Ha Hc Hu C

TS Phan Thanh Sn Nam

B mn K Thut Hu C Khoa K Thut Ha Hc Trng i Hc Bch Khoa TP. HCM in thoi: 8647256 ext. 5681 Email: ptsnam@hcmut.edu.vn
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Chng 10: ALCOHOL-PHENOL Chng 10A: Alcohol

R-OH trong : R: no hay khng no CH3-CH2-OH CH2=CH-CH2-OH R: nhnh ca arene C6H5-CH2-OH
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I. Danh php
I.1. Tn thng thng (dng cho alcohol n gin) Gc alkyl + alcohol CH3-CH -OH (CH3)2CH-OH (CH3)2CH-CH2-OH (CH3)3C-OH C6H5-CH2-OH CH2=CH-CH2-OH ethyl alcohol isopropyl alcohol isobutyl alcohol tert-butyl alcohol benzyl alcohol allyl alcohol

C th gi CH3-OH l carbinol, cc alcohol khc l dn xut ca carbinol, v d: methyl carbinol 3 (ethyl alcohol)

I.2. Tn IUPAC Chn mch di nht c cha nhm OH lm mch chnh Ly tn alkane, i ane anol

nh s mch chnh t u gn nhm OH nht Khi c nhiu nhm th, sp xp theo th t alphabetical CH3-OH CH3-CH2-OH methanol ethanol
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CH3 H3C C CH2-OH CH3

2,2-dimethyl-1-propanol

CH3 CH3-CH-CH-CH3 OH

3-methyl-2-butanol

OH

7-ethyl-8,9-dimethyl-5-dodecanol

C6H5-CH2-OH

phenylmethanol
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II. Cc phng php iu ch

II.1. Cng hp nc vo alkene Phn ng cn xc tc acid: H2SO4, H3PO4 (khng dng HX)

CH3-CH=CH2 + H2O

H2SO4

CH3-CH-CH3 OH

Tun theo quy tc Markonikov

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Phn ng quan trng iu ch alcohol bc 1 & 2 t alkene, ngc vi sn phm Markonikov:

CH3-CH=CH2

1. B2H6 2. H2O2 / NaOH

CH3-CH2-CH2-OH

II.2. Kh ha carbonyl, carboxylic acid v dn xut Kh bng H2

R C R' O

+ H2

Ni

H R C R' OH

aldehyde alcohol bc 1 ketone alcohol bc 2

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 Kh bng LiAlH4, NaBH4 R-CHO + LiAlH4 R-COOH + LiAlH4 R-CH2-OH + R-CH2-OH

Kh bng [(CH3)2CH-O]3Al trong (CH3)2CH-OH R-CHO + [(CH3)2CH-O]3Al/(CH3)2CH-OH R-CH2-OH + (CH3)2CO

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II.3. i t hp cht Grignar

+ O CH3-CH2-MgBr + H C C H 3 + OH H3C C H C2H5 O-MgBr H2O /H+ H3C C H C2H5

+ HO-MgBr

II.4. Thy phn R-X, dn xut ca ester

O R C OR' + H2 O OHR-COO+ R'-OH

R-X + OH-

R-OH + X-

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III. Tnh cht vt l

R-OH to lin kt H to si cao hn cc dn xut ca hydrocarbon c khi lng phn t tng ng C1-C3: tan tt trong nc C4-C7: tan 1 phn trong nc >C7: khng tan trong nc
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IV. Tnh cht ha hc

IV.1. Gii thiu chung a. Kh nng t lin kt C-O Ch xy ra trong mi trng acid
R OH + H
+

+ H R O H

R+

+ H2 O

Kh nng phn ng: bc 1 < bc 2 < bc 3 C-OH cha nhiu nhm th y in t

12 thun li

b. Kh nng t lin kt O-H Ch xy ra trong mi trng base mnh

R OH

R-O

+ H+

Kh nng phn ng: bc 1> bc 2> bc 3 R cha nhiu nhm y in t khng thun li
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IV.2. Tnh acid-base Tnh acid ca alcohol rt yu Tnh acid: C2H5-OH (Ka 1.3x10-18) < H2O (1.3x10-14) < C6H5-OH (1.3x10-10) < CH3COOH (1.8x10-5) Alcohol hu nh khng phn ng vi NaOH

R OH

+ NaOH

R-ONa + H2O
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 Alcohol ch tc dng vi Na hay NaNH2

R OH R OH + Na + NaNH2 R-ONa + H2 R-ONa + NH3

Mui alkoxide l base rt mnh Tnh base: (CH3)3C-O- > (CH3)2CH-O- > CH3-CH2-O> CH3-O- > OH15

