Organic Chemistry Final

Front 1

System for nomenclature of ethers

Back 1

list two alkane groups in alphabetical order and add ether to end

Front 2

Oxane

Back 2

Front 3

oxirane

Back 3

Front 4

oxitane

Back 4

Front 5

oxolane

Back 5

Front 6

thiirane

Back 6

Front 7

diglyme

Back 7

Front 8

What is a special characteristic of cyclo ethers?

Back 8

Under extreme ring strain

Front 9

What is a characteristic of the boiling points of ethers?

Back 9

They have low boiling points similar to alkanes

Front 10

What is the solubility of an ether in water?

Back 10

Highly soluble due to oxygen being able to bond a hydrogen from the water molecule

Front 11

What characteristics allow ethers to bond with metals and become complexes?

Back 11

-The polar carbon-oxygen bond

-Lone electrons

Front 12

Draw 12-crown-4 molecule

Back 12

Front 13

Draw 18-crown-6 molecule

Back 13

Front 14

What is the first number in a crown molecule? Second?

Back 14

1. Number of atoms in ring

2. Number of oxygens in ring

Front 15

Draw a methoxy group

Back 15

O-CH3

Front 16

What are crown molecules used for?

Back 16

The isolation of cations from difficult to extract compounds such as sodium from KOH

Front 17

Host-guest chemistry

Back 17

-Crown molecules are an example

-Help us understand biological processes

Front 18

What is special about the structure of crown molecules?

Back 18

The diameter of the interior of the molecule exactly matches a specific ion

Front 19

REACTION:

Acid catalyzed ether preperation

Back 19

Front 20

Williamson ether synthesis

Back 20

Works best with methyl and primary alkyl halides

-Does not work with secondary and tertiary alkyl halides

Front 21

Why are ethers good solvents?

Back 21

-Very unreactive

-Dissolves nonpolar substances

Front 22

REACTION:

Acid catalyzed cleavage of ethers

Back 22

Produces 2 Alkyl halides

-SN2

Front 23

REACTION:

Epoxidation of Alkenes

Back 23

-Stereospecific

-Syn addition

-Produces enantiomers

Front 24

REACTION:

Sharpless epoxidation

Back 24

-Allylic alcohols to epoxides

-Enantioselective

-R,R yields S,S vice versa

-Syn addition

Front 25

What compound is used to protect OH?

Back 25

Tertbutyl group

Front 26

REACTION:

Vicinal halohydrins

Back 26

-Cis yields cis

Front 27

REACTION:

Nucleophile + Epoxide

Back 27

-Similar to grignard reaction with epoxides

Front 28

REACTION:

Nucleophile + Epoxide Ring Opening Special Characteristc

Back 28

-Inversion at carbon attacked by nucleophile

-Nucleophile attacks less substituted carbon

Front 29

REACTION:

Acid catalyzed epoxide ring opening

Back 29

-Reaction occurs at more substituted carbon

Front 30

REACTION:

Preparation of Sulfides

Back 30

Front 31

Oxidation of sulfides

Back 31

Front 32

REACTION:

Oxidation of Sulfide to Sulfoxide

Back 32

NaIO4 best reagent to use because it doesnt oxidize all the way to sulfone

Front 33

REACTION:

Oxidation of Sulfide to Sulfones

Back 33

-1 equivalent gives sulfoxide

-2 equivalents gives sulfone

Front 34

REACTION:

Production of sulfonium salts

Back 34

- Sulfur is more nucleophilic than oxygen causing it to react better with alkyl halides

Front 35

What will be produced from a Williamson reaction with secondary or tertiary halide?

Back 35

An alkene + an alcohol

Front 36

Partial mechanism of halohydrin involving alcohol and primary alkyl halide.

Back 36

Front 37

How should you draw epoxides when drawing molecules?

Back 37

With the filled or dashed lines so you know that both bonds are cis

Front 38

Reactions of sulfides stereochemistry is...

Back 38

inversed

Front 39

Carbonyl group resonance structures

Back 39

Front 40

What do more substituents do to carbonyl group?

