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CHEM 322 - Organic Chemistry > Prelim Exam 3: Carboxylic Acids and Derivatives; Carbonyl Alpha Substitution Reactions; Carbonyl Condensation Reactions; Amines (Chem 322 - Organic Chemistry) > Flashcards

Prelim Exam 3: Carboxylic Acids and Derivatives; Carbonyl Alpha Substitution Reactions; Carbonyl Condensation Reactions; Amines (Chem 322 - Organic Chemistry) Flashcards

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1
Q

acid halide (RCOX) nomenclature

A

identify first acyl group then halide… suffix “oyl” (or “carbonyl” for cyclic acid halides)… “alkanoyl halide” or “cycloalkanecarbonyl halide”

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2
Q

acid anhydrides (RCO2COR’) nomenclature

A

symmetrical anhydrides of unsubstituted monocarboxylic acids and cyclic anhydrides of dicarboxylic acids are named with ending “anhydride”… unsymmetrical anhydrides are named by listing two acids alphabetically then adding “anhydride”… “alkanoic anhydride” or “alkanoic alkanoic anhydride”

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3
Q

esters (RCO2R’) nomenclature

A

identify alkyl group attached to oxygen and then carboxylic acid with “ate” suffix… “alkyl alkanoate”

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4
Q

amides (RCONH2) nomenclature

A

“amide” suffix or “carboxamide” suffix (for cyclic compounds)… if nitrogen atom is further substituted, compound is named by identifying substituent groups then parent amide: substituents are preceded by letter “N” to identify them as being attached to nitrogen… “alkanamide” or “cycloalkanecarboxamide” or “N-alkylalkanamide”

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5
Q

thioesters (RCOSR’) nomenclature

A

prefix “thio” if a common related ester name… suffix “thioate” or “carbothioate”… “alkyl alkanethioate” or “alkyl cycloalkanecarbothioate”

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6
Q

acyl phosphates (RCO2PO3 2- and RCO2PO3R’-) nomenclature

A

cite the acyl groups and add the word “phosphate”… “alkoyl phosphate”

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7
Q

nucleophilic acyl substitution reactions

A

net effect: substitution of nucleophile for -Y group originally bonded to acyl carbon… takes place in two steps and involves a tetrahedral intermediate

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8
Q

relative reactivity of carboxylic acid derivatives

A

sterically, unhindered/accessible carbonyl groups react with nucleophiles more readily than do sterically hindered groups… electronically, strongly polarized acyl compounds react more readily than less polar ones

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9
Q

nomenclature of amides with competing substituents

A

alphabetize substituents… di, tri, tetra if more than one substituent… N-substituents come before numerical-substituents

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10
Q

conversion of carboxylic acids into acid chlorides

A

nucleophilic acyl substitution using SOCl2

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11
Q

conversion of carboxylic acids into acid anhydrides

A

using heat

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12
Q

conversion of carboxylic acids into esters

A

SN2 reaction of carboxylate anion with primary alkyl halides

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13
Q

Fischer esterification reaction

A

acid-catalyzed (strong acid like HCl) nucleophilic acyl substitution reaction of a carboxylic acid with alcohol

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14
Q

conversion of carboxylic acids into amides

A

use DCC (dicyclohexylcarbodimide)

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15
Q

conversion of carboxylic acid into alcohols

A

using 1) LiAlH4 / 2) H3O+ or 1) BH3, THF / 2) H3O+

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16
Q

preparation of acid halides

A

conversion of a carboxylic acid using SOCl2

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17
Q

acyl substitution – basic conditions

A

using NaOEt, HOEt… occurs through addition and elimination

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18
Q

acyl substitution – acidic conditions

A

(Fischer esterification reaction) using H3O+… occurs through protonation -> addition -> deprotonation -> protonation -> elimination -> deprotonation

