Chap 7: Alcohols, Phenols, & Thiols

Chap 7: Alcohols, Phenols, & Thiols

Objectives: Chap 7: Alcohols, Phenols, & Thiols (Chapter 7 and pages 283-285 & 296-297, A-1 & A-2 in lab manual)

1. Identify molecules as an alcohol, phenol, glycol, glycerol, quinone, aldehyde, ketone, carboxylic acid, ether, ester, thiol, and thiophenol
2. Uses, dangers, common names/nicknames, biological significance from notes, reading assignments, class discussions
3. Determine the IUPAC name of alcohols, phenols, thiols, thiophenols, carboxylic acids, esters, or their structures.
4. Classify alcohols as 1o, 2o, 3o
5. Explain the properties of acidity & boiling point as relates to alcohols & phenols.
6. Rank given molecules according to acidity
7. Define and identify acids and bases according to the Arrhenius, Bronsted-Lowry and Lewis models
8. Identify conjugate acid-base pairs, acid ionization equations, acid strength using Ka and pKa
9. Determine equations, reactants, catalysts, products and predominant products for the following reactions of alcohols & phenols.
10. Dehydration
11. Halogenation; (PX3 vs. HX for alcohols) (X2 w/FeX3 for phenols)
12. Oxidation; Jones (CrO3, Acetone, H2SO4) vs. PCC
13. Nitration
14. Oxidation of Thiols
15. Ester formation
16. Miscellaneous phenol reactions – see Reaction Summary Sheet or Chapter 4

Alcohol: ______

Phenol: ______

Thiol: ______

Thiophenol: ______

Alcohol Names

IUPAC name:

1. Hydroxyl group ______
2. Use longest chain w/-OH
3. Number beginning nearest the -OH
4. Common name: Alkyl group name followed by “alcohol”
5. Examples:

1. Unsaturated alcohols: 2 endings
2. ene or yne for double/triple bond
3. ol for the hydroxyl group. (Listed last & given numbering priority)
4. Example:

Phenol Names:

1. Phenol: Parent name

1. Hydroxy: To name -OH as substituent group when benzene ring has larger substituent w/common name

Thiols & thiophenol Names:

1. Thiols: Named like alcohols except ______

1. Thiophenol: common name of benzene ring ______

1. Mercapto: ______

Name
Formula
Old common name / Uses / Dangers
Methanol (methyl alcohol)
Ethanol (ethyl alcohol):
2-propanol:

Classification of Alcohols

1. Based on ______

1. Methanol considered _____

Hydrogen Bonding in Alcohols & Phenols

1. Hydrogen bonds form ______

1. ______than alkanes of similar molecular mass

1. Low mass alcohols ______

1. May be ______in nonpolar solvents ______

Acids & Bases

Arrhenius Model

1. Acid: Substance that ______

1. Base: Substance that ______

1. Shortcomings:
2. ______

1. ______

Bronsted-Lowry Model

1. May not CONTAIN H+ or OH-, just ______

1. Acid: ______

1. Base: ______

1. Conjugate acid-base pair: ______

______

1. Example:

HClO2 + H2O  H3O+ + ClO2-1

1. Acid: Left side that ______

1. Conjugate Base: Other side of equation ______

1. Conjugate pair: ______

1. Base: Left side that ______

1. Conjugate Acid: Right side ______

1. Conjugate Pair: ______

1. Amphoteric: Substances that can act ______. Example ______

1. Example of water as an acid:

NH3 + H2O 

Lewis Acids & Bases ______

1. Lewis Acid: Substance that ______when forming a bond

1. ______

1. Has an ______OR ______

1. Lewis Base: Substance that ______to form a bond

1. ______

1. ______

Acid vs. Base Determination? The following questions may be helpful;

1. Was H+ transferred? If so, it probably follows the ______

1. Is the valence complete (especially in the center atom)? No- it might be a ______
2. Is there a + charge that could be neutralized by accepting an e- pair? If so, it might be a ______
3. If the valence is ok, are there any unshared electron pairs that can be donated and used to make a bond? If so, it might be a ______.

