Chapter 17 Study Guide

Transcription

1 Chptr 7 Stuy Gui Som smpl pk.8 N α-hyrogns(hyrogns on rons nxt to ronyls) r firly ii. This is u to th rsonn-stiliztion of th rsulting rnion. - Bs rnion nolt KET form + ENL form ) Know Kto-Enol Tutomrism spil typ of onstitutionl isomrs, quikly intrhng in prsn of i

2 ) Know formtion of Enolt/Crnion y s - N ) Know rmiztion/pimriztion of α-ron if th α-ron is strontr, rmiztion n our quit simply with th ition of s. C N Bss turn α-rons into rnions whih thn n onvrt into nolts. Th nolt ron is sp hyriiz, whih rsults in loss of strohmistry. ) Know hli ition nolts n pik up groups othr thn hyrogn ) N ) Br Br ) Know hloform rtion mthyl ktons will thr hlogns to form trihli, whih is susptil to hyrolysis to n i n hloform(ron with thr hlogns tth, suh s hloroform). ) Br / N + CBr )

3 A lortory tst for mthyl ktons or sonry lohols(nxt to mthyl groups) is to I. If yllow pripitt of iooform(ci ) forms, this onfirms th prsn of mthyl ktons or mthyl sonry lohols. ) Know lol ition/onnstion rtions sin α-hyrogns r so sily rmov to form nolts/rnions, this hmistry is of grt importn. n of th most importnt rtions is th Alol rtion. In this rtion rnion is form y ing s to rmov n α- hyrogn. Thn rtiv lhy is. Th rnion ttks th lhy forming nw ron-ron on. Th oxygn of th lhy forms n lohol tht n rmov with ht to form n lkn. ) N ) pntnl ) + ) N ) pntnl ) + /ht Th lol rtions shown ov r whn th rnion tht forms is rt with sprt lhy. This is spifilly ll ross-lol sin you us two iffrnt moluls. Alols n lso form whn th originl molul us to form th rnion is lso us s th lhy tht gts ttk in th son stp. IMPRTANT. It is lwys th CARBANIN rsonn form tht is rtiv. Evn though th nolt is mor stl, it n not rt to form th lol prout.

4 ) N ) N nothr molul of strting mtril - 7) Know mhnism for lol rtion - - +

5 As sn oth on prvious xmpl n low, th rnion os th ttking not th nol. Bs KET rtiv form ENL nonrtiv form + /ht + lol onnstion lol ition ow woul you gnrt ths lol prouts? I II III IV Br

6 TE ALDL IS A REACTIN WERE A CARBNYL (KETNE R ALDEYDE) IS DEPRTNATED WIT A BASE (N most sustitut or LDA lst sustitut ). most sustitut ( o ) N f g f g LDA f g lst sustitut ( o ) TE RESULTIN CARBANIN WILL TEN ATTACK AN CARBNYL. TE CARBNYL WEN ATTACKED BY A NUCLEPILE WILL TURN INT AN ALCL (). g f ) N ) Pntnl ) + g f g f ) LDA ) Pntnl ) + f g

7 IF EAT IS APPLIED, TE DEYDRATES T AN ALKENE. g f ) N ) Pntnl ) + /ht g f g f ) LDA ) Pntnl ) + /ht g f IF A CMPUND CNTAINS CARBNYLS SEPARATED BY R CARBNS, AN INTRAMLECULAR ALDL WILL YIELD A R MEMBERED RING. f N f f N f 7

8 8 EXAMPLES ) N ) Pntnl ) + ) N ) Butnl ) + ) N ) ) + ) LDA ) Butnl ) + ) LDA ) Propnl ) + ) LDA ) ) +

9 9 ) N ) ) + ) LDA ) Butnl ) N NTE: NLY or mmr rings will form, not, 7, Wht is th prout(s) of th following? ) N ) Propnl ) + /ht ) LDA ) Propnl ) + N