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19
Q

preparation of acid anhydrides

A

nucleophilic acyl substitution reaction of acid chloride with carboxylate anion

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20
Q

conversion of an acid chloride into an carboxylic acid

A

hydrolysis – using H2O

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21
Q

conversion of an acid chloride into an acid anhydride

A

using R’CO2-

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22
Q

conversion of an acid chloride into an ester

A

alcoholysis… using R’OH

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23
Q

conversion of an acid chloride into an amide

A

aminolysis… using NH3

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24
Q

conversion of an acid chloride into a ketone

A

reduction/grignard reaction… using R’2CuLi

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25
Q

conversion of an acid anhydride into a carboxylic acid

A

hydrolysis… using H2O

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26
Q

conversion of an acid anhydride into an ester

A

alcoholysis… using R’OH

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27
Q

conversion of an acid anhydride into an amide

A

aminolysis… using NH3

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28
Q

conversion of an acid anhydride into an alcohol

A

reduction… one round [H-] yields aldehyde, two rounds [H-] yields alcohol

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29
Q

lactone

A

cyclic ester

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30
Q

preparation of esters

A

carboxylic acid + 1) SOCl2 / 2) R’OH… carboxylic acid + R’OH, HCl… carboxylic acid + 1) NaOH / 2) RX

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31
Q

conversion of an ester into an alcohol and carboxylic acid

A

hydrolysis… using H2O, NaOH, or H3O+

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32
Q

saponification

A

conversion of an ester into an alcohol and carboxylic acid in basic conditions… uses H2O, NaOH

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33
Q

conversion of an ester into an amide and an alcohol

A

aminolysis… using NH3

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34
Q

conversion of an ester into an aldehyde and an alcohol

A

reduction… using 1) DIBAH / 2) H3O+

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35
Q

conversion of an ester into primary alcohols

A

reduction… using 1) LiAlH4 / 2) H3O+

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36
Q

conversion of an ester into a tertiary alcohol

A

grignard reaction… using 1) 2 R’MgBr / 2) H3O+

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37
Q

preparation of amides

A

acid chloride + NH3… acid chloride + R’NH2… acid chloride + R’2NH

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38
Q

lactam

A

cyclic amide

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39
Q

conversion of an amide into a carboxylic acid + H3O+ + NH3

A

hydrolysis… using H3O+

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40
Q

conversion of an amide into an amine

A

reduction… using 1) LiAlH4 / 2) H2O

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41
Q

primary amine

A

R-NH2

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42
Q

secondary amine

A

R2 - NH

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43
Q

tertiary amine

A

R3 - N

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44
Q

quaternary ammonium salt

A

R4N+ X-

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45
Q

acid chloride + 1) 2 RMgX / 2) H3O+

A

yields a tertiary alcohol with two identical substituents

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46
Q

most reactive acid derivative

A

acid chloride

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47
Q

least reactive acid derivative

A

amides/nitriles

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48
Q

acid chloride + 1) R2CuLi / 2) H3O+

A

yields a ketone

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49
Q

least reactive carbon nucleophile

A

cuprates

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50
Q

most reactive carbon nucleophile

A

grignards

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51
Q

nitrile + 1) RMgX / 2) H3O+

A

yields a ketone

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52
Q

thiol/thioester reactions

A

thiol formed by phosphoric anhydride linkage (O=P-O-P=O)… partial reduction of thioester using a hydride ion to form an aldehyde

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53
Q

chain growth polymer

A

produced in a chain-reaction process where an initiator adds to a C=C bond to give a reactive intermediate, which adds to a second alkene molecule to produce a new intermediate, which adds to a third molecule, and so on

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54
Q

step-growth polymer

A

each bond in a polymer is independently formed in a discrete step (often by nucleophilic acyl substitution of a carboxylic acid derivative)

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55
Q

polyamides (nylons)

A

step-growth polymer… heat a diamine with a diacid… nylon #__ (first number is the number of carbons in a diamine, second number is the number of carbons in diacid)

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56
Q

polyesters

A

step-growth polymer… diester and dialcohol

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57
Q

sutures and biodegradable polymers

A

common biodegradable polymers: poly(glycolic acid) [PGA], poly(lactic acid) [PLA], poly(hydroxybutyrate) [PHB]

