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CHEM 322 - Organic Chemistry > Prelim Exam 2: Sulfur Compounds; Aldehydes and Ketones; Carboxylic Acids, Carboxylates, and Nitriles; Multistep Synthesis; Polymers and Cyclic Compounds (Chem 322- Organic Chemistry) > Flashcards

Prelim Exam 2: Sulfur Compounds; Aldehydes and Ketones; Carboxylic Acids, Carboxylates, and Nitriles; Multistep Synthesis; Polymers and Cyclic Compounds (Chem 322- Organic Chemistry) Flashcards

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1
Q

thiols

A

R-SH

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2
Q

mercapto group

A

-SH group

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3
Q

thiol nomenclature

A

name parent alkane and add “thiol” to the end of the name

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4
Q

sulfide nomenclature

A

named as “sulfide” compounds: alkyl sulfide or alkyl-thio alkane

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5
Q

sulfide

A

R-S-R

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6
Q

thiol preparation

A

from alkyl halides through Sn2 displacement with sulfur nucleophile such as SH- anion (works poorly unless excess SH is present due to competing Sn2 reaction with alkyl halide to give sulfide as by-product); using thiourea works better

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7
Q

thiol reaction

A

2 R-SH oxidized by Br2 or I2 to yield disulfides (R-S-S-R)

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8
Q

sulfide preparation

A

treatment of thiol with base gives thiolate ion (RS-) which undergoes reaction with primary or secondary alkyl halide [R-SH –1) NaH 2) R-X –> R-S-R]

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9
Q

sulfur compounds are more nucleophilic than ethers

A

because electrons are farther from the nucleus and less tightly held than those on oxygen

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10
Q

sulfide reactions

A

dialkyl sulfides react rapidly with primary halides by Sn2 to give sulfonium ions (R3S+) – which are useful alkylating agents because a nucleophile can attack one of groups bonded to positively charged sulfur to displace a neutral sulfide as leaving group……. oxidation of sulfide with H2O2 to yield sulfoxide (R2SO) with further oxidation of sulfoxide with peroxyacid yielding a sulfone (R2SO2) [ R-S-R –H2O2–> RSOR –CH3CO2H–> RSOOR]

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11
Q

DMSO (dimethyl sulfoxide)

A

common polar aprotic solvent

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12
Q

spectroscopy of ethers

A

infrared spectroscopy– absorption due to C-O single bond at 1050-1150 cm^-1… NMR spectroscopy– H NMR absorptions in 3.4-4.5 delta region for H on carbon next to O in ether and epoxide hydrogens absorb at 2.5-3.5 delta region

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13
Q

1) NaH 2) RCH2X

A

williamson ether synthesis from primary alcohols to form ethers

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14
Q

1) ROH, (CF3CO2)2Hg / 2) NaBH4

A

alkoxymercuration/demercuration from alkene to form ethers

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15
Q

HX, H2O

A

cleavage of ethers by HBr or HI to form an alkyl halide and alcohol

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16
Q

H3O or HBr

A

acid-catalyzed epoxide opening to yield a diol or an alkyl halide alcohol

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17
Q

RO-, ROH or 1) ether / 2) H3O+

A

base-catalyzed epoxide opening to yield a alkyl ether alcohol or a primary alcohol

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18
Q

1) (H2N)2C=S / 2) H2O, NaOH

A

reaction of alkyl halide to yield thiol

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19
Q

I2, H2O

A

oxidation of 2 RSH to yield disulfide (R-S-S-R)

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20
Q

RS- + alkyl halide

A

yields sulfide (R-S-alkyl)

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21
Q

H2O2

A

oxidation of sulfides to sulfoxides

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22
Q

RCO3H

A

oxidation of sulfides to sulfones

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23
Q

sulfoxide

A

R2S=O

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24
Q

sulfone

A

R-SO2-R

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25
Q

sulfonic acid

A

SO3H

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26
Q

sulfuric acid

A

H2SO4

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27
Q

dialkyl sulfate

A

R2SO4

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28
Q

nucleophile

A

nucleus loving; attracted to positive charge… has a negative charge, a partial negative charge, or a pi bond… provides pair of electrons to form bond

