IMPORTANT REAGENTS AND REACTIONS

1. KOH (alc.) & Et3N Et = C2H5

(Satzaff Elemination) KOH (alc.)
(Hoffman Elemination) Et3N

Dehydro halogenation
KOH
CH3CHCH2CH3 CH3CH=CHCH3
alc.
Et3N (Major)
x
CH2 = CH CH2CH3 (Major)

In open chain main product is trans.

But in cyclo main product is cis.

H2 / Pd H2 / Pd
2.1 (A) (B) B2H6 (C) Ni2B (P-2 catalyst) (D)
CaCO3 BaSO4
Reduction of Alkyne to give cis alkene by these reagents
H H
CH3C CCH3 " CH3C = CCH3
cis

2.2 (A) Li, in NH3 (B) Na in NH3

Reduction of alkyne to give trans alkene.
H
|
CH3C CCH3 " CH3C = CCH3
|
H

3. NBS (NBromo Succianamide)

Allylic free radical attacker

Br
|
NBS
CH2 = CHCH3 CH2 = CHCH2

CH2 = CH2 " X no reaction

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4. B2H6 Hydroboration
For reduction, Oxidation and Increasing chain.
BH3 / OH
H 2 O2
Hyboration Oxidation (HBO) Markonikov

BH2 H2O2
RCH = CH2 (RCH2CH2)3B RCH2CH2
OH
|
H+ AgNO3/NaOH
OH
RCH2CH3 RCH2CH2CH2CH2R

5. Sia2BH/ACOH
Less substituted alkene is reduced.

''

6. Cu or ZnO / 3000C Oxidation

1 alcohol aldehyde 2 alcohol ketone 3 alcohol alkene

7. Aq. KOH or AgOH or moist Ag2O

Halogen is replaced by OH
"
RX
ROH

Cl OH H2O
C '' C >C==O
Cl OH

Hg(OOCCH3 )2 / OH
8. Mercuration and Demercuration
NaBH4

Mercuration and Demercuration addition of OH on alkene according to Markoni

Kov. without rearrangement.

24
9. Dil. H2SO4 or Conc. H2SO4+ H2O
Hydrating Agent (Hydrolysis)

OH
|
CH3CH = CH2 '' CH3CHCH3
Rearrangement is there according to Markoni-Kov Rule.

10. Br2 (Liquid)

trans addition
cis alkene + Br2 Racemic mixture
trans alkene + Br2 Meso Racemic.

11. CHCl3/tBuO K+ or NaOH (50%)

CCl2 addition to alkene

HC CH
'' CCl2
HC CH

12. LUCAS REAGENT

HCl (Conc.)/ ZnCl2 (anhy.)
Used for differenciate between P, S & T alcohols and order is as : T > S > P

13. Soda Lime (NaOH + CaO)

R C*OOH R H + Na2C*O3
NaOD
RCOOH R D + Na2C*O3
De-carboxylation
OH
R " ROH

COOH
14. Zn-dust
CH = CHOH, OH is removed. Vinylic alcohol gives up OH
Zn
OH
dust

25
 COOH COOH

"
OH

CH2 CH2 " CH2 = CH2

| |
Cl Cl
Cl Cl
CHCH " CH CH
Cl Cl

15. CH2I2/CuZn

: CH2 addition to alkene

16. Isomerisation
For Alkane Use AlCl3/HCl
Alkene Use Al2(SO)4
For
KOH (alc.)
1-alkyne to 2-alkyne
Alkyne
NaNH2
2-alkyne to 1-alkyne
KOH (alc.)
CH CCH2CH3 CH3C CCH3
NaNH2 Paraffin

CH3
|
AlCl3
CH3CH2CH2 CH3 CH3CHCH3
HCl
Butane

Singlet
17. : CH2 (Carbene)
Triplet

CH2N2 :CH2 + N2
"
CH2CO
:CH2 + CO

26
18. Important About RX

KCN
RCN
AgCN
RNC
KNO2
RONO
RX AgNO2
RNO2
KOH(aq)
ROH
THF
RH

19. Important About NH2 and HNO2

HNO
NH2
2
OH
HNO
RNH2
2
ROH
HNO
RCONH2
2
RCOOH

HNO
NH2CONH2
2
HO OH(H2CO3)
But in these cases
HNO
CH3NH2
2
CH3OCH3
HNO
C6H5NH2 2

NaNO /HCl C6H5N2Cl
2

NaNO +HCl
H2C = CHNH2
2
H2C = CHN2Cl

20. HINSBERGS REAGENT

SO2Cl

For the separation of 1o, 2o & 3o Amines.

