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Fund of Organic Chemistry II

by: Dominic Kling

Fund of Organic Chemistry II CHEM 3332

Marketplace > University of Houston > Chemistry > CHEM 3332 > Fund of Organic Chemistry II
Dominic Kling
GPA 3.71

Mary Bean

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This 85 page Class Notes was uploaded by Dominic Kling on Saturday September 19, 2015. The Class Notes belongs to CHEM 3332 at University of Houston taught by Mary Bean in Fall. Since its upload, it has received 171 views. For similar materials see /class/208155/chem-3332-university-of-houston in Chemistry at University of Houston.


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Date Created: 09/19/15
6a n 7 CHAPTER 19 AMINES omit sections 7 8 11BD 14 16 17 24 plum 333 many have important biological activity some serve as important synthetic intermediates I Nomenclature general R NH2 R2NH R3N A Common Names named as alkyl amines name of alkyl groups bonded to N amine CH3NHCH20H3 CH30H23N ON B IUPAC the suffix quotaminequot replaces the quotequot of the alkanealkenealkynecycloalkane alkene name for 2 and 3 amines the largest group is the parent use quotNquot to designate substituents on N CH3 NHCHQCH3 CHSCH22N CHSCH2 O NHZ oHa CH3 I CHaCHCHZNHCHZCHa CH3C CH3 l NHCHQCHg C When higher priority groups are present NH2 is called quotaminoquot H2NCH2CHQCH20H CHacHzNHCHchchzcozH ll StructureBonding chiral or achiral quot X Z 39ltgtz Pyramidal Inversion Walden Inversion R R1 1 XI X R2 NR4 gt39 R4 N R2 s 9 3 Y F gt GgtN Y R R3 2 V 47 Z X Y CH3 H C 4 H C 3 CH3 3 B 7 g l N 39 CH3 HaC quot N 2 III Physical Properties H2N39CH24 NH2 H2NCH25 NH2 Boiling Point CHaOCHQ CH30H2NH2 CH3CH20H S CHa C H CH3NHCH3 CH33N IV Amine Basicity ability to accept a proton BronstedLowry ability to donate an electron pair Lewis Amines are more basic than ethers alcohols water Why RNH2 H3O RNH3 H20 1 Consider stability of species after proton is accepted Factors that stabilize charge increase basicity Factors that destabilize charge decrease basicity 2 Consider availability of electron pair Compare Basicity Alkyl Amines H30 39lN39 CH3 H 39ri CH3 CH3 CH3 i W H H I I H3CNCH3 H N CH3 I CH3 CH3 Amine vs Amide 3 R NHz R C 39N39H2 Heterocyclic Amines Alkyl vs Aryi NH2 H2 H I CH3 H 1 H H rJ CHQ H H H l H H H N H I H Substituted Aryl Amines If Y is electron donating electron pair of amine is more available Y NH2 electron donation stabilizes charge In product Increase in baSICIty If Y is electron withdrawing electron pair of amine is less available Y NH2 electron withdrawal destabilizes charge in product decrease In basrcity NH2 NH2 39N39H2 NH2 N02 CHO Br OCH3 V Reactions of Amines A Reaction with Aldehydes or Ketones Review Ch 18 H RNH2 H 2 R39 c R2N B Alkylation of Amines by Alkyl Halides limited synthetic applications because multiple alkylations occur H I I I I R NH2 R39 X gt RNRI m RTJ R39 521 R I H H R39 RI R N LR39 i X R 39lri R39 R39 R39 Useful cases 1 CHscHe NHQ w Br I I 2 CHQCH COQH NH3 gt C Acylation of Amines by Acid Chlorides Review Ch 2021 0 II R NH2 RC CI D Electrophilic Aromatic Substitution of Aniline NH2 is a powerful activating group and can cause problems with some EAS reactions NH2 BI39 NH2 3 CHa CCl 2 AICI3 NH2 H N03 H2804 Solution acylate amino group first then hydrolyze after desired reaction 9 0 ll NH2 0 CHa CNH CH3cC CHa C Cl G Aioi3 gt Br2 FeBra E Hofmann Elimination U RCHchz NHz M RCHZCHQ CH33139 A9 0 H 0 13 RCHgCHz NCH33 OH AgI Example r gt TH2 VIKCHala 39OH CH Ixs CH30H2 CH CH3 2 A920 H20 A CH3CIJH CH cHg H H gt F Reaction of Amines with Nitrous Acid HNOZ HN02 is not stable generate from NaN02 and HCl H Nap N5 Hqu gt HQ NIOI M HmN6 gt 353549 Naaz 1 Reaction of Alkyl Amines with HNOZ NOT synthetically useful 2 Reaction of Aryl Amines with HNOZ VERY useful H grim BEES quotH N39o39gl N o H NO H20 H2 0 lt20 2 lt 0 Before examples of arenediazonium salt reactions The Best Synthesis of Aniline reduce No2 HNO Q 304 L choice of H 1 catalytic reduction Hg with Pt Pd or Ni 2 quotactivequot metal acid catalyst Fe Zn Sn or SnCl2 in acid followed by base for quotfreequot amine Synthesis Examples Br 1 gt CH3 Br CH3 OH 7 20 Br VI Synthesis