Organic Chemistry Midterm 1 Content

Chapter 13, 14, 15

Nitration reagents and product

HNO₃, H₂SO₄. Adds nitro (-NO₂) group.

Sulfonation reagents and product

SO₃,H2SO₄. Adds sulfonic acid (-SO₃H) group.

Halogenation reagents and product

Br₂, Cl₂, and AlX₃. Adds halogen (-X) group.

Friedel-Crafts Alkylation reagents and products

Alkyl halides and AlX₃. Adds alkyl group (-R) to aromatic ring.

Friedel-Crafts Acylation reagents and products

Acyl halides (C=O with attached chlorine halogen) and AlCl₃. Adds acyl group (-C(O)R) to aromatic ring.

Benzylic oxidation reagents and products

1)KMnO₄, H₂O

2)HCl

OR

1) Na₂Cr₂O₇ (or K₂Cr₂O₇), H₂O

2) H₂SO₄, heat

Turns benzylic hydrogen into carboxylic acid (C=O with OH attached).

Nitro reduction reagents and products

H₂, Pd

OR
1) Fe (or Sn), HCl

2) NaOH

Converts nitro group (-NO2) to amine group (-NH2) on aromatic ring.

Wolf-Kishner reduction reagents and products

1) NH₂NH₂, KOH, HO(CH₂)₂OH

Turns ketones into alkyl groups.

Clemmonson reduction reagents and products

1) Zn(Hg), HCl

Just reduces ketones to alkyl groups.

2) NaOH

Additionally reduces nitro groups to amines.

Nitration can’t happen with:

Amines (-NH₂), explosive

Halogenation cant happen with:

Amines (-NH₂), alcohols (-OH), and ethers (-OR). Polyhalogenation occurs (halogens in all ortho/para positions).

Organolithium prep reactants and products

R-X + 2Li —> R-Li + LiX

Grignard prep reactants and products

R - X + Mg —> R - MgX

Organometallic reagent and what gives a primary alcohol?

Formaldehyde H₂(C=O) w/ Et₂O and 2)H₃O⁺

Organometallic reagent and what gives a secondary alcohol?

Aldehyde R(C=O)H w/ Et₂O and 2) H₃O⁺

Organometallic reagent and what gives a tertiary alcohol?

Ketone R₂(C=O) w/ Et₂O and 2)H₃O⁺

CH₃MgBr, Et₂O, 2) H₃O⁺ with alcohol gives what?

Deprotonated alcohol + CH₄. Essentially no net rxn for alcohol compound of interest.

What reagent can be used instead of an organometallic one?

Sodium acetylide. (R-CN-H) + NaNH₂ = Acetylide ion (R-CN:^-)

Organometallic reagent w/ ethylene oxide and H₃O⁺

Forms primary alcohol w/ 2 carbons as substituent.

What double bonds does H₂, Pd reduce? What reaction is this?

Nitro reduction. Turns both C=O AND C=C (except aromatics) into single bonds. Turns C=O into C - OH

What bonds does NaBH₄ , MeOH reduce?

Reduces aldehydes to primary alcohols, and ketones into secondary alcohols.

Mechanism for NaBH₄, MeOH with a ketone

What bonds does 1) LiAlH₄, Et₂O 2) H₃O⁺ reduce?

Aldehydes to primary alcohols, ketones to secondary alcohols, CARBOXYLIC ACID TO PRIMARY ALCOHOL! R(C=O)OH → R-COH

How can tertiary alcohol be reduced/oxidized?

It can’t, you need an H-C bond at the alpha position for oxidation. Reduction is ridiculous, you’d need a double bond and 3 substituents, which is not possible.

What does PCC, CH₂Cl₂ do?

Oxidizes primary and secondary alcohols into aldehydes and ketones respectively.

What does PDC, CH₂Cl₂ do?

Oxidizes primary and secondary alcohols into aldehydes and ketones respectively.

Swern oxidation. 1)DMSO, (COCl)_2, CH₂Cl₂ ~78°C 2)NEt₂

Oxidizes primary and secondary alcohols into aldehydes and ketones respectively.

Na₂Cr₂O₇, H₂SO₄, H₂O, heat.

Can use Kr₂Cr₂O₇ as well.

Benzylic oxidation! Turns primary alcohols into CARBOXYLIC ACIDS. Turns secondary alcohols into ketones.

1) O₃, CH₃OH

2) (CH₃)₂S (or H₂O, Zn)

Ozonolysis to split C=C into two C=O bonds.

1)OsO_4, tBuOOH, tBuOH

2)HIO₄

Vicinal diol into split aldehydes (be wary of other substituents).

Ether synthesis from ethanol reactants and mechanism

Primary alcohols only.

Diol to ether synthesis reactants and products

Must for a 5-6 membered ring. Primary alcohols.