CHAPTER Chemistry HandBook

ALLEN

ALCOHOL
Di. H,SO, (EAR) Pd+H, or LIAIH,/NaB ,
CH,-CH H,O CHCHO
GMP
HglOAc)H,O Pd+H, or LIAIH,/NaBH,
CHCH
CH-CH NaBH CH,OH H,O
CH CH-OH
B.H THF (EAR
CH-CH, HONaOH
CH-CH-CH,OH LIAIH,/NaBH CHCCE
HO AE. NAR
CHCH-CH,
RMgX (NAR) OH
LAP SAE,NAR) CH OH|
CH-CHO H,O R-OH H,O
) Invertase LIAIH,
CHO+H,O
sucrose
(i) Zymase
HO S,AE,NARCH fCH

CH,
dil. CH-C-ÇH-CH,
CH OH CH,
CH-¢-CH-CH
( C H J , C - C H - C H B . H / T H F

H,0/NaOH CH,
OH
H CH HalOAc)/HO,
NaBH
CH,--CH-CH,
CH,OH

,O
1H-GH0H HC-¢-HHH CH-CHa CH-CHCH OH
Ho H,O
H Grignard OH
CHECH-CH
OH CH-H
Reagent CH-CH-CH-CH,
2H,C--CH HO
H
(NAR)CH,MgBr O/60°C
2CH,OH
OH
-2/HO
CH,- -CH, (NAR) OH
3CH-CCH,
CH, CHC-O CH-C-CH CH¢-CH
(SAE) (NAR) CH
OH
CH-C
3CH-C-CH, CH,-C-CH,S.AE H-COEt -H,C- -H HC-CH-CH
(SAE) H,O OH
CH, (NAR) Et,o Mg (NAR)
(dry
L CH-Br KOCH-OH

n < iso < neo (isomeric)

Solubility of alcohol increase with increase branching
in

Relative order of reactivity

2°> 1° (Dehydration)
(i) 1°>2°>3° (0-H bond fission) (i) 3° > 2°> 1°(C-O bond fission) (ii) 3°>

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 Chemistry HandBook CHAPTER

ALLN
ALCOHOL
PCl,
(NSR) Na CH,CH-ONa-
POCl+CH,-CH-Cl
H,PO,+3CH-CH-Cl- PCl, CHMgBrCH,+CH-CH,OMgBr9
SAE) CHCOHCH-C-0-CH-CH
H.PO,+3CH,-CH-Br PBr Conc. H,SO,

HCl+SO,+CH-CH-ClSOCl, (CHC >CH-C-0-CH-CH,

SAE)
OSO,+CH-CH-C
NH'C SOd/ HCl/ZnCh
Lucas Reagent -CHCI

(3-Alkene) CH-CHI Hlor CH-CH-Br

Ki/HPO, HBr
NaBr + H,SO, 13°R-0-H> Alkene

CH-0-CH CH SO,/A/140°Cc NH CH-CH-NH,

Al,O
CH-CH,
Conc. H,S0, AlLO, CH-CH,
170°C 620 K (Elimination)

CH-CHHSO, HSO Na
100°C CH-CH(19 CH,CH-0-CH-CH,

DEHYDROGENATIONS

H QH CH
Reagent H,C-CH-CH=H, H,C-CHCH-CH HCOH
1° Alcohol 2° Alcohol CH
3° Alcohol
PCC/PDC Anhy. CrO
HC-CH-CHC-H HC-CH C-CH, No reaction

K,Cr,0,/H
KMnO /H /0H/ A No reaction
Jones Rea gent_ H,C-CHCH-C-OH H.c--OH+CH--OH
Cu/500°C
H,C-CHCH-C-H CH-CH-C-CH H,C-C-CH
Lucas Reagent Cloudiness appear within five min. Immediately
HCVZnCl, upon heating after 30 mins.