Back 40

Increase stability

Front 41

REACTION:

Ozonolysis of Alkene

Back 41

-Alkene produces aldehyde or ketone

-Must be in a reducing agent

Front 42

REACTION:

Hydration of Alkynes

Back 42

-Follows M's rule

-produces Ketone

Front 43

REACTION:

Friedel Craft Acylation

Back 43

-No rearrangement

-Electriophilic aromatic substitution

Front 44

Draw an acyl group

Back 44

Front 45

REACTION:

Oxidation of alcohols

Back 45

-Occurs with primary or secondary alcohols not tertiary

-PCC/PDC in CH2I2will reduce to aldehyde

-Na2Cr2O7 in H2SO4, H2O will reduce to ketones

Front 46

REACTION:

Aldehyde from Carboxylic Acid

Back 46

-Can only be done indirectly

Front 47

REACTION:

Ketone from Aldehyde

Back 47

-Indirectly using Grignard reagents

Front 48

REACTION:

Reduction of Ketones/Aldehydes to Hydrocarbons(1)

Back 48

-Acylation produces ketone/aldehyde

-Clemmenson reduction

-REAGENT Zn(Hg) in HCl

Front 49

REACTION:

Ketones/Aldehydes to Hydrocarbons(2)

Back 49

-Acylation produces ketone/aldehyde

-Wolff Kischner reduction produces hydrocarbon

-REAGENT H2NNH2, KOH in Triethylene glycol heated

Front 50

REACTION:

Reduction of Aldehydes/Ketones to Alcohols

Back 50

-H2 with metal catalyst makes primary alcohol

-NaBH4 in ethanol makes 1°or 2°

-LiAlH4 in diethyl ether makes 1° or 2° (can reduce carboxylic acid)

Front 51

REACTION:

Reduction of Aldehydes/Ketones to Alcohols using Grignard reagents

Back 51

Can produce 1°(formaldehyde), 2°(aldehyde), 3°(ketones) alcohols

Front 52

REACTION:

General mechanism of carbonyl nucleophilic addition

Back 52

Front 53

What do substituents do to the reaction rate of carbonyl groups with water?

Back 53

-More substituents increases stability which decreases reaction rate

Front 54

What effect do electronegative atoms have on reaction rate of carbonyl groups?

Back 54

They increase it because they destabilize the group

Front 55

What effect does the size of a molecule have on the reaction rate?

Back 55

Larger size decreases reaction rate

Front 56

What is the RDS of hydration of aldehyde/ketones in basic solution?

Back 56

The first step

Front 57

Draw the mechanism of acid catalyzed hydration of aldehyde/ketone

Back 57

Find

Front 58

Draw the mechanism of base catalyzed hydration of aldehyde/ketone

Back 58

Front 59

What is the rate determining step of acid catalyzed hydration of ketone/aldehyde?

Back 59

The second step.

Front 60

REACTION:

Formation of cyanohydrin

Back 60

Front 61

Which compounds react most readily with hydrogen cyanide?

Back 61

The least substituted carbonyl groups.

Front 62

Cyanohydrin

Back 62

Front 63

Hemiacetal

Back 63

Front 64

Acetal

Back 64

Front 65

REACTION:

Carbonyl group with Alcohol

Back 65

Front 66

In what form are ketals more stable?

Back 66

Cyclic form

Front 67

REACTION:

Diols + 1,2 or 1,3 aldehydes

Back 67

reversible

Front 68

Groups used for carbonyl protection

Back 68

Acetals and ketals

Front 69

REACTION:

Protection step of carbonyl group

Back 69

-produces ketal

Front 70

REACTION:

Alkylation of ketal

Back 70

Front 71

REACTION:

Removal of protecting group

Back 71

Front 72

Hemiaminal group

Back 72

Front 73

Imine

Back 73

R2C=NR

Front 74

aldimine

Back 74

Front 75

Ketimine

Back 75

Front 76

REACTION:

Primary amine + aldehyde

Back 76

Front 77

Draw primary amine + aldehyde mechanism

Back 77

See 17.5 Mechanism

Front 78

Enamine

Back 78

-Produced by reaction of secondary amine with aldehyde or ketone

-Alkenyl substituted amine

Front 79

Draw mechanism of enamine formation

Back 79

See Mechanism 17.6

Front 80

What are Witting reactions used for?

Back 80

-Regiospecific synthesis of alkenes from aldehydes and ketones

Front 81

Wittig reagent and its resonance

Back 81

Front 82

Wittig intermediate and product

Back 82

Front 83

What type of steroisomers do simple ylides yield?

Back 83

Z dominates

Front 84

What type of stereoisomers are formed when an ylide contains a strong withdrawing group?

Back 84

E dominates

Front 85

REACTION:

Oxidation of aldehyde to carboxylic acid

Back 85

Front 86

Nomenclature of Carboxylic Acids

Back 86

-Count longest chain of carbons that include the carboxylic acid

-Replace -e ending of alkane with -oic acid

-Numbering of chain begins at the carboxylic acid

Front 87

Double bonds in main chain of carboxylic acid name

Back 87

-enoic acid

Front 88

Two carboxylic acids in a group nomenclature

Back 88

-dioic acid or dicarboxylic acid

-e of alkane is retained

Front 89

Resonance structures of carboxylic acids

Back 89

-stabilizes group

-sp2 hybridization

Front 90

WHich is more electrophilic aldehyde/ketone or carboxylic acid?

