THEME: Heterofunctional carboxylic acids .

1. LECTURE № 9 THEME: Heterofunctionalcarboxylicacids. associate. prof. Ye. B. Dmukhalska, assistant. I.I. Medvid

2. Outline • Physical and chemical properties of oxoacids. Acetoacetic ester. • Physical and chemical properties of halogenacids • Physical and chemical properties of hydroxyacids. • Physical and chemical properties of phenolacids. • Physical and chemical properties of aminoacids. • Chloranhydrides of carbonicacid a) Physical and chemical properties of aphosgene 7. Amides of carbonic acid • Physical and chemical properties of an urea • Physical and chemical properties of a guanidine 8. Sulfoacids: aliphatic and aromatic. 9. Aminoacids. Peptides.

3. 1. Oxoacids To oxoacids include aldehydo- and ketonoacids. These compounds include in the structure of the carboxyl group, aldehyde functional group or ketone functional group. pyroracemic acid, 2-oxopropanoic acid glyoxylic acid, oxoethanoic acid acetoacetic acid, 3-oxobutanoic acid, β-ketobutyric acid γ-ketovaleric acid, 4-oxopentanoic acid, levulinic acid oxalacetic acid, oxobutanedioic acid, ketosuccinic acid

4. Methods of extraction of oxoacids: • Oxidation of hydroxyacids: • Hydrolysis dihalogenocarboxylic acids lactic acid pyroracemic acid 2,2-dichlorpropanoic acid pyroracemic acid (pyruvic acid)

5. Chemical properties of oxoacids • Decarboxylation of α-oxoacids • Decarboxylation of β-oxoacids

6. Acetoacetic ester Acetoacetic ester synthesis is a chemical reaction where ethylacetate is alkylated at the α-carbon to both carbonyl groups and then converted into a ketone, or more specifically an α-substituted acetone. Acetoacetic ester is a tautomeric substance. He characterized keto-enol tautomery.

7. Chemical properties of acetoacetic ester: • Reactions of ketone form:

8. 2. Reactions to enol form: • interaction of “acetoacetic ester” with metallic sodium • interaction of “acetoacetic ester” with NaOH c) interaction “acetoacetic ester” with PCL5 ethyl-3-chlorbutene-2-oate

9. d) interaction of “acetoacetic ester” with bromine water. The discoloration of bromine water, that explained unsaturated of "acetoacetic ester”. e) interaction of “acetoacetic ester” with FeCl3

10. The characteristic feature of “acetoacetic ester” is the ability to ketone decompositionand acid decomposition. Ketone decompositionoccurs when heated in the presence of the dilute solutions of acids or alkalis. Acid decomposition of “acetoacetic ester”

11. An “acetoacetic ester” used in the organic synthesis for the extraction of difference ketones and carboxylic acids.

12. 2. Halogenoacids Halogenoacids are the derivatives of carboxyl acids that contain halogen radical (1 or more). α-bromopropanoic acid 2-bromopropanoic acid 2-bromo-3-methylbutanoic acid, α - bromoisovaleric acid

13. Methods of extraction of halogenocarboxylic acid: • Halogenation of saturated carboxylic acids: • Hydrohalogenation of unsaturated carboxylic acids • Halogenation of aromatic carboxylic acids: acrylic acid β-chloropropanoic acid m-chlorobenzoic acid

14. I. Carboxyl group can react with formation of: • Salts chloroacetate sodium

15. b) complex ethers: c) amides: methyl ether of β-chloropropanoic acid amide β-chloropropanoic acid

16. II. Halogen radical can react with: • ammonium: b) NaOH (water solution): 1) for α-halogenoacids ammonium salt of β-aminopropanoic acid lactic acid

17. 2) for β-halogenoacids 3) for γ,σ-halogenoacids β-chloropropanoic acid β-hydroxypropanoic acid acrylic acid γ-butyrolactone

18. Monochloroacetic acid Trichloroacetic acid Dichloroacetic acid Representatives of halogenocarboxylic acid : These acids are used in organic synthesis Ureide of α-bromoisovaleric acid (bromisoval) used in medical practice as a hypnotic.