of Amines A Reductive Aminaton of Aldehydes and Ketones In true reductive amination the amine the reducing agent and the aldehyde or ketone are mixed together NHsorNHZOH H co R CNR H CHNHR H L c RQ CH NRQ H choices 1 LiAH4 must be used as a sceond step 2 NaBH3CN similar to NaBH4 but does not reduce aldehydes or ketones used particularly in the formation of 3 amines because the iminium salt cannot be isolated Examples O 1CH32NH NaBHacN gt B Acylation IReduction Review 0 O quot 1 LiAlH RquotNH2 RCCl gt RNH CR R39NH CH2R 2 9 CH OH NH CH CCl gt 1 WW 3 2 2 3 2 H20 C Reduction of Nitriles Review 1 LiAlH RCEN 4 gt 2 H20 or H30 RCH2 NH or H2 Pt or Ni CH3CEN 1 LiAIH 2 H20 or H30 or H2 Pt or Ni D Fomation and Reduction of Azides forms 1 Ines only x Kl ii quot 1 LiAlH4 U aquot R Pi N E 21120 RNH2 N2 or H2Pd Mechanis 39 i I H 1 I O 7 R N m R NQ R H N2 H OH RNH2 Example 1 NaN3 2 CH30H20H2 39 Br E Hofmann Rearrangement 1 amide forms a 1 amine that is one carbon smaller and 002 0 II n R CNH2 X2 H20 NaOH RNH2 002 Mechanism 0 IR m H H H II H H H OH O RC N BraHZONaOH R NH2 Nlt CA 39 r 49H R W I R C N 113 9 9H OH H R c H Br Example 5 3 l CH33C Br2 H20 NaOH CH3 NH2 F Curtius Rearrangement problem 19 37 forms 1 amines closely related to above process 0 II RcCI 313Tgt R NH2 CO2 N2 on 1LNaNNN 0 o quot quotJ9 R C NN A Cl 1 NaN 2 H20 IA Spectroscopy Review The Basics of the Basics Infrared Spectroscopy allows us to determine functional groups present in a molecule Characteristic arrangements of atoms functional groups have about the same frequencies of vibration in any molecule Stronger the bond higher the vibrational frequency higher the wavenumber Heavier the atoms lower the vibrational frequency lower the wavenumber Nuclear Magnetic Resonance Spectroscopy allows us to determine the carbonhydrogen skeleton chemical shift where the signal occurs compared to standard TMS depends on the magnetic field strength quotfeltquot by the nucleus effective field strength He Hequot depends on the electron density around the nucleus because the circulation of electrons generates a magnetic field Hithat shields the nucleus from the field applied by instrument lb greater the electron density the more quotshieldedquot the nucleus the higher the necessary field strength Hoto produce a signal therefore the more upfield the signal smaller the electron density the less quotshieldedquot the nucleus the lower the necessary field strength to produce a signal therefore the more downfield the signal factors that affect electron density affect chemical shift electronegative atoms pi electrons of a double bond pi electrons of a triple bond signal multiplicity appearance of signal how many peaks adjacent nonequivalent nuclei generate magnetic fields that affect the appearance of a signal in the NMR spectrum N 1 Rule The signal for a given nucleus is split into N 1 peaks by N adjacent nuclei remember The N nuclei must be nonequivalent to the nucleus of interest and must be equivalent to each other If the nucleus of interest is adjacent to more than one kind of nucleus the N 1 rule is used for each kind Examples 9H3 0 0 Hz CH CH quot 39 3 CH3CCHZCH2 CCHZCH3 CHSCHZCHzBr CHaCHCHS Sean UV W 33 3 L CHAPTER 18 KETONES AND ALDEHYDES Carbonyl compounds reagents Isolvents and constituents of fabrics flavorings plastics drugs proteins Icarbohydrates nucleic acids C o 0 0 0 El H H il n R C R R C H R C OH R C Ci R C OR R C NH2 I Structure 0 n H u n c C H CH3 CH3 CH3 OCH3 CH3CH2O H II Physical Properties A Boiling Point O 0 II II CH30H30H20H3 CHa O CH20H3 CH3CH2 C H CH3 C CH3 CHaCHchzO H B Solubility O O H H 0 C W CH3 CH3 Ill Reactivity A Acidity of Alhpa Hydrogens H O I II B39 RC C R gt H B Reactivity of Aldehyde vs Ketone IV Aldehyde and Ketone Nomenclature A As parent priority over alcohols amines alkenes alkynes ethers 1 Aldehydes drop quot9quot from alkane add quotalquot 939 0 CH3CHZCH2E393H CHaCHCHz CHCH CHZCHzCHs o HO CHZCHchZCHQCIDH For cyclic aldehydes add quotcarbaldehydequot O CHO CHO ICH3 2 Ketones drop quotequot from alkane name add quotonequot H H I I OH 00 0 CH3CHCH2CHCCHQCH3 CHabCH2 CH25CH3 I CH3 For cyclic ketones since carbonyl is part of ring same as acyclic ketones