HOAÙ HOÏC HÖÕU CÔHOAÙ HOÏC HÖÕU CÔOrganic ChemistryOrganic Chemistry

CHÖÔNG 10 (t.t)ALCOHOLS & PHENOLS

Mendeleev Hamilton Hartree

GIÔÙI THIEÄU CHÖÔNG

10.1. RÖÔÏU10.1.1.DANH PHAÙP & ÑOÀNG PHAÂN10.1.2.CAÙC PHÖÔNG PHAÙP ÑIEÀU CHEÁ10.1.3. TÍNH CHAÁT10.1.4.ÖÙNG DUÏNG

10.2. PHENOL10.2.1. DANH PHAÙP & ÑOÀNG PHAÂN10.2.2. CAÙC PHÖÔNG PHAÙP ÑIEÀU CHEÁ10.2.3. TÍNH CHAÁT10.2.4. ÖÙNG DUÏNG

DANH PHAÙP

OHCH3

Br

4-Bromo-3-methyl-phenol

OH

CH2CH2OH

o-(2-Hydroxyethyl)phenol

(o = ortho(1,2), m = meta(1,3), p = para(1,4))

2-(2-Hydroxyethyl)phenol

OH

salicylic acid

O OH

OH

CH2OH

saligenin

OH

O OCH3

methyl salicylate

vanillinHO

H3COH

OOH

HO OH

COOH

gallic acidCOOH

OH

shikimic acid

HO OH

- 6 1C C : Alcohol, Aldehyde, Acid

OH

phenol

OH

OH

catechol

OH

OHHO

phloroglucinolOH

HO OH

pyrogallol

OH

OH

resorcinol

6C

OH

OH

orcinolH3C

COOH

HO ferulic acidOCH3

COOH

HO caffeic acidOH

COOH

HOp-coumaric acid

COOH

cinnamic acid

- 6 3C C : Phenylpropanoid

C6-C3 : Coumarin, ChC6-C3 : Coumarin, Chromoneromone

O

Ochromone

O

OH

H3CO CH3

Oeugenin

O O

coumarin

O OHO

HO

aesculetin (esculetin)

- ::::::::::::64- ::::::::::::64

neneO

O

naphthoquinone

OH

OH

O

O

lawsone

OH

O

O

CH3

plumbagin

C6-C1-C6 : XanthonesC6-C1-C6 : Xanthones

O

HO

O OH

OCH3

gentisin

O

Oxanthone

Gentisin GentisinGuttiferaGuttiferaee

Gentian r Gentian rootoot

C6-C1-C6 : XanthonesC6-C1-C6 : Xanthones

O

O

OHHO

HO

OH

OH O

OH

OHHOH2C

mangiferin

O

Oxanthone

Mangiferin Mangiferin CratCrat oxylem pruniflor oxylem pruniflor

umum Swertia chirata Swertia chirata HypericumHypericum -Anti inflammato-Anti inflammato

ry, antihepatoto ry, antihepatoto xic, antiviral xic, antiviral

C6-C2-C6 : StilbenesC6-C2-C6 : Stilbenes

HC

HC OH

HO

HO resveratrol

HC

HC

stilbene

Resveratrol ResveratrolArachis,Cassia, Arachis,Cassia, Eucalyptus, Eucalyptus, Polygonum, Polygonum, VeratrumVeratrum

Antioxidant, Antioxidant, anti-anti-inflammatory, inflammatory, anticancer, anticancer, coronary heart coronary heart diseasedisease