VICTOR MAYER'S TEST

CH
P/l, CH CH CH CHH H,C-CHaCH-I H,C-c
CH
CH
AgNO CH-CH-CH-NO, H,C-CH-CH-NO0, (CH),CN0
CH
H,C-CHC-NO,
HNO N-OH H,C-CHC-NO, No reaction: Colourles5
N=O
Nitrolic acid Bluecolour
NaOH Red Color No reaction
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ALLEN- CHAPTER
Chemistry HandBook

GMP
F Reactions
2C,H-OH
wiliamson conunuous etherfication
H,SO,/140°C
ETHER 0 Q

(NSR) IS,2] Cl CI
Dark H,C-CH-0-¢H-H,
CI
HC-CHÖNa
Williamson synthesis]|3|R-X] Alkene]N CH-CH- HCI
(NSR) IS,2 HC-CHO-CH CH Cy,o C
H1
H.C-CH 0-CH
2CH Dry Ag,O (H1 HBr>HC
R-O-R HVco CH CHl+CH CH-OH
(NSR)
(Zisel Method)

CH-CHOCH, CH,N/BF HI/A

excess CH-CH+CH-CH

PHENOL
SONa GMP CH
6) NaOH (6) O2, hv HC-C-H
(i) H (i) H'H,O
-(CH,COCHJ

NCr H0/A OH
Cl
NaOH/Cu-Fe 300°C/200 atm

MgBr Aq. Na,CO,

O/60°C/A Dow's process)
HO/H PHENOL
H
COOH
NaOH+Ca0/A O] V205
OH 250°C

OCH, pCH,
OCH, OCH3
cOCH,
Br Br, in CH,C0OH CH,COC O O
Bromination OCH, AICl,
Friedel-Cralts reactionn
COCH,
Br OCH OCH,
OCH, pCH, conc. HSO NO
CH, AICl/CH,C conc. HNO
Friedel-crafts reaction (nitration)

CH 153
Chemistry HandBook CHAPTER

-ALLEN
PHENOL

60°C
C CH
Reactions O-CH3
NaOH
HC-C-Ca
O-CH
Fries
120C Rearangement CH,N
OH BF

+ NH
Zna 300°C
Zn
A
FeCl
3HCI+[(Ph,O).Fel3<
Violet Colour
Neutral PHENOL
PCIg +(Ph-0),PO
No effervences NaHCO major)

NaOH
Na,CO
Ph-C-Cl
-o--Ph
Schotten Baumann Reaction

OH
O,N NO2 OH
Conc. HNO,+H_SO, DI

H,O
2,4,6-Trlbromophenol
(major) NO Br
OH OH
OH Br2 Br
CS,
NaNO
HSO Br

RedHO OH
excess ssGreen | O N=O OH N

Conc. H,S0
SO;H
NaOH
Blue
OH 100C
NO2
Kolbes H125C CO,/NaOH
Schimdt SOH
Reactionn H
OH QH
QH CHOH
CH,-0
CC NaOH
NaOH Bakelite
poymer
CH,OH
OH
NENO-OH NaOH

-NeNCT CHCl
NaOH O
H Riemer Tiemann Reaction

OH OH
HO- O-OH Acetone
Conc. HCI
ZnCl,H0
HCN+HCI
Gatteman
Reaction

,AC
CHO
AcCl (major)
C-OHor OH
(AcO),O OH CO/NaOH
Aspinin 125°C
Phenophithalein NaOH (Pink cdouration
HO
OMe MeOH
OMeH
Na,Cr,O, CO,/NaOH QH OH
Oil of wintergreen
o o HSO 125CH
OHPOd Phenyl salicyiate

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154
 CHAPTER Chemistry HandBook
ALLEN.

Comparision Comparision
of of
S1 and S,2 E and E

Sl Sy2 E1 E2
REACTIONS
REACTIONS
1 order 2 order 2dorder
A Kinetics Kinetics 1 order
Rate kIRX k[RXI|B:]
B Rate
kRX RXINu: Anti-
C Stereochemistry No special
CStereochemistry| Kacemisation Inversion periplanar
geometry 3 2° >1°
Substrate 3°>2°>>>1°|
D Substrate 3° MeX
Rate Needs Strong
2°>1>MeX Base Strength
(reactivity) >1>2>3 Independent bases
Nucleophile Rate Needs Strong Polarity not
Solvent Good ionizing
Independent Nu import
Good ionizing Faster in aprotic Needs Good
F Solvent Leaving Group Needs Good

Needs Good LG | Needs Good LG LG LG

G LeavingGroup Not Possible
Possible
H Rearrangement
H Rearangement Possible Not Possible

