ALLEN

7 Chemistry HandBook

HALOALKANE
HC-CH-OH PCL NaBr+HS0, H,C-CHOH
3 H,C-CH2-OH PCl HI
KI/HPO, H,C-CH-OH
3 H,C-CH-OH Red P Br NBS
CCL HC-CH-CH2
H,C-CH-OH SOCl CH-X ClL/hv
alyfic substitu bon)

SOCl2
CH,-CH-x CH-CH,
H,C-CH-OH R-X HBr
SN X-FCI, Br, ) CC CHCH,
H,C-COAg Nal
CC. H,C-CH5-CI
Hunsdiecker Reaction) Acetone (Finkelstein Reaction)

H,C-CHOH HC/ZnClL
Lucas Reagent AgF or HgF, H,C-CH-CI
(Swart reaction)

Br HBr
Peroxide
HBr Br
HC-CH-CH, CC HC-CH-CH
Br Br,/800K HCI C
CH CHCH, HC-CH=CH2 H,c-CH-CH,
Br NBS
Br/CC, H,C-ÇH-CHBr
CHCHCH, CCl Br

Nucleophilic substitution
S1 3>2>1 CH-X (Reactivity order)
(R>R-Br>R-a>R-
S,2 1>2>3 CH-CHX Ambident NucdeophideN. õ-N=O
p*******aannsn* ************ R-X
(X=FCI, Br, )
*****s*a*************************sasa
HC-CH-1 N
-aron H,C-CH CHCH3
reacuon
Et,O
O
Aq KOH
HC-CHOH
HC-CHCH CH4 GHCli
Corey house synthesis
Moist AsOO

HC-CH-NH2 WAurtz-itug
Reaction
H Na/EtO
RCN

EOH HC-CHCEN
AgCN
H,c-CH-CEC-HH-CE N CH, MgBr Mg/EO HC-CH NET
AHF0 KO N-O HC-CHO-N=Op
HC-CH-H Alc. KOH
(1,2 not 3R-X) HC=CH
NaBH/EOH->2°& 3not 1 R--X AgON-O HC-CH;N
HC-CH-SH
HC-HN NaNO,
DMF
CH-CH
FC. Alkylatin
H-O-CH ******i H,C-CH-S-CH CHSNa
R-Br>19 CH-CHONE
RMgX R-R

RCOOCH
PHYSICAL PROPERTIES (3)Boiling point R-I>R-Br>R-CDR-F|
: (4) Density:
n-CH,Ckn-CH,Br<n-C,HI
(1)Dipole moment CH-Cl>CH,-F>CH,-Br>CH Y Br
(5) Solubility >
sligthly soluble in water

2) Bondenthalpies CH-F>CH, CI>CH, Br>CH1 Br

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CHAPTER
ALLEN

TRI-HALO ALKANE

OH O O-C +HC
CI,+NaOH Light
CH-&R or H,C-H-H or NaOCl Cl
(Haloform test)
O
HNO Cl,C-NO2
CaOCl2
(Chloropicrin) (tear gas)
HC-C-CH Beachtng powder

NaOH CHC1 AgA HCEC-H

Ci,c--H H-CONa Chloroform

Fe/HCI NaOH
CCl OH
Reimer Tiemann
reaction

3Cl/hv CI1,NI, CH N=C

CH- (Test of Primary amine)

HALO-ARENE
CI
Conc. HNO+ Conc. HSO, Ci/FeCl CI

NO, (ESR)
(ESR)

NO Cl

Ph
HC Ph-Br
CH,CI
AlCl (ESR) Na/Et,O
Fitlg Reaction

CH
CHBr
HC- Cl Na/Et,O O
Wurtz-Fittig Reaction
AlCl3 (ESR
oCH NH,
NaNH
C-C=o NH3
CCN O Conc. H,SOP
(ESR) ArSN

DDT OH
(Dichloro diphenyl trichloro ethane) (1) NaOI 1. 623K, 300 atm
(2) H
Ni-Al
NaOH
Conc. HSO,
ON NO2H.O O,N Q-HNO,|
SOH (ESR) warm

NO2
NO
So.H

(A) Reactivity toward Nucleophilel B) Boiling point

(C) Melting point
C Br Br C C1

NO2 NO2 NO, NO2 C

CI CI
NO, O,N
NO, NO

NO NO CI

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GRIGNARD REAGENT
REACTION
GRIGNARD REAGENT as Nucleophile

R--0-H C-0 R-C-OEt OH

HO RMgX in excess/H0
R--R
R
H-C-H
(1) R-CH-H R-C-CI
H,0 R-C-R
OH leq. RMgX

0-H Hc-C-H
(2) R-CH-CH R-C-CI OH
H,0 RMgX in excess/ H,0 R-C-R
R
0-H R-C-R
R-C-R R-CEN
R--R
R
HO H,0

H-C-R
H-C-OEt OH
leq.
HO R-CH-CH
OH OMgBr RMgBr -
R-CH-R H-C-R H-C-OEt R-CH-CH,
R
RMgX in excess RMgK itH,0 R-CH-CHR

R-C-OEt
R-C-R R-O-H
leq..RMgX H,0
-OEt
0-H Q-H
R-C-R OEt Cl-C-C
R H0 RMgX in excess /H0+ R-C-R
R

eRMgx
q Cl-CEN
R-CEN+MgaBr
R-C-C Cl-C-CI

Cl-C-OCI 2 eq. Cl-NH2 Br

R-C-R
RMgx R-NH, +MgC

GRIGNARD REAGENT as BASE

(Active H-containing compound)

MglOH)Br + R-H- H-O-H H-N-R NH-R

R-H+Mg.
Br
R
MglOR)Br + R-H R-0-H
HN-R
R-H +Mg
D-0-D
Mg(OD)Br+ R-D RMgBr
R-CEC-H
R-H +R-C:CMgBr
MgBr+R-H
H-NH,
MgNH JBr+R-H R-H+ MgBr

149