Organic Chemistry CHEM 2443
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This 9 page Class Notes was uploaded by Esteban Towne on Thursday September 17, 2015. The Class Notes belongs to CHEM 2443 at University of Connecticut taught by Michael Smith in Fall. Since its upload, it has received 7 views. For similar materials see /class/205914/chem-2443-university-of-connecticut in Chemistry at University of Connecticut.
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Date Created: 09/17/15
Reactions of Alkenes H2 Pd or Pt syn addition HX XCI Br I or OSO3H Markovnikov addition H3O Markovnikov addition 1 HgOAc2 HzOTHIF 2 NaBH4 Q Markovnikov addition H3 C H NOTES A wavy bond eg WW means either up or down ie not stereospecific 1 BH3 THF 2 H202 0H X2 XCI Br Anti addition X2 H20 Anti addition follows Markovnikov39s rule 9 RCOOH Peroxy acid 1 03 2 ZnH3O HX ROOR antiMarkovnikov addition A H H CH3 X H CH3 OH H CH3 OH H C H H OH CH3 X A X H CH3 X OH H CH3 H 13 Hydrogenation Ionic Addition of HX Acidcatalyzed Hydration Hydration by Oxymercuration Hydration by Hydroboration Oxidation Halogenation Halohydrin formation Epoxidation Ozonolysis oxidative cleavage Radical Addition of HX Reactions of Alkynes R CEC R Internal Alkyne R CEC H Terminal Alkyne H2 NizB or Lindlar catalyst Syn addition Li NH3 Anti addition 2 H2 Pt or PdC l HX X Cl Br Anti addition follows Markovnjkov s rule X2 Xc1 Br Anti addition KMnO4 H3O H2804 H20 HgSO4 1BH3 gt 2 H202 HO39 NaNH2 NH3 1 NaNHz NH3 2 RCHZBr 103 2 HOAc or R 39 CC Hydrogenat1on gtC Hydrogenation H 1F 1 HC EH Hydrogenation ll H C Add1t1on of HX R A C Halogenat1on OH RCquotO I Oxidative cleava e 0 R g HO R H Mercuric R gtCClt ic CgH sulfatecatalyzed HO O H hydration methyl ketone O R CHZ Hj H Hydroborationoxidation R CC Formation of Acetylide Anions R CEC CHZR Acetylide Anion Alkylation converting 1 If 10 or 207156 SOCIZ 1 1 If 1 or 2 use PBr3 13911 Alcohols to RZ C OH RZ C Cl Rz IZ OH RZ ll Br Alkyl Halides 1amp3 1m Hcl 1amp3 R3 3 v HE R3 0 O NBS M d Br Chemist N B we ry r M N H alkene or O O benzyl N bromosuccmlmlde NBS 233352 1 Mg 1quot g RZ E x RZ IZ Mg X R3 R3 Gilman R X 2 Li R Li 2 Lix Reagents 2 R Li Cul R Cu R LiI Li R CuR L R39x R R RCu Lix Lithium diaklycuprate alkane Gilman reagent pmduCt Summary of SNl SNZ E1 and E2 Reactions Halide Type SNl SNZ E1 E2 10 R CHZX Does not occur Highly favored Does not occur Competes with SN2 but orgy strong bases 20 RzCHX May occur Competes with E2 May occur Favored with strong benzylic 0r allylic benzylic allylic bases 3 R3CX Favored esp in protic Does not occur Competes with SNl Favored with strong polar solvents bases Nucleophilicity N basicity Strong bases examples alkoxides RO39 hydroxide HO39 hydrosul de HS39 hydride H39 Weak bases examples halides F39 Br39 Cl39 139 ammonia NH3 alkyl amines RNHz RzNH R3N CH3 Sterically hindered nucleophile example tertbutyl butoxide Hsc O these often help enhance elimination over substitution Allylic and benzylic alkyl halides help E1 and SNl reactions relative to E2 and SN2 CH3 Reactions of Benzene X2 FeX3 X Br or Cl X Bromination 0r Chlorination Iodination I2 1012 Q HNO3 H2304 No2 0 Nitration SO3H SO3 H2804 Sulfonation R RX A1013 F riedelCrafts R methyl ethyl 2 3 alkylation Deactivated rings do not react Primary alkyl halides may have carbocation rearrangements 0 II R R cc1 AICI3 Q FriedelCrafts acylation Electrophilic Aromatic Substitution of Benzene Derivatives X X other reagents to add Y to ring i Y Substituent X Reactivity Orientation Inductive effect Resonance effect Alkyl Activating Ortho para Weak e39 donating None OH NH Activating Ortho para Weak e39 withdrawing Strong e39 donating 39 2 Halogen S hd W k d t F Cl Br I Deacnvatmg 011110 para trong e w1t raw1ng ea e ona mg 39NCH33 Deactivating Meta Strong e39 withdrawing None ggaSER Deactivatng Meta Strong e39 withdrawing Strong e39 withdrawing COCH3 Notes 1 Halogens and groups containing a highly electronegative atom that is not