OAT Organic Chem: Reactions

HBr (or HCl, HI)

to alkyne, alkene

add Br and H

Markovnikov, rearrangements possible

Alkyne + 1 eq HBr = Alkene with Br at most substituted

+ 2nd eq HBr = Alkane with 2 Br at most substituted

hydrohalogenation

H3O+

to alkene

add -OH and H

markovnikov, rearrangements possible

hydration

H+, ROH

to epoxide

add -OR and H

markovnikov, rearrangements possible

addition of alcohol

Br2 or Cl2/

CCl4

to alkyne, alkene

anti-addition of 2 Br

Alkyne + 1 eq Br2 = Alkene with Br at each side,

+ 2nd eq Br2 = Alkane with 2 Br at each side

bromination

Br2 or Cl2/

H2O

to alkene

add Br and OH- (Halogen on least substituted)

markovnikov, anti-addition

bromination in H2O

Br2 or Cl2/

ROH

to alkene

add Br and -OR (Halogen on least substituted)

markovnikov, anti addition

bromination in alcohol

1) Hg(OAc)2, H2O

2) NaBH4

to alkene

Add H and -OH

markov, anti-addition

Oxymercuration/demurcuration

1) Hg(OAc)2, ROH

2) NaBH4

to alkene

add H and -OR

markov, anti-addition

alkoxymercuration-demurcuration

1) BH3 • THF

2) H2O2, -OH, H2O

to alkene

add H and -OH

anti-markov, syn-addition

hydroboration-oxidation

H2,

Pd/C or Pt/C or Ni

to alkyne, alkene

adds 2 H, syn addition

Alkene → Alkane

Alkyne → Alkane

Catalytic Hydrogenation/reduction

HBr/

ROOR (peroxide)

to alkene

adds H• and Br•

anti-markov

hydrobromination with peroxide

MCPBA or RCO3H

to alkene

adds epoxide ring between double bond

epoxidation

1. RCO3H (MCPBA)

2. H3O+

to alkene

adds 2 -OH

anti-addition

anti-hydroxylation

1) OsO4

2) H2O2

to alkene

alkane to double alcohol

syn-addition

syn-hydroxylation

KMnO4 (cold, dilute)/

-OH

to alkyne, alkene

alkene -> double alcohol

(syn-addition)

alkyne -> double ketone

syn-hydroxylation

1. O3

2. (CH3)2S

or

2. Zn/H2O

to alkene

cleaves alkene =

1º -> aldehyde

2º -> ketone

ozonolysis under reducing conditions

1) O3

2) H2O2, NaOH, H2O

to alkyne, alkene

cleaves double bond into ketone (2º substituted) and carboxylic acid (1º)

alkyne -> 2 carboxylic acids

terminal alkyne -> 1 carboxylic acid and 1 CO2

ozonolysis under oxidizing conditions

KMnO4 (hot, concentrated)/

H3O+

to alkyne, alkene

cleaves alkene into ketone (2º substituted) and carboxylic acid (1º substituted)

cleaves alkyne into 2 carboxylic acids

(ozonolysis under oxidizing conditions)

Br2, light or heat

to alkene

adds Br anywhere there's an available H

favors 3º cation, high selectivity

free radical bromination

Cl2, light or heat

to alkene

adds Cl where there's an available H

selective for what is most available

free radical chlorination

NBS

light or heat or ROOR (peroxide)

to alkene

adds Br to allylic/benzylic carbon, keeps alkene

allylic/benzylic bromination

1) Mg/ether

2) ethyl methyl ketone

3) H3O+

to phenyl bromine

Br replaced with ketone at most substituted (ketone is reduced to alcohol)

nucleophilic addition of a grignard reagent to a ketone

1) Mg/ether

2) epoxide

3) H3O+

to phenyl bromide

Br replaced with epoxide at least substituted (epoxide ring opens to most substituted and alcohol forms)