19. 3. Hydroxyacids Hydroxyacids are the derivatives of carboxyl acids that contain –OH group (1 or more). β α 2-hydroxypropanoic acid α-hydroxypropanoic acid

20. glycolic acid, hydroxyacetic acid, hydroxyethanoic acid tartaric acid α,α’-dihydroxysuccinic acid, 2,3-dihydroxybutandioic acid, lactic acid, α- hydroxypropanoic acid, 2- hydroxypropanoic acid malic acid, hydroxysuccinic acid hydroxybutanedioic acid citric acid, 2-hydroxy-1,2,3-propantricarboxylic acid

21. In a row of hydroxyacids often found the optical isomery. D-, or (R,R)-tartaric acid L-, or (S,S)-tartaric acid mezo-, or (R,S)-tartaric acid

22. Methods of peparetion of hydroxyacids: • Hydrolysis of α-halogenoacids • Oxidations of diols and hydroxyaldehydes • Hydration of α,β-unsaturated carboxylic acids • Hydrolysis of hydroxynitriles (cyanohydrins) lactic acid β-hydroxypropanoic acid

23. Physical and chemical properties of hydroxycarboxylicacid For physical properties of hydroxycarboxylic acids are colorless liquids or crystalline substance, soluble in water. Chemical properties: in the molecule of hydroxyacids ether –OH group or carboxyl group can react. Carboxyl group can react forming: a) salts: sodium β-hydroxypropanoic acid

24. b) complex ethers: methyl ether of β-hydroxypropanoic acid

25. c) amides: II. –OH group can react with: • hydrohalogens (HCl, HBr, HI, HF) b) can oxidize amide of β-hydroxypropanoic acid β-oxopropanoic acid

26. Related to heat of: 1. α-hydroxyacids lactic acid lactide 2. β-hydroxyacids heating 3-hydroxybutanoic acid butene-2-onic (crotonic) acid

27. heating 3. γ-hydroxyacids 4-hydroxybutanic acid γ-butyrolacton

28. Decomposition of α-hydroxyacids acetic acid formic acid

29. Phenolacids are the derivatives of aromatic carboxyl acids that contain –OH group (1 or more). Phenolacids. salicylic acid, 2-hydroxybenzoic acid o-hydroxycinnamic acid 4-hydroxybenzoic acid 3,4,5-trihydroxybenzoic acid, gallic acid

30. Methods of phenolacids extraction: • Carboxylation of phenols by carbon oxide (IV): In the Kolbe synthesis, also known as the Kolbe–Schmitt reaction, sodium phenoxide is heated with carbon dioxide under pressure, and the reaction mixture is subsequently acidified to yield salicylic acid: 2. Hydroxylation of arenecarboxylic acids

31. 3. Alloying of sulphobenzoic acid with alkalis m-sulphobenzoic acid potassium salt of 3-hydroxybenzoic acid

32. Chemical properties of phenoloacids: Chemical properties of phenoloacids due to the presence in their structure of carboxyl group, phenolic hydroxyl and the aromatic nucleus. Decarboxylation

34. O O H O H C C O O N a P O C l , C H O N a N a H C O 3 6 5 3 O C H 6 5 - C O , - H O - N a C l , - N a P O 2 2 3 Phenylsalicylate, salol Sodium salicylate O O H N H C H C O 2 3 C O O H ( C H C O ) O 3 2 C O O H - C H O H 6 5 - C H C O O H 3 Salicylic acid Acetylsalicylic acid, O H aspirin C H O H 3 - H O ( H S O ) 2 2 4 O O O H O H O H C C C O O C H 3 N H N H N H 3 2 Salicylamide Methylsalicylate Oxaphenamide O H

35. The best known aryl ester is O-acetylsalicylic acid, better known as aspirin. It is prepared by acetylation of the phenolic hydroxyl group of salicylic acid:

36. 5. Aminoacids • An aminoacid is an organic compound that contains both a amino (–NН2) group and a carboxyl (-СООН) group. The amino acids found in proteins are always α-amino acids.

38. Methods of aminoacids extraction: • Effects of ammonia on halogencarboxylic acids : • Effects of ammonia and HCN on aldehydes α-chlorpropanoic acid α-aminopropanoic acid α-aminopropanonitrile acetalaldehyde aldimine α-aminopropanoic acid

39. 3. Accession of ammoniato the α, β–unsatured acids acrylic acid β-aminopropanoic acid 4. Reduce of nitrobenzoic acid n-nitrobenzoic acid n-aminobenzoic acid

40. Optical properties

41. Physical and chemical properties of aminoacids Both an acidic group (-СООН) and а basic group (-NН2) are present on the same carbon in an α-amino acid. The net result is that in neutral solution, amino acid molecules have the structure: А zwitter-ion is а molecule that has а positive charge on one atom and а negative charge on another atom.

42. Reactions on amino-group:

43. Reactions on carboxylic group:

44. Heating of: • α-aminoacids • β-aminoacids α-aminopropanoic acid 3,6-dimethyl-2,5-diketopiperazine β-aminooil acid crotonic acid

45. 3. γ-aminoacids γ-aminooil acid γ-lactam

46. React α-aminoacids with ninhydrin

47. Functional derivatesofcarbonicacid.

48. 6. Chloranhydrides of carbonic acid Produces phosgene by interaction of carbon oxide (II) with chlorine on the light.

49. 7. Amides of carbonic acid Esters of carbamic acid are named urethanes

50. Meprothan used in a medicine as a medicament, which has tranquilization and hypnotic effects.