PGS.TS NGUY~N HOU aiNH (Chu bien) - PGS.

TS ao aiNH RANG

HOA HOC HOU CO

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NHA XUAT BAN GIAo Dl)C

547

GD _ 03 829/32 ~ 03

Mll s6 : 7K547M3

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LUi noi diu ======================

Di ndng ceo chdt luqng hoc t.,p, giang dQY va nghi~n CtlU Hoci hoc Huu ca nheft thitt phdi co nhCing b¢ giao trinh Hod hoc HCtu· ca v6'i n¢i dung vua ca ban vua hi~n dQi v~ mc;it II thuylt va phudng phdp thljc nghi~m vua phong phU va cg:p nh.,t v~ mc;it thljc t~ d6ng thCti phai chc;it che, logic v~ m~t b6 cue, chua'n xdc ve mc;it khoa hoc IQi sang sua va d~ hiiu.

Nhlim dap ling nhu cdu tr~n, 13'1 man Hod hqc Huu ca Truemg DQi hoc Su phQm Ha N¢i co kl hOQch xudt ban b¢ Gillo trinh Hoci hoc Hou ca g6m 3 cu6n ;-

HOel h9C Hilu co 1 g6m 7 chuang. Cdc chuang I, II, III, IV va V do PGs. TS Nguy~n Huu Dfnh bi~n soan. Cac chuang VI va VII do PGS. TS D6 Dinh Rang bi~n socn,

Cdc chuang I va II de c~p nhung vefn d~ v~ c{{u truc phdn tu hCtu ca, Mn chat, dt,'ic diim va Slj biin ddi lien ke't trong hqp chert hCiu co a trQng thai tfnh cung nhu khi tham gia phon ung hod hoc, Hai chuang nay nh6m cung cap co so I( thuylt va du Ii~u ue cau true, ue nhi~t d¢ng hoc di vi~c nghien CtlU cdc IOQi hqp chat huu ca a cdc chuang sou duqc thu<J:n l<;>'i ua sou sdc.

Chudng III giCti thi~u 4 phuong phdp phd thong dl,lng trong Hod hoc Huu ca la phd tli ngog:i - kha kiln, phd h6ng ngor;li, ph6 c¢ng huang tu hQt nhan ua phd kh6i luqng, day la nhung cong cu khang thi thie'u

•

d6i 00i Hod hoc HCiu ca. Ocac chuang nay, phdn co sa If thuyit dulJC

trinh bay ngdn g(;m, cdc du Ii~u duoc sdp xlp a dQng b4ng ti~n 1<;>'i cho ui~e Sll dl,lng, dt;ie bi~t co duo nhieu th{ dl,l minh h~ nhdm giup ngum doc khang nhCtng ndm duac II thuyit ma con bitt each u4n dl,Jng chung~

Cdc chuang IV, V va VI trinh bay cau true,· d6ng pMn, danh phdp, tlnh eh(ft, phuang phdp dieu chi va tlng dvng cua ankan, xic/oankan,

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anken, ankin, dien, sa htqc ve tecpen va aren. Chuang VII giOi thi~u cdc ngu6n hidrocacbon trong thlen nhien (dau rna, kh{ thien nhien va than ma) cung cdc phudng phap che hod chung thanh thuang phti'm.

6 cdc chuanc; nay, nhfmg vcfn de If thuyet lien tien, nhftng phudng phdp t6ng hc;1p mm 19 trong ph6ng thf nghi~m va nhti't la trang cong nghi~p dii duoc chu trc;>ng dua VaG thay the cho nhiing gi da 19C h~u.

Hoo h9C Huu co 2 va Hoo h9c Hiiu co 3 g6m tl1 chuonq VlII den chuang XVII, Idn lut;1t trinh bciy cdc dan xwft chU yeu cua hidrocacbon :

Dan xuat halogen; Hop cheft Cd nguyen to; Ancol, phenol, ete ; Hap cheit cacbonyl ; Axit cachoxylic va dan xudt ; Amin va cdc h9'P cheft chua nitd khdc ; Hap chat d! vong ; Cacbohidrat ; Aminoaxit - protein va Hap cheft coo phtm tu.

Bien socn thea chuang trinh hoc ph6n I man Hod hoc Huu ca do Be? Gido dl;JC va Dao t90 ban hanh nom 2001, cuon Hod hoc Hiiu co 1 co thi duac dung lam gido trinh cho sinh vien cdc chuyen nganh Hod su pham, Hod t6ng hQ'P, Hod ducc, Hod sinh, H06 ddu, Hod thl/c pheim, ... Nqoo! ra sdch con 10 tal li¢u tham khao tot doi vm hoc vlen cao bee, nghien Cltu sinh nganh Hod va ki sir nganh Hod cfmg nhu nhiing ngudi quan tam t6'i Hod hoc Huu ca.

D9C bi~t, cuon Hod noc Hisu ca 1 con la m¢t tai Ii¢u tham khcio lchong thi thieu do! vm giao vien Hoa hoc THPT khi giang d9Y man Hod hQc thea Chudng trinh va Sdch gido khoa do B9 Glao due va DaD t90 m6'i ban hanh.

Cuon sach duac bien soan tren Cd sO' kinh nghi~m nhieu n6m giang dQY m6n Hoa hQC Hftu ca d b~c d9i hoc cu~ cdc tdc gia d6ng thdi thorn khOo cdc giao trinh Hoa hqc Hisu Cd trong nuac vel quoc te. Tuy nhien, cuon sach kh6ng tranl: khoi con co nhftng thieu sot.

Tac gia xin chOn thelnh cam an cdc d6ng nghi¢p da dong gop nhieu y kien quy bciu cho ban thao va mong muon nh~n duoc nhftng y kien phe binh xay d~g cho cu6n sach duo: hoan chinh han.

Ha Noi, thong 5 nom 2003

PGS. TS Nguyin Him Dinh, PGS. TS Del Dinh Rang

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Chuang I

HoA HQC HUU Cd vA HOP CHAT HW co

§ 1. HOA HOC HUU CIf

~ """ """., (I< _

I - DOl TUQNG VA VAl TRO CUA HOA HQC HUlJ CO

Hoa hoc hiiu ca la nganh Hod hoc chuyen nghien Cltu cdc hap chat eLta cacbon. Vi sao lai c6 d. mot nganh khoa hoc Ion chuyen nghien crru cac hop chat chi cua cacbon ? B6i VI cacbon la mot nguyen t6 d~c biet, co mot khong hai : nguyen tll cacbon khong chi lien ket duqc v6i cac nguyen tli cua cac nguyen t6 khac rna con lien ket duqc voi nhau bang cac lien ket wong d6i ben tao ra cac dang mach ha, mach vong, tu dan gian den eire kl plurc tap va da dang, Chinh VI the so hrong cac hop chat cua cacbon dii len tai con so hang chuc trieu, gap han rmroi Ian soluqng cac hop chat khong chua cacbon cua tat d. cac nguyen to khac, va ti so nay se ngay cang tang them.

Trong t6ng so cac hop chat chua cacbon, chi co mot so'rfii it la hap chdt vb ca. D6 lit cac oxit cacbon, rnuoi cacbonat, xiarrua va cacbua kim loai, ... con llIy¢{ dai da so'la cdc hap chat hiiu ca. D6 Ut cac hidrocacbon (hop chat htru co don gian nhat chi cau tao bai cacbon va hidro) va cac hop chat plnrc tap han rna trong pharr tir ngoai C, H con c6 cac nguyen t6 khac nhu 0, N, S, P, halogen .... Trong do da so c6 th~ duoc coi la ddn xtuit Clia hidrocacbon ..

Tam quan trong cua cac hop chat htru co khong chi bOi so Iuong ap dolo cua chung rna con boi vai tro eire ki to IOn cua chung trong dbi s6ng Nhan loai. Cac hop chat hiiu co tao ra thirc an, d6 mac, thu6c chua benh, va nhieu vat dung thiet yeu khac. Cac hop chat hiru co co mat a tat ca cac nganhkinh te va cac linh vJ!C khoa hoc, ki thuat, Chang han, trong Nong nghiep, cachop chat htru cogiup bao v~ va tang nang suat cay tr6ng va v~t nuoi ; trong COng nghe thong tin, cac man hlnh tinh th~ long tu cac hop chAt hiiu co dang dan thay the cac man hlnh truyen thong. computer sir dung cac pharr tll' AND dang

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a trong giai doan nghien ciru, ... Ron the nua, hop chat httu co con la nhung hop chAt trung tam cua su song tren hanh tinh ciia cluing tao Thuc vay, cac hop chat hiiu co tao ra co th~ moi sinh vat, tao ra protein cua mau, thit, da, ... tao ra cac enzirn xiic tac cho cac phan img xay ra trong co th~, va cung voi oxi cua qua trinh ho hap, cac hop chat hiiu co cung cAp nang hrong cho rnoi hoat dong cua co the song. Cung chinh til cac hop chAt hiru co da hlnh thanh nen cac phan tii axit deoxiribonucleic (ADN) la nhung phan tti khong 16 chira dung thong tin di truyen cua moi sinh vat.

Nhiem V1,l co ban cua Hoa hoc Htru cola: Nghien ciru t6ng hop cac hop chat hiiu co va tach biet cac hop chat hiiu co til cac san pham thien nhien ; Nghien cuu, xac dinh cau tnic cac hop chat hiiu co; Nghien cuu tinh chat va co che phan ilng cua cac hqp chat hOU co. Tat ca nham dua den nhimg irng dung thuc tien de nang cao chat Iuong cuoc song cua con nguoi. Nhil'ng thanh nru cua Hoa hoc Hiiu co con la co sa de nghien CUu hoa hoc cua su s6ng va ca qua trinh nr duy cua con ngiroi.

11- 50 LUQC LlcH 5lr PHAT TRIEN ClIA HOA HQC HO'u CO

TrM qua nhieu the ki khai thac, Slr dung va nghien cuu cac san pham ciia thien nhien, den the ki XVIII, con nguoi da biet duqc kha nhieu nguyen t6 hoa hoc va cac hQP chat cua chung, trong s6 do co nhtrng hop chat do cac co the song tao ra (nhu dubng kinh til mia, axit axetic tir giam, etanol til nrou nho, ure til mroc tieu, ... ). Vao khoang cuoi the kl XVIII, d~u the ki XIX, khi bat d~u h¢ thong hoa cac kien thuc ve hoa hQC, cac nha khoa hQC (nhu 1. Berzelius, 1779 -1848, ... ) dii dung thuat ngu hap chat hilu ca de chi cac chat duoc tao ra til cac co the song, tuc la ttr sinh vat, d~ phAn biet vm cac hop chat vo co duqc tao ra til cac khoang v~t. Thai do ngtroi ta cho rang, cac hop chat hiiu co chi duoc tao thanh dum tac dung cua "life song" trong co the sinh v~t, vi the mac nhien ngum ta khong nghi den viec t6ng hop chung trong phong thf nghiern.

NAm 1828, F. Vole (F. Wohler) t6ng hop daqc ure bang each dun nong arnoni xianat, rna nhu ong n6i : "khong can den con meo, con ch6 hay con lac da MO ca.".

NH/Orn-

~N-C-~ [I

o

- Sau do vao nam 1845, H. Kolbe t6ng hop duqc axil axetic, vao khoang nam 1856- 1863; Berthelot t6ng hop dircc axetilen va rnetan ... Tat ca deu khOng can den "luc song". Nhfrng thanh cOng do dii lam thay d6i quan niem ve hop chat hiiu CrJ va rna ra rn~t thOi ki nghien cuu t6ng hop cac hop chat hiiu co trong phong thi nghiem, Vi vay, s6 luong ding vm sl! hieu biet ve cac hop chat hiiu co tang len mot each d~t bien. D!n thm

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kl do, nguoi ta dii nhan thay rang tat Cel cac hop chat hihl co d~u chua cacbon va cacbon thuong chiem ham Iuong 100 nhat, dong thai cac hop chat hihl co ciing co nhUng d~c diem chung khac voi cac hop chat vO ca. Chfnh vi vay, ngay trong cuon sach xuat ban tit nam 1861, Kekule da cho Hoa hoc hlru co mot dinh nghia hien dai "Hod hoc Hiiu co la su nghien CUu cac h9'[J chdt cua cacbon",

Nhtrng luan diem v~ cacbon hod tri 4 va mach cacbon da duqc Kekule va S. Couper dua ra tit nam 1858, nlnrng chi den nam 1861 Thuyet cdu tao hoa hoc rnoi duoc A.M. Butlerop d~ xuat. Nam 1860, L. Pasta phat hien ra hien nrong dOng pharr quang hQC. Nam

1874, Leben (Le Bel) va Van HOp (Van't Hoff) de ra Thuye't cdu tao ttt dien cua cacbon.

Thuytt Cdn tao hod hoc va thuyet Cacbon tit dien da lam sang to hien nrong dong d!ng, d6ng phan cau tao va d6ng phan lap th~ trong Hoa hQC Hiru co, han the cluing con d~t co sa cho mot trong nhtrng If thuyet co ban nhat cua Hoa hQC : Li thuye't cdn true.

Sau phat minh ra electron (J. Thomson, 1898), cac thuyet electron ve lien ket hoa hoc IAn hrot ra doi : Thuyet ve lien ket ion cua Kosen (W. Kossel) vao nam 1916, thuyet ve lien ket cong hoa tri cua Liuyt (O.N. Lewis) va I. Langmuir vao narn 1916 - 1919. SI! xuat hien cua Co hoc luqng tir vao nam 1926 (boi E. Schodinger, W. Heisenberg va Paul Dirac) dii rna dau cho thm ki phat trien If thuyet obitan ve cau true nguyen tir va phan tiro Di dau trong linh vue nay la Helo (Heitler), London va Huckel. SI,l tham nhap cua Co hQC hrong tir vao Hoa hoc Hiru co ngay cang sau rong, tir pharn vi cac lien ket hoa h9C a nira dau the ki xx dii chuyen sang pham vi cac tinh chat quang phd va co che' ciia cac phltn tl'ng hoa h9C vao nira cuoi the ki xx.

o the ki xx, Hoa hoc Hiru co dii dong gop cho nhan loai nhUng phat minh co y nghia thuc tien quan trong, Chang han, nhimg thanh tuu nghien cuu trong linh vue polime da sinh fa nganh cong nghiep Char deo, Cao su nhan tao va To sci hoa hoc ~ Nhirng nghien cuu ve phan Ung cracking va refoming dii dl)t nen tang cho rung nghiep Hoa dau -xuong song cua cac nganh cong nghiep nhien lieu va hoa chat ; viec 16ng hop ra cac loai thu6c dii lam nay sinh ra nganh Cong nghiep Hoa duoc ...

Sau chua day hai the ki k~ tit khi ra doi, Hoa hQC Hihl co dii phat trien mot each manh me, c6 nhieu linh vue duoc tach ra thanh cac nganh Hoa hQC moi •. hay diroc chuyen bier hoa nhu : Hod Sinh hoc, nghien ciiu thanh phan, cau tao va cac qua trlnh chuyen hoa cac chat (chii yeu la chat hOu co) trong co tM song; Hod hoc cac h9'[J chd: cao phan til, nghien ctiu cac polime t6ng hop va polime thien nhien ; Hod hoc cac h9'[J chdt thien nhien, nghien cuu cac hop cbat hOu co c6 ngu6n g6c thuc vat va dong vat ; Hod hoc cae h9'[J coot ca kim, nghien cuu cac hop chat hihl co chua lien ket kim loai - cacbon, nhai la cac he co kim co tinh chat xiic tac ; ... Cac nha nghien CUn Hoa hQC hihJ

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co co the chuyen mon hoa a linh vue nay hay Iinh vue khac, tuy vay deu thuc hien nhilng nghien CUu d~c tnmg cua Hoa hQC Htru co- tuu trung nhu sau ;

T6ng hop htru co Tun toi cac plnrong phap de di tir cac phan til dan gian xay dung nen cac phan tu phirc tap han v6i nhtrng tinh chit mong doi. Dac biet la ban tong hop va tOng hop toan phan cac hop chat thien nhien co hoat tinh, k€ ca peptit va protein. Viec tach bier cac hQP chat thien nhien, ke ca. bang phtrong phap sac ki, cilng la nhilng cong doan quen thuoc cua t6ng hop hiiu co.

Hoa Ii hUD co Nghien cuu nhfrng nguyen li co ban ve cau true va phan trng cua cac hop chat hiiu co. Dac biet la nghien CUu ca cht phdn Wig. tuc la nhilng thay d6i chi tiel ve cau true va nang hrong cua cac chat phan ung trong qua trlnh bien d6i thanh san pham. Chinh nhtrng nghien cuu do dii gop phan lam cho Hoa hoc Huu co ngay nay tra thanh mot nganh Hoa hQC co co sa If thuyet viing chaco Nhfrng thanh uru cua Hoa hoc Hiiu co Ii thuyet khong nhfrng lam phong phu cho li thuyet hoa h9C noi chung rna con soi sang cho viec nghien CUll hoa hoc su song. hOi VI chinh nhtmg nguyen ll chi phoi Hoa hoc Hiiu co trong blnh phan ling cung chi phoi cac phan tir trong cac co the s6ng.