1o Amine Nalkyl benzene derivation soluble in alkali.
2o Amine N, Ndialkyl benzene derivative insoluble in alkali
3o Amine No reaction.

SO2 Cl + H N SO2N

27
21. CANNIZZARO REACTION
Given by aldehyde with No -Hydrogen
It is redox reaction.
KOH
Alcohol + Acid salt
KOH*
2HCHO CH3OH* + HCOOK (Inter molecular)
KOH
COOK
| (Intra molecular)
CH2OH

CH3
Note : CHCHO with -Hydrogen give Cannizaro reaction.
CH3

22. CLAISEN CONDENSATION

NaOH
CHO + CH3CHO CH = CHCHO

One is aliphatic aldehyde or Ketone another is Aromatic.

Also known as Claisen Schemidt reaction.
CHO
|
23. CHLOROFORM TEST CHO
CaOCl2 / H2O (Bleaching powder)it used for chloroform formation.
NaCl(aq)Brine solution on electrolysis gives NaOH + Cl2 used for chloroform
test.
Weak reducer, reduces S and T alkyl halide to alkane and P alkyl halide No
reaction.

Halo Form Test is given by the groups

CHCH3 , CHCH3 , CCH3
| | ||
Cl OH O
Attacker for Iodoform test are I2 + NaOH, NaOI, I2 + OH, OI

28
24. PCl5 / PCl3 / SOCl2
PCl
5
ROH RCl + POCl3 + HCl
PCl 5
COOH COCl
PCl 5
ROR RCl
PCl 5
RCOOR RCOCl + RCl
Cl
PCl
5 >C
>C=O
Cl
Note : SOCl2 is best.

25. KCN, AgCN

KCN H3O+
RX RCN RCOOH
AgCN

H2O
RNC RNH2 + HCOOH

26. ALDOL CONDENSATION

Aldehyde or ketone with alpha-hydrogen atom will give this test.
CH3CHO CH3COCH3 HCHO

27. TISCHENKO REACTION

Aldehyde in presence of Al(OC2H5)3 give ester.
Al(OC H )
2 5 3 Esters.
All adehydes
Al(OC H )
2 5 3 RCOOCH R (Ester)
Ex. RCHO 2

28. BENZOIN CONDENSATION

KCN
Aromatic aldehyde Benzoin

29. HOFF-MANN BROMIDE REACTION

Br2
Acid amide
Alkali
Primary Amine

29
30. GATIERMANN REACTION
Benzene diazonium salt Cu/HX
X

31. AlCl3(Anhydrous)
For the generation of electrophile.
Cl
|
Cl2
AlCl3

32. REDUCING AGENTS (LiAlH4)

Strong reducer and reduces P and S alkyl halide to alkane. T to alkene
P Cl CH3 CH3
| | LiAlH 4
|
CH2CHCCH3 CH 3 CH = CCH 3
| | H+

Cl S Cl T

33. Zn / H+, Zn / OH (ZnCu/ether, or NaHg or AlHg / ether)

RX + 2H RH + HX (always alkanes)
34. Na/EtOH
"
>C=O
alcohol
"
RCN
RCH2NH2 (Mendivs Reaction)

35. NaHg / Conc. HCl

"
>C=O
> CHOH

36. HOFFMANN MUSTARD OIL

Reaction with CS2 + HgCl2
For separation between 1o, 2o and 3o amines
CS HgCl
RNH2
2
Positive
2
HgS (Black)
" "
RNHR
Positive
X (No reaction)
"
R N R X (No reaction)

|
R
Not given by aromatic.

