Orgo Reactions

8/11/2019 Orgo Reactions

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Alkanes

Combustion

Radical

Initiation, propagation, and termination

Bromine more selective and chooses stable tertiary radical

Substitution with halogens

Uses hv (UV) or peroxides


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Alcohols

Sn1: tertiary carbon, protic solvent

Sn2: primary carbon, polar aprotic center

Oxidation: PCC (primary), CrO, KMnO, AgO

Reduction: LAH, NaBH4

Pinacol rrg

Protection

Trmethylsilyl to cap alcohols, F deprotects

SOCl2 and PBr change alcohols for X

Mesylates and Tosylates are considered excellent leaving groups and made with alcohols

Fischer Esterification


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Aldehydyes/Ketones

Nucleic addition when nucleophile attacks carbonyl

Acetal/ketal

Imine

Enamine

Haloform


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Aldol condensation

Keto/enol tautomerism

Organometallic (eg. Grignard)

Li or Mg (Grignard) can be added to haloalkane and these can make R-R bonds


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Wolff-Kishner Reduction

N2released

Clemson Reduction


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Carboxylic Acids

Nuc attack

Reduction with LiAlH can convert to a primary alcohol

Decarboxylation

Beta-keto acids can do this

Hell-Volhard-Zelinsky Halogenation


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Substitution and alpha positions

COOH converted to enolizable form

Halogen or some other electrophile gets attacked by double bond

Reverts back to COOH form (net: alpha H replaced by electrophile)


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Acid Derivatives

Preparation

COOH +SOCl acid chloride

COOH + COOH (heat) anhydride

Acid chloride + COOH + (base)

anhydride Acode chloride + alcohol (base) ester

Acid chloride + amine amide

Acid chloride + water COOH

Nucleophilic substitution is when some Nuc basically knocks off a LG

Hoffman RRG

Transesterification

Saponification

Amide hydrolysis

Decarboxylation


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Beta-keto esters beta-keto acids enols ketos

Esters to acids by hydrolysis

Acetoacetic ester synthesis

Acetoacetic ester is synthesized by claisen condensation of 2 ethyl acetates

Claisen condensation

Aldol condensation


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Amines

Amide formation: amine + C=O with good LG (can be an acid derivative)

Amine rxn with nitric acid

Primary amines react with nitrous acid to yield a diazonium salt, which is highly unstableand degradates into a carbocation that is capable of reaction with any nucleophile insolution. Therefore, reacting primary amines with nitrous acid leads to a mixture ofalcohol, alkenes, and alkyl halides.

Alkylation

Amines with alkyl halides can substitute for polyalkylation in presence of base

Hofmann elimination

Less substituted alkene can be formed, as opposed to Zaitsevs rule

Wittig Rxn

Carbonyl + phosphorus ylide alkene

C1=O +Ph3P=C2C1=C2

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