1. Ch. 14 Alcohols, Phenols, and Ethers Milbank High School

2. Chapter Objectives 1.What is the general structure for an alcohol? A phenol? An ether? 2.What are functional groups? Why are they useful in the study of organic chemistry? 3.What structural feature is used to classify alcohols as primary, secondary, or tertiary? 4.How are alcohols named by the common and IUPAC systems? 5.Why are the boiling points of alcohols higher than those of ethers and alkanes of similar molar masses?

3. Objectives Con’t 6.Why are alcohols and ethers of four carbons or less soluble in water while comparable alkanes are not? 7.How are alcohols prepared from alkenes? What is Markovnikov's rule? 8.How do various alcohols affect the human body? 9.What are the major reactions of alcohols? 10.What product is formed by the oxidation of a primary alcohol? A secondary alcohol? A tertiary alcohol?

4. Objectives Con’t 11.Describe the structure and uses of some common polyhydric alcohols. 12.Describe the structure and uses of some phenols. 13.How does the structural difference between alcohols and ethers affect their physical characteristics and reactivity? 14.How are simple ethers named? Describe the structure and uses of some ethers.

5. Sec. 14.1 General Formulas and Functional Groups Two of the three families contain a hydroxyl group (OH)  Alcohols  Phenols Ethers  Often made from alcohols and phenols All are considered organic derivatives of water.

6. General Formulas Bent molecule  Central oxygen atom  Hydrogen and alkyl group attached (R) or an aryl group (Ar)

7. General Formulas Con’t Alcohols  R-O-H Phenols  Ar-OH  Benzene ring with an OH Ethers  R-O-R

8. Functional Groups Group of atoms which confers characteristic properties on a family of organic compounds  OH  COOH  Alkanes: none

9. Sec. 14.2 Classification and Nomenclature of Alcohols Properties of alcohols depend on the arrangement of the carbon atoms of the molecule Primary (1°) carbon atom Secondary (2°) carbon atom Tertiary (3°) carbon atom

10. Classification and Nomenclature of Alcohols Primary Alcohol  RCH 2 OH Secondary Alcohol  R 2 CHOH Tertiary Alcohol  R 3 COH

11. IUPAC Naming Name the longest continous chain of carbons containing the –OH group Number which carbon the –OH is attached to End name in –ol If more than one hydroxyl group, use suffixes –diol, -triol, etc.

12. Physical Properties of Alcohols Replacement of hydrogen with a hydroxyl group greatly changes properties Not as homologous as alkanes Higher boiling points  Due to strong intermolecular attractions Solubility  The more compact the molecule is, the more soluble it is  4-5 carbons or less—soluble in water

13. Sec. 14.4 Preparation of Alcohols Hydration Reactions

14. Markovnikov’s Rule The hydroxyl group goes on the carbon with fewer hydrogens

15. Production of alcohols Methanol 1.7 billion gallons produced a year Used in formaldehyde, acetic acid, fuels (MTBE), silicones, refrigerants

16. Production of Alcohols Ethanol  Produced from sugars or starches by fermentation  C 6 H 10 O 5  C 6 H 12 O 6  2CH 3 CH 2 OH + 2CO 2 (Enzymes as catalysts) It’s the alcohol that’s found in those certain beverages that people shouldn’t drink

17. Production of Alcohols Con’t  Wines 12% ethanol  Champagnes 14-20% ethanol  Beers 4% ethanol  Whiskey 50% ethanol Proof spirit: alcoholic content of a beverage, twice that of the alcohol content by volume (whiskey: 100 proof)

18. Sec. 14.5 Physiological Effects of Alcohols LD 50 (Lethal dose to 50% of a population) Tested on animals Varies per species though See table 14.5

19. Methanol Can cause permanent blindness or death in high amounts Vapors are very dangerous as well

20. Ethanol Toxic to humans Acute poisoning kills several hundred a year (drinking contests) Long term poisioning  Most serious drug problem in US  40 times more addicts than heroin

21. Isopropyl Alcohol Rubbing alcohol Rapid evaporation Antiseptic More toxic than ethanol, but induces vomitting Used for the manufacture of acetone

22. Sec. 14.6 Chemical Properties of Alcohols Reactions  Occur on the functional groups  May involve hydrogen atoms as well  Dehydration  Oxidation

23. Dehydration Removal of water Sulfuric acid as a catalyst Produces:  Ether (excess ROH) + water  Alkene (excess H 2 SO 4 ) + water

24. Oxidation Result depends on if alcohol is primary, secondary, or tertiary Primary  Produces an aldehyde  Then goes through further oxidation to produce a carboxylic acid Secondary  Produces a ketone Tertiary  No reaction  Can’t break the carbon-carbon bond

25. Oxidation Con’t

26. Sec. 14.7 Multifunctional Alcohols: Glycols and Glycerol More than one hydroxyl group Polyhydric groups Dihydric alcohols Trihydric alcohols

27. Glycols Dihydric alcohols 1,2 ethanediol (ethylene glycol) HOCH 2 CH 2 OH Two hydroxyl groups—extensive intermolecular hydrogen bonding  Higher boiling point  Used as anti-freeze

28. Glycerol Most important trihydric alcohol Syrupy liquid Nontoxic, product of the hydrolysis of fats and oils Nitroglycerin  Detonates on slight impact  Reaction produces temps of 3000 °C and pressures above 2000 atm

29. Sec. 14.8 Phenols Slightly acidic Neutralized by strong bases

30. Phenols Used as:  Antiseptic  Disinfectants First used was pure phenol—proved to be too toxic Methyl derivatives  Cresols Creosote

31. Phenols Dihydroxybenzenes Components of biochemical molecules

32. Sec. 14.9 Ethers Derivatives of water Both hydrogen atoms are replaced Naming  Symmetrical  Name groups attached and add ether

33. Properties Quite inert Although react violently in the air Low boiling points—no hydrogen bonds Diethyl ether  Forms a peroxide in air  First general anesthetic