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58
Q

transesterification

A

The process that transforms one ester to another when an alcohol acts as a nucleophile and displaces the alkoxy group on an ester… using HOR’’, H+

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59
Q

infrared spectroscopy of carboxylic acid derivatives

A

intense IR absorptions in 1650 - 1850 cm^-1… acid chlorides have absorption near 1810 cm^-1… acid anhydrides have absorptions at 1820 cm^-1 and 1760 cm^-1… esters have absorption at 1735 cm^-1

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60
Q

nuclear magnetic resonance spectroscopy of carboxylic acid derivatives

A

H’s near carbonyl group absorb near 2 delta in H NMR… but cannot identify the type of carbonyl group

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61
Q

SOCl2

A

conversion of carboxylic acid into acid chloride

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62
Q

alkyl halide, Sn2 reaction

A

conversion of carboxylic acid into ester

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63
Q

R’OH, acid catalyst

A

conversion of carboxylic acid into ester + H2O

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64
Q

RNH2, DCC

A

conversion of carboxylic acid into an amide

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65
Q

carboxylic acid + 1) LiAlH4 / 2) H3O+

A

yields a primary alcohol

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66
Q

acid chloride + H2O

A

hydrolysis to yield a carboxylic acid and HCl

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67
Q

acid chloride + carboxylate (RCO2-)

A

yields anhydride + Cl-

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68
Q

acid chloride + R’OH, pyridine

A

yields ester and HCl

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69
Q

acid chloride + 2 NH3

A

yields amine and NH4Cl

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70
Q

acid chloride + 1) LiAlH4 / 2) H3O+

A

yields a primary alcohol

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71
Q

acid chloride + R2CuLi

A

yields a ketone

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72
Q

acid anhydride + H2O

A

yields 2 carboxylic acids

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73
Q

acid anhydride + ROH

A

yields ester and carboxylic acid

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74
Q

acid anhydride + 2 NH3

A

yields an amide and a quaternary ammonium salt

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75
Q

ester + H3O+ or NaOH or H2O

A

yields a carboxylic acid and an alcohol

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76
Q

ester + 1) LiAlH4 / 2) H3O+

A

yields two primary alcohols

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77
Q

ester + 1) DIBAH / 2) H3O+

A

yields an aldehyde and an alcohol

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78
Q

ester + 1) 2 RMgX / 2) H3O+

A

yields a tertiary alcohol (with two identical substituents) and an alcohol

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79
Q

amide + H3O+ or NaOH or H2O

A

yields a carboxylic acid + NH3

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80
Q

amide + 1) LiAlH4 / 2) H3O+

A

yields an amine

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81
Q

n*peptide

A

possibilities of peptides: n!

[ex: tetrapeptide = 4 x 3 x 2 x 1 = 24 possibilites]

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82
Q

making amines

A

R-X + NaCN -> R-CN + 1) LiAlH4 / 2) H2O -> R-CH2-NH2…

RCONH2 + 1) LiAlH4 / 2) H2O -> R-CH2-NH2…

RCONHR + 1) LiAlH4 / 2) H2O -> R-CH2-NHR…

RCONR2 + 1) LiAlH4 / 2) H2O -> R-CH2-NR2

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83
Q

α-substitution reaction

A

occurs at position next to carbonyl group (α position) and involve substitution of a α hydrogen by electrophile through either an enol or enolate intermediate

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84
Q

tautomers

A

rapidly interconverting isomers differing in a H position or a pi bond position

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85
Q

keto-enol tautomerism

A

tautomers are constitutional isomers (different compound with different structures)… enol can only predominate when stabilized by conjugation or intramolecular hydrogen bonding… only hydrogens at α position of carbonyl groups are acidic

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86
Q

enols

A

act as nucleophiles to react with electrophiles; reacts to yield α-substituted carbonyl compound

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87
Q

alpha halogenation of aldehydes/ketones

A

depends on aldehyde/ketone and acid concentrations…. α-bromo ketones can be dehydrobrominated to yield α, β-unsaturated ketones… deuteration (D3O+) can also slowly occur, where D adds to α

