Prelim Exam 3: Carboxylic Acids and Derivatives; Carbonyl Alpha Substitution Reactions; Carbonyl Condensation Reactions; Amines (Chem 322 - Organic Chemistry) Flashcards
(241 cards)
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”
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”
3
Q
esters (RCO2R’) nomenclature
A
identify alkyl group attached to oxygen and then carboxylic acid with “ate” suffix… “alkyl alkanoate”
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”
5
Q
thioesters (RCOSR’) nomenclature
A
prefix “thio” if a common related ester name… suffix “thioate” or “carbothioate”… “alkyl alkanethioate” or “alkyl cycloalkanecarbothioate”
6
Q
acyl phosphates (RCO2PO3 2- and RCO2PO3R’-) nomenclature
A
cite the acyl groups and add the word “phosphate”… “alkoyl phosphate”
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
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
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
10
Q
conversion of carboxylic acids into acid chlorides
A
nucleophilic acyl substitution using SOCl2
11
Q
conversion of carboxylic acids into acid anhydrides
A
using heat
12
Q
conversion of carboxylic acids into esters
A
SN2 reaction of carboxylate anion with primary alkyl halides
13
Q
Fischer esterification reaction
A
acid-catalyzed (strong acid like HCl) nucleophilic acyl substitution reaction of a carboxylic acid with alcohol
14
Q
conversion of carboxylic acids into amides
A
use DCC (dicyclohexylcarbodimide)
15
Q
conversion of carboxylic acid into alcohols
A
using 1) LiAlH4 / 2) H3O+ or 1) BH3, THF / 2) H3O+
16
Q
preparation of acid halides
A
conversion of a carboxylic acid using SOCl2
17
Q
acyl substitution – basic conditions
A
using NaOEt, HOEt… occurs through addition and elimination
18
Q
acyl substitution – acidic conditions
A
(Fischer esterification reaction) using H3O+… occurs through protonation -> addition -> deprotonation -> protonation -> elimination -> deprotonation
19
Q
preparation of acid anhydrides
A
nucleophilic acyl substitution reaction of acid chloride with carboxylate anion
20
Q
conversion of an acid chloride into an carboxylic acid
A
hydrolysis – using H2O
21
Q
conversion of an acid chloride into an acid anhydride
A
using R’CO2-
22
Q
conversion of an acid chloride into an ester
A
alcoholysis… using R’OH
23
Q
conversion of an acid chloride into an amide
A
aminolysis… using NH3
24
Q
conversion of an acid chloride into a ketone
A
reduction/grignard reaction… using R’2CuLi
25
conversion of an acid anhydride into a carboxylic acid
hydrolysis... using H2O
26
conversion of an acid anhydride into an ester
alcoholysis... using R'OH
27
conversion of an acid anhydride into an amide
aminolysis... using NH3
28
conversion of an acid anhydride into an alcohol
reduction... one round [H-] yields aldehyde, two rounds [H-] yields alcohol
29
lactone
cyclic ester
30
preparation of esters
carboxylic acid + 1) SOCl2 / 2) R'OH... carboxylic acid + R'OH, HCl... carboxylic acid + 1) NaOH / 2) RX
31
conversion of an ester into an alcohol and carboxylic acid
hydrolysis... using H2O, NaOH, or H3O+
32
saponification
conversion of an ester into an alcohol and carboxylic acid in basic conditions... uses H2O, NaOH
33
conversion of an ester into an amide and an alcohol
aminolysis... using NH3
34
conversion of an ester into an aldehyde and an alcohol
