Aldehdydes , ketones, carboxylic acids

1
Aldehdydes , ketones, carboxylic acids amino
acids
By
Dr/ Amani S. Awaad Professor of pharmacognosy,
King Saud University
2
Aldehydes ketones
CnH2nO
()CO(-) polar react with acid and
base
3
Nomenclature
A Aldehyde
1 Ald. up to 4 c by common name of the acids to
which they related 2 More than 4 by replacing
e(from alkane) by al 3 C of ald. Always No. 1
(not appear in the name)
CH3CH2CH2CHO (IUPAC Butanal /
Comm. Butyraldehyde)
4 Substituted ald. By alphabet. If (OH gt CC or
C?C )
ClCH2CH2CH2CH2CHO CH3CH2CHCHCHO
5-Chloropentanal
2-Pentenal
CH3CHOHCHClCH2CHO
3-Chloro-4-hydroxy pentanal
4
5 Aromatic aldehyd derivatives of simplest
aromatic (bezald.)
B Ketones
1) Simple by alkyl substituent and word ketone
5
2 complicated ketones by IUPAC by replacing (e)
by(-one) (in longest cont. chain with CO) ket.
Take lower no.
CH3CH2COCH3
CH3COCH2CH2CH2CH3
Butanone
2-Hexanone
CH3CH2COCH2CH2CH3
CH3CH2CHClCOCH2CH3
3-hexanone
4-chloro-3-hexanone
CH3CH2CHCHCOCH3
3-hexene-2-one
3 If position of CO not clear no. is needed
for no.
6
Physical Properties.
Solubility
-Simple (1-6) ald. keto. Soli. in H2O - If R
(inc) soli. (dec.) - more than 6 C insole.
Boiling point
CO polar, So Ald. ket Polar (intermolecular
attraction)
Dipole- dipol attractions
B.P ald ket. gt alkane (same m.wt)
7
Preparation of Aldehydes ketones
1 Oxidation of 1? 2? alcohol
2 Ozonolysis of alkenes
3 Hydrolysis of alkynes
HCCH H2SO4 aldhyde
8
4 Friedel Craft acylation
9
Reactions of Aldehydes and ketones
1 Addition of metal hydrides( formation of
alcohol)
0
0
0
0
10
2 Reactions with Grignard reagent
o
11
3Addition of alkynide ions R-CC(-)

4Addition of hydrogen cyanide (cyanohydrins
formations)
12

H2O
CH3

13
5 Addition of alcohols
Ald.. alcoh. H---
hemiacital Ket. alcoh. H---
hemiketal
a) Hemiacitals formation
b) Hemiketals formation
14
c) Acetal formation
d) Ketal formation
OH
15
6 Addition of ammonia and it's derivatives
16
Reduction of oxime
O
0
7 Iodoform reaction
17
8Aldol condensation
Aldehydes
Ketones