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88
Q

alpha bromination of carboxylic acids

A

acids/esters/amides cannot enolize to a sufficient extent to undergo alpha bromination… carboxylic acids can be alpha brominated by a mixture of Br2 and PBr3 in Hell-Volhard-Zelinski (HVZ) reaction

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89
Q

pyridine

A

pulls off the beta hydrogen to produce a α, β-unsaturated carbonyl compound

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90
Q

strong base is needed for enolate ion formation because

A

carbonyl compounds are weakly acidic

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91
Q

LDA

A

commonly used for making enolate ions from carbonyl compounds

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92
Q

when a hydrogen atom is between two carbonyl groups

A

its acidity increases

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93
Q

enolate ions are more useful than enols

A

stable solutions of pure enolate ions are easily prepared from most carbonyl compounds by reaction with a strong base… enolate ions are more reactive than enols and undergo many reactions that enols do not (because enolate ions are negatively charged, making them better nucleophiles)

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94
Q

haloform reaction

A

*when a base is used with a methyl ketone, the alpha carbon will become completely halogenated.

*this trihalo product reacts further with the base to produce a carboxylic acid and a haloform (CHX3)

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95
Q

forming alkenes through Sn2 using primary alcohol

A

convert to a primary alkyl halide, then use a bulky base (NaOt-butyl)

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96
Q

forming alkenes through E1 using secondary or tertiary alcohol

A

use H2SO4, H2O

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97
Q

haloform

A

CHX3

98
Q

alkylation of enolate ions

A

leaving group X in alkylating agent can be chloride, bromide, iodide, or tosylate…. R alkyl group should be primary, methyl, allylic, or benzyllic (but not tertiary)

99
Q

malonic ester synthesis

A

prepares a carboxylic acid from alkyl halide while lengthening the carbon chain by two atoms… 1) NaOEt / 2) RX / 3) NaOEt / 4) RX / 5) H3O+, Δ

100
Q

only substituted malonic acids and beta-keto acids

A

undergo loss of CO2 upon application of H3O+ and heat

101
Q

acetoacetic ester synthesis

A

converts an alkyl halide into a methyl ketone having 3+ carbons… 1) NaOEt / 2) RX / 3) NaOEt / 4) RX / 5) H3O+, Δ

102
Q

direct alkylation of ketones, esters, and nitriles

A

alkylated using LDA, replacing the acidic H with an alkyl group… 1) LDA / 2) RX

103
Q

aldehyde/ketone + X2/CH3CO2H

A

yields an alpha-halogen ketone/aldehyde + HX

104
Q

carboxylic acid + 1) Br2, PBr3 / 2) H2O

A

yields an alpha-bromo ketone/aldehyde

105
Q

alpha-bromo ketone + pyridine

A

yields an alpha, beta unsaturated ketone

106
Q

ketone + X2, NaOH

A

yields an carboxylate ion and CHX3

107
Q

malonic ester + 1) NaOEt / 2) RX / 3) H3O+, Δ

A

yields a carboxylic acid + CO2 + 2 EtOH

108
Q

acetoacetic ester + 1) NaOEt / 2) RX / 3) H3O+, Δ

A

yields a methyl ketone + CO2 + EtOH

109
Q

direct alkylation of ketones, esters, nitriles + 1) LDA / 2) RX

A

yields an alkyl alpha-substituted ketone, ester, or nitrile

110
Q

acetoacetic ester synthesis makes

A

alpha-substituted methyl ketone

111
Q

malonic ester synthesis

A

alpha-substituted carboxylic acid

112
Q

carbonyl condensation reactions

A

take place between 2 carbonyl partners and involve a combination of nucleophilic addition and alpha substitution steps… one partner is converted into an enolate ion nucleophile and adds to electrophilic carbonyl group of second partner… nucleophilic partner undergoes an alpha substitution reaction and electrophilic partner undergoes a nucleophilic addition