Phan tfeh hfi'll co nham xac dinh cau tnic phan tir chat htru co. Tnroc day, phan tich httu co chu yeu dira vao cac loai phan ung hoa hoc khac nhau (phuong phap hoa hQC). D61a phueng phap tieu t6n nhieu hoa chat, thai gian va cong sue. Ngay nay, nho nhtrng thay d6i co tfnh chat each rnang trong linh vue cac phuong phap phO do tin hQC mang lai tu hai thap kl cuol cua the ki 20. cac phuong phap v~t Ii nhu pho tir ngoai - kha kien (UV-Vis), pho hong ngoai (IR), phd Raman. ph6 huynh quang. phuong phap nhieu xa tia X •... d~c biet ia phc cong huang tu hat nhan (NMR) va phO kh6i hrong (MS) khOng nhiing dii thay the hau nhu hoan toan cac phuong phap hoa hQC rna con tao ra nhUng thay d6i that dieu ki. Chimg han, morphin (dung trong y, diroc) tach duqc duoi

dang tinh khier tir nam 1803 (cong thirc phan tir C17HI9N03) nhung cau true thuc su dung ciia no thi mai tai nam 1925 m6i thiet lap xong. Thuoc chong khoi u vinbrastin (cong thee phan tit C46HssN409) tach diroc tit thirc vat nam 1958 nhtrng cau tnic cua no t6i nam 1965 moi duoc hoan roan xac dinh, Ngay nay, nhtrng hop chat thien nhien ki€u phirc tap nhu vay co the diroc xac dinh cau tnic trong vai tuan,

Sang the' ki 21. Hoa hQC Hiiu co se cang phat trien manh me han : Cac chien hroc rnoi trong t6ng- hop hiiU co se duoc ap dung ; Cac van de Ii thuyet se dtroc hoan thien, Tin hQC va plnrong phap vat li hien dai se dtroc img dung vao moi linh vue, ttt viec mo hinh hoa cac tfnh chat cua phan tit. chon dieu kien cho t6ng hop huu co •... den nghien ciiu co che' phan ting, nghien CUu va xac dinh cau tnic phan tit hiiu co... Hoa hoc Htru co se mang lai cho con nguai nhilng loi Ich vat chat to IOn va nhttng hieu bie't sau sac hen ve str s6ng va va chfnh nr duy cua mlnh.

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§2. Hqp cHir HOO CO'

_ .J .... .... " _

1- {)~C DIEM VA PHAN LO~I HQP CHAT HlIU CO

1. D~c di~m chung cua cac hqp chat hftu co

Mac du khong co ranh gicri that r6 ret gitra hop chat vO co va hop chat hilu co, cac hop chat hftu co co cac dac diem chung sau :

Ve' call tao

Hop chat htru co nhat thiet phai chua cacbon, ngoai fa con co H, 0, N, halogen, S, P va cac nguyen to khac. Lien ket hoa hoc trong hop chat huu co thuong la lien kel cong hoa tri, rat it khi co lien ket ion.

Nguyen tiI cacbon khong chi lien ket voi nguyen tiI cua nguyen to khac rna con lien ket vcri nhau bang cac lien ket nrong doi ben tao ra cac dang mach ha, mach vong rat da dang,

Ve'tfnh chat vg,t Ii

Cac hop chat hii'u co nrong d6i de n6ng chay va de bay hoi, thuong khong tan hoac it tan trong nacre nhung de tan trong cac dung moi htru ca.

V l tinh chat hod h9C

Da so cac hop chat hii'u co chay khi bi dot. Cac hop chat huu co thtrong kern ben voi nhiet nen de bi phan huy bOi nhiet.

Phan ling cua cac hop chat hOU co thirong dien fa cham, khong hoan toan va khong theo mot hirong nhat dinh nen thuong sinh ra nhieu san pham phu.

2. Phan lo~ hQp chat hftu co

Cac hop chat hiru co thuong duoc phan loai theo mach cacbon hoac thea nhorn chirc. Thea mach cacbon :

Cac hop chat hilu co duoc phan thanh hop chat mach htl va hop chat mach vong. Hop chat mach ha, con goi Ia khong vong (acyclic) hoac beo (alyphatic), lai diroc phan thanh hop chat no (bao hoa, saturated) neu mach cacbon chi chua cac lien ket don, va hop chat khong no (khong bao hoa, unsaturated) neu mach cacbon c6 chira lien ket boi cacbon - cacbon.

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Hop chat mach yang (cyclic compounds) gem co hop chat dong yang (isocyclic, mach yang chi gorn cac nguyen tu cacbon) va hop chat di yang (heterocyclic, a mach yang ngoai nguyen t6 cacbon ra con co cac di t6 nhir 0, $, N, ... ). Hop chat dong yang lai dtroc phan thanh hop chat yang thorn (aromatic) va hop chat yang beo (alicyclic). Hop chat yang beo co the Ia no hoac khong no. Hop chat di yang cling diroc phan thanh di yang thorn va di vong khong thorn, Di yang khong thorn cling co the la no hoac khong no. each phan loai theo mach cacbon duoc tom tilt nhu a bang 1.1.

PHAN LO~I

Bang 1.1. Phan loal hQp chat hOU co theo mach cacbon

THfDV

{ thom : I'"' 9

khllng thorn : Q

no:

~ HOp,",' khOo, ""0, {

Kh6ng no:

O~OQ 0
~
~ =sss ~
0 00 (tN).
N
'"" -
-
o 0 ()NH
NH 0 CO HQP CHAT HOlJ CCI

{ thom :

,---+- Hap chat dong vong

kh6ng tncm :

Theo nh6m chuc :

Nguyen ltf hodc nh6m nguyen tu quyet dfnh ddc tinh hOG hoc cua hap chat hiiu ca duac goi la nh6m chuc. Vi vay cac hop chat huu co can co the duoc phan loai thee nhom clnrc, dai th~ nhu a bang 1.2.

Ngoai cac loai hop chat voi cac nhom chirc nhu ghi a bang 1.2, can co nhieu loai hop chat chua cac nhom chtrc khac ntra. Chang han, cac hop chat co kim (chua lien ket cacbon - kim 10~i), hop chat co photpho (chua lien ket cacbon - photpho), h'JP chat azo (chua nhom -N=N-), dan xuat cua axit cacbonic, polirne, ... Co nhieu hop chat chua

dong thai cac nhom chirc khac nhau, nhu aminoaxit (chua nhorn -NH2 va -COOH), hidroxiandehitIchua nhorn -OH va -CH=O), ... cluing duoc goi 1a hap chat tap chuc. Do tinh chat Cl,IC kl da dang cua cac hop chat httu co, trong nhieu tnrong hop nguoi ta sir dung dong thai ca hai each phan loai ke tren, Trong cu6n sach nay. cac hop chat duoc pharr loai chu yeu theo nhorn chirc,

Hop cMt vong -

........,. H\lp chit d! vong

10

Sang 1.2. Phin lo,i hQP chat hihl ce theo nh6m chU'c

PHAN LO~I NH6M CHUC CONG THUC CHUNG THfDV
Ankan, xic\oankan C~C, C~ H no R-H CH3-CH3, 0
Ankan, xic\oanken, ~C=C~ R1 R3 CH2=CH2, 0
, ?
polien R2/C = c...R" ,CH2", CH - CH '" CH2
Ankin, xicloankln, -C .. C- R1-C"'C-R~ H-C .. C-H,IO
poliin
Aren E>6ng vOng thorn Ar-H © 00 Q
Hetaran D[ vOngthom Hr- H © 00
Dim xuat halogen - F, - C/, - Sr, - I R-X,Ar-X C2HsCI, CHeI3, ©Tsr
Aneol, phenol -OH R-OH,Ar- OH C2Hs-OH, ©rOH
Eta C-O-C Rl-0-R2,Ar-0-R (C2Hs)p· Cd ,CH30-(Q)
CH3
H'1J) ehat nitro - N -+ 0 R - N02, Ar - N02 CH3-N02• 02N-r¢.rN02
II
0 N02
Amln - N( R - NH2, R2NH, R3N CH3NH2, Q ©rNHCH3
AI - NH2, ArNHR
AncJehit -C-H R - CH '" 0, Ar - CHO CH3 -CH= O. @-CH=O
II
0
Xeton -c- R1 - C - R2 Ar - C - R CHJ - C - CH3, <Q)-C-CH3
II II ' II II II
0 0 0 0 0
Axit cacboxylic -C-OH R - C - OH, Ar- COOH CHJCOOH, @-C ~ OH
II II II
0 0 0
Este -C-O-C- Rl_ C -OR2,Ar-C- OR CH3 - C - OC2Hs, @-c - aCH]
II II II II II
0 ° ° 0 a
R-C-NH ,Ar-C-NHR
-C-N/ II 2 II
Ami! II ' 0 0 CH3 - C - NH2, CH3 - C - NHCeHs
II II
0 R-C - NHAr,N'- C - NH 0 0
• II 2
° °
0
II
AnhicJrit axil -C-O-C- (R- C)O,R-C-O-C-Ar (CH3-gt-Q, ©C~
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Halogenua axil -C-X R - C - X,Ar- C-X CH3 - If - Ct, @-If - CI
" II II
0 0 0 0 0
Nim! -CsN· R-C;o;; N,Ar-C!!! N CH3C !! N, @-C '" N 11

'" 41 .- "" It! J_

II - PHUONG PHAP TACH 81~T VA TINH CHE HQP CHAT HUU CO

Tit nguon thien nhien hay bang con dirong tong hop, thuong nguoi ta khong thu dtroc ngay mot hop chat hiru co rna duoc mot h6n hop cac chat hiru co voi ham IUQ'Ilg khac nhau. De nghien cuu cau true, tfnh chat hoac ling dung cua mot hop chat, can phai tach no ra khoi hon hop, nrc III tinh che' no thanh chat tinh khie't (con goi III chat nguyen chat), Cac phuong phap tach biet vll tinh che hay dung d6i voi chat hiru co III chung cat, chiet, ket tinh va sac kl,

1. Phudng philp chu'ng cAt

Khi dun soi mot hon hop, chat nao co nhiet d¢ soi thap han se chuyen vao pha hoi sam han va nhieu han. Khi gap lanh, pha hoi se ngung tu thanh pha long chua chu yeu la chat co nhiet d¢ soi thap han. Qua trlnh do goi la S~( chung edt. Co cac kieu chirng cat chu yeu sau:

a) Chung edt thuong

Khi ca.n tach lay mot chat long co nhiet d¢ soi khong cao lam ra khoicac chat co nhiet d¢ soi khac biet dang ke so voi n6, ngiroi ta dung phirong phap chung cat dan gian nhat goi la chung cat thuong. Thi du, sau khi tinh bot len men nrou se thu diroc mot hon

hop gom mroc (t~ 100°C), etanol (t~ 78,3°q, mot chut axit axetic «( 118°C) ... va ba nrou. Khi nau nrou (thuc chat III chung cat thirong), dau tien thu duoc mot dung dich chua nhieu etanol hon mroc, sau d6 ham luong etanol giam dan, ta duoc nrou trang. Cho nrou trang vao blnh cau co nhanh (binh Vuyec), Mp ong sinh han, nhie: ke roi chung cAt

thuong va thu doan soi a 78, 17°C se duoc hon hop dang phi chua 96% etanol va 4% mroc. Tit nrou 96%, dung chat lam khan. roi lai chung cat, thu doan soi a 78,3°C se diroc etanol gan 100%, thuong goi la nrou tuyet doL

b) Chung cd: phdn doan

Chung cat don gian mot Ian tlurong khong thu duqc chat tinh khiet, nhat 13 doi voi hen hop cac chat co nhiet d¢ soi khac nhau khong nhieu. De khong phai chung cat nhieu Ian, ngtroi ta thay blnh Vuyec bang blnh call noi voi cot edt phdn doan. Cot cat phan dean gom nhieu nac, a moi nac pha hoi diroc ngirng tu thanh long roi lai chuyen thanh hoi lien 11:1C. Nhir the, mOi nac la mot Ian chung cat va chung cat phan doan thirc chat lit clurng cat lien tiep nhieu Ian tren cung mot dung cu. nho vay rna thu dtroc cac chat voi d¢ tinh khiet cao hon so voi clnrng cat thuong. Trang cong nghiep, nguoi ta dung thap

cat phan doan, chang han, a nha may nrou, de cat lay c6n 90°, c6n 96° hoac b nha may IQc dau, d~ cat lay cac phan doan khac nhau cjra dau mo.

12

c) C hung edt duai dp sudt thdp

Khi ap suat tren mat thoang giarn thi nhiet d¢ soi cua chat long se giam theo, Vi vay, d6i voi nhUng chat co nhiet d¢ soi cao hoac de bi phan huy i:J nhiet d¢ cao, can phai chung edt duoi tip sudt thdp de giam nhiet d¢ soi va tranh sv phan huy, D6i voi dung moi co nhiet d¢ soi thap nhu hexan, benzen, clorofom ... ngiroi ta thuong cat loai cluing bang may cat quay, thuc chat la cat b ap suat 20 - 40 mmHg. D6i voi cac chat co nhiet d¢ soi cao hon thi phai dung born lam giam ap suat xu6ng con mot vai mmHg. Doi voi nlumg chat soi b nhiet de) cao va de bi tac dung boi nhiet, ngiroi ta dung phuong phap

chang edt lap mong va chung cdt phdn ttt 0 ap suat thap toi 10-3 - 10--4 mmHg. Khi d6 nhiet de) sci co the giam di 200 - 300°C.

d) Chung edt 16i cuon hoi nude

Nhirng hop chat huu co khong tan hoac rat it tan trong mroc, mac dil co nhiet d¢ soi cao nhirng khi tron voi mroc se tao ra hon hop soi 0 nhiet dQ xap xi 100°C (a ap suat thtrong). Khi do 0 pha hoi s6 mol chat huu co (nchc) va so mol mroc (nn) se Ii le thuan voi ap suat hoi rieng phan cua cluing a nhiet do soi cua hon hop :

nchc : on = Pchc : Pn

Lam lanh pha hoi se thu duoc pha hiru co (long hoac ran) cung voi nude long. Sau khi chiet hoac IQc se tho diroc pha hiiu co. Do Ia noi dung cua phirong phap chirng cat 16i cuon hoi mroc,

Nguoi ta ap dung phuong phap chung cat 16i cuon hoi nude de tach biet nhUng chat soi 0 nhiet d¢ cao va hi bien d6i 0 nhiet de) do, hoac de tach lay chat de bay hoi cung voi hoi mroc tll non hop cac chat kh6 bay hoi hon, hay tir hon hop cac chat nhua. Thi du, khir nitrobenzen bang sat trong axil clohidric roi trung hoa bang NaOH nguoi ta thu diroc mot hon hop sen set, mall den g6m mroc, sat oxit, sat hidroxit, bot sat du, nitrobenzen du, ... va san pharn chfnh la anilin, Trong tnrong hop nay, plurong phap thich hop nhat d6 tach lay anilin la chung cat 16i cuon hoi mroc.

Ngay tit thai xa xua, con ngirci da biet clurng cat 16i cuon hoi nuac de! tach lay tinh dau thuc v~t lam huong lieu va duoc lieu,

2. Phudng phap chie't

Chiet lil phirong phap dung mot dung moi thich hop hoa tan chat can tach thanh mot pha long (goi la dich chie!) phan chia khoi pha long (hoac pha nin) chua hOn hop cac chit con lai, Tach hfy dich chiet, giai ph6ng dung m6i se thu duoc chat can tach. Nguai ta tlurong dung phuong phap chiet de tach lay chat hiru co khi no a dang nhtl nrong hose

13

huyen phu trong mroc, hay de tach lay chat huu co ra khoi mot hon hop a the ran. Dung moi thuong dung la ete, benzen, cloroforn, hexan, ...

Thi dLJ, khi cat loi cu6n hoi mroc de tach lay anilin (xern muc Phuong phap cat loi cu6n hoi rnroc) nguoi ta thu diroc nhu urong cua anilin trong nuoc. Lac nhil nrong d6 vOi benzen trong phfu chitt, anilin hoa tan vao benzen tao thanh dich chiet n6i len phia tren lap nuoc. Mb khoa duai cho lOp mroc chay het se thu duoc dich chiet. cat quay (xern muc cat dum ap suat thap) de du6i het benzen se thu duoc anilin.

Ngoai pheu chiet thong thuong, trong phong thi nghiern con su dung cac dung cu cho phep chiet lien tuc bang dung moi n6ng nham tang cuong hieu suat cua viec chiet.

Tu xa xua, nhan dan dii biet dung phirong phap chiet, chdng han ngam thao duoc vao nrou de su dung cac hoat chat tan vao nrou, ngam ia cay cham giii nho trong mroc de tach lay pham cham nhuom vai, ...

3. Phudng philp ke't tinh

Ket tinh la phuong phap don gian nhung rat hieu qua de tinh che cac chat hnu co a the ran. Dua vao su thay d6i d~ tan thea nhiet dQ, nguoi ta hoa tan chat can tinh che vao dung moi thich hop thuong la a nhiet dQ soi cua dung moi, IQC n6ng, be can khong tan r6i de nguoi hoac lam lanh til til, chat ran se tach ra duoi dang tinh the nam can bang voi dung dich bao hoa cua n6. LQc, nra, lam kho se thu duqc tinh the chat cill tinh che, Vi mang tinh the chi chua nhtrng phan tit gi6ng nhau nen neu mot chat thu dugc a dang tinh the d6ng nhat thl no dii diroc xern nhu Ul tuong d6i sach. Mot chat ran ducc coi la tinh khiet neu sau nhieu lao ket tinh trong nhiing dung moi khac nhau rna nhiet dQ n6ng chay cua no van kh6ng thay d6i.