IV.3. Phn ng to ether

2 CH3-CH2-OH H2SO4 CH3-CH2-O-CH2-CH3 + H2O

2 CH3-CH2-OH

Al2O3 350-400 C
o

CH3-CH2-O-CH2-CH3

+ H2O

Alcohol bc 1: SN2 Alcohol bc 3: SN1 ***Danh php ca ether: tn gc alkyl + ether C2H5-O-C2H5 diethyl ether
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CH3-O-C(CH3)3 tert-butyl methyl ether

Nu gc alkyl phc tp, c th xem l nhm th alkoxy

CH3-CH2-CH2-CH-CH2-CH3 OCH3

3-methoxyhexane

CH2 OH
H3C CH3

CH2 OC2H5

2-ethoxyethanol

CH3-CH-CH CH3 OC2H5

2-ethoxy-2,3-dimethylbutane
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IV.4. Phn ng ester ha

R C OH O R C Cl O O R C O R C O + R'-OH H2SO4 R C O-R' O R C O-R' O + H2O

+ R'-OH

+ HCl

+ R'-OH

R C O-R' O

+ RCOOH

Kh nng phn ng: RCO-Cl (khng cn xc tc) > (RCO)2O (khng cn xc tc) > RCOOH 18

R'-OH + R C OH O + H O R' R C OH OH O R' R C OH + HSO4-H+

C ch phn ng:

+ H

+ R C OH OH

O R' R C OH OH2 + O R' R C O

-H2O

Kh nng phn ng: alcohol bc 1> bc 2> bc 3 HCOOH > CH3COOH > RCH2COOH > R2CHCOOH > 19 R3CCOOH

IV.5. Phn ng th -OH bi halogen a.Tc nhn HX

CH3-CH2-OH + HBr H2SO4 ZnCl2 CH3-CH2-Br + H2O CH3-CH2-Cl + H2O

CH3-CH2-OH + HCl

Kh nng phn ng: HI > HBr > HCl > HF HCl kh phn ng, cn xc tc ZnCl2 Lewis acid tn cng vo O lin kt C-O d t Kh nng thay th: bc 3 > bc 2 > bc 1
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b. Tc nhn PX3, PX5, SOCl2

R-OH R-OH R-OH

+ + +

PCl3 PCl5 SOCl2

pyridine pyridine pyridine

R-Cl R-Cl R-Cl

+ H3PO3 + POCl3 + SO2 + HCl

+ HCl

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IV.6. Phn ng dehydro ha v oxy ha a. Phn ng dehydro ha

R-CH2OH Cu 200-300 oC R-CHO + H2

R R C H OH

Cu 200-300 C
o

R C R O

+ H2

CH3 CH3-C-CH2-CH3 OH

Cu 200-300 oC

CH3 CH3-C=CH-CH3

+ H2O
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b. Phn ng oxy ha Tc nhn oxy ha: KMnO4, K2Cr2O7, CrO3 Alcohol bc 1 aldehyde carboxylic acid thng i

Rt kh dng li giai on aldehyde thng n RCOOH

R-CH2OH + KMnO4 R-COOK H+ RCOOH

+ MnO2 + KOH

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 Mun dng li giai on aldehyde: phi dng pyridinium chlorocromate C5H5NH+CrO3Cl- (PCC):
R-CH2OH C5H5NH+CrO3ClCH2Cl2 RCHO + Cr3+

Alcohol bc 2
(H3C)3C OH Na2Cr2O7 CH3COOH, H2O to

ketone
(H3C)3C O

Alcohol bc 3 ch b oxy ha trong acid (tch nc thnh alkene oxy ha ct mch alkene)
CH3 CH3-C-CH2-CH3 OH KMnO4 H2SO4, t
o

H3C C CH3 O

+ CH3-COOH
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Chng 10B:

Phenol

-OH lin kt trc tip vi nhn thm

o

1,36 A

109 o

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I. Danh php
OH OH CH3 CH3 OH OH

phenol

o-cresol

m-cresol

CH3

p-cresol
OH OH OH OH O2N OH OH NO2 OH NO2

Tn thng thng

catechol
OH OCH3

resorcinol

hydroquinone
OH CH(CH3)2

picric acid
OH

OH

H3C CH2CH CH2

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eugenol

Thymol

-naphthol

-naphthol

Tn IUPAC
OH OH OH CH3 Br OCH3 Cl Cl

4-methoxyphenol

3-bromo-4-chlorophenol 5-chloro-2-methylphenol

OH OH

OH

OH

OH

OH

1,2-benzenediol

1,3-benzenediol

1,4-benzenediol

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II. Cc phng php iu ch

II.1. Chng ct nha than Ly phn on 170-240 oC Tch phenol bng cch chuyn thnh phenolate ha tan Hon nguyn phenol C6H5ONa + CO2 + H2O C6H5OH + NaHCO3
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II.2. Thy phn chlorobenzene