Order of reactioity of
Summary of Sl, S2, E, and E, Reactions
20000000

Alkyl Halide towards

Mechanism Saluent
Nu/B SlBenzyic>Allylic>3°>2>1°
Better
Sy2
Low SlStability of carbocation
OH,CH,O Polar aprotic !S,2c 1° >2°>3
Strong & bulky base
E2 High
(CHs) CO
Low Steric hindrance
Sy2 HO;CH, O
Polar aprotc Reactivity order towards
E2 (CH3) CO High
2 S,1 or S,2 and E, or E,
(Lo)
S) (Solvent
Polar aprotic R-I> R-Br> R-Cl>R-F

(Sotvent) (High)
E1) With increase in number of strong
Protic Low at ortho
Sl Sotvent electron withrawing group
of
Solvent Protic High Iand para position, reactivity X,
El towards aromatic nucleophilic

Primary (1°) Secondaryv Tertiary (3)|

substitution increases.
(2)
S2+ E
(if weak base, E2 CI CI NO
S2 >>E2
Strong nucleophile S2 favored
Mostly Sy l at

Mostly Sy2/Sl low T mostly

Weak nucleophile weak ko, No, NO
Mostly Sy2 Elat high T ko,
base
Mostly E2 E2
Weak nucleophile strong Mostly E2
hase 155
 Chemistry HandBook CHAPTER
ALLE

& Ketone both

Freparation of Aldehyde
aq,KOH RCH,CHC
R-OHK.Cr0/H,SO
(1.29
H,SO RC CH
R-OH PCC Hg
(1.29
BH/THE RC-CH
Cu or Ag RCHO
R-OH
(1.29 300°C RCOR
HO/OH

R-CH-CH-R- HIO 2(RCOO).Ca

OH OH MnO 2RCOOH
R-CH-CHR HO/Zn O 300°C

Preparation of Aldehyde only

RCN
DIBAL-H CHCO,O/CrO
H,O/A
Ar-CH,
HO

RCOOR DIBAL-H CrO,Ch Ar-CH

HO HO(Etard reduction)
RCHO Cl/hv Ar-CH
ArCHO H,O

H/Pd CO+HCI
RCOCI anhyd AlC,
(Rosenmund Reduction) BaSO (Gatterman Koch aldehyde synthesis)

) SnCl./HCa HCN+HCI - O
RCN anhyd AlC
(Stephen's Reduction) i) H,O
(Gatterman aldehyde synthesis)

Preparation of Ketone only

RCd RCOCI

RMgX
RCN
H.O
RCOR
ArCOR

RCOa-
anhyd. AlCl,

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 Chemistry HandBook
ALLEN-

Reaction of Aldehyde & Ketone

HO H Partial
CH-OHMetal/H HCN OH
cONHhydrobss)
or LiAlH,
or NaBH
or Na+CH,OH
(NAR) CN OH (Complete
COOH drohats)

OH
Wolfreduction
kishnerCH, N(i)H , HCHO LAH CHNH
ÕH/A
NaHSO, OH

rectuctionCH,- H a / H a
Clemenson's H
ONa
Bisulphite compound
(White crystaline)

R
c-O ROH/H
OR
OH ROH/H
OR
OR

CH,Rei P/HI Hemi-acetal) (Acetal

Z-H-R-OH,-NH,

HC=CNa OH
(Acetylinic alcoho
NH-0)NHCONC-N-Z HNZ
NH-No,
CH
NO C RMgX OH
PCLor SOC (Alcohol

Reaction of only Ketone

CHC, CH OH (Chloretone)

CH CH CH
CHOH OHCH,
Mg-Hg
HO CHpaO
CH,
OCHCoOH+I Co,+HO
(Pinacol

Aldol Reaction (Aldehyde orketone withaH)

() 2CH,CHO dil. NaOH CH-CH-CH-CHO >CH-CH-CH-CHO
(Aldol condensation product)
OH
Aldol
CH CH
Na CH-CH,COCH, CHC-CH-COCH,|
Gi) 2CH,COCH, (Aldol condensation product
OH
Ketol

Cannizzaro reaction (Aldehyde with no a H)

conc. NaOH
2HCHO CH,OH+HCoONa
TESTS
Fehling's test
Tollen's test OH RCO0+ Cu.O+2H o
RCO0+2Ag +2H,0 + 4NH|RCHO
+ 2C1+5
(Given by Aliphatic akdehyde) (Red-Brown ppt.)
RCHO+ 2Ag(NH,)J +3 OH akdehyde)
aromatic
(Given by Aliphatic and
157
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