Preparation of 2-chloro-2-methylbutane .. An SN1 reaction

Substitution Reactions Two mechanisms possible – SN1 – unimolecular transition state – formation of carbocation intermediate Preferred for tertiary carbons and polar solvents. SN2 – bimolecular transition state – no intermediate formed Preferred by primary carbons and less polar solvents.

Reaction Mechanism Tertiary alcohol and polar solvent Acid catalyzed – creates good leaving group (i.e. water) Tertiary carbocation intermediate does not rearrange – accepts the good nucleophile chloride anion

Competition? SN1 favored over SN2, if… Sterics effects : Tertiary (3°) carbon in C-LvG bond (bulky alcohol) Electronic effects: More alkyl groups on the carbon atom of C-LvG bond to stabilize carbocation formed. Polar solvent is used. Principle side reaction for SN1 in a polar solvent is E1 SN1 favored over E1, if… Nucleophile is weakly basic and highly polarizable (in other words, won’t “want” to pull of a hydrogen/proton as much, and will instead favor nucleophilic attack on the carbocation). Nucleophile is not very bulky. Under the reaction conditions used today, however, ELIMINATION IS REVERSIBLE! Excess of HCl Chloride (Cl-) is a good nucleophile (weakly basic, highly polarizable) SN1 favored over SN2 if the substrate is bulky with more alkyl groups (EDGs) to stablize (+)-charge on carbon. Polar solvent promotes SN1 mechanism b/c a CHARGED carbocation intermediate it formed – “Like dissolves like.” Elimination products are reversible (if and when they form) b/c excess HCl is used. When elimination products form (i.e. alkenes), HCl will add across the alkene in a Markovnikov manner to covert it to the intended alkyl halide product.

Procedure – pg.475-476 Mix 10 mL of 2-methyl-2-butanol and 25 mL of conc. HCl in a separatory funnel. Swirl to mix without the top. Note whether there are 2 layers or not. Put the top on and shake for 1 minute – then vent. (expect a good “burp”) Continue shaking and venting for about 5 minutes. Allow the layers to separate & determine which is the organic layer. Wash to remove impurities – 1st wash with 10 mL aq. NaCl 2nd wash with 10 mL cold aq NaHCO3 (expect gas!!) 3rd wash with 10 mL water 4th wash with 10 mL aq. NaCl Remove organic layer and dry over small amount anhydrous sodium sulfate. Carefully separate the product from the sodium sulfate, bottle, determine %-yield and submit. (no simple distillation!) If time permits, conduct Silver Nitrate classification test (procedure for which is on middle of pg. 870 in book).

How do we know that a chemical change has occurred? Both the reagent and the product are clear, colorless liquids. The alcohol (starting material) is soluble in the aqueous HCl ... Is the alkyl chloride (product)? Silver Nitrate Classification Test (see pg. 870 in book): Tertiary alkyl halides react with ethanolic AgNO3 to produce a precipitate of AgCl. RCl + AgNO3 = AgCl(s) + RONO2 curdly white precipitate Is the intended product a tertiary alcohol?

To prepare your NB… Table of 9 Chemicals: water, concentrated HCl, 2-chloro-2-methylbutane, 2-methyl-2-butanol, saturated sodium bicarbonate solution, saturated sodium chloride solution, anhydrous sodium sulfate, silver nitrate, ethanol 2 Chemical Reactions: Figures: Just reference pgs. in your NB from Extraction experiment to illustrate how to use a Separatory Funnel. + H2O ethanol + AgNO3 + AgCl ONO2

Calculations Theoretical yield of product – requires balanced equation. - What is the limiting reagent? (Used excess HCl, so…?) - Use unit analysis (calc. shown below) to find Theoretical Yield of alkyl chloride (RCl): mL ROH * g ROH * mole ROH * mole RCl * g RCl mL ROH g ROH mole ROH mole RCl = Theoretical yield of RCl in grams!!! Percent Yield = grams RCl obtained × 100 theo. yield of RCl