Exam 2 Study Guide (Montague-Smith Fall 2015)
Exam 2 Study Guide (Montague-Smith Fall 2015) CHEM241
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This 30 page Study Guide was uploaded by Carianne Powers on Monday October 26, 2015. The Study Guide belongs to CHEM241 at University of Maryland taught by Dr. Montague-Smith in Summer 2015. Since its upload, it has received 170 views. For similar materials see Organic Chemistry 2 in Chemistry at University of Maryland.
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Date Created: 10/26/15
CHEM241 Exam 2 Study Guide This study guide provides a detailed VERBAL explanation of each of the mechanisms on the list given out by Dr MontagueSmith This is so you understand the general concept behind each mechanism instead of the exact arrow pushing since the arrows can vary depending on the problem However I will attach the arrowpushing example that he provided in class at the end There will also be mechanisms Dr MS has listed in passing that will most likely appear on the exams These do not have mechanism explanations Acetal and hemiacetal formation and hydrolysis in ACID 0 ROH XSL OR KAR Ht 39 RR l OR Mechanism HEMIACETAL 5 OH o H L lt1 1 R R R R R 9 R W0 39l lmes I Turn O into OH by Attach the R39OH by e OR e attack on the attack on the positive free proton charge Remove the H Use resonance to from the newly attached Tum OH 39nto H20 place the positive R39OH using another 900039 LGquot leaves39 charge onto the R39OH e attack on the H gaitizznscgig tert39ar carbon I y pmton charge onto the OR group I OR I R R R OH R Y R a J we hmes o 39 OR 99 R Attach the R39OH by e attack on the carbon Acetal formation is transferring the pi bond REVERSIBLE using H30 onto the OR group and hydrolysis so you have to use cancelling out the positive DOUBLE ARROWS he will charge Remove the H dock points if you use single from the newly attached direction arrows R39OH using another R39OH e attack on the proton Imine and enamine formation and hydrolysis in ACID NR39 0 RLNH Imine KJKK fiquot RIL Px HEMIAMINAL Mechanism 0 OH RH OH x L i N 23 R R R R R C9 R wo imeS R39 N H Tum 0 into OH by Attach the R39NH2 by e 9 attack on the attack on the positive free proton charge Remove the H Ilgfvggoase Use resonance to from the nery attaChed gesonahc to Iac the place the pOSitiVe R39NH2 usmg anOther positive charggonto the charge onto the e attaCk 0n the group tertiary carbon Proton 39 R R quot R R Y I C R quot NHZ I N R or 7 R N quot39 H H20 Remove the H using R39NH2 or H20 e attack on the proton O Enamine I RkR Mechanism KN Turn 0 into OH by e attack on the free proton Use resonance to place the positive charge onto the tertiary carbon R N Rquot KL NH H OH II quot K R 122 N H K 9 ero limes Attach the Rquot2 NH by e attack on the positive charge Remove the H from the newly attached Rquot2 NH using another Rquot2 NH e attack on the proton RTo KNH P VNR Use Rquot2 NH e attack on the nearby H transfer sigma bond onto the positively charged carbon to create a double bond RR R HEMIAMINAL OH R l R llNR Turn OH into H20 good LG leaves H H H R 3 I R an Ru Acid catalyzed esterification and hydrolysis AKA Fischer Esterification Turns a carboxylic acid into an ester 0 I k ROH R OH H A R OR39 TETRAHEDRAL INTERMEDIATE Mechanism o l 39 OH O H H R OH 1 R 9 OH ero James I R OH OR Turn 0 into OH by Attach the R39OH by e e attack on the attack on the positive free proton charge Remove the H Tum OH 39nto H20 900039 Use resonance to from the newly attached H LGquot leaVeS39 USe resonance place the positive R39OH using another to place thep9339t39ve Charge on charge onto the R39OH e attack on the the rema39n39ng OH group39 