Prelim Exam 3: Carboxylic Acids and Derivatives; Carbonyl Alpha Substitution Reactions; Carbonyl Condensation Reactions; Amines (Chem 322 - Organic Chemistry) Flashcards
acid halide (RCOX) nomenclature
identify first acyl group then halide… suffix “oyl” (or “carbonyl” for cyclic acid halides)… “alkanoyl halide” or “cycloalkanecarbonyl halide”
acid anhydrides (RCO2COR’) nomenclature
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”
esters (RCO2R’) nomenclature
identify alkyl group attached to oxygen and then carboxylic acid with “ate” suffix… “alkyl alkanoate”
amides (RCONH2) nomenclature
“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”
thioesters (RCOSR’) nomenclature
prefix “thio” if a common related ester name… suffix “thioate” or “carbothioate”… “alkyl alkanethioate” or “alkyl cycloalkanecarbothioate”
acyl phosphates (RCO2PO3 2- and RCO2PO3R’-) nomenclature
cite the acyl groups and add the word “phosphate”… “alkoyl phosphate”
nucleophilic acyl substitution reactions
net effect: substitution of nucleophile for -Y group originally bonded to acyl carbon… takes place in two steps and involves a tetrahedral intermediate
relative reactivity of carboxylic acid derivatives
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
nomenclature of amides with competing substituents
alphabetize substituents… di, tri, tetra if more than one substituent… N-substituents come before numerical-substituents
conversion of carboxylic acids into acid chlorides
nucleophilic acyl substitution using SOCl2
conversion of carboxylic acids into acid anhydrides
using heat
conversion of carboxylic acids into esters
SN2 reaction of carboxylate anion with primary alkyl halides
Fischer esterification reaction
acid-catalyzed (strong acid like HCl) nucleophilic acyl substitution reaction of a carboxylic acid with alcohol
conversion of carboxylic acids into amides
use DCC (dicyclohexylcarbodimide)
conversion of carboxylic acid into alcohols
using 1) LiAlH4 / 2) H3O+ or 1) BH3, THF / 2) H3O+
preparation of acid halides
conversion of a carboxylic acid using SOCl2
acyl substitution – basic conditions
using NaOEt, HOEt… occurs through addition and elimination
acyl substitution – acidic conditions
(Fischer esterification reaction) using H3O+… occurs through protonation -> addition -> deprotonation -> protonation -> elimination -> deprotonation
preparation of acid anhydrides
nucleophilic acyl substitution reaction of acid chloride with carboxylate anion
conversion of an acid chloride into an carboxylic acid
hydrolysis – using H2O
conversion of an acid chloride into an acid anhydride
using R’CO2-
conversion of an acid chloride into an ester
alcoholysis… using R’OH
conversion of an acid chloride into an amide
aminolysis… using NH3
conversion of an acid chloride into a ketone
reduction/grignard reaction… using R’2CuLi
conversion of an acid anhydride into a carboxylic acid
hydrolysis… using H2O
conversion of an acid anhydride into an ester
alcoholysis… using R’OH
conversion of an acid anhydride into an amide
aminolysis… using NH3
conversion of an acid anhydride into an alcohol
reduction… one round [H-] yields aldehyde, two rounds [H-] yields alcohol
lactone
cyclic ester
preparation of esters
carboxylic acid + 1) SOCl2 / 2) R’OH… carboxylic acid + R’OH, HCl… carboxylic acid + 1) NaOH / 2) RX
conversion of an ester into an alcohol and carboxylic acid
hydrolysis… using H2O, NaOH, or H3O+
saponification
conversion of an ester into an alcohol and carboxylic acid in basic conditions… uses H2O, NaOH
conversion of an ester into an amide and an alcohol
aminolysis… using NH3
conversion of an ester into an aldehyde and an alcohol
reduction… using 1) DIBAH / 2) H3O+
conversion of an ester into primary alcohols
reduction… using 1) LiAlH4 / 2) H3O+
conversion of an ester into a tertiary alcohol
grignard reaction… using 1) 2 R’MgBr / 2) H3O+
preparation of amides
acid chloride + NH3… acid chloride + R’NH2… acid chloride + R’2NH
lactam
cyclic amide
conversion of an amide into a carboxylic acid + H3O+ + NH3
hydrolysis… using H3O+
conversion of an amide into an amine
reduction… using 1) LiAlH4 / 2) H2O
primary amine
R-NH2
secondary amine
R2 - NH
tertiary amine
R3 - N
quaternary ammonium salt
R4N+ X-
acid chloride + 1) 2 RMgX / 2) H3O+
yields a tertiary alcohol with two identical substituents
most reactive acid derivative
acid chloride
least reactive acid derivative
amides/nitriles
acid chloride + 1) R2CuLi / 2) H3O+
yields a ketone
least reactive carbon nucleophile
cuprates
most reactive carbon nucleophile
grignards
nitrile + 1) RMgX / 2) H3O+
yields a ketone