113
Q

aldol reaction

A

base-catalyzed carbonyl condensation reaction involving an aldehyde or ketone with an alpha hydrogen atom

114
Q

aldol

A

a beta hydroxy carbonyl compound

115
Q

dehydration of aldol products: synthesis of enones

A

beta-hydroxy aldehydes/ketones are dehydrated to yield an alpha, beta unsaturated products (conjugated enones)

116
Q

mixed aldol reactions

A

leads to a mixture of products UNLESS– one of the carbonyl partners has no acidic alpha hydrogens but is a good electrophile OR is an unusually acidic nucleophilic donor

117
Q

intramolecular aldol reactions

A

dicarbonyl compounds treated with base leads to formation of a cyclic product… nucleophilic carbonyl anion donor and electrophilic carbonyl acceptor are in same molecule… can lead to a mixture of products, depending on which enolate ion is formed… occurs until equilibrium is reached with most stable, least strained compound

118
Q

claisen condensation reaction

A

reaction between two ester molecules with a base (NaOEt) to yield a beta-keto ester… nucleophilic addition of an ester enolate ion to carbonyl group of a second ester molecule… tetrahedral intermediate expels an alkoxide leaving group to yield an acyl substitution product… high yields are typically obtained due to deprotonation of a highly acidic hydrogen

119
Q

claisen reaction makes

A

beta-ketoester

120
Q

mixed claisen reaction

A

produce a mixture of products UNLESS only one reactant has alpha hydrogens and is converted to 100% enolate

121
Q

intramolecular claisen reaction (dieckmann cyclization)

A

forms a beta-ketoester cyclic compound, but only if 5 or 6 membered ring will form

122
Q

michael addition nucleophile

A

1,3-dicarbonyl compound (enolate)

123
Q

michael addition yields

A

1,5 dicarbonyl compound

124
Q

michael addition

A

1) NaOEt / 2) H3O+, Δ

125
Q

stork enamine synthesis nucleophile

A

enamine

126
Q

stork enamine synthesis

A

1) pyrrolidine / 2) H2O

127
Q

no mixtures of products from mixed aldol reactions if

A

one reactant is much more acidic and one reactant has no acidic hydrogens

128
Q

intramolecular aldol reaction

A

will occur if it will form a 5 or 6 membered ring… uses NaOH

129
Q

mixed claisen condensation

A

forms a mixture of products unless only one ester component has no alpha hydrogens… reaction can occur with ester and ketone, resulting in a beta-diketone

130
Q

michael reaction

A

nucleophilic enolate reacts with an alpha, beta-unsaturated carbonyl compound… addition of a nucleophilic enolate ion donor to beta carbon of an alpha, beta unsaturated carbonyl acceptor

131
Q

michael acceptors

A

conjugated ketones, unsaturated aldehydes, esters, thioesters, nitriles, amides, and nitro compounds

132
Q

michael donors

A

beta-diketones, beta-keto esters, malonic esters, beta-keto nitriles, and nitro compounds

133
Q

stork reaction

A

enamine adds to alpha, beta-unsaturated carbonyl acceptor in a michael-like process, then hydrolyzed by aqueous acid to yield a 1,5 dicarbonyl compound…. steps: enamine formation from ketone -> michael addition to alpha, beta-unsaturated carbonyl compound -> enamine hydrolysis back to ketone… advantages: enamine is neutral and enamine from a monoketone can be used

134
Q

robinson annulation reaction

A

synthesis of polycyclic molecules, combining Michael reaction with intramolecular aldol reaction… takes place between a nucleophilic donor (beta-keto ester, enamine, or beta-diketone) and an alpha, beta-unsaturated ketone acceptor to produce a substituted 2-cyclohexanone

