Terpinene, from oil of savin
gamma-Terpinene, coriander, cumin lemon, samphire
Terpineol, C10H18O, α-terpineol, from pine oil
Terpinoline, C10H16, flavour and fragrance agent
Terpinyl acetate, C12H20O2, oleoresin from pine oil
Terpyridine, C15H11N3, tridentate ligand
Thymol, C10H14O, monoterpenoid
Verbenone, C10H14O, pleasant odour, lemon verbena Aloysia citrodora

16.3.5.02 Isoprene units, (C5H8)
Different structural forms are called isomers.
Isoprene: [2-methyl-1,3-butadiene], [CH2=C(CH3)CH=CH2], (C5H8)
Isoprenoids are compounds derived from isoprene, often showing repeated occurrence of isoprene units.
Terpenes have linked isoprene units that occur in natural rubber.

16.3.5.1.0 Hemiterpenes, (one isoprene unit), (C5H8)
Prenol hemiterpenoids, prenols are alcohols of general formula H-[CH2C(Me)=CHCH2]nOH  in which the carbon skeleton is
composed of one or more isoprene units.
So terpenes can be defined as a class of compounds composed of repeating 5-carbon units of hemiterpenes.

16.3.5.1.1 Monoterpenes, (two isoprene units), (C10H16)
α-pinene in turpentine, (pine needles flavour),
β-linene,  camphor C10H16O,
Citronellal C10H18O, (aldehyde),
Citronellol,
Geraniol, (rose flavour),
Anethole, C10H12O: 16.3.6.8
Eucalyptol, C10H18O
Menthol, C10H20O: 16.3.6.7
Myrcene,
Pinene
Thujane, ketone, monoterpene, menthol odour, in oil of wormwood, from (Artemisia absinthium), used in the alcoholic drink absinthe,
Thujene, α-thujene
Thymol, C10H14O,  monoterpene phenol derivative of alkylbenzene cymene, C10H4, used as a topical antifungal,  from Thymus
vulgaris
, (thyme), and  Origanum vulgare, (origano).

16.3.5.1.2 Terpinenes, (cyclic terpenes)
Terpinenes, (C10H16), Terpinenes are cyclic terpenes and occur as three isomers:
1. α-terpinene is an oil with a lemon smell.
It occurs in cardamom, coriander, and marjoram.
2. β-terpinene occurs in oil of savin.
3. γ-terpinene occurs in coriander, cumin, lemon, samphire.
It can be formed from the action of alcoholic sulfuric acid solution on pinene from turpentine.

16.3.5.1.3 Sesquiterpenes, (three isoprene units), C15, terpene with formula C15H24
Sesquiterpenes are hydrocarbons (terpenes) with 15 carbon atoms.
They are naturally occurring alcohols that very rarely exist as volatile oils.
Sesquiterpenes, along with monoterpenes, are an important constituent of essential oils in plants though from the same family of terpenes.
Sesquiterpenes are larger molecules than monoterpenes.
When distilled from the plant matter, these compounds stimulate glands and the liver, and have anti-allergen, antispasmodic, and
anti-inflammatory properties.
Sesquiterpenes are formed from three isoprene units.
They may be acyclic, mono-, di-, or tricyclic; synthesized from farnesylpyrophosphate.
In turn, farnesylpyrophophate is a pyrophosphoryl derivative of farnesol.
Sesquiterpenes are isolated from their natural sources by distillation with steam or by extraction.
They are purified by vacuum fractional distillation or by chromatography.
Sesquiterpenoids are 15 C compounds

