N-Ethanamide Synthesis Overview
N-Ethanamide Synthesis Overview
1. Acylation :- Replacement of a hydrogen atom bonded to the nitrogen atom of ammonia or an amine or H atom of
C6H6 ringby an acyl group.
CH3CH2NH2 + CH3COCl CH3CH2NHCOCH3
ethanamine ethanoyl N-ethanamide
chloride
Pyridine
C6H6 + CH3COCl C6H5COCH3
2. Aldol Condensation :- Condensation reaction between two molecules of a carbonyl compound (aldehydes or
ketones) containing - hydrogen atom in the presence of dilute akali. For example, acetaldehyde (ethanal) gives a -
hydroxy aldehyde.
O OH O
NaOH
2CH3 C H CH3 C CH2 C H
ethanol
H
3-hydroxy butanal (Aldol)
3. Alkylation :- Replacement of a hydrogen atom bonded to the nitrogen atom of ammonia or an amine or H atom of
C6H6 ring by an alkyl group. Methylation is replacement by a methyl group.
CH3
OH −
CH3 - CH2 - NH2 + CH3I CH3 - CH2 - NH + H 2O
ethanamine iodomethane N-methyl ethanamine
FeCl 3
C6H6 + CH3Cl C6H5CH3 + HCl
4. Acyloin Condensation :- Acyloin is -hydroxy ketone. Acyloins are produced when aliphatic carboxylic esters
perfectly methyl or ethyl esters are treated with sodium in an inert solvent like ether, benzene or toluene followed by
treatment with acid.
Na + ether
2CH3COOC2H5 CH3 – C – C – CH3 + 2C2H5Ona
O O
disketone
2H+
CH3 – C – C – CH3 CH3 – C – CH – CH3
O O O OH
(acyolin)
5. Arndt-Eistert Synthesis :- It involves the conversion of carboxylic acid into next higher homologue i.e. RCOOH to
RCH2COOH.
O
PCl 5 CH 2 N 2
R – COOH R – COCl R – C – CHN2
acid chlorine (diazomethane) diazoketone
Ag 2 O H2 O
R – CH = C = O R – CH2COOH
ketene acid
6. Aromatisation :- It involves the conversion of an aliphatic compound into aromatic one.
Catalyst
NaBF 4
N2Cl F
benzne diazonium Fluorobenzene
chloride
9. Baeyer’s Test :- Decolorisation of cold, dil and neutral aq. Soln. Of KmnO4 (purple) by unsaturated hydrocarbons
(a test for unsaturation).
CH3 = CH2 + H2O + O HOCH2 – CH2OH
(from KmnO4) glycol
10. Benzoin Condensation :- Two molecules of benzaldehde on condensation in presence of alcohol KCN give
benzoin.
alc . KCN
2C6H5CHO C6H5 – CH – C – C6H5
benzaldehyde
OH O
(benzoin)
11. Birch Reduction :- It involves the reduction of olefinic bond by sodium in liquid ammonia in presence of a alcohol.
Na/NH3 ( alc. )
Birch reduction
(1, 4-cyclohexadiene)
12. Baeyer-Villiger Oxidation :- It involves the oxidation of ketones with organic peroxy acid like perbenzoic acid
C6H5CO3H or per acetic acid (CH3CO3H) to form esters.
O O
Peracetic acid
C6H5COCl +
Zn−Hg/ HCl
C=O CH2
Zn−Hg/ HCl
O
cyclohexanone cyclohexane
19. Carbylamine Reaction (Isocyanide Test) :- Foul smelling isocyanides are formed on warming primary amines with
chloroform and alcoholic KOH. Due to offensive of isocyanide (carbylamine). The reaction is a test for primary
amines and is also known as isocyanide test.
RCH2NH2 + CHCl3 + 3KOH RCH2NC + 3KCl + 3H2O
(primary amine) alkyl isocyanide
20. Coupling Reaction :- It involves the condensation between the N atom of a diazo group and a carbon atom of a ring
of phenol or aromatic amines. It is an important reaction for the synthesis of azo dyes. The coupling with phenols
takes place in mild alkaline solution while
OH
− amines show coupling in mild acidic solution.
N2Cl + OH 273 K
aniline
N=N NH2 + HCl
p-amino azobezene
(yellow dyn)
21. Corey-House Reaction :- Alkyl halides on treatment with lithium dialkyl copper in presence of ether give rise to the
formation of alkanes with odd number of carbon atoms.
Ether
R2CuLi + RX R - R+ RCu + LiX
Alkane alkyl copper
For example, theLiformation of pentane from ethyl bromide
CuI
C2H5Br ( ether) C2H5Li (C2H5)2 LiCu
ethyl lithium
Ether
(C2H5)2LiCu + CH3CH2CH2Br C2H5CH2CH2CH3 + C2H5Cu + LiBr
n-pentane
22. Curtius Reaction :- It involves the conversion of acid azide
(R – CON3) into primary amine
O H O
CH 3 OH NaOH
R – C – N3 R – N – C – OCH3 R – NH2
acid azide 1° amine
Acid azide can be obtained from acid chlorides or esters by treatment with hydrazine (NH2 – NH2)
O O O
NH 2− NH 2 HNO 2
R – C – Cl R – C – NH – NH2
R – C – N3
acid azide
23. Decarboxylation :- It involves the removal of CO2 from a carboxylic acid or its sodium salt e.g.,
Soda−lim e
RCOOH R – H + CO2
Soda−lim e
RCOONa R – H + Na2CO3
24. Dehydration
The process of removal of H2O molecule from a reactant.
