CHEM 110 [2015

]
CHEMISTRY OF THE LIVING WORLD

Block 6: Units 1 & 2
ALCOHOLS, ALDEHYDES & KETONES

Lecturer: Dr Viji Sarojini
v.sarojini@auckland.ac.nz

Alcohols - 1.1 Introduction
Nomenclature
C OH
Delete “e” of alkane and add “ol”
Don’t forget priority for numbering
Classification
1°, 2° or 3° (as for alkyl halides)
1 2 3 groups attached to C of C-OH
OH
CH3CH2OH OH CH3 C CH3
CH3
1° 2° 3°
ethanol cyclohexanol 2-methylpropan-2-ol

1

(or HX) X = Cl. I Examples: SN 2 CH3Br + OH CH3OH + Br SN1 (CH3)3CCl + H2O (CH3)3COH + HCl 30 1.2 Preparations of alcohols 1.2.(or H2O) ROH + X. -H+ through both SN1 and SN2 Cl 2 .1 Alkyl halide hydrolysis RX + HO. Br. Alcohols vs Phenols Alcohol –OH bonded to sp3 carbon C OH Phenol –OH bonded to the sp2 carbon on an aromatic ring OH H 3C OH m-methylphenol 1. H2O 20 cango (CH3)3C 2.

2 Alcohols from alkenes Acid catalysed addition of water OH H+ CH3CH CH2 + H2O CH3CHCH3 major + “rich get richer” “Markownikoff” minor CH3CH2CH2OH type addition Mechanism: 2o CH3CH CH3 H2O OH CH3CH CH2 H+ CH3CH CH3 Hydroboration – oxidation 1. H2O2 major + “Anti .Markownikoff” OH type addition minor CH3CHCH3 Mechanism: Electrophile: BH3 Nucleophile: H- H BH2   CH3CH CH2 H BH2 CH3CH CH2 CH3CH2CH2OH 3 .2. B2H6 CH3CH CH2 CH3CH2CH2OH 2.1. HO-.

g.3 Design a synthetic route The remaining methods for the preparation of alcohols are concerned with the addition of a nucleophile to a carbonyl group.2. RMgX) 4 . General mechanism for the addition of a nucleophile to a carbonyl group: H3O+ Nu C O Nu C O Nu C OH   Nu =H (hydride anion.2. from NaBH4) R (carbanion. from Grignard reagent. e.

followed by treatment “workup” which is usually with H2O / H3O+ Examples: 1.4 Grignard reagent addition Mg RX RMgX dry ether Mg  CH3CH2Br CH3CH2MgBr dry ether Effectively reacts as ‘ CH3CH2.1.2.’ 5 . H 2 O ester . NaBH4 CH3CHO CH3CH2OH Aldehyde 1° 2. H2O O 1. H2O O OH 1.needs LiAlH 4 (stronger reducing agent) No tertiary alcohols from the acyl component of the ester 2. LiAlH 4 CH 3 CH 2 OH + HOCH(CH 3 )2 CH 3COCH(CH 3 )2 2. ketone.3 Reduction of aldehyde. ester Using NaBH4. NaBH4 CH3CCH2CH3 CH3CHCH2CH3 Ketone 2° 2.

H O + 3 Grignard reagent and methanal give 1° alcohols with one more carbon Grignard reagent with epoxides  O H3O+ R + RCH2CH2O RCH2CH2OH H2C CH2  Ethylene oxide O 1. H3 O+ 1° alcohol with 2 more C's 6 .H2C CH2 (CH3)2CHCH2CH2OH (CH3)2CH MgBr 2.Grignard reagent with methanal O O H 3O + R + H C H H C H RCH 2OH R 1. HCHO (CH 3)2CHCH 2 OH (CH 3)2CH MgBr 2.

Modules 4-6 now open.H O+ (CH3)2CH C CH3 3 H Grignard reagent and aldehydes RCHO (R≠H) give 2° alcohols 7 . BEST CHOICE – Assessed Module 3 due Tuesday (22/9). OFFICE HOURS –By appointment Grignard reagent with aldehydes RCHO (R≠H) O O OH H 3O + R + R1 C H 1 R C H R1 C H R R O OH 1. LAB ASSIGNMENTS – Pre-lab 4 is open now – due before your lab. CHEM110 Week 8 comm. Mastery Quiz 2 due Friday (25/9) HELP SESSIONS – Wednesday 8-9 in 303-B07 and Thurs 1-2 Eng3408. Post-lab 3 due Wednesday (23/9). 21th September LECTURES –Block 5 [Dr Viji Sarojini] LAB SESSIONS – None this week. HC CH 3 (CH3)2CH MgBr 2.