List of common sesquiterpenes
9.1.7.5 Abscisic acid, C15H20O4, isoprenoid plant hormone, guard cells
Bergamotene, C15H24, α-bergamotene, Cinnamomum zeylandicum
Cadalene, in essential oils many plants
Capsidiol, in tobacco Nicotiana tabacum, chili pepper Capsicum annuum
Caryophyllene, C15H24,
Cedrol, C15H26O, sesquiterpene alcohol, cedarwood oil
Curcumene, C15H22, alpha-curcumene, sesquiterpene,Curcuma xanthorrhiza, Javanese tumeric, wild tomato Lycopersicon
hirsutum, insecticide, insect repellent in tumeric, bright yellow
Farnesol, C15H26O
Germacrene, C15H24
Geosmin, C12H22O, earth smell, muddy fish smell, after rain smell, cut grass smells
Globulol, C15H26O, floral roseodour, in perfumes
Gossypol phenol, C30H30O8, terpenoid alkaloid, inhibits some dehydrogenase enzymes, in cotton plant Gossypium, yellow pigment,
former contraceptive but causes low blood potassium
Humulene, C15H24, alpha caryophyllene , monocyclic sesquiterpene, in essential oil hops Humulis lupulus
Juvabione, C16H26O3, paper factor, wood of Abies, balsum fir, anti-insect
Lactucin, C11H14O4
Laurene, C15H20, Laurencia glandulifera
Longifolene, C15H24, tricyclic sesquiterpene, Pinus roxberghii, lapsang souchong tea
8-Deoxylactucin, C15H16O4
Nerolidol, C15H26O, peruvidol, (in neroli, ginger, jasmine, lavender, tea tree and lemon grass, Cannibis sativa), oleoresin, fresh bark
smell, flavour, perfume
Patachoulol, C15H26O, sesquiterpene alcohol, in Pogostemon cablin
Picrotoxins, C30H34O13
β-Selinene, in celery oil,
Thujopsene, Turpentine --> rosin
Zingiberine, C15H24, monocyclic sesquiterpene, ginger flavour, in ginger

16.3.5.1.4 Diterpenes, (four isoprene units), C20H32
In perfumes and resins, pine turpentine, distilled essential oil,
Casbene, (disease resistance),
Crocin, (in saffron),
Cembrene phytol, a building block of the chlorophyll molecule
Dehydroleucodine, (medicine from Artemisia douglasiana),
Gibberellin, (phytohormones and germination), gibberellin A1, gibberellin plant hormones.(stem elongation),
Podocarpic acid, (disease resistance),
Retinol, (vitamin A activity),
Steviol C20H30O3, from Stevia rebaudiana, artificial sweetener
Taxadiene, taxol, (in yew tree bark, anticancer)
Taxol
Trisporic acid, (fungal hormones).

16.3.5.1.5 Sesterterpenes, (five isoprene units)
Sesterterpenes, C25, insect waxes, fungi products, phytotoxins, geranyl, farnesol, ceroplastol, insect gascardic acid

16.3.5.1.6 Triterpenes, (six isoprene units), (C30H48)
Triterpenes C30, steroids and sterols
β-amyrin
Squalene in amaranth seed, rice bran, wheat germ olives, used in cosmetics
Ambrein, C30H52O, a triterpene alcohol, is the main constituent of ambergris found in the sperm whales or floating on the sea as whale
barf (vomit), whale spit.
It is supposed to protect the intestines of whales from the sharp beaks of cuttlefish.
It was used for food flavouring and in the perfume industry to prevent scent from dissipating too quickly.
Since 1970 the perfume industry has turned to substitutes to protect whales.
It is supposed to be an aphrodisiac.
Saponins are toxic glycosides forming frothy colloidal solutions when agitated in water.
Some saponins cause breakdown of red blood cells but some saponins occur in traditional medicines, e.g.  Maesa balansae  in
Vietnam is used to treat leishmaniasis
Saponins that foam in water occur in the horse chestnut, Aesculus hippocastanum.
One triterpene saponin has formula C30H48O4.hederagenin
sterols, (steroids) in animal sex hormones, squalene, (in shark liver oil), cephalosporin, gonane, hopane, diplotene, lupeole
Squalene, in liver oil of sharks
16.3.5.1.6a Tests for saponins
Add ground plant material to test-tube of water, heat to boiling, add stopper and shake the test-tube.
Note presence of stable froth.

16.3.5.1.8 Tetraterpenes, (eight isoprene units), C40H56, carotenoid pigments
Tetraterpenes are terpenes with 8 isoprene subunits, (C40H64) lycopene,
Phytoene

16.3.5.1.9 Polyterpenes, (thousands of isoprene units)
Polyterpenes contain a long chain of thousands of C5H8 isoprene subunits in milky latex sap
5.1 Natural rubber, (C5H8)n, [n = 4,0005,000], (Hevea brasiliensis), and (Ficus elastica), polyisoprene, cis double bonds
5.2 Gutta-percha, (Palaquium gutta), polyisoprene, trans double bonds
5.3 Chicle polyterpene from the sapodilla tree, (Manilkara zapota), used for chewing gums.
Norisoprenoids, C13, Vitis vinifera

