Alcohols R-O-H Classification CH3, 1o, 2o, 3o Nomenclature:

Alcohols R-O-H Classification CH3, 1o, 2o, 3o Nomenclature:

Alcohols R-O-H Classification CH3, 1o, 2o, 3o Nomenclature: Common names: alkyl alcohol IUPAC: parent = longest continuous carbon chain containing the OH group. alkane drop -e, add ol prefix locant for OH (lower number for OH) CH3 CH3CHCH2CHCH3 OH 4-methyl-2-pentanol 2o CH3 CH3CCH3 OH tert-butyl alcohol 2-methyl-2-propanol 3o

CH3 HO-CHCH2CH3 CH3CH2CH2-OH sec-butyl alcohol 2-butanol 2o n-propyl alcohol 1-propanol 1o Physical properties of alcohols: polar + hydrogen bonding relatively higher mp/bp water insoluble! (except for alcohols of three carbons or less) CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2-OH hydrophobic hydrophilic

Oldest known organic synthesis: fermentation Sugar + yeast Grape juice => wine Barley => beer Honey => mead Rice => sake ~5-11% ethanol ethyl alcohol + CO2 Alcohols, synthesis: 1. 2.

3. 4. Hydrolysis of alkyl halides (CH3 or 1o) 5. 6. 7. 8. R-H R-X R-OH Acids NR NR Bases NR some

Active metals NR Oxidation NR NR 1o/2o Reduction NR NR Halogens

NR NR NR Alcohols, reactions: R-|-OH 1. With HX 2. With PX3 3. (later) RO-|-H 4. As acids 5. Ester formation 6. Oxidation 1. Reaction of alcohols with HX: (#1 synthesis of RX) R-OH + a) HX: HX

R-X + H2O HI > HBr > HCl b) ROH: 3o > 2o > CH3 > 1o c) May be acid catalyzed d) Rearrangements are possible except with most 1o alcohols. CH3CH2CH2CH2-OH + NaBr, H2SO4, heat CH3CH2CH2CH2-Br n-butyl alcohol n-butyl bromide 1-butanol

1-bromobutane CH3 CH3C-OH CH3 + HCl CH3 CH3C-Cl CH3 (room temperature) tert-butyl alcohol tert-butyl chloride 2-methyl-2-propanol 2-chloro-2-methylpropane

CH3CH2-OH + HI, H+, heat CH3CH2-I ethyl alcohol ethyl iodide ethanol iodoethane Mechanism? CH3-OH and most 1o alcohols react with HX via SN2 mechanism 3o and 2o react with HX via SN1 mechanism Both mechanisms include an additional, first step, protonation

of the alcohol oxygen: R-OH + H+ R-OH2+ oxonium ion Whenever an oxygen containing compound is placed into an acidic solution, the oxygen will be protonated, forming an oxonium ion. Mechanism for reaction of an alcohol with HX: CH3OH or 1o alcohols: SN2 1) 2) R-OH X + +

R-OH2 HX R-OH2 RDS R-X + + X H2O Mechanism for reaction of an alcohol with HX: 2o or 3o alcohols: SN1 1) R-OH

2) R-OH2 3) R + + HX RDS X R-OH2 R R-X + H2O

+ X May be catalyzed by acid. SN2 rate = k [ ROH2+ ] [ X- ] SN1 rate = k [ ROH2+ ] Acid protonates the -OH, converting it into a better leaving group (H2O), increasing the concentration of the oxonium ion, and increasing the rate of the reaction. Rearrangements are possible (except with most 1o alcohols): CH3 CH3CHCHCH3 + HBr CH3 CH3CCH2CH3 OH Br

CH3 CH3CHCHCH3 OH2+ Br- CH3 [1,2-H] CH3 CH3CHCHCH3 CH3CCH2CH3 + + 2o carbocation 3o carbocation In the reaction of most 1o alcohols with HX you don't have to worry about the possibility of rearrangements. The mechanism is SN2 and does not involve carbocations. CH3CH2CH2CH2CH2-OH +

HBr, H+, heat 1-pentanol CH3CH2CH2CH2CH2-Br 1o alcohol: No rearrangement, SN2 1-bromopentane Most 1o? If large steric requirement CH3 CH3CCH2-OH + CH3 neopentyl alcohol HBr CH3 CH3CCH2CH3 Br 2-bromo-2-methylbutane

CH3 CH3CCH2-OH2+ CH3 CH3 CH3CCH2+ CH3 1o carbocation CH3 CH3CCH2CH3 + 3o carbocation [1,2-CH3] 2. With PX3 ROH + PX3 RX

a) PX3 = PCl3, PBr3, P + I2 b) No rearrangements c) ROH: CH3 > 1o > 2o CH3 CH3CCH2-OH CH3 neopentyl alcohol + PBr3 CH3 CH3CCH2-Br CH3 2,2-dimethyl-1-bromopropane 3. Dehydration (later)

4) As acids. a) With active metals: ROH + Na RONa + H2 b) With bases: ROH + NaOH NR! CH4 < NH3 < ROH < H2O < HF CH3CH2OH + NaOH WA

WB CH3CH2OH + SA SB + NaNH2 SB + CH3CH2ONa SA CH3MgBr SA

CH3OH H2O SB CH4 + MgBr(OCH2CH3) WA NH3 WA + WB

CH3ONa WB 5. Ester formation. CH3CH2-OH + CH3CO2H, H+ CH3CH2-OH + CH3COCl CH3-OH CH3SO2Cl + Esters are alkyl salts of acids.

CH3CO2CH2CH3 CH3CO2CH2CH3 CH3SO3CH3 + HCl + + H 2O HCl O R C OH O R C

ONa O R C OR' ester carboxylic acid sodium salt O R S OH O O R S OK O sulfonic acid potassium salt O HO P OH OH

O HO P OR OH O HO P OR OR monoester diester phosphoric acid O R S OR' O ester O RO P OR OR triester "Lasso" chemistry O

+ R C O H O CH3C O H acetic acid H-O-R' + H+ O + R C O R' CH3 H-O CHCH3 isopropyl alcohol H+ H2O

O + H2O CH3C CH3 O CHCH3 isopropyl acetate acid chloride + alcohol --> ester O R C Cl O CH3C Cl + H-O-R' + H+ O + R C

O R' CH3 H-O CHCH3 acetyl chloride isopropyl alcohol H+ HCl O + HCl CH3C CH3 O CHCH3 isopropyl acetate O R S Cl O sulfonyl chloride + H-O-R alcohol

O R S O-R + HCl O sulfonate ester oxidation states of carbon - oxidation CH4 CH3OH CH2O -4 -2 0 reduction - HCO2H CO2 +2

+4 6. Oxidation Oxidizing agents: KMnO4, K2Cr2O7, CrO3, NaOCl, etc. Primary alcohols: CH3CH2CH2-OH + KMnO4, etc. CH3CH2CO2H carboxylic acid Secondary alcohols: OH CH3CH2CHCH3 O + K2Cr2O7, etc. CH3CH2CCH3 ketone Teriary alcohols: no reaction. Primary alcohols ONLY can be oxidized to aldehydes: CH3CH2CH2-OH + C5H5NHCrO3Cl pyridinium chlorochromate (PCC)

CH3CH2CHO aldehyde or CH3CH2CH2-OH + K2Cr2O7, special conditions Alcohols, synthesis: 1. 2. 3. 4. Hydrolysis of alkyl halides (CH3 or 1o) 5. 6. 7. 8. Alcohols, reactions: R-|-OH 1. With HX 2. With PX3 3. (later) RO-|-H 4. As acids

5. Ester formation 6. Oxidation

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