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Reagent Function Notes: Any/all 2° R-L
Reagent Function Notes: Any/all 2° R-L
Reagent Function Notes: Any/all 2° R-L
-OH Good Nuc, Strong Base SN2 conditions, normal 2 R-L leads to E2
(use synth. eq. acetate)
Converts R-L to R-OH for 1
and activated 2 R-L
-OR Good Nuc, Strong Base SN2 conditions, normal 2 R-L leads to
Converts R-L to R-OR for 1 E2. Known as Williamson Ether
and activated 2 R-L Synthesis
CH3CO2 Fair Nuc, Weak Base SN2 conditions, will work fine for any 1
Is a synth. eq. for OH or 2 R-L
(unmasked with KOH/H2O)
Na (also Na) Sodium metal acts as a base, Harsh conditions that require p/p alcohol
removing H+ from ROH to as the solvent (the CA of RO)
create RO (alkoxide)
K2CO3 Weak base used to Will not work for normal alcohols, only
deprotonate (remove H+) from phenols
phenols
RCO2- Fair Nuc, Weak Base (E2 SN2 conditions, will work well for 1 and
competition minimized) any/all 2 R-L
HCl Strong acid which converts OH Can be used only on 3 alcohols. Must
into Cl add ZnCl2 for 1 or 2 ROH
SOCl2 Converts OH into Cl All three work well for 1 and 2 alcohol
conversion. If 3 ROH, H-X is the best
PBr3 Converts OH into Br reagent.
-CN Fair nucleophile, weak base SN2 reagent, works well with both 1 and
2 R-L
-C=CH Good nucleophile, strong base SN2 reagent, works with 1 only, if 2, E2
Acetylide is the major product
SR or Ph3P Fair nucleophiles, weak bases SN2 reagents, works well with both 1
and 2 R-L
HBr or HI Strong acids that cleave ethers 1 (SN2) and 2 & 3 (SN1)
-OH or -OR Strong bases, Good Nuc Lead to SN2 when 1 or 2 (aprotic); but
E2 when 2 (p/p solvent) or 3
(regardless of solvent)
-OH, or NaNH2 Very strong basic conditions Used to prepare alkynes (E2 twice)
NaOCl Only does 2 ROH --> ketone Environmentally friendly Oxidizing Agent
HF, HCl, HBr, or HI Acids that add H-X to alkenes Markovnikov addition via carbocation, so
(or alkynes) watch out for rearrangements!
H2O with H2SO4 Adds H2O to alkenes to yield Markovnikov addition via carbocation, so
alcohols (hydration) watch out for rearrangements!
Cl2 or Br2 Halogens that add X2 to Use inert solvents; Follows the
alkenes (or alkynes) borderline SN2 mechanism, results in
anti addition
Br2/H2O or Cl2/H2O Adds 1 X and 1 OH to a C=C Anti addition (inversion) occurs through
(produces a product called a the bromonium (or chloronium) ion, the
halohydrin) water attacks 3>2>1 (borderline SN2)
H2O, H2SO4, Hg2+(often Adds H and OH to an alkyne-- Markovnikov addition, an enol initially is
HgSO4 or HgO) > results in the formation of a formed, but spontaneously tautomerizes
ketone to the keto form as the product
Ch2I2 with Zn(Cu) alloy Adds a CH2 (carbene) to a Simmons-Smith reaction; adds with syn
C=C --> forms a cyclopropane addition
CHX3 with strong bases Adds a CX2 (carbene) to a Adds with syn addition; make sure to
C=C --> forms a cyclopropane add CX2, NOT CH2
Reagent Function Notes
RCO3H or MCPBA Adds the 3rd (extra) oxygen to Adds with syn addition, which is
a C=C --> forms an epoxide important when product is chiral
1) OsO4 Adds 1 OH group to each Addition occurs with syn (same side)
KMnO4 carbon of a C=C --> forms diol addition
----------> or --------->
2)Na2SO3 H2O
NaOH
HNO3 + H2SO4 Substitutes -NO2 on aromatic No limitations; heat reaction or use more
(Nitration) rings vigorous conditions to get disubstituted
product
Br2 or Cl2 + Lewis Acid Substitutes -Br or -Cl on Requires Lewis acid unless ring is
(AlX3, FeX3) aromatic rings strongly activated (e.g. phenol and
(Halogenation) aniline, in which case, beware of
disubstitution)
Friedel-Crafts Alkylation
Friedel-Crafts Acylation
NaNO2/H+ Converts NH2 to N2, which can N2 is a good leaving group and can be
be replaced by nucleophile replaced with a variety of reagents
Reagent Function Notes
Nucleophile + aromatic Nucleophile replaces halide in The ring must have an electron
halide (Nucleophilic a 2-step process; Nuc attacks, withdrawing group o- or p- to the halide.