135
Q

2 aldehydes + NaOH

A

yields an aldol

136
Q

diketone (1,7) + NaOH

A

yields a cyclic enone

137
Q

beta-hydroxy ketone + NaOH or H3O+

A

yields an enone

138
Q

2 esters + NaOEt

A

yields a beta-ketoester + HOR

139
Q

diester + NaOEt

A

yields a cyclic beta-ketoester + HOEt

140
Q

diketone + enone + NaOEt

A

yields 1,5 dicarbonyl compound

141
Q

enamine + enone + H3O+

A

yields a 1,5 dicarbonyl compound

142
Q

amine

A

nitrogen with three bonds and a lone pair

143
Q

alkylamine

A

amines that are alkyl substituted

144
Q

arylamine

A

amines that are aryl-substituted

145
Q

heterocyclic amine

A

compounds in which the nitrogen atom occurs as part of a ring

146
Q

amine nomenclature

A

for simple amines: suffix “amine” is added to name of alkyl substituent… suffix “amine” replaces “e” of parent name… amines with more than one functional group are named considering NH2 as an amino substituent on parent molecule… symmetrical secondary/primary amines are named by adding prefix di or tri to alkyl group… unsymmetrically substituted secondary/tertiary amines are referred to as N-substituted primary amines– largest alkyl group takes parent name and other alkyl groups are considered N-substituents

147
Q

pyridine

A

C5H5N

148
Q

pyridine

A

C4H5N

149
Q

quindine

A

C9H7N

150
Q

imidazole

A

C3H4N2

151
Q

indole

A

C8H7N

152
Q

pyrimidine

A

C4H4N2

153
Q

pyrrolidine

A

C4H8NH

154
Q

piperidine

A

C5H10NH

155
Q

structure and properties of amines

A

nitrogen is sp^3 hybridized… C-N-C bond angles 109 degrees… amine with 3 different substituents is chiral (interconvert rapidly by pyramidal inversion– rehybridization of N atom to sp^2 followed by rehybridization to sp^3)…. higher boiling points than similar alkanes (form hydrogen bonds, causing higher association)… have appalling/yucky odors

156
Q

basicity of amines

A

dominated by lone pair on nitrogen, making amines basic and nucleophilic… react with acids to form acid-base salts and react with electrophiles… stronger bases than alcohols/ethers (oxygen containing analogs)… separate amines using acid-base extraction techniques… primary and secondary amines also act as weak acids because an N-H proton can be removed by a sufficiently strong base

157
Q

aniline

A

benzene with NH2

158
Q

basicity of arylamines

A

arylamines are less basic than alkylamines because lone pair electrons are delocalized by interaction with aromatic ring’s pi electron system and are less available for bonding to H+… upon protonation, resonance stabilization is lost, so there is greater energy difference between protonated and nonprotonated forms for arylamines than alkylamines (arylamines are less basic)… electron-donating groups increase basicity of arylamine (electron-withdrawing groups decrease bascity of arylamines)

159
Q

biological amine form

A

positively charged amine site (NH3+) and negatively charged carboxyl site (CO2-)

160
Q

ester nomenclature

A

circle and name the alkyl group replacing the acidic H –> circle and name the acid portion of the molecule (drop the “ic acid” and add “ate”)… name: alkyl alkanoate

161
Q

acid halide nomenclature

A

circle and name the carboxylic acid portion of the molecule (drop the “ic acid” and add “yl”) –> add the name of the halogen attached written as if an ion (chloride, bromide, iodide, etc)… name: alkanoyl halide

162
Q

amide nomenclature

A

circle and name the acid portion of the molecule (drop the “oic acid” and add “amide”) –> circle and name the alkyl groups attached to nitrogen… name: N-alkyl-N-alkylalkanamide

163
Q

acid anhydride nomenclature

A

circle and name the two carboxylic acids making up the molecule… if the two acids are the same then name as alkanoic anhydride… if the two acids are different then name as alkanoic alkanoic anhydride

