Chemistry 110. Bettelheim, Brown, Campbell & Farrell. Ninth Edition

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1 hemistry 110 Bettelheim, Brown, ampbell & Farrell inth Edition Introduction to General, rganic and Biochemistry hapter 16 Amines Amine Molecules are Weak Bases

2 Aliphatic & Aromatic Amines Amines are relatives of ammonia, 3, in which the hydrogen atoms on nitrogen have been replaced by one or more noncarbonyl substituent groups. Aliphatic amines in which alkyl groups replace hydrogen are slightly more basic than ammonia. Aromatic amines in which one or more of the substituent groups is an arene, are considerably less basic than ammonia. eterocyclic amines have the nitrogen atom within a ring. The ring may be aliphatic or aromatic. eterocyclic aliphatic amines are stronger bases than ammonia. eterocyclic aromatic amines are considerably weaker bases than ammonia. In these rings the nitrogen atom contributes one or two electrons to the aromatic sextet of electrons.

3 Aromatic versus Aliphatic Amines Aliphatic Amines have the amino- group attached by tetrahedral carbon: 3 2 Ammonia primary, 1E secondary, 2E tertiary, 3E Aromatic amines have the amino- group bonded to a benzene ring: 2 3 ( 3 ) 2 aniline -methylaniline,-dimethylaniline Aliphatic amines can have aromatic rings as long as the nitrogen is attached by tetrahedral carbon.

4 eterocyclic Aliphatic/Aromatic Amines eterocyclic aliphatic amines the nitrogen is incorporated into a ring and is connected by two tetrahedral carbons. 3 -methylpyrrolidine 3E heterocyclic aliphatic amine eterocyclic aromatic amines the nitrogen is incorporated into an aromatic ring contributes to the aromatic sextet. piperidine 2E heterocyclic aliphatic amine pyridine pyramidine imidazole purene

5 aming of Amines IUPA names for aliphatic amines follow that for alcohols. Drop the final -e of the parent alkane and replace it with amine. Use a number to locate the amino group on the parent chain. ame unsymmetrical secondary and tertiary amines as -substituted primary amines. In this case take the largest group bonded to nitrogen as the parent amine. ame the smaller group(s) bonded to nitrogen, and show that their location is bonded to nitrogen by using the prefix - before the listing of that substituent ,-dimethylaniline propanamine -methylpropanamine

6 aming of Amines IUPA nomenclature retains the common name aniline for 6 5 2, the simplest aromatic amine. ame simple derivatives of aniline by using locator numbers starting with the amino group, or locate substituents by using the prefixes ortho (o), meta (m), and para (p). Several derivatives of aniline have common names that are still widely used; among them is toluidine. If another substituent overides with a special name locate the amine substituent with a locator number starting at the other substituent aniline 2-methylaniline 2-aminobenzoic acid o-toluidine o-aminobenzoic acid

7 aming of Amines ommon ames For most aliphatic amines, list the groups bonded to nitrogen in alphabetical order in one word ending in the suffix amine. 2 isopropylamine ethylisopropylamine cyclopentyldiethylamine Because amines are bases they react with strong acids to form ammonium salts. In these salts nitrogen has four bonds, has a positive charge and is associated with an anion. 3 l l isopropylammonium ethylisopropylammonium cyclopentyldiethylammonium chloride chloride chloride l

8 Properties of Amines Amines are polar, hydrogen bond with water, and 1Eand 2E with each other, but more weakly than alcohols Amines have lower boiling points than alcohols of similar molecular weight, they are also soluble in water if the substituent group part is not too large and non-polar. 1-7 = miscible to slightly soluble, 8 and higher are insoluble. Amines are basic in water, the p will go to higher values. Amines readily react with acid. The resulting ammonium ion are much more soluble than the parent amines. R R

9 Properties of Amines The ---- hydrogen bond is weaker than an ---- hydrogen bond because the difference in electronegativity between and ( = 0.9) is less than that between and ( = 1.4). The effect of hydrogen bonding between molecules of comparable molecular weight can be seen by comparing the boiling points of ethane, methanamine, and methanol. MW (amu) bp ( ) Like ammonia, low-molecular-weight amines have very sharp, penetrating odors; for example, rotting fish = trimethylamine.

10 ydrogen Bonds Amines in Water R R R

11 ydrogen Bonds Pure Amines Except 3E R R R R R R R

12 an You ame these Amines? lassify them as aromatic, aliphatic, and as primary, secondary or tertiary ( 3 2 )

13 Amines Are Relatives of Ammonia Amines are basic: ( Aliphatic amines about as basic as ammonia) 3 2 primary secondary tertiary 4 2 And make ammonium salts in acidic solution. ote: has 3 bonds in amines, but 4 bonds in ammonium ions.

14 Ammonium Ions React with Base Ammonium salts are weakly acidic: primary secondary tertiary And react with hydroxide ion to regenerate the original amine + water

15 Reaction of Amines with Water Reaction of Ammonium Ions with Water

16 What is the form of amines in blood plasma? p of blood is 7.4, [] = 2.5 x 10-7 Ethylamine: Kb = 4.3 x 10-4 = [ ] [ - ] [ ] Kb [ - ] = [ ] [ ] 4.3 x 10 = x 10-7 = 1720 An aliphatic amine is mostly in the ammonium form in blood! Pyridine: Kb = 1.5 x 10-9 = [ ] [ - ] [ 5 5 ] Kb [ - ] = [ ] [ 5 5 ] 1.5 x 10 = x 10-7 = An aromatic amine is mostly in the amine form in blood!

17 arboxylic Acids & Amines Give Salts Amine Ethylmethylamine + 3 arboxylic Acid Acetic Acid 100% Ammonium Ion Ethylmethylammonium 3 arboxylate Anion Acetate Aminoacids exist in vivo only in their ionized form! Tyrosine isoelectric form

18 What Products are Formed? If o Reaction write R l + a a l + l l

BRCC CHM102 Chapter 16 Notes Class Notes Page 1 of 7 H 3 C N CH 3 CH 3 CHCH 3

BRCC CHM102 Chapter 16 Notes Class Notes Page 1 of 7 H 3 C N CH 3 CH 3 CHCH 3 BR M102 hapter 16 otes lass otes Page 1 of 7 hapter 16 Amines Amines derivatives of ammonia R 2 primary amine 3 R 1 R 2 secondary amine 3 R 1 R 2 R 3 tertiary amine 3 * Remember that classification of