Back 90

Aldehyde/Ketone

Front 91

Relative melting and boiling points of carboxylic acids.

Back 91

Relatively high compared to hydrocarbons and oxygen containing compounds due to strong intermolecular forces

Front 92

Relative acidity of carboxylic acids.

Back 92

Most acidic group that contain hydrogen, oxygen and carbons

Front 93

Average pKa of carboxylic acids

Back 93

5

Front 94

Henderson Hasselbach equation

Back 94

Front 95

Equation for determining relative quantities of acid or base at given pH

Back 95

Front 96

Alkyl substituent effect on carboxylic acid acidity

Back 96

Negligible all around 5 pKa

Front 97

Alpha halogen effect on carboxylic acid acidity.

Back 97

Increase acidity, the more electronegative atoms the more acidic.

pKa ranges from 3-1

Front 98

Electron attracting groups effect on carboxylic acidity.

Back 98

Increase acidity

pKa 2-4

Front 99

WHat is the relationship between number of bonds and inductive effect?

Back 99

Inductive effect decreases as the number of sigma bonds in between carbon and other atom increases.

Front 100

Relative acidities of acetic to benzoic acid.

Back 100

Benzoic acids are slightly more acidic than other carboxylic acids due to sp2 hybridzed carbons

Front 101

What increases with s character?

Back 101

-Electron withdrawing effects and therefore acidity increases

Front 102

When are benzoic acids the most acidic?

Back 102

When strong electron withdrawing groups are ortho.

Front 103

Are carboxylic groups hydrophilic or phobic?

Back 103

Philic

Front 104

What can carboxylic acids due to hydrophobic molecules?

Back 104

They can cause them to become more hydrophilic and dissolve in water

Front 105

Micelle definition

Back 105

A spherical aggregate of species such as carboxylate salts of fatty acids that contain a lipophilic end and a hydrophilic end. Micelles containing 50–100 carboxylate salts of fatty acids are soaps.

Front 106

In dicarboxylic acids which pK is larger?

Back 106

The first pKa because

-more sites to attack

-one carboxylic acid electron withdraws from the other allowing easier dissociation

Front 107

What happens to the acidity of a dicarboxylic compounds when the amounts of bonds between them increases?

Back 107

The acidity of the compound decreases

Front 108

IUPAC name of NaHCO3

Back 108

Sodium hydrogen carbonate

Front 109

REACTION:

Formation of carbonic acid and bicarbonate

Back 109

Front 110

Which is a stronger acid bicarbonate or carboxylic acid?

Back 110

Bicarbonate is a weaker acid than carboxylic acids but a stronger acid than water and alcohols

Front 111

REACTION:

Side chain oxidation of alkylbenzens

Back 111

Front 112

General mechanism for reacting grignard reagents with CO2

Back 112

Grignard + CO2= Carboxylic acid

Front 113

REACTION:

Grignard Reagent + CO2

Back 113

Reagent cannot have OH, NH, SH, or CO groups

Front 114

General reaction of nitrile with carboxylic acid

Back 114

Primary or secondary alkyl halides

Front 115

REACTION:

Nitrile + Carboxylic Acids

Back 115

Front 116

REACTION:

Conversion of Carboxylic acid to Acyl Chlorides

Back 116

Front 117

Acid catalyzed esterification mechanism

Back 117

See Mechanism 18.1

Front 118

Lactone definition

Back 118

Cyclic ester

Front 119

REACTION:

Intramolecular esterification to produce lactones

Back 119

-Produces 5-6 six membered rings

-much have hydroxyl and carboxylic acid group

Front 120

Decarboxylation

Back 120

Front 121

REACTION:

Decarboxylation reaction

Back 121

-only one carboxyl group is lost

Front 122

In Williamson sythesis what type of alkyl halides can be used?

Back 122

Primary only

Front 123

In Williamson synthesis what type of alkoxide can be used?

Back 123

Any

Front 124

List reactions to produce epoxides

Back 124

1. Alkene + Peroxyacid

2. Conversion of vicinal halohydrin to epoxide in basic conditions

Front 125

What is the difference between epoxide reaction in basic then acidic conditions?

Back 125

Basic conditions adds to least substituted carbon

Acidic adds to most substituted

Front 126

HNMR of H on epoxide ring

Back 126

2.5

Front 127

Chemical shift of ether hydrogen

Back 127

3.2-4

Front 128

HClO4 vs OsO4 dihydroxilation

Back 128

HClO4 anti

OsO4 syn

Front 129

Ether boiling point relative to water and alkanes.

Back 129

Lower than water and alkanes

Front 130

LiAlH4 + epoxide

Back 130

Makes same product as acid catalyzed epoxide opening