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29
Q

electrophile

A

electron loving; attracted to negative charge… has positive charge, a partial positive charge, or a leaving group… accepts pair of electrons to form bond

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30
Q

deprotonates phenols

A

NaOH or NaH

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31
Q

deprotonates alcohols

A

NaH

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32
Q

aldehyde nomenclature

A

replace “e” of parent name with “al”; no number necessary because aldehydes are always carbon 1 and must always be in parent chain; cyclic aldehydes are named with suffix “carbaldehyde” on end of parent name

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33
Q

nomenclature ending priority

A

carboxylic acid > nitrile > aldehyde > ketone > alcohol > alkyne > alkene > halogens, alkyl, alkoxy

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34
Q

ketone nomenclature

A

replace “e” ending with “one”; no number if ketone can only be in one position in a parent chain; numbering of parent chain begins at end closest to carbonyl carbon; locant must be used with ketone name

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35
Q

acyl group

A

RC=O

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36
Q

formyl group

A

HC=O

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37
Q

acetyl group

A

CH3-C=O

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38
Q

benzoyl group

A

benzene-C=O

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39
Q

benzyl group

A

-CH2-benzene

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40
Q

1) RCOCl / 2) AlCl3

A

friedel-crafts acylation to convert a benzene into a phenyl ketone

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41
Q

HgSO4, H2SO4, H2O

A

conversion of alkynes into ketones

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42
Q

DMP, PCC or KMnO4 or CrO3

A

oxidation of secondary alcohols to ketone

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43
Q

1) O3 / 2) Zn, H+

A

ozonolysis of alkenes to yield a ketone or aldehyde

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44
Q

R2CuLi, -:R

A

reaction of cuprates with acid chlorides to yield ketones

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45
Q

DMP or PCC

A

oxidation of primary alcohols to yield aldehydes

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46
Q

1) BH3 / 2) H2O2, -OH

A

hydration of terminal alkynes to yield an aldehyde

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47
Q

1) DIBAH / 2) H3O+

A

partial reduction of esters to yield an aldehyde and an alcohol

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48
Q

carbonyl group

A

C=O

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49
Q

carbonyl characteristics

A

carbonyl carbon sp^2 hybridized and forms 3 sigma bonds and 1 pi bond… planar about double bond and have 120 degree bond angles… carbon-oxygen bond is strongly polarized because of high electronegativity of oxygen relative to carbon (carbonyl carbon acts as electrophile and carbonyl oxygen acts as nucleophile)… electron withdrawing group

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50
Q

oxo

A

name of ketone functional group substituent when other priority groups are in the compound

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51
Q

aldehydes are generally more reactive than ketones in nucleophilic addition reactions

A

because there is less steric crowding from large substituents and because a primary carbocation is higher in energy and thus more reactive

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52
Q

aldehydes/ketones + carbon nucleophile

A

yields alcohol

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53
Q

aldehydes/ketones + nitrogen nucleophile

A

yields imine

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54
Q

aldehydes/ketones + oxygen nucleophile

A

yields acetal

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55
Q

Wolff-Kishner Reaction

A

treatment of aldehyde/ketone with hydrazine (H2NNH2) in presence of KOH to yield an alkane (through intermediate hydrazone intermediate (R2C=NNH2)

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56
Q

acetal

A

R2C(OR)2; formed upon reaction of aldehydes/ketones with 2 equivalents of alcohol; act as protecting groups for aldehydes/ketones and can be removed with H3O+

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57
Q

hemiacetal

A

R2C(OH)OR; formed upon reaction of aldehydes/ketones with 1 equivalent of alcohol

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58
Q

carboxylic acid

A

RCOOH

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59
Q

ester

A

RCOOR

60
Q

acid chloride

A

RCOCl

61
Q

ketone

A

RCOR

62
Q

anhydride

A

RCOOCOR

63
Q

aldehyde

A

RCOH

64
Q

amide

A

RCONR2

65
Q

epoxide ring opening occurs by Sn2

A

attacks least substituted carbon if no tertiary carbon is present or ALWAYS when the nucleophile is negative or a nitrogen

66
Q

epoxide ring opening occurs by Sn1

A

attacks most substituted carbon only if tertiary carbon is present (and no negative nucleophiles)