reduction... using 1) DIBAH / 2) H3O+
35
conversion of an ester into primary alcohols
reduction... using 1) LiAlH4 / 2) H3O+
36
conversion of an ester into a tertiary alcohol
grignard reaction... using 1) 2 R'MgBr / 2) H3O+
37
preparation of amides
acid chloride + NH3... acid chloride + R'NH2... acid chloride + R'2NH
38
lactam
cyclic amide
39
conversion of an amide into a carboxylic acid + H3O+ + NH3
hydrolysis... using H3O+
40
conversion of an amide into an amine
reduction... using 1) LiAlH4 / 2) H2O
41
primary amine
R-NH2
42
secondary amine
R2 - NH
43
tertiary amine
R3 - N
44
quaternary ammonium salt
R4N+ X-
45
acid chloride + 1) 2 RMgX / 2) H3O+
yields a tertiary alcohol with two identical substituents
46
most reactive acid derivative
acid chloride
47
least reactive acid derivative
amides/nitriles
48
acid chloride + 1) R2CuLi / 2) H3O+
yields a ketone
49
least reactive carbon nucleophile
cuprates
50
most reactive carbon nucleophile
grignards
51
nitrile + 1) RMgX / 2) H3O+
yields a ketone
52
thiol/thioester reactions
thiol formed by phosphoric anhydride linkage (O=P-O-P=O)... partial reduction of thioester using a hydride ion to form an aldehyde
53
chain growth polymer
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
54
step-growth polymer
each bond in a polymer is independently formed in a discrete step (often by nucleophilic acyl substitution of a carboxylic acid derivative)
55
polyamides (nylons)
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)
56
polyesters
step-growth polymer... diester and dialcohol
57
sutures and biodegradable polymers
common biodegradable polymers: poly(glycolic acid) [PGA], poly(lactic acid) [PLA], poly(hydroxybutyrate) [PHB]
58
transesterification
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+
59
infrared spectroscopy of carboxylic acid derivatives
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
60
nuclear magnetic resonance spectroscopy of carboxylic acid derivatives
H's near carbonyl group absorb near 2 delta in H NMR... but cannot identify the type of carbonyl group
61
SOCl2
conversion of carboxylic acid into acid chloride
62
alkyl halide, Sn2 reaction
conversion of carboxylic acid into ester
63
R'OH, acid catalyst
conversion of carboxylic acid into ester + H2O
64
RNH2, DCC
conversion of carboxylic acid into an amide
65
carboxylic acid + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
66
acid chloride + H2O
hydrolysis to yield a carboxylic acid and HCl
67
acid chloride + carboxylate (RCO2-)
yields anhydride + Cl-
68
acid chloride + R'OH, pyridine
yields ester and HCl
69
acid chloride + 2 NH3
yields amine and NH4Cl
70
acid chloride + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
71
acid chloride + R2CuLi
yields a ketone
72
acid anhydride + H2O
yields 2 carboxylic acids
73
acid anhydride + ROH
yields ester and carboxylic acid
74
acid anhydride + 2 NH3
yields an amide and a quaternary ammonium salt
75
ester + H3O+ or NaOH or H2O
yields a carboxylic acid and an alcohol
76
ester + 1) LiAlH4 / 2) H3O+
yields two primary alcohols
77
ester + 1) DIBAH / 2) H3O+
yields an aldehyde and an alcohol
78
ester + 1) 2 RMgX / 2) H3O+
yields a tertiary alcohol (with two identical substituents) and an alcohol
79
amide + H3O+ or NaOH or H2O
yields a carboxylic acid + NH3
80
amide + 1) LiAlH4 / 2) H3O+
yields an amine
81
n*peptide
possibilities of peptides: n!