Aromatic Substitution: and then halide leaves Leaving group ability:
Addition-Elimination) F > Cl > Br > I
Very strong base (e.g. Eliminates H-X on an aromatic Results in 2 different products if the ring
NaNH2) or base and high ring, creating a reactive is asymmetric because both carbons of
heat (NaOH, ) benzyne intermediate which the intermediate alkyne will be attacked.
(Nucleophilic Aromatic then is attacked by anion
Substitution: Elimination-
Addition)
H2/metal catalyst or Metal Converts NO2 --> NH2 Important synthetic step as a diazonium
(Fe, Sn, SnCl2) + HCl ion precursor
Reagent Function Notes
Clemmensen: Zn(Hg) + Converts C=O --> CH2 H2/metal catalyst will work only if the
HCl or C=O is attached directly to the aromatic
Wolf-Kishner: NH2NH2 + ring
KOH, or H2/metal
catalyst
1)KMnO4, NaOH, Converts an R on an aromatic Reaction will not work if the substituent
2) H3O+ ring --> CO2H C is quaternary (4)
[CN]
-
Adds a CN to the C and an H Only catalytic amounts of -CN are
HCN -------------> to the O of a C=O, forming a needed; follows the basic mechanism
H2O cyanohydrin
NH4Cl A weak acid (H+ donor) used to Avoids the E1 result for 3 alcohols
protonate the Td of carbonyl
addition reactions
+ - Ylide attacks C=O, resulting in Witting reaction; BuLi is usually the base
Ph3P--CR2 its eventual conversion to C=C used to make the ylide from its
(P loves O!) phosphonium salt precursor
H2/metal or NaBH3CN C=N reacts more easily than Either reagent can be used in the initial
C=O, allowing conversion of reaction mixture, so the imine is never
imines to amines isolated
LiAlH4 Reacts with all C=O Has 4 H- available, converts C=O to CH2-
compounds from table 19.1 OH (except for ketones)
NaBH4 Reacts only with ketones and Has 4 H- available, can use in presence
higher on table 19.1 of H2O, ROH, etc.
2 mol Grignard + acyl Reacts twice (cannot stop at Use NH4Cl as workup acid to avoid E1
chloride, anhydride, or ketone) to yield alcohol. elimination if 3 ROH
ester
(R)2CuLi Adds only 1 R group to an acyl Same reagent that gave conjugate
chloride, yielding a ketone. addition (Sec. 18.10)
Grignard + nitrile Grignard adds to the nitrile Hydrolysis is exact reverse of imine
once, and the resulting imine is formation (Fig. 18.3)
hydrolyzed back to a ketone by
H3O+.
TsCl or MsCl Converts -OH into -OTs or Reaction proceeds just like acyl
-OMs, which are much better chlorides, but attack is at S
leaving groups.
LDA, NaNH2, NaH Very strong bases Used to deprotonate Hs a to the C=O.
pKa=35-38 LDA is used most often because it is
totally non-nucleophilic (steric hindrance)
Replaces X with H