14d final

watch me come out of this final crying :(

Hydrohalogenation, Adding Br, I, or Cl to an alkene

H-X, Markovnikov addition (more substituted side of alkene)

Adding HBr Anti-Markovnikov (less substituted side of alkene)

HBr, ROOR

Acid Catalyzed Hydration (adds H and OH to sides of alkene)

H3O+

• acid must be dilute to favor addition reactions. Concentrated acid favors elimination of H2O

Oximercuration Demercuration (adding OH to an alkene with no rearrangements)

1. Hg(AcO)2, H2O

2. NaBH4

Hydroboration-oxidation (adding OH to an alkene anti-markovnikov)

1. BH3, THF

2. H2O2, NaOH

Syn Addition

catalytic hydrogenation (add 2 H to an alkene)

H2, metal

• examples of metals: Pd/C, Ni, Pt

Halogenation (add 2 Br anti to an alkene)

Br2

• adds a Br to each side of an alkene

halohydrin formation (adds Br and OH anti to an alkene)

Br2, H2O

• OH adds to more substituted side of alkene

form an epoxide from an alkene

MCPBA

anti-dihydroxylation (adds 2 OH to an alkene anti)

MCPBA, H3O+

syn-dihydroxylation (adds 2 OH to an alkene syn)

1. OsO4

2. KHSO3

ozonolysis (oxidative cleavage, splitting an alkene into two sides with a double bonded oxygen)

O3, DMS

formation of an alkyne from an alkyl dihalide (alkane with a halogen on each side)

1. excess NaNH2

2. H2O

two successive E2 reactions with 2 equiv of a strong base

adding an alkyl group to a terminal alkyne

1. NaNH2

2. alkyl group with an I (ex: CH3CH2I

formation of an alkane from an alkyne

H2, Pt

formation of cis alkene from an alkyne

H2, Lindlar’s catalyst

• lindlar’s catalyst is a “poisoned” catalyst

formation of trans alkene from an alkyne

Na, NH3 (l)

hydrohalogenation of alkyne (adding a halogen and H to an alkyne)

H-X (ex: H-Br)

• halogen adds to more substituted side

• adding 2 equiv. gives 2 halogens to more substituted side

acid-catalyzed hydration of alkyne (add OH to most substituted side of alkyne)

HgSO4, H2SO4, H2O

• OH becomes a ketone through tautomerization

acid-catalyzed tautomerization

double bond on C-C acts as nucleophile, (+) charge goes to OH, H2O grabs proton from OH

base-catalyzed tautomerization

OH (base) grabs proton from OH group on molecule, (-) charge goes to carbon, grabs proton from H2O

hydroboration-oxidation of alkyne (add OH to alkyne, makes aldehyde)

1. 9-BBN

2. NaOH, H2O2

(tautomerization makes OH group into aldehyde)

• OH goes on less substituted side

halogenation of alkyne (adds Halogen to both sides of alkyne)

excess X2, CCl4 —> 4 halogens added to alkyne, makes single bond with 4 halogens

1 eq. X2, CCl4 —> 2 halogens added to allkyne, makes double bond with 2 halogens

ozonolysis of alkyne

splits molecule across alkyne and makes 2 carboxylic acids

1. O3

2. H2O

• terminal alkyne becomes CO2

reducing an aldehyde or ketone to an alcohol

NaBH4, EtOH (or another proton source)

OR

1. LiAlH4

2. H3O+ or H2O

LiAlH4 is stronger and can reduce an ester/carboxylic acid. NaBH4 cannot

making a grignard reagent from an alkyl halide

Mg, Et2O

• adds Mg to something with a Br already on it, making MgBr (aka a grignard reagent)

• MgBr (+) detaches, leaving a C with a (-) charge

radical bromination (adding a Br to an alkane with no functional groups)

hv, Br2 (or NBS)

