ALCOHOLS PHENOLS and ETHERS Functional group of an

ALCOHOLS, PHENOLS and ETHERS Functional group of an alcohol molecule R-OH C 2 H 5 OH ethanol ethyl alcohol propan-2 -ol, 2 -propanol, iso, isoprop, C H OH rubbing alcohol, or 3 7 the abbreviation IPA – isopropyl alcohol) Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS cholestero Menthol is a major component of mint. The best source is probably Mentha arvensis, Corn Mint, whose oil is up to 85% (-)-menthol. High-density lipoprotein (HDL) Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Glycerin, glycerine, propane-1, 2, 3 -triol Bombykol The sex pheromone of the silk moth A fatty alcohol with two double bonds, bombykol (tr-10, cis-12 -hexadecadien-1 -ol), was also shown to be excreted as a very strong attractive substance by the female of silk-worm (Bombyx mori). The bombyx mori silk moth Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS water alcohol phenol water ether group ether phenol group -OH diethyl ether (ether) hydroxyl group propan-1 -ol Chemistry 21 A R~ alkyl group diphenyl ether Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Nomenclature of Alcohols 1. Alcohols are named by finding the longest continues carbon chain and changing the ending to –ol (e. g. , methanol, propanol, etc. ). 2. With unsaturated alcohols, two endings are needed, one for the double or triple bond and one for the hydroxyl group. The –ol suffix is last and takes precedence in the numbering. 3. If the hydroxyl group is directly attached to an aromatic ring, the compound is named as a phenol. 4. If the hydroxyl group occurs in a carboxylic acid, aldehyde, or ketone, it is named as a substituent (hydroxy) because the former functionalities have higher priority. 5. The common names for the alcohols are the alkane chain named as a substituent followed by the word alcohol (e. g. , methyl alcohol, etc. ) methanol propan-1 -ol, 1 -propanol, propan-2 -ol, 2 -propanol, methyl alcohol ethanol ethyl alcohol Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS C 4 H 9 OH alcohols 1 -butanol 2 -butanol n-butyl alcohol sec-butyl alcohol 2 -methyl-1 -propanol 2 -methyl-2 -propanol isobutyl alcohol tert-butyl alcohol trans-3 -methylcyclohexanol ethanediol ethylene glycol 1, 2, 3 -propanetriol glycerin Chemistry 21 A 1 -methylcyclopentano Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS phenol 3 -methylphenol 4 -ethylphenol alcoh ol 2, 4, 6 -trichlorophenol Chemistry 21 A benzyl alcohol Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS 1 -butanol 2 -butanol n-butyl alcohol sec-butyl alcohol 2 -methyl-1 -propanol 2 -methyl-2 -propanol isobutyl alcohol primary alcohol secondary alcoholprimary alcohol ethanediol ethylene glycoltrans-3 -methylcyclohexanol Chemistry 21 A tert-butyl alcohol tertiary alcohol 1 -methylcyclopentano Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Water has an unusually high boiling point because of the hydrogen bonds between the H 2 O molecules. Alcohols can form similar hydrogen bonds. As a result, alcohols have boiling points that The difference in boiling are much higher than alkanes with similar molecular weights. points between alkanes The boiling point of ethanol, for example, is 78. 5ºC, whereas propane, and alcohols with the with about the same molecular weight, boils at -42. 1ºC. same number of carbon atoms decreases when the total number of carbons increases (i. e. with the increase of hydrophobic character of alcohols). CH 3 CH 2 OCH 2 CH 3 CH 2 CH 2 OH BP = 34. 5ºC BP = 117. 2ºC d = 0. 7138 g/m. L d = 0. 8098 g/m. L insoluble in water Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Solubilities of Alcohols in Water Solubility in Formula Name Water (g/100 g) CH 3 OH methanol infinitely soluble CH 3 CH 2 OH ethanol infinitely soluble CH 3(CH 2)2 OH propanol infinitely soluble CH 3(CH 2)3 OH butanol 9 CH 3(CH 2)4 OH pentanol 2. 7 CH 3(CH 2)5 OH hexanol 0. 6 CH 3(CH 2)6 OH heptanol 0. 18 CH 3(CH 2)7 OH octanol 0. 054 CH 3(CH 2)9 OH decanol insoluble in water hydrophilic part of the molecule hydrophobic part of the molecul Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS As the length of the alcohol increases, the effect of hydrogen bonding decreases and hydrophobic forces become dominant. The difference in boiling points between alkanes and alcohols with thw same number of carbon atoms decreases when the total number of carbons increases (i. e. with the increase of hydrophobic character of alcohols). Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS dehydration reaction synthesis of ethers Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS oxydation ethanol Chemistry 21 A oxydation acetaldehyde acetic acid Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS oxydation secondary alcohol isopropyl alcohol (2 -propanol) dimethyl ketone (acetone) no reaction oxydation tertiary alcohol oxydation Chemistry 21 A no reaction Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Pure 100% ethanol has an octane rating of 113. Adding 10% ethanol to gasoline raises the overall octane by 2 to 3 points. Lower BTU value than gasoline C 2 H 5 OH ethanol ethyl alcohol Made from corn and other crops (fermentation) yeast C 6 H 12 O 6 → 2 C 2 H 5 OH + 2 CO 2 C 2 H 5 OH + O 2 ethylene CH 3 COOH + H 2 O(ethene) → For most of human history, acetic acid, in the form of vinegar, has been made by acetic acid bacteria of the genus Acetobacter. Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Methanol is produced naturally CO + 2 H 2 CH 3 in the anaerobic metabolism of OH many varieties of bacteria heat, pressure, catalyst CH 3 OH → H 2 C=O → HCOOH methanol formaldehyde formic acid common laboratory solvent Aqueous solution of formaldehyde traditional denaturant for ethanol, thus giving the term methylated sp is called formalin used for storing specimens and cadavers. About 40% of methanol is converted to formaldehyde, and from there into products as diverse as plastics, plywood, paints, explosives, and permanent press textiles. Drag racers and mud racers also use methanol as their primary fuel source. Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Ethylene glycol Monoethylene glycol MEG 1, 2 -ethanediol propan-2 -ol, 2 -propanol, iso, isoprop, C H OH rubbing alcohol, or 3 7 the abbreviation IPA – isopropyl alcohol) widely used as an automotive antifreeze odorless, colorless, syrupy sweet tasting, toxic liquid propylene glycol, 1, 2 -propanediol, 1, 2 -Dihydroxypropane, methyl glycol (MEG), methylene glycol, PG, Sirlene, Dowfrost moisturizer in medicines, cosmetics, food, toothpaste, mouth wash, and tobacco products Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Glycerin, glycerine, propane-1, 2, 3 -triol In foods and beverages, Example of an unsaturated fat triglyceride. glycerol serves as a humectants, solvent and sweetener, and may help preserve foods. It is also used as filler in commercially prepared low-fat foods (e. g. , cookies), and as a thickening agent in liqueurs. Glycerol also serves as a way, along with water, to preserve certain types of leaves. Glycerol is also used as a sugar substitute. In this regard, it has approximately 27 calories per teaspoon and is 60% as sweet as sucrose. Although it has about the same food energy as table sugar, it does not raise blood sugar levels, nor does it feed the bacteria that form plaques and cause dental cavities. As a food additive, glycerol is also known as E number E 422. Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS CH 4 < NH 3 < HC CH < ROH < H 2 O < phenols < H 2 CO 3 < RCOOH < HF Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Joseph Lister, 1 st Baron Lister, (1827 – 1912) was an English surgeon who promoted the idea of sterile surgery while working at the Glasgow Royal Infirmary. He successfully introduced carbolic acid (phenol) to sterilize surgical instruments and to clean wounds, which led to reduced post-operative infections and made surgery safer for patients. 2 -Phenylphenol, or ortho-phenylphenol, is an ingredient in Lysol, and is an agricultural fungicide. Chemistry 21 A 2 -Benzyl-4 chlorophenol is an ingredient in Lysol. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS 4 -Chloro-3, 5 -dimethylphenol, or chloroxylen is a nonirritating topical antiseptic used in a number of antibacterial soaps. Butylated hydroxytoluene (BHT), also known as butylhydroxytoluene, is a organic compound that is primarily used as an antioxidant food additive (E number E 321) as well as in cosmetics, pharmaceuticals, jet fuels, rubber, petroleum products, and embalming fluid 2, 6 -di-tert-butyl-4 -methylphenol; 2, 6 -di-tert-butyl-p-cresol (DBPC); butylated hydroxytoluene; BHT Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS 4 -Hexylresorcinol is a chemical compound with anaesthetic, antiseptic and antihelmintic propertie It can be used topically on small skin infections, or as an ingredient in throat lozenges. Anthelmintics or antihelminthics are drugs that expel parasitic worms (helminths) from the body, by either stunning or killing them. They may also be called vermifuges (stunning) or vermicides (killing). 4 -hexylbenzene-1, 3 -diol Raspberry ketone is a natural phenolic compound that is the primary aroma compound of red raspberries. It is used in perfumery, in cosmetics, and as a food additive to impart a fruity odor. Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS PHENOLS are next-generation anti-oxidant found throughout natu in some of the healthiest foods. PHENOLS are the common health-giving link that ties together foo such as Red Wine, Green Tea, Dark Chocolate, and Super-Berries. A polyphenol antioxidant is a type of antioxidant containing a polyphenolic substructure. In human health these compounds, numbering over 4000 distinct species, are thought to be instrumental in combating oxidative stress, a process associated with Molecular structure of apigenin, some neurodegenerative diseases a polyphenol antioxidant and some cardiovascular diseases. Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS ether group ether dimethyl ether, an aerosol spray propellant A common low boiling solvent diethyl ether (b. p. 34. 6°C), and an early anaesthetic. (ether) Polyethylene glycol has a low toxicity and is used in a variety of products. It is the basis of a number of laxatives (such as Movicol and polyethylene glycol 3350, or Mira. Lax or Glyco. Lax). It is the basis of many Polyethylene glycol (PEG) skin creams, as cetomacrogol, and sexual lubricants, diphenyl ether Chemistry 21 A Anisole (methoxybenzene) An aryl ether and a major constituent of the essential oil of anise seed. Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Physical Properties: The polar nature of the C-O bond (due to the electronegativity difference of the atoms ) results in intermolecular dipole interactions. An ether cannot form hydrogen bonds with other ether molecules since there is no H to be donated (no -OH group) Ethers can be involved in H-bonding with systems able to donate H (e. g. water). The implications of these effects are: lower melting and boiling points compared to analogous alcohols solubility in aqueous media similar to analogous alcohols. CH 3 CH 2 OCH 2 CH 3 CH 2 CH 2 OH BP = 34. 5ºC BP = 117. 2ºC d = 0. 7138 g/m. L d = 0. 8098 g/m. L insoluble in water Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Ethers can act as a hydrogen-bond acceptor, as shown in the figure below. But, they can't act as hydrogen-bond donors. As a result, ethers are less likely to be soluble in water than the alcohol with the same molecular weight. The absence of an -OH group in an ether also has important consequences for its chemical properties. Unlike alcohols, ethers are essentially inert to chemical reactions. They don't react with most oxidizing or reducing agents, and they are stable to most acids and bases, except at high temperatures. They are therefore frequently used as solvents for chemical reactions. However, ethers are generally extremely FLAMMABLE and tend, If exposed to air for longer periods of time, to form EXPLOSIVE PEROXIDES. Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS A thiol is a compound that contains the functional group composed of a sulfur atom and a hydrogen atom (-SH). Being the sulfur analogue of an alcohol group (-OH), this functional group is referred to either as a thiol group or a sulfhydryl group. More traditionally, thiols are often referred to as mercaptans. The preferred method (used by the IUPAC) is to add the suffix -thiol to the name of the alkane. The method is nearly identical to naming an alcohol. Example: CH 3 SH would be methanethiol. An older method, the word mercaptan replaces alcohol in the name of the equivalent alcohol compound. Example: CH 3 SH would be methyl mercaptan. (CH 3 OH would be methyl alcohol) Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Many thiols are colorless liquids having an odor resembling that of garlic. The odor of thiols is often strong and repulsive, particularly Natural gas distributors began adding various forms of pungent thiols, originally for those of low molecular weight ethanthiol, to natural gas, which is naturally odorless, after the deadly 1937 New London School explosion in New London, Texas. Most gas odorants utilized in the world contain mixtures of mercaptans and sulfides, with t-butyl mercaptan as the main odor constituent. Cysteine Chemistry 21 A (oxydation) Cystine, showing disulfide bond Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Diallyl disulfide (4, 5 -dithia-1, 7 octadiene) is an organosulfur compound, along with diallyl trisulfide and diallyl tetrasulfide it is one of the principal components of the distilled oil of garlic. Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS 2 R-SH + (O) → R-S-S-R + H 2 O 2 CH 3 SH + (O) → CH 3 -S-S-CH 3 thiol disulfide 2 CH 3 SH + Pb 2+ → CH 3 -S-Pb-S-CH 3 + 2 H+ Coenzyme A (Co. A, Co. ASH, or HSCo. A) is a coenzyme, notable for its role in the synthesis and oxidation of fatty acids, and the oxidation of pyruvate in the citric acid cycle. Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Chemistry 21 A Dr. Dragan Marinkovic

ALCOHOLS, PHENOLS and ETHERS Chemistry 21 A Dr. Dragan Marinkovic