16.3.5.0 Terpenoids
The largest group of natural products and are responsible for many scents and flavours..
erpenoids including terpenes, diterpenes, sesquiterpenes and others, have formula (C5H8)n, and molecules composed of linked
isoprene units.
Terpenoids are terpenes modified by oxidation or rearrangement of the carbon skeleton.
Terpenoids are natural products and related compounds derived from isoprene units.
They contain oxygen in various functional groups and are subdivided as follows:
16.3.5.1 Monoterpenoids, C10
Thymol
Neral
Iridoids are cyclic monoterpenoids having the iridane skeleton, (1-isopropyl-2,3-dimethylcyclopentane)
16.3.5.2 Sesquiterpenoids, C15
Artemisisn
Cyperene
Fusarin
Germacrane
Vulgarin
16.3.5.3 Diterpenoids, C20
Forskolin, C22H34O7, Coleus forskolin, anti-hypertensive
Ginkgolides, Ginkgo biloba, leaves
Gingolide A, C20H24O9, antioxidant
Gingolide B, C20H24O10, treat gardivascular diseases, possibly anti-cancer, neuroprotective
Gibberellin
Lupulin A
Pachydictol A
Retinoid
Taxodone
16.3.5.4 Triterpenoids, C30
Triterpenoids -->saponins
Sapogenins, aglycone of saponins
non-ionic surfactant to form protective colloid, adjuvant
Quillaja saponaria (bark has sapogenin content 10 %, harmful, irritant).
Azadirachtin, C34H44O16, triterpenoid, natural pesticide ,in seeds
Saponins, e.g. solanine, C47H73NO15
Oleanoic acid, C30H48O3, in Olea europea, (olive oil).  Phytolacca, Syzygium, Hyptis
Ursolic acid, C30H48O3, in apple wax, Mirabilis japanica
Betulinic acid
Betulone
deltonin
Isobrucein
Moronic acid
Picrasin
Soyasapogenol B, C30H50O3, triterpenoid saponin
Steroids, sterols
Yamogenin

16.3.5.2.1 Tetrapyrroles, related compounds
See diagram 16.3.5.2: Bilin, haeme (heme) | See diagram 16.3.5.2.1: Haeme (heme) | See diagram 16.3.5.2.2 Tetrapyrroles
Tetrapyrroles are natural pigments containing four pyrrole rings joined by one-carbon units linking position 2 of one pyrrole ring to
position 5 of the next pyrrole ring.
Porphyrins are macrocyclic tetrapyrroles, e.g. bilin, (a linear tetrapyrrole).
Tetrapyrroles have the following related compounds: haemin, haematin, haemoglobin, myoglobin, cytochromes, chlorophylls a and b,
bile pigments biliverdin and bilirubin, vitamin B12, bilin, in congenital disease polyphyria, tetrapyrrole derivative DPEP in geological
deposits possibly from chlorophyll, chlorin, (2,3-dihydroporphyrin).
Haeme, (heme), in haemoglobin, globular protein in animals, oxygen carriers
Haeme A, C49H56O6N4Fe, (cytochrome oxidase ligand complex) tetradentate ligand],
Haeme, Constituents of blood: 9.214

16.3.5.2.2 Porphyrins
See diagram 16.3.5.01: Porphine | See diagram 16.3.5.2: Porphyrins, porphine | See diagram 16.3.5.0: Porphyrins (IUPAC)
Porphyrins are natural pigments containing a fundamental skeleton of four pyrrole nuclei united through the α-positions by four methine
groups to form a macrocyclic structure.
(IUPAC)
Porphyrins refers to any of a group of compounds containing the porphyrin structure of four pyrrole rings connected by methine
bridges in a cyclic configuration with usually metal side chains attached, e.g. with iron to form heme, (haeme).
Porphyrin chelates include haeme, in haemoglobin, bonded to iron (II) ion, and chlorophyll bonded to Mg (II) ion.
The heme component of the protein haemoglobin has four iron porphyrins.
Porphyrins occur in iron-containing cytochrome pigments in mitochondria in plants, animals and bacteria.
For oxidative phosphorylation, electron transport system, and ATP production.

16.3.5.2.4 Legheamoglobin
Legheamoglobin, leghemoglobin, legoglobin) occurs in nitrogen-fixing bacteria in the root nodules of legumes.
It is an oxygen carrier and a hemoprotein, produced by legumes in response to the roots being infected by nitrogen-fixing bacteria,
Rhizobium.
like hemoglobin, it is red in colour.
The apoprotein is produced by the plant and the heme (an iron atom bound in a porphyrin ring) is also produced by the plant.
It stores enough oxygen to support nodule respiration for a few seconds.
Its function is to help transport oxygen to the respiring symbiotic bacterial cells, analogous to hemoglobin transporting oxygen to
respiring tissues in animals.

