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Class Note for CHEM 3332 with Professor Bean at UH 2


Class Note for CHEM 3332 with Professor Bean at UH 2

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Date Created: 02/06/15
694V 0 Chen1333 Chapter 22 Alpha Substitutions and Condensations of Enols and Enolate Ions Review So far 2 reaction pathways for carbonyl compounds 1 Nucleophilic Addition aldehydes and ketones 2 Nucleophilic Acyl Substitution carboxylic acids and derivatives In these pathways a nucleophile attacks the electrophilic carbonyl carbon Ch 22 introduces a third pathway many reactions but only one new process some reactions combine this new process with the old processes 3 Alpha carbon reactions a alpha substitutions b condensations In these pathways a carbonyl compound is the nucleophile HOW A carbonyl compound can become a nucleophile because its alpha hydrogens are slightly acidic can be deprotonated by strong bases Alpha Carbon Reactions 1 Alpha Substitutions A alphahalogenation of ketones and carboxylic acids B alkylation of enolate anions of ketones and esters and nitriles C alkylation of enamines Stork 39 D alkylation of beta dicarbonyl compounds malonic and acetoacetic ester syn II Condensation Reactions aldol condensation mixed aldol intramolecular aldol claisen condensation mixed claisen intramolecular claisen Michael reaction FQTUFUUOFI Robinson annulation ACIDITY OF CARBONYL COMPOUNDS 9 H3CC 39 CH3 0 H3C C S 9 CHSCHZO CCHzC OCHgCHs S S CHa CCHZCOCH2CH3 S E CH3CCH2CCH3 KETO ENOL TAUTOMERIZATION W H O 1 O 7 O H B C C 4L C C lt gt CC l If E is present O 0 E I Acid alalyzed H 39r 39r 739 HOH HO c c 239 c C lt gt crc A l If E is present HO CC lt gt yE We first encountered keto enol tautomerization in the hydration of alkynes Which is the major tautomer at E0 Example Ill H H39O quot c c H C 0 H quot4 Ol OH H H Are Chapter 22 reactions important I Alpha Substitution A Alpha Halogenation of Ketones 1 acidic conditions 0 n X2 lacetic aCId R C CH2R Example 0 Br2 acetic acid a gt t H H o o I H gt H 5 Br Br CH 3 Bra acetic acid gt 2 basic conditions O H O C393H OH CC Br Br R IL Base promoted halogenation cannot be used to form monobrominated product Br Br Br 0 39 39OH Br 0 39 39OH Br 0 39 C 3H gt enolate C C3 Br gt enoate C Cl3 Br R H R H R Br Haloform Reaction R CuJ x2 xs R 3 OH quot s gt x gt CH3 NaOH xs CX3 B Alpha Bromination of Carboxylic Acids Hell Volhard Zelinsky Carboxylic acids do not enolize under acidic or basic conditions 0 0 II OH H H 0 Convert to acid bromide first Ii 9 PBr III I OH c C 3 c c 23 OH Br HBr I UCWCHzCOzH 1 PBr3 Br2 gt 2 H20 C Alkylation of ketones and esters and nitriles H o o 7 o xC C B C C CC Fl Y ahydrogens of ketones pKa 1920 and esters pKa 24 are only weakly acidic if base used is hydroxide EQ lies far to keto tautomer so enolate anion is produced slowly problem hydroxide attacks RY solution use stronger base that gives 100 enolate NH Bu Li Examples 0 quot 1 LDA a CH3 2 CH3CH2BT 9 C 1 LDA b 0 2 CH3BI 1 LDA c CH3CH2CN W CH3 1 DA d L 2 CH3Bf D Alkylation of Enamine Review 0 H C C NHR2 Enamine is similar to enolate anion F2N E 30 CC gt SIQLSymnesis enamine serves as Nu in the formation of alpha substituted aldehydes and ketones 1 form enamine 2 add R Y 3 hydrolysis 0 ll RY Ph CHzX CC R C CI CH2X Examples 0 O W CH 5 Cl a Z 3 N H Hgol H30 1 CH32NH 0 CHzBr b Hac o CH2CH3 2 3 H30 E Alkyiation of Beta Dicarbonyl Compounds 9 S S S 9 S CH3CH20C39CH239C39OCHQCH3 CH3 C39CH239C39OCH2CH3 CH339CCH239C39CH3 more acidic than mono carbonyl compounds and y 6 etc dicarbonyl cpds do not need LDA to obtain a good yield of enolate ion 0 0 II II CH339C39CH239C39CH3 Na 1 Malonic Ester Synthesis a sesuence of reactions that converts an alkyl halide to an asubstituted or disubstituted acetic acid multistep O malonic ester quot R X synthesis R 39 CHZ39C39OH S S 9 S gt R0 CCHzCOR CH3CH20 C CHzCOCH2CH3 a malonic ester Steps 1 treat malonic ester with base to form enolate