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CHE 242 Unit VII The Physical and Chemical Properties, and Reactions of Ketones, Aldehydes, and Amines CHAPTER NINETEEN Terrence P. Sherlock Burlington.

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Presentation on theme: "CHE 242 Unit VII The Physical and Chemical Properties, and Reactions of Ketones, Aldehydes, and Amines CHAPTER NINETEEN Terrence P. Sherlock Burlington."— Presentation transcript:

1 CHE 242 Unit VII The Physical and Chemical Properties, and Reactions of Ketones, Aldehydes, and Amines CHAPTER NINETEEN Terrence P. Sherlock Burlington County College 2004

2 Chapter 192 Introduction Organic derivatives of ammonia Many are biologically active. =>

3 Chapter 193 Classes of Amines Primary (1  ): one C-N bond, 2 N-H bonds. Secondary (2  ): two C-N bonds, 1 N-H bond. Tertiary (3  ): three C-N bonds, no N-H bond. Quaternary (4  ): four C-N bonds, nitrogen has a + formal charge. =>

4 Chapter 194 Classify: =>

5 Chapter 195 Common Names Name the alkyl or aryl groups bonded to nitrogen, then add suffix -amine. diethylmethylamine cyclopentylmethylamine Diphenylamine =>

6 Chapter 196 Amine as Substituent On a molecule with a higher priority functional group the amine is named as a substituent.  -aminobutyric acid or 4-aminobutanoic acid 2-methylaminophenol =>

7 Chapter 197 IUPAC Names Name is based on longest carbon chain. -e of alkane is replaced with -amine. Substituents on nitrogen have N- prefix. 3-bromo-1-pentanamineN,N-dimethyl-3-hexanamine =>

8 Chapter 198 Aromatic Amines Amino group is bonded to a benzene ring. Parent compound is called aniline. aniline N,N-dimethylaniline => 4-methylaniline or p-toluidine

9 Chapter 199 Heterocyclic Amines The nitrogen is assigned the number 1. => aziridine Pyrrole Pyrrolidine Pyridine 2-methylpyridine

10 Chapter 1910 Structure of Amines Nitrogen is sp 3 hybridized with a lone pair of electrons in an sp 3 orbital. =>

11 Chapter 1911 Chirality of Amines Nitrogen may have 3 different groups and a lone pair, but enantiomers cannot be isolated due to inversion around N. =>

12 Chapter 1912 Boiling Points N-H less polar than O-H. Weaker hydrogen bonding. Tertiary amines cannot hydrogen bond. =>

13 Chapter 1913 Solubility and Odor Small amines (<6 C) soluble in water. All amines accept hydrogen bonds from water and alcohol. Branching increases solubility. Most amines smell like rotting fish. 1,5-pentanediamine or cadaverine =>

14 Chapter 1914 Basicity of Amines Lone pair of electrons on nitrogen can accept a proton from an acid Aqueous solutions are basic to litmus. Ammonia pK b = 4.74 Alkyl amines are usually stronger bases than ammonia. Increasing the number of alkyl groups decreases solvation of ion, so 2  and 3  amines are similar to 1  amines in basicity. =>

15 Chapter 1915 Energy Diagram Alkyl groups are electron-donating and stabilize the cation. =>

16 Chapter 1916 Resonance Effects Any delocalization of the electron pair weakens the base. =>

17 Chapter 1917 Hybridization Effects Electrons are held more tightly in orbitals with more s character, so those compounds are weaker bases. =>

18 Chapter 1918 Amine Salts Ionic solids with high melting points Soluble in water No fishy odor =>

19 Chapter 1919 IR Spectroscopy N-H stretch between cm -1. Two peaks for 1  amine, one for 2 . =>

20 Chapter 1920 NMR Spectrum =>

21 Chapter 1921 Electrophilic Substitution of Aniline -NH 2 is strong activator, o-,p-directing. May trisubstitute with excess reagent. H + changes -NH 2 to -NH 3 +, a meta- directing deactivator. Attempt to nitrate aniline may explode. =>

22 Chapter 1922 Aniline Substitution =>

23 Chapter 1923 Electrophilic Substitution of Pyridine Strongly deactivated by electronegative N. Substitutes in the 3-position. Electrons on N react with electrophile. =>