67
Q

aldehyde/ketone + carbon nucleophile

A

yields an alcohol through 1) addition then 2) protonation

68
Q

aldehyde/ketone + nitrogen nucleophile (primary amine)

A

yields an imine

69
Q

aldehyde/ketone + nitrogen nucleophile (primary amine) STEPS

A
  1. addition (of NH2-R)… 2. proton transfer (H from N to O)… 3. protonation (of hydroxyl group)… 4. elimination (of water)… 5. deprotonation (remove H from N using water to form C=N bond)
70
Q

REVERSE REACTION: imine to aldehyde/ketone STEPS

A
  1. protonation (of N of C=N)… 2. addition (of water)… 3. deprotonation (remove H from water group using water)… 4. protonation (add H to N using H3O+)… 5. elimination (remove NH2-R group)… 6. deprotonation (remove H from O using water to form C=O bond)
71
Q

aldehyde/ketone + oxygen nucleophile (alcohol) STEPS

A
  1. protonation (H from H3O+ adds to O)… 2. addition (of ROH to electrophilic C)… 3. deprotonation (removed H from OR group to yield hemiacetal)… 4. protonation (add H to OH group from H3O+)… 5. substitution (Sn1) (water group leaves followed by addition of ROH)… 6. deprotonation (H from ROH is removed to form acetal)
72
Q

aldehyde/ketone + oxygen nucleophile (alcohol)

A

yields acetal

73
Q

REVERSE REACTION: acetal to aldehyde/ketone STEPS

A
  1. protonation (add H to OR group using H3O+)… 2. substitution (kick off ROH group followed by addition of water group)… 3. deprotonation (remove H from water group using water)… 4. protonation (of OR group with H from H3O+)… 5. elimination (remove ROH group)… 6. deprotonation (remove H from O to form C=O bond)
74
Q

wittig reaction

A

conversion of aldehydes/ketones to alkenes using a ylide (R2C=PPh3); prepares mono/di/tri substituted alkenes (not a tetra substituted alkene); yields a pure alkene of predictable structure: the C=C bond always forms where C=O group was

75
Q

cannizzaro reaction

A

nucleophilic addition of -OH to an aldehyde to give a tetrahedral intermediate, which expels a hydride ion as a leaving group is oxidized, while a second aldehyde accepts the hydride ion in another nucleophilic addition step and is reduced

76
Q

conjugated (1,4) addition to α, β unsaturated aldehydes/ketones

A

nucleophile adds to beta carbon and a hydrogen adds to alpha carbon (adding to the alkene portion to form an alkane portion) while ketone/aldehyde is retained

77
Q

conjugate addition of amines

A

primary and secondary amines add to α, β unsaturated aldehydes/ketones to yield β-amino aldehydes/ketones; proceed with thermodynamic control to form more stable addition product

78
Q

conjugate addition of water

A

H2O can add to α, β unsaturated aldehydes/ketones to yield β-hydroxyl aldehydes/ketones, but unsaturated aldehydes/ketones predominate at equilibrium

79
Q

conjugate addition of alkyl groups: organocopper reactions

A

alkyl group adds to α, β unsaturated ketones (NOT aldehydes) in a 1,4 addition reaction; uses lithium diorganocopper reagent (R2CuLi) to ensure conjugate addition (grignard reagents would add to ketone)

80
Q

addition of primary amine to ketone/aldehyde

A

yields imine

81
Q

addition of secondary amine to ketone/aldehyde

A

yields enamine

82
Q

stronger base

A

more electropositive atom with negative charge

83
Q

better nucleophile

A

larger atom and more electropositive

84
Q

forming wittig reaction reagent

A

MUST start with a PRIMARY alkyl halide + Ph3P (as it is an Sn2 reaction)… add butyl lithium to form RC=P+Ph3

85
Q

wittig reaction steps

A
  1. Ph3P… 2. butyl lithium (CH3CH2CH2CH2Li)… 3. ketone or aldehyde
86
Q

infrared spectroscopy of aldehydes/ketones

A

strong C=O absorption at 1660-1770 cm^-1; aldehydes have additional C-H absorptions at 2700-2760 cm^-1 and 2800-2860 cm^-1 (which is the distinguishing characteristic between aldehydes and ketones)