Kh6ng chi trong phong thi nghiern rna trong san xuat cung thuong dung phuong phap ket tinh. Chang han, ket tinh de tao ra duong kinh, rnu6i tinh, ml chinh canh, ...

4. Phuong philp sAc ki

Phuong phap sac ki, khoi dtiu chi diroc dung de phan tach cac chat co mau, ngay nay dii phat trien manh me va diroc tIng dung rong riii trong phong thi nghiem de tach biet, tinh che va dung trong phan tich dinh tinh, dinh luong cac hOn hop tir don gian den phirc tap, Phuong phap sac ki dua tren 51! khac biet ve t6c dQ di chuyen cua cac chat trong pha dong khi tiep xuc mat thiet voi mot pha tinh, Nguyen nhan cua 51! khac nhau d6 la do kha nang bi hap phu va phan hap phu khac nhau hoac kha nang trao d6i khac nhau cua cac chat a pha dong voi cac chat a pha tinh, C6 nhieu kieu sac ki khac nhau : sac ki C91, sdc ki /tIP mong, sdc ki khi ....

14

Mot loai sac ki don gian nhat duoc lay lam thi du la sdc ki cot, Trong do, pha tinh la bot silicagen (SiOz. nHzO) hoac bot nhom oxit, ... diroc nhoi trong mot 6ng thuy tinh thang dirng (goi la cot), pha dong gem hon hop chat can phan tach va dung moi thich hop diroc d6 vao phia tren cot. Trong qua trinh pha dong di chuyen tir tren xu6ng durn dQC thee cot, chat nao co t6c dQ di chuyen 1&1 hon (hi hap phu kern hon) se cling vai dung moi thoat ra tnroc. Lam bay hoi dung moi, se thu duoc chat can tach. Phuong phap nay tieu ton kha nhieu thoi gian VI the chi ap dung doi vci cac hon hop khong the tinh ch€ bang cac phuong phap thong thuong.

§3. CAD T40 pHAN Tir HIJP CHAT HW CO

I ~ CONG THlIC PHAN TlI HQP CHAT Hlru CO

1. Phan tich nguyen t6 va cong thuc kinh nghi~m

De xac dinh va bieu dien thanh phan nguyen t6 cua mot hop chat, ngtroi ta can tien hanh pharr tlch dinh tlnh va dinh hrong rOi thiet l~p cong thuc kinh nghiem,

a) Phon tich dinn tinh, phon tich dinh. IUQ'11g nguyen t6'

Phon tich dinh rinh de xac dinh xem hop chat (hay h6n hop) co chua nhiing nguyen to nao, Muon vay, ngtrci ta dung cac phan irng hoa h9C chuyen cac nguyen to trong hop chat huu co thanh cac hop Chllt vo co don gian va de nhan biet.

Thi du, Khi dot chay hoan toan hop chat hiru co thi cachon chuyen thanh COz • hidro chuyen thanh HzO, cIo chuyen thanh HCI, ... Nguoi ta nhan ra COz nho mroc voi trong, nhan ra HzO nho CuS04 khan, nhan fa HCI nho dung dich AgN03 trong HN03 •...

Thuong thi ket qua cua phan tich dinh tinh direc Illy ngay tif ket qua cua phan tich dinh hrong,

Phon rich dinl: luang nham xac dinh ham luong cac nguyen to co trong ·hqp chat (ti l~ % ve khci hrong hoac tl s6 nguyen tl'r). Cling giong nhu phan tich dinh tfnh, nguai ta dung cac phan Ung hoa hoc de chuyen cac nguyen to trong hop chat hOU co thanh cac

hop chat vo eo don giim nhu COz, HzO, N2, ... rOi dinh hrong cac san pham do bang phuong phap trong hrong, phuong phap the tich hoac cac phirong phap hien dai khac nhu sac ki khi, ...

15

Thuong thi cacbon va hidro diroc xac dinh dong thoi bang each nung nong mot hrong can chfnh xac (toi 0,1 mg hoac thap hem) hop chat httu co voi Cuo trong dong oxi,

rOi dinh hrong CO2 va H20 sinh ra, chang han hap thu H20 bang Mg(CI04h. hap thu CO2 bang KOH ... SI! co mat hoac yang mat cua cac chat khac nhu N. S. halogen .... va ham luong cua cluing duoc xac dinh bang cac 1&1 phan tich rieng biet khac. Ham hrong oxi rat it khi duqc phan tieh tI1!C tiep rna thuong duoc tinh bang each lay J 00% trir di phan tram cac nguyen to' khac dii xac dinh duoc. Cac kim loai thirong duqc xac dinh bang phuang phap phd http thu nguyen tit.

Hien nay, viec phan tich dinh hrong (dong thai cling la phan tich dinh tinh) duoc thuc hien trong cac phong thi nghiem chuyen biet vci cac may phan tich tu dong, May tinh se tinh ham hrong va in cho ket qua. Chang han, C : 45,80% ; H : 10,57% ; N : 13,24%. tong cong lit 69,61 %. Neu hop chat khong chua nguyen to' nao khac thi 30,39% con lai duoc coi la cua oxi.

b) Cong thuc kinn nghiem

Til ket qua phan tich dinh Iuong, ngiroi ta tinh diroc tl sO' mol nguyen tir cua cac nguyen to' cau thanh hop chat bang each chia ti sO' % cho nguyen tir khoi trung binh cua nguyen to'. Chang han, voi ket qua phan tich dii neu i:J tren thi ti sO' mol nguyen tir, cling chinh lit ti so nguyen til cua C, H, N. 0 trong phan til hop chat dii cho, Ia :

45,80 10,57 13,24 30.39

n~ . n . n . n - . . .

• ~. H' N' 0 - 12,01' 1,008'14.01 '16,00

; 3,813: 10,49: 0,945 : 1,899

Ti sO' nguyen til duoc quy v~ ti sO' cua cac so nguyen t6i gian, chang han bang each chia cho sO' nho nhat trong chung (0,945), r6i ghi vito duoi chan cac kl hieu nguyen t6 thl thu diroc cong thuc kinh nghiem.

3,813 10.49 0,945 1,899.

DC : nH: nN: no ; 0,945 : 0,945 : 0,945 : 0,945

; 4,03 : 11,1

;4 :11

: 1,00 : 2,01

: 1 : 2

Cong thirc kinh nghiem lit C4HlIN02.

Khi lap cong thirc kinh nghiem, ti sO' nguyen til dii duoc quy ve ti socac sO' nguyen t6i gian, vi the cong thirc kinh nghiem con diroc goi fa cong thuc dan gidn nhdt. C6ng thirc kinh nghiem cho biet thanh phan dinh tinh, dinh hrong cac nguyen to' eo mat trong phan til nhirng khong dong nhat vci cong thuc phan til boi VI mot cong thirc kinh nghiem

16

c6 tht bieu dien thanh phan cua nhieu chi It rna cong thuc phan tu cua chung la boi s6 cua cOng thirc kinh nghiern, N6i mot each khac, cong thtrc kinh nghiem la cong thirc t6i

gian cua cOng thtrc phan tu. Thi du, cac cong thirc phan tu CH20, ~H402' C3H603, ... deu co cung cong thrrc kinh nghiem (cong thtrc don gian nhat) 1a CH20.

can luu y rang, viec lam tron s6 trong khi lap cong thuc dan gian nhat (cling nhu khi lap cOng thirc phan tu) deu phai chu y toi sai s6 thuc nghiem (sai s6 trong phep phan tfch nguyen to, phep xac dinh kh6i IUQ"Ilg phan til). Do sai s6 thuc nghiern, tir cac so lieu phan tfch nguyen t6 c6 th~ xac dinh duoc mot vai cong thirc kinh nghiem, Chang han, voi so lieu phan tich nguyen to: C 76,31 %; H 10,.18% ; N 13,52%, neu sai s6 cua moi phep xac dinh la ±O,3% thi ta se xac dinh duoc cac cong thirc kinh nghiern sau :

Ci3H2oN"2 ; Ci3H2IN2 ; ~OH32N3 ; ... D~ lua chon lay cong thuc kinh nghi¢,? dung, va dt thiet lap cong thirc phan tll can phai biet them mot dai hrong quan trong Iii. phon tukhtii.

2. Xitc dinh phan tit kh6i

.

a) Dua VaG dinh lua: Av6gadr6

Theo dinh luat Avogadro, d6i voi hai chat khi A va B bat ki, ta c6

Tit do suy ra MA = MB . dAIB

dA/B la ti khoi cua khi A so voi khi B. Ti khoi dA/B diroc tinh bang ti so kh6i hrong ella cung mot tht tich khi A va khi B b cimg dieu kien nhiet d¢ va ap suat : dNa = rnA: mB-

Khong khi duoc coi la co phan tit khoi bang 29 dvC, 1 lit khong khi b dieu kien tieu chuan co khoi luong IA 1,293 g. Ngum ta thuong xac dinh trkhoi cua mot chat khi X

(chua bier phan tir kh6i) so vm khong khi (?XJkk) r6i tioh philo tu khoi ella X theo cong thirc Mx = 29. dX/lck

b) Dua vao tinh chat cua dung dick

Dung dich cua mot chat r~n hoac mot chat long kho bay hoi dong dac b nhiet dQ thap han va soi b nhiet oQ ea? hon so v6i dung moi nguyen chat, Trong phuang phdp nghiem lanh, ngmri ta do d¢ giam nhiet d¢ dong d~e goi la d9 ha hang'dilm, trong phuang phdp nghiem soi, nguoi ta do d¢ tang nhiet d¢ soi va goi la d9 tang phi diim, cluing duoc ki hieu la dt. Phan tic khol M ella chat tao khong dien li, khong bay hoi diroc tfnh theo bieu thirc :

M=K. m.IOOO p.at

2 - HHHC1

17

K 18. hang 56 nghiem lanh neu lit 18. dQ ha bang diem, K 18. hang 56 nghiem 50i neu 6t la dQ tang phi diem ; m la 56 gam chat tan trong p gam dung mOL Hang 56 K chi phu thuoc ban chat cua dung moi, ducc xac dinh tit thirc nghiern va duoc ghi trong cac bang tinh chat cua dung moi. Chang han d6i voi _ nuoc, K nghiem lanh Hi. 1,86 ; K nghiem 56i

1a 0.51 ; D6i voi benzen, K nghiern lanh la 5,12, K nghiem 56i la 2,53 (°C.glmol).

Thi du J. Xac dinh phan tir khoi cua homon thiroxin biet rang dung dich chua 0,546 g thiroxin trong 15,0 g benzen dong dac b 5,26°C.

lit = 5,50 - 5,26 = 0,24 °c (benzen dong d~c b 5,50°C)

0,546.1000

Mtbiroxin = 5,12. 15.0,24 = 776 (g/mol),

Thi du 2. Hoa tan 18,00 g glucozo vao 150,00 g mroc thi thu duoc mot dung dich soi b 100,34°C. Hay tinh kh6i lucng phan til cua glucozo.

M 0 51 18,00.1000' = 180 (g/mol),

glucow=' .

150,00.(100,34 -100,00)

Dung dich khi ngan each voi dung moi bang mot mang ban tham (cho dung moi di qua nhung khong cho chat tan di qua) thi gay ra mot ap sua{ thdm thdu 7r ti l¢ voi nong dQ mol cua chat tan :

m 7t=C. RT= --. RT M.V

C : ncng dQ mol/l ; m : kh6i lirong chat tan trong V lit dung dich, g ; M : phan tlr kh6i (g/mol) ; R : hang s6 khf If nreng, bang 0,08206 lit.atm/K.mol ; T : nhiet dQ Kenvin,

Tu bieu thirc tren se tinh duoc phan til kh6i.

Thi du : Hoa tan 1,00 mg mot protein vao mroc thanh 1,00 ml dung dich roi doap suat tharn thau b 25°C thi ducc gia tri 7t = 1,12 mmHg. Hay tinh phan tlr kh6i cua protein dii cho.

7t = 1,12mmHg = 1,47 . 10-3 atm ; 1 rng/I ml nrong irng vai 1 gill. 760mmHg

M = n.V = 1.47.10-3.1 = 1,66.104 (g/mol), m.RT 1.0,08206.298

18

e) Dua VaG phd khdi luang

Phuong phap xac dinh phan tir kh6i hien dai va chinh xac nhat la dung may ph6 khoi Iuong. Phuong phap nay nhanh chong, chinh xac rna chi can mot hrong mau rat nho (co microgam). May pho kh6i luong t1,1' dong ghi va in ra ket qua pho khoi hrong cua chat, Til pho do ta doc diroc kh6i hrong phan tu cua chat. Thi du, hinh 1.1 la pho khoi hrong cua xylopinine, mot ancaloit tach diroc til' thuc vat. Pho do cho biet phan tu khoi cua xylopinine la 355 dve, ngoai ra no con cho biet nhieu thong tin khac ve cau tnic phan tir (xem chirong III).

100

164

Cl 0::: .:0

a 20

CHP~I

CHP :::,..

¥

:::,... I OCH3

OCH3

e 80 "$.

~o ~60

0:::

~

mfz 100 120 140 160 180 200 220 240 260 280 300 320 340 360

190

354 340(M-CH~

Hinh 11. Phd kh6i lut;1ng ctia xylopinine

3. Cong thiic phfut tit

C ong thuc phdn ti'! la. cong thee chi r6 s6 hrong nguyen tir ciia tirng nguyen t6 trong phan tu. Thi du, cong thirc phan tu cua etan la CzH6 ' cua axit axetic la CzH402, cua axit aminoaxetic Ia C2H5N0z, ...

D~ thiet lap cong thtic phan tir, thong thuong phai tien hanh phan tich dinh hrong nguyen to (rnuc a) va xac dinh phan tu khoi cua hop chat (muc c). Til ket qua phan tich nguyen to se thiet lap diroc cong thirc kinh nghiem (cong thirc don gian nhat). Neu cong

thirc don gian nhat cua hop chat la CxHyNzOt thi cong thirc phan tir cua no co dang <=nxHnyNnzOnt hoac viet gon lii (CXHyNzOt)n (n = 1. 2, 3, ... ). Neu phan tir khoi cua n6 xac dinh dtroc la M thi tinh duoc gia tri cua n nhu sau :

M = (l2x + y + 14z + 16t) . n n = M : (12x + y + 14z + 16t)

Thi du, mot hop chat co thanh phan nguyen t6 la : C 45,80% ; H 10,57% ; N 13,24% ; conlai la 0. Ti khei hoi cua hop chlft so voi kh6ng khi la 3,62. Hay lap cong thirc phan tir cua hop chat.

19

Tir so lieu phan tlch nguyen to, ta lap diroc cong thirc kinh nghiern cua hop chat lit C4H]]N02 (rnuc b). Dua vao ti kh6i hoi so voi khong khi ta tinh diroc phan til kh6i

M = 3,62.29 == 104,98 ~ 105.

Ta co: (C4HIlNOZ)n = 105

n = 105: (12.4 + 11 + 14 + 16.2) == I

Vay cong thirc phan til cua hop chat da cho la C4HllNOz trimg voi cong thuc kinh nghiern.'

Ngiroi ta co the lap cong thirc phan tu cua hop chat bang cac each tinh toan khac khong qua cong thirc kinh nghiem, Tuy nhien, thirc chat cua moi each tfnh toan khong co gl khac nhau, tat ca deu phai dua VaG s6 lieu phan tich dinh luong va xac dinh phan tir kh6i.

Phuong phap hien dai xac dinh cong tlnrc phan ttt la dua vao pho' khdi luang phdn gidi cao (xem chuong III). 6 phd kh6i luong phan giai cao, pharr tu khoi va khoi luong cac manh phan ttt diroc xac dinh chinh xac toi < 10--4 dvC. May tinh se chi ra mot vai to hop nguyen tit cac nguyen to phu hop voi phan ttt khoi va kh6i 111qJlg cac rnanh do, nrc la dua ra mot vai cong thirc phil hop voi ket qua ghi pho. Nha nghien ciru se lira chon lay

ket qua dung. D¢ pharr giai cang cao tduai 10--4 dvC) thl ket qua rna may dira ra cang dan toi dan gia (nrc 13. chi mot cong thirc xac dinh), Ngay nay, plurong phap nay con chua duoc pho bien rong rai chu yeu Ia vi gia may con qua cao.

II - CAU TAO HoA HQC VA nONG PHAN CAU TAO

1. Thuyit ca'u tao hoil h9c

Ngay tir khi Hoa hoc Hiru co moi ra doi, vao dau the ki XIX, cac Nha hoa hoc da no hrc tim hieu van de thii w va each thirc lien ket cua cac nguyen tu trong phan nr, Nhung phai den nam 1861, Thuyel CQU tao hod h9C rnoi diroc Nha hoa hoc Nga A. M. Butlerop dira ra. Day la mot biroc nhay vot ve If thuyet cua Hoa hoc Htru co thai bay gio, Nbiing luan diem co ban cua Thuyet cau tao hoa hoc Iii :

1- Trang phan ti( hap chat hiiu ca, cac nguyen tii kel hap viii nhau thea mot tiuc tt! nhdt dinh. va thea dung hod tri cua chung. Thu l{f kel hap d6 dune goi fa cau tao hod h9C. Su thay do'i thu tu kel hap cua co.c nguyen ttl trong phan tlt (tuc /Q thay do'i cau tao hoa h9C) se tao ra phon ttl hap chat khac.

