DAT Organic Chemistry Reactions etc.

Fuming sulfuric Acid (SO₃/H₂SO₄) + Heat

Nitric and Sulfuric acids (H₂SO₄/HNO₃), nitronium intermediate

Carbocation electrophile (usually acyl) is incorporated into aromatic ring, catalyzed by AlCl₃

ortho/para-directing NH₂>NR₂>OH>NHCOR>OR>OCOR>R

F>Cl>Br>I

(e⁻ withdrawing): NO₂>SO₃H>carbonyl, COOH, COOR, COR, CHO

Requires a good nucleophile

Requires a strong base

Addition of water to double bonds to form an alcohol

RMgBr + carbonyl -> Alcohol

Aldehyde/Ketone/Carbox acid/Ester + LiAlH₄ or NaBH₄ -> Alcohol

Hydrolysis of diazonium salts

Requires Strong acid i.e. H₂SO₄ and heat

-OH is not a good leaving group so hard to do. Best to add change -OH into a H₂O or add tosyl chloride and form a tosylate (great leaving group)

Can also be done with PBr₃ to create alkyl bromides

PCC yields aldehydes, KMnO₄ will create a carboxylic acid or ketone

Condensation of R-OH in ACID

Follows SN2 mechanism

Used to form an oxirane, can also be used on a hexene (1 double bond)

Produces a carboxylic acid. KMnO₄, CrO₃, Ag₂O or TOLLEN’s Reagent

Does not exist

Michael Addition

H₂O acts as the nucleophile

Aldehyde and ketone react with HCN

Reagent = H₂NNH₂

C=O →C=C

Reagents: KMnO₄, K₂Cr₂O₇, CrO₃

CH₃CH=CHCH₂CH₃ →1)KMnO₄, OH⁻, heat 2)H⁺→ CH₃COOH + CH₃CH₂COOH

Yields two carboxylic acids at site of cleavage

(CH₃)₃CBr →Mg/ether→(CH₃)₃MgBr → 1.CO₂ 2. H⁺, H₂O → (CH₃)₃CCOOH

Yields carboxylic acid and NH₄⁺

Yields a ketone where the Nu⁻ takes the place of the alcohol

Results in corresponding primary alcohol

Requires an alcohol under acidic conditions, yields an ester and water. Water is used as a leaving group

Reagents: Carboxylic acid and SOCl₂ or other halide

Carboxylic acids react with NaOH to form salts, organize non-polar tails around a non-polar substance and polar heads facing water. Spherical structure is called micelles.

Results in loss of CO₂ and thus loss of entire carboxyl when heated

Very rapid reaction

Reaction of carboxylate salt (RCOO⁻) and acyl chloride (RCOCl) produces an anhydride

Nucleophilic attack by an alcohol results in replacement of the halide in an acyl halide with an ester
EtOH + CH₃COX -> CH₃COOEt + HX

Nucleophilic substitution
CH₃COX + 2NH₃ → CH₃CONH₂ + NH₄Cl

CH₃COX + H₂/Pd/BaSO₄/quionoline/Lindlar’s Catalyst → CH₃OH

Only 5 and 6 membered rings are easily made

Carboxylic acids under anhydrous conditions results in an anhydride and loss of H₂O

Results in 2 equivalents of carboxylic acids when exposed to water

Cleaved by NH₃ to produce an amide and a carboxylic acid. The COOH and NH₃ can react further to create an ammonium carboxylate

Reacting with -OH will produce one ester and one molecule of COOH. “Splits” the original molecule

Reagents: AlCl₃ or other Lewis acid will produce an aryl ketone (benzene with a ketone) and a carboxylic acid

Transform one ester into another, -OH acts as a nucleophile and displaces alkoxy on original ester

Results in a tertiary alcohol if enough reagent is added and the intermediate ketone is not too bulky (MgBr)

Produces two different alcohols

Results in COOH + NH₃, occurs under acidic conditions via nucleophilic substitution

Converts amides to 1° amines with loss of carbonyl as CO₂

Reagent: LAH, results in corresponding amine, no C atom is lost

Most reactive (least stable) carboxyl derivative, can do Friedel-Crafts acylation, and can be reduced to alcohols or aldehydes

Second most reactive carboxyl derivative, can be formed via substitution or condensation and can perform Friedel-Crafts acylation

Not very reactive carboxyl derivative, hydrolyze to yield acids + alcohols, can react with Grignard reagents to produce a 3° alcohol

Least reactive carboxyl derivative, can be formed by reacting many substrates with amines or ammonia, can be transformed to 1° amines via Hofmann rearrangement

Iron or Zn as a catalyst

LAH = lithium aluminum hydride, produces a primary amine

Aldehyde or ketone reacted with ammonia, then reduced with hydrogen and a Ni catalyst

Reacting an amide with LAH produces RCH₂NH₂

Amine → ammonium iodide →ammonium hydroxide → least substituted alkene

1750-1800 (sharp)

3200 – 3600 (broad)

3400 – 3500 (sharp)

They must be anti-periplanar to one another

The lowest priority group (usually H) should be facing away from you in a Fischer projection

Syn-diol addition

Peak at ~1710 cm⁻¹

A substance that does not turn into a gas easily, i.e. thing layer chromatography is a method sufficient for separating non-volatile substances

isomer that differs in the placement of groups around a double bond; cis/trans isomerism