• adds to more substituted carbon

“protecting” an alcohol from deprotonation

TMSCl, ET3N

• Use TBAF to reverse protection and make it an OH again

replace an OH with a Cl

SOCl2, Pyr

replace an OH with a Br

PBr3

oxidation of OH to carboxylic acid

Na2Cr2O7, H2SO4, H2O

oxidation of OH to aldehyde

PCC, CH2Cl2

williamson ether synthesis (ether from an OH)

1. NaH (strong base to deprotonate OH)

2. alkyl halide (any carbon chain with I at the end)

acidic cleavage of an ether

xs HX, heat

epoxide opening with a strong nucleophile

1. strong nuc (ex: LiAlH4)

2. H3O+

• strong nucleophile attacks less substituted side of epoxide

• H3O+ protonates the O

acid catalyzed epoxide ring opening

H2SO4, EtOH (or other nuc)

• H3O+ from H2SO4 protonates oxygen (gives + charge)

• weaker nucleophile attacks more substituted side of epoxide

oxidizing a thiol (SH) to form a disulfide (S-S)

NaOH, H2O, Br2

• NaIO4 (adds O double bonded to an S)

• 2 eq H2O2 adds 2 O double bonded to an S)

adding Br to a conjugated diene (using HBr)

• low temp: Br will attach at less stable position (double bond less substituted) —> kinetic control

• high temp: Br will attach at more stable position (double bond more substituted) —> thermodynamic control

add bromine to a benzene

FeBr3, Br2

add chlorine to benzene

AlCl3, Cl2

add SO3H to benzene (sulfonation)

fuming H2SO4

• concentrated H2SO4 has SO3 in it (S has partial + charge, acts as electrophile)

• reversed using dilute H2SO4

add NO2 to benzene (nitration)

H2SO4, HNO3

convert NO2 to amine (NH2)

Fe or Zn, HCl

OR Pd/c +H2

convert NH2 to nitro group (N triple bond N with + charge)

NaNO2, HCl (0ºC)

Sandmeyer reactions

convert nitro group (N triple bond N with + charge) to another group using a copper salt

• CuBr: Br

• CuCl: Cl

• CuCN: CN —> LiAlH4, H2O: NH2

• H3O+: OH

• H3PO2: removes nitro group, leaves plain benzene

friedel-crafts alkylation

alkyl chloride, AlCl3

• becomes AlCl4(-) and an alkane with a (+) charge

friedel-crafts acylation

acid chloride, AlCl3

• becomes AlCl4(-) and an aldehyde with a (+) charge (basically an aldehyde without the H)

remove ketone from carbon chain on benzene (clemmensen reduction)

Zn(Hg), HCl

nucleophilic aromatic substitution

ring needs EWG (NO2) and a leaving group ortho/para to the EWG (ex: Br)

elimination addition

Replaces a leaving group on a benzene (ex: Cl) with something else (ex: OH)

1. base at high temp (ex: NaOH or NaNH2)

2. H3O+ (acid workup)

oxidation at benzylic position (turning an alkane into a carboxylic acid)

Na2Cr2O7, H2SO4, H2O

acetal formation (turning a ketone into two groups)

[H+], 2 ROH, -H2O

acetal protecting group

base tolerant, can protect part of a molecule (ex: ketone) from being attacked by grignard

• HO——OH, [H+], -H2O

imine formation (replacing ketone with primary amine)

[H+], RNH2, -H2O

enamine formation (replacing ketone with secondary amine)

[H+], R2NH, -H2O

wolf-kishner reduction (ketone to imine to alkane)

turn ketone into hydrazone (N-NH2)

• [H+], H2N-NH2, -H2O

turn hydrazone into alkane (N2 as byproduct)

• KOH/H2O, heat

hydrolysis of acetal (turning acetal back into ketone)

acetal, H2O, [H+]

cyanohydrin formation (ketone to acetal with OH and CN groups)