20

2- Trang phdn tit hap chdt half co, cacbon luon co hod tri 4. Cdc nguyen tu cacbon khong nhiing co the' lien ktl viti nguyen tit cua cac nguyen to' khac rna con lien ktl vai nhau tao thann nhiing mack cacbon khdc nhau (mach khong nhanh, mack co nhdnh, macn vong, ... ).

3- Tinb chdt cLla JU;p chdt hiiu ca phu thuoc vao thanb phdn phdn tit (bdn chat, so' luang nguyen tit) va cdu tao hod hoc (thu II! lien ket cac nguyen tit). Cdc nguyen tit trong phdn tit co dnh huang qua lai Ian nhau.

Thuyet cau tao hoa hoc d5. giup lam sang to ban chat cua hien nrong dong acing, dong phdn va bieu dien chiing bang cong thuc GlUl tao. Tren co sa Thuyet cau tao hoa hQC, nguoi ta da tien doan va dieu ch€ duoc rat nhieu hop chat hiru co rnci. H~ ch€ cua Thuyet cau tao hoa h9C la khong d6 cap tai cau true khong gian cua phan tit, phan tit chi diroc bieu dien tren mat phang,

Ngay nay, cac Nha hoa h9C eta xay dung diroc li thuyet ve Call true khong gian va Call true electron cua phan tit. Nhimg thuyet nay bao trum ca noi dung cua Thuyet cau tao hoa h9C va mang lai nhtrng hieu biet sau sac v~ ban chat cua khai niern cau tao hoa hoc. Tuy vay, ngiroi ta vAn thuong dung thuat ngir "cau tao hoa h9C" voi nghia ban dau cua no, nrc la thir t~ Iienket ella cac nguyen tir trong phan tir the hien tren mat phAng rna chua bao ham su phan b6 trong khong gian,

2. Cong thuc ca'n tao

Cong thirc cau tao bieu dien thutu va each' thuc lien ket cua cac nguyen tit trong phan tit. Thi du :

Cong thirc phan tiI : C4H lO (butan)

C4Hg (xiclobutan) HH

I ~ H-C-C-H

I I H-C-C-H

I I

HH

HHHH

I I I I Cong thirc cau tao : H - C -C -C -C - H I 1 I I HHHH

HHHH

I I I I H-C=C-C-C-H I I HH

m cho gian tien, ngiroi ta thuong sir dung cong thuc cau tao thu gon bang each viet gQP nguyen til cacbon va cac nguyen tll hidro lien ket vdi no thanh mot nhom (-CH3 :

\ \

nhom metyl ; CH2: nhom metilen ; - CH : nhom metin) roi viet cac nhom d6 canh

I I .

nhau thee dung thu 11.1 va each thuc lien ket (lien ket dan, doi, hay ba) cua clning, rieng lien ket dan co th~ bo qua. D6i khi ngtroi ta chi can dung cac dean th~ng d~ bieu di~n lien ket gitra cac nguyen tll cacbon va quy iroc rang dau rrnit cua cac lien ket do chinh Ia

21

cac nhom CHx vOi x dam bao cho C luon du hoa tri 4, neu diu mut cua lien ket la nguyen tir khac cacbon thi phai ghi dung ki hieu cua no. Cich dung cac doan th4ng va goc nhu v~y co the tarn goi la cong thuc cdu tao thu gon nhdt. Thi du :

Cong thirc cau tao thu gon :

CH3 - CH2 - CH2 - CH3 CH2 = CH - CH2 - CH3

ho~c

CH ~ ,

HC CH

1 I

HC CH

" , CH

CfiH6

CH3CH2CH2CH3 CH1 = CHCH2CH3

COng thirc cau tao thu gon nhat tuong ling :

r-:> ~

NoH

D

o

COng thirc cau tao thu gon nhat duoc sir dung rfit ph6 bien trong cac tai Iieu hoa hoc hien nay, nhat la d6i voi nhtrng hop chat plnrc tap,

3. Khai ni~m dang ding, dang phan a) Dong diing :

N hiing hap chat hi'lu co co thann phdn phdn til han kern nhau mot hay nhieu nhom nguyen tu nhdt dink nhung co tinh chdt hOG hoc tuang tI! nhau goi Ia nhiing chat d6ng ddng. Noi f6 hem, nhiing chat htru co co thanh phdn phan tit han kern nhau mot hay nhieu nhom nguyen til nhd: dinb. nhtrng co diu tao hOG hoc tuang tif nhau, do do tinh chat hOG h9C cling tuong tl! nhau, goi la nhtmg chat dong dAng, chung hop thanh day dong dAng.

Thi du 1. Cic dong d~ng hem kern nhau mot hay nhieu nhorn CH2, nhu :

Day dong d~ng cua metan : CH4 ; ~H6 ; C3HS; ... CnH2n+2

Day dong d~ng cua metanol: CH30H; ~H50H; C3H70H; ... ~H2n+l0H Day d6ng d~ng cua axit fomic : HCOOH ; CH3COOH ; ~H5COOH

~H2n+lCOOH

Viec dira them (hay bot di) nhom CH2 (mot nguyen tli C no va hai nguyen tll' H) vao phan tu thtreng khong lam bien dOi dang ke cfiu tao hoa hoc, nhat la khong lam bien d6i bin chat cua nhom chec, vi the khong lam thay dOi dang ke tfnh chat hoa hQC.

Thi du 2. Cac hop chat sau day co thanh philo hon kern nhau mot hay nhieu nhom

-CH(OH) :

C~-CH=O ;CHz -CH-CH=O ;CHz -CH:-CH-CH=O ;CHz -CH-CH-CH:-CH=O

I I I I I I I I I I

OH OH OH OH OH OH OH OH OH OR

22

Chung co cau tao va tinh cha:t nrong 11,1' nhau nen cling duoc xem la mot day dong d£ng.

b) Dong phan :

Nhilng IWp chdt khac nhau nhung co cung cong thuc phdn tu goi iii nhiing chat ddng phdn. Noi r5 hem, nntrng hop chat co cung cong thuc phdn ttl nhung co cdu truc hod h9C khac nhau nen eo tinh chat khac nhau goi la nhiing chat dong phan.

Khai niern cdu true hoa hoc, goi dcm gian la cau tnic (structure), bao gem thu 11,1', each thuc lien ket cua cac nguyen tit trong phan tit (cau tao hoa hoc, constitution) va d. sl! phan bO khong gian cua cac nguyen tu trong phan tu (cau tnic khong gian).

Thi du, but-l-en va but-2-en deu co cong thirc phan nr C4Hg nhung co ca:u tao khac nhau : CH2=CH-CH2--CH3 va CHrCH=CH-CH3 ; But-z-en co hai dang trans va cis khac nhau ve vi tri khong gian cua cac nhom nguyen tir trong phantir :

c~ H

\ I

C=C I \

H CH3

va

CH3 CH3

\ / c=c

I \

H H

trans-but-2-en

cis- but - 2-en

Hai chat tren la dong phan lap th~ cua nhau va cling la dong phan cua but-l-en :

H C2HS

\ / C=C

I \

H H

4. n6ng phan cau tao

Nhirng dong phan khac nhau ve" cau tao hod h9C goi la nhiing dong phan cau tao, D6ng phan cau tao duoc chia thanh cac loai sau :

a) Dong phan macb cacbon. Thi du :

CSH12 : CH3 - CH2 - CH2 - CH2 - CH3

o

0-

CH3 - TH - CH2 - CH3 , CH3

~

b) Dong phan nhom chuc. Thi du :

CJiI2:CH2=CHCH:f:H2CH2CH3 va 0;

23

c) Dong phdn vi tri nh6m chia: Thi du :

C4HH : CH2=CH-CHrCH", va CH3-CH=CH-CH3 ; C4HJ(P : CH3CH2CH2CH20H va CH3- rH - CH2CH3 OH

OH OH

©-OH,©loH va

OH

~

OH

d) Dong phdn h6 bien. La mot loai dong phan cau tao d*c biet. Dac biet acho hai dong phan h6 bienton tai trong mot can bang, dong phan nay bien dOi thanh d6ng phan kia chi do su thay d6i vi tri mot nguyen ta H, dan tbi sl! thay d6i vi trf mot n6i doi. Sl,r bien dOi gifra hai dong phan h6 bien (tautomer) goi la sf! h6 bien hoac din bang h6 bien

(tautomerization). Thi du :

SI! h6 bien xeto - enol

CH3 - C - CH2 - COOEf II

o Dang xeto

CH3 - C = CH - COOEt" I

OH Dang enol

SI! ho bien nitro - axi

R-CH -R' I O=N--+O Dang nitro

-

-

R-C-R' II HO-N -+ 0 Dang axi

Sl,l bien d6i gitta hai dong phan ho bien thirong xay ra rA'! nhanh trong dung dich khi co mat vet axit, baw hoac nuoc. Vi the, ngtroi ta thirong nhan biet va xac dinh ham luong cac dang h6 bien bang cac phuong phap var Ii nhu phuong phap ph6 hong ngoai, tu ngoai - kha kien hoac cong huang tu hat nhan va thu diroc cac se lieu, chang han nhu :

Dang xeto

CH3 - C - CH2 - C - CH~

. II II'

o 0

* Et == goc etyl CZHj

24

- ...--

Dang enol % dang xeto % dang enol
Q--IZ = C - CH3 -100 0,00025
I
OH
O-OH 99,98 0,02
CH3 -C= CH- C-CH3 24 76
I II
O-H .. · 0
O:~H 0 100
O· Trong mo; s6 tnrong hop, ngiroi ta da tach rieng duoc hai dang hO bien. Thi du, ngay tir nam 1911, Nha hoa hoc Due Ludwig Knorr da tach rieng duoc hai dong phan hO bien cua etyl axetoaxetat bang each lam lanh dung dich axetoaxetat den -7SoC, thu duoc ket tua khong tac dung vOi,Br2 (thuoc thirnhan ra noi doi C=C) va khong tac dung voi FeCl3 (thuoc thir nhan biet enol). Do chinh la dang xeto. Khi cho ket tua do phan irng voi bern roi trung hoa bang He} thl thu duoc mot chat ran, chat nay phan img tuc thai voi Br2 va FeCl3. Do la dang enol.

5. each viit d6ngphfut cau tao

Trong qua trlnh hoc tap va nghien CUu hop chat huu co, cluing ta thuong phai viet cong thirc diu tao cua cac dong phan irng voi mot cong thirc phan til tim diroc (viet dong phan cau tao), De tranh trung lap va sai sot, nen thuc hien theo cac buoc sau.

a) Tinh d¢ kh6ng no

Ngirci ta goi d¢ khong no cua phan tir (kf hieu la U, dan vi ta °kn) la tong s6 vong va s6 lien ket tt co trong phan tir (mot lien ket doi co mot lien ket tt, mot lien ket ba co hai lien ket n, vong benzen diroc coi la co 3 lien ket doi nen co ba lien ket rr, ... ). Ankan la hop chat no co cong thirc chung la ~H2n+2' Neu goi s6 nguyen tu eacbon va so nguyen tu hidro trong phan tu la nc va nH thi d¢ khong no cua mot hidrocacbon bat ki duoc tinh bOi cong thuc sau :

U 20c + 2 - nH " ,. k ' °

RH = = 56 vong + so hen et tt ( kn)

2

Thi du :

UC6Hl4 = (2.6 + 2 - 14) : 2 = O°kn (khong chira vong, khong cohen ket tt) UC6Hu = (2.6 + 2 - 12) : 2 = Ib (chua 1 vong hoac 1 n6i doi)

U C6HlO = (2.6 + 2 - 10) : 2 = 2°kn .(chua 2 vong hoac 1 vong + 1 n6i doi, hoac chua 2 noi doi, hay mot n6i bal.

o cac dan xuat halogen, mot nguyen tu halogen thay cho mot nguyen tu hidro, vi the khi tinh d¢ khong no phai ke den s6 nguyen tu halogen:

URX = (2.ne + 2 - nH - ox) : 2 (°kn)

Thi du : U C2H3C1 = (2.2 + 2 -- 3 -1) : 2 = 1 °kn (chua 1 n6i doi) '

U C6 Ht;Cl 6 = (2.6 + 2 - 6 - 6) : 2 = 1 °kn (chua 1 vong hoac 1 noi doi)

25

or mei nguyen tiI nita lam cho s6 nguyen tit hidro trong phan tu tang them 1 so voi l:J hop chat khong chua nita co cung sO' nguyen tll cacbon. Thi du, CH3NH2 so v6i CH4, C6HSNH2 so voi C6H6, CH3N02 so voi CH202 ... VI the, d¢ khong no cua cac hop chat chua N diroc tfnh nhu sau :

U(N) = (2.ne + 2 + nN - nH - nx) : 2 (°kn)

Thi du : U C~H NH = (2.2 + 2 + 1 - 7) : 2 = O°kn (khong vong, khong n6i doi)

_ 5 2

U CfiHsNH2 = (2.6 + 2 + 1 - 7) : 2 = 4°kn (chua 1 yang + 3 n6i doi)

Cac nguyen til oxi va luu huynh trong pharr tit khong rum huang den s6 lirong nguyen tu hidro so voi phan tu tirong img khong chua chung (thi du so CH30H voi CH4, ... ), VI the trong c6ng thirc tfnh d¢ khong no khong phai ke den s6 hrong nguyen tir ° va S.

Thi du : U C2HfiO = (2.2 + 2 - 6) : 2 = 0 "kn (khong Yang, kh6ng n6i doi) U C2H40 = (2.2 + 2 - 4)': 2 = 1 °kn (chua 1 yang hoac 1 n6i doi) UC6H4CIN02 = (2.6 + 2 + nN -fiet - 4) : 2 = 5 aim.

Biet do kh6ng no cua phan tir, ta phan chia thanh loai co yang, kh6ng vong, co lien ket doi, co lien ket ba. lien ket d6i a mach eacbon, lien ket doi b nhom chirc, roi thuc hien buoc tiep theo la viet cac "mach cacbon dong pharr".

b) Xic dinh. ban chili nh6m chuc

Neu dau bai khong cho biet ro hop chat thuoc chirc nao thi can chi ro xem rmg voi cong thirc pharr tir va d¢ khong no tinh diroc thl hop chili co the co nhtrng nhorn chirc nao, nhom chirc do tach khoi mach cacbon diroc hay khong. Thi du nhom -C=C-. -C=C- khong tach khoi mach cacbon, nhung nhom -COOH, nguyen tir oxi lien ket d6i (=0) co the tach khoi mach cacbon.

c) V itt mach cacbon d6ng phan

Thi du, phan tU co 6 nguyen tu C (da trir nhom chirc) se co cac dang mach cacbon hb dong pharr la A, B, C, D va E ; cac dang mach mot Yang la V I + V 10' mach hai vong

la V 12'- V 13"" C

t

Mach ha : c-c-c-c-c-c c---c-c-c---c c-c-c-c-c e-c-c-e e-c-c-e

t I I I I

C C C C C

(A) (8) (C) (D) (E)

(VI)

(V2)

(V3) (V4)

~

(V5)

Mach vong :

o

0-

(V6)

(V7)

CJ>[I]

(V8)

(V9)

(VlO)

(V II)

(VU)

(VI3)

26

Khong phai bao gio' cOng c:in viet tAt d. cac loai mach cacbon rna phai can cu vao dieu kien cu th~. Thf du, d¢ khong no bang 0 thi chi co mach hl1 khong the co mach vong, D¢ khong no bang 1 rna co chua lien ket doi thi cling khong the co mach vong, nell khong chua lien ket doi thl co 1 vong.i.. Biroc tiep theo 18. xac dinh nhom chuc va viet dong phan vi tri nhom chirc.

d) Xdc dinh nhom chuc va viet dong phon vi tri nhom chuc

Nhom chirc co the 18. no nhu halogen (X), hidroxyl (-OR), amino (-NH2)' ete (-0), ... hoac chua no (coi nhu lien ket rc), nhom oxo (=0), nhom cacboxyl (-COOH), nitro (-N02), ... Sau khi da xac dinh diroc hoac phan chia duoc thanh cac nhom chirc co the co d6i vOi phan tll da cho thl dinh cac nhom clurc do vao cac vi tri khac nhau (khong tU<1I1g duang) tren cac mach cacbon dong phan cho dung hoa tri se thu duoc cac dong phan ve vi tri nhom chtrc.

Thi du :

Cong thuc philo 111 C6H12• mach ha thi 1 °kn ling voi 1 lien ket doi C=C, cho lien ket 1t dich chuyen tren mach cacbon A duoc 3 dong phan, tren mach cacbon B diroc 4 dong phan, tren mach cacbon C diroc 3 dong phan, tren mach cacbon D duoc 2 dong phan, tren mach cacbon E diroc 1 dong phan (tong cong 13 dong phan).

Cong thtrc phan tit C6HI40 co d¢ khong no bang 0 (no, mach ha), neu nhom chirc la OH di chuyen tren mach A diroc 3 dong philo, tren mach B diroc 5 dong philo, tren mach C duoc 4 dong phan, tren mach D duoc 2 dong phan, tren mach E duoc 3 dong phan (tong cong 17 dong phan). Ciing cong tlurc do, neu nhom chirc III ete (-0-), cho nhom -0- xen vao gitra hai nguyen tu C a mach cacbon A thu duoc 3 dong philo, mach B duoc 4 dong phan, mach C duoc 3 dong phan, mach D diroc 2 dong phan va mach E duoc 3 dong phan (tong cong 15 dong phan),

C6ng thirc philo tll C6HI20, neu la andehit hoac xeton (nhom chirc 18. oxo). Cho nhom =0 di chuyen tren mach cacbon A thu diroc 3 dong philo, tren mach B diroc 4 dong phan, tren mach C duoc 3 dong phan, tren mach D diroc 1 dong philo, tren mach E dtroc 3 dong phan (t6ng cong 14 dong phan).

