Organic Chemistry 2 Reagents

Hydrogenation: H2,Ni high pressure/ H2,Pd

Reducing agent... Reduces Alkynes and Alkenes - Alkanes

Aldehydes- primary alcohols

Ketones- secondary alcohols

Esters- two alcohols

Imine- amine

Amide- amine

Nitrile- primary amine

Nitro- amine

10% NaOH

Aldol Condensation

1.O3

2.Zn or Me2S

Or

1.03

2.H2O2

1.Ozonolysis (oxidation of an alkene)

2.Hydrogen peroxide does further oxidation. Product = carboxylic acid

Carboxylic acid + 1. Alcohol 2. H3O+ (Work-up step)

Fischer esterification.

Carboxylic acid turns into an ester.

Alcohol + PCC

Primary alcohol + PCC = Aldehyde

Secondary alcohol + PCC = Ketone

"Please stop oxidation at aldehyde & ketone"

Aldehyde or ketone + ethylene glycol and acid

Cyclic acetal

This serves as a protecting group for aldehydes or ketones. You can then react another part of the molecule without touching the aldehyde or ketone part.

You deprotect the cyclic acetal and get your ketone or aldehyde back by acid and water.

R-MgBr

Grignards reagent

The purpose is to add carbons to a molecule.

Grignard workup

Nitrile + 1. R-MgBr 2. H3O+

Ketone

H3O+ (Acidic work-up step)

Purposes: a)acidic work-up step

b) acidic hydrolysis

c) Cleaves =N+ to =O

LAH (Lithium Aluminum Hydride)

STRONG REDUCING AGENT

Carboxylic acid - primary alcohol

All Carboxylic acid derivatives- primary alcohol

Aldehyde- primary alcohol(use NaBH4 rather)

ketone- secondary alcohol(use NaBH4 rather)

"Lets reduce everything"

CrO3 or H2CrO4

Oxidizing agent

"Crap lets oxidize everything"

Ph3P=CH2

WITTIG REAGENT

Ketone or aldehyde- carbon to a double bond

"Please make the double bond"

**If you write this as a reagent: alkyl halide + Ph3P + n-butyl lithium

anti-Markovnikov

electrophile adds to the less substituted carbon, usually happens with a peroxide

1.BH3

2.H2O2

Hydroboration

Alkene to an alcohol - alcohol

Anti-markovnikov

Ag(NH3)2+

Tollens reagent and aldehyde to a carboxylate

Ag2O

NaOH

Tollens test

Aldehyde to carboxylate

PBr3 (Phosphorus Tribromide) w/alcohol

Alcohol to alkyl halide without rearrangement

Ag2O

NH4OH

Tollens test with an "acidic work-up step"

Aldehyde to carboxylic acid

SOCl2 w/carboxylic acid

Thionyl Chloride

With Carboxylic acid

Makes for a good leaving group

Acyl Chloride from carboxylic acid + SOCl2 + pyridine

SOCl2(Thionyl Chloride) w/amide

Amide to Nitrile

Grignard + 1. CO2 2. H3O+

Product = carboxylic acid

1.Oxidation and 2.Reduction

1.Removing electrons, oxidation state of the C becomes more positive

2.Gaining electrons, oxidation state becomes more negative

SOCl2+DMF (thionyl Chloride) w/alcohol

Alcohol to Chloride

Ketone + 1.HCN (Cyanohydrin) 2.HCl, H2O, heat

Ketone gets hydrolyzed to carboxylic acid and then to alpha-hydroxy acid

PBr3

With Carboxylic acid

Makes for a good leaving group

Hell-Volhard-Zelinsky halogenation reaction- alpha position on carboxylic acid

H2CrO4 (Chromic acid)

A VERY STRONG OXIDIZING AGENT.

Can use CrO3 "crap lets oxidize all the way"

Chromic acid or chromium trioxide will oxidize:

a primary alcohol to carboxylic acid

a secondary alcohol to ketone

KMnO4 (potassium permanganate), cold +alkene

Potassium permanganate is an oxidizing agent but cold and hot will give different products.