Cl + KOH 300 oC 280 atm OH + KCl

Khng xy ra iu kin thng II.3. Phng php kim chy

SO3H + NaOH R 300 oC ONa + Na2SO3 H+ OH
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II.4. Oxy ha cumene (dng trong cng nghip)

CH(CH3)2 O2

OH O H3C C CH3 H2O, H+ cumene hydroperoxide

OH + H3C C CH3 O

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II.5. Thy phn mui diazonium (phng TN)

N+ N Cl+ H2O 40-50 oC OH + N2 + HCl

iu ch mui diazonium:
NH2 + NaNO2 + HCl N+ N Cl+ NaCl + H2O

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III. Tnh cht vt l +C ca OH vi nhn thm O-H phn cc mnh

kh nng to lin kt H ca phenol > alcohol to si , to nng chy, ha tan trong nc > alcohol tng ng phenol tosi (oC) 180 tonc 41 ha tan (g/100g H2O)9.3 cyclohexanol 161 25.5 3.6
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IV. Tnh cht ha hc

O H

IV.1. Tnh acid

O-H phn cc
OH NaOH OH Na ONa + H2

tnh acid > HOH > alcohol

ONa + H2O

Tnh acid: phenol < H2CO3 : C6H5ONa + CO2 + H2O C6H5OH + NaHCO3
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So snh tnh acid ca 1 s phenol:

OH > pKa NO2 7.15 OH > 10.08 CH3 CH3 OH NO2 > NO2 7.23 OH > 10.14 8.4 OH CH3 OH

OH
10.28

OH > OCH3 OCH3 >

OH

9.65 OH Cl >

9.98 OH > Cl 9.02

OCH3 10.21 OH

8.48

Cl 34

9.38

IV.2. Phn ng to ether Khc vi alcohol

OH + C2H5OH H+

OH +

OH H+

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 Gii thch:
CH3-CH2-OH H+ + + H CH2-CH2-O H

O H

+C ca OH lm gim mt in t ca O khng c kh nng tn cng vo oxonium cation khng c SN2

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 Ngoi l:
OH + CH3OH O-CH3 + H2O methyl ethyl ether /nerolin

H2SO4

Mt in t O trn naphthol > trn phenol iu ch ether ca phenol bng phng php Williamson:
ONa + C2H5-Br O C2H5 + NaBr
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ONa + CH2=CH-CH2-I

O CH2

CH

CH2 + NaBr

ONa +

O CH3 H3C O O S H3C O O I O + +

Na O O S H3C O O

ONa

+ NaI
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 Lu : iu ch C6H5-O-C2H5 , cn i t C6H5ONa+ C2H5-Br nhng khng i t C6H5-Br + C2H5ONa Ether ca phenol c th b ct mch:
OCH3 57% HI 120-130 oC OH + CH3I
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IV.3. Phn ng ester ha Khc vi alcohol

OH + CH3COOH H+

Phi dng dn xut chloride hay anhydride ca carboxylic acid

OH + H3C C Cl O acetyl chloride O C CH3 O + HCl
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OH + C6H5 C Cl O benzoyl chloride OH +

O C C6H5 O + HCl

O H3C C O H3C C O

O C CH3 O + CH3COOH

Lu :
O C C2H5 O OH O C OH C2H5 + O C C2H5
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AlCl3 t
o

IV.4. Phn ng th nhm OH Khc vi alcohol

OH + X-

Ngoi l:
OH O2N NO2 + PCl5 NO2 NO2 O2N Cl NO2 + POCl3 + HCl

OH Zn 400 C
o

+ ZnO

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IV.5. Phn ng th i in t -OH (+C>-I) vng thm tham gia SE d dng, sn phm o-, p Halogen ha
OH + Br2 H2O -HBr Br OH + Br2 CS2 -HBr Br
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OH Br Br

OH Br +

OH

 Nitro ha phenol: Khng cn H2SO4, xy ra to thng, ng phn od tch bng chng ct li cun hi nc
OH HNO3 OH NO2 + NO2 35% 65%
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OH

 Sulfo ha
OH SO3H OH H2SO4 15-20 oC H2SO4 100 oC OH

100 oC

SO3H

Friedel-Crafts: thng cho hiu sut thp (cn dng xc tc HF, H3PO4)
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IV.6. Phn ng Kolbe (trong cng nghip)

O-Na+ + + O C O 125 oC 4-7 atm O O H C

ONa

OH O C

ONa

H+

OH O C

OH

Sn phm ph l p-hydroxybenzoic acid, c th tch khi salicylic acid bng chng ct li cun hi nc 46

IV.7. Phn ng vi formaldehyde Trong mi trng base:

O+ H + C O H SE HOCH2OH OH H+ + CH2OH OH CH2OH O+ OCH2OH

Trong mi trng acid:

OH OH H + C O H H+ H+ C OH H + SE CH2OH

OH CH2OH

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