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
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
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)
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)
polyesters
step-growth polymer… diester and dialcohol
sutures and biodegradable polymers
common biodegradable polymers: poly(glycolic acid) [PGA], poly(lactic acid) [PLA], poly(hydroxybutyrate) [PHB]
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+
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
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
SOCl2
conversion of carboxylic acid into acid chloride
alkyl halide, Sn2 reaction
conversion of carboxylic acid into ester
R’OH, acid catalyst
conversion of carboxylic acid into ester + H2O
RNH2, DCC
conversion of carboxylic acid into an amide
carboxylic acid + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
acid chloride + H2O
hydrolysis to yield a carboxylic acid and HCl
acid chloride + carboxylate (RCO2-)
yields anhydride + Cl-
acid chloride + R’OH, pyridine
yields ester and HCl
acid chloride + 2 NH3
yields amine and NH4Cl
acid chloride + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
acid chloride + R2CuLi
yields a ketone
acid anhydride + H2O
yields 2 carboxylic acids
acid anhydride + ROH
yields ester and carboxylic acid
acid anhydride + 2 NH3
yields an amide and a quaternary ammonium salt
ester + H3O+ or NaOH or H2O
yields a carboxylic acid and an alcohol
ester + 1) LiAlH4 / 2) H3O+
yields two primary alcohols
ester + 1) DIBAH / 2) H3O+
yields an aldehyde and an alcohol
ester + 1) 2 RMgX / 2) H3O+
yields a tertiary alcohol (with two identical substituents) and an alcohol
amide + H3O+ or NaOH or H2O
yields a carboxylic acid + NH3
amide + 1) LiAlH4 / 2) H3O+
yields an amine
n*peptide
possibilities of peptides: n!
[ex: tetrapeptide = 4 x 3 x 2 x 1 = 24 possibilites]
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
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
tautomers
rapidly interconverting isomers differing in a H position or a pi bond position
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
enols
act as nucleophiles to react with electrophiles; reacts to yield α-substituted carbonyl compound
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
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
pyridine
pulls off the beta hydrogen to produce a α, β-unsaturated carbonyl compound
strong base is needed for enolate ion formation because
carbonyl compounds are weakly acidic
LDA
commonly used for making enolate ions from carbonyl compounds
when a hydrogen atom is between two carbonyl groups
its acidity increases
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)
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)
forming alkenes through Sn2 using primary alcohol
convert to a primary alkyl halide, then use a bulky base (NaOt-butyl)
forming alkenes through E1 using secondary or tertiary alcohol
use H2SO4, H2O
haloform
CHX3
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)
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
only substituted malonic acids and beta-keto acids
undergo loss of CO2 upon application of H3O+ and heat
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
direct alkylation of ketones, esters, and nitriles
alkylated using LDA, replacing the acidic H with an alkyl group… 1) LDA / 2) RX
aldehyde/ketone + X2/CH3CO2H
yields an alpha-halogen ketone/aldehyde + HX
carboxylic acid + 1) Br2, PBr3 / 2) H2O
yields an alpha-bromo ketone/aldehyde
alpha-bromo ketone + pyridine
yields an alpha, beta unsaturated ketone
ketone + X2, NaOH
yields an carboxylate ion and CHX3
malonic ester + 1) NaOEt / 2) RX / 3) H3O+, Δ
yields a carboxylic acid + CO2 + 2 EtOH
acetoacetic ester + 1) NaOEt / 2) RX / 3) H3O+, Δ
yields a methyl ketone + CO2 + EtOH
direct alkylation of ketones, esters, nitriles + 1) LDA / 2) RX
yields an alkyl alpha-substituted ketone, ester, or nitrile
acetoacetic ester synthesis makes
alpha-substituted methyl ketone
malonic ester synthesis
alpha-substituted carboxylic acid
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
aldol reaction
base-catalyzed carbonyl condensation reaction involving an aldehyde or ketone with an alpha hydrogen atom
aldol
a beta hydroxy carbonyl compound
dehydration of aldol products: synthesis of enones
beta-hydroxy aldehydes/ketones are dehydrated to yield an alpha, beta unsaturated products (conjugated enones)
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
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