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37. TRIDENT REACTION
NOCl Nitrosyl chloride gives this test
RNH2 RCl

Not given by aromatic.

38. FENTONS REAGENT

FeSO4 + H2O2
Used for separation between aldehyde and ketones

39. BENDICT SOLUTION

(CuSO4 + Na2CO3 , NaK Citrate)
Used for separation between aldehyde and ketones

40. ROSENMUND REDUCTION

Acid chloride gives aldehyde. RCOCl Aldehyde

Used for separation between aldehyde and ketones

41. TOLLENTS REAGENT

(AgNO3 + NH4OH)
Used for distinct between aldehyde and ketones
O
||
CH2CR also gives this test (-Hydroxy Ketone).
|
OH

42. ALLYLIC SUBSTITUTION BY Cl2/600oC

31
43. WURTZS REACTION
2Na
2RCl
dry ether

RR
CH4 is not prepared by this method.
Symmetric alkane is formed.
First alkane prepared by this is CH3CH3.
Alkyne halide with more then one carbon give by products e.g., CH3CH2Cl gives
CH3CH2CH2CH3, CH2 = CH2, CH3CH3.

Corey house is best method for preportion of alkane in case of symmetric or

unsymmetric alkane.

44. Peroxy Acids

H2SO5, HCOOOH, RCOOOH
It form ester on bulky side.
O O
|| ||
CH3CC2H5 "
CH3COC2H5
45. NaHSO3
It gives crystal formation with > C = O
Less reaction in aromatic carbonyl group.

46. RMgX (Grignard Reagent)

It reacts with hydrogen bonded with (SON)

S O N
| | |
H H H

32
 HO
RMgX RH
It reacts with

O O
RMgX
C OR C R
H3O+

O OH
RMgX
C R C R
H3O+
R
It reacts with

RMgX
RCN H3O+
RC==O
|
R

RMgX
CC H3O+
CCH
| |
O OH R

H O
CO2 + RMgX
3
RCOOH

47. FEHLING SOLUTION (CuSO4 + NaOH + Rochells salt)

It is a mixture of felhing A and B.
Used distinction between aldehydes and ketones.
HCOOH reduces it. RCHO reduces it C6H5CHO doesnt

give this test.

Test for 1-alkyne
CCH2
|| | -hydroxy ketone) also gives this test.
(
O OH

H2 / Pd
48. ROSENMUND REDUCTION By
BaSO4

" H /Pd
Acid chlorides
Aldehyde RCOCl
2
BaSO
RCHO
4

33
 Note :
OH O
| ||
CrO2Cl2

Phenol ||
O Quinone

OH O
| ||
CrO2Cl2
+ 2AgOH

Phenol ||
O Quinone

49. ZnHg / Conc. HCl (Clemmensen Reduction)

>C==O >CH2
ZnHg/HCl NH2NH2|C2H5ONa
Clemmensen Wolf-Kishner
Reduction Reduction
P/HI - Best ReducerIt can reduce acid and acid derivatives to alkane. This change is
not given by Zn-Hg/HCl and NH2NH2/C2H5ONa.

50. MOZINGO METHOD

"
>C==O
>CH2
CH2SH
| Et2O + BF3
CH2SH

51. SnCl2 / HCl or Sn / HCl

NO2 " NH2

34
52. Red P / HI
RCOR or RCOOH or RCHO or ROH gives alkane.

53. KHSO4 (Dehydration)

Alcohol Alkene
Glycerine Acrolene

54. Important Reactions

OH
|
1. + PCl5 " PO3 + 3HCl
3

CH3CHCH3 OH
| | O
||
2. + CH3CCH3
Oxidation

OH CH3 CH3
| | |
NH2 NO2 NO2
SnCl2 NH4HS
3. HCl

| | |
NO2 NO2 NH2

N2BF4 F
| |
D
4. N2 + BF3

NH2 O
| ||
air or
5.
oxidation
||
O

35