tertiary carbon proton O R 39oH 69 z RJL OR RJL OR39 Remove the H from the OH group by using R39OH e attack on the proton WolffKishner Reduction 0 HzN NHZ H H RAR OHA RXR Mechanism creates 39 H20 o quot H N NH IMINE FORMATION N N H OH gt A R K R39 NH2 R R Remove an H from the R E R NH2 group using OH e attack on the proton Transfer the lone pair on the N to the sigma bond to create a double bond between the two N39s H Pi bond transfers a Add a Prom onto the negative charge onto Garbo by E attaCk the carbon on the H in H20 R K e N NdH HgtltH H OH R R NZN39 5H e re e H R 9 K R Add a proton onto the carbon by e attack H Transfer the lone H Remove the H H from the NH group using OH e attack on the proton on the H in H20 pair on the N to the double bond to create a triple bond between the two N39s nitrogen gas great LG leaves Pinacol Rearrangement R O OH OH A R R R Mechanism 6 R OH R OH O OH R iR L R R 6 9 R L R V G R Tum OH into HZO R Use resonance to R good LG leaves create 3 dOUb39e Transfer R rou onto bond between g p the C and O Remove H from OH the posmvely charged carbon in order to place HZSOLI QFOUP USlng H2304 6 attack on the proton positive charge onto the carbon attached to the remaining OH group Swern Oxidation O O OH IN Hm DMSO 0 RXR 23 Raw C Ci K45 l D K N 39 395 Mechanism ch 075 g lH 9 19H a R CR R K K C R l s Create reagent O ll H l e S 5 S Use 0 e attack on the carbon to attach the O to the carbon and simultaneously kick off the Cl Use Cl e attack on the positively charged 8 to attach the Cl and kick off the 0 group Resonance Create product c D 8 I l 5 H H gt O 3 VA V q H R R K R Att h th s R R R R Remove the H ac e from the OH group by USlng 0 Transfer the sigma b usin CI 639 attaCk 0 the bond between the C y g e t l h ol attack on the pOS3939Ve y C arge and H to the bond t 8 S39mUItaneOUSIV between the C and 0 pro 0 kickin off the Cl 9 to create a double bond simultaneously kicking off the 8 group OTHER S m nesis ff R cuz OH JE a RC H ACoho 0H 3 C R R jones 20 Akcohd O 10mg Ra CHZ OH f a RCOH O O l5 l C Cl was kK JOL CEO INC13 H O 2 R CECH m R C CHS H1Oq O H 239 20 HC OTHER Reduc dons O 9 xz cu OH g H 3 H i Z R 23 so 9 3 QR 1 C R 1 ci R Mechanism 6 O lt8 R xLc R a H R K H H a2 G n NOBL Cgt H O RIC H R CHz OH 7 130 3BH3 Aka u gt 7 H30 I3 L Amq LAH 1 HBOr LnJ hlum Alumnum Hydride OTHER HMS n Madam gt C3 30 OH OH 1 H3O H 0 RCR lt RXR 13 BH3THF unsmbxe 23 30 0 I LAH 30quot 23 H30 b gt N 1 c O OH XLH H303 you cl Cl 0 C H soooe Chom 39 Chlorat m5de Caadg4ic Hyatmgena on O O Carbonyls aren39t 6 2 lt5 affected by H2Pd 49 Pd H 0 0R Ni H7 3 gt Loo ATM 200 C H O OH 9 5 i3 OTHER C ggbow Organomdauig K qu R L nqnams 7 Yilae 6 II R O 6 01239 Li R 39 K Ric R Z H30 2 R O K R R o H3 0 H5ccuz cm 23 H30 add 0wa 0 0H ll 0 R Mggtlt R Cl Addmon o RLt and R c H 2 30 0 R R MO SX 0 30 7 m is lrreversable 0 09 H 3 2 MQX y R OTHER voi edinq C39VDULPS Mr usumk A F A 2 7 X lt1 gt i lt1 lt1 3 D 6 E TwoRC 39B A 3 A F F Ck a Q A O gt B B B S E Sep 139 Segt 239 pvoe c depm re c quot Aceas m e carbonws Mquot O o O R Br L R MgBr o lt5 23 H304 Br 0H lHDr IJHH r1 0 0397 0 3 3 o 6 M90 L3 H30 3 OTHER Rgsi 3 Speci cally M633 pYMec Hng gvoup Cor alcohols R A OT MS i 9 R A 0H TBARH J x F 9 Jr Te rmbu l Ammaniuun Flounde g M l39 o o H O O 0 Bones H M H 392 N H H O o 0H T nor23H H O o M H Aones o 0 H OH o JTMS Cl OTHER Stun Enam3n Stanthesis Q e RAoTos 66 o N gt quot 4 SN UR 30LA O lt20 9 N R MR k A kg Starts pulling proton away R K A R from N makes N more nucleophilic charge 1 H A 30 attacks the carbon H 12L 6 HOH PKOt 21b 9 wt EAD LG7 quot M C 0 or ogJuOH to R R we gt e67 a y IN N H 12 39 12quot Ce 2 e0H OTHER Mm Reac gn G9 GR R R O RQP CR i 1 R