ion 2 alkylate add RX 3 hydrolyzedecarboxylate Mechanism 1 i S 3 03 0 08 I I HClH Na OET H z 9 OEt D OEt O O 2 S 0 03 I H l32 R X 1Na39OEt C OEt X 90 3 c OB I R CID R H 0 03 moo 0 Example CH3CHZCH2I3HCOZH CHZCH3 lt O O 9 II II CH3CH20 CCH2COCH2CH3 Formation of cyclic carboxylic acids with malonic ester synthesis ring size 3 6 S c Oa H H 9 03 0 Na 39 OEt M 0 03 I H c OB t Br 39 CH20H2CH2 Br gt 2 Acetoacetic Ester Synthesis similar to malonic ester synthesis but uses a beta keto ester rather than a beta diester o o quotJ Cquot ethylSoxobutanoate u u eth acetoacetate R C39CHzC39OR39 CH3 C39CHZ39C39OCHZCHS acetoacetic ester multistep O acetacetic ester quot R X RCH2CCH3 Steps 1 treat acetoacetic ester with base to form enolate ion 2 alkylate add RX 3 hydrolyzedecarboxylate Example 0 O O O I II 1 NaOEtEtOH II II CHa CCHzCOCHchs CH3 CQHCOCHZCH3 CH20H3 1 NaOEtEtOH 2 CH3CHzBr CH CH CH C39 O 3 2 CH CH CC lt 3 2 COH H30 CHCH2CO3l120i3 CH CH H 3 2 C 3 CH3CH2 30 180 C CH3CH2 9CH3 CH3 0 H3O Synthesis Example 0 o 0 II I QCH2 39 CHz39C39CHa 4 CHs CCHZdOCHZCH3 D II Condensation Reactions A combination of the old carbonyl pathways nucleophilic addition or nucleophilic acyl substitution with the new pathway alpha substitution A Aldol Condensation for aldehydes and ketones that have alpha hydrogens produces a beta hydroxy aldehyde or ketone steric factors are important ketones and alpha disubstituted aldehydes give poor yields strength of base used is important only necessary to convert small to enolate ion do not want 100 enolate Example S quot3 NaOEtEtOH CHsCHzCH CH3CH2CH gt Dehydrationbf Aldol Eroducts warming the aldol product readily leads to an alpha beta unsaturated carbonyl With dehydration most aldehydes and ketones can successfully be used in aldol condensations Example 0 NaOEtEtOH heat 4 gt Synthesis Practice From ethanal synthesize the compound below 9H 63 CH3CH20H2CHCIDHCH CHQCH3 B Crodssed Mixed Aldol condesation between two different aldehydes or ketones onsr er Cquot i NaOEtEtOH CH3CH CHacHzCH gt Successful Crossed Aldol One reactant has NO alpha hydrogens cannot form enolate 0 o quot3 H II NaOEtEtOH CH3CH2CH 0 00 l C Intramolecular Aldol enolate anion and the carbonyl attacked are in the same molecule 5 and 6 membered rings readily form I I NaOEtEtOH CH339C39CH20H239C39CH3 heat D Claisen Condensation Forms betaketo esters from esters I 0 ll QHZCOCHZCHa CH3COCHZCH3 H NaOEtEtOH 1 eq E Crossed Mixed Claisen one reactant must have no alphahydrogens O o H 1NaOEtEt H 1 QC39OCH2CH3 CH3l5OCH20H3 Ogt2 H3O O O n 1 NaOEUEtQH 2 CH36CH3 QC39OCHchs 2 H3O i1 12 F Intramolecular Claisen Dieckmann Cyclization similar to intramolecular aldol forms cyclic betaketo esters O O 1 NaOEtEtQH ll CH30Cn3CHzCH2CHZCH2COCH3 2Hay Synthesis of alphasubstituted cyclopentanones and cyclohexanones using Dieckmann followed by acetoacetic esterlike synthesis H O 1NaOEtEtOH II COCH3 2 CH3CH23I 3H3Oheat G The Michael reaction a conjugate addition to an alpha betaunsaturated system such as an enone also described as a reaction between a Michael donor and a Michael acceptor see Table 222 page 1046 Grignard and organolithium reagents LiAlH4 I ll t 39 n39 i i t amines cyanide anion Michael donors listed in Table 222 Examples 0 O CH NH CH3NH2 NaCNH 3 2 NaCNH l1CH3MgBr 2 H3O systems that have particularly acidic alphahydrogens such as betaketo esters betadiesters betadicarbonyls beta keto nitriles betaketo nitro Michaeljcceptors alpha beta unsaturated systems CC conjugated with XY Michael Example and Mechanism 0 O H H n N OEtEtOH CH3 CCH2COCH20H3 HZCCHCCH3 i More Michael Examples C NaOEtEtOH CH3CH2039C39CH239CEN CH3CH20 C39CID CH2 CH 3 9 9 syntheSize CH3CH239C39CEH39CH2CH239C39CH3 CH3 H Robinson Annulation an important ring forming reaction 2 parts 1 Michael addition 2 Intramolecular aldoldehydration O o O o N EtO H II H2CCHCCH3 aOEtEtOH I O o o o I EtO39 l H o o 0 lt lt lt O O O o O OH 0 H20 M


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