10 0 ) N ) Propnl ) + /ht ) LDA ) Propnl ) N N 7 8

11 8) Know rvrs lol s you noti in th rtions, quilirium rrows r rwn. This mns th rtion n rvrs itslf k to th originl ronyls. - + B - 9) Know Clisn-Shmit Rtion sin most synthsis n to mploy th ross lol s oppos to th slf-onnsing lol, r ns to tkn in th sltion of rgnts. If you us somthing lik pntnl n try n mk n nolt of it n ross it with nzlhy, you n gt th prout you r looking for. But you n lso gt slf-onnstion of pntnl with itslf. ftn ktons r us sin thy o not unrgo slf-onnstion. Whn ktons r us, this is ll th Clisn-Shmit Rtions. Quit oftn hyrtion ours in ths rtions vn without th ition of ht. 0) Know nitril/nitrolkn onnstion inst of strting with ronyl, nitrils n nitro n us. Th -rons r still quit ii. ) N CN ) Propnl CN N ) N ) Propnl N

12 ) Know intrmolulr lol yliztion rtions if ikton or ilhy is us, slf-onnstion ling to ring formtion is oftn sn spilly if n mmr rings r form. If multipl rtions r possil, n mmr rings r prfrr. N N ) Thrmoynmi vs. kinti nolt us of this phnomn, you n sily hoos whih si of th ronyl to hv th lol/ition rtion tk pl y hnging th s. Th us of lithium form nolts is vry prvlnt in ross lol(clisn-shmit) rtions. TD nolt mor sustitut ron, wk s(n), proti solvnt(mthnol,thnol ) Kinti nolt lss sustitut ron, strong s(lda), proti solvnt(tf, DMS, DME ) N - LDA -

13 ) Alkyltion y lithium nolt inst of prforming n lol rtion to hin of rons, irt lkyltion n tk pl. In this rtion th nolt tht forms rts with lkyl hli in n S N typ rtion. Primry lkyl hlis, primry nzyli hlis n primry llyli hlis must us(sonry n trtiry l to limintions). ) LDA ) mthyl ioi ) Silyltion of nolt in vry rtion so fr th rnion hs n th rtiv spis. Th lkoxi nion n rt in spil ss, spifilly with th ition of TMS-Cl, TBDMS-Cl or TBDPS-Cl. Ths silyl groups hv trmnous ttrtion for oxygn. Thrfor SN typ of rtion ours twn th lkoxi nion n th silyl group. This trps th nolt in non-rtiv form. thr hmistry n tk pl(for xmpl if you wnt to rt on ronyl inst of nothr, you n trp th first ronyl s silyl nol thr n thn rt th othr). As for TBAF(or mthyl lithium n us to rgnrt th nolt. ) LDA ) TMS-Cl TMS T M S-C l C l C S i C T B A F or C L i C C C T B D M S-C l C l Si C C - C C C T B D PS -C l C l S i C C C

14 ) α-slntion/ oul on α,β to th ronyl n y ing slni to th -ron n thn rmoving th slni unr mil, nutrl onitions. This ls to α, β-unsturt ronyls. ) LDA ) C SBr SC S - C ), vs, ition to α, β-unsturt ronyls just lik w sw with ins in hptr, th prsn of two unsturt groups llows us th possiility of hving, vs, ition. In ins,, ition l to movmnt of th oul on. Although th oul on is mov in th mhnism, it ultimtly is rmov., ition ours t th ronyl. r th ronyl is turn into n lohol n th nulophil s t th ronyl ron whil th oul on is unhng. This is known s simpl ition. In, ition, th nulophil s on th outsi of th oul on using n nolt to form(from th movmnt of th oul on). Th nolt is tutomriz to th kto form in th finl prout. Th offshoot is th nulophil s to th outsi of th oul on, with th oul on isppring. This is ll onjugt ition. Most ss involv omintion of oth simpl n onjugt ition. Simpl ition is fvor y strong nulophils(orgnomtllis, grignrs) whil onjugt ition is fvor y wk nulophils(uprts, mins n CN)., strong nulophils, wk nulophils, uprts to ylis giv trns prouts if vill

15 N (wk nulophil) C MgBr N C C Cu (C C )CuLi 7) Mihl ition/roinson nnultion if n nolt is us to ttk n α,β-unsturt ronyl it will o so through, ition. This is ll Mihl ition(ny, ition is ll Mihl ition). If th originl nolt is ikton whih n follow th Mihl ition with slf-lol onnstion ling to yliztion, tht is ll Roinson Annultion. Mihl ition, ition y lithium nolt Roinson nnultion Mihl ition follow y lol yliztion N +