Substances used from dehydration are known as dehydrating agents.
Different dehydrating agents (conc. H2SO4, Al2O3, P2O5, KHSO4 etc.) are used in different reaction e.g.
(i) Catalytic dehydration :
Al2 O3
KHSO 4
CHOHCHOHCH2OH Δ CH2 = CHCHO + 2H2O
(glycerol) (acrolein)
conc. H 2 SO 4
HCOOH Δ H2O + CO
(formic acid)
COOH
conc. H 2 SO 4
Δ H2O+ CO
COOH
(oxalic acid)
P 2 O5
unsaturated acid
25. Dehydrogenation :- It involves removal of a H2 molecule from a substrate molecule.
Cu
CH3CH2OH 300 ° C CH3CHO + H2
Cu
CH3CHOHCH3 300 ° C CH3COCH3 + H2
26. Dehydrohalogenation :-
(i) The process of removing a hydrogen halide molecule from a substrate molecule e.g.
NaNH2 or KOH alc .
-HX
CH3CH2X CH2 = CH2
KOH alc .
OCCH3 OH OH
COCH3
+
39. Gabriel phthalimide Reaction (primary amine synthesis):- Potassium salt of phathalimide on heating with an alkyl
halide yields N-alkyl phthalimide which hydrolyses to primary amine on heating with HCl or KOH.
CO KOH CO CO
RI
NH NK NR
CO CO CO
phthalimide pot-phthalimide alkyl phthalimide
CO 2H2O COOH
NR Hydrolysis + RNH2
CO COOH
Phthalic acid p-amine
40. Gatternann Reaction :- The reaction involves the preparation of chloro or bromo benzene from benzene diazonium
chloride by treatment with Cu/HCl or Cu/HBr respectively.
N2+Cl- Cu / HCl
Cl
+ N2
chlorobenzene
N2+Cl- Cu/ HBr
Br
+ N2 + HCl
bromobenzene
41. Gattermann-Koch Reaction :- It involves direct introduction of -CHO group in the benzenering i.e., formylation of
benzene ring (a modification of Friedel-Craft’s reaction_. Here, a mixture of CO and HCl gas passed through
benzene containing anhydrous AlCl3 and a small amount of CuCl.
O + HCl HCOCl
AlCl 3 , CuCl methanoyl chloride
CH CH + H2 O Hg
2+
CH3CHO
As above
CH3 – C CH + H2O CH3COCH2
CH2 = C = O + H2O CH3COOH
(ketene)
CH3CN + H2O CH3CONH2
49. Hell-Volhard-Zelinsky Reaction (or HVZ Reaction) :- Aliphatic carboxylic acids containing -H ato m by halogen to
give -haloacids.
Cl 2 P Cl 2 P Cl 2 ; P
R R R
HOH /H +
C = O + 2HCOONH4 CH – NH – CHO CHNH2 + HCOOH
H H H
ketone amm. formate 1° amine
55. Libermann Nitroso Reaction :- Aliphatic and aromatic secondary amines react with nitrous acid (naNO 2 + HCl) to
give yellow coloured oily nitrosoamines.
R R
NH + HONO N – N = O + H 2O
H R
nitrosoamine
The nitrosoamines on warming with a crystal of phenol and few drops of H 2SO give green solution which on further addition
of NaOH changes to deep blue colour. The reaction is used to distinguish secondary amines from primary
56. Molisch Test :- It is rest for carbohydrates where a deep violet ring is formed when 2-3 drops of 1 % alc. Solution of
-naphthol are added to an aq. Solution of carbohydrate followed by careful addition of conc. Sulphuric acid.
57. Mendius Reaction :- The reduction of alkyl or aryl nitriles to primary amines by sodium and alcohol or LiAlH4.
Na/C2 H5 OH
R – CN + 4H or LiAlH4 RCH2NH2
C6H5 – CN + 4H C6H5CH2NH2
58. Meerwein-Ponndrof – Verley Reduction:- It involves the reduction of aldehyde or ketones to alcohols with
aluminium isopropoxide in 2-propanol solution.
R R
3 C = O + [(CH3)2CHO]3Al CHO Al + 3CH3COCH3
R ketone aluminium R 3
isopropoxide
R R
Dil . H 2 SO4
61. Perkins Reaction :- The reaction between aromatic aldehyde and an anhydride of aliphatic acid in the presence of sodium
salt of the same acid gives , -unsaturated acid. E.g., benzaldehyde and acetic anhydride give cinnamic acid.