R LmE Making kjLiau 0 W gtR3quot 19 OK 1 12x12 05 Jr Ra Br hr39gtneny phosyhine ri ouIl phosph39me RABr Ml 5 93 3 Vl l qrMLPS39 pkg 1 0 CH quot Wquot gt a RL 2 R R q 1 Ye W P R 3 P RHS EtaC R4 Madnamm g 0X avhosphamne 0 Iva5 O PR3 O 9 21 H 4 r a c J Cl H EH a H CPR H 9 e 1C R3 Con 9 w OH CH3 CH 30 G G 2 04C LIA q 0 Cgt 0 0 Hzc th3 4 04 CH NNM 39n lou mom C 739 OTHER 0 gawk Ui139c5er Rm 0 u MCPle A CO MCPBA SCcJr 6 3c 0 O 0 KM MCPBA P O K R akgS cer 6 MCPBA 935 N f quot di elem slzc 0 25323 MC PBA gt O lk Awath O MCPBA 0 Hi MCvBA O H C mlzmm Pemdion O o HLX L Cow oongs O O O KMnO ONZ39S 4 k H OH 0H AOH OTHER Sggnlhesis O bones l RAOH 9 R 0H KMnOLl 4 ll OH H l O R koH e9 0 IX C02 53 AK 39 gt R39 o 0 0333 M 2 H HOOH R OH R UOH FL O OH r Cant use a Fischer sterlflcatlon wrth R Km T N a phenol or tbutyl alcohol but can a A do reverse as if the forward was possible 0 l on 50 o RUO A P OH 0 OTHER Direct Alkylation of Carboxylic Acids o 0 lEC1S OH U P RAGR R 8 2 K AOTos H OH Any good leaving group doesn39t have to be OTos 0 I 2x0 J1 3 RioR Nucleophile Diazomethane G 9 O O diazome onne RlkCQHRQ GD RkOCHg 1x 2H FAST 0 9 o ch NEN gt N RUN DU e ROC 3 Ill Z I o XCl Br 3 Rko RXX Acid halide Pd 2 0 cu m l Co7 C VBV H i RA Br 0 O 0 PO ZRJLOH 254 Rko kk Anhydride Cyclic An hyd rides O HO OH v7 05 O M a 9 O 0 O POC3 O O OH o O phthalic acid Phthalic anhydride OTHER Reductions i I LAH RAoH R OH 23 430 KBHg THF H a H 2 30 I3 NOBih N 2 30 sows or KMnoqbH Jones 0 0 KMan 390 PCC RJL H 39 Rio L4 H OY BHEK WW O m biBAL 13 O A H Lquot 2amp0 25 430 RJKH Disobutyl aluminum hydride quotDiBALquot OTHER Decarboxylation R a C02 Most carboxylic acids DO NOT lose 002 or K KH I COZ P OH H304 93 ceJro odd 0 0 w i Co 2 HOMOH 0quot HO CH3 50 Malonic aCld O O O 1 A H A quot39 O 0 HO O Carbonate baking soda Carbonic acid Decarboxylates almost instantaneously Acetal and hemiacetal formation and hydrolysis in ACID ARROW PUSHING MECHANISM Some kind of alcohol AGeHMs and a little bit of acid I 0 l2 OH x3 OR 2 7 p 0 qenerod dieher 2 R H39 R ocelal quot W Oll CH CielH OH K R l u mng H R o R 39o39u A 9 2 ii ESH R R Q R O Y 2 PH K of 0 2 OR I hemloceJcod m1me llnere R R R BH Q R OH N H rok 094 9 OR R R 9 R R Imine and enamine formation and hydrolysis in ACID ARROW PUSHING MECHANISM 39 R39 O R39NHZ N R R H Rig R NHZ 1quot Amine 0 amine RZ39NH 2 amiru RgN 3 amim Mechom39rsm RwNquot 4 ammonium sal Oo gtH39 Hm 39 NH 1L R 739 H c canHz 80H on on 0 J R R 99 gt z KR 11511 lt R k RIVPR lt i Nlt R N H RI H R 93 H hem39mm39mm 2 KquotN z K 12 R R K R g lt CD gtlt Y R39N39H R39 NH Q99 NR Imine K39iz or 420 Y 39 I KNR O 39 N K L 1214 RJWR K 9 1 MIN CWWW R Ru R39 N R jY z 39 u H u H RlVR Mdehvde or W 0 Kama 0 cmonql 2 Mme Cnaw ne Mechamswx 39 39 H hemammm O OH 0 OH RJKR39 E9 W69 aIVR gt R 2 a R gt H I RI lt K 39 2quot NH 1239 w N R z Ru Ru Ru IZ 2NH my 1 K g Q WA R K 3942 LO Hz 7 R R N Z R N g R 392 IN V K Yul Ru N 2 u 0 0 RM 2 Ex 2 II N 39 quot 392 2N 2 kR Acid catalyzed esterification and hydrolysis ARROW PUSHING MECHANISM 0H R 0H2 R 0 7 R0H OR39 139 m 635 1L 9 o ZSH QOH 9 94 0 WolffKishner Reduction ARROW PUSHING MECHANISM WolffKischner Reduction 1 IN N397 K quotOH A a H 439 2kg 11 11 Sleps NvNiH h dm2one ng H Iman 19quot i H L NzNH Isl N H N 313 a fkk We Rum R K gtltu H a T 04 4 6 R K a 391 4 RJ H NEN Pinacol Rearrangement ARROW PUSHING MECHANISM R 0 OH OH R HZSOquot R K A R R K R Mechanism ooH 0 OH orlz 0H 0H R R 39RFAR4l RF RGE J Re R GER R R R R R R R 0 ll 9 o Swern Oxidation ARROW PUSHING MECHANISM 5w em Ox dai on O 0 o o 0 LZ39hW O R K R m C C C CI DV 0 K K 2 KEN O R C AzOR R C H 2 WW 1 2 3m 3 dimy m 5 Souoxide C01 CO
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