Sau cung can dien them cac nguyen tu R sao cho dii hoa tri cua cac nguyen tu trong phan tu.

27

§4. CAD TRUC PHAN Tii vA DONG PHAN L4P THE

oJ (II- ..... ., 'IIi.; A ~ J:' J 41-

I ~ .CAU TRUC PHAN TU VA CAC CONG THUC BIEU OlEN CAU TRUC

1. Khai ni~m vi ca'u true phan tit va cong thitc cAu true

Khi noi den cdu tao hod hoc, nguoi ta chi bao ham thu til va each thirc lien ket cac nguyen tir ella phan til trong khong gian hai chieu. Th1,Ie ra, cac nguyen tii trong phan tu dtroc phan b6 trong khong gian ba chieu thea mot trat til xac dinh. Phan tu, cling nhu rnoi vat the bat ki, deu eo mot kien true nhat dinh.

Ngay tit narn 1874, La ben va Van Hop da de ra Thuye: cacbon tit dien cho rang trong phan tir hop chat hfru cc, bon hoa tri cua nguyen tll cae bon huang ve bon dinh ella mot tu dien. Chang han, phan tir metan duoc coi la mot tiC dien deu rna tam 13. nguyen tii C, bon dinh la b6n nguyen tit H ; Phan tiI etan duoc mo ta la g6m hai ttl dien, m6i til dien co tam la mot nguyen tii C, ba dinh la ba nguyen tiI H, eon dinh thir tu thl chung nhau ; Phan til etilen diroc xem 13 g6m hai til dien chung nhau mot canh, con phan til axetilen dircc xem la g6m hai ttl dien chung nhau mot mat, Mac du thai bay gio, ngtroi ta chua co nhtrng hieu biet ve cau true electron cuaphan tir, nhung Thuyet cacbon tu dien dii mo ta dung s1,I phan bo khong gian cua cac nguyen tu hoac nhom nguyen tit lien ket voi cacbon va da giai thich thoa dang hien nrong dong phan quang hoc va dong phan hlnh hQC,

Ngiroi ta ding nhan thay rang, tinh chat cua hop chat khong chi phu thuoc vao diu tao hod hoc rna con phu thuoc vao su sdp .xtp trong kh6ng gian cac nguyen tu trong phan tir, Hai yeu t6 do hop thanh Call true hod hoc clla phdn tIt, rna thong thtrong chi goi dan gian la cau true phan tii'. Ngay nay, chiing ta deu hieu r5 rang chinh cau true electron (xem chuang II) quyet dinh cau tnic phan tii, den lirot no, cau true phan tir lai chi ph6i moi tfnh chat boa h9C va tinh chat vat If cua hop chat, vi vay rat can co cac cong thirc bieu di~n diroc Sl! sap xep trong khong gian cac nguyen tu cua phan tfr. Oic cong thirc nhu the goi la eong thuc cau true de phan biet voi cong thirc cau tao,

2. Cong thuc ph6i canh

Cong thirc phoi canh nham mo ta vi tri cac nguyen tii trong phan tu dung nhu each sap xep khong gian thuc SI! ella cluing. Dua vao thuc tf:' la mot v~t cang & xa mat thl ta cang cam thay no nh6 di va ngiroc lai. Ngiroi ta quy UDC nhu sau : Lien ket & gan diroc ve dam han lien ket a xa, dau lien ket nao a gftu ve to han dftu lien ket a xa mat ngmri quan sat, nhfrng lien ket nam tren mat giay duoc ve bang net gach blnh thirong, nhtrng

28

lien ket huang ve phia -truae mat giay diroc ve net darn, nhtrng lien ket huang ve phia sau mat giay diroc ve bang net gian doan, Thi du, cong thirc phoi canh ella metan, etan va xiclohexan (dang ghe) diroc ve nhu (j hinh 1.2.

~ H H
H
I \ ~/H
____ c H
H 1111117"" H 1IIIIIic .\. H
HII H
H
H H H HiM 12. C6ng thirc ph6i canh cua metan, etan va xiclohexan (dang gh€!)

De cho de viet, nguoi ta co the: bieu dien cac cong thiic phoi canh tren mot each dan gian han, nhu 6 hlnh 1.3.

H

H

H

I

_ c

w-I"

H H

H

H

H

H

Hinh 13. Cong thirc ph6i canh kiiu don gian htdJ.1g U'ng vCli hinh 1.2

3. Cong thitc chie'u Niumen

De co cong thuc chieu Niumen (Newman), cluing ta nhin phan tir doc thea mot lien k6t nao d6, thuong la lien ket cacbon-cacbon duqc lira chon co muc dich r6i chieu tAt ca

cac nguyen nr len mat giay. Nguyen tir C 6 dau lien ket gan mat ta (Cl) diroc the hien bang mot hlnh tron va che khuat nguyen tir C 6 dau kia cua lien ket (Cz). Cac lien ket voi C1 duoc nhin thay toan bo, chung xuat phat tir tarn cua hinh tron C]. Cac lien ket vui Cz chi nhin thay diroc phan 16 ra tir chu vi cua hinh tron C1• Thf du, neu nhin phan tir etan (hinh 1.2) doc thea lien ket C-C tir trai sang phai ta se nhan duoc cong thirc chieu Niumen nhu 6 hinh 1.4a ; Neu nhin phan til cis-but-2-en va trans-but-2-en doc thea lien kel C=C ta se duoc cac cong thrrc chieu Niumen nhu 6 hinb lAb va c luang irng.

H

:*:

H

CH3 ;-0--H

CH3 H

a)

b)

c)

Hinh 14. C6ng tlurc chieu Niumen : a) etan, b) cis-but-2-en, c) trans-bur-z-en

29

4. Cong thitc chie'u Fisd (Fischer)

Dt bieu dien cau trtic ba chieu b nguyen tic cacbon no rna khong dung den each ve ph6i canh phirc tap, nhir a hinh 1.5a chang han, ngtroi ta quy uac nhtt sau : D~t cong thuc ph6i canh cua phan tiI sao cho nguyen tiI C diroc chon nam trong mat phang trang giay, 2 nguyen tir (hoac nhom nguyen til) oben phai va ben trw nguyen tu C do thi nam b ben tren trang giay, con hai nguyen til (hoac nhorn nguyen tu) con lai narn a duai trang giAy nhu a hlnh 1.5b ; Chieu cong thirc phei .canh do 'len mat giay, ta diroc cong thuc chieu Fisc, nhir a hlnh l.5c rna a do dirong nam ngang bi~u dien hai lien ket huang ve mat ngiroi quan sat, dirong thang dung bieu dien 2 lien ket huong ra xa mat ngiroi quan sat, giao diem cua chung bieu dien nguyen til cacbon no. Ngirei ta con quy uoc, de mach chinh cua phan tir nam doc thea dirong thang dimg va nhom nguyen tic co rmrc oxi hoa

cao han. thl diroc viet ophfa tren (---COOH > -CH=O > -CH20H > CH3).

CH=O

I

H---2",

~ OH

CH20H

a)

H __ C __ OH

Hinh IS. a) C6ng thirc ph6i canh eua D-glixerandehit d~t kh6ng thea quy tide

b) Cong thtrc ph6i canh cua D-glixerandehit d~t thea quy tioe

c) C6ng thirc chieu Fiso nrong U:ng

COng thuc chieu Fisc thoat nhin thl gi6ng vdi cong thtrc cau tao thong thuong, nhung no khac b cho kl hieu cua nguyen t11 C trung tam khong diroc ghi ra. Diem khac co ban la cong thirc chieu Fisc chobiet su phan b6 trong khong gian cac nhom the n6i voi C trung tam, con cong thuc cau tao thi khong. Noi mot each khac, tir cong tlurc chieu Fisc cua cac hop chat co C bat d6i, ta co tM suy ra cong thuc phoi canh.hoac cong thirc Niumen cua chiing (chang han tir c suy ra b va a a hlnh 1.5), trong khi dO tir cong thirc cau tao binh thuong thi khong the suy ra diroc.

rung thirc phoi canh va cong thrrc chieu Niurnen giu diroc quan h¢ khong gian ba chieu thuc su cua phan tir (phiU-trai, tren-duoi, tnrec-sau). VI the, ctlng gi6ng nhu phan tiT thuc, co thl duac xoay theo nhiing goc bat ki rna khong bao gio chuyen thanh phan tir chat khac diroc, ChAng han, b hlnh 1.5, quay cong thirc (a) quanh true di qua lien ket

OHC-e* mot goc 90° ta duqc cong thirc (b). Hai cong thee dola dong nhAt va cung bieu

dien mot chat duy nhat la D-glixerandehit. -

o cong thuc chieu Fisc chi thay co quan h¢ khong gian phai-trai, tren-diroi, con quan he tnroc-sau khong thay duoc ttr cong thuc rna chi nhan ra duqc qua suy luan tu

30

quy uae 13. cac nhom & hai dau doan narn ngang thl & ben tren trang giay, hai nhom & hai dau dtrong thang dung thl nam & ben du6i trang giay, VI the, khong duac tuy tien xoay cong thuc chieu Fisa. Chang han, neu xoay cong thirc (e) a hlnh 1.5 quanh true vuong

goc v6i mat giily mot g6c 90° ta se dtroc cong thirc chieu Fiso khong phai cua Dglixerandehit nil'a rna la ella cua L-glixerandehit.

II - eONG PHAN HiNH HQC

1. Khiti ni~m vi dang phan hinh hC}c

Nhimg nguyen tir lien ket voi nhau bang lien ket doi (chang han C=C, C=N, N=N, ... ) hoac tao thanh cac canh cua nhtrng yang nho thi khong quay diroc nr do quanh true lien ket, chiing tao thanh mot bo phan "cling nhac" trong phan tiro VI vay, cac nhom the dinh voi nhirng nguyen til kieu do eo the duoc sap xep thea nhi1'ng quan h¢ khong gian khac nhau, khong til chuyen deli cho nhau diroc, dan den tao ra nhirng dong phon khong gian (dong phdn ItJp the) thuoc Ioai dong phan hinh hoc,

Trong tnrong hop anken, nell mach chinh b cling mot phia cua n6i doi C=C thi goi la dong phan cis, neu mach chinh b khac phia cua noi doi thi goi la dong phan trans. Doi vci hop chat vong, neu hai nhom the a cung phia so voi mat phang yang (hoac mot mat phang chuan nao do) thi diroc goi la dong phan cis, neu a khac phia la dong phan trans. Thidl,l :

cis-pent-2-en

trans-pent-2-en

cis-

trans-l ,2 -dimetylxiclobutan

Tuong tu nhu a olefin, cac hop chat e6 lien ket doi N=N hoac C~N cling c6 dong phan hinh hoc nhirng dtroc goi la syn va anti, thf du :

sYIl-azobenzen

anti -azobenzen

sYII-axetandoxim

alit i - axetandoxim

6 mot s6 hop chat hfru co plurc tap khac ciing nhu.o cac hop cha] co kim va phuc chat eiing thuong xuat hien dong phan hinh hoc, Do la nhung dong phon co cung cdu tao hod h9C nhung khdc nhau vi" dang hinh. h9C cua phdn lit, khong tl! chuyen dOi cho nhau do su quay tl! do ella cac nhom nguyen til trong phan tii. Hien nrong dong phan

31

hinh hoc rat ph6 bien va da dang, VI vay tuy timg loai hop chat rna ta xer dieu kien can va du dt! xuat hien dong phan hlnh hoc, Chang han d6i voi olefin, dieu kien can va du la rnoi cacbon mang nci d6i phai dinh voi hai nhom nguyen tir khac nhau (abC:; Cab hoac abC:; Cde, ... ) ~ Doi voi hop chat vong thi a it nhat hai nguyen tii C trong vong deu phai mang hai nhorn nguyen tu khac nhau ; Doi voi hop chat loai cumulen (n6i d6i lien) thl s6 noi d6i ph iii la so Ie va rnoi cae bon b dau mach phai mang hai nhom nguyen tir khac nhau.

2. So simh CZlp cua cac nhom the'

Dt! goi ten cac dong phdn cdu hinh (Hie dong' phan hinh hQC va dong phan quang hoc), nguai ta phai dua ra mot khai niern goi la "cap" cua cac nhom nguyen tir dua vao s6 thli nr cac nguyen tu tao thanh nhom do. Viec so sanh dip cua cac nhom nguyen tii diroc tien hanh thee he thong Can-Ingon-Preloc (Cahn-Ingold-Prelog). Gia sir phai so sanh cap cua cac nhom sau :

--CI , -D ,-F ,-CH3 ' -H , -CH2-CH3 ' -OH , -CH20H va -NHz

Xet cac nguyen tu lien ket tnrc tiep voi trung tim can xac dinh cau hlnh, do III cac nguyen tir in darn a cac nhorn tren, chiing diroc goi Iii nguyen tit thy nhdt cua nhorn. Nguyen tlf thy nhd; cua nhom nao co so' (hz( tu lan han thi nhom do co cap cao han ..

Theo so thu tu thl : J7Cl > 9F >gO>7N >6C>rH(D)!':::: IIH

Do do cap cua cac nhom dtroc slip xep tarn thoi nhir sau :

--CJ > -F > -OH > -NH2 > -CH) !':::: --CHz--CH3 i<:::' --CHzOH > -D I:l;:-H

D va H Ia hai dong vi. D co so khoi Ian han nen co cap eao han : -D > -H. Doi vUi cac nhom rna nguyen tir thu nhat eo s6 thu tu nhu nhau thi phai xet tiep den cdc nguyen tit lap {hit hai tuc la cac nguyen tir lien ket true tiep voi nguyen tu thu nhat, Khi do,

nhom -CH) duoc viet la C(H, H, H) ; nhom -CHzCH) duoc viet la C(C, H, H) va nhom -CHzOH duoc viet la qo, H, H). So sanh s6 thu nr cua cac nguyen tic dtmg dc1u trong 3 bQ ba tren ta thay : gO> 6C > IH vi vay, cap cua cac nhom tuong ling dtroc xep nhir sau ;

--CHzOH > --CHz-CH3 > --CH)

Tnrong hop trong nhom eo hai nguyen tu tham gia lien ket d6i hoac lien ket ba thl nguyen tir nay dtroc coi nhtr da: lien ket don vui hai hoac ba nguyen tu kia. Thi du :

OH I

Nhorn -C::; 0 diroc coi nhir

OH I

+C ..-0 ,co nghia 13. nguyen tic cacbon in dam dircc

I I

(0) (C)

32

coi nhu lien ket don voi ba nguyen tu 0, ghi 1a C(O,O,O), nguyen tu a in darn duqc coi nhu lien ker don v& hai nguyen tir C, ghi la O(C,C).

Tirong U!, cac nhom -COCH3, -C=CH, -C=Nduqc chuyen d6i va ghi nhu sau:

~

I

-C=O

CH3 I

_::) - C - 0 ~ C(O,O,C) ; O(C,C)

I I

(O)(C)

(C) (C)

I 2 I I

-C=CH=> -C -C-H ~CI(C,C,C); C2(C,C,H)

I I

(C) (C)

(N) I

-C == N ~ - C -N -(C) ~ C(N,N,N) ; N(C,C,C) I I

(N) (C)

Sau khi chuyen d6i nhu tren, thay VI phai so sanh cap ella cac nhom rnang lien ket b¢i ta chi can so sanh cap ella cac nhom rnang lien ket dan tirong dirong. Viec so sanh

cap ella cac nhom : -COOH ; -COCH3 ; -C=CH va -C=N diroc thay bang viec so sanh cap ella cac nhom nrong Urig C(O,O,O) ; C(O,O,C) ; C(C,C,C) va C(N,N,N) do d6 de dang nhan thay cap ella chung giam theo trat nr sau :

C(O,O,O) > C(O,O,C) > C(N,N,N) > C(C,C,C)

Nhu vay : -COOH > -COCH3> -C=N> -C=CH.

Neu xet het cac nguyen tir lap thu hai rna van chua quyet dinh duoc thl chuyen sang xet tiep lap thu ba, r6i tha tu, ...

3. H~ danh phap Z - E

Danh phap cis - trans trong nhieu tnrong hop to ra bat l1!C, chang han d6i vm cac cap hop chat a va b ; c va d sau :

CH3..... ....F CH3 . a

C C' ..... C=c/

H/ = '0 H/ 'F

(b) .

(c)

(d)

Danh phap syn - anti d6i VOl hop chat chua nita lien ket doi cling co nhtrng chb khong th6ng nhat, thi du d6i voi hop chat azo thi tirong tu nhu danh phap cis - trans nhung d6i voi hop chat oxirn thi lai theo quy uoe khac (xern thi du a rnuc 1).

3 - HHHC1

33

Hien nay, nguoi ta dung ph6 bien h¢ danh phdp Z - E kh6ng nhtrng khacphuc duoc nhUng kh6 khan ke tren rna con tao diroc mot su nhat quan trong viec goi ten cac dong phan l~..nh hoc.