carbonyl is always 1 O I OH B As substituents CHO 9 CH quotformylquot lt1 COZH 3 9 9 0 0X0 CH3CCH2 CH V Spectroscopy of Aldehydes and Ketones Summary A IR look for carbonyl stretch O O n C R H R conjugation lowers frequency 0 u 0 C II CH3 CHa CHCH C H ring strain raises frequency 0 o B1HNMR 0 0 II R39CHz C H CH3 C R c 130 NMR n RCHz C R D UV H H CH3 H CH3 H C C C C C C H CH3 CH3 H H CHa C9H1002 IR 1695 cm 1 z 3 10 8 6 4 2 0 ppm Chemical shift 5 C10H120 IR 1710 cm391 5 E 10 8 6 4 2 0 ppm Chemical shift 5 VI Aldehyde and Ketone Synthesis AD are Review A Oxidation of Alcohols PCC 1 alcohol W aldehyde 2 alcohol PCC A ketone or Jones39 ox Ol39 NazCF207stO4H2O B Cleavage of Alkenes by Ozonolysis CH3C CCH3 139 O3 CH3C O 2 CH32 H CH3 H C FriedelCrafts Acylation 0 ll 0 R CCl n C R Q A39CI3 Q S COHCi Q AlCl3CuCI QC H No strong deactivators on ring halogens OK No amino groups on ring D Hydration of Alkynes R H H20H2304 HO H 1 SiagBH 2 H202NaOH R H 00 ll R39CH2 H OH R CEC R39 MEL CH3 CH3 R39 CCH3 mixture of ketones E 1 3 Dithiane Synthesis of Aldehydes and Ketones a multistep synthesis m CH3CH22CH2 Li gt S S Hgtlt or 0 Li I gt 5 CH3CH2QCH2 Li Li I I X I 33 S S R39 X gt X R Example 0 ll CHSCH2 C CH2 F Ketones from Carboxylic Acids a multistep synthesis 0 II 39 39 1 R C O H w p 0 II R39 Li 2 Fi C O39Li gt CIT Li 3 R C O39 Li amp RI Example I 39 OHS C OH 1 CH3CH2CH2 LI 2 eq 2 H3O G Ketones from Nitriles R CEN R39 MgX gt Example MgBr CHs CEN 0 ether H Aldehydes and Ketones from Acid Chlorides 1 reduction to aldehydes 0 II II R 0 OH O C39 2 R c Cl 1 LiAlH4 l LiAH4 o 0 II II Fl C H R C H R CH20H R CHQOH mechanism 3 RCCI H AIH3LI a a milder reagent lithium aluminum tritbutoxyhydride OCCH33 Li H Al OCCH33 OCCH33 39 R C Cl LIAlHOtBu3 b The Rosenmund Reduction RgCl H2 Pd lBaSO4S Example COQH 9 CHO I O 2 conversion to ketones with lithium dialkylcuprates Gilman reagent 0 ll R C Cl R39uLi gt R Example CH3CH2 C C CH32CULi 39gt i A Reminder Use of Gilman reagent in the CoreyHouse Reaction R39 tIuLi R x RI CH30H2 Br CH32CULi gt VII Reactions of Aldehydes and Ketones 0 A AlphaCarbon Reactions covered in Chapter 22 RCCHQR B Nucleophilic Addition Reactions 039 OH I H I R CID Nu IO 1 Grignard Reaction 9 939 R39MgX R C OH HZOH R R i 3 12 2 Addition of Acetylide OH H 0H I 2 R c cEcR39 00 R NaCECR39 V CEC39R39 i 3 0 0 3 Addition of Hydride Cl I R Cf H RcH R R Li HZiHs 4 Catalytic Hydrogenation similar to hydrogenation of alkenes but aldehydes and ketones are less reactive O c U H HZ RaneyNi gt II 5 Hydration a The reaction 3 C H o R R 2 v S FCH H20 CQ HaC CH 20 9 HCH H20 V cquot c H0 crac H 2 How to predict EQ the more stable the aldehyde or ketone the more the EQ lies to the aldehyde or ketone not the hydrate the less positive the carbonyl carbon the more stable the aldehyde or ketone 9 9 S C C C R R R H H H Clac H c Reaction Rate and Catalysis 1 acid catalyst R 2 base catalyst 6 Addition of HCN C HCN R R 9 C H CN 2 R H Mechanism 9 39CN R H39 Example 9 NaCN H CH30H2 H 7 Addition of Amines a 1 amines O H quot3 RNH2 amp 12 Mechanism of Imine Formation I I H5H 9H c RNH2 C iHR 39 E C NHR i H H H 6H H H20 CN CNf lt gt E NHR C NHR R R Example 0 H2N H gt Important Uses of lmines 1 product characterization derivatives 0 NH2NHPh Isl NH20HH gt O NH2NH2H n NH2NHCNH2H 2 quotdeoxygenationquot of carbonyls O II 1 NH2NH2 H CH gt Wolf Klschner C 2 KOH IDMSO 2 Mechanism H30 H C H 0 H30 00 NH2NH2 3 H0 3 CN CN H C N H30 HaC VIIH H30 N H H3C N H H 1 l HOH 39 0 39f HO39 39 Hac C H H30 4 Hac clN H33 H30 H30 N H Example 0 II CH2 C39CH20H3 1 NH2NH2 IH 2 KOH DMSO 1 ZnHg lHCI H20 b addition of 2 amines to aldehydesketones 0 C H H30 R C RZNH Mechanism of Enamine Formation 939 3 H II I H0H I R39 C C RZNH R39 C 3 239quot 2 R39 ccl NR NR H2 H2 ino H H T C T H5H C 39 39 l W 1quot r 2 5 NR2 NR2 NR2 39 Fin O C II I NRz H H20 RI CC Example 0 II H CHgCCHQCHs CH32NH gt 8 Addition of Alcohols Acetal Formation H H C ROH Hp Example 0 CHgCH H 2quot 3 ZCH3CH20H gt Mechanism H 0H R 0H II H n ROH Bo R O R R C O R R n n A H R H5H R OR I I R BO 5 H R C o R R C o R R C O R I I A H R R R Acetals are quotprotected carbonylsquot I 2ROH carbonyl acetal H20 ROH Example 0 O C39OCH3 p O Mechanism of deprotection