16 REVERSE ALDL I + II I + II I + II

17 7 REVERSE ALDL Br Br I II - N - - mmr ring mmr ring mmr ring

18 - N - - f f f mmr ring 7 mmr ring 8

19 N G F B C D E A - - G F E D C B A + G F B C D E A + B 9

20 i g f h j k i g f h j k R f j k h i g i h f g j k + 0

21 Complt th following rtion shms A. ) LDA ) hxnl ) + /ht ) LDA ) Br ) N ) TMS-Cl TBDMS ) N/ Br ) ) LDA ) Propyl ioi ) TBAF ) PCC ) LDA ) N ) hxnl ) +

22 B. C Li N (C C ) CuLi + N Giv th mhnism for th following ) N ) Pntnl ) +

23 KEY Complt th following rtion shms A. TBDMS TBDMS ) LDA ) hxnl ) + /ht ) LDA ) Br ) N ) TMS-Cl TBDMS Br TMS TBDMS ) N/ Br ) TBDMS ) LDA ) Propyl ioi ) TBAF ) PCC ) LDA ) N ) hxnl ) + TBDMS TBDMS

24 B. points h N C Li N (C C ) CuLi C C + N Giv th mhnism for th following ) N ) Pntnl )

25 Nm: ) LDA ) Ethyl Ioi ) LDA ) TBDMS-Cl ) N ) Br ) LDA ) Pntnl ) + ) LDA ) Pntnl ) + /ht ) LDA ) PhSBr ) ) LDA ) Butnl ) + ) N ) Butnl ) + NC C MgBr TBDMS (C ) CuLi

26 Show th prout n mhnism for th following rtions: ) LDA )

27 7 N

28 8 Roinson nnultion

29 9 KEY TBDMS ) LDA ) Ethyl Ioi ) LDA ) TBDMS-Cl Br ) N ) Br ) LDA ) Pntnl ) + ) LDA ) Pntnl ) + /ht ) LDA ) PhSBr )

30 0 ) LDA ) Butnl ) + ) N ) Butnl ) + A B A B C NC C C MgBr TBDMS (C ) CuLi C

31 Show th prout n mhnism for th following rtions: ) LDA ) - LDA N 7 7 8

32 Bs Bs

33 Prt I: Giv th prout for th following. PCC Cr ) DIBAL- ) C N ) N ) Pntnl ) + (C C C C ) CuLi Cl -romonzn, AlCl

34 + N NC N(C ) ) N ) Pntyl ioi (Ph) PCC C mcpba

35 ) LDA ) PhSBr ) (C ) CuLi ) C MgBr ) + N

36 Prt II: Giv th rgnts n for th following. C This isomr is th only on prou.

37 7 Giv th hmils n rgnts n to prou th following lol prouts.

38 8 Prt I: Giv th prout for th following. PCC Cr ) DIBAL-h= ) C N ) N ) Pntnl ) + C N Cl (C C C C ) CuLi Br -romonzn, AlCl

39 9 + N NC NN C N N(C ) ) N ) Pntyl ioi C C C (Ph) PCC C mcpba

40 0 ) LDA ) PhSBr ) C B A (C ) CuLi ) C MgBr ) + N A B C A A B B C C

41 Prt II: Giv th rgnts n for th following. ) + ) CN ) Cl,, t C ) KMn, - ht ) + R ) ) Zn, A ) DIBAL- ) + gs, S Et P CC C Et This isomr is th only on prou. ) BF SS ) Rny Ni

42 Giv th hmils n rgnts n to prou th following lol prouts. ) N ) Butnl ) + LDA ) N ) Propnl ) +, t ) N ) +

43 MEWRK # Nm: Giv th prouts of th following. CN ) N ) Pntnl ) LDA ) PhSBr ) ) N ) utyl hlori ) PCC ) N ) Pntnl ) = /ht TBDMS ) TBAF ) Jons ) N

44 TBDMS ) TBAF ) PCC ) N ) C C Li ) + NCN (C C ) CuLi N Giv th mhnisms for th following ) N ) Propnl ) +

45 MEWRK # KEY Giv th prouts of th following. CN CN ) N ) Pntnl ) LDA ) PhSBr ) ) N ) utyl hlori TBDMS ) PCC ) N ) Pntnl ) = /ht TBDMS ) TBAF ) Jons ) N

46 TBDMS ) TBAF ) PCC ) N CN ) C C Li ) + NCN (C C ) CuLi N Giv th mhnisms for th following ) N ) Propnl )