Reactions Review

Create a markovnikov alkyl halide

Start with an alkene. Add HX with CH2Cl2 solvent. This is nonstereospecific

Create a markovnikov alcohol

Start with an alkene. Add H2O and H2SO4 as a catalyst. This is nonstereospecific

Create a markovnikov ether

Start with an alkene. Add ROH and H2SO4 as a catalyst. This is nonstereospecific

Create a vicinal dihalide (on adjacent carbons)

Start with an alkene. Add X2 and CH2Cl2 solvent. This is anti

Create a vicinal halohydrin (alcohol on markovnikov carbon)

Start with an alkene. Add X2 and H2O solvent. This is anti

Create a vicinal haloether (ether on markovnikov carbon)

Start with an alkene. Add X2 and ROH solvent. This is anti

Create an alkane

Start with an alkene. Add H2, Pd/C. This is syn

Start with an alkyne. Add excess H2, Pd/C

Create an epoxide

Start with an alkene. Add a peroxyacid (ex. mCPBA) and CH2Cl2. This is syn

Create an antimarkovnikov alcohol

Start with an alkene. Add 1. BH3/THF and 2. H2O, H2O2, NaOH. This is syn

Split a double bond to form ketone/aldehyde

Start with an alkene. Add 1. O3, -78 degrees C and 2. (CH3)2S

Create a Z-alkene

Start with an alkyne. Add H2 and Lindlar’s catalyst. This is syn

Create an E-alkene

Start with an alkyne. Add Na and NH3 (liq) at -78 degrees C. This is anti

Create an acetylide ion

Start with a terminal alkyne. Add NaNH2 and NH3 (liq)

Do chain elongation

Start with an acetylide ion. Add a methyl or primary alkyl bromide

Create a terminal aldehyde

Start with a terminal alkyne. Add 1. BH3, THF and 2. H2O, H2O2, NaOH. Tautomerization from enol

Create a terminal ketone

Start with a terminal alkyne. Add H2O, H2SO4, and HgSO4. Tautomerization from enol

Create a geminal dihalide

Start with an alkyne. Add excess HX and CH2Cl2

Relocate a double bond (more substituted to less substituted)

Add HX. Then add strong bulky base (tertbutoxide) and heat

Relocate a double bond (less substituted to more substituted)

Add HX. Then add a strong base (NaOH) and heat

Add an alkyl group to an -SH or -OH

Add NaH to deprotonate. Then add a methyl or primary alkyl bromide

Form an alkene (less substituted)

Start with an alkyl halide. Then add tertbutoxide

Form an alkene (more substituted)

Start with an alkyl halide. Then add NaOH

What makes a bond more polarized?

Greater difference in electronegativity

What type of molecular orbital is this?

sigma

What type of molecular orbital is this?

pi

What type of molecular orbital is this?

sigma star

What type of molecular orbital is this?

pi star

To do an intramolecular reaction

Catalyze with H2SO4

Lower heat of hydrogenation means ______

more stable alkene

Reacting most rapidly with HX means ________

higher energy

How to form kinetic product; what type of addition?

50 degrees C, 1,2 addition

how to form thermodynamic product, and what is it?

-78 degrees C, most stable product

In a polar protic solution, look at ______ of nucleophile

Size, basicity

Strong bases

O- sp3, N- sp3, acetylide ion

SN2 transition state bond angles: Nuc-C-LG, R-C-R

180, 120

Replace an OH group with a halide

Add HI, HBr, or HCl and heat. Reaction will be either Sn2 or Sn1 depending on the starting substrate

To replace a secondary OH with X, use PBr3 and pyridine to avoid Sn1

Methyl is faster than primary!

Replace an OH group with a double bond

Add H2SO4 and heat. Reaction will be either E2 or E1 depending on the starting substrate

Create an ether from an alcohol (Williamson-Ether synthesis)

Deprotonate the alcohol with NaH. Add a primary or methyl alkyl bromide to do Sn2

Ether mechanism reaction rate order

secondary, primary, methyl, tertiary

With epoxide cleavage, under acidic conditions, the nuc attacks at ________. use______

most substituted carbon, stereoinversion at attacked carbon; use an acid or water/alcohol catalyzed with h2so4

Create an alkyl halide (ONE halogen only) from an alkane

Add Br2 and light

Add an antimarkovnikov halide

Start with an alkene. Add HBr, peroxide, and light. Radical addition is nonstereospecific

Create a grignard reagent

Start with an alkyl halide. Add Mg and Et2O

Add carbons to chain along with OH group

Start with a grignard regent. Add 1. epoxide 2. H3O+. Grignard reacts at lesser-substituted carbon of epoxide