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
claisen reaction makes
beta-ketoester
mixed claisen reaction
produce a mixture of products UNLESS only one reactant has alpha hydrogens and is converted to 100% enolate
intramolecular claisen reaction (dieckmann cyclization)
forms a beta-ketoester cyclic compound, but only if 5 or 6 membered ring will form
michael addition nucleophile
1,3-dicarbonyl compound (enolate)
michael addition yields
1,5 dicarbonyl compound
michael addition
1) NaOEt / 2) H3O+, Δ
stork enamine synthesis nucleophile
enamine
stork enamine synthesis
1) pyrrolidine / 2) H2O
no mixtures of products from mixed aldol reactions if
one reactant is much more acidic and one reactant has no acidic hydrogens
intramolecular aldol reaction
will occur if it will form a 5 or 6 membered ring… uses NaOH
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
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
michael acceptors
conjugated ketones, unsaturated aldehydes, esters, thioesters, nitriles, amides, and nitro compounds
michael donors
beta-diketones, beta-keto esters, malonic esters, beta-keto nitriles, and nitro compounds
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
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
2 aldehydes + NaOH
yields an aldol
diketone (1,7) + NaOH
yields a cyclic enone
beta-hydroxy ketone + NaOH or H3O+
yields an enone
2 esters + NaOEt
yields a beta-ketoester + HOR
diester + NaOEt
yields a cyclic beta-ketoester + HOEt
diketone + enone + NaOEt
yields 1,5 dicarbonyl compound
enamine + enone + H3O+
yields a 1,5 dicarbonyl compound
amine
nitrogen with three bonds and a lone pair
alkylamine
amines that are alkyl substituted
arylamine
amines that are aryl-substituted
heterocyclic amine
compounds in which the nitrogen atom occurs as part of a ring
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
pyridine
C5H5N
pyridine
C4H5N
quindine
C9H7N
imidazole
C3H4N2
indole
C8H7N
pyrimidine
C4H4N2
pyrrolidine
C4H8NH
piperidine
C5H10NH
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
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
aniline
benzene with NH2
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)
biological amine form
positively charged amine site (NH3+) and negatively charged carboxyl site (CO2-)
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
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
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
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
RX + 1) Mg / 2) CO2 / 3) H3O+
yields a carboxylic acid
RX + 1) NaCN / 2) H3O+
yields a carboxylic acid
RCOOH + SOCl2
yields an acid chloride
RCOOH + R’COOH, Δ
yields an acid anhydride
RCOOH + HOR’, H+
yields an ester
RCOOH + HNR2
yields an amide
RCOCl + R’COOH
yields an acid anhydride
RCOCl + H2O
yields a carboxylic acid + HCl
RCOOCOR + R’OH
yields an ester
RCOOCOR + H2O
yields a carboxylic acid
RCOOR + HNR2
yields an amide
RCOOR + H+, H2O
yields a carboxylic acid
RCONR2 + H+, H2O
yields a carboxylic acid
acyl group
RC=O
acyl substitution steps with negative nucleophile
1) addition –> 2) elimination
acyl substitution steps with positive/neutral nucleophile (in acidic solution)
1) protonation –> 2) addition –> 3) deprotonation –> 4) protonation –> 5) elimination –> 6) deprotonation
RCOCl + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
RCOCl + 1) LiAlH(O-t-butoxy)3 / 2) H3O+
yields an aldehyde
RCOOCOR + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
RCOOR + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
RCOOR + 1) DIBAH / 2) H3O+
yields an aldehyde
RCOOH + 1) LiAlH4 / 2) H3O+
yields a primary alcohol
RCONH2 + 1) LiAlH4 / 2) H3O+
yields an imine
RCONH2 + 1) DIBAH / 2) H3O+
yields an imine
RCN + 1) LiAlH4 / 2) H3O+
yields an amine
RCN + 1) DIBAH / 2) H3O+
yields an imine
RCHN (imine) + H3O+
yields an aldehyde
RCOCl + 1) 2 RMgX / 2) H3O+
yields a tertiary alcohol with two identical substituents
RCOCl + 1) (R)2CuLi / 2) H3O+
yields a ketone
RCOOR + 1) 2 RMgX / 2) H3O+
yields a tertiary alcohol with two identical substituents
RCN + RMgX
yields an imine
R2CN (imine) + H3O+
yields a ketone
three kinds of esters
carboxylate ester (from carboxylic acid + alcohol)… sulfate ester (from sulfuric acid + alcohol)… phosphate ester (from phosphoric acid + alcohol
phosphate anhydride
contain two phosphoryl groups bonded to an oxygen
carboxylate ester
Contains a carbonyl group bonded to an alkoxy group (-O-C)
sulfate ester
An alcohol derivative with the formula ROSO2OR’ , in which alkyl groups replace both of the hydrogen atoms in sulfuric acid, HOSO2OH.