Cold products- diol

KMnO4 with aromatic alkane

Aromatic alkane give aromatic ring with carboxy acid (reaction only works if there is a hydrogen attach to the Carbon) **Carboxy acid attaches to the benzylic position (spot directly adjacent to the aromatic group)

K2CO3

A mild base that de-protonates readily available hydrogens

example: carboxylic acid to carboxylate

1.O3

2.DMSO +alkene

1.ozonolyis (oxidation)

2. Oxidation stops at aldehyde or ketone depending on how substituted the double bond is.

Ketone + 1.HCN (Cyanohydrin) 2. H2SO4, heat

Ketone gets hydrolyzed to alpha, beta-unsaturated acid. The difference from the alpa-hydroxy acid to alpha,beta- unsaturated acid is the acid strength. H2SO4 is a much stronger acid than HCl is.

Acid Chloride

This is the most reactive carboxylic acid derivative and as a reagent, it can synthesis less reactive carboxylic acid derivatives.

Carboxylic acid + Thionyl chloride (SOCl2) + pyridine

Acid Chloride , a carboxylic acid derivative

KMnO4 (potassium permanganate), acetone

-OH

A base. Will deprotonate any readily available hydrogens. If no hydrogens, will act like a nucleophile.

Anhydride + alcohol

Ester synthesis

With an acidic workup step - 2 esters

** side note: 2nd way to make ester is fischer esterification- carboxylic acid + alcohol

mCPBA +Ketone

OXIDIZING AGENT

Ketone + mCPBA = ester

METHYL KETONE + NaOH & I2

Haloform reaction

Carboxylate & Haloform (o- & CHI3)

Carboxylic acid + 1.Br2,P 2.H2O

Hell-Volhard Zelinski Reaction

alpha- halo acid...leads to the selective alpha-bromination of carboxylic acids

alpha-halo acid + 1.OH- 2.H3O+

HVZ product + basic hydrolysis = alpha-hydroxy acid.

alpha-halo acid + NH3

HVZ product +ammonia = amino acid at neutral pH and at pH of 9 = Zwitterion

Na+ -:C(C6H5)3

Will allow for an ester with ONLY ONE ALPHA HYDROGEN to undergo Claisen Condensation. It is a carbon with a negative charge and three phenyl groups attached which further increases its basicity.

n-butyl lithium + diisopropyl amine OVER THF

LDA synthesis

1.NaOH

2.H3O+

Saponification / basic hydrolysis

Carboxylic acid + NH3 (ammonia)

Amide

NaCN (Sodium cyanide)

A nucleophile

R-CN (Nitrile) + H3O+ heat

Nitrile is a carboxylic acid.

Acidic hydrolysis back to carboxylic acid

Alcohol + H3O+ and heat

Dehydration

B-dicarboyl + H3O+ and heat

Decarboxylation

**ALPHA AND BETA POSITION IS YOUR HINT**

Me2 (or R2)CuLi +alkyl halide

Corey posner whitesides-house synthesis (Lithium dialkylcuprate)

Adds carbons! Easiest way to add a carbon.

ALKENE + 1.KMnO4, HEAT

2. H3O+

Potassium permanganate is an oxidizing agent and when hot in temperature, alkenes are oxidized to aldehydes or ketones depending on how substituted the double bond is.

ALDEHYDE + 1.KMnO4, HEAT

2. H3O+

Aldehyde is oxidized to carboxylate without workup step and carboxylic acid WITH a workup step

Alkyl benzene (the first carbon with atleast one hydrogen) + 1.KMnO4, HEAT

2. H3O+

The alkyl group is oxidized to carboxylate WITHOUT workup step and carboxylic acid WITH workup step.

Alkene + X2( halogens)/ low concentration or high temperature

Allylic radical substitution

Halide on allylic position

(use for chlorine and NBS for bromine)

NBS/ Light or ROOR

or

Br2

Allylic radical substitution

Halide on allylic position

(Use for bromine and Cl2/ High temperature for Chlorine)

IF YOU USE NBS IN A MECHANISM, YOU MUST SHOW HOW NBS AND HBR REACT !!!!!

Diene (conjugated system) + H-Br/ 25 degrees celsius and lower

1,2- addition (Kinetic and markovnikov product)

Diene (conjugated system) + H-Br/ 60 degrees celsius and higher

1,4-addition (Thermodynamic product)

Diene (conjugated system) + dienophile (an alkene)

Ring synthesis (2 new sigma bonds and 1 pie bond formed)

Alkene + X2/ CCl4, LOW TEMPERATURE

2 halogens added across the double bond

Aromatic ring + Br2,

FeBr3

Electrophilic Aromatic Substitution reaction

Halogenation of benzene ring

Bromine on the aromatic ring = the product

Aromatic ring + HNO3,

H2SO4

Electrophilic Aromatic Substitution reaction

Nitration of benzene ring

Nitro group on the benzene ring = the product

Aromatic ring + SO3

H2SO4

Electrophilic Aromatic Substitution reaction

Sulfonation of benzene ring

Sulfuric acid group on the benzene ring = the product

Aromatic ring + R-X

AlCl3 (or FeBr3)

