ALCOHOLS, PHENOLS and ETHERS

1. ALCOHOLS, PHENOLS and ETHERS R-OH C2H5OH Functional group of an alcohol molecule ethanol ethyl alcohol propan-2-ol, 2-propanol, iso, isopro, isoprop, rubbing alcohol, or the abbreviation IPA – isopropyl alcohol) C3H7OH Chemistry 21A Dr. Dragan Marinkovic

2. ALCOHOLS, PHENOLS and ETHERS cholesterol 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 21A Dr. Dragan Marinkovic

3. 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 21A Dr. Dragan Marinkovic

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

5. 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, ethanol, 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, ethyl alcohol, etc.) methanol methyl alcohol ethanol ethyl alcohol propan-1-ol, 1-propanol, propan-2-ol, 2-propanol, Chemistry 21A Dr. Dragan Marinkovic

6. ALCOHOLS, PHENOLS and ETHERS C4H9OH alcohols 1-butanol 2-butanol 2-methyl-1-propanol 2-methyl-2-propanol n-butyl alcohol sec-butyl alcohol isobutyl alcohol tert-butyl alcohol trans-3-methylcyclohexanol ethanediol ethylene glycol 1,2,3-propanetriol glycerin 1-methylcyclopentanol Chemistry 21A Dr. Dragan Marinkovic

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

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

9. ALCOHOLS, PHENOLS and ETHERS Water has an unusually high boiling point because of the hydrogen bonds between the H2O molecules. Alcohols can form similar hydrogen bonds. As a result, alcohols have boiling points that are much higher than alkanes with similar molecular weights. The boiling point of ethanol, for example, is 78.5ºC, whereas propane, with about the same molecular weight, boils at -42.1ºC. The difference in boiling points between alkanes and alcohols with the same number of carbon atoms decreases when the total number of carbons increases (i.e. with the increase of hydrophobic character of alcohols). Chemistry 21A Dr. Dragan Marinkovic

10. ALCOHOLS, PHENOLS and ETHERS Solubilities of Alcohols in Water hydrophilic part of the molecule hydrophobic part of the molecule Chemistry 21A Dr. Dragan Marinkovic

11. 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 21A Dr. Dragan Marinkovic

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

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

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

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

16. 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 C2H5OH ethanol ethyl alcohol Made from corn and other crops (fermentation) yeast C6H12O6→ 2C2H5OH + 2CO2 ethylene (ethene) C2H5OH + O2→ CH3COOH + H2O For most of human history, acetic acid, in the form of vinegar, has been made by acetic acid bacteria of the genus Acetobacter. Chemistry 21A Dr. Dragan Marinkovic

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

18. ALCOHOLS, PHENOLS and ETHERS Methanol is produced naturally in the anaerobic metabolism of many varieties of bacteria heat, pressure, catalyst CO + 2H2 CH3OH CH3OH → H2C=O → HCOOH methanol formaldehyde formic acid common laboratory solvent traditional denaturant for ethanol, thus giving the term methylated spirit Aqueous solution of formaldehyde 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 21A Dr. Dragan Marinkovic

19. ALCOHOLS, PHENOLS and ETHERS Ethylene glycolMonoethylene glycolMEG1,2-ethanediol propan-2-ol, 2-propanol, iso, isopro, isoprop, rubbing alcohol, or the abbreviation IPA – isopropyl alcohol) C3H7OH widely used as an automotive antifreeze odorless, colorless, syrupy, sweet tasting, toxic liquid propylene glycol, 1,2-propanediol, 1,2-Dihydroxypropane, methyl ethyl glycol (MEG), methylethylene glycol, PG, Sirlene, Dowfrost moisturizer in medicines,cosmetics, food, toothpaste, mouth wash, and tobacco products Chemistry 21A Dr. Dragan Marinkovic

20. ALCOHOLS, PHENOLS and ETHERS Glycerin, glycerine, propane-1,2,3-triol In foods and beverages, 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 E422. Example of an unsaturated fat triglyceride. Chemistry 21A Dr. Dragan Marinkovic

21. ALCOHOLS, PHENOLS and ETHERS CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF Chemistry 21A Dr. Dragan Marinkovic

22. ALCOHOLS, PHENOLS and ETHERS Joseph Lister, 1st 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 21A Dr. Dragan Marinkovic

23. ALCOHOLS, PHENOLS and ETHERS 4-Chloro-3,5-dimethylphenol, or chloroxylenol, 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 E321) 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 21A Dr. Dragan Marinkovic

24. ALCOHOLS, PHENOLS and ETHERS 4-Hexylresorcinol is a chemical compound with anaesthetic, antiseptic and antihelmintic properties. 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 21A Dr. Dragan Marinkovic

25. ALCOHOLS, PHENOLS and ETHERS PHENOLS are next-generation anti-oxidant found throughout nature in some of the healthiest foods. PHENOLS are the common health-giving link that ties together foods 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 some neurodegenerative diseases and some cardiovascular diseases. Molecular structure of apigenin, a polyphenol antioxidant Chemistry 21A Dr. Dragan Marinkovic

26. ALCOHOLS, PHENOLS and ETHERS dimethyl ether, an aerosol spray propellant ether group ether A common low boiling solvent (b.p. 34.6°C), and an early anaesthetic. diethyl ether (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 MiraLax or GlycoLax). It is the basis of many skin creams, as cetomacrogol, and sexual lubricants, Polyethylene glycol (PEG) Anisole (methoxybenzene) An aryl ether and a major constituent of the essential oil of anise seed. diphenyl ether Chemistry 21A Dr. Dragan Marinkovic

27. 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-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. Chemistry 21A Dr. Dragan Marinkovic

28. 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 21A Dr. Dragan Marinkovic

29. 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: CH3SH would be methanethiol. An older method, the word mercaptan replaces alcohol in the name of the equivalent alcohol compound. Example: CH3SH would be methyl mercaptan. (CH3OH would be methyl alcohol) Chemistry 21A Dr. Dragan Marinkovic

30. 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 for those of low molecular weight Natural gas distributors began adding various forms of pungent thiols, originally 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. (oxydation) Cysteine  Cystine, showing disulfide bond Chemistry 21A Dr. Dragan Marinkovic

31. 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 21A Dr. Dragan Marinkovic

32. ALCOHOLS, PHENOLS and ETHERS 2R-SH + (O) → R-S-S-R + H2O 2CH3SH + (O) → CH3-S-S-CH3 thiol disulfide 2CH3SH + Pb2+ → CH3-S-Pb-S-CH3 + 2H+ Coenzyme A (CoA, CoASH, or HSCoA) 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 21A Dr. Dragan Marinkovic

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

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