CARBOXYLIC ACIDS AND ESTERS Physical Properties of Carboxylic Acids

SOLUBILITY C1 C4: very soluble in water because the carboxyl group forms H bond with H2O molecules higher molecular weight carboxylic acids are insoluble since the length of the nonpolar carbon chain reduces solubility in water BOILING POINT the formation of H bonds between two carboxylic acids to form a dimer accounts for the high boiling points of carboxylic acids -COOH > -OH > C=O > R-H O ---- H O - H II I CH3 C C CH3 I II O H ---- O

Chemical Properties of Carboxylic acids

ACIDITY ionize in water to form weak acids more acidic than other organic compounds including phenols R COOH + H2O RCOO+ H3O+ carboxylate ion hydronium ion NEUTRALIZATION completely neutralized by strong bases e.g. NaOH & KOH R COOH + NaOH RCOO-Na+ + H2O carboxylate salt water carboxylic acid salts are solids at room temperature and have high melting points carboxylic acid salts are ionic compounds thus, soluble in water ESTERIFICATION carboxylic acid reacts with an alcohol when heated in the presence of an acid catalyst (e.g. conc. H2SO4 ) to form esters

H2O is produced from: -C OH of the carboxylic acid and R O H of the alcohol II O in naming esters, the 1st word indicates the alkyl part of the alcohol; the 2nd word, the carboxylate name of the carboxylic acid O O II II CH3C - OH + CH3CH2O - H CH3 C O CH2CH3 , H+ common name: acetic acid ethyl acohol ethyl acetate

IUPAC name: ethanoic acid ethanol ethyl ethanoate fragrances of perfumes & flowers, and the flavors of fruits are due to esters

Properties of Esters

ACID HYDROLYSIS water splits apart esters when heated in the presence of strong acid (e.g. H2SO4 & HCl) products of acid hydrolysis are carboxylic acid and alcohol O O II II CH3 C OCH2CH3 + conc. H2SO4 CH3C OH + CH3CH2 O H , H+ BASE HYDROLYSIS (SAPONIFICATION) esters undergo hydrolysis when heated with a strong base e.g. NaOH, KOH to form carboxylate salts and the corresponding alcohols CH3CO OCH3 + NaO H CH3COO-Na+ + CH3OH

saponification base hydrolysis of long-chain fatty acids with NaOH to make soaps

AMINES AND AMIDES Physical Properties of Amines

CLASSIFICATION OF AMINES
1) 1 amines CH3 N H I H .. 2) 2o amines CH3 N CH3 I 3) 3o amines CH3 N CH3 I CH3 H ..
o

..

4) quaternary ammonium salt CH3 I CH3 N+ - CH3 I CH3

SOLUBILITY smaller amines including 3o ones are soluble in water because they can form H bonds amines with more than 6 carbon atoms decrease their solubility in water BOILING POINT nitrogen is not as electronegative than oxygen, which makes the H bonds in amines weaker

1o amines make more H bonds thus, higher boiling points than 2o amines; 3o amines, not possible to hydrogen bond with each other which makes their boiling points similar to alkanes: -COOH > -OH > -N-H > C=O > R-H

Chemical Properties of Amines

BASICITY in water, amines act as Bronsted bases in which the lone pair on nitrogen accepts a proton from water .. CH3 NH2 + H2O CH3 NH3+ + OH methyl amine methyl ammonium ion methanamine NEUTRALIZATION amines act as bases and react with acids to form soluble amine salts .. CH3 NH + HCl CH3 NH2+ClI I CH3 CH3 dimethlyamine dimethylammonium chloride amine salts are solids at room temperature, odorless and soluble in water and in body fluids amines used as drugs (bronchodilator, decongestants, anti-histamine) are converted to their amine salts amine salts react with NaOH and are converted back to amines .. CH3 NH2+Cl- + NaOH CH3 NH + NaCl + H2O I I CH3 CH3

Properties of Amides
PHYSICAL PROPERTIES O

II amides functional group: C NH neutral compounds, neither acidic like the carboxylic acids nor basic like the amines only liquid amide is formamide melting point: primary amides can form more H bonds O O O II II II R C NH2 > R C NH R > R C N R2

1o amide

2o amide

3o amide

solubility: amides with one to five carbons are soluble because they can hydrogen bond with water simplest natural amide is urea, NH2 CO NH2, an end product of protein metabolism; also a component of fertilizer to increase nitrogen in soil synthetic amides such as aspartame (made from amino acids: aspartic acid & phenylalanine) as sugar substitutes barbiturates (cyclic amides) like valium act as sedatives or sleep inducers; acetaminophen reduces fever and pain ACID HYDROLYSIS O O II HCl II CH3 C NH2 + HOH CH3 C OH + NH4Cl carboxylic acid ammonium salt BASE HYDROLYSIS O O II II CH3 C NH2 + NaOH CH3 C ONa + NH3 carboxylate salt ammonia