Electrophilic Aromatic Substitution reaction

Friedel-Crafts Alkylation of benzene ring

Alkyl group on the benzene ring = the product

Aromatic ring + Acid chloride

AlCl3

Electrophilic Aromatic Substitution reaction

Friedel-Crafts Acylation of the benzene ring

Acyl group on the benzene ring = the product

Friedel-Crafts Acylation product + Zn(Hg), HCl

Clemmensons reduction of acyl group

Solves the rearrangement issue

REDUCES THE CARBONYL GROUP TO -CH2

USE IF MOLECULE IS SENSITIVE TO BASE!!!

Friedel-Crafts Acylation product + H2N-NH2 +KOH

Wolf-Kischner reduction of acyl group

Solves the rearrangement issue

REDUCES THE CARBONYL GROUP TO -CH2

USE IF MOLECULE IS SENSITIVE TO ACID!!!

Aromatic ring + Na*, NH3, EtOH

Birsch reduction of aromatic ring into 2 NON-AROMATIC, NON-CONJUGATED RINGS

PRODUCT = 2 CYCLOHEXADIENES

Ester + 1.DIBAL-H

2.H2O

Aldehyde

"Dear DIBAL, please stop reduction at aldehyde"

Acid Chloride + 1. DIBAL-H

2. H2O

Aldehyde

"Dear DIBAL, please stop reduction at aldehyde"

Nitrile + 1. DIBAL-H

2. H2O

Aldehyde

"Dear DIBAL, please stop reduction at aldehyde"

Ester + 1. LiAl(OtBu)3H

2. H2O

Aldehyde

*Works the same as DIBAL-H

Acid Chloride + 1. LiAl(OtBu)3H

2. H2O

Aldehyde

*Works the same as DIBAL-H

Alkyne + H2O

H2SO4

HgSO4

Tautomerization

Enol--> Keto

R-Li

Works the same as grignard

NaBH4 (Sodium Borohydride)

REDUCING AGENT.... WEAKER THAN LAH

Reduces Aldehydes and ketones to its respective alcohol.

Ketone + H3O+

Geminal Diol

Ketone + OH-

Geminal Diol

Ketone + R-OH

H3O+

Hemiacetal----> Acetal ( a protecting group for aldehydes and ketones)

Ketone + R-OH

OH-

Hemiacetal

To proceed to acetal (the protecting group), you need acidic conditions.

Aldehyde + R-OH

H3O+

Hemiacetal----> Acetal ( a protecting group for aldehydes and ketones)

Aldehyde + R-OH

OH-

Hemiacetal

To proceed to acetal (the protecting group), you need acidic conditions.

Ketone + primary amine & mild acid

Imine formation

Ketone + secondary amine

Enamine formation

beta- keto ester + 1.NaOR

2.R-X

3.OH-, H2O

4.H3O+, heat

The product is a longer ketone

This reaction can be performed with anything that is a di-carbonyl and has an ester

beta-dicarbonyl compound + KOtBu

Use for second alkylation or acylation!

Br-R-Br

Ring closure

Nucleophile + a conjugated system

Michaels addition

a)simple addition 1,2-addition

b)conjugated addition 1,4-addition AND THEN PRODUCT = ALPHA, BETA-UNSATURATED SYSTEM BECAUSE OF ENOL--->KETO

Cyanide + a conjugated system

Michaels addition (any nucleophile)

a)simple addition 1,2-addition

b)conjugated addition 1,4-addition AND THEN PRODUCT = ALPHA, BETA-UNSATURATED SYSTEM BECAUSE OF ENOL--->KETO

Amine + a conjugated system

Michaels addition (any nucleophile)

a)simple addition 1,2-addition

b)conjugated addition 1,4-addition AND THEN PRODUCT = ALPHA, BETA-UNSATURATED SYSTEM BECAUSE OF ENOL--->KETO

Di-carbonyl + a conjugated system

+ OH-

+ROH

Michaels addition (any nucleophile)

a)simple addition 1,2-addition

b)conjugated addition 1,4-addition AND THEN PRODUCT = ALPHA, BETA-UNSATURATED SYSTEM BECAUSE OF ENOL--->KETO