1.

Cch v cng thc chiu Newman

Cng thc chiu ny c v bng cch nhn dc mt trc lin kt C - C v cc nhm th c phn b i xng trn mi nguyn t C. Cch v ny s dn n cc nguyn t khng phi nguyn t trung tm (to lin kt C - C ta nhn) c phn b nh sau:

c th v c cng thc Newman t cng thc chiu phi cnh th iu quan trng l ta phi t con mt sao cho nm dc trc lin kt C - C Gi chng ta s xt mt v d, l v cng thc chiu Newman ca propan khi nhn cng thc ca propan t pha tri. Cch lm nh sau: 1) V vng trn (c tm) hin th hai nguyn t C pha trc v pha sau. 2) V nguyn t H nm trong mt phng trc (vo bt k ch no). 3) Nguyn t cacbon cn li cng c H nm trong mt phng th ta s v i xng vi n qua tm. 4) V cu dng xen k ca cng thc Newman 5) Cc nhm i v pha ngi quan st trong cng thc phi cnh c chuyn ht v bn phi 6) Cc nhm i v pha xa ngi quan st trong cng thc phi cnh c chuyn ht v pha tri Nu nhn pha phi ta cng lm tng t Nh vy ta s v c cng thc Newman nh sau:

2. Danh php R, S Sau khi v cng thc chiu phi cnh th by gi ta nhn dc trc lin kt C*- d, lin kt C d buc phi i xa khi ngi quan st (d l nhm th c hn cp nh nht, trong hnh l Me) th ng phn R l ng phn c cc nhm th c sp xp theo chiu kim ng h, cn ng phn S th ngc kim.

Ch rng nu nhn vo cng thc Fischer m nhm th d cnh ngang th ng phn R theo trnh t ngc kim, cn S th cng kim ng h nh. 3. Gii thiu cch chuyn cc cng thc chiu: Fischer - Phi cnh - Newman: Cch lm: Chuyn cng thc Fischer v dng che khut ca phi cnh hay Newman ri quay quanh C3 mt gc 180 c cng thc bnh thng hay Newman. Lm ngc li cng theo trnh t nh vy. Xem v d sau nh:

I.

Cc vn v sc cng vng Sc cng xut hin trong mt hp cht khi cc lin kt ca hp cht ny b "p" to thnh cc gc lin kt khng bnh thng. C 3 loi sc cng chnh l sc cng Baeyer, sc cng Prelog v cui cng l sc cng Pitze. Trc ht ta i vo thuyt sc cng ng ch nht,lin quan mt thit v c sc nh hng ln nht khi ta xt v cu to vng cyclopropane , l sc cng Baeyer. Cyclopropane l hp cht vng no n gin nht,v cc C trn vng u no,nn theo l thuyt vng c mong i cu to bng m hnh t din(M hnh trong nguyn t C lai ho sp3,to nn 4 AO sp3 tng ng,c cc gc lin kt m cosin c gi tr l -1/3,hay 108 28' 16.3'' ~ 109.5 ). Baeyer cho rng tt c cc nguyn t carbon u nm trn mt mt phng,do xt i vi vng cyclopropane, gc lk gia 2 AO sp3 to nn vng l 180:3 = 60,m trn l thuyt ca m hnh t din, gc ny phi l 109 28' nn ta d dng suy ra lch m mi AO phi chu l: (109 28' - 60) : 2 = 24 44'. i vi cc vng ln hn, lch gc anpha uc tnh theo cng thc: anpha = 1/2[109.5 - 2.90.(n-2)/n] V do c lch ny ta ni vng cyclopropane phi chu mt sc cng,v cc lin kt trong vng ny khng bnh thng nh cc lin kt sigma khc,m cc AO lin kt b un cong nh qu chui (Bent bonds),ta xt k m hnh lin kt b b cong bi sau khi i su phn tch cu to vng cyclopropane. Thuyt sc cng Baeyer ng khi t lin h gia nng lng ca hp cht vi sc cng ni phn t,v c sc thuyt phc khi thc t chng minh c sc cng ca vng gim t vng 3 - vng 6 cnh l ng. Sc cng ca mt vng l ln hay khng ph thuc vo Nng lng sc cng(Strain energy)-cch tnh Nng lng sc cng cng s c trnh by di y. Tuy nhin n cng c im bt hp l l ngoi vng 3,cc vng ln hn cc C khng cng nm trn mt mt phng nh Baeyer gi nh,nu tnh theo cng thc a ra trn
3