87
Q

nuclear magnetic resonance spectroscopy

A

aldehyde protons absorb at 10 delta (distinctive because no other absorptions occur in this region); hydrogens on the carbon next to a carbonyl group normally absorb at 2-2.3 delta… carbonyl group carbon atoms have distinctive 13C NMR resonances from 190-215 delta (no other kinds of carbons absorb in this region)

88
Q

mass spectrometry

A

fragment ions from Mclafferty rearrangement and alpha cleavage are visible in mass spectrum

89
Q

1) NaBH4 / 2) H3O+

A

addition of hydride to aldehydes/ketones to give alcohols

90
Q

1) RMgX / 2) H3O+

A

addition of grignard reagent to aldehydes/ketones to yield alcohols

91
Q

1) HCN

A

addition of HCN to aldehydes/ketones to yield cyanohydrins (CN and OH groups)

92
Q

RNH2, H3O+

A

addition of primary amines to aldehydes/ketones to give imines

93
Q

HNR2, H3O+

A

addition of secondary amines to aldehydes/ketones to give enamines

94
Q

NH2NH2, KOH

A

wolff-kishner reaction to aldehydes/ketones to give alkanes

95
Q

2 ROH, H3O+

A

addition of alcohols to aldehydes/ketones to yield acetals (or hemiacetals with addition of one mol of alcohol)

96
Q

1) Ph3P… 2) BuLi… 3) aldehyde/ketone

A

wittig reaction: converts primary alkyl halide to yield an alkene

97
Q

RNH2 to α, β unsaturated aldehydes/ketones

A

yields a β-amino aldehydes/ketones

98
Q

H2O to α, β unsaturated aldehydes/ketones

A

yields a β-hydroxyl aldehydes/ketones

99
Q

1) R2CuLi / 2) H3O+ to α, β unsaturated aldehydes/ketones

A

yields a 1,4 addition product to form a longer alkane chain and a ketone

100
Q

carboxylic acid nomenclature

A

replace terminal “e” of parent name with “oic acid” (CO2H carbon is Carbon 1)… CO2H bonded to a ring causes the compound to have the suffix “carboxylic acid” at end of parent name; conjugate base name has “oate” ending

101
Q

carboxyl group

A

CO2H as a substituent

102
Q

acyl groups

A

COR; derived from parent carboxylic acids and are named with “yl” endings or “oyl” endings

103
Q

nitrile

A

RCN (C is triple bonded to N)

104
Q

nitrile nomenclature

A

“nitrile” suffix at end of parent name (nitrile carbon is carbon 1)…. or can be named as carboxylic acid derivatives: “onitrile” suffix for open chain parent or “carbonitrile” suffix for ring parent (nitrile carbon is attached to carbon 1 but not numbered)

105
Q

properties of carboxylic acids

A

carboxyl carbon is sp^2 hybridized… carboxylic groups are planar with C-C=O and O=C-O bond angles of approximately 120 degrees… are strongly associated due to hydrogen bonding… higher boiling points than corresponding alcohols… are acidic and react with bases to give metal carboxylate salts (RCO2- Metal+), with the salts being very water soluble and allows purification of acid (acid-base extractions)… more acidic than alcohols due to delocalization of negative charge over two equivalent oxygen atoms (ie– stabilized by resonance)

106
Q

henderson-hasselbalch equation

A

pH = pKa + log [A-]/[HA]

107
Q

substituent effects on acidity

A

more stabilization of carboxylate anion relative to undissociated carboxylic acid will drive equilibrium toward increased dissociation and increased acidity, with more electron-withdrawing atoms helping to delocalize negative charge… halogens closer to carboxylic acid increase acidity due to inductive effects operating through sigma bonds…. benzoic acids with deactivating groups are more acidic

108
Q

carboxylate ion nomenclature

A

metal alkanOATE

109
Q

oxidation of substituted alkyl benzene with KMnO4 or Na2Cr2O7

A

yields carboxylic acid

110
Q

oxidation of a primary alcohol or aldehyde with CrO3

A

yields carboxylic acid

111
Q

hydrolysis of nitriles using 1) NaOH, H2O / 2) H3O+

A

yields carboxylic acid

112
Q

converting an alkyl halide to a nitrile

A

use NaCN

113
Q

carboxylation of grignard reagents using CO2, H3O+

A

yields carboxylic acid

114
Q

for 1,2 addition

A

use grignard reagents (RMgX) or alkyl lithium (RLi)