C6-C2-C6 : StilbenesC6-C2-C6 : Stilbenes

HC

HC OCH3

HO

O rhaponticin

OH

C6H11O5

HC

HC

stilbene RhaponticRhapontic

in inRhapontic Rhapontic RhubarbRhubarb

Blue in Blue in ultravioletultraviolet

- - 6 2 6C C C : Anthraquinone- - 6 2 6C C C : Anthraquinone

Oanthraquinone

O O

O

OH

CH3

OH

HO

emodin

C6-C3-C6 : FlavonoidC6-C3-C6 : FlavonoidO

O flavonol

O

OH

OH

OH

HO

OH

O

quercetin

OH

O

O

isoflavone

O

OHOOH

HO

genistein

(C6-C3)(C6-C3)22 : Lignans : Lignans

OH OH

magnolol

Magnolia officinali Magnolia officinali s s

M. obovata M. obovata MagnoliaceaeMagnoliaceae CNS depressant, CNS depressant,

muscle relaxant, a muscle relaxant, a ntiplatelet, antimi ntiplatelet, antimi

crobial, anticancer crobial, anticancer , insecticide , insecticide

(C6-C3)(C6-C3)22 : Lignans : Lignans

HO

HO

O

O

H

COOH

H O

HOOC

O

OH

OH

chicoric acid

caffeic acid derivative caffeic acid derivative Echinacea angustifolia Echinacea angustifolia, E. purpurea, E. purpurea (C(C

oneflower) oneflower) Compositae (Asteraceae) Compositae (Asteraceae) immunostimulantimmunostimulant

Ginkgo s Ginkgo spppp

HypericuHypericu m spp m spp

Rhus spp Rhus spp

O

O

O OH

OH

OH

OOH

HO

HO

amentoflavone

(C6-C3-C6)(C6-C3-C6)22 : Biflavono : Biflavono

idid

(C6-C3-C6)(C6-C3-C6)22 : Biflavon : Biflavon

oidoid

Have activity against influenza A v Have activity against influenza A v - - irus, HSV 1 and HSV 2 viruses - - irus, HSV 1 and HSV 2 viruses

O

OH

O

OH

O

O

HO

OHOH

HO

robustaflavone

::::::::::::::::

Capsicum annuum Capsicum annuum ((พริ�กหยวกพริ�กหยวก),), C C.. frutesce frutesce ns ns ((พริ�กขี้��หนู�พริ�กขี้��หนู� ) )

SolanaceaeSolanaceae Counter irritant, relief of pain in osteoar Counter irritant, relief of pain in osteoar

thritis, post herpetic neuralgia and pain thritis, post herpetic neuralgia and pain ful diabetic neuropathy ful diabetic neuropathy

CH2NHCO(CH2)4CH=CHCH(CH3)2

H3CO

HO

capsaicin (vanillyl amide of isodecenoic acid)

Uva Ursi / Bearberry lUva Ursi / Bearberry leaveseaves

-Arctostaphylos uva ursi -Arctostaphylos uva ursi EricaceaeEricaceae diuretic, astringent, urinary a diuretic, astringent, urinary a

ntisepticntiseptic

O-C6H11O5

OH

H2O+

OH

OH

+ C6H12O6

glucose

hydroquinonearbutin

::::::::ee Thymus vulgaris, Thymus vulgaris,

T. zygis T. zygis LabiataeLabiatae volatile oil 1 .2 % (t volatile oil 1 .2 % (t

- 3655hymol %, car - 3655hymol %, car -14vacrol %) -14vacrol %)

antiseptic, antitus antiseptic, antitus sive, expectorant sive, expectorant

export : Spain export : Spain

H3C CH3

OH

CH3

H3C CH3

CH3

OH

thymol carvacrol

Clove( Clove( กานพลูกานพลู)) Syzygium aroma Syzygium aroma

ticum (Eugenia c ticum (Eugenia caryophyllus)aryophyllus)

MyrtaceaeMyrtaceae -142volatile oil -142volatile oil

1 8% (eugenol 1 8% (eugenol-495-495

flavouring agent flavouring agent , stimulant, antis , stimulant, antis

epticeptic

bbb b b: bbb b b: bbb, bbb,

onesia, Brazil onesia, Brazil b b bbbbb: b b bbbbb:

bbbbbbbb, bbbbbbbb, b b bbb: b b bbb:

gascar, Tanzania, I ndonesi a gascar, Tanzania, I ndonesi a

H3CO

HOeugenol vanillin

HO

H3COH

O

Opt : phenol content low, use in pharmacy

Strong : phenol content high , use in the manufacture

of vanillin

- Medicinol (clove) oil has a phenol content 8 5 9 0 %

Deterioration

Gi ngerGi nger Zingiber officinale Zingiber officinale bbbbbbbbbbbbbbbbbbbbbbbbbb bbbb bbbbbb bbbbbbbbbb b( bbbb bbbbbb bbbbbbbbbb b(

bbb bbbbbbb bbbbbbbb) bbb bbbbbbb bbbbbbbb) pungency of ginger pungency of ginger inhibit prostaglandin synthetase ( inhibit prostaglandin synthetase (

