CHM2211 Exam 2 Condensed

IUPAC priority

Principal functional groups at C1 and double and triples bonds up next for lowest possible numbers.

Acidity ranking

• EWG strength: NO2 > CF3 > CN > Cl > Br.

• The closer, the more, the better.

Hydrate formation

• C=O is less sterically hindered, EWG’s help.

• Great EW’s > formaldehyde > aldehyde > ketone.

Hydrolysis rate

• Acid chloride > anhydride > ester > amide.

• Better LG increases rate.

NaBH4

Ketone/aldehyde → OH, acid untouched.

1. LiAlH4

2. HCl, H2O

Everything → OH, C=C untouched.

HO-CH2-CH2-OH / H2SO4 (cat.)

Forms a 5-membered cyclic acetal ring in place of C=O.

HO-CH2-CH2-OH, H2SO4 (cat.) / 1. LiAlH4, 2. HCl, H2O

Forms ring, converts acid/ester to CH2OH.

Acid chloride + CH3OH, py

Ester (OCH3)

Acid chloride + (2 eq.) R-NH, R-NH2

Amide

Acid chloride + R2CuLi

Ketone, adds 1 addition of R.

R-X to acid

1. Mg / 2. CO2, 3. HCl, H2O

Add on 1 C and form acid.

Ester/anhydride to acid

H2O / H2SO4 (cat.)

Ester to acid

1. NaOH, H2O, Δ / 2. aq. HCl

Cyanohydrin

Ketone/aldehyde + NaCN / HCN → HO-C-CN.

Cyclic acetal + H2O / aq. HCl

Original C=O + diol

C=O stays as is

• R-OH swaps Cl with OR.

• R-NH2 swaps Cl with NR.

• R2CuLi swaps Cl with 1 R.

• SOCl2, py swaps OH with Cl.

C=O becomes OH

• NaBH4 makes aldehydes/ketones only OH.

• 1. LiAlH4 / 2. HCl, H2O makes all but alkene OH.

• Acid chloride or ester + (2 eq.) R-MgBr → tertiary OH with 2 R groups.

• NaNH2?

H2/Pd vs H2(2 atm)/Rh

• H2/Pd reduces C=O (aldehydes, ketones) and C=C.

• H2(2 atm)/Rh reduces C=C only.

C=O erased

• Zn(Hg) / HCl under acidic conditions.

• H2N-NH2 / KOH under basic conditions.

Adding onto terminal alkyne

• 1. NaNH2, THF / 2. HCl, H2O for alkynyl alcohol.

• 1. NaNH2, THF / 2. R-Br for adding R onto alkyne.

NH3 alone

• Acid chloride + 2 eq. NH3 → amide.

• Aldehyde/ketone + NH3 + NaBH3CN → amine

Wittig reaction

• Aldehyde/ketone + Ph3P=CR2 → Alkene (C=C).

• Start R-X, add PPh3, then 1. NaH / 2. aldehyde or ketone to swap C=O for C=C.

Imine vs. enamine

• Primary amine → imine C=N-R (draw E/Z).

• Secondary amine → enamine N-C=C (drawn E/Z).

Fischer esterification

Acid + R’OH/cat. H2SO4 → ester.

Thermal decarboxylation

Ketone-CH2-COOH →Δ→ ketone-CH3 + CO2

NaOH, H2O

• -CN to -COOH with acid workup.

• Cuts esters, amides, and anhydrides without touching ketals or acetals.

HCl, H2O alone

Reverses back to an -OH and C=O.

CH2N2, Et2O

Turns acids into methyl esters (-OCH3).

Grignard/Organolithium

• Ester/acid chloride → 2 R, tertiary OH.

• Aldehyde → 1 R, secondary OH.

• Ketone → 1 R, tertiary OH.