attached directly to the ring will deactivate the ring 2 Some substituents have the inductive effects and resonance effects working against each other e g OH NH2 halogens The stronger effect wins out 3 There are no known groups the are meta directing as well as activating 4 Halogens are the only type of substituent that are orthopara directing and deactivating All other deactivators are meta directing Alcohol Reactions Reduction of carbonyls Synthesis of alcohols Carbonyl Grignard reactions O O 1 RM Br ether 1 L1AlII4 ether RCHZQH g RCHZ OH C C R H 2H30 H H 2 H3O ICI 1 LiAlH4 ether H OH ICI 1 RMgBr ether H OH gt gt c c c 1 c R R 2 H30 R R R H 2 H3O R R O V II 1 L1A1H4 ether RCHZQH R OH 1 RMgBr ether R OH c i gt c R ORY 2 H3O RyCRu 2 H304r R Rv O 1 L1A1H ether 4 RCHZOH 1 2 RMan ether R OH C gt c R OH 2 H3O R1cORH 2H301 R K can also use NaBH4 instead of LiAlH4 RquotOH Reactions of alcohols Alkyl halide synthesis Oxidation O a PCC 39 0012 RCHZCI RCHZOH gt u g a RCH OH 0 2 0 RCHZBr CH2C12 R H g g 1 or2 PBr3 a o 5 CE HCl R3CC1 Jone s reagent g o RCH OH gt H H R3COH 2 c s a R CB H O t E a 30 only HBI 3 r 2 ace one R OH E 5350 O H I H OH Jone s rea em 0 Dehydration g E B 5 C H OH R R R39 orPCCCH2C12 R R H3O cc quotllR 30 only R Acidity R ROH NaH gt RO39Na H2 H OH POCl cc 2 ROH 2Na gt 2 RO39Na H2 W quot pyridine 20 or 3 Carbonyl Reactions Aldehydes and Ketones Aldehyde Preparation Nucleophilie Addition Reactions 0 1NaBH4 0 OH PCC gt CH 2 H3O CH2 CHZCIZ H R OH 1 RMgX gt C 103 TI 2 1130 CR gt IC 2 Zn CH co H C 0 39 3 2 H HCN gt lt CCN cyanohydrin Ketone Preparation TI N R C RNHZ OH o lt 0 me I Jones Reagent or gt C RCH R R R NR2 I quot RZNH I enamme lt C R R C o H c 103 n 2 g H k C 2Z CH CO H HNNH 3 am R R n 3 2 R R 2 2 cH WolffKishner KOH o 0 OR H A1013 R 2 ROH acetal C gt gt COR R CI H30 R R Ph3PCR2 c alumna o h if gt H Wittig I et er THF C chuLI C gt R CI R R C ory39ugatea39 Addition Reactions 0 0 g 0 g C R C R C NHR H H2 fl 1R 2CuLi ether CI C C C C R CH 2H20 R E R 2 Carbonyl xSubstitution and Condensation Reactions Endformation Dieckmann Cyclization II IDH O o o C H gt C 39039 g C R lt R Y H C OR Base HZC CH OR 2 U 4 Alkylati on H2CCORH A cyclic Bketo ester 0 If I H g H 1 Base C R O R gt R 74 2 R39X Michael Reaction I O II II E M alonic Ester Syntheszs C C C H C O R39 C R I II I II H2 1 Base C R39 A An Bunsaturated B keto ester or 06 C C gt HO O I 39 t carbonyl RO C 2 RIX H2 ma 0111 CS er H2 39 Base h t co 2 ROH A malonic ester 339 H3O ea 2 R OC Aldol Synthesis o o OH CH CCHC Base ICI ICH R oc I C gt H C R lt H CH CH2 R39 H2 Fe Can also use ketones but slower will get a Bhydroxy ketone A B hydroxy aldehyde Stork Enamine Reaction Aldol Dehydration if at o N I t H c c c C c c H CH gt HCC R C C I or HO I I I An enamine An Dillunsaturated A Bhydroxy aldehyde Can also stalt with Bhydroxy ketones carbonyl l THF Claisen Condensation Reaction 2 H3O o I II o 2 g Base C C k C E RHzc OR39 lt RHzc fH OR39 R C c R H A 15 di ketone A Bketo ester Carboxylic Acid and Derivatives Reactions C arboxyli c Acid Preparation 0 CH KMnO4 II Ph 3 gt C H20 heat ph OH KMnO4 O cclt g H3O OH Jones I OH OH gt 2 CrO3H3O COH O H Jones 0 C H orAgNH4OH COH 1 H3O O 2 NaOH H20 COH 1 CO2 O R MgX gt g 2 H30 OH General nucleophilic acyl substitutions 0 Nu W H C Y Y NU where Y Br Cl I acid halide OR ester 0 OICI R anhydride NH2 amide and Nu nucleophile such as NH3 NHZR NHRZ NR3 OH39 H20 H39 ROH RO39 CN39 Reactions of carboxylic acids 0 I 30012 Id C C chlorlde OH CI 0 o 0 heat 200 C I H anhydnde Cl C C OH o I 25 C ether If c gt c 0 CI O anhydride 0 O 1BaseR39X H II gt C ester COH 2 R X OR39 I R OH 393 gt I ester C COH Acid catalyst OR Speci c nucleophilic acyl substitutions O O H 0 2 g Y C Y hydrolysis OH H or 0H catalyzed O ROH H II gt C Y CY alcoholysis OR o 1 LiAlH4 ether OH g 2 H3O CH2 Y Y gt reduction 0 l 2 R39MgX ether OH R39 2 H 0 0 Y C 3 Y R39 Grlgnard O NH3 E g C Y Y aminolysis NH
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