16.3.5.2.5 Phycobiliproteins
Phycobiliproteins occur in cyanobacteria and red algae are composed of water-soluble phycobilin pigments and protein.
N-fixing cyanobacteria such as Anabaena azollae live symbiotically within leaf cavities of the water fern Azolla.

16.3.5.2.6 Phycobilins
Phycobilins include the blue-green pigment phycocyanin and the red pigment phycoerythrin to enable red algae to be photosynthetically
efficient in deep water where blue light predominates.
Phycobilin pigments are soluble in water-soluble and occur in the cytoplasm and stroma of chloroplast.
They occur only in Cyanobacteria and Rhodophyta.
The blue green pigment phycocyanin occurs in the Cyanobacteria their name.
The red brown pigment phycoerythrin occurs in the red algae.
Phycobilin pigments absorb light energy that is passed on to other processes.
Pycocyanin and phycoerythrin fluoresce are fluorescent.

16.3.5.2.7 Phytochromes
Phytochromes are phycobilin-protein pigments involved in floral induction, activated by the length of day, hours of darkness.

16.3.5.2.8 Polyvinyl pyrrolidene, povidone, PVP
See diagram 16.3.5.2: Povidone, PVP
Polyvinyl pyrrolidene, povidone, PVP, is a water-soluble polymer, E1201, used as a coating or binder in medical tablets,
e.g. povidone-iodine complex (PVD-iodine) in the antiseptic "Betadine", that nowadays has replaced tincture of iodine solution in
medicine.

16.3.5.3a Steroids, sterols, steroid alcohols, natural steroids
| See diagram 19.2.1.7: Steroids
| See diagram 16.3.5.3: Cholesterol, cholic acid, bile salt, estradiol, progesterone, northindrone,
RU 486, (mifepristone), testosterone, androsterone, cortisone
The sterols, (steroid alcohols), androstane steroids, (testosterone), C20 steroids, 19-norpregnane, pregnane steroids, (progesterone).
Steroids are naturally occurring compounds and synthetic analogues, based on the cyclopenta[a]phenanthrene carbon skeleton, partially
or completely hydrogenated, and usually with methyl groups at C-10 and C-13, and an alkyl group at C-17.
natural steroids are derived biogenetically from triterpenoids.
Sterols are natural products derived from the steroid skeleton and containing a hydroxy group in the 3 position, closely related to
cholestan-3-ol.
Steroids have a saturated 4 ring steroid structure.
Steroids include sex hormones, coricosteroid hormones, cardiac glycosides, bile acids, cholesterol lanosterol, (animal sterols),
β-sitosteron, (plant sterol), ergosterol, (fungus sterol), estrogen, cardiac glucosides, diosgenin, androstane, 19-norpregnane,
7-dehydrocholesterol, previtamin D3, ergocalciferol, (vitamin D2), cholecalciferol, (vitamin D3).
Sterols are anti  inflammatory and analgesic agents.
Plant sterols are extracts of certain plants that, when ingested, inhibit the absorption of cholesterol in the small intestine.
Sterolins are glucosides, which are molecular structures joined to the sterol.
Sterolin is easily destroyed, and without it, the sterol does not have the same immuneenhancing benefits.
In nature, plants never contain sterols only becauset the sterols are always associated with their glucoside sterolin.

Sitosterol, C29H50O, is a phytosterol, similar to cholesterol, extracted from wheat germ oil, corn oil, and other grain or nut oils,
Amaranthus species, rice bran, soybean, Prunus africana, Serenoa repens, Lycium barbarum, Cucurbita pepo
Sitosterol use is not recommended during pregnancy
Beta-sitosterol (C29H50O), phytosterol, similar to cholesterol, oestrogenic activity, inhibits proliferation of human leukemia cells,
reducing serum cholesterol levels. natural prostate health. reduce the growth of human prostate and colon cancer cells.
Campesterol, C28H48O, is a phytosterol in wild mustard (Brassica campestris), margarines, vegetable oils, seeds, nuts, fruits,
vegetables, beans and avocados.
It is said to have cholesterol-lowering and anti-carcinogenic effects.
Naturally occurring non-delta-5 plant sterols include cycloartenol, 24-methylene cycloartenol, cycloeucalenol, and obtusifoliol.