HCN

• in real life you would use KCN, HCl

reducing a cyano group (CN)

replace with NH2

1. LiAlH4

2. H2O

replace with carboxylic acid

• H3O+

witting reaction (replacing a ketone with an an alkene)

Ph3PCH3 (or some other carbon chain attached to P)

raney nickel (removes ketone)

1. HS——SH, [H+], -H2O

2. Raney Ni

turn carboxylic acid into acid chloride

SOCl2

hydrolysis of acid chloride (turn back into carboxylic acid)

H2O, Pyr

• can also turn into ester using ROH, pyr

replace Cl in acid chloride with NH2

2 eq. NH3

• can replace Cl with secondary amide (R2-NH) using 2 eq. R-NH2

• can replace Cl with tertiary amide (R3-N) using 2 eq. R2-NH

acid chloride to aldehyde

1. DIBAH

2. H3O+

gilman reagent (adding a nucleophile once, acid chloride to ketone)

R2CuLi (Ex: Et2CuLi)

making an acid anhydride from an acid chloride

add ester with positive charge on the O to an acid chloride, Cl leaves

fischer esterification (create and ester from a carboxylic acid)

ROH, [H+]

• add to carboxylic acid, creates ester and H2O

saponification (ester into carboxylic acid in basic conditions)

OH (-)

• creates the enolate (negative charge on o) and ROH

reduction of ester to alcohol

1. LiAlH4

2. H2O

produces alcohol and ROH

reduction of ester to aldehyde

1. DIBAH

2. H2O

produces aldehyde and ROH

hydrolysis of amide in acidic conditions (NH2 to OH)

H3O+

NH2 gets protonated and leaves as NH3+

hydrolysis of amide in basic conditions (NH2 to OH)

OH (-)

NH2 can act as a leaving group, then takes proton from OH to create enolate

dehydration of amide to nitrile (NH2 to CN, gets rid of ketone)

SOCl2

• products are R-CN, SO2, and HCl

acid-catalyzed hydrolysis of nitriles (CN to amide)

N gets protonated, H2O attacks C and N becomes an imine. Proton transfers create the ketone/amide

base-catalyzed hydrolysis of nitriles (CN to amide)

OH attacks C and N becomes negatively charged. proton transfers create the ketone/amide

ketone to enolate

LDA (makes enolate irreversible)

• double bond on enolates attack electrophiles

add halogen at more substituted position of ketone

[H3O+], Br2

• ketone gets protonated, and alpha proton removed to form enol. Then double bond attacks halogen

alpha-bromination of carboxylic acid (hell-volhard-zelinsky)

PBr3, Br2, H2O

• adds bromine to alpha position next to ketone

alpha halogenation in basic conditions

• NaOH, Br2

if 3 alpha protons available, add 3 Br to create CBr3 leaving group and replace it with OH

1. NaOH, Br

2. H3O+

adding a carboxylic acid using a grignard

attack CO2 with a grignard

aldol addition (reaction between aldehyde and enolate)

NaOH deprotonates alpha position of aldehyde, then double bond attacks keton. H2O protonates O

• aldol is a ketone and an alcohol

retro-aldol reaction (creates ketones from aldol)

NaOH, H2O

• OH (-) deprotonates OH on aldol. (-) charge on O moves down and breaks bond, forming enolate and ketone. Enolate gets protonated by H2O

aldol condensation (H2O gets removed from aldol and creates double bond)

[H+] or [OH-], H2O, heat

Alpha proton gets removed, then (-) charge from O kicks OH out (in basic conditions). Creates ketone with conjugated system (driving force)

• tip: draw double bond between alpha hydrogen and ketone

claisen condensation

add two esters together (makes molecule with two ketones and an ester)

1. LDA

2. ketone with OR group (same OR group as ester)

3. H3O+

alkylation of alpha position of ketone

less substituted (kinetic enolate)

1. LDA, cold temp.

2. R-X

more substituted (thermodynamic enolate)

1. NaH

2. R-X