Chapter

HALOALKANE
PREPARATION Alkene)
(3
Al(3kene)
H,C-CH, OH PCl,
NaBr+H,SOA H,C-CH, OH
3H,C-CH,-OH PCl, HI
KI/HPO4 H,C-CH,-OH
3 H,C-CH,-OH Red P + Br NBS
CCl H.C-CH=CH2
(allylic substitution)
H,C-CH,-OH SOCl, CH CI,/hv
CH C CH,-CH,
H,C-CH,-OH SOCl2 HBr
(SN?) CCi,
CH,=CH,
H,C-ÇOAg Br,
CCI,
Nal
Acetone
H,C-CH,-CI
(Hunsdiecker Reaction) bund (Finkelstein Reaction)
H,C-CH, OH HCI/ZnCi,
Lucas Reagent
AgF or Hg,F,
H,C-CH, C
(Swart reaction)

Br HBr HBr Br
H,C-CH, CH, Peroxide
HC-CH CH,
Br Br80OK HCI
CH, CH=CH, H,C-CH=CH
H,C-H-CH
Br NBS Br/Cc, H,C-ÇH-CH,Br|
CH, CH=CH, CCI. Br
PHYSICAL
ERTIES
2) (4) REACTIONS
BondDipole synthesis
Corey
house CH,
CH-0-CH,H,C-CH,N 3°R-X)
(1°2°not H,C-CH,-NH, H,C-CHCEC-H
H-czCN H,C-CH;CH; Nucleophilic
substitution
alpies
moment H,C-CH,H
NaBH/EOH-->2° H,C-CHl
(R-Br 19 1>2>3
S2:3>2>1
S,1:
:
H,l CH,
CH,CH,0Na 3&
LiAlH,/Et,0 (C,H}Culi Acetone
excess
r>CH,l DMFNaNO2
not NH, Nal
1°R+X

Reaction with metal

Wurtz-Fittig
Reaction reactionWurtz

(3) H,C-CH,CH,CH, +
Boiling
H,C-CH;S-CH, H,C-CHH (X=FCI,Br, I)
point H,C-CH, SH
+ MgBr
C,H, CH
X
CHX
H,C-CH, R-X
Br
:
Br>R-CIbR-F|
Br
Na/Et,O Et,0 Na
KOHAlc. Mg/Et,O
CH,SNa NaSH
Alc.
Br B

(5) (4)
Solubility
Density
N=0KO Molst
Ag,0 KOH Aq Ambident
RCOO.. RMgX AICl, Ag-O-N=O AgCN EtOH KCN
ÖH
’ : (R->R-Br>R-C>R-F)
H,Br<n-C,
sligthlyH,I Nucleophile(Reactivity
:. order)
RCOOCH, R-R
soluble N
H,C-CH;H,C-CH;
0-N=0 H,C-CH;CENH,C-CH;OH
H,C-CH-GzC
AlkylationFC.
-CH,CH, N.
in
water Õ
N=O)
 TRI-HALOALKANE
QH C
CH--R or H,C-H-H Cl,+NaOH
or NaOCI 0- +HCI
(Haloform test) Lighi
CI
Ca0CI,
H,c--CH, Bleachtng powder
HNO,
+ Cl,C-NO,
(Chloropicrin)Reaction
(tear gas)

a,c--H NaOH

HçÕNa CHCI,
Chloroform
Ag
+ HCEC-H

Fe/HCI
CCl, NaOH
H
-OH
Reimer Tiemann
reaction
CH, 3CI,/Ahv CH,NH,
(Test of Primary amine) CH,G=
CI
Conc. HNO,+ Conc. H,SO,
HALO-ARENE
NO, CI/FeCl, C CI
(ESR)
(ESR)
NO, CI
C
Ph
H,C,
+ CH,CI
Ph-Br
AIC, (ESR) Na/Et,0
CH, Fittig Reaction
CI CI
CH,Br
H,C--CI Na/Et,O
AlCI, (ESRY Wurtz-Fittig Reaction
ozCH, NH,
-a
CCl,- =0 NaNH,
Ca lig. NH3
-C
Conc. H,SO, (ESR)
H ArSN
DDT
OH
(Dichloro diphenyl trichloro ethane)
(1)NaOH. 623K, 300 at1n
Ni-Al
(2) H
NaOH C
0-H (HSN)
C
SO,H Conc. H,SO, NO, H,0 O,N NO.,
A (ESR) warmn

SO,H
NO, NO,

(A) (Reactivity toward Nucleophile] (B) Boiling point

(C) Meltng pont
Bi
C C
(1) (0) C

NO2 CI
NO, NO,
C C
NO, O,N
(4) NO, (i)

NO, NO,
 GRGNARD REAGENT
REACTION
GRIGNARD REAGENT as Nucleophile

R-C-OEt
R--0-H C=0
H,0+ RMgX inexcess/H,0+
R-C-R

H-C-H R-C-CI
(19 R-CHH H,0* leq. RMgX
OH
OH
Q-H H,C--H R-C-CI R-Ç-R
(29 R-H-CH, H0* RMgX in excess/H,0+ R

Q-H R--R R-CEN

R-¢--R H,0* H,0*
R
OH
H-C-OEt
H0*
R-CHCH,
leq.
H
RMgBr R-C4CH
OH
R-CH-R
H,0* õMgBr
H-¢-R H-C--OEt R-H-CH,R
RMgX in excess
RMgX in H,0*
R

R- -0Et R-0-H
R--R leg. RMgX
H0*

O-H
0-H OEt R-¢-R
R-C-R RMgX in excess /H,0+
R
R H,0*

Cl-CN Br
C-C-CI 1eq. R-CN+ Mg-Cl
RMgX

Cl-NH, Br
2 eq.
RMgX
+R-NH, +Mg
R-C-R

GRIGNARD REAGENT as BASE

(Active H-containing compound)
H
H-N-R NH-R
R-H + Mg.
H-0-H Br
MgOH)Br + R-H R
R-0-H H-N-R R-H + MoNR
MgOR)Br + R-H + Br
D-0-D RMgBr R'-CEC-H
MglOD)Br + R-D R-H +R-C=CMgBr

MgBr +R-H
H-NH,
R-H + MgBr

Mg(NH)Br+R-H