-Anti inflammatory)-Anti inflammatory) bbbbbbbbbbbb bbbbbbbbbbbbbbbbbbbbbbb bbbbbbbbbbb

O

H3CO

HO

OH

(CH2)NCH3

gingerols n=4,6,8

CAÙC PHÖÔNG PHAÙP ÑIEÀU CHEÁ PHENOL

CAÙC PHÖÔNG PHAÙP ÑIEÀU CHEÁ PHENOL

+ HO

H

OH

+ +H

OH

HO-

1. Why does the reaction shift to the right?

2. Why is phenoxide ion stable?

3. Why is phenol acidic (compare to water)?

…….

Resonance, Stability, Acid StrengthResonance, Stability, Acid Strength

1. Resonance structures implies stability.

2. Stable anion implies the following reaction will proceed to the right,

+ + +H

OH

HH

OH

OH

O-

3. Stable anion also implies that phenol is a stronger acid than water.

O- O- O- O

-

O

-

OH

Which one is more acidic and why?

Substituted Phenol

OH

NO2

OH

NO2

OH

NO2

OH

N

O

O+

OH

NO2

To examine the acid strength,

OH

N

O

O+

-H+ O

N

O

O+

Resonance, Stability, Acid StrengthResonance, Stability, Acid Strength

2. Fifth structure shows that nitro is an electron-withdrawing group.

O

N

O

O

-

+

1. O

N

O

O+

has more resonance structures thanO

,so it is more stable.

3. Since 1 is true, that meansOH

N

O

O+

is more reactive thanOH

.

4. Since 3 is true, OH

N

O

O+

is more acidic thanOH

.

5. See page 663 for para position effect.

O

N

O

O

-O

N

O

O

- O

N

O

O-+ + +

O

N

O

O

+-

O

N

O

O+

Resonance, Stability, Acid StrengthResonance, Stability, Acid Strength

1. Phenol is more acidic than p-methylphenol.

OH OH

CH3

pKa 9.95 10.17

2. pKa indicates that CH3– is an electron-donating group.

Arrange the order of acidity (from highest to lowest) of the Arrange the order of acidity (from highest to lowest) of the following compounds and explain why.following compounds and explain why.

OH

NO2

OH

OMe

OH

Answer

Key

4-nitrobenzylphenol(most acidic)

phenol 4-methoxylphenol(least acidic)

Reason: The nitro- on 4-nitrobenzylphenol is an electron-withdrawing groupwhich enhances the aciditiy compare to phenol. The methoxy- of4-methoxylphenol is an electron-donating group, thus it is less acidic thanphenol.

OH

NO2

OH

OMe

OH

+

PHAÛN ÖÙNG THEÁ AÙI ÑIEÄN TÖÛ CUÛA PHENOL

PHAÛN ÖÙNG THEÁ AÙI ÑIEÄN TÖÛ CUÛA PHENOL

PHAÛN ÖÙNG THEÁ AÙI ÑIEÄN TÖÛ CUÛA PHENOL

PHAÛN ÖÙNG THEÁ AÙI ÑIEÄN TÖÛ CUÛA PHENOL

ACYLATION OF PHENOL

ACYLATION OF PHENOL

ACYLATION OF PHENOL

ACYLATION OF PHENOL

ACYLATION OF PHENOL

PHAÛN ÖÙNG KOLBE-SCHMITT

PHAÛN ÖÙNG KOLBE-SCHMITT

PHAÛN ÖÙNG KOLBE-SCHMITT

PHAÛN ÖÙNG KOLBE-SCHMITT

PHAÛN ÖÙNG TAÏO ARYL ETHER

PHAÛN ÖÙNG OXI HOÙA PHENOL

PHAÛN ÖÙNG OXI HOÙA PHENOL

PHAÛN ÖÙNG OXI HOÙA PHENOL

CHAÁT ÑOÄC DA CAM VAØ DIOXIN

CHAÁT ÑOÄC DA CAM VAØ DIOXIN

CHAÁT ÑOÄC DA CAM VAØ DIOXIN

CAÛM ÔN SÖÏ THEO DOÕI CUÛA CAÙC BAÏN

CHUÙC MOÏI ÑIEÀU TOÁT ÑEÏP