Dt goi ten d6ng phan h111h hoc theo M Z-E, ngiroi ta so sanh cap cua hai oh6m the cung dinh vao cacbon mang n6i doi, nita mang n6i d6i hoac cacbon cua vong no (each so sanh xern b muc 2). Xet hai cap oh6m the quan tam (b6n nh6m) : Neu hai nhom c6 cap cao hon nam cung mot phia cua n6i doi hoac cung phia so v6i mat phang ella vong thi nguoi ta goi Ia ni'u hinh Z va hop chat thuoc loai d6ng phdn Z. Neu hai nhorn co cap cao hon nam khac phfa cua o6i dci hoac khac phia cua mat phang chuan thl do la cdu hinh E va hop chat thuoc loai ddng phan E. Thi du, d6i vci cac hop chat a, b, c, d a tren ta lam nhu sau :

Tnroc het, ta so srum cap cua hai nhom the a moi cap nhom the cung dinh vao mot nguyen tiI cachon mang n6i doi, Tir ket qua phan tfch a muc b ta thay :

-Cl > -F , -CH3 > -H ,-CH20H > -CH2CH3

Tiep theo, ta xet Sl,1 phan b6 khong gian ciia hai nhorn hon cap so vci lien ket e=c. o hop chat (a) hai nhom hon cap nam a hai phla cua n6i d6i nen (a) thuoc cau hlnh E. 0 (b) hai nhom hon cap nam cung mot phia cua n6i d6i nen (b) thuoc cau hlnh Z :

Opcooh@ apm~hoo

~ ;/

CH3 F

\ I

. - - - - -- C = C--- - - --

HI 'Cl

/' "

CA'p thap hem CA'p cao hen

a) (E)-l-Clo-l-floprop-l-en

Cap cao han Cap cao hem

"'" /

CH3 Cl

\ I

. - - - - -- C = C- - - - - --

HI \F

/' "-

CA'p thap han cap thap hem

b) (Zj-l-Clo-l- floprop-l-en

o hop chat (c) hai nhom hon cap nam cung mot phia ciia n6i doi nen no thuoc cau hinh Z ; 0 hop chat (d) hai nhorn hon cap nam a hai phia cua o6i doi nen co cau hlnh E :

Cap cao hem ap cao hem CA'p cao han cap thap hon

"'" / '\.. /

Cl CH20H Cl CH2CH3

\ I \ I .

-------C=C------- ·------C=C-------

I \ I ,

F CH20I3 F CH20H

/'" /'"

CAp thap hem cap thap han Cap thap hon Cap cao han

c) (Z)-3-0o·2-etyl-3-floprop-2·en-l-ol

d)

(E)- 3-00- 2-etyl- 3-floprop- 2-en-I-ol

34

VI nita mang n6i doi chi dinh vai mt')t nhom thi! nen nhom the do hien nhien d1Jqc coi la co cap cao han, va viec quy dinh cau hinh cling diroc lam luang nr nhu d6i voi cachon mang n6idOi. Thi du .-

(Zj-Azobenzen

C6HS

.... ..

N=N

.. ....

Ct;Hs

(E)- Azobenzen

CH3 ' OH

.... /' Co;;:N

/' ..

H

(Z)- Axetandoxim

CH3

.... ..

C=N /' ....

H OH

(E)- Axetandoxim

D6i voi cac hop chat vong, viec xet cau hlnh Z-E cling duoc lam tuong tl,l nhu tren, Thi du :

CH3 H
H3~ r=v H3p H3P
CH3
H CH3 H3C CH3 HOOC HOOC
(e) (f) (g) (h)
CAu hlnh E CAu hlnhZ CAu hinh E Cau hinh Z can chti y rang, khong phai bao gib cling co s\l nrong 6ng giita cac c:~p cis-trans, syn-anti va Z - E. Chang han b thf du tren, hop chat (f) thuoc cau hinh Z chfnh la dong phan cis ; hop chat (e) thuoc cau hlnh E Ia d6ng phan trans, con hop chat (g) thuoc cau hinh E thi lai la dong phan cis (vl trong tnrong hop nay ngtroi ta thuong so sanh vi tri cua hai nhom th€ gi6ng nhau, hai nhom metyl a (g) va (hj).

4. S1l khac nhau vt! tinh chit cua cac dang phan hinh h9C

Hai dong phan hlnh hQC mac do co diu tao hoa hoc giong nhau nhung do khoang each gitta cac nguyen til (nhom nguyen til) khac nhau nen chung c6 nhieu nnh cMt khac

nhau nhu : d¢ ben nhiet dong (the hien a gia tri cua AGo hlnh thanh), nhiet d¢ nong chay

(tric)' nhiet d¢ soi (t~), momen IUOng cue (u), tfnh chat quang phd, .. , va ca met s6 diem trong tinh chat hoa hQC nira.

Thuong thl dong phan trans ben ve mat nhiet d¢ng han dong phan cis (AGo nho han). Dong phan trans co tinh d6i xirng cao han dong phan cis, d~ sap xep chat khit han nen thirong co nhiet de) nong chay cao han so v6i dong phan cis. v« nhiet de) soi, momen luang cue, ... thi phai xem xet tirng tnrong hop c1} the. Thi du :

H" c( CI H.... c( H

C(C = H HOOC /C = COOH

H , /COOH

HOOC;C=c....H

t~c (oC) -80,5 -50,0 130,5 287,0
t~ (oC) 60,2 48,3 Phan buy tnroc soi Thang boa
J.1 (D) 1,89 0,0 2,38 2,46
35 Axit maleic dl: dang tao thanh anhidrit axit con axit fumaric thl kho :

H ...... /COOH C

!!

/C,

H COOH

lOO"C

)-

H <, /COOH C

!!

/C,

HOOC H

D~ phan biet (nhan bi€t) dong phan Z va E, ngay nay ngtroi ta thuong dung cac phuong phap phd: htru hieu nhat la phd cong huang tir hat nhan.

III - OONG PHAN QUANG HOC

1. Anh simg philn c,!c phiing va tinh quang ho~t

Anh sang thirong, du Ut dan sac. cling gam cac song dien 'tir rna vecto dao dong cua cluing huang thea tilt cit cac huang trong khong gian mien la vuong goc voi phirong truyen cua tia sang (hlnh J.6a). Khi cho anh sang thuong di qua lang kinh Nicon se nhan duoc anh sang rna cac vecto dao d¢ng cua cluing narn trong cung mot mat phang goi Ia mdt phdng phdn cue. Do Ia dnh sang phdn cue phdng (doi khi gqi Ia anh sang phan cue thang hoac dan gian chi Ia ann sang phdn cue (xern hinh J.6a).

C6 nhtmg chat khi d~t tren duong truyen cua anh sang phan cue phang thi lam quay mat phang phan cue mot g6e a nao d6 (hlnh I.6b). Tinh chat "d6 diroc goi la tinh hoat dong Quang hay la tinh Quang hoat. Cac chat c6 tinh quang hoat dtroc goi Ia chat Quang hoat,

CD

a)

b)

Hinh 16. a) A : tia sang thirong, B : lang kinh Nicon, eva D : hai tia sang. phan eire phang ma m~t phAng phan eire cua chung vu6ng g6c voi nhau.

b) G6c quay ~t phing phan cue. Duong net dUt bie'u thi ~t phing phan ql'C tnroc khi di qua chit quang hoat, duong net liJn sau khi di qua ch€lt quang hoat,

36

Ngiroi ta do goc quay matphang anh sang phan cue a nho mot dung cu goi HI. phan cue ke, Gia tri ella goc a phu thuoc vao buoc song cua tia sang phan eire, vao nhiet dQ, vao be day lap chat rna anh sang phan cue di qua va vao n6ng d¢ cua chat Quang hoat. Vi vay, de: d~e tnmg cho tinh quang hoat cua mot chat, nguoi ta dung d¢ quay cue rieng tfnh thea cong thirc (a) d6i voi chat nguyen chat, cong thirc (b) d6i voi chat trong dung dich :

[0 a

[a L = l.d (a)

[0.]10 = a.V

t.· l.d

(b)

Trong do : [a] la dQ quay eire rieng ~ e Ia nhiet dQ khi do ; Ala buoc song cua anh sang phan Cl,IC, nguoi ta thuong dung tia vang cua den hoi natri co bircc song la 589 nm ki hieu la D ; a la goc quay mat phang phan cue do dtroc nho phan cue ke, tinh ra dQ ; d la ti kh6i cua chat nguyen chat; l la be day cua lap chat rna anh sang phan cue di qua, tfnh ra dm ~ a la khoi hrong chat quang hoat (gam) trong V (ml) dung dich.

Thi du : DQ quay eire rieng ella mot s6 chat nhu sau

D-glixerandehit co [a]~ .= + 14°, [a]~ = +8,7° ; L-glixerandehit co [a J~ = - 14°, [a]~ = _8,7° ; d-campho co [a ]~o = 41,4° .

2. Tinh khang trimg v~t - anh

a) Lien quan giiia tinn khong trung vdt - dnh va tinh quang hoat

C6 nhtrng chat 6 dang tinh the: thi co tfnh quang hoat, khi lam nong chay hoac pha thanh dung dich thi khong con tfnh quang hoat nira, Trong wang hop nay, tinh quang hoat lien quan t61 cau tnic tinh the chir khong lien quan toi cau true phan tiI. Ngtroc lai, co nhieu chat .6 dang tinh the, dang long hay pha thanh dung dich van gifr duqc tinh Quang hoat. Trong tnrong hop nay, tinh Quang hoat ro rang 13. do cau true pharr tir gay nen, Van de dat ra la "Phan tu co cau true nlur the nao thi co tinh Quang hoat?", de:'tra

Ioi, tnroc het ta hay xet phan tir cua mot chat khong Quang hoat lit CH2FCI va mQl chat Quang hoat 13. CHFClBr. Hai phan tu don gian nay co cau tao hoa hoc nrong t1! nhau, co dang hlnh hoc cling nrong til nhau. V~y ta hay phan tich net khac biet trong cau true khong gian cua cluing (hlnh 1.7).

37

H

I

C/ .. ,III \' H' F

H

I

.,IIIC\:----......

C/' Br

F

H

I

-r:

Br 'C/

F

H

I

-r:

H' 'C/

F

(rum)

(v~t)

Hinh 17. Phan hlCH2FCl, CHFCiBr (ben trai) va rum gU'dng cua cluing (ben phai) r----I : ~t guong (m~t ph~ng d6i xung)

o hinh 1.7, neu xoay phan tu CH2FCI (ben trail 1800 theo plnrong thang dirng sao cho H cua no trung voi H' cua anh ella no thi cac nguyen tir con lai .se trung khit len nhau tire 13. eo the lam cho no va anh girong ella no trimg khit vao nhau, D6i voi phan tir CHFCIBr thi du eo xoay va tinn tien theo each nao cling kh6ng thllam eho no trung khit viii dnh guang cua no diroc. Ngiroi ta noi phan tii CHFCIBr co tinh khong trimg v~t - anh (chirality).

Nghien ciru nhieu Ioai hop chat co cau tnic ra't khac nhau, nguoi ta da di den ket luan la nhiing phan ttl eo tinh kh6ng trung v(it - dnh tht eo tinh quang hoat. MQt s6 tinh

th~ nhu thach anh thien nhien (Si02), natri elorat, hidrazin sunfat, ... co tinh quang hoat la do tinh the cua cluing co cau tnic khong trung vat - anh. Tinh khong trung v~t - anh ciing g~p a nhieu vat the vi mo nhu hai ban tay cua mot ngum binh thuong chinh la v~t va anh girong cua nhau, cluing khong the 16ng khit vao nhau duoc.

b) Die'u ki~n dl co tinh khong trung v4t - dnh

Cau hoi tiep theo duoc d~t ra lit "Lam the nao de bier mot vat the noi chung cung nhu mot phan tu noi rieng eo hoac khong co tinh khong trung vat - anh?". m co c~u tra 1m diiy dll nhat, can biet nhiing ben thirc ve Ii thuyet d6i ximg ngoai pham vi cua cu6n sach nay. Vi vay, cluing ta dirng lai a cau tra 1m tarn du. la : nhiing v(it thl nao khong co tam d61 xung va khong co m{it pMng dtfi xung thi co tinh khong trung v~t - dnh. Thi du,

a hlnh 1.7," cac phan tir CH2FO va CHFClBr dell khongco tarn d6i xung, nhung phan tir CH2FCI co mat phAng d6i xrrng nen khong co tinh khOng trlmg vat - anh, con pharr tir CHFClBr khong co mat phang d6i ximg nen co tinh khong trung vat - oinh (hinh L8a). Cfing nrong nr, phan ti'r cis·l,2-dimetylxiclopropan khong co tam deli ximg nhung co mat

38"

phang d6i xirng nen khong co tinh khong trung v~t - anh, con phan tu trans-A ,2- dimetylxiclopropan vira khong eo tam d6i xirng vira kh6ng co mat phang d6i ximg nen e6 tinh khong trung vat - anh (hinh 1.8b).

H

H

a)

b)

. ,

Hinh 18. a) CHiFCl co m.;it phang d6i xirng : CHFCIBr thi khong

b) cis-l,2-dimetylxic1opropan co mat phang d6i xung con dong phan trans thl khOng

Can chu y rang, khi xet mat phang va tarn d6i ximg ella phan tu phai dung cong tlurc ph6i canh, co the dung cong thirc chien Niumen nhung khong nen dung cong thirc chieu Fisc. Boi vi cong thirc chieu Fisc (do nhfrng quy tree khi 'viet n6) da khong con phan anh dung tinh doi xirng eiia phan tir that. Thi du, axit mesotaetrie (hinh 1.9) b dang ben nhat cua n6 (a) khong c6 mat phang doi xirng rna c6 tarn d6i xirng (i tai trung diem

2 3

cua lien ket c- C). De viet cong thirc chieu Fiso, ta d1i chuyen no ve dang kern ben nhat

(b). Khi do no trc nen co mat phang doi xirng rna khong con tarn doi xirng ntta. Hau qua la cong thirc chieu Fisc (c) e6 mat phang doi xirng (dirong net dirt) rna khong co tam doi xirng, khac han voi dang t6n tai thuc cua phan tu .

{1} qOOH

. H'§~OH (2) e

t (i)

(3) e

III III

HO'" ! "'H

(4) eOOH a)

yOOH

H,§/OH

e

~--------~--------I

eOOH

H OH

~-------- --------1

H OH

eOOH b}

eOOH c)

Hinh 19. Axit mesotactric. a) dang ~n nM't b) dang kern ~n nhat c) cong thirc chieu Fiso

Doi vai axit (-)-taetric (hinh 1.10) cling vay, nhtrng dang t6n tai thirc eiia n6 (a) va (b) chang han, khong.he eo tam doi xirng va mat phang doi ximg, nhung cong thee chieu Fisc cua n6 (e) lai co tam doi ximg (i) :

39

<;:OOH <;:OOH eOOH
HO'~_'" H Ha,~_'" H
t e H H
I
(i)
III elll e H aH
HO .,1 j "'H H"....~~aH
eOOH eOOH eaOH
a) b) c) Hinh lIO. Axit (-) -tactric,

a) dang ~n nhA't b) dang kern ben nhA't c) cOng thirc chieu Fiso

c ) Nguyen tu cae bon bat dlJl

o hop chat CHFCIBr (hinh 1.7,1.8), nguyen ti'r cacbon dinh voi bon nguyen ni khac nhau (H *' F *' Cl *' Br) lam cho phan ti':t khong co mot yeu to d6i ximg nao, N hiing nguyen tii cacbon dinl: viti 4 nguyen til ho{ic nhom nguyen tii khac nhau duac gQi Iii

* •

cae bon bat d6i vii duac ki hi¢u Iii C . d hinh 19 va 1.10, nguyen tii C2 va C3 cua axit

taetrie cilng la nhiing nguyen tit cacbon bat doi.

Hiin nhien Ill. neu phan tir co mot nguyen tii cacbon bat d6i thl no se co tinh khong

..

trung v~t - anh. Nhiing phan tii co nhieu C thl cilng se co tinh khong trung vat - anh,

trir tnrong hop phan tir lai co tarn d6i ximg hoac mat phang d6i xirng. Phan ti':t axit

..

mesotatric (hinh 1.9) cung co hai nguyen tir C nhung lai co tam d6i xirng (a) hoac mat

phang d6i xung (b), vi the- no khong the c6 tinh khong trung v~t - anh. Thuc te cho thay,

axit (-)-tactric lam quay m*t phang anh sang phan Cl,IC qaJ~ = _12°), con axit rnesotactric thi khong ([ a]~ = 0°).

3. Khili ni~m v~ d6ng phan quang h9C

Khi nghien cuu axit tactric (HOOCCH(OH)CH(OH)COOH. thu duqc trong qua trmh lam nrou nho), nam 1860, L. Pasta di'i tach duqc hai dang axit tactric khac nhau :

mot dang Hun quay m~t phang anh sang phan cue sang phai ([ a]~ =-1:"12°), dang kia

lam quay mat phang phan eire sang trai <[a]~ = _12°) . Den nam 1890, ngum ta cung nhan fa hai dang khac nhau cua axit lactic CH3CH(OH)COOH. thu diroc tit sUa chua.