is the reverse of acetal formation Remember the hydrolysis below o R R Similar I I H30 O I I ogtlto H902 A HO OH R R R I H20 H o 0 o 0 H20 OgtltOH A H H A H R R R R R R Selective Acetal Formation alcohols are weak nucleophiles therefore selective nucleophiles aldehydes are more reactive than ketones therefore alcohols selectively react with aldehydes to form acetals In the presence of ketones l8 Examples 0 1 OH OH 1 eq gt H H O O 2 1 CH3MgBr H 2 H30 O O HO CH3 3 H V H 0 o 9 Oxidation of Aldehydes to Carboxylic Acids O O u u a R CH gt R C OH b Silver Reagents 1 AgzOTHFHZO 2 Toiien39s Reagent AgNH32 OHquot ii AgNH32 R C H OT Example CHZOH A920fi39H FHZO gt H 10 Addition of phosphorous ylides The Wittig Reaction 0 A phosphorous alkene ylide Prep of the Ylide 8N2 reaction of triphenylphosphine with methyl 1 or unhindered 2 alkyl halide R R BU39Li P CH X P C H X39 gt 3 R 3 R The Wittig Reaction R39 R R39 R CO QEP C gt C lt gtpo R39 R R R 3 Examples H H Que 3 CH3 gt CCH2 CH3 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 IQWWUOCDgt Robinson annulation ACIDITY OF CARBONYL COMPOUNDS 9 H3CC 39 CH3 0 H3C C 0 II II CHSCHZO CCHzC OCHgCHs S S CHa CCHZCOCH2CH3 0 II II CH3CCH2CCH3 KETO ENOL TAUTOMERIZATION O l 39 O 90 c c 45 C C H If E is present O C C 4 Cc E Acid alalyzed H 39r 39r HOH c C 239 c C lt gt I If E is present HO E CC lt gt y We first encountered keto enol tautomerization in the hydration of alkynes Which is the major tautomer at E0 Example 39 H HO C C H H 4 or 390H H Are Chapter 22 reactions important I Alpha Substitution A Alpha Halogenation of Ketones 1 acidic conditions n X2 acetic acid R C CH2R Example 0 Br2 acetic acid 39 gt H 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 I O R H R H Haloform Reaction X2 X3 ll OH ll R C 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 ll H 0 Convert to acid bromide first H O H O OH I ll PBr I ll c COH 3gt C CB HBr 1 CC ML I r Br UCWCHzCOzH 1 PBr3 Br2 gt 2 H20 O i l CiH gIi enolate Er C Br Hgt enoate 8 C Br Br Br C Alkylation of ketones and esters and nitriles H O l 3 O C C i C C 4 CC 1 I 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 Bu Li gt N H Nz39u Bu H 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 RzN H O CC E 3 Wheels 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 CH2x CC R X R C CI CH2X Examples 0 O W CH 5 Cl a Z 3 N H Hgol H30 1 CH32NH 0 CHzBr b Hac CH2CH3 HOT 39 3 E Alkyiation of Beta Dicarbonyl Compounds II II II II II II 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 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 gt R0 CCHzCOR CH3CH20 CCHzCOCHQCHs 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 HC 9 OEt D OEt O O 2 0 03 I H l32 R X 1Na39OEt C OEt X u c OB R c R H 0 I o COEt 180 C Example CH3CHZCH2I3HCOZH CHZCH3 Clquot 0 FCC O H lt0 OH O 4 7 0 II II CH3CH20 CCH2COCH2CH3 Formation of cyclic carboxylic acids with malonic ester synthesis ring size 3 6 M 0 03 I HClH Na OEt OEt O M 0 03 I H c quotD OEt O 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 O O ethyl3oxobutanoate u u quot quot eth I 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 II II 1 NaOEtEtOH II H CH3 CCHzCOCHchs CH3 CQHCOCHZCHs CHZCHs 1 NaOEtEtOH 2 CH3CH2 Br 0 CH30H2 OH 0 II C CH3CH2CCOH H30 CH30H2Cc39OCHZCH3 o CH30H2 CH3 CH3CH2 clo 80 C CHSCHZ CCH3 CH3 0 H3O Synthesis Example 0 o 0 II I QCH2 39 CHz39C39CHa lt 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 0 quot CH3CH2CH CH3CH2CH 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 Synthesis Practice From ethanal synthesize the compound below 9H 9 CH3CH20H2CHCIDHCH CHZCH3 B Crodssed Mixed Aldol condesation between two different aldehydes or ketones onsr er ll 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 9 9 NaOEtEtOH CHaCCHZCHZCCH3 W D Claisen Condensation Forms betaketo esters from esters O 0 II QHz39C39OCH2CHs CH3l3lOCH2cni3 W H E Crossed Mixed Claisen one reactant must have no alphahydrogens O o quot 1 NaOEUEtQH 1 CH339CI539OCHZCH3 2 H3o o O n 1 NaOEtEtQH 2 CHac39iCH3 QC39OCH2CH3 2 H3O F Intramolecular Claisen Dieckmann Cyclization similar to intramolecular aldol forms cyclic betaketo esters 1 NaOEtEtQH ll CH30Cn3CHzCH2CHZCH2COCH3 2Hay Synthesis of alphasubstituted cyclopentanones