Grignard reagent with ketones O O OH H3O+ 1 R + R1 C R2 R1 C R 2 R C R2 R R O OH CH 1.H3O+ CH(CH3)2 Grignard reagent (2 moles) and ester (or acyl halide) give 3° alcohols with two groups the same 8 . 3 C CH 3 (CH ) CH C CH (CH3)2CH MgBr + 3 2 3 2. 3 C Z 2 (CH3)2CH MgBr (CH3)2CH C CH3 2.H3O CH3 Grignard reagent and ketones give 3° alcohols Grignard reagent with esters and acid chlorides O O O OH H3O+ R + R'C Z R'C R R'C R R'C R Z = OR2 or Cl R R R O OH CH 1.

5 Exercises How would you prepare the following compounds from starting materials containing no more than three carbon atoms? (i) 3-pentanol H3O+ CH3CH2CHO + OH CH3CH2MgBr (ii) 1-pentanol O OH H3 O+ + CH3CH2CH2MgBr (iii) 2-pentanol OH CH3CHO H3O+ + CH3CH2CH2MgBr (iv) 3-ethyl-3-pentanol O ester or acyl OH chloride H3O+ CH3CH2CZ + 2 CH3CH2MgBr 9 .2.

3. 1.1 Acid / Base properties R O H Alcohols up ~C5 . phenoxide ion resonance stabilised O O O O Phenol acidity OH EWG Electron-withdrawing groups INCREASE ACIDITY OH Electron-donating groups EDG DECREASE ACIDITY 10 .3 Reactions and properties of alcohols 1.pH neutral solutions OH O H2O + H3O+ Phenols weakly acidic.water soluble .

11 . CH3CH2O + Na+ + NH3 Sodium amide alkoxide  O CH3CH2O .3.1 Acid / Base properties R O H The -OH group has the ability to react either as an acid or as a base.. H + H O S OH CH3CH2O H + HSO4- O oxonium ion H Both the conjugate base (alkoxide) and the conjugate acid (oxonium ion) are important species since the formation of one of them is usually the first step in reaction of alcohols. OH O H2O + H3O+ O O O O C O O O C O C O 1. CH3CH2O H + Na+NH2.

+ R'_X ROR' + X- Oxonium ion: e. Nu- R OH R OH R-Nu + H2O acid H 12 .g. in alkyl halide synthesis conc. in ether synthesis RO.g. Alkoxides: e.

H 2O Cl Cl CH3CCH2CH3 CH3CCH2CH3 CH3 CH3 13 . the reaction proceeds via the SN1 mechanism (stable carbocation) H OH OH conc. As shown above for the onium ion. HCl will yield the corresponding tertiary alkyl halides.2 Substitution reactions Formation of alkyl halides from alcohols.3. reaction of a tertiary alcohol with conc. For tertiary alcohols. 1. CH3CCH2CH3 CH3CCH2CH3 HCl CH3 CH3 . OH Cl conc. CH3CCH2CH3 CH3CCH2CH3 + H2O HCl CH3 CH3 Does this reaction proceed via SN1 OR SN2 ? Answer: as for alkyl halides.

and into alkyl chlorides by use of thionyl chloride (sometimes in the presence of pyridine). the reaction proceeds via an SN2 mechanism. For primary alcohols. the reaction proceeds via either SN1 or SN2 mechanism. conc. H HCl Cl CH3CH2OH CH3CH2OH CH3CH2Cl Secondary alcohols. A more general procedure for converting alcohols to alkyl bromides is by reaction with phosphorus tribromide. pyridine CH3CH2CH2OH + SOCl2 CH3CH2CH2Cl 14 .

H2SO4 C C H C C H C C heat H OH H O H H H+ HSO4 H Secondary alcohols proceed via either E1 or E2 mechanism 15 . 1. forming an alkene.3. H2SO4 .H2O C C C C C C heat H OH H+ H O H HSO4 H H C C Primary alcohols proceed via E2 mechanism H H H conc.3 Elimination reactions Alcohols eliminate water when reacted with conc. conc. Tertiary alcohols proceed via E1 mechanism (stable carbocation). H2SO4 and heat.

Zaitsev / Saytzeff rule Where more than one alkene product can be formed the most substituted alkene is the major product (Zaitsev / Saytzeff rule). OH H CH3 CH3 CH3 conc. H2SO4 H + heat major minor 16 .