40

Sau nay ngum ta da chung to rang hai dang do co cung cau tao hoa h9C, co cung dang hinh h9C phdn tit (khodng each giNa cac nhom nguyen lit), co cac linh chat v¢t Ii va hod hoc gidng nhau, chi khac nhau ve' khd nang lam quay m{il phdng anh sang phan Ci!C va tinh. chdt sinh hoa. Ngiroi ta goi chung li. nhiing dong phan Quang hoc. Cau tnic va mot vai tfnh chat cua hai dong phan quang hoc ella axit lactic diroc ghi a hinh L 11.

t~c (0C) t~ (oe) pKa

[a]~

Axil L (+) . lactic Axil 0 (-) . lactic
eOCH COOH
I I
. ,.IJ" /~I" .
CH H H CH
3 3
HO OH
26 26
122/14 mmllg 122/14 mmHg
3,8 3,8
+ 3,8° _ 3,80 Hinh 111. Hai d6i quang ella axit lactic

Axit L-Iactic lam quay mat phang anh sang phan cue sang phai mot goc 3,8°, ki hieu la +3,8°, nen ngiroi ta d~t them dau (+) vao ten cua no va goi do la chdt quay phdi. Axit D-laetic lam quay mat phang anh sang phan cue sang trai mot g6c 3,8°, kf hieu la _3,8°, nen ngiroi ta d~t them dau (-) VaG ten ella no va goi d6 la chat quay trdi (cac chtr D va L chi cau hmh urong d6i, se diroc sang to a muc saul. Hai dong phan Quang hoc c6 tri s6 dQ quay cue rieng nhu nhau nhimg dau thl d6i nhau dtroc goi la hai chat doi Quang hay don gian la hai d6i quang (enantiomer).

Vi sao axit lactic va nhieu chat khac lai co kha nang tao thanhnhtmg dong phan quang hoc ? Cau hoi do da duoc giai dap mot phan a muc (b). Do la vi phan tu axit lactic

*

co chua mot nguyen tir C khien cho no co tinh khong trung vat - anh. Vi the, axit lactic

co the t6n tai a hai dang doi ximg nhau qua mat phang gucng va khong the long khit vao nhau duoc (hinh I. 11). SI,l' khac nhau ve cau tnic gifra axi t L( + )-lactic va axit

*

D(-)-lactic la a SI,l phan b6 khong gian cua bon nh6rn nguyen tiI xung quanh C . Chi can

thay dOi V! tri cua hai trong bon nh6m d6 cho nhau, chang han thay d6i vi trf nhom OH va H thi dang nay se bien thanh dang kia (hlnh 1.11).

41

Thong thuong thi s6 luong dong phan quang hoc ciia mot chat chua n nguyen til cacbon bat d6i la 2n. Nhung neu cac nguyen tu cacbon bat d6i lai thuoc hai nira phan tit co cau tao hoa h9C nhu nhau thl so luong d6ng phan quang hoc se nho hon 2". Thi du :

Hop chat :

HOCH2 - CH - CH - CHO HOOC - CH .'- CH - COOH

I I I : I

OH OH OH: OH

SOC* 2

D~ ditm: Hai "Ua khac nhau

56 dong phan Quang h9C : 4

2

2 2

Hai mill gi6ng nhau 3

Hai rura khac nhau Hai mrs gi6ng nhau

4 3

4. D6ng philo d6i quang va hop chAt meso

. -

De hieu vi sao s6 dong phan quang h9C a hop chat co n nguyen til cacbon bat d6i lai bang hoac nho hon 2n, tnroc het hay xet hop chat 2, 3, 4-trihidroxibutanal. Chat nay co

'"

2 C thl se co 4 dong phan quang h9C (gom 2 d6i d6i quang) nhu a hinh l.12.

CHO

H ........ § ~OH C

I

.,\~\\ C ~'f- ' HO .. •· , ''''H

CH20H

CHO

CH20H D(-) - ErithrozCl

rHO

HO ........ § ~H C

I

"'~~ C #U"',.

H , OH

CH20H

rHO

HO ........ § ~H C

I

"\\~C~,,

HO' , 'H

CHzOH

rHO

K ........ ,e ~OH C

I

_,~~Cqbtl'

H'" , "OH

CH20H

CHO

CHO

CHO

CHzOH L(-) - Thrsozo

a hlnh 1.12, phan til D-Erithroza va L-Erithroza d6i xung nhau qua mat phang gUC1Ilg, Chung dell khong co mat ph~ng va tam d6i xtmg do d6 cluing khong the long khit vao nhau duoc. Cling tUC1Ilg nr nhu vay d6i voi c~p D- va L- Threozo, Nhu vay ca. tMy c6 4 dong phan quang hQC.

Tiep theo, hay xem xet phan tir axit tactric, HOOCCH(OH)CH(OH)COOH. Hinh 1.10 cho thay phan tir axil (- )-tactric khong co m~t phang va tam d6i xtmg do d6 dang

42

CHpH L(+) - ErilhrozCl

CHpH 0(+) - Threozo

Hinh 112 Hai dOi d6i quang cua 2,3,4-trihidroxibutanai

d6i xirng qua guong cua no khong the long khit voi no duoc. Do la mot chlit khac : axit (+)-tactric, chat d6i quang cua axit (-)-tactric (hinh 1.13).

;.,+""

H+OH

eOOH

yOOH HO,~/H

e2

~ 13

HO··~". H eOOH

Axlt (-) - tactric ({ufo5 = -12°)

eOOH H,£/OH

e2

13 ~

H.·~'~~.OH eOOH

"+"00

HO+H

eOOH

Hlnh II3. Hai doi d6i quang cua axit tactric

Axit mesotactric co Him d6i xiing (hlnh 1.9) nen anh guong cua no lai chinh 13. no (hlnh 114). That vay, a hlnh 114 neu quay phan tu axit mesotactric xung quanh true

nam tren m~t giay va vuong goc voi lien ket Cz - C, tai trung diem cua n6 mot g6c 1800, roi dung phep tinh tien thi se lam eho no trimg khit vci rum guong cua mlnh.

"+0"

H+OH

eooH

Axil mesotaetric ({uG5 = 0°)

Hlnh I14. Axit mesotactric va rum guong cua no chi la m()t

"0+""

HO+H

eOOH

6 hlnh 1.14, phan tir axit taetric do co tam d6i ximg nen khong co tinh khong trung vat - anh, khong lam quay mat phang anh sang phan Q1'e. De phan biet no voi hai dong phan quay phai va quay trai, nguoi ta goi d6 Ia axit mesotactrie. Nhiing d6ng phan

quang h9C co chua nhie'u C* nhung do co mdt phdng hoiJc tam dOl xung rna khong co tinh quang hoat diroc goi la hqp chat meso.

Nhu vay, axit tactric tuy co hai nguyen tir C· nhung chi co 3 dong phan quang hQC : . 2 d6i quang (1 quay phai va 1 quay trai) va 1 hop chat meso (khong quang hoat).

43

.~+;. @'

...

5. Bie'n th~ raxemic

Axit tactric tach duoc tu san phdm len men nuoc ep qua nho, cling la mot chat khong quang hoar. Nho nhimg nghien ctru cua L. Pasta rna ngtroi ta da biet duoc rang do 1a hon hop dang phan tit cua axit (+ )-tactric va axit (- )-taetric chir khong phai la chat nguyen chat nhu tnroc do van tuong, Ngirci ta goi do la axit (tactric) raxemie va viet la axit (±)-tactrie.

Ngiroi ta goi tap hap ddilg phdn tit (s6 mol bang nhau) cua hai ddi quang Iii. bien th~ raxemic. Khac voi dong phan meso chi gom mot loai phan ui khong quang hoar, bien the raxemic gem hai loai phan nr d6i xirng nhau qua girong, loai nay lam quay mat phang anh sang phan eire sang phai, loai kia lam quay mat phang anh sang phan cue sang trai voi tri s6 nhu nhau, do do triet tieu W.n nhau lam eho bien the raxemic tra thaHh khong quang hoat. Nho cac phuong phap khac nhau nguci ta co the tach rieng duoc tirng d6i quang fa khoi bien the raxemic. Hay xern diu true va mot s6 tinh chat cua cac dang axit taetric khac nhau a hlnh 1.15.

Axit : (-) Tactric (+) Tactric Mesotactric (±) Tactric (Raxemic]
eOOH COOH eOOH [HO$= + H$~H]
HO$H H$OH H$OH
Diu true:
HO H H OH 'HO H HO H H OH
eOOH eOOH eOOH eOOH eOOH
[a]"if -12" +12u Oll 0°
t~c tc) 171 171 140 205
D¢ tan (g/ 1 00 g nuoc) 139 139 125 20,6
pKaJ 2,93 2,93 3.11 2,96
pKa2 4.23 4,23 4.80 3.11 Hinh LIS eAu tnie va tinh chAt cua cac dang axit tactric khac nhau

6 hlnh 1.15, axit mesotaetric lit dong phan quang hoc loai dia ella cap d6i quang axil (+) va (-)-tactric, con axit (±)-tactric kh6ng phai III d6ng phftn quang hoc rna III bien the raxemic,

6. Ciu hinh tuOOg d6i va cau hinh tuy~t d6i

Thuat ngii cdu hlnn duoc dung de chi str phan b6 khong gian cua cac nguyen tir hoac nhom nguyen tir xung quanh phan cirng nhac cua phan tii hoac xung quanh nguyen

44

~'.": ) ..

~.

',

tu cacbon bat d6L D~ chi Call hinh cua cac dong phan hinh hoc, nguoi ta dung cac ki hieu cis-trans, syn-anti va Z-E (da xet 0 muc II). 0 day, ta xet cau hmh cua cac dong phan quang hQC co chua cacbon bat doi trong phan tiI.

a) Cclu hinlt tuang do'i

Phan tiI glixerandehit co mot nguyen tiI C* nen co hai dong phan quang hoc, dang quay phai ki hieu Iii. D( + r-glixerandehit, dang quay trai kf hieu 13. L( - )-glixerandehit. Trang ten goi do, dau + hoac - chi huang quay mat phang anh sang phan eire con chit D

va L chi cau hlnh cua nguyen tiI C*. Cac hop chat kieu tuong tt! nhu glixerandehit, uic Hi

, ,

co cong thirc R-CH(Y)-R trong do R-C-R la mach chinh, Y Iii mot nhom the khac v6i

H va thuong co chua di to, neu co cau hinh gi6ng nhu D'-glixerandehit thl cOng duoc kl hieu boi chit D, neu co Call hloh giong voi Lvglixerandehit thl duoc ki hieu boi chir L. Cau hlnh diroc quy dinh thee each nhu vay goi 13 Call hinh tuong doi (vi can phai so sanh v6i cau hlnh glixerandehit). Thi du, cau hinh nrong d6i cua mot so hop chat duoc chi ra diroi day:

CHO H-f: CHO COOH
H+OH H+B, H+NH2
CH20H CH3 CHO CH3
D( + )-glixerandehit D-2.:..O-propanol D-2-brompropanal D( - )-alanin
CHO CH~OH CHO eaOH
HO+H D+H B'+H H2N+H
CH20H CH) CH) CH3
L( - )-glixerandehit L-2-D-propanol L-2-brompropanal L( + )-alanin
b) Cdu hinb tuy¢t do'i H~ danh phap D-L khong co tinh tOng quat bbi vi no khong ap dung diroc cho cac hop chat, hoac khong co gi tirong nr de so sanh voi glixerandehit, hoac co cau tao nhieu vong voi nhieu cacbon bat d6i ... Chinh vi vay, VaG khoang nhtrng nam 1951 - 1956, Can, Ingol va Preloc dii dira ra each xac dinh cap cua cac nhorn nguyen tit (xem muc §4.lL2). tren co so do dii d~ nghi h¢ danh phap cau hlnh R-S d6i v<'1i cac dong phan

•

quang hoc co chua C .

'"

De xac dinh xem 1 nguyen tiI C co cau hinh R hay S can lam nhu sau :

45

'"

So sanh cap cua 4 nhom nguyen ttt dinh vci C do, nhom nao cap cao nhat duoc kf

hieu lit a, ke den lit b, c, va d. Dat phan ttt sao cho nhom co cap thap nhat (d) cr xa mat ta nhat, nrc lit nhln phan tii' thee huang C· __, d (hinh 1.16). Neu thay ba nhorn con lal s~p xep thee thu tu giam cap dan (nrc lit a> b > c) thuan thee chieu kim dong ho thl nguyen tir C· do thuoc cau hlnh R. Neu thay ba nh6m con lai s~p xep thee thu 11,r giam cap dan

•

ngiroc voi chieu kim dong h6 thi nguyen tir C d6 thuoc cau hlnh S. au hlnh xac dinh

duoc thee quy lac tren goi Iii can hinh tuyet doi (vi khong phai so sanh vai mot chat nao khac),

d

Cliu hinh R

d

cau hlnh S

Hinh 116. each xac dinh cau hinh tuyet d6i ( a > b > e > d)

Mot s6 thi du xac dinh cau hinh tuyet doi ducc neu ra a hinh 1.17.

r -
(b)CHO CHO(b) (e)CHO :'fi ?: CHO(e)
r: \ / \ . , /
~ , .
« ·······--111 C- H H - C Ilr----"-- 11111I111C-F F-C~II",
(a)HO 11111',/ ,III" OHIO) HOCH2 'I (0) (0) CH20H
(c)CH2OH CH2OH(c) (b)OH OH(b)
(R) • Glixeran(!ehit (S) - Glixerandehit (R) - Ct - Floglixerandehit (S) • Ct - Floglixerandehit
(D (+). Glixerandehll) (L H - Glixerandehit) (L - Ct - Floglixerandehit) (0 - Ct - Floglixerandehit) Hinh 117. Xac dinh e:lu hinh tuyet d6i ella glixerandehit va a.-floglixerandehit

Hinh 1.17 cho thay, gina cau hinh luang d6i D-L va cau hlnh tuyet d6i R-5 cling nhir huang cua g6c quay m~i phang phan cue (+). (-) khong co mdi lien quan luang ling. nghia Iii khong the tll dau cua goc quay suy ra cau hlnh, hoac tu cau hlnh luang doi suy ra cau hlnh tuyet doi (va ngtroc 1<;\0 dune.

46

...

IV - CAU D~NG

1. Khai ni~m cau d~ng. cau d~ng cua etan

Cac nh6m nguyen tir lien ket v{ri nhau bang lien ket don (lien ket 0") c6 th~ quay quanh true lien ket d6 tao nen v6 so dang cau tnic khong gian khac nhau goi la nhimg

call dang. Thi du, 2 nh6m CH3 a phan tir etan c6 the quay quanh true lien ket C-C rna khong anh huang den cau tao cua phan tir. S,! quay do doi hoi mot nang hrong khong 160 (khong virot qua 12,5 kl/mol), vi the co the cho rang no xay ra mot each nr do ngay a nhiet d¢ rhirong, khong the phan lap rieng diroc tung cau dang, Trong vo van cau dang tao thanh, co hai cau dang dac biet Ia edit dang che khudt va cdu dang xen kf.

Cdu dang che khudt la cau dang rna neu nhln phan tir thea each chieu Niumen (rnuc 1.3) thl se thay cac nguyen ta H a nhorn metyl nay hoan loan che khuat cac nguyen tll H 0 nh6m metyl kia tirng doi mot (0 hlnh 1.12 d5 ve chech di mot chiit de co the thay

duoc). a cau dang nay cac goc nhi dien gifia hai mat ph~ng H-C,-Cz va C2-C,-H deu bang 00. Cac obitan lien ket C-H a gan nhau nen day nhau. VI the, cau dang che khuat irng vai eire dai tren gian do nang lirong (hlnh 1.18) va lil cau dang khong ben.

Cdu dang xen kf lil diu dang rna neu nhln phan tir theo each chieu Niumen thi se thay cac nguyen tir H a hai nh6m rnetyl narn xen ke nhau. d cau dang nay. goc nhi dien bang 60°. Cac lien ket C - H thuoc hai nguyen tll eacbon nam a xa nhau nhat, vi the cau dang xen ke irng voi eire tieu tren gian do nang Iirong va la cau dang ben.

HH H H &
~ ~ H~
H
H
a)
H H H H
c!J; ~H $ H~
H 120 180 240 300 360
b) c) Hinh 118. a,b) C6c nhi di~n H-CrC2-H

c) Cian d6 nang luong ella phan tlt etan khi nhom metyl quay quanh true lien k€t C-C

47

2. cau d~ng eua xiclohexan

Cau dang ben nhat va quan trong nhar cua xiclohexan la dang ghe, ta hay xern xet rieng diu dang nay. 0 dang ghe, quan he khong gian gitra 6 nguyen tir C la nhu sau : 4 nguyen til C2, C3, C5, C6 tao thanh mot mat phang, nguyen tir Cl nam ben tren con nguyen til C4 nam ben diroi mat phang d6 (hlnh I.l9a) ; 3 nguyen til Cl , C3, C5 nam cung tren mot mat phang va tao thanh mot tam giac deu ; 3 nguyen tu C2, C4, C6 tao thanh mot tam giac d~u a mot mat phang khac (hlnh I.l9b) ; hai mat ph~ng do song

song voi nhau va each nhau 50 pm (pm = 1O-12m = 10-2 A) nhu chi ra a hinh 1.19c.