18
(No Transcript)
19
Carboxylic acid
R-COOH
Ar-COOH Aliphatic (carboxylic cid)
aromatic (benzoic acid)
Nomenclature
1) replace ane by -ic acid
20
2) Longest continuous chain
CH3CH2CHCH2CH2COOH 4-Methyl
hexanoic acid CH3
? ? ? ? ? C-C-C-C-C-COOH
CH3CH2CHCH2CH2COOH ?-Methyl
hexenoic acid CH3
commmone ?-?- Dimethyl butyric acid IUPAC
2,3-Dimethyl butanoic a
CH3-CHBr-CHCl-CO2H 3-Bromo-2-chlorobutnoi
c acid
21
3) In cyclic ring ------ cycloalkane carb. a'
5) Aromatic acid by common name
22
Physical properties
1 They form hydrogen 2 comp. 1-7 soli in H2O
. 3 mor than 7 carbon less soli. (bec. R
increased) 4 Aromatic acids insoluble. In
H2O 5 BP. Acid gt Alcohol
Deac. gps inc. acidity Acti gps dec.
acidity
23
HCOOH gt CH3COOH gt CH3CH2COOH gt CH3 CH2
CH2COOH
More acidity
Substitution with halogen CH3CH2COOH
lt CH2Cl-CH2COOH (more acidic)
CH3CH2COOH lt CH2ClCOOH lt CHCl2COOH lt CCl3COOH
More acidity
24
Preparation of carboxylic acid
1 Oxidation
a) 1? alcohols Aldehydes
25
b) of alkyl benzene
26
2)Hydrolysis of nitriles
27
3 Carbonation of Grignard reagent
28
Reactions of acids
1)Salt formation
it react with strong base we can use Ca or K
It reacts with weak base
Sodium bicarb. Can be used to distinguish between
carboxylic acid and phenols
29
2) Formation of Easter
3) Formation of amide
4) Formation of acid anhydride
5) Formation of acid chloride
30
Nomenclature of carboxylic acid derivatives
When Oxygen of Carboxylic acid is replaced with
Nu.------ Carb. a' deriv
31
1 Salt
2 Acid chloride
32
4 Ester
The alkyl gp. Named 1st then the name of parent
acid with ending ate in place of -ic acid
33
4Amides
-oic acid or -ice a' by amide .f
1 or 2 subst. on nitrogen we say N-subs. or
N,N-disubs. (sub. Name 1st )
34
4 Acid anhydride
replacing -acid with anhydride
Order of reaction
R-CO-Cl gt R-(CO)2O-R gt RCO2R gt
RCO2H gt RCONH2 Acid chloride Acid
anhydride Ester Acid
Amide
35
Reactions of acid derivatives
a) Acid chlorides
Reduction
36
B Acid anhydride
Reduction
37
C Esters
Reduction
38
d Amide
Reduction
Dehydration
Hoffman degradation
39
Amines
-Intermediate in organic chemistry
reactions -Amino acids (proteins DNA,
RNA) -Alkaloids and drugs
Structure and classification of Amines
It is derived from ammonia by replacing 1,2 or
three H by alkyl or aryl gp. -Aliphatic amines
contain only alkyl gps. bonded directly to
nitrogen atom. -Aromatic one or more aryl gps.
bonded to N.
40
Aliphatic amines
Aromatic amines
-1? , 2? 3? or quaternary ammonium salt
according to (R) or (Aryl) gp. attached to N
atom.

X
41
Nomenclature of amines
1 Simple aliphatic by alphabetical order to gp.
Attached to N and adding -amine
42
2 Complicated amine we consider (NH)as
substituent it's position will take the lowest
possible number.
43
3 Amine salt by replacing Amine by ammonium
4Aromatic amine
e
44
Physical properties
- Amines are solutions are basic (ammonia or
died fish odor) - 1-3(methyl, dimethyl trimethy)
are gases (aliphatic only)- - 1? , 2? amine can
form H bond So their MP gt alkane of similar M.Wt
(B.P Amine gt Alkane)
Basicity of amines
-Amines basic because N has non bonded pair of
electrons which can be donated to an acid to form
ammonium salt.
- base strength depend on the degree of
substitution on N. - More basic CH3-NH-CH3 gt
NH2-CH3 gt NH3
45
- Activating gps. Increase basic properties. -
RNH2 gt ArNH2 aliphatic more basic than
aromatic - Amine gt RCONH2 (Amide) less basic from
amine
46
Preparation of amines
1 Reduction of
a) nitro compounds
b) Of Amide
47
c) Of Imines
d) Of Oxime
e)Of nitriles
48
(No Transcript)
49
2 Alkylation of Ammonia
50
3 Hofmann degradation of amides
51
Reactions of amines
1 With acid chloride
acid chloride react with 1? 2? amine only(no
3? )
52
Reactions of Diazonium salt
yellow azocompound
53
(No Transcript)
54
(No Transcript)