164
Q

RX + 1) Mg / 2) CO2 / 3) H3O+

A

yields a carboxylic acid

165
Q

RX + 1) NaCN / 2) H3O+

A

yields a carboxylic acid

166
Q

RCOOH + SOCl2

A

yields an acid chloride

167
Q

RCOOH + R’COOH, Δ

A

yields an acid anhydride

168
Q

RCOOH + HOR’, H+

A

yields an ester

169
Q

RCOOH + HNR2

A

yields an amide

170
Q

RCOCl + R’COOH

A

yields an acid anhydride

171
Q

RCOCl + H2O

A

yields a carboxylic acid + HCl

172
Q

RCOOCOR + R’OH

A

yields an ester

173
Q

RCOOCOR + H2O

A

yields a carboxylic acid

174
Q

RCOOR + HNR2

A

yields an amide

175
Q

RCOOR + H+, H2O

A

yields a carboxylic acid

176
Q

RCONR2 + H+, H2O

A

yields a carboxylic acid

177
Q

acyl group

A

RC=O

178
Q

acyl substitution steps with negative nucleophile

A

1) addition –> 2) elimination

179
Q

acyl substitution steps with positive/neutral nucleophile (in acidic solution)

A

1) protonation –> 2) addition –> 3) deprotonation –> 4) protonation –> 5) elimination –> 6) deprotonation

180
Q

RCOCl + 1) LiAlH4 / 2) H3O+

A

yields a primary alcohol

181
Q

RCOCl + 1) LiAlH(O-t-butoxy)3 / 2) H3O+

A

yields an aldehyde

182
Q

RCOOCOR + 1) LiAlH4 / 2) H3O+

A

yields a primary alcohol

183
Q

RCOOR + 1) LiAlH4 / 2) H3O+

A

yields a primary alcohol

184
Q

RCOOR + 1) DIBAH / 2) H3O+

A

yields an aldehyde

185
Q

RCOOH + 1) LiAlH4 / 2) H3O+

A

yields a primary alcohol

186
Q

RCONH2 + 1) LiAlH4 / 2) H3O+

A

yields an imine

187
Q

RCONH2 + 1) DIBAH / 2) H3O+

A

yields an imine

188
Q

RCN + 1) LiAlH4 / 2) H3O+

A

yields an amine

189
Q

RCN + 1) DIBAH / 2) H3O+

A

yields an imine

190
Q

RCHN (imine) + H3O+

A

yields an aldehyde

191
Q

RCOCl + 1) 2 RMgX / 2) H3O+

A

yields a tertiary alcohol with two identical substituents

192
Q

RCOCl + 1) (R)2CuLi / 2) H3O+

A

yields a ketone

193
Q

RCOOR + 1) 2 RMgX / 2) H3O+

A

yields a tertiary alcohol with two identical substituents

194
Q

RCN + RMgX

A

yields an imine

195
Q

R2CN (imine) + H3O+

A

yields a ketone

196
Q

three kinds of esters

A

carboxylate ester (from carboxylic acid + alcohol)… sulfate ester (from sulfuric acid + alcohol)… phosphate ester (from phosphoric acid + alcohol

197
Q

phosphate anhydride

A

contain two phosphoryl groups bonded to an oxygen

198
Q

carboxylate ester

A

Contains a carbonyl group bonded to an alkoxy group (-O-C)

199
Q

sulfate ester

A

An alcohol derivative with the formula ROSO2OR’ , in which alkyl groups replace both of the hydrogen atoms in sulfuric acid, HOSO2OH.

200
Q

phosphate ester

A

contain a phosphoryl group bonded to a carbon

201
Q

carboxylate thioester

A

contains a thiol (SH) group bonded to a acyl group (RC=O)

202
Q

carboxylic acid anhydride

A

contains two carbonyls linked through an oxygen

203
Q

acyl phosphate

A

a carboxylic acid derivative with a phosphate leaving group

204
Q

retrosynthetic analysis

A
  1. identify type of compound (product)… 2. identify type of reaction… 3. draw a line through the bond formed in reaction… 4. do the separation… 5. write the reagents
205
Q

do the 1,5 separation

A

BEFORE the 1,3 separation unless in a ring, then do the opposite

206
Q

quaternary ammonium salt nomenclature

A

alkylalkyl ammonium halide

207
Q

electron withdrawing groups

A

decrease basicity and increase acidity

208
Q

electron donating groups

A

increase basicity and decrease acidity

209
Q

tautomerization

A

proton transfer between a compound allowing it to interconvert between an enol to a ketone