24 Chapter 1924 Nucleophilic Substitution of Pyridine Deactivated toward electrophilic attack. Activated toward nucleophilic attack. Nucleophile will replace a good leaving group in the 2- or 4-position. =>

25 Chapter 1925 Alkylation of Amines Amines react with 1  alkyl halides via the S N 2 mechanism. Mixtures of the mono-, di-, and tri- alkylated products are obtained. =>

26 Chapter 1926 Useful Alkylations Exhaustive alkylation to form the tetraalkylammonium salt. Reaction with large excess of NH 3 to form the primary amine. =>

27 Chapter 1927 Acylation of Amines by Acid Chlorides Amine attacks C=O, chloride ion leaves. Product is amide, neutral, not basic. Useful for decreasing activity of aniline toward electrophilic aromatic substitution. to remove HCl =>

28 Chapter 1928 Formation of Sulfonamides Primary or secondary amines react with sulfonyl chloride. Sulfa drugs are sulfonamides that are antibacterial agents. =>

29 Chapter 1929 Oxidation of Amines Amines are easily oxidized, even in air. Common oxidizing agents: H 2 O 2, MCPBA. 2  Amines oxidize to hydroxylamine (-NOH) 3  Amines oxidize to amine oxide (-N + -O - ) =>

30 Chapter 1930 Nitrous Acid Reagent Nitrous acid is produced in situ by mixing sodium nitrite with HCl. The nitrous acid is protonated, loses water to form the nitrosonium ion. =>

31 Chapter 1931 Reaction with Nitrous Acid 1  Amines form diazonium salts, R-N +  N. Alkyldiazonium salts are unstable, but arenediazonium salts are widely used for synthesis. 2  Amines form N-nitrosoamines, R 2 N-N=O, found to cause cancer in laboratory animals. =>

32 Chapter 1932 Arenediazonium Salts Stable in solution at 0°–10°C. The - + N  N group is easily replaced by many different groups. Nitrogen gas, N 2, is a by-product. =>

33 Chapter 1933 Synthesis by Reductive Amination To produce a 1  amine, react an aldehyde or ketone with hydroxylamine, then reduce the oxime. To produce a 2  amine, react an aldehyde or ketone with a 1  amine, then reduce the imine. To produce a 3  amine, react an aldehyde or ketone with a 2  amine, then reduce the imine salt. =>

34 Chapter 1934 Examples primary amine secondary amine tertiary amine =>

35 Chapter 1935 Acylation-Reduction An acid chloride reacts with ammonia or a 1  amine or a 2  amine to form an amide. The C=O of the amide is reduced to CH 2 with lithium aluminum hydride. Ammonia yields a 1  amine. A 1  amine yields a 2  amine. A 2  amine yields a 3  amine. =>

36 Chapter 1936 Examples primary amine tertiary amine =>

37 Chapter 1937 Direct Alkylation (1  ) Use a large excess (10:1) of ammonia with a primary alkyl halide or tosylate. Reaction mechanism is S N 2. =>

38 Chapter 1938 Gabriel Synthesis (1  ) Use the phthalimide anion as a form of ammonia that can only alkylate once. React the anion with a good S N 2 substrate, then heat with hydrazine. =>

39 Chapter 1939 Azide Reduction (1  ) Azide ion, N 3 -, is a good nucleophile. React azide with unhindered 1  or 2  halide or tosylate (S N 2). Alkyl azides are explosive! Do not isolate. =>

40 Chapter 1940 Nitrile Reduction (1  ) Nitrile, -C  N, is a good S N 2 nucleophile. Reduction with H 2 or LiAlH 4 adds -CH 2 NH 2. =>

41 Chapter 1941 Reduction of Nitro Compounds (1  ) -NO 2 is reduced to -NH 2 by catalytic hydrogenation, or active metal with acid. Commonly used to synthesize anilines. =>

42 Chapter 1942 Hofmann Rearrangement of Amides (1  ) In the presence of a strong base, primary amides react with chlorine or bromine to form amines with one less C. =>

43 Chapter 1943 POWER POINT IMAGES FROM “ORGANIC CHEMISTRY, 5 TH EDITION” L.G. WADE ALL MATERIALS USED WITH PERMISSION OF AUTHOR PRESENTATION ADAPTED FOR BURLINGTON COUNTY COLLEGE ORGANIC CHEMISTRY COURSE BY: ANNALICIA POEHLER STEFANIE LAYMAN CALY MARTIN


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