[ex: tetrapeptide = 4 x 3 x 2 x 1 = 24 possibilites]
82
making amines
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
83
α-substitution reaction
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
84
tautomers
rapidly interconverting isomers differing in a H position or a pi bond position
85
keto-enol tautomerism
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
86
enols
act as nucleophiles to react with electrophiles; reacts to yield α-substituted carbonyl compound
87
alpha halogenation of aldehydes/ketones
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
88
alpha bromination of carboxylic acids
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
89
pyridine
pulls off the beta hydrogen to produce a α, β-unsaturated carbonyl compound
90
strong base is needed for enolate ion formation because
carbonyl compounds are weakly acidic
91
LDA
commonly used for making enolate ions from carbonyl compounds
92
when a hydrogen atom is between two carbonyl groups
its acidity increases
93
enolate ions are more useful than enols
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)
94
haloform reaction
*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)
95
forming alkenes through Sn2 using primary alcohol
convert to a primary alkyl halide, then use a bulky base (NaOt-butyl)
96
forming alkenes through E1 using secondary or tertiary alcohol
use H2SO4, H2O
97
haloform
CHX3
98
alkylation of enolate ions
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
malonic ester synthesis
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
only substituted malonic acids and beta-keto acids
undergo loss of CO2 upon application of H3O+ and heat
101
acetoacetic ester synthesis
converts an alkyl halide into a methyl ketone having 3+ carbons... 1) NaOEt / 2) RX / 3) NaOEt / 4) RX / 5) H3O+, Δ
102
direct alkylation of ketones, esters, and nitriles
alkylated using LDA, replacing the acidic H with an alkyl group... 1) LDA / 2) RX
103
aldehyde/ketone + X2/CH3CO2H
yields an alpha-halogen ketone/aldehyde + HX
104
carboxylic acid + 1) Br2, PBr3 / 2) H2O
yields an alpha-bromo ketone/aldehyde
105
alpha-bromo ketone + pyridine
yields an alpha, beta unsaturated ketone
106
ketone + X2, NaOH
yields an carboxylate ion and CHX3
107
malonic ester + 1) NaOEt / 2) RX / 3) H3O+, Δ
yields a carboxylic acid + CO2 + 2 EtOH
108
acetoacetic ester + 1) NaOEt / 2) RX / 3) H3O+, Δ
yields a methyl ketone + CO2 + EtOH
109
direct alkylation of ketones, esters, nitriles + 1) LDA / 2) RX
yields an alkyl alpha-substituted ketone, ester, or nitrile
110
acetoacetic ester synthesis makes
alpha-substituted methyl ketone
111
malonic ester synthesis
alpha-substituted carboxylic acid
112
carbonyl condensation reactions
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
aldol reaction
base-catalyzed carbonyl condensation reaction involving an aldehyde or ketone with an alpha hydrogen atom
114
aldol
a beta hydroxy carbonyl compound
115
dehydration of aldol products: synthesis of enones
beta-hydroxy aldehydes/ketones are dehydrated to yield an alpha, beta unsaturated products (conjugated enones)
116
mixed aldol reactions
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
intramolecular aldol reactions
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
claisen condensation reaction
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
claisen reaction makes
beta-ketoester
120
mixed claisen reaction
produce a mixture of products UNLESS only one reactant has alpha hydrogens and is converted to 100% enolate
121
intramolecular claisen reaction (dieckmann cyclization)
forms a beta-ketoester cyclic compound, but only if 5 or 6 membered ring will form
122
michael addition nucleophile
1,3-dicarbonyl compound (enolate)
123
michael addition yields
1,5 dicarbonyl compound
124
michael addition
1) NaOEt / 2) H3O+, Δ
125
stork enamine synthesis nucleophile
enamine
126
stork enamine synthesis
1) pyrrolidine / 2) H2O
127
no mixtures of products from mixed aldol reactions if
one reactant is much more acidic and one reactant has no acidic hydrogens
128
intramolecular aldol reaction
will occur if it will form a 5 or 6 membered ring... uses NaOH
129
mixed claisen condensation
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