2

5 1

.t;:::i

50pm

a) b)

c)

Hinh 119. Quan h¢ khong gian giii'a 6 nguyen tlt Cd xiclohexan

D€ dam bao g6e lai hoa ttl dien (109,5°), hai lien ket C-H 0 moi nguyen tu C sap xep nhu nhau : Mot lien ket C-H song song voi true thang dung, d6 la true di qua tam i cua tam giac Cl ; C3, C5 va vuong goc voi n6 (true d6i xirng b~c ba cua phan tir). Lien ket C-H do goi Ht lien ker true, kl hieu la a (axial, hinh 1.20a). Can lien ket C-H tlnr hai thl huang ra phia ngoai yang, goi la lien klt bien, ki hieu la e (equatorial, hinh 1.20b). Tat ca co 6 lien ket a : 3 huang len tren, 3 huang xu6ng duoi (hinh 1.20a) va 6 lien ket e (3 venh len tren, 3 venh xu6ng dum (hlnh 1.20b). Dang ghe ella xiclohexan dl1Q'C bieu dien day dil nhu a hinh 1.20e.

a)

b)

c).

Hinh l20. Cac Hen ket true (a) va lien k€t bien (b) d dang ghe' etra xiclohexan (e)

Ngay a nhiet d¢ thirong, cac cau dang cua xiclohexan Iuon chuyen d6i eho nhau.

Chang han, hai dang ghe a hlnh I.21 chuyen doi.cho nhau, khi do6 lien ket true chuyen thanh 6 lien ket bien va nguoc lai :

48

Hinh 121. SI! chuyen d6i giira hai dang gh€ cua xiclohexan

a nhiet d¢ thuong, t6c d¢ chuyen d6i nit Ion, dm song (thoi gian ton tai) cua moi diu dang chua de~ 1 O---{i s, vi the khong th~ phan lap diroc chung.

D6i v6i cac dan xuat the cua xiclohexan, cau dang rna cac nhom the Ian a lien ket e thuong ben han so v6i khi chung a lien ket a. Khi co nhieu nhom the thi tuy thea vi tri nrong d6i gitra cluing va tuy thea chung a lien ket a hay e sf: tao fa cac dong phan hinh hQC va dong phan quang hQC khac nhau,

Ctiu hoi 6n t<tp

1. Th6 nao la hQP chat hOlJ 00, cho bi6t d~c diem va each pMn lot;li hqp chat hOlJ ca.

H~" CH3

. OH

". -'H

H C3Hri

2. PMn bi~t cac ~p khili ni~m sau : Cau tao hail hoc va cau truc hoa hoc ct1a phan tU, d6ng phan cau iao va d6ng pMn l~p th~.

3. Hay pMn l~i d6ng phan cau tso va tho thi du minh hoa,

4. . Th6 nao la "d~ khOng no" ? H~y thiet I~p cOng thuc tinh d~ khOng no cho cac hqp cMt chUa d6ng thOi C, H, 0, N va CI.

5. Hay v~n d~ng each viet d6ng phan cau tao (0 muc §3.11.5) d~ vi6t e6ng thuc tat ca cac d6ng pMn cau tao cua hop chat mach ho c6 cOng thue phan tll C6H120.

6. £)it1u ki~n cau tao de c6 d6ng phan hinh hoc ? Phan bi~t cac each gqi tAn d6ng pMn hlnh hQC theo danh phap cis-trans, syn-antiva Z-E.

7. £)i~u ki~n cau truc d~ c6 d6ng phan quang hoc ? Ntlu y nghTa ella cac kf. hi~u d~t truac tlln gQi cua d6ng phan Quang hoc : (+), (-), 0, L, R, S.

8. Phan.bi~t cac ~p khai ni~m sau : d6ng phan d6i quang va d6ng phan dia, hqp chat meso va bien the raxemie.

9. Cau dt;lng khac cau hlnh nhu the nao? chUng c6lilln quan gl VOl nhau kh6ng ?

10. Hay viet cOng thae tau true kh6ng gian ella cau dt;lng ~n ella cac d6ng pMn l~p the dllOi day va n~u rO quan h~ d6ng pMn giO'a hai cau true canh nhau va giO'a ca 4 cau true VOl nhau (d6ng pMn l~i gl ?).

'X~:

YOH

H C3H7-i

Mentol

Neomentol

lsomentol

N eoisomentol

4·HHHC1

49

Chuang II

u£N m vA su B~ D61 u£N m 0 HoP CHAT HO'u Cd

§1. LIEN KET CONO HoA TRI

I - BIEU OlEN LIEN KEr CQNG HOA TR!

1. Cang thuc Uuyt

Ngay til nhUng nam 1916 - 1919, tnroc khi xuat hien Co hoc Iuong tit, W. Cotsen (W. Kossel) va G. N. Liuyt (G. N. Lewis) dii dua ra thuyet electron ve han chat cua lien ket hoa hQC. Hai loai lien ket hoa hQC co han dircc de nghi la :

a) Lien ktt ion (lien ket dien hoa tri) duqc hlnh thanh do su chuyen mot hoac nhieu electron til nguyen tit nay den nguyen tit kia, tao ra cac ion duong va am lien ket voi nhau bang 11!C hut tinh dien,

b) Lien kel c(mg hod trj duoc hinh thanh giiia cac nguyen tit do su dung chung cac cap electron hoa trio

De hieu dien lien ket cong hoa tri trong phan tir, nguoi ta dung cong thuc Liuyt, a d6 cac c*p electron hoa tri duqc bieu thi hang hai dau cham hoac thay hang mot net gach, Thf du:

H

·

·C· + 4H· ~

..

H:C:H

..

hoac

H

· ..

·C· + 2H' + : 0

· ..

..

.~ H: C:: 0

II. ...

·

CH3CN - 2·<;. + 3H· + : N :

H H

_. H: C: C :: N:

..

H

..

hoac H -C=O

I ••

HH

I .

hoac H - C - C == N :

I H

50

Khi viet cong tlnrc Liuyt, ngiroi ta chi ghi cac electron hoa tri va can chii y sao cho rn6i nguyen ti'r deu dat diroc cau hlnh khi hiem (2 electron d6i vdi nguyen tiI H, 8 electron d6i voi nguyen ti'r C, N, 0 •... ). Tuy nhien, quy tde bat tu(quy tac 8 electron) do khong phai hie nao cfing thuc hien duoc. Thi du, nguyennr B trong phan tiI thuong chi kern theo 6 electron, con nguyen tiI P co the tui 10 electron va nguyen tir S tui 12 electron:

.. ..

CH3 - 0 - g - 0 - CH3

II. I ••

:g- CH3

..

: Cl : •• .. \ /C/:

:C/- p ..

/ ..

C/: .ci.

..

: F:

:p, I,.......p:

.. S .•

",....... , ..

:F I F: .. : F: ~.

Can nho rang, truce khi viet cong thuc Liuyt cho m¢t chat phai biet r6 thu nr lien ket cua cac nguyen tu trong phan tu chat do, nghia la hiet r6 cau tao hoa hoc cua no. Thf du, v6i cong thirc phan tii CHNO co hai cong tlnrc Liuyt ling voi hai chat khac nhau:

.. .. .

H:q:C::N: (H-q-C=N:) va H:N::C::O: (H-N=C=O:)

Axit xianic

Axit isoxianic

Cuoi cung ciing can ghi chu them la a cac cong thirc cau .tao do Kekule, Couper (1858) va Butlerop (1861) dua ra cung da dung cac net gach nci, nhung chi don thuan la de bieu dien lien ket gifra cac nguyen tit chii chua phoii la de chi doi electron dung chung (vi hie d6 chua phat hien. ra electron).

2. Di~ ticb quy l1iJc

Dei voi cac tieu phAn tich dien nhu NH4+, BF4-, C032-. CH3+, CH3-, ... tuy dien tich ducc phan b6 cho Illt ca cac nguyen tit co mat trong do nhimg ngirci ta ctlng can phai ghi r6 tirng don vi dien tfch Am va dirong cho nhtrng nguyen tiI nhat dinh goi la.di~n tich quy uOc. m tinh dien tich quy uuc tren mot nguyen tir nao do, ta Illy s6 electron hoa tri cua n6 b trang thai nguyen tit tv do trung hoa (chfnh bang s6 thu 11! nhom trong bang tuan hoan) trir di s6 electron hoa tri quy cho no a trang thai lien ket (g6m mot nita s6 electron lien ket va tAt ca s6 electron hoa tri chua chia, tuc la chua lien ket), Thf du:

(-) D6ivm F B
:F: SO thu tl! nh6m la 7 3
.. .. ..
:F:B:F SO electron hoa tri quy cho 7 4
.. .. ..
:F: Dien tfch quy u6'c 0 - 1
L.
51 D6i v6i N o (lien ktl dan)
" 56 thu t1:1' nh6m la 5 6
,0:
R"N:'_·, 56 electron hoa tri quy cho 4 7
'·0:
Dien tieh quy uac +1 -1 V~y, hai cong thirc tren duqc vi~t vui dien tfch quy uGe nhu sau:

F

I _

F-B=F I

F

o +#'

R-N

'0-

..

o cac cong thnc e6 ghi dien tieh quy uoc, tling dai so'tat cd cdc di¢n ticn quy udc phdi bting di¢n tich t6ng cong cua ion hoiJc phan tit. That vay, d6i vm [BF4f ta e6 4 x 0 + (-1) :;:; -1; d6i v6i nhom nitro b phan tir R-N02 ta e6 +1 + (-1) - 0 = 0 (nguyen tu ° mang n6i d6i co dien nch quy u6c bang 0),

Viec tinh dien tieh quy u6c tuy lit dan gian nhung t6t han ta nen ghi nho cau tao cua nhiing nguyen tir thuong g~p cung voi dien tich quy u6c cua cluing nhu dii t60g k~t a bing n.t.

Bang II. I, Ol.n tich quy vac 6 cae cc5u tQo thvong 9QP

s6 TH(f TV £)I~N TlcH QUY lICC
NH6M - 1 0 + 1
r
3 -8- -8-
I I
"- ",c-: I + • +
4 -c- =c-: -c- =c- .. c- -c- "'C ",c
I I I I I I
.,- "'tf: I, + +
5 -N - -N- :N- .. N: -N- =N- .. N-
I I I
-0: ". +
6 -0- ""2 -0 - "'2 -
I
"- ".
7 :X: (X '" F, C/, Br, I) -~: -X - 52

3. Cong thuc c9n9 hl1dng

Cong thirc Liuyt xem cac electron nhu IA c6 dinh tai nhtrng vi tri nha't dinh (dioh vi), vi the cung mot hop chat co the bieu dien boi cac cong thuc khac nhau. Thi du, d6i

voi hop chat nitro R-N02 co hai cong thuc Liuyt nhu sau:.

0:+/ ..

R-N, .. 0:

o m6i cong thtrc nay deu co mot lien ket don N-O va mot lien ket dOi N=O. Khong mot cong thirc nao trong chung phil hop voi thuc te Ia d(> dai hai lien ket gilla N va 0 deu bang nhau (::::: 125 pm). Trong khi do d(> dai lien ket don N-O Ia ~135 pm, con lien ket doi IA ~115 pm.

Hai cong thirc tren chi khac nhau ve vi trf cua cac electron hoa tri nen chang khOng phai Ia dong nhat rna IA nrong duong. Neu ta dich chuyen cac dOi electron theo chieu mui ten cong thl tu cong tlnrc nay se thu duqc cong thuc kia:

+ CO:

R_N-;?o .

<, 0'U·'

Thuyer cong hudng cho rang :

I - Bat cu phan ti'r hoac ion nao cting c6 the duoc hieu dien boi hai hoac nhieu cong thee Liuyt khac nhau chi a vi tri cua cdc electron, goi 13. cong thuc cong huang hay cong thuc giili han.

2 - Khong mot cong thuc nao trong cluing bidu dien dung duqc phan tu. Khong mQt cong thirc cong huang nao phil hop hoan toan voi tinh chat v~t If hoac tinh chat hoa hQC 'cua chat,

3 - Pha.n tirhoac ion thuc se duqc bieu dien t6t hon bang S1:f "Iai hoa'' giiia cac cong thirc cong huang.

Nhu vay, cong thUG cong hubng khong phai l3. cong thtic cua phan tir hoac ion thuc, chiing chi ton tai trong If thuyet, chiing chi la nhfrng cong thuc gia thiet, con cong thuc thuc cua phan tu IA Sl! lai hoa giifa cac cong thuc cong huang. Mfii ten hai chieu (++) gifra cac cong thirc cong huong chi de noi len chung la cac cong thee gilt thiet, khOng phai IA cong thirc th~t. vi the khOng nen nham Ian n6 v6'i hai mtii ten ngiroc chieu (p)

dung de chi mot can bang c6 thuc.

53

Cac titu phan trong can bang khac nhau ve vi trf cua cac nguyen tir trong phan tir va do Ia cac titu phan co thuc, con cac cong thirc cong huang thi khac nhau chi a vi tri cac electron va la nhUng cong thuc gia thiet. Thi du:

?"o ;= ....... 0
CH3-N CH2=N,
....... 0 O-H
..
+?"Q: + /g:-
CH3-N, .. -- CH3-N ..
0:- "0:
..
nO O+-H
H-C +H+ - H-C;
-
'H 'H
+ ..
..,::::;O-H +/g-H
17" ••
H-C -- H-C
'H 'H : can bang nitro - axi, c6 thuc,

: Khong c6 thuc, chi d~ bieu dien CH3N02·

: Proton hoa nh6m C = 0, c6 thuc,

: Khong c6 thuc, chi d~ bieu dien (H2COH)+.

+

CH2 = CH - CH = CH2· + ~+ ;p: CH3 - CH - CH = CH2 : SV proton hoa butadien, co thuc,

+ +

~-CH-CH=~ H ~-rn=CH-~

: Ca hai chi d~ bi~u dien

san ph&n proton hoa butadien

Trong nhirng tnrong hop nrong nr nhu tren, de bieu dien dung diroc cong thirc phil hop thuc te rna khong phai viet nhieu cong tlnrc gioi han, ngirci ta viet nhu sau:

+ H-C!..!..:.O-H I

H

+ s" s"

CH3 - CH.!..!..!CH!..!..:.CH2 hoac CH3 - CH!..!..:.CH!..!..:.CH2

o cac cong thirc tren, dau gach lien (-) chi cac lien ket co mat b t~t ca. cac cong thuc gioi han, con dau gach dUt doan ( ... ) chi cac lien ket xuat hien a mot hoac nhieu cong thirc nhung khong phai a tat ca 'cac cong thec gioi han, Ki hieu 0+ (hoac .0-) a nguyen tir nao, thi c6 nghia nguyen tit do mang mot phan chu khong phai toan b!.') mot dien tich duang (hoac am). Nhirng lien ket duoc ghi bang mot gach lien va mot gach dUt

(::.:) khong phai la nhimg lien ket dci, ciing khOng phai la lien ket dan rna la trung gian gifra cluing,

54

II ~ LI~N KEY C¢NG HoA TRI THEO CO HQC LUQNG TlI

1. SI! xen phu obitan. Uen kit a va Hen kit 7t

Theo quan diem cua Co hoc hrong tu, diem mau ch6t trong su hinh thanh lien ket cong hoa tri 13 SI1 xen phil cac obitan cua hai nguyen tic tham gia lien ket, lam tang cuong mat d¢ electron (xac suat tlm thay electron) b giCi'a hai hat nhan, dan den su hut nhau gitra hai nguyen tu. Nguoi ta phan biet hai loai xen phu: Xen phu cling dau (cung pha) hay ta xen phil duang, lam tang mat d¢ electron giita hai hat nhan dan den tao thrum obitan phan fU lien kit (MO) va xen phu trai dau (nguoc pha) hay Iii xen plul am, lam giam mat d¢ electron giii'a hai hat nhan, tao thanh obitan phdn Iii phon lien kli (MO·, co ghi dau >I<).l1mh II.I mo ta su xen phil c6 obitan p tham gia,

~

OCXJ~

. ~~

a) Xen phu true S + P

-

o·

-

~CXJCXJ/

'-,..~-

b) Xen phu tn,Jc p + P

~ttJ

c)XenphubIAnp+ p m

C1

C)o

- .. ,

OC)

n·

C)

- ..

C)

Hinh Ill. a) va b) S'=' xen pho. true din d~ hinh thanh obitan 0 lien k€t va o· - c) 51! xen pho. bien din d&t hinh thanh obitan 1tli&l k~t va 1['

55

a hlnh 1I.1 a va b, su xen phu C\lC dai nam tren true n6i hai hat nhan lien k€t (true lien ket) nen diroc goi la xen phil true, o hlnh II.lc, su xen phu nam b hai ben true n6i hai h{lt nhan lien ket nen diroc goi la xen phil ben.

Cac obitan phan tir (lien k€t va phan lien kei) 6 hlnh II.la va b nhan true lien ket lam true doi xirng (chung co d6i xtmg true) ducc goi Ia obitan e, Obitan o rna mat d~ electron diroc tang cuong a giU'a hai hat nhan duqc goi Ia obitan cr lien ket va tao thanh lien ket cr.

Lien ket cr duqc tao thanh do S,! xen phii true nen la lien ket Mn veng. Hai nguyen tir hoac nhom nguyen tii lien ket voi nhau chi bang lien ket o thl co the quay t,! do quanh true -lien ket rna khong pha va lien k~"t. S'! quay do dan toi hinh thanh vO s6 cau dang khac nhau (chuang I, muc §4.1V.l). Nguoc voi obitan cr lien ket, obitan c phan lien ket

*

(ki hieu cr ) khong tao ra lien ket gi giira hai nguyen tii.

Cac obitan phan tu 6 hinh II.lc ~~n