phosphate ester
contain a phosphoryl group bonded to a carbon
carboxylate thioester
contains a thiol (SH) group bonded to a acyl group (RC=O)
carboxylic acid anhydride
contains two carbonyls linked through an oxygen
acyl phosphate
a carboxylic acid derivative with a phosphate leaving group
retrosynthetic analysis
- 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
do the 1,5 separation
BEFORE the 1,3 separation unless in a ring, then do the opposite
quaternary ammonium salt nomenclature
alkylalkyl ammonium halide
electron withdrawing groups
decrease basicity and increase acidity
electron donating groups
increase basicity and decrease acidity
tautomerization
proton transfer between a compound allowing it to interconvert between an enol to a ketone
beta branching
indicates prior double bond on initial reactant
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)
amine acid/base reaction
RNH2 + RCOOH –> RNH3+ + RCOO-
amine substitution reaction
RNH2 + R’X –> +NRH2R’ + Br-
amine reaction with carbonyl (addition -> elimination)
RNH2 + RCOH –> RCHNR …. R2NH + RCOCH3 –> RCNR2CH2
amine reaction with acid derivative (addition -> elimination)
RNH2 + RCOCl –> RCONHR … R2NH + ROCl –> RCONR2
aniline protection/deprotection
Protection: aniline + acid anhydride –> amide // Deprotection: amide + H2O, NaOH –> aniline
fischer projections
vertical lines go into the page and horizontal lines are coming out of the page, with the “spine” resembling the main chain
fischer projection enantiomers
all horizontal lines switch
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
RCH2X + 1) NaCN / 2) LiAlH4 / 3) H3O+
yields an amine (RCH2CH2NH2)
RCONH2 + 1)LiAlH4 / 2) H3O+
yields an amine (RCH2NH2)
nitrobenzene + H2/Pt or SnCl2/H3O+
yields an aniline
ammonia (NH3) + 1) RX / 2)NaOH
yields a primary amine
primary amine + 1) RX / 2) NaOH
yields a secondary amine
secondary amine + 1) RX / 2) NaOH
yields a tertiary amine
tertiary amine + RX
yields a quaternary ammonium salt
gabriel amine synthesis: phthalimide + 1) KOH / 2) RX / 3) NaOH, H2O
yields a primary amine
RCH2X + 1) NaN3 / 2) LiAlH4 / 2) H3O+
yields a primary amine (RCH2NH2)
R2CO + NH3, NaBH4
yields an amine
RCONH2 + NaOH, Br2, H2O
yields a primary amine and CO2
RCOCl + 1) NaN3 / 2) H2O, heat
yields a primary amine, CO2, and N2
hofmann elimination: amine + 1) CH3I / 2) Ag2O, heat
yields least substituted alkene E2 product
aniline + HNO2, H2SO4
yields arenediazonium salt
arenediazonium salt + HCl, CuCl
yields chlorobenzene
arenediazonium salt + HBr, CuBr
yields bromobenzene
arenediazonium salt + NaI
yields iodobenzene
arenediazonium salt + KCN, CuCN
yields cyanobenzene
arenediazonium salt + Cu2O, H2O, Cu(NO3)2
yields phenol
arenediazonium salt + H3PO2
yields benzene
arenediazonium salt + phenol or aniline
yields diazonium coupling product
solvolysis
a nucleophilic substitution or elimination where the solvent serves as the attacking reagent