michael reaction
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
michael acceptors
conjugated ketones, unsaturated aldehydes, esters, thioesters, nitriles, amides, and nitro compounds
132
michael donors
beta-diketones, beta-keto esters, malonic esters, beta-keto nitriles, and nitro compounds
133
stork reaction
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
robinson annulation reaction
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
2 aldehydes + NaOH
yields an aldol
136
diketone (1,7) + NaOH
yields a cyclic enone
137
beta-hydroxy ketone + NaOH or H3O+
yields an enone
138
2 esters + NaOEt
yields a beta-ketoester + HOR
139
diester + NaOEt
yields a cyclic beta-ketoester + HOEt
140
diketone + enone + NaOEt
yields 1,5 dicarbonyl compound
141
enamine + enone + H3O+
yields a 1,5 dicarbonyl compound
142
amine
nitrogen with three bonds and a lone pair
143
alkylamine
amines that are alkyl substituted
144
arylamine
amines that are aryl-substituted
145
heterocyclic amine
compounds in which the nitrogen atom occurs as part of a ring
146
amine nomenclature
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
pyridine
C5H5N
148
pyridine
C4H5N
149
quindine
C9H7N
150
imidazole
C3H4N2
151
indole
C8H7N
152
pyrimidine
C4H4N2
153
pyrrolidine
C4H8NH
154
piperidine
C5H10NH
155
structure and properties of amines
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
basicity of amines
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
aniline
benzene with NH2
158
basicity of arylamines
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
biological amine form
positively charged amine site (NH3+) and negatively charged carboxyl site (CO2-)
160
ester nomenclature
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
acid halide nomenclature
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
amide nomenclature
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
acid anhydride nomenclature
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
RX + 1) Mg / 2) CO2 / 3) H3O+
yields a carboxylic acid
165
RX + 1) NaCN / 2) H3O+
yields a carboxylic acid
166
RCOOH + SOCl2
yields an acid chloride
167
RCOOH + R'COOH, Δ
yields an acid anhydride
168
RCOOH + HOR', H+
yields an ester
169
RCOOH + HNR2
yields an amide
170
RCOCl + R'COOH
yields an acid anhydride
171
RCOCl + H2O
yields a carboxylic acid + HCl
172
RCOOCOR + R'OH
yields an ester
173
RCOOCOR + H2O
yields a carboxylic acid
174
RCOOR + HNR2
yields an amide
175
RCOOR + H+, H2O
yields a carboxylic acid
176
RCONR2 + H+, H2O
yields a carboxylic acid
177
acyl group
RC=O
178
acyl substitution steps with negative nucleophile
1) addition --> 2) elimination
179
acyl substitution steps with positive/neutral nucleophile (in acidic solution)
1) protonation --> 2) addition --> 3) deprotonation --> 4) protonation --> 5) elimination --> 6) deprotonation
180
RCOCl + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
181
RCOCl + 1) LiAlH(O-t-butoxy)3 / 2) H3O+
yields an aldehyde
182
RCOOCOR + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
183
RCOOR + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
184
RCOOR + 1) DIBAH / 2) H3O+
yields an aldehyde
185
RCOOH + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
186
RCONH2 + 1) LiAlH4 / 2) H3O+
yields an imine
187
RCONH2 + 1) DIBAH / 2) H3O+
yields an imine
188
RCN + 1) LiAlH4 / 2) H3O+
yields an amine
189
RCN + 1) DIBAH / 2) H3O+
yields an imine
190
RCHN (imine) + H3O+
yields an aldehyde
191
RCOCl + 1) 2 RMgX / 2) H3O+
yields a tertiary alcohol with two identical substituents
192
RCOCl + 1) (R)2CuLi / 2) H3O+
yields a ketone
193
RCOOR + 1) 2 RMgX / 2) H3O+
yields a tertiary alcohol with two identical substituents
194
RCN + RMgX
yields an imine
195
R2CN (imine) + H3O+
yields a ketone
196
three kinds of esters
carboxylate ester (from carboxylic acid + alcohol)... sulfate ester (from sulfuric acid + alcohol)... phosphate ester (from phosphoric acid + alcohol
197
phosphate anhydride
contain two phosphoryl groups bonded to an oxygen
198
carboxylate ester
Contains a carbonyl group bonded to an alkoxy group (-O-C)
199
sulfate ester
An alcohol derivative with the formula ROSO2OR' , in which alkyl groups replace both of the hydrogen atoms in sulfuric acid, HOSO2OH.
