Carboxylic acids and their derivatives. Structure. Structure of derivatives. acyl halide. anhydride. acid halide. ester. amide. The acyl group. Nomenclature. HCO 2 H formic acid (from Latin formica , ant). CH 3 CO 2 H acetic acid (from Latin acetum , vinegar)
HCO2H formic acid (from Latin formica, ant)
CH3CO2H acetic acid (from Latin acetum, vinegar)
CH3CH2CO2H propionic acid (from Greek protos, first and piôn, fat)
CH3(CH2)2CO2H butyric acid (from Latin butyrum, butter)
CH3(CH2)3CO2H valeric acid (valerian root)
CH3(CH2)4CO2H caproic acid (from Latin caper, goat)
CH3(CH2)6CO2H caprylic acid
CH3(CH2)8CO2H capric acid
-hydroxypropionic acid or lactic acid
Saturated cyclic acids are named as cycloalkanecarboxylic acids:
(CH3CO2)2Ca calcium acetate or calcium ethanoate
Change -ic acid to -yl halide
change acid to anhydride
change -icor -oic acid to -amide
change -ic acidto name of alcohol group or phenol + -ate
Intermolecular hydrogen bonding is very important.
In the solid and liquid states, carboxylic acids exist as dimers. Mp and bp values are far higher than the corresponding alcohols.
Polar compounds: the acyl halides, anhydrides, and esters
have boiling points which are very similar to those of
aldehydes and ketones of equivalent molecular weight.
However, the amides.......
CH3CO2H ClCH2CO2H Cl2CHCO2H Cl3CCO2H
Ka 1.76x10-5 136x10-5 5530x10-5 23200x10-5
HCO2H CH3CO2H CH3CH2CH2CO2H
Ka 17.7x10-5 1.76x10-5 1.52x10-5
NB: Phenols do not react with bicarbonate.
CH3CH2CH2CH2Br + CN- CH3CH2CH2CH2CN
(CH3)3CBr + CN- (CH3)2C=CH2 + HCN
CH3CH2CN - 3 carbon chain
propane + nitrile = propanenitrile
propionic acid - ic acid + onitrile = propiononitrile
G = -OH, -X, -OOCR, -NH2, or -OR
The ease of loss of the leaving group, G, depends on its
G = HO-, X-, RCO2-, NH2-, or RO-
G = H-, R- ?
Use thionyl chloride (SOCl2), phosphorus trichloride (PCl3) or phosphorus pentachloride (PCl5).
A Gilman reagent
RCHO or ArCHO
A special catalyst is used: palladium on barium sulfate which has been deactivated (poisoned) with an amine such as quinoline.
Nucleophilic substitution of an acyl halide with a carboxylate anion.
rate = k[OH-][ester]
How can we prove that OH- attacks the acyl carbon and not the alkyl carbon?
 = +13.8o
So what happens when we perform the reaction?
(+)-2-butanol is obtained -  = +13.8o
acyl - oxygen bond breaking occurs
C=O stretching ~ 1710 cm-1 (dimer), ~1760 cm-1 (monomer)
O-H stretching - broad range (3400 - 3600 cm-1)
OH proton occurs in the region = 9-13 ppm.