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friedel-craffs alkylation
limitations
any alkyl halide can be used (single bonds only)
impossible to stop at mono-alkylation (multiple substitutions)
wont react if theres a strong deactivator
friedel-acylation
reduction
diazonium
aromatic rxns
activating groups
faster rxn, lone pair e- directly connected to benzene, neg or partial neg charge
ortho/para director
deactivating groups
slower rxn, pos or partiall pos charge
meta director
exception: halogens ortho/para deactivators
NAS
3-chloro-4-cyclohexylbutanone
IUPAC
2-ethyl-6-isopropoxy-5-oxocental
IUPAC
nona-4,8-diene-2,7-dione
IUPAC
5-oxohexanedial
IUPAC
aldehydes
when naming these,
-al on end
highest priority in naming
ketones
when naming these,
-one on end
-oxo internal
cyclopentanecarbaldehyde
formaldehyde
acetaldehyde
acrolein
crotonaldehyde
acetone
reduction
reduction
poisoned pd
gutterman ruch
ozone cleavage
silver mirror test
nucleophilic addition rxn
aldehydes
more reactive than ketones for two reasons:
sterics: h smaller group, more room for nucleophile to attack
electronics: alkyl gets past e- density easier, less electrophilic, attracts nucleophile more readily
acids
when naming these,
methane → methanoic acid
on chain names, drop the ending e and replace with -oic acid
heptanedioic acid
IUPAC
7-chlorooctanoic acid
IUPAC
nitrile
when naming these,
add nitrile at the end of the chain name
ethane → ethanenitrile
properties of carboxylic acids
dimerize, high boiling point
acidic
pka usuallly from 4-5 when in the body
right
more acidic?
right
more acidic?
right
more acidic?
right
more acidic?
right
more acidic?
CN, hydrolysis
prep of carb acids
Na2CrO7, LAH
prep of carb acids
cleavage (KMnO4, acid/neutral)
prep of carb acids
cleavage (KMnO4 or O3)
prep of carb acids
KMnO4
prep of carb acids
CO2, H3O
prep of carb acids, grignard
KCN
prep of nitrilles
SOCl2
prep of nitriles
degradation of a primary amide
LAH, H2O
carb acid rxn
BH3, THF
carb acid rxn
BH3, THF
carb acid rxn
NAH, iodopropyl OR propanol, H3O
carb acid rxn
fischer tropsch esterification
acid/base with heat
nitrile rxn
LAH, H3O
nitrile rxn
nitrile to primary amine
RMgX, H3O
nitrile rxn
grignard
acid halides
when naming these:
formic acid → formyl chloride
propionic acid → propionyl acid
ending ic swap to yl
benzoyl bromide
IUPAC
esters
when naming these:
name the substituent not attached to the carbonyl first, then the parent chain
ethane → ethanoate
replace e with -oate
isopropylpentanoate
IUPAC
ethylethanoate (ethylacetate)
IUPAC
t-butylcyclohexane carboxylate
IUPAC
amides
when naming these:
ethane → ethanamide
replace e with -amide
use N- to indicate groups attached
ethanamide (acetamide)
IUPAC
N-methylacetamide
IUPAC
N,N-dimethylacetamide
IUPAC
N-isopropylbutanamide
IUPAC
N-ethyl-N-methylacetamide
IUPAC
thioesters
when naming these:
name the substituent not attached to the carbonyl first, then the parent chain
ethane → ethanoate
replace e with -oate
then, add thio- in front of the parent chain
ethylthiobutanoate (ethylbutanethioate)
IUPAC
methylcyclopentanecarbothioate
IUPAC
acid anhydride
when naming these;
name the substituents same as an acid then add anhydride at the end
benzoic acid → benzoic anhydride
benzoic anhydride
IUPAC
acetic benzoic anhydride
IUPAC
nucleophilic aryl substitution
SOCl2/CHCl3 or PBr3
carb acid → acid halide
heat
carb acid → acid anhydride
NaH/iodopropane
carb acid → ester
H3O
carb acid → ester
fischer tropsch esterification
R2NH
carb acid → amide
DCCI/propylamine
carb acid → amide
LAH/H2O
carb acid → alcohol
BH3, THF/H3O
carb acid → alcohol
NaOH/H2O pyr
acid halide → acid
ethanol/pyr
acid halide → ester
sterics are critical here, 1 > 2 > 3
2 NH3
acid halide → amide
2 eq. dimethylamine
acid halide → amide
LAH/H3O
acid halide → alcohol
CH3MgCl/H3O
acid halide → alcohol
grignard
(CH3)2CuLi OR Li(O-tBu)3AlH
acid halide → ketone
ethanol/NaOH
acid anhydride → ester
ethylamine/NaOH
acid anhydride → amide
H3O
acid anhydride → carb acid
H3O
ester → carb acid
NH3/ether
ester → amide
ester to alcohol
ways for _______________
LAH
DIBAH → aldehyde
RMgX
H3O
amide → carb acid
LAH/H3O
amide → amine
SOCl2/pyr OR P2O5/pyr OR POCl3/pyr
amide → nitrile
2-methylpropylbutanoate
IUPAC
alpha carbon
bulky base vs regular base
alpha carbon