Key to Chemistry Part-II 443 ° oO ll I H —C —OCH2 —CH: —CH3 (CH3 —CH2 —CH2 —' n-propyl formate Ethyl butyrate (4) Acid Anhydrides: “When two molecules of organic acid lose a molecule of water between two OH groups, the derivative formed is called acid anhydride. ° oO ° ° I I ao il I R—C —o|H + HO] —C —R————» R—C—O—C—R Acid Anhydride For Example: oO oO oO oO i i = i l CH; —C —O|H+HO| C —CH; > CH;—C—O—C—CH; (Acetic acid-two molecules) Acetic anhydride i a C—O] HC—C 01 oO Maleic Acid (1) From Alcohols and Aldeh Primary alcohol on oxidation changes to aldehyde and, aldehydes on oxidation changes to carboxylic acids. Oxidation takjes place with the mixture of KxCrO> and cone, H2SOs K.Cr.0; —CH:—OH +[0] ——> — RCHO +H. SO Primary Alcohol Aldehyde KC; R—CHO + [0] ——> — RCOOH HySOs444 [CH.13] Carboxylic Acids CH; —CH,OH + [0] CHsCHO + H20 Ethanol Ethanal K.Crs0; CHCHO + [0] ——> — CH,COOH H,SO, Ethanal Ethanoic acid (2) From Alkyl Nit les: Compounds having a cyanide (- C =N) group are called nitriles. Hydrolysis of an alkyl nitrile on boiling with mineral acids or alkalis yields corresponding carboxylic acid. H’ or OH R—C=N +2Hx0 ———+ RCOOH + NH CH; C =N + 2H20 + HC1———> CH;COOH + NH.Cl Alkyl nitriles can be prepared by treating alkyl halide with alocholic potassium cyanide Alcohol R—X+KCN ———> R—CN+KX eg; CHsCl+KCN ———> CH; —CN+KCI It may be noted but acid produced has one carbon atom more than the original alkyl halide. (3) From Grignard Reagent: Carboxyli can be prepared by the action of Grignard reagent with carbon dioxide. This reaction is either carried out by passing carbon dioxide through the ethercal solution of corresponding Grignard reagent or by adding Grignard reagent to crushed dry ice suspended in ether. The addition product on reaction with a mineral acid produces carboxylic acid oO ° a ROMex + oC 0 > [R—C—OMgx] GHG? R—C—OH + Mg ether Vv OH x Pen a ‘ H 4 / CHMgBr + O=C—=0 ig? [R—C— OMgBr] 4.9% CH,COOH + MgC “OH