th vng 17 cnh sc cng li ln nh vng ba, tuy nhin t thc t ta bit rng mc d cc vng t 7 n 12 khng loi b c ht mi sc cng nh vng 6 (vng 6 khng c sc cng,tc l nh mt n-alkane), v km bn hn vng 6,nhng khi n>12.mi sc cng hu nh c loi b,tri vi cng thc m Baeyer a ra.Tuy khng thc s chnh xc v ng n,nhng thuyt sc cng Baeyer t tin cho vic t vn xc nh sc cng trong cc hp cht vng. Khp li thuyt sc cng gc Baeyer,chng ta chuyn sang hai loi sc cng gc cn li. Loi sc cng th hai,sc cng Prelog, cn c tn gi l sc cng qua nhn, khi cc nhm th cng pha v gn nhau n mc c tng tc vi nhau bng lc y Van der Waals. Chng ta ly v d hp cht methylcyclohexane,trong e-methylcyclohexane bn hn cu dng a tng ng ca n l 7.4 kJ/mol,v cu dng a- chu lc y gia nhm methyl v 2 nguyn t H lk a cng pha vi n,lc y ny c gi l tng tc 1,3-a,a v l mt v d in hnh v sc cng Prelog.

Cui cng l sc cng Pitze, l loi sc cng gy ra bi s phn b che khut cc lin kt C-H gia hai C gn nhau. Chng hn vng cyclopropane c su lin kt C-H u dng che khut hon ton lm xut hin lc y tnh in gia cc AO sigma C-H che khut nhau. Ngoi sc cng Baeyer,sc cng Pitze ng gp mt phn khng nh lm cho vng cyclopropane tr nn km bn v mt nhit ng hc (delta H hnh thnh = +53.4 kJ/mol),v km bn nht trong cc cyclan.

Ngoi ra,trong cc hp cht vng cn c sc cng Van der Waals (tn gi thng dng hn l lc y Van der Waals) do s y cc nhm th C gn nhau,sc cng ny tng khi th tich nhm th tng v gim khong cch so vi tng bn knh Van der Waals. Chng hn ta xt cu dng thuyn ca vng cyclohexane,tuy tt c cc gc u tha mn gc lai ho sp3(c ngha l khng tn ti sc cng gc Baeyer),nhng ngoi lc dy ca 8 lin kt C-H cu dng che khut (sc cng Pitze), cn c lc y Van der Waals ca hai nguyn t H hai mi thuyn (hai nguyn t ny cch nhau 183 pm, nh hn tng bn knh Van der Waals ca chng l 2 x 124 pm),do cu dng thuyn l cu dng km bn.Loi sc cng ny ch yu gp cc hp cht mch h khi ta xt cc cu dng(conformers) ca hp cht :

T ta rt ra kt lun i vi cc vng cycloalkanes vng nh (3,4 cnh) ch yu l do sc cng Baeyer v Pitze,vng bnh thng(5,6,7 cnh), c sc cng nh m ch yu l sc cng Pitze,cng trung bnh (8 n 12 cnh) ch yu do tng tc qua nhn ca nh th(sc cng Prelog). By gi ta xt n cch xc nh nng lng sc cng ni trn.Mt phn t c sc cng s l mt phn t m nng lng ca phn t y(chnh xc hn l nng lng tim
5

n trong mi phn t-potential energy) l cao hn so vi l thuyt nu ta gi s phn t y khng c sc cng. Cng nh nng lng cng hng(resonance energy)*, nng lng sc cng khng th xc nh chnh xc l bao nhiu,bi nng lng thc ca phn t khng th o m c.Tuy nhin ta c cch xc nh nng lng cng hng cng nh nng lng sc cng c th tnh ton c nh sinh nhit[5] (nhit hnh thnh), hay thiu nhit,... Hnh v bn di ch r cch xc nh nng lng cng hng:

Ly v d c th tnh nng lng sc cng: Cyclohexane (C6H12 hay (CH2)6) l vng 6 cnh, hu nh khng c sc cng(t "hu nh" y l do cyclohexane c nhiu cu dng : bn gh,thuyn,xon,gh trong bn cu dng tng dn,v cu dng gh chim ti 99% tng s cc cu dng c mt trong hn hp cb cc cu dng, cu dng ny khng c sc cng), nn thiu nhit tng t n-alkane, nn tin li ngi ta dng lm chun tnh nng lng sc cng ca cc vng cn li. Sinh nhit ca cyclohexane l -29.5 kcal/mol nn sinh nhit tnh cho mi nhm [CH2] l -29.5/6 = -4.92 kcal/mol.Nu ta mun tnh nng lng sc cng ca vng cyclopentane C5H10 hay (CH2)5, ta gi s rng vng cyclopentane khng c sc cng nn sinh nhit l thuyt ca cyclopentane l 5 x (-4.92) = -24.6 kcal/mol,m trn thc t ta thu c sinh nhit ca vng ny li l -18.4 kcal/mol, tc l nng lng sc cng ca vng cyclopentane chnh l s sai lch nng lng ca hai gi tr l thuyt v thc nghim trn trn: (-18.4) - (-24.6) = 6.2 (kcal/mol). II. Kho st cc h thng vng nh t 3 - 5 cnh 1. Vng xiclopropan Vng xiclopropan l mt h thng vng 3 cnh phng trong cc H buc phi che khut nhau hon ton (nh hnh v). Vng ny tn ti mt sc cng che khut v sc

cng gc ln (s km bn vng ch yu do sc cng gc) nn vng s tr nn km bn v c kh nng phn ng rt cao. Phn ng ch yu l cc phn ng cng m vng:

Mt khc do cu trc ca vng l cng nhc nn s c s xut hin ca cc ng phn hnh hc trong h thng ny. Di y l v d minh ha vi 1,2-dimetylxiclopropan:

Ngoi ra do nh hng ca cc lin kt "qu chui" trong vng xiclopropan nn kiu lai ha ca cacbon khng cn l sp3 na, m tr thnh trng thi trung gian gia sp2 v sp3.

Kt qu l nguyn t H trong vng xiclopropan tr nn c tnh axit yu, v to thnh cacbanion bn vng trong mt s phn ng nht nh. Bn cnh vi kiu lin kt c bit ny n cho php c kh nng to lin hp vi lin kt i to thnh mt s sn phm bt thng:

2. Vng xiclobutan
7

Nu nh vng xiclobutan l phng th iu ny tuy lm gim i phn no sc cng v gc nhng li gy ra mt sc cng che khut ln do c 4 cp H - H che khut nhau (nhn hnh v). V vy gim thiu sc cng Pitzer th xiclobutan buc phi c cu trc khng phng dng ging nh cnh chim (hnh di): Xiclobutan c kh nng chuyn ha cu dng cao bng cch a ln lt cc nhm CH2 thay nhau i ra khi mt phng ca 3 cacbon cn li (qua trung gian phng) nh hnh v:

Do trong xiclobutan sc cng che khut gim i mt t nn kh nng tham gia phn ng m vng c km hn so vi xiclopropan. N khng cho phn ng m vng vi brom m ch cho phn ng vi hydro xc tc Niken to thnh n - butan i vi cc h thng vng xiclobutan mt ln th th s c mt cn bng gia cu dng c nhm th cha v tr trc v nhm th cha v tr xch o trong cu dng c nhm th xch o l cu trng u i (G = 1kcal/mol vi R l Me, Br), nu R l Cl th s khc bit nng lng ch l 0,49 kcal/mol Vi cc xiclobutan hai ln th c cc nhm th v tr 1,2 th cu dng u i l trans (e,e)-1,2 dixiclobutan (bn hn cis 1,3 kcal/mol i vi dn xut diaxid) v cis (e,e) 1,3-dixiclobutan (bn hn trans 0,58 kcal/mol trong dn xut dibrom) do trnh tng tc van der Waals gia cc nhm th. Hnh v di y s gii thiu cn bng cu dng ca dn xut mt ln th cng nh cu dng u i ca cc dn xut 2 ln th 1,2- v 1,3- ca xiclobutan:

1. Xiclohexan

Vng xiclohexan l mt h vng c bit c kho st k lng, v b khung vng xiclohexan l b khung ch yu ca rt nhiu hp cht t nhin v tng hp nn n c kho st mt phn ring tch bit so vi cc h thng khc:

Da trn cc d kin thc nghim kho st c th vng xiclohexan hon ton khng c sc cng. V th phn t cn phi c cu to khng phng trnh sc cng gc v c s sp xp trong khng gian ph hp trnh c sc cng che khut (l cu dng gh nh hnh v trn). Vo nm 1890 th Sachse v Mohr a ra 2 cu dng gh ca xiclohexan, v y l mt m hnh hon ho gii thch nhng vn v sc cng ca xiclohexan. M hnh ny ban u c n nhn nng nhit nhng v sau li i vo qun lng v mi s tch ring ra hai cu dng ring r ny hon ton tht bi. L do mi v sau mi c gii thch l do hai cu dng ny chuyn ha cho nhau rt nhanh nhit phng qua mt s cc trng thi trung gian nh c biu din trong s di y (Tuy nhin nhng nghin cu gn y cho kt qu l khi h nhit xung rt thp th c th pht hin c tng cu dng da trn NMR). Ro nng lng chuyn i cu dng l kh thp nn mi nghin cu c lp tng cu dng ring r hon ton tht bi.

Nhn hnh v u tin ta thy c 6H nm song song vi trc chnh ca phn t (l ng thng vung gc i qua tm phn t), 6H c gi l 6H axial (hay 6H trc) c k hiu bng mu v 6H nm vung gc vi trc chnh phn t gi l 6H equatorial hay 6H bin c k hiu bng mu xanh. 6 cacbon ca xiclohexan c phn b trn hai mt phng song song nhau, trong C1, 3, 5 thuc mt mt phng v C2, 4, 6 thuc mt phng khc. Trong cu dng gh ny hon ton khng tn ti sc cng no nn vng xiclohexan th hin tnh tr ha hc mnh. Kh nng phn ng ca n khng khc nhiu so vi ankan tng ng c cng s cacbon.
9

2. Dn xut mt ln th ca xiclohexan Vi dn xut th mt ln ca xiclohexan th tn ti cn bng sau:

Gi tr -Go hay A c gi l nng lng cu dng, ngoi vic n cho bit cu dng no chim u th trong cn bng chuyn i gia cc cu dng th chng cn cho bit mt cch tng i kch thc ca cc nhm th (nhm th no c A cng ln th kch thc cng ln, xc sut tn ti cu dng trc cng nh). Di y l bng gi tr A ca mt s nhm th hay gp.

Da vo bng trn th thy tt c u l cc gi tr dng, tc y cu trng vi nhm th xch o bn hn so vi cu trng trc. iu ny c cho v hai l do: L do th nht l vi nhm R v tr trc th s tn ti tng tc kiu xen k k butan v bn cnh l s xut hin tng tc van der Waals ca nhm th v tr trc vi cc nguyn t hydro C3 v C5, tng

10

tc van der Waals trong trng hp ny cn c gi l tng tc 1,3-diaxial. nhm th xch o th khng c cc tng tc ny.

3. Dn xut hai ln th ca xiclohexan i vi cc dn xut ca xiclohexan m hai nhm th cng nm trn mt cacbon th nhm th no c kch thc to hn (A ln hn) th s chim v tr e. Cn nu hai nhm th v tr khc nhau th do s cng nhc ca vng nn s c s xut hin cc ng phn hnh hc. Mi quan h ca chng c biu din nh sau: 1,2-cis: ae hoc ea 1,2-trans: aa hoc ee 1,3-cis: aa hoc ee 1,3-trans: ae hoc ea 1,4-cis: ae hoc ea 1,4-trans: aa hoc ee Thng cc ng phn bn vng hn l ng phn c nhm th e. Tuy nhin trong trng hp nu c hai nhm th u l nhm c th tch ln chng hn nh cc nhm tert-butyl th s ng gp ca cc cu trng trung gian s tr nn ng k. Th d trong trng hp ca di-tert-butylxiclohexan th hai nhm t-butyl phi v tr xch o trong cu dng gh ca ng phn cis, cn mt trong hai nhm t-butyl phi v tr trc trong cu dng gh ca ng phn trans lm s tng tc 1,3-diaxial s tr nn rt ln. Do trans-1,3-di-tertbutylxiclohexan khng th tn ti di cu trng gh. gim bt mc nng lng th cu trng gh phi chuyn thnh cu trng thuyn xon m bo cc nhm t-butyl u v tr xch o.

4. Kh nng phn ng
11

 y vi cu dng gh th kh nng phn ng ca cc nhm th a v e l khc nhau. Thng th a nhy hn trong cc phn ng ca vng. V d:

iu tng t cng xy ra i vi cc phn ng tch theo E2. cu dng cn cho phn ng tch th cc tm phn ng phi v tr anti i vi nhau mi c th tch loi c (do c th to thnh trng thi chuyn tip phng):

12