210
Q

beta branching

A

indicates prior double bond on initial reactant

211
Q

acid derivative order of best leaving groups

A

acid chloride (Cl- is best leaving group – most electronegative, largest atom) > anhydride (resonance stabilized -OCOR leaving group) > ester (-OR is electronegative) > amide (-NH2 is worst leaving group – negative charge on electropositive nitrogen)

212
Q

amine acid/base reaction

A

RNH2 + RCOOH –> RNH3+ + RCOO-

213
Q

amine substitution reaction

A

RNH2 + R’X –> +NRH2R’ + Br-

214
Q

amine reaction with carbonyl (addition -> elimination)

A

RNH2 + RCOH –> RCHNR …. R2NH + RCOCH3 –> RCNR2CH2

215
Q

amine reaction with acid derivative (addition -> elimination)

A

RNH2 + RCOCl –> RCONHR … R2NH + ROCl –> RCONR2

216
Q

aniline protection/deprotection

A

Protection: aniline + acid anhydride –> amide // Deprotection: amide + H2O, NaOH –> aniline

217
Q

fischer projections

A

vertical lines go into the page and horizontal lines are coming out of the page, with the “spine” resembling the main chain

218
Q

fischer projection enantiomers

A

all horizontal lines switch

219
Q

amine spectroscopy

A

IR: NH absorbing region 3300 to 3500 cm^-1 and generally sharper and less intense // NMR: broad signals over a range // Mass: odd numbered molecular weight = 1 or 3 nitrogens present…. even numbered molecular weight = 0 or 2 nitrogens present

220
Q

RCH2X + 1) NaCN / 2) LiAlH4 / 3) H3O+

A

yields an amine (RCH2CH2NH2)

221
Q

RCONH2 + 1)LiAlH4 / 2) H3O+

A

yields an amine (RCH2NH2)

222
Q

nitrobenzene + H2/Pt or SnCl2/H3O+

A

yields an aniline

223
Q

ammonia (NH3) + 1) RX / 2)NaOH

A

yields a primary amine

224
Q

primary amine + 1) RX / 2) NaOH

A

yields a secondary amine

225
Q

secondary amine + 1) RX / 2) NaOH

A

yields a tertiary amine

226
Q

tertiary amine + RX

A

yields a quaternary ammonium salt

227
Q

gabriel amine synthesis: phthalimide + 1) KOH / 2) RX / 3) NaOH, H2O

A

yields a primary amine

228
Q

RCH2X + 1) NaN3 / 2) LiAlH4 / 2) H3O+

A

yields a primary amine (RCH2NH2)

229
Q

R2CO + NH3, NaBH4

A

yields an amine

230
Q

RCONH2 + NaOH, Br2, H2O

A

yields a primary amine and CO2

231
Q

RCOCl + 1) NaN3 / 2) H2O, heat

A

yields a primary amine, CO2, and N2

232
Q

hofmann elimination: amine + 1) CH3I / 2) Ag2O, heat

A

yields least substituted alkene E2 product

233
Q

aniline + HNO2, H2SO4

A

yields arenediazonium salt

234
Q

arenediazonium salt + HCl, CuCl

A

yields chlorobenzene

235
Q

arenediazonium salt + HBr, CuBr

A

yields bromobenzene

236
Q

arenediazonium salt + NaI

A

yields iodobenzene

237
Q

arenediazonium salt + KCN, CuCN

A

yields cyanobenzene

238
Q

arenediazonium salt + Cu2O, H2O, Cu(NO3)2

A

yields phenol

239
Q

arenediazonium salt + H3PO2

A

yields benzene

240
Q

arenediazonium salt + phenol or aniline

A

yields diazonium coupling product

241
Q

solvolysis

A

a nucleophilic substitution or elimination where the solvent serves as the attacking reagent

CHEM 322 - Organic Chemistry (3 decks)

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