ORGANIC CHEMISTRY A Study Guide for alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, amines and polymers

ALCOHOLS THE NAMING OF ALCOHOLS The iupac naming of alcohols begins by choosing the longest hydrocarbon chain containing the OH functional group. 1) Locate the OH group using the lowest possible numbering and 2) The ending e is removed form the base name replaced by ol. (The common naming system involves using the base name with a yl ending. Example methyl alcohol. Eg. CH3 CH2 CH2 OH 1- propanol EXERCISE 1. Name and classify each of the following (using the IUPAC system): b) HO CH2 CH CH3 l CH3 2-methyl-1-propanol CH3 CH CH2 -CH3 | OH 2 butanol

a) CH3 CH2 CH CH2 CH CH3 l l OH CH3 2o 5-methyl-3-hexanol OH | 2-methyl-2-propanol c) H3C C CH3 | 3o CH3 2.

1o

Draw the condensed structural formula for: c) 2 methyl 2- propanol CH3 OH \/ CH3-C-CH3

a) 2 pentanol CH3-CH2-CH2-CH-CH3 | OH b) 4,4 dimethyl -1- hexanol

HO

Questions 1. Write the reaction of how you would prepare 2-pentanol. Could you produce this in 100% yield? a. Add 1-pentene to water (Markovnikov Addition) and 2-pentanol will be prepared in a 100% yield

b. 2.

If you tried 2-pentene you would only get a 50/50 mixture of 2-pentanol and 3-pentanol

What functional group would be the result of the addition of KMnO 4 to: a) 2-butanol ketone b) 3-methyl-3-hexanol n.r. (alcohol) c) ethanol aldehyde or carboxylic acid Write the balanced chemical equation for the combustion of 1-propanol. 2 C3H7OH + 9 O2 6 CO2 + 8 H2O If methanol was oxidized to methanal (aldehyde) and KMnO4 was reduced to MnO2; give the balanced redox reaction if it took place in an acidic solution. CH3OH CH2O + 2H+ + 2e- (X3) 3e- + 4H+ + MnO41- MnO2 + 2H2O (X2) 2H+ + 2MnO41- + 3CH3OH 2 MnO2 + 4H2O + 3CH2O

3. 4.

ETHERS NAMING OF ETHERS 1) 2) Choose the longest alkyl group as the parent alkane. Treat the second alkyl group as the branch alkyl group. This is named by replacing the yl with oxy. The alkoxy group that is adding on to the main chain should be located onto the main chain with an appropriate number. CH3 CH2 O CH CH3 \ CH3 2- ethoxypropane

Eg. CH3 O CH2 CH3

methoxyethane

EXERCISE 1. Name the following ethers. 1-methoxybutane

a) CH3 CH2 CH2 CH2 O CH3 b) CH3CH2CH2CH2 O CHCH2CH2CHCH2CH3 | | CH3 CH3 c) CH3 CH O CH2 CH CH2 CH3 | | CH3 CH3 Draw the following ethers. a) 1-methoxy propane

2-butoxy-5-methylheptane

1-isopropoxy-2-methylbutane

2.

b) 3 ethoxy-4-methylheptane CH3 CH2 O CH3 | | CH3 CH2 CH CH CH2 CH2 CH3

CH3 O CH2 CH2 CH3

c) 2 methoxy 2- methylpropane CH3 O CH3 \ / CH3 C CH3

ALDEHYDES AND KETONES THE NAMING OF ALDEHYDES AND KETONES The naming of aldehydes and ketones begins by choosing the longest chain containing the carbonyl group to obtain the base name. The ending e is removed from the base name and replaced by the suffix al in the case of aldehydes and one in the case of ketones. Since the carbonyl group of an aldehyde is always at one end of the main chain, its position does not require a number. However, for ketones, we use a number to show the location of the carbonyl group (starting the count from the end closest to the carbonyl group). Examples: CH3 | CH3-CH-CH2-C-H 3-methylbutanal EXERCISE: 1. Name the following using IUPAC system: CH3 | O || b) CH3 O | || CH3 C C -H | CH3 O || O || CH3 |

CH3 C CH2 CH CH3 4-methyl-2-pentanone

a) CH3 CH CH2 CH2 C CH3

2. Draw the structural formula for: a) 3-pentanone CH3-CH2-CO-CH2-CH3 c) 2-methylpentanal O

||

b) butanal CH3-CH2-CH2-CHO d) 2,4-dimethyl-3-hexanone

|| O Questions 1. Write an equation for each of the following reactions: a) Balance the reaction between methanal and acidified Cr2O72- ions. Hint: This reaction is a redox reaction. Combine the following two half reactions to obtain a balanced equation.