Acid / Base
Bronsted-Lowry
Lewis

Acid ionization constants

1. Ionization equation for hydrocyanic acid, HCN

1. Acid ionization constant, K a

1. Indicates the ______

1. ______number is ______

1. Examples of typical numbers:

Hydrofluoric Acid: HF 6.3 x 10-4

Hypochlorous HClO 4.0 x 10-8

1. PKa
2. = -log Ka

1. ______pKa is the ______acid ______

Sec 7.6 Acidity of Alcohols & Phenols

Alcohols:

1. Alkoxide ion ______

1. Acidity strength varies due to

1. ______

1. Size-must be ______

1. Shape-Acidity of ______if same size

Phenols

1. ______acids than alcohols

1. Anion formed = ______

1.  Acidity when ______is stabilized by 1 of:

a) ______

b) ______

1. Caused by ______on an adjacent carbon

1. Ie: ______

1. Ie: ______

1.  acidity when ______(Exception-______)

1. Examples: Rank from lowest to highest acidity:

Basicity of Alcohols and Phenols

1. ______bases
2. Can be______by strong acids

1. ______is used to initiate some alcohol reactions. Examples:

1. ______

1. ______

Comparison Alcohols to Phenols

1. Difficult to break the ______during protonation (______difficult to form)

1. ______

1. ______

REACTIONS

DEHYDRATION of alcohols to alkenes

1. Reaction summary:

STEPS:

1. Ease of Rx: Easiest ______Hardest

1. NOTE: Possible to have >= 2 alkene products as, the H+ can come from any adjacent C

1. Zaitsev’s Rule: Most ______double bond predominates. (Greatest ______attached to the carbons of the double bond). Example:

ALKYL HALIDE FORMATION-1st method; w/HX X = Cl, Br, I

1. Rx rate: ______

1. Examples & steps:

ALKYL HALIDE FORMATION-2ND method; w/PX3

1. Used w/______alcohols for ______

1. Also produces a 2nd reaction product;______

1. Has high ______& can be separated from the alkyl halide by ______

1. Summary

Review of Phenol reactions: ______

Other Functional Groups to know:

1. Carbonyl: Many variations-subgroups following

1. Aldehyde:

1. Ketone:

1. Carboxylic Acid:

1. Naming of carboxylic acids: Change the ”e” in the name of the alkane of the same length with the suffix –oic acid. The –COOH group is on carbon #1
2. Examples:

1. Ether

1. Ester

1. Formed in a 2-step process from alcohols;
2. 1st the _____ of the alcohol is converted to a ______of a carboxylic acid

1. 2nd the ______of the carboxylic acid is converted to an _____ group

1. Naming of esters:
2. 1st the R part of the –OR group is named R group name; methyl, ethyl, …
3. 2nd use the name of the carboxylic acid, with the “ic” ending changed to “oate”
4. Examples:

Which of the following is more oxidized? Why?

Special Alcohols:

1. Glycol-______

 Ethylene glycol: ______

1. Glycerol-______Many derivatives of glycerol.

1. Triglyceride: ______added to glycerol

1. ______

1. ______

1. Formed w/______

1. Phospholipids: 2 fatty acids & 1 phosphate group attached to glycerol

1. ______

1. Nitroglycerin: ______of glycerol

1. ______

1. ______

Nitration of Alcohols

REVIEW of nitration of phenol:

Oxidation of Alcohols

1. Oxidation: ______

1. The number of oxidation steps an alcohol can go through is ______

a) 1o alcohols go through the following oxidation steps: ______

_

b) 2o alcohols  ______

c) 3o –______

1. Oxidizing Reagents:

a) Jones’ Reagent: ______

b) PCC (pyridium chlorochromate): ______

1. Example alcohol oxidation reactions:

1. EtOH oxidation in the human body after drinking alcoholic beverages:

Oxidation of Special Phenols (2-OH groups)

1. Produces ______called 1,4-______, sometimes 1,2

1. Reversible to ______

1. Quinones uses/functions:

a) ______

b) ______.

c) ______

d) ______

e) ______

Aromatic Substitution in Phenols

 See page 133: OH- more ______than most except for _____, so OH- usually______

Phenols as Antioxidants

1. ______are phenolic antioxidant ______

a) Destroy ______that cause ______

1. ______natural antioxidant

a) Neutralizes (slows) ______

Thiols

1. ______.

1. Naming

a) like alcohol, ______

b) –SH is ______group

1. Oxidation of thiols to disulfides:

1. Disulfide significance:

a) ______

b) Create ______between ______within a protein molecule

 used to ______

1. Example Oxidation of Thiol problems:

Chap 7 Organic Chem Note Outline-Alcohols 5/14/19

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