Carbonyl Chemistry IV + C O C. Lecture 10. Chemistry /30/02

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1 arbonyl hemistry IV Ō - + Lecture 10

2 Addition of Nitrogen Nucleophiles Primary Amines RN 2 Imines Secondary Amines R 2 N Enamines ydrazine derivatives RNN 2 ydrazones ydroxyl Amine N 2 ximes

3 Imine Formation Step 2: protonation of the - followed by loss of 2 and proton transfer to solvent + N-R + N-R N-R An imine

4 Imines ne value of imines is that the carbon-nitrogen double bond can be reduced to a carbon-nitrogen single bond + 2 N yclohexanone yclohexylamine N (An imine) 2 /Ni N Dicyclohexylamine

5 Enamine Formation Secondary amines react with the = group of aldehydes and ketones to form enamines + + -N N + 2 Piperidine (a secondary amine) An enamine

6 Mechanism of enamine formation 2 N N 2 N 2 N N 3 + Enamine

7 Example NN phenylhydrazine NN a phenylhydrazone

8 Example 3 ( 2 ) NNN 2 semicarbazide NNN 2 3 ( 2 ) a semicarbazone

9

10 xidation and Reduction Aldehydes are oxidized to carboxylic acids by a variety of oxidizing agents and it is possible to do some selective reduction reactions xidation Reduction

11 xidation and Reduction Some selective reduction reactions Wolf-Kishner lemmensen NaB 4 LiAl 4

12 Metal ydride Reduction The most selective reagents for the reduction of aldehydes and ketones are NaB 4 and LiAl 4 both are sources of hydride ion, : -, a very powerful nucleophile Na + -B- Sodium borohydride Li + -Al- BBBBBBBBBB Lithium aluminum hydride (LA) ydride ion

13 NaB 4 Reduction The key step in metal hydride reduction is transfer of a hydride ion to the = group to form a tetrahedral carbonyl addition compound B R R - R + - R R R

14 NaB 4 Reduction Reductions with NaB 4 are most commonly carried out in aqueous methanol, in pure methanol, or in ethanol R + NaB 4 R 2 3

15 LiAl 4 Reduction Unlike NaB 4, LiAl 4 reacts violently with water, methanol, and other protic solvents. Reductions using it are carried out in ethers such as tetrahydrofuran (TF) R 2 3 1)TF + LiAl 4 2) 2 R 2 3

16 atalytic Reduction atalytic reductions are generally carried out from 25 to 100 and from 1 to 5 atm 2 arbon-carbon double bonds can be selectively reduced using Rhodium catalysts (sort of) 2 /Rh NaB 4 Me

17 ydrogenolysis of benzylic carbonyls Palladium catalysis of hydrogenation reduces only benzylic - bonds to methylene groups. Benzyl ethers, aldehydes and alcohols are also reduced to the corresponding methylene group 2, Pd/ 2, Pd/

18 lemmensen Reduction Refluxing an aldehyde or ketone with amalgamated zinc in concentrated l converts the carbonyl group to a methylene group Limitations?? ( 2 ) 5 3 Zn(g), l 2 ( 2 ) 5 3

19 Wolff-Kishner Reduction If aldehydes or ketones are refluxed with hydrazine and K in a high-boiling solvent, the reaction converts carbonyls into methylenes. Diethyleneglycol K, 2 NN 2,

20 xidation and Reduction Another way to look at selective reduction reactions NaB Wolf Kishner lemmenson LiAl 4

21 xidation and Reduction special selective reduction reactions There is no rhyme or reason to this selectivity but it is very valuable 2 Pd/ 2 Rh/ NaB (Dil)

22 xidation and Reduction Some selective oxidation reactions in review P 4 3 Jones Reagent

23 xidation and Reduction selective oxidation reactions review K 2 r S KMn 4 too 3 1) 3 2) ( 3 ) 2 S 3 Ag(N 3 ) 2 + Ag (s) I 4 1) KMn 4, - 2) 3 + ( dichromate too)

24 Selective xidation Reactions Jones Reagent ( 2 r 4 in acetone) takes primary alcohols to acids and secondary alcohols to ketones The Tollen s Test Ag(N 3 ) 2 the silver mirror reaction is a qualitative test for aldehydes and an efficient but expensive way to make acids form aldehydes

25 Examples 2 r 4, Acetone 2 S 4 2 r 4, Acetone 3 2 S 4 2 r 4, Acetone 3 3 Ag(N 3 ) Ag 0

26 Keto-enol enol Tautomerism 3 3 Ketone R 2 R' 3 2 Enol

27 Keto-Enol Tautomerism Keto-enol equilibria for simple aldehydes and ketones lie far toward the keto form Keto form Enol form 2 = % Enol at Equilibrium 6 x = 2 6 x x 10-5