nucleophilic addition of a grignard reagent to an epoxide

1) Mg/ether

2) CO2

3) H3O+

to phenyl bromide

Br replaced with carboxylic acid

nucleophilic addition of a grignard reagent to CO2

1) Mg/ether

2) H2O

grignards are protonated in protic solutions

protonation of a grignard reagent

H2,

Lindlar's catalyst

to alkyne

alkyne --> cis (Z) alkene

reduction to cis-alkene

Na or Li,

NH3 (l)

to alkyne

alkyne --> trans (E) alkene

reduction to trans-alkene

H2SO4

or

1) Sia2BH THF

2) H2O2, OH-, H2O

to alkyne

reduces internal alkyne to ketone

ketone forms on either side of the bond

enol intermediate tautomerizes to ketone

HgSO4/

H2SO4

to alkyne

reduces terminal alkyne to ketone

markov

enol intermediate tautomerizes to ketone

hydration

1) Sia2BH THF

2) H2O2, OH-, H2O

to alkyne

reduces terminal alkyne to aldehyde

anti-markov

enol intermediate tautomerizes to ketone

hydration

1. NaNH2,

2. R-X

to alkyne

deprotonates terminal alkynes, -R attaches where halide was

keeps alkene structure

(addition of an acetylide ion)

1. NaNH2,

2. ketone, H2O

to alkyne

deprotonates terminal alkynes,

ketone attached at most substituted and reduced to alcohol

keeps alkene structure

1. NaNH2,

2. epoxide, H2O

to alkyne

deprotonates terminal alkynes,

epoxide attaches at least substituted side and ring opens to most substituted side, epoxide reduces to alcohol

keeps alkene structure

HNO3/

H2SO4

to benzene ring

attaches -NO2 to benzene ring

nitration (EAS)

SO3/

H2SO4

to benzene ring

adds -SO3H to benzene

sulfonation (EAS)

Cl2

AlCl3

to benzene ring

add Cl to aromatic ring

chlorination (EAS)

Br2/

FeBr3

to benzene ring

adds Br to aromatic ring

bromination (EAS)

X-R

AlCl3

to benzene ring

adds -R to aromatic ring

*can rearrange

Friedel-Crafts Alkylation

X-ketone

AlCl3

to benzene ring

adds -ketone to aromatic ring where X was

Friedel-Crafts Acylation

ortho/para directors

activating, electron donators

-NH2, -OH, -OR, NHCOCH3, -R, -aryl

meta directors

deactivating, electron pulling

carbonyls, -NO2, -SO3H, -CF3, -CN, -+NR3 (*halogens are ortho/para)

ortho/meta/para reagents

Br2/Cl2

AlCl3/FeBr3

Zn(Hg)/

HCl

to ketone

reduces carbonyl to an alkane using acid

Clemmenson Reduction

H2NNH2,

KOH, heat

to ketone

reduces carbonyl to alkane using acid

Wolff-Kishner Reduction

1) KMnO4, OH-, boil

2) H3O+

to phenylpropene

adds carboxylic acid at benzylic position, cuts off the rest

side-chain oxidation, benzylic oxidation

H-X or

HCl/ZnCl2

to alcohol

alcohol to alkyl chloride

SN1 for 2º and 3º alcohols,

SN2 for methanol 1º alcohols

SOCl2

to alcohol, carboxylic acid

replaces -OH with -Cl

only for 1º and 2º

works for alcohols and carboxylic acids

(conversion to an alkyl chloride with thionyl chloride)

PBr3

to alcohol, carboxylic acid

replaces -OH with -Br

only for 1º and 2º, via SN2 (inversion of stereochemistry)

works for alcohols and carboxylic acids

(conversion to an alkyl bromide)

TsCl

to alcohol

Replaces -OH with -OTs

Retain stereochemistry

Conversion to a tosylate ester

H2SO4 or H3PO4

to alcohol

replaces -OH with double bond

acid-catalyzed dehydration

Na2Cr2O7 or H2CrO4 or CrO3 (Jone's reagent)

