Organics II Final Review

Conformers

These rotate around a bond but have the same number of elements

Isomers

These move atoms around

What equilibrium favors

The more stable base/ weak acid

How bond number impacts acidity

More bonds more acidic

pKa > pH

Keep the proton on

Enantiomers

Have the same physical properties

How does nucleophilicity increase

Down the table and when there is less electronegativity

SN2 traits

Walden Inversions, E2 must have H be periplanar, and must have an aprotic base

SN1 traits

Carbocation shifts

How PCC reacts with 1, 2, and 3 alcohols

Forms an aldehyde and forms a carboxylic acid and no reaction

How strong oxidizers react with 1, 2, and 3 alcohols

Forms a carboxylic acid, forms a ketone, and no reaction

Heck Reaction

Has a leaving group and creates a trans alkene (uses PdL2 or Pd(OAc)2 with PPh3, Et2N)

Suzuki Reaction

Has a leaving group with boron and keeps stereochem and uses PdL2 w/ NaOH

Stille reaction

has a leaving group with tin and keeps sterochem and uses PdL2

Simmons Smith

CHCl2 with Zn(Cu) ether and forms a carbon epoxide thing

Grubb’s Cross Metathesis

Clicks the same molecule together by clicking the alkenes together in E and Z ratios

Grubb’s Ring Closing and Ring Opening Metathesis

Lose two carbons and gain two carbons

How conjugation impacts wavelength and energy

More of this longer the wave and smaller the delta E

Diene traits

Wants EDGs that donate to the ring

Dienophile traits

Wants EWGs that take electrons away from the ring and if cis/trans, the product is cus/trans

Limitations on Friedel Crafts (FC)

Only works on Ph or Ph-X

FC Alkylation

Has C+ shift and forms a new bond

FC Acylation

Does not have a C+, most likely has a C=O, and also forms a new bond

Halogenation

Looks like X2FeX3 and just adds X

Sulfonation

Fuming H2SO4 adds SO3H and adding dilute H2SO4 removes the SO3H

KMnO4 needs what to form COOH?

All carbons present (a benzylic carbon) and sp3 pond

Wolff - Kishner

H2NNH2 with KOH and delta. This will scrap all carbonyls.

Clemmensen

Zn(Hg) with HCl. This will scrap only c=o and reduces NO2.

Two ways to reduce NO2

[1. Zn, Fe, Sn, or HCl 2. NaOH] or [H2, Pd/C (must be next to a benze)]

Diazonium Salts

[NaNO2, HCl]. Must be an amine before these reagents are used.

What NaBH4 and LiAlH4 to do ketones

Reduces to alcohols

Steps in acid

Proton on, Nu attack, Proton off, Proton on, Collapse and Kick, Nu attack, and Proton off

Steps in base

Nu attack, Proton on, Collapse and kick, and Proton off

Imines and Enamines create what when reacted with H3O?

These will create a >=O

What things can reduce imines and enamines in one step?

[H2, Pt] and NaBH3CN

NaBH4 attacks what only

This attacks ketones only

Wolff - Kishner does what to a hydroxyl-amine?

Reduces he OH to a NH2

Prepare COOH: Grignard needs what, Nitrile needs what, Alkyne needs what, and primary alcohol needs what?

[CO2, H+], [H3O+, delta], [O3, H2O], and strong oxidizer.

Reacting acid chlorides to things: need what to make COOH, need what to make an anhydride, need what to make an ester, and need what to make an amide?

[H2O], [COOH], [ROH, base], and [R2NH w/ two equivalents]

Reacting anhydrides to things: need what to make COOH, need what to make an ester, and need what to make an amide?

[H2O, delta, H], [ROH, base], and [R2NH w/ two equiv]

Amides react with what to form a nitrile

SOCl2 or P2O5

Nitriles form COOH by what and amine by what?

H3O+ and LAH

EDGs do what to acidity?

These increase acidity

In acid with alpha halogenations versus when in base with alpha halogenations

Only one halogenation on the more substituted side whereas in base all alpha protons are gone and if a CH3 exists, COOH replaces it

Aldol reactions

Forms a beta hydroxy with to an aldehyde and ketone and when reacted with H2O conjugation with the c=o occurs

Malonic Ester Synthesis

Exploits the alpha carbon, adds R to where alpha carbon once was, H= makes the esters Oh, and delta removes one COOH group

Stork Enamine Rxn

Enamines can be nucleophile — they replace the O from a carbonyl and form a new bond with conjugated carbonyl molecule. When reacted with [H=, H2O], the N goes back to a carbonyl and the once negative oxygen becomes a carbonyl as well.

Robinson Annulation

Deprotonates alpha carbon, forms new bond with conjugated carbonyl molecule, forms a ring, reacts with H2O to make OH and then delta to condensate.

Gabriel Synthesis

Converts primary RBr to primary RNH2

Stretcher Synthesis

Creates an amino acid from an aldehyde

Stretcher Synthesis reagent options

[1. NH3, HCN 2. H3O+, delta]

[1. NH4Cl, NaCN 2. H3O+, delta]

[1. NH3, H+ 2. KCN, H+ 3. H3O+, H+]