28 Keto-Enol Tautomerism For certain types of molecules, the enol is the major form present at equilibrium for β-diketones, the enol is stabilized by conjugation of the pi system of the carbon-carbon double bond and the carbonyl group

29 Keto-Enol Tautomerism in β- diketones pen-chain β-diketones are further stabilized by intramolecular hydrogen bonding hydrogen bonding 3 δ- δ+ 3 20% 2,4-Pentanedione (Acetylacetone) 80%

30 Deuterium Exchange Deuterium exchange at an α-carbon may be catalyzed by either acid or base D D 2 D 3 D D Acetone or D - Acetone-d 6

31 α-alogenation α-alogenation: aldehydes and ketones with at least one α-hydrogen react at an α - carbon with Br 2 and l 2 action is catalyzed by both acid and base 3 Acetophenone + Br Br + Br

32 Mechanism of α alogenation Experimental Facts specific for replacement of at the α carbon equal rates for chlorination, bromination, and iodination first order in ketone; zero order in halogen Interpretation no involvement of halogen until after the rate-determining step

33 Mechanism of α alogenation R 2 R' slow X 2 R R' fast enol Enol is the key intermediate RR' X

34 Mechanism of α alogenation Two stages: first stage is slow conversion of aldehyde or ketone to the corresponding enol; is ratedetermining second stage is fast reaction of enol with halogen; is faster than the first stage

35 General Reaction R 2 R' + X 2 + R 2 R' + X X X 2 can be l 2, Br 2, or I 2. Substitution is specific for replacement of α hydrogen. Not a free-radical reaction.

36 An Example + 1l 2 2 l + l

37 Another Example + Br 2 l 3 Br + Br Notice that it is the proton on the α carbon that is replaced, not the one on the carbonyl carbon.

38 Acid catalyzed α- alogenation Acid-catalyzed α-halogenation Step 1: acid-catalyzed enolization R'---R R slow - Step 2: Nucleophilic attack of the enol on halogen R' R R - R' R R + Br-Br fast R' Br R R + -Br

39 Acid catalyzed a-alogenationa vs. l 2 l 3 I, 2 3

40 What about Base atalysis?? ydrogens α to carbonyls are acidic Resonance stabilized enolate anion 3-2

41 Acidity of protons α to carbonyls The anion is stabilized by resonsance the better the stabilization, the more acidic the α proton Acidity of a protons on normal aldehydes and ketones is about that of alcohols and less than water pka ~ Some are far more acidic, i.e. β-dicarbonyl compounds that have quite low pka s

42 3 2 F l !! pka of some acids and some α protons A span of 59 powers of 10!!!

43 Base catalyzed α- alogenation Base-promoted α-halogenation Step 1: formation of an enolate anion

44 Base catalyzed α- alogenation Base-promoted α-halogenation Step 2: nucleophilic attack of the enolate anion on halogen 2 Br Br 2 Br Br -

45 α-alogenation So there are major differences between acid-catalyzed catalyzed and base-promoted α- halogenation Acid catalysis gives the most substituted product The rate of acid-catalyzed introduction of a second halogen is slower than the first introduction of the electronegative halogen on the α- carbon decreases the basicity of the carbonyl oxygen toward protonation

46 α-alogenation In base catalyzed α-halogenation, each successive halogenation is more rapid than the previous one the introduction of the electronegative halogen on the α-carbon increases the acidity of the remaining α-hydrogens and, thus, each successive α-hydrogen is removed more rapidly than the previous one

47 aloform Reaction Iodoform Reaction A qualitative test for methyl ketones A decent way to synthesize carboxylic acids R 3 3I 2 Na R I I I - R - + I 3 Iodoform

48 The aloform Reaction Under basic conditions, halogenation of a methyl ketone often leads to carbon-carbon bond cleavage. Such cleavage is called the haloform reaction because chloroform, bromoform, or iodoform is one of the products.

49 Example ( 3 ) 3 3 Br 2, Na,, 2 ( 3 ) 3 Na + + Br 3 ( 3 ) 3

50 First stage is substitution of all available α hydrogens by halogen R 3 RX 3 X 2, X 2, R 2 X X 2, RX 2

51 Formation of the trihalomethyl ketone is followed by its hydroxide-induced induced cleavage + R X 3 R X 3 R + X 3 R + X 3

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