H2SO4

to alcohol, aldehyde

makes carboxylic acids when it can or ketones

1º alcohol -> carboxylic acid

aldehyde -> carboxylic acid

2º alcohol -> ketone

PCC

to alcohol

turns -OH to -O double bond

1º alcohol -> aldehyde

2º alcohol -> ketone

NaH (or Na or K)

to alcohol

deprotonates alcohol allowing addition to make an ether

2nd step is SN2

Williamson Ether Synthesis

Excess HBr (or HI or HCl)

to ether

splits an ether with -Br at each end

acid-catalyzed cleavage of ethers

NaOCH3

CH3OH

to epoxide

attaches at less-substituted side and opens epoxide ring (SN2)

base-catalyzed ring opening of an epoxide

H+

CH3OH

to epoxide

attaches at more substituted side and opens epoxide ring (SN2)

acid-catalyzed opening of an epoxide

NaBH4,

EtOH/MeOH/H2O

to ketone, aldehyde, acid halide

reduces ketone/aldehyde/acid halides to alcohols

1) LiAlH4

2) H3O+

to ketone, aldehyde, acid halides, esters, carboxylic acids, amides

reduces ketones, aldehydes, acid chlorides, esters, carboxylic acids, and amides

ketone/aldehyde/acid chloride -> alcohol

carboxylic acid -> remove ketone to make alcohol

ester -> split and add -OH, makes 2 alcohols

amide -> amine (remove double O bond) (no loss of C)

1. DIBALH, -78º

2. H2O

to ester

cleaves ester to make an aldehyde and alcohol

LiAl[OC(CH3)3]3H

-78C

to acid halide

reduces acid chloride to aldehyde

-Cl leaves

Br2

OH-

to amide

amide -> amine (with loss of a C)

Hoffman Rearrangement

Diels-Alder Reaction, ∆

cycloaddition reaction

H2O

H+ or OH-

to ketone, aldehyde

ketone -> geminal diol

RO-

ROH

to ketone, aldehyde

ketone/aldehyde -> hemi-ketal

basic conditions

ROH

H+

to ketone, aldehyde

addition of 1 eq of an alcohol in acid to form a hemi-ketal and then a 2nd eq to form a ketal

ethylene glycol

to ketone, aldehyde

ketone/aldehyde -> cyclic ketal

functions as a protecting group for ketones and aldehydes

H3O is used to reverse

RNH2

H+

to ketone, aldehyde

ketone/aldehyde -> imine

addition of a 1º amine to form an imine (Schiff base)

(can be reversed with H3O+)

R2NH

H+

to ketone, aldehyde

ketone/aldehyde -> enamine

forms double bond on less substituted side if there's a difference

addition of a 2º amine to form an enamine

can be reversed with H3O+

+PPh3 (phosphylide)

to ketone, aldehyde

C=O bond --> C=C-R bond

addition of a phosphylide to form an alkene

Wittig Reaction

Michael Addition

an enolate attacks an α,β-conjugated carbonyl, attaching at ß position

(ß-addition or conjugate addition)

(CH3)2CuLi

H2O

to α,β-conjugated carbonyl

methyl attaches at ß position of an α,β-conjugated carbonyl

Michael Addition with a lithium dialkylcuprate

Br2

-OH (base)

to ketone, aldehyde

Br attaches to alpha position of ketone/aldehyde

XS can yield 2 Br additions to each alpha carbon

(alpha halogenation)

Br2

H+ (Acid)

to ketone, aldehyde

Br attaches to alpha position of ketone/aldehyde

cannot attach more

(alpha halogenation)

1. LDA

2. R-X

to ketone, aldehyde

addition of -R at alpha position of ketone/aldehyde

1) LDA

2) ester

3) H2O

to ketone, aldehyde

LDA deprotonates alpha carbon of ketone/aldehyde and ester attaches (OEt leaves) and makes ßdicarbonyl compoud

Claisen addtion to an ester

Malonic Ester

1. NaOEt

2. R-X

3. NaOEt

4. R-X

5. H3O+, ∆

carboxylic acid with 2 & 4 attached at alpha carbon

+CO2

(ß-decarboyxylation)

Acetoacetic Ester

1. NaOEt

2. R-X

3. NaOEt

4. R-X

5. H3O+, ∆

methyl ketone with 2 & 4 attached at alpha carbon

+CO2