CHO O CH = CH – COOH
CH3 – C
CH3 COONa
+ O 455 K + CH3COOH
CH3 – C
benzaldehyde cinnamic acid
C
acetic anhydride
62. Pyrolysis :- Breaking of a larger molecule into smaller ones on heating in presence of suitable catalyst is known as
pyrolysis. If higher hydrocarbons are decomposed, the reaction is known as cracking.
Δ
ZnBr R CH3
H 3 O+
CH3CHCOOC2H5 + R – C = O R – C – CHCOOC2H5 + Zn(OH)Br
R OH
68. Sabatier-Senderens Reduction :- The reduction of unsaturated hydrcarbon to saturated ones by passing H 2 in
presence of Raney nickel (catalyst) at around 500 K.
RaneyNi
CH2 = CH2 + H2 473−573 K CH3 – CH3
ethane ethane
69. Strecker’s Synthesis :- Aldehydes are converted to -amino acids on reaction with sodium cyanide and NH 4Cl
followed by hydrolysis.
+
NaCN H
Cl
CuCl/HCl
chlorobenzene
N2+Cl Br
CuBr/HBr + HCl
+ HCl
benzene bromobenzene
diazonium chloride
CN
CuCN/HCN
+ HCl
benzonitrile
72. Schotten Baumann Reaction :- This reaction involves benzoylation of the compounds containing active hydrogen
such as phenols, primary and secondary amines and alcohols, with benzoyl chloride under the influence of aqueous
sodium hydroxide or pyridine.
Base
C6H5NH2 + ClCOC6H5 C6H5NHCOC6H5 + HCl
aniline benzoyl chloride benzanilide
Base
C6H5OH + ClCOC6H5 C6H5OCOC6H5 + HCl
phenol benzoyl chloride phenyl benzoate
Base
C2H5OH + ClCOC6H5 C6H5COOC2H5 + HCl
Ethyl alcohol ethyl benzoat
73. Schiff’s Test :- Aldehydes on reaction with Schiffs reagent (aqueous solution of a dye rosaniline hydrochloride
decolorized by saturating with SO2) restore the pink colour of the dye. Ketones do not undergo this test.
74. Saponification :- The hydrolysis of an ester (usually triglycerides or fats) by an aqueous base
CH2OOCR CH2OH
NaOH
CHOOCR CHOH + RCOONa + RCOONa + RCOONa
CH2OOCR CH2OH soaps
fat glycerol
75. Simonini Reaction :- It involves the reaction of silver salts of fatty acids with iodine to give esters.
O O
2R – C – OAg + I2 R – C – OR + 2CO2 + 2AgI
O O
2CH3 – C – OAg + I2 CH – C – OCH3 + 2CO2 + 2AgI
silver acetate methyl acetate
76. Transesterification :- An ester on treatment with an excess of an alcohol (different from which parent ester is made)
in the presence of acids form a new ester
O O
H+
CH3 – C – OCH3 + CH3CH2OH CH3 – C – OCH2CH3 + CH3OH
methyl ethanoate ethanol ethyl ethanoate methanol
77. Tollen’s Test :- A shining deposit of silver on the inner wall of test tube occurs when aldehydes are warmed with
Tollens reagent (amm. Silver nitrate)/ Ketones do not give this test.
Δ
R – CHO + 2Ag(NH3)2OH CH3COONH4 + 2Ag + H2O + 3NH3
aldehyde amm. silver nitrate silver
mirror
78. Tischenko Reaction :- Aldehydes on heating with aluminium ethoxide form esters. This is a modified Cannizzaro
reaction.
( C2 H 5 O )3 Al
2CH3CHO CH3COOCH2CH3
acetaldehyde ethyl acetage
(C H O ) Al
2 5 3
2C6H3CHO Δ C6H3COOCH2C6H3
benzaldehyde benzyl benzoate
79. Ulmann Reaction :- Iodobenzene on heating with Cu powder in a sealed tube gives diphenyl.
2C6H5I + 2Cu C6H5 – C6H5 + 2CuO
iodobenzene diphenyl
80. Wolff-Kishner Reduction :- The reduction of aldehydes and ketones to hydrocarbons on heating with hydrazine and
KOH.
NH 2 NH 2 KOH
R – CHO R – CH = NNH2 R – CH3 + N2
aldehyde hydrazone
81. Williamson’s Synthesis :- A method for the synthesis of ethers by the reaction of alkyl halides and alkoxides or
phenoxide.
CH3Br + CH3ONa CH3OCH3 + NaBr
methyl bromide sod. methoxide dimethyl ether
CH3Br + C6H5ONa CH3OC6H3 + NaBr
sod. phenoxide methyl-phenyl ether
82. Wurtz Reaction :- Ethereal solution of alkyl halide with metallic sodium produces alkanes (not suitable for alkanes
with odd number of carbon atoms). Methane can not be produced by this method. Generally bromo or iodo alkanes
are used because of higher reactivity
Na
2RX Ether R – R + 2NaX
83. Wurtz-Fitting Reaction :- Aryl halide and alkyl halide on warming with metallic Na in dry ether give aromatic
hydrocarbons.
C6H5Br + 2Na + BrCH3 C6H5CH3
bromobenzene toluene