115
Q

for 1,4 addition

A

organo cuprate (R2CuLi), RNH2, R2NH

116
Q

enamine formation (secondary amine + aldehyde/ketone)

A
  1. addition
  2. proton transfer
  3. protonation
  4. elimination
  5. deprotonation
117
Q

wolff-kishner reaction (NH2NH2, OH)

A

Carbonyl converted to a hydrazone (NNH2) then N2 removed with base to yield an alkane… once the base is added to N=N compound, the rest of the reaction is irreversible

118
Q

wittig reaction from primary alkyl halide

A
  1. Ph3P… 2. butyl lithium… 3. ketone/aldehyde… formation of an alkene, with the double bond being where the C=O bond was prior
119
Q

1,2 / 1,4 addition to alpha,beta-unsaturated carbonyls

A
  1. Nucleophile (1,2: RMgX, RLi… 1,4: R2CuLi, RNH2, R2NH)… 2. H3O+ (unless using RNH2 or R2NH, then no H3O+ is needed)
120
Q

formic acid

A

aka methanoic acid; has one carbon; is a chemical weapon used by ants

121
Q

acetic acid

A

aka ethanoic acid; has two carbons; is found in vinegar

122
Q

propionic acid

A

aka propanoic acid; has two carbons; is rancid and pungent

123
Q

buteric acid

A

aka butanoic acid; has four carbons; is found in rancid butter

124
Q

valeric acid

A

aka pentanoic acid; has five carbons; is found in valerion root (a sedative)

125
Q

caproic acid

A

aka hexanoic acid; has six carbons; is the essence of goat

125
Q

caproic acid

A

aka hexanoic acid; has six carbons; is the essence of goat

126
Q

oxalic acid

A

dicarboxylic acid with two carbons

127
Q

malonic

A

dicarboxylic acid with three carbons

128
Q

succinic acid

A

dicarboxylic acid with four carbons

129
Q

glutaric acid

A

dicarboxylic acid with five carbons

130
Q

adipic acid

A

dicarboxylic acid with six carbons

131
Q

pimelic acid

A

dicarboxylic acid with seven carbons

132
Q

acidity of carboxylic acids increases with

A

closer electron withdrawing groups (strong deactivators) due to higher inductive effect; having greater delocalization through resonance

133
Q

1) CO2 / 2) H3O+

A

grignard reagent to carboxylic acid

134
Q

1) NaCN / 2) excess H3O+

A

converting an alkyl halide into a carboxylic acid

135
Q

1) SOCl2, benzene to an amide

A

converts the amide to a nitrile

136
Q

1) LiAlH4 / 2) H2O

A

conversion of nitriles into amines

137
Q

nitrile + grignard reagent

A

converts nitrile into a ketone

138
Q

spectroscopy of carboxylic acids

A

IR: OH bond of carboxyl group has broad absorption at 2500-3300 cm^-1 and C=O bond has absorption 1710-1760 cm^-1… NMR: acidic CO2H protons absorbs around 12 delta

139
Q

IR spectroscopy of nitriles

A

C-N bond absorption between 2230-2250 cm^-1

140
Q

acids with ortho substituents

A

generally the more acidic form of the acid

141
Q

carboxylic acid + excess NaOH, NaHCO3, NH3, or NH2R

A

forms conjugate base of the acid

142
Q

epoxide + grignard is classified as

A

SUBSTITUTION because only a sigma bond is formed and broken

143
Q

deprotonates carboxylic acids

A

NaOH or NH3 or RNH2 or NaHCO3

144
Q

naming carboxylic acids

A

find the longest carbon chain including the acid group and begin numbering from the acid carbon… drop the “e” from alkane and add “oic acid”… label substituents as normal and complete the name

145
Q

naming nitriles

A

circle and name the longest carbon chain containing the nitrile carbon… number from the nitrile carbon and name as alkanenitrile

CHEM 322 - Organic Chemistry (3 decks)

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