200
phosphate ester
contain a phosphoryl group bonded to a carbon
201
carboxylate thioester
contains a thiol (SH) group bonded to a acyl group (RC=O)
202
carboxylic acid anhydride
contains two carbonyls linked through an oxygen
203
acyl phosphate
a carboxylic acid derivative with a phosphate leaving group
204
retrosynthetic analysis
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
do the 1,5 separation
BEFORE the 1,3 separation unless in a ring, then do the opposite
206
quaternary ammonium salt nomenclature
alkylalkyl ammonium halide
207
electron withdrawing groups
decrease basicity and increase acidity
208
electron donating groups
increase basicity and decrease acidity
209
tautomerization
proton transfer between a compound allowing it to interconvert between an enol to a ketone
210
beta branching
indicates prior double bond on initial reactant
211
acid derivative order of best leaving groups
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
amine acid/base reaction
RNH2 + RCOOH --> RNH3+ + RCOO-
213
amine substitution reaction
RNH2 + R'X --> +NRH2R' + Br-
214
amine reaction with carbonyl (addition -> elimination)
RNH2 + RCOH --> RCHNR .... R2NH + RCOCH3 --> RCNR2CH2
215
amine reaction with acid derivative (addition -> elimination)
RNH2 + RCOCl --> RCONHR ... R2NH + ROCl --> RCONR2
216
aniline protection/deprotection
Protection: aniline + acid anhydride --> amide // Deprotection: amide + H2O, NaOH --> aniline
217
fischer projections
vertical lines go into the page and horizontal lines are coming out of the page, with the "spine" resembling the main chain
218
fischer projection enantiomers
all horizontal lines switch
219
amine spectroscopy
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
RCH2X + 1) NaCN / 2) LiAlH4 / 3) H3O+
yields an amine (RCH2CH2NH2)
221
RCONH2 + 1)LiAlH4 / 2) H3O+
yields an amine (RCH2NH2)
222
nitrobenzene + H2/Pt or SnCl2/H3O+
yields an aniline
223
ammonia (NH3) + 1) RX / 2)NaOH
yields a primary amine
224
primary amine + 1) RX / 2) NaOH
yields a secondary amine
225
secondary amine + 1) RX / 2) NaOH
yields a tertiary amine
226
tertiary amine + RX
yields a quaternary ammonium salt
227
gabriel amine synthesis: phthalimide + 1) KOH / 2) RX / 3) NaOH, H2O
yields a primary amine
228
RCH2X + 1) NaN3 / 2) LiAlH4 / 2) H3O+
yields a primary amine (RCH2NH2)
229
R2CO + NH3, NaBH4
yields an amine
230
RCONH2 + NaOH, Br2, H2O
yields a primary amine and CO2
231
RCOCl + 1) NaN3 / 2) H2O, heat
yields a primary amine, CO2, and N2
232
hofmann elimination: amine + 1) CH3I / 2) Ag2O, heat
yields least substituted alkene E2 product
233
aniline + HNO2, H2SO4
yields arenediazonium salt
234
arenediazonium salt + HCl, CuCl
yields chlorobenzene
235
arenediazonium salt + HBr, CuBr
yields bromobenzene
236
arenediazonium salt + NaI
yields iodobenzene
237
arenediazonium salt + KCN, CuCN
yields cyanobenzene
238
arenediazonium salt + Cu2O, H2O, Cu(NO3)2
yields phenol
239
arenediazonium salt + H3PO2
yields benzene
240
arenediazonium salt + phenol or aniline
yields diazonium coupling product
241
solvolysis
a nucleophilic substitution or elimination where the solvent serves as the attacking reagent