The oxidation half-reaction: The reduction half-reaction:

H2O + HCHO 6e- + 14 H+ +

Cr2O72-

HCOOH + 2H+ + 2 e> 2 Cr3+ + 7 H2O

(X3)

8H+ + 3HCHO + Cr2O72- 3HCOOH + 4H2O + 2 Cr3+

b)The reaction between propanal and hydrogen gas over platinum as a catalyst. CH3-CH2-CHO + H2,Pt CH3-CH2-OH 1-propanol

c) The oxidation of 2-methylpropanal with acidified potassium dichromate ions. CH3-CH-CHO + [O] CH3-CH-COOH | CH3 | CH3 2-methylpropanoic acid

2. Which alcohol would you oxidize to prepare a) pentanal and b) 3-pentanone. Write a balanced half reaction for each reaction. a) b) CH3-CH2-CH2-CH2-CH2-OH CH3-CH2-CH-CH2-CH3 | CH3 CARBOXYLIC ACIDS THE NAMING OF CARBOXYLIC ACIDS The IUPAC names of CARBOXYLIC ACIDS are obtained by selecting the longest carbon chain containing the CARBOXYL group and replace the ending of the alkane name with the ending oic acid. If an alkyl group is present, the numbering starts from the carbon of the carboxyl group. 1-pentanol 3-pentanol

EXAMPLE:

O ||

CH3 CH2 CH CH2 CH2 C OH | CH2 - CH3

4-ethylhexanoic acid

EXERCISE: 1. Name the following carboxylic acids using IUPAC system: a) CH3 CH3 \ / O || b) CH3 CH3 | |

CH3 CH2 C CH2 C OH 3,3-dimethylpentanoic acid

CH3 CH CH - COOH 2,3-dimethylbutanoic

2. Draw the condensed formula for: a) Heptanoic acid CH3-CH2-CH2-CH2-CH2-CH2-COOH b) 4-methylhexanoic acid CH3-CH2-CH-CH2-CH2-COOH | CH3 QUESTIONS 1. What ions form when propanoic acid reacts with water? CH3-CH2-COOH + H2O CH3-CH2-COO- + H3O+ 2. Why does butanoic acid have a higher BP than 3-pentanone?

CH3-CH2-CH2-COOH and CH3-CH2-CO-CH2-CH3 have roughly the same London forces and both contain a carbonyl group (C=O) so they both have a polar area. However, they differ because butanoic acid has an OH bond so it has hydrogen bonding as an IMF.

3.

If ethanoic acid is reduced with H2, what two possible products can form? (name and draw their condensed structural formulas) CH3CHO + H2, Pt Ethanal CH3CH2OH ethanoic acid

CH3COOH + H2, Pt

4.

What alcohol needs to be oxidized to prepare 3-methylpentanoic acid? 3-methyl-1-pentanol

CH3-CH2-CH-CH2-CH2-OH

| CH3
Oxidation ADD A STRONG OXIDIZING AGENT TO THE FOLLOWING ORGANIC COMPOUNDS. NAME THE PRODUCTS. a) ethanol CH3-CH2-OH + [O] CH3-CHO + [O] ethanal CH3-COOH ethanoic acid

b) 3 - methyl-3-pentanol

CH3-CH2 C CH2 CH3 + [O] nr / \ CH3 OH CH3 CH CHO + [O] CH3 CH COOH | | CH3 CH3 2-methylpropanoic acid

c) 2 methylpropanal

d) 3,3 dimethyl -2-pentanol

O || CH3-CH2 C CH CH3 + [O] CH3-CH2 C C CH3 / \ \ / \ CH3 CH3 OH CH3 CH3 3,3 dimethyl -2- pentanone

REDUCTION REACTIONS

DRAW THE FOLLOWING COMPOUNDS AND SHOW THE REDUCTION PRODUCT. Name all the new compounds. a) 3-pentanone + H2, Pt O b) 3,4 dimethylpentanal CH3 CH CH CH2-CHO + H2, Pt | | CH3 CH3 OH CH3 CH CH CH2-CH2OH | CH3 3-pentanol

c) 2,4,4 trimethyl-2pentene + H2, Pt

2,2,4-trimethylpentane d) methanal HCHO + H2, Pt CH3OH methanol

ESTERS NAMING OF ESTERS In naming esters, we obtain the first part of the name from the name of the alkyl group attached to the oxygen; the second part is obtained by changing the -ic acid ending of the acid to -ate. EXAMPLES O || CH3 C O CH3 methyl ethanoate O || CH3 CH2 CH2 C O CH CH3 2 propylbutanoate | CH3

