Orgo 2 Test 2

Naming oxygen sandwiched between two groups

R1 R2 Ether

Naming ether with other functional groups

use ____ oxy as functional group

Williamson Ether Synthesis

Sn2 rxn

Alkoxymeryuration/demercuration

The OR group ends up on the more substituted side.

Cleavage by HBR or HI

O grabs H and creates great leaving group. X then attacks less hindered side

Base Catalyzed Epoxide Opening (attacks less substituted side)

Acid Catalyzed Opening (attacks more substituted side)

Sn2 Backside attack when 1 or 2 (if 1 and 2 will attack less substituted)

If tertiary present will attack the tertiary

Synthesis of Thiols using thiourea

Sn2 displacement where S attacks

Oxidation of Thiols

Can also work with H2O2 or other mild oxidizers

Reversible using Zn and H+, or FADH2

Synthesis of sulfides

S- can be stablized with Na+

Oxidation of sulfides

Preperation of ethers from alchohol

ROH + R’OH with acid-catalyzed rxn. Kicks off one OH and uses Sn2 Method to join

Prep of epoxide from alkene using Oxygen

O2

—>

Ag2O

300˚C

Prep of epoxide from alkene using peroxyacid

RCO3H

—>

CH2Cl2

Naming if have SH group (mercaptan)

thiol if primary substituant, n-meracpto… if part of multiple group molecule

Acetal mechanism (two OR groups)

1. Acid H attacks OR group, creating good leaving group

2. OR group leaves and other becomes double bond

3. Conj base (H2O) attack O=C (electrophilic carbon)

4. Repeat acid protinaton and group leaves forming ketone

MCPBA with Alkene

Epoxide

Formation of R-PPh3 (2 step)

Oxydation Primary Alc

Nucleophiles that participate in 1,4

Amines (NH2)

CN-

RS-

Enolates (- charge O + C that resonate)

Orgaocuperates

enamines (—NH—)

Alkene

Naming of

• carbox Acid

• Dioic Acid

• Nitriles (CN)

• e replaced with oic acid (propanoic acid)

• add diol acid (propanediol acid)

• Add nitrile to hydrocarbon (ethane nitrile) replace ic or oic acid *acetonitrile),

  • Also cyano substituent (2-cyanopropanoic acid)

Pka

• ethanol

• Phenol

• Acetic Acid

• 16

• 10

• 5

Factors that influence acidity ranked

1. Bond strength (HF stronger than HI)

2. Electronegativity (more EN means more stable conj base)

3. Resonance (more resonance spreads charge)

4. Hybridization (More S character means stability as closer to nucleus)

5. Inductive and Field Effects (having a carbon bonded to 3 carbon makes more acidic)

Henderson-Hasselbalch eq (Pka as it relates to carbox acid)

Carbox acids mostly exist in deprot form

Oxidation to Alchohol to carbox acid

Strong Oxidizer KMNO4 or H2CrO4

Oxidation Aldehyde

Na2Cr2O7/H2SO4, KMnO4, CrO4, Tollens’ (Ag), Benedict Reagent (Cu) specifically for aldehyde to carboxylic acid

Oxidation benzylic CH containing group + KMNO4

KMnO4 with HNO3 will cleave any R group

Grinard, Organolithium, or organosodium reagents with CO2

Acid-catalyzed hydrolysis of nitrile

Ozonation of alkene followed by oxadative workup or H2O2

Carbox Acid

Ozonation of alkene followed by Reductive workup (DMS or Zinc)

Ketone or Aldehyde

Hydrolysis under acidic conditions

Dehydration of amides to nitriles

RCONH2 —>

Use SOCl2, P4O10, or POCL3

RCN