and cyclohexanones using Dieckmann followed by acetoacetic esterlike synthesis 1 NaOEtEtOH 2 CH3CH2 Br 3 H3Olheat H II cOCH3 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 H H n N OEtEtOH CH3 CCH2COCH20H3 HZCCHCCH3 i More Michael Examples C NaOEtEtOH CH3CH2039C39CH239CEN CH3CH20 C39CID CH2 CH 3 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 EtOH II H20CHCCH3 aOEtEtOH I gt O O O O O H 2C EtO39 l H O O O O lt lt lt O O o O O 0 OH H20 Stan a C h e m 3 3 3 2 CHAPTER 15 Conjugated Systems Orbital Symmetry UV Spectroscopy Types of Dienes FlCH CH CHCHR RCHCH CH2 CH CHR RCHCCHR Nomenclature review alkenes diene Preparation of Conjugated diene elimination of HX from allylic halide O Nasnigm gt Stability of Conjugated Dienes Compare heats of hydrogenation 1 2 3 H 2 IP dgt expeth observe 3 CH2CH CHCH2 m expect observe 4 CH2CH CHCH CH3 33239 expect observe Explanation of Stability CH2CH CHCH2 VS CH30H2quot CH2CH3 Allyl Cation H20 2 CH CH2 H C Stability CH3 1 2 allyl 3 substituted allyl How does conjugation affect reactivity HBr CH2CH CHCH2 Br2 V H3O Mechanism of addition of HBr H Br CH2 CH2 HBr 0 C ICHQ ICH CH2CH2 H Br H Br ratio of products at low temperature at high temperature HBr 40 C H Br ICH2 CHCH ICH2 H Br The process above is an example of Hate Kinetic versus Equilibrium Thermodynamic Control Agt6C D EM 1 n 0 0 N38 C 13m womb I w 1 I C H3CHCH Hz 39 25JL 5 W c Hg g vCHE39CHz CH 4quot 2 quot 39 cbn chem M MD gt Km 6001229 12 moo CH3 ICHCHCHZ 8r 19 ADD CHBCH CHCHzBr 5 Allylic Bromination B Br2 low conc gt light Consider allylic bromination in an asymmetric alkene Br gt H Br Br CH2 CH CHCH3 CH2 CH CHCH3 8N2 Displacement Reactions of Allylic Halides and Tosylates Nu A CH3CH2CH2 Br gt B CH2CH CH2 Br LNL Nu A CHSCH2 HH NU Cquot H lC39IIIIIH gt f 3 2 H CH30H2 H Br 3339 00 0 Nu 839 CH2C H NU H H Nu HCAH gt H26 OCLH IO lH Br H CH2CH CH2Br gt Example The Diels Alder Reaction a 4 2 cycloaddition and a Nobel Prize winning reaction D w A gt D w Mechanism gt gt The dienophile 1 Must have at least one good electron withdrawing group to be reactive electron withdrawal by resonance IS best 0 H CH OCH CH 3 2 3 O o O 0 if C H example other dienophiles TcozCHs 2 Stereochemistry of the dienophile is maintained gt0on3 alt A 00on3 CHsOgC A b I gt c302cgtH3 3 The Endo Rule The electron withdrawing substituent of the dienophile prefers to occupy the endo position on the new ring system Y X Example a gt J A H gt C n O O bgt lEKO A O Explanation One more quotendoquot example CH3OQC A Q l COQCHg The Diene 1 Electron donating groups enhance reactivity but are not required Examples alkyl groups R alkoxy groups RO K CH3O 2 Conformation H H CH3 CH3 H30 H gt H CH3 3 Translating the stereochemistry of the diene to the product H CH0 a CH3 A I H l CH0 CH3 lo DielsAlder Reactions Using Unsymmetrical Reagents Two possible orientations for reagents in the transition state Example 1 D A l E 23 l D 2 Example 2 U lp E o l E Explanation Stability of imaginary intermediate that results from imaginary electron flow from donating to wrthdrawrng group or the quotpush pullquot mechanism CH3O CH30 CH3 139 u H quot C H quotO c H C O M OCH3 l l CH30 M in l l Unsymmetrical Example CH3 H A H H30 CN H UV VIS Spectroscopy our most quotexcitingquot technique Pi molecular orbitals of CH2 CH CHCH2 CH2 CH2 W glean 7 CHAPTER 21 CARBOXYLIC ACID DERIVATIVES acyl derivatives and nitriles alum 3 I 3 L most can be directly or indirectly prepared from RCOZH all can be hydrolyzed to RCOZH Physical Properties see section 21 3 Boiling Point in general 0 O Cquot El u n R C NH2 R C OH R OH R CEN R C OR R C Cl Reactivity I lnterconversion of Derivatives Nucleophilic Acyl Substitution 3 0 3 E 3 R C Cl R C O C R R C OR R C NHZ Order of reactivity results from a combination of factors 1 Basicity stability of the leaving group 3 Cl 0 C R OR NH2 2 Resonance stabilization in derivative or How is the carbonyl carbon the more the more reactive II II n 9 l R C Cl R C O C R R C OR R C NH2 3 Steric factors consider when comparing different compounds of the same derivative Naming Carboxylic Acid Derivatives From Carboxylic Acid Names drop quotic aci quot add quotylhalidequot or drop quotcarboxylic