QUESTIONS I. Give the IUPAC name for: a) O || HC-O-CH2 CH2 CH3 Propyl methanoate b) O || CH2 CH3 |

CH3 CH2 - C O CH CH2 CH3 3-pentyl propanoate

2. There are two esters with the formula C3H6O2 a) Draw their condensed formulas. CH3-COO-CH3 AND HCOO-CH2-CH3

b) Give their IUPAC names methyl ethanoate and ethyl methanoate c) Identify the alcohol and the carboxylic acid used in the preparation of each ester. Methanol and ethanoic acid ethanol and methanoic acid

d) Name and draw the isomeric carboxylic acid. CH3-CH2-COOH propanoic acid

e) Compare the BP of either ester to (d). Propanoic acid has a higher BP because it has hydrogen bonding either ester has only a dipole force. London forces are roughly equal. 3. Write the esterification reaction between: a) ethanoic acid and ethanol. CH3-COOH + HOCH2-CH3 CH3 COO CH2-CH3

b) methanoic acid and 1-butanol. HCOOH + HOCH2-CH2-CH2-CH3 HCOO CH2-CH2-CH2-CH3 c) propanoic acid and 2-methyl-2-propanol. CH3-CH2-COOH + HOC - C -CH3 CH3-CH2COO C -CH3 / \ CH3 CH3 / \ CH3 CH3

4. Write a balanced equation to show how each ester below is prepared a) CH3 CH2 COO CH2 CH2 CH2 CH2 - CH2 CH3 CH3-CH2-COOH + HOCH2-CH2-CH2-CH2-CH2-CH3 b) H COO CH2 CH2 CH2 CH3 HCOOH + HO-CH2-CH2-CH2-CH3 AMINES THE NAMING OF AMINES: The IUPAC names of amines are formed by adding the prefix amino- to the corresponding alkane name of the amine. As usual, numbers are used to indicate the carbon to which the amine substituent is attached. The functional group takes priority over the alkyl group. (In this course we will only have to name primary amines). CH3-NH2 CH3 CH CH2 CH CH2 CH3 | | 3-amino-5-methylhexane

aminomethane QUESTIONS

CH3

NH2

1. Name and classify the following amines. a) NH2 CH2 CH2 CH CH3 | NH2 1,3 diaminopropane 1,4-diamino-2-methyl b) NH2 NH2

c) NH2 CH2 CH2 CH2 CH CH CH3 | |

1-amino 4,5-dimethylhexane

CH3 CH3

2. Draw the structural formulas of four amines that have the molecular formula C 3H9N (two primary, one secondary, and one tertiary amine). Classify the amines and name the primary amines among them.

1) CH3-CH2-CH2-NH2 2) CH3- CH -CH3 | NH2 AMIDE NAMING OF AMIDES 1) 2) 3)

1-aminopropane primary 2-aminopropane primary

3) CH3-NH-CH2-CH3 4) CH3 \ CH3 - N CH3

-secondary -tertiary

Locate the carbonyl group and name the parent carboxylic acid. Replace the oic acid with the ending amide. A - Primary Amide if there are two hydrogen atoms bonded to the nitrogen. This name needs no prefix. B Secondary Amide if there is one alkyl group attached to the nitrogen. Name and locate the alkyl group, use the letter N to indicate that it is bonded to the nitrogen atom. C Tertiary Amide if there are two alkyl groups attached to the nitrogen. Name and locate each alkyl group alphabetically, use the letter N to locate before each group.

Eg.

O || CH3-CH-C-NH2 | CH3 2-methylpropanamide

O || CH3-CH2-CH2-C-NH-CH2-CH3

O || CH3-C-N-CH3 \ CH2-CH3 N-ethyl-N-methylethanamide

N-ethylbutanamide

EXERCISE 1. Name and classify the following amides. a) O || CH3-CH2-CH-CH2-C-NH2 | CH2-CH3 3-ethylpentanamide 1o b) O || CH3-CH-CH-C-NH-CH3 | | CH3 CH3 N methyl-2,3-dimethylbutanamide 2O c) O || CH3 CH2-C-N-CH2-CH2-CH3 \ CH2-CH2-CH3 N,N - dipropylpropanamide 3O

2. Give the condensed structural formulas for the following amides classify each. a) N-methylpentanamide b) N,N-diethylbutanamide c) hexanamide CH3-CH2-CH2-CH2-CH2-CO-NH2 1O

CH3-CH2-CH2-CH2-CO-NH-CH3 CH3-CH2-CH2-CO-NH-CH2-CH3 2O \ 3O CH2-CH3