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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
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)
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
+ 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
-
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
+