aci quot add quotcarbonyl halidequot o a V H H CH3CHZCOH CHSCHltCCI O o i O I 7 w II Anhydrides Symmetrical drop quotacidquot add quotanhydridequot 0 O O O 39 i U 1 l CHfHZdocuLcuj Ctsc c o ccl Unsymmetrical name both acids composing the anhydride omit each quot acidquot and add quotanhydridequot 9 0 9 I III Esters Writen as name of alkyl group attached to 0 plus acid name drop quotic aci quot add quotatequot 0 n K C oR O o H U cu CH c 3 2 0 LCH3 CF C Ocu CH3 5 9 CH3 0 Quietch IV Amides Unsubstituted NH2 replace quoticoic acidquot with quot quotamidequot orgcarboxylic acidquot with quotcarboxamidequot Q I M C 2 o H 39 2 CH3 Substituted NHR or NR2 writen as name of substituent bonded to nitrogen pre ceeded by quotEquot followed by amide name formed as above o 39u O CH CH lt1 u 3 Z NHLHZCH3 CLL3IHCHZCNCHJ7 C H 3 C 3 V Nim39les Add quotnitr equot to corresponding IUPAC alkane name or for alkanecarboxylic acids replace quotcarboxylic acidquot with quotcarbonitrilequot O C CN H CH3CH1CHCHZCHZC39E N O CHSC CHZ CN C l39 Nitrile name39derived from an acid39s common name drop quotic or oic ac1dquot and add quotonitrilequot 7076 CE As a substituent name as a cyano group CEN lt2 39 n v I cuBCH CHLCHZCOH CH3CH CHLCKNHZ Synthesis and Reactions of Acid Chlorides RCOCI O R c39 OH 39 1 R39MgX or R39Li R ZCULI 2H3O O 2 g R cquot lt R39M X rR Li AC3 Cl 9 1LiAH4 H20 0 R39OH NH3 R39CO39 Na or RNH2 or R2NH v Example Mechanisms o HO Rita Lgt O o H R39CO39 Na n etc Synthesis and Reactions of Anhydrides O NaOH 3 R R C OH O R CI 0 O 7 II II RCOC R AICI3 H2 Example Mechanism II II move R m Cyclic Anhydrides 8 H 0 OH HEAT gt C OH 9 0 Example 0 CE O Synthesis and Reactions of Esters O 0 II n R CC R COH 1 RquotMg or R39Li R39Ol39 R39OH H 2 H30 if H 0 Hi or OH R COR Rquotng or RquotLi 1 LiAH4 RquotOH H H30 NH3 or RIINH2 1 DIBAH or Rquot2NH 2 H30 Cyclic Esters II H H39O39CHchZCHZ39C gt OH Saponification 3 NaOH39 393 El R C R C OH OR R C OR39 Synthesis and Reactions of Amides Few reactions fortunately PM 5 2 0 T3 ll NH2CHC NHCHC NHCHCOH o O NH3 II Rg or RNH2 R C39NRz cu or R2NH fl R CNHR II HZOlieat RCNH2 POCI3 0 SOCI2 or P205 H or OH 1 LiAIH4 Br2 0 2 H20 OI39 H3O Reduction of Amide to Amine 0 II RCNH2 H AIH3 Ll 0 Ni 1 LiAH4 gt 2 H20 OI H30 Dehydration to Nitrile 1 amide only 0 0 II R C39NHZ Cl S CI ll CH3CH2 CNH2 04 Synthesis and Reactions of Nitriles I R CNH2 R X NaCN POC3 or SOCI2 or P205 H20Heat 1 R39MQX lt RC EN gt H or 390H 2 Hao 1 LiAIH4 2 H20 or H30 or H2 Pt or Ni Hydrolysis basic conditions O H O H CN 39 I 0H R RCN R39CNH Reduction to Amine MEN H AIH339 Li Examples 1 CHaCHgCEN NaOH I Heat 2 CH30H2CEN 1 LiAlH4 2 H20 or H30 or H2Pt or Ni 1 CHaCHgMgBr CH E 3 3CH2 C N 2 H30 Spectroscopy Summary of Carboxylic Acid Derivatives 0 II c stretch IR 0 carbon 30 NMR other 0 R E cr 1800 1775 cm391 170 ppm 3 lt3 1800 cm391 R C O C R 1750 cm391 170 ppm 0 ll R C OR 1735 cm391 170 180 ppm 0 1 IR NH stretch RCNH2 1640 1680 cm 180 ppm 32003500 cmt 1 2 peaks 2 1 peak 3 no peak 1H NMR N 59 0 often broad D20 exchangeable RCEN IR GEN stretch 2200 cmquot sharp medium Example CGHHNO f 333532 39 sous 1 Hvlllluttllltltu uqrurluu HI 6 s 4 5 2 Chemical shift ppm C6H15NO frTY r l vflTlvv 33 32 315 1 10 0945 TMS nnunn1muqu mmnrlmunulu1nu uuwu n Wm nyIHIHHIl39MKIHVHIV 1400 600 10 9 8 7 6 5 4 3 2 1 06 quot Chemical shift ppm BrN 3rg L IZS 539 775 1 O r3 n 59 CHAPTER 20 Carboxylic Acids RCOOH RCOZH CAIm 3 3 3 L aliphatic acids aromatic acids fatty acids STRUCTURE 0 R4 II R PHYSICAL PROPERTIES I Boiling Point gt alkanes ethers aldehydes ketones 0 vs R O ll Melting Point crystal packing ef ciency is important presence of double bonds especially cisdouble bonds lowers MP H CO2H H COQH I I H COQH H020 H Stearic acid C17 saturated Linoleic acid C17 tWO CiS Solubility in H20 greater solubility than alcohols more than 6 carbons only slightly soluble in water the salts of most carboxylic acids are water soluble CARBOXYLIC ACID NOMENCLATURE I Open chain acyclic drop quotequot from alkanealkenealkyne name add quotoic acidquot QOOH carbon is always 1 priority over all functional groups studied so far see table p 985 3 3 i CH3CIJCHQCH2 COH H20 CHCH20HQCH2COH CH3 0 O O 0 El II II CHgCCHQCHg COH HCCHQCHgCOH HOCHchecHzCOH ll Cyclic add quotcarboxylic acidquot to the cycloalkane or cycloalkene name Q COOH is always 1 002H Br 002H OH I Dicarboxylic acids add quotdioic acidquot acyclic or quotdicarboxylic acidquot cyclic CH3 Br CO2H l HOZC CHQCHgCHCHCHQCOZH l CH3 r cogH quot coZH COZH ACIDITY OF CARBOXYLIC ACIDS I Strength weak acids 0 II II R COH H2O R CO H3O E E R COH NaOH R CO Na 4 H20 Factors that Affect Acidity HA H A39 A Resonance 3 CH3COH VS CH3CH20 H l B Electron withdrawing groups CF3002H CCi3COZH CIZCHCOZH CH30H2CHC02H CH3HCH2COZH FHQ39CHgCHZ39COQH III Cl Cl C Electron donating groups COgH 002H cogH H30 CI HO CICHZCOZH CH3CH2 CH2COZH COQH can c02H Synthesis of Carboxylic Acids Review I Oxidation of 1 alcohols and aldehydes KMnO4 O or CrO3H2804ll20acetoneJones39 ox II RCHZOH or Na20r207A12804 i20 r R39C39OH 0 any of above reagents or O u 39 l RCH 139 AgNH32 OH gt RCOH 2 H or Aggon39 H FHZO II Oxidative cleavage of alkenes and alkynes H H KMnO4concwarmH20 I C CC AV RCOH R39coH R R39 39 1 KMnO4H20OH39lheat A II D R CC R 2 H RCOH mom or 1 03 2 H20 Ill Oxidation of alkylbenzene side chains R 1 KMNO4H20heat COOH 2 H or 39 NazCr207HZSO4heat NOTE These conditions oxidize other oxidizable functional groups IV Carboxylation of Grignard Reagents R X Mg ether R ng 1 002 ether 2 H3O MgBr 1 C02 ether y 2 H30 V Hydrolysis of Nitriles NEWI mechanism in Ch 21 H30 OR 39OH R CN heat CHacHzCHgCN H30 gt heat OVERVIEW OF REACTIONS OF CARBOXYLIC ACIDS AND THEIR DERIVATIVES 3 9 Wm R H Fi CR vs FiCY YOH Y Cl Br Y OR The carbonyl carbon in an acyl compound does not react by the same mechanism as the carbonyl in an Y NH2 NHR NR2 aldehyde or ketone O n aldehyde lketone Y O C R acyl compound REACTIONS OF CARBOXYLIC ACIDS l Synthesis and Reactions of Acid Chlorides 9 S reactivity RCOH vs RCCl A Synthesis 1 Review Most common reagent and mechanism thionyl chloride 0 o o I o O o O 0 II II II II II H II RCOH S RC SCl gt RCS CI gt RCOS CI gt RCCI Cl CI H CI 2 oxalyl chloride better yields but expensive 0 H II II R COH CI C C CI quot gt COgH cool2 gt B Reactions of Acid Chlorides more later 1 Review Ester formation 0 0 II I ll RC CI R39OH gt RC39DCl gt RCo gt Rquot9 H R COCI CH30H20H gt 2 Amide formation BEST method 9 l i H RCCl R39 NH2 gt Rc oi gt RC H gt NH R39 R39 H COCI CH3CH2NH2 gt Synthesis of Esters A Review Fischer Esterification 0 II II RCOH R39OH gt RC0R39 H20 Proposed mechanism 1 O II 0 I RCOH ii H20 H mm E RABH R39C O R39 gt RCo R39 lt I lt H Proposed mechanism 2 B Esterification with Diazomethane 0 ll R39C39O39H CH2N2 gt O n I CO H 00 0 m 0 CHgNEN gt l Direct Amide Synthesis 0 quot R NH II heat RCOH 2 gt RCO H3NR gtH20 IV Reduction of R002H A Review LAH reduction not selective 3 1 LiAIH4Et20 RC39OH H30 0 0 II CHaC CH25OH 1 LiAlH4Et20 gt 2 H3O NC B Diborane reduction very selective COZH reacts faster with 32H6 than any other functional group C 0 CH c quot 3 CHZC OH 1 3sz ldiglyme gt 2 H3o NC C Review Reduction to aldehydes u some 9 LIrAHOtBu3 RCOH gt Rcc H2PdBaSO4S 002H CHO V Ketone Formation Review OL39 quot 2R39LI I 39 H30 9H RCOH gt Rco Ll gt RCOH gt R39 51 S 120H3Li CHaCHgCOH 2 H30 VI Decarboxylation The Hunsdiecker Reaction converts heavy metal salts of RCOgH into aikyl halides with 1 less carbon II HgO or A920 or PbOAC4 R39C39OH heat Br2 ICCI4 Mechanism first carboxylic acid salt is formed with metal then 0 0 II II RCO Ag Br Br gt RCO Br II II RCO Br h eat gt RCO Br 0 II R CO gt R C02 0 0 II R RCO Br RBr R C O HgO I heat Br2 ICCI4 CHSCHZCHzEOH o SPECTROSCOPYSUMMARY O IR R3lt 1710 1760 cmquot1 o H L 2500 3300 cmquot1 often very broad see spectrum below 1H NMR R g 11 12 0 OH always a singlet often broad D20 exchangeable 130 NMR C 200 215 ppm Isolated RC 190 200 ppm conjugated gto H wavelength pm sample IR 100 so 60 20 2500 1800 1400 1200 600 wavenumber cm l 339 unknown 39g C4H602 3 10 8 6 4 2 0 ppm Chemical shift 8 3661 n 2 CHAPTER 14 Ethers Epoxides Sulfides 7 CV m 3331 Importance Structure Polarity Physical Properties CH3OCH3 CH 3CH2CH3 CH 3CH2OH O R dipole moment boiling point Ethers as Solvents limited reactivity not as toxic as chlorinated solvents such as CCI4 CHCI3 CH2CI2 low boiling so easily removed large dipole moments and H bond acceptors so dissolve polar substances no Hbonds between ether molecules so dissolve nonpolar substances no Hbonds to disrupt no acidic hydrogens so can serve as solvents under strong basic conditions 0 O 18crown6 CH30H2 o CH20H3 2 0 CH3 Ether Complexes a Grignard reagent b Boron reagents 0 Crown ether cations Nomenclature of Ethers I Acyclic Ethers 2 accepted systems A As alkyl alkyl ether Name each alkyl group attached to oxygen in alphabetical order and add quotetherquot common name EH3 CH3 l CH3CH20H2 39 O 39 CHQCH3 CHa39cl O CH39CH3 CH30H20H2 39quot O quotquot CHQCHQOH CH3 B As alkoxy alkane Name the RO group as an alkoxy group The larger or more complex group is chosen as the parent name 9H3 9H3 CHgCHgCHg o CHQCH3 CHsg 0 CH39CHs CH3CH2CH2 o CHQCH2OH CH3 ll Cyclic ethers Epoxides 3 accepted systems A Common name Name of alkene used to form the epoxide plus quotoxidequot industry uses RCO3H 0 RCO3H O CH2CH2 gt CH2CHCH3 gt H20 CH2 H20 CHCH3 B Name the oxygen of the epoxide ring as an epoxy substituent Use both numbers of the carbons bonded to oxygen to designate position 0 O H o H H20 CHCH3 OH I CH3 CH2CHCH3 C Name as derivative of oxirane O O O HIz H C2H3 CH3 CH2 39 CHaCHCHA CHacHQCH OH I 2 CH3 CH3 H20 209 Nzozwmzo mO 2qu Nxozofo 10m 5 I Illllv vImmz All fozwmzo fo 5 foa az waxo o o 1000 mIOomIo mI o o Nolzofo A fmmz m IomIoEEova I mO A 10m All NI H m 10m E2051 o 0 0 EmEEoo z 0H0 CongEwEchozEomEgtxovlt Immz N 10m hwy65 IIIV fouzofololo b T xolm Y mzozo okzofo fo T N I I u I XIO m mZO EImZ hov o 52 IO I lt mww cgtm 55m owEmgtgt mmmrhm m0 mwmzgtm ii Ill Symmetrical ethers through intermolecular dehydration of 1 alcohols RO H HOR Hgt H20 H so Ex 2 CHSCHgOH Woo 4 Mechanism H ROH Hgt RIOH gt R oR gt R OFl ROH H 30 NOT for unsymmetrical ethers CHSCHgOH CHa O39H REACTIONS OF ETHERS ethers are unrective to many organic reagents ether bond 00 is stable to l Cleavage by strong acids HI and HBr not HCI ROR Hl or HBr XS ea Mechanism CH3 CH3 H I CHQCHQ O CHCHQCHg W CHQCH2 9 CHCHQCH3 gt H CH3 r H l O CHCHQCHa XS ll Autoxidation DANGERll I 02 XS I l R O C H gt R O C OOH RO O C H I slow Synthesis of Epoxides I Epoxidation of alkenes with peroxyacids n CC RC 00H gt Mech a concerted process 00 H 1 0 g C I O C Hll o HJ Electron rich 7 bonds react fastest I MCPBA gt 1 eq Stereochemistry of the alkene is maintained H CH3 CC H30 H MCPBA 39 gt ll lntramolecular Williamson l 8 x I NaOH H CH3 1 Br2H20 CC gt H30 H 2 NaOH Larger cyclic ethers can also be formed H O NaOH gt Cl REACTIONS OF EPOXIDES l Acid catalyzed cleavage O H 0 Nu ll Base catalyzed cleavage If the epoxide is symmetrical the results of acid cat and base cat are the same Consider each process with asymmetrical epoxides l Acid catalyzed cleavage CH3 CH3 H C CID CH H Cat 39CH 3 2 CH30H H30 C 2 9 H II Base catalyzed cleavage CH3 I H c c CH CHso Na 3 O 2 CH3OH Summary 1 Weak nucleophiles H20 ROH Cl 39 only react with protonated epoxide 2 Strong nucleophiles OH 39 RO 39 NH2 39 CN 39 carbanions react with unprotonated epoxide 3 Acid cat process Nu attacks the more substituted carbon 4 Base cat process Nu attacks the less substituted carbon Ill Reaction of Epoxide with GrignardOrganolithium Reagents o H c CH CH 3 4 5 l 2 3 CH3CH2 MgBr H CH3 IV Reaction of Epoxide with Acetylide Ion O i 2 CH3 CH3CEC39Na gt CH3 Compareto 0 ll CH3CEC Na CH3 C CH3 gt A Biosyhthesis squalene23epoxide squalene several steps HO cholesterol The organic Chemist39s mechanism squalene23epoxide cholesterol Tseveral steps HO Spectroscopy of Ethers IR absence of 0H stretch alcohols and carbonyl CO stretch aldehydeketoneacids CO stretch between 10501150 cm 391 is usually strong I 1HNMR Ro Iz H 34455 13 CNMR39 no c R 65906 CH3 O CH2CH2 CH3 H Spectroscopy of Epoxides 1H NMR protons of carbons adjacent to epoxide oxygen slightly higher field upfield than those of of other ethers 25 35 6 H3C 0 H H H Unknown Example CSH14O I v I v I I I r 1 I T I I 1 I a lllLLLLllllllLLlLL L1 Li 1 1111 l l 3 I D I 0 75006 Mel 20w MSW MC Nw lg JIM loo 7 l l l l 2 I 3 l e l x L L 4 I 39 g1 19 7D 0 5 u 30 1H NMR Spectrum of 12epoxypropane H30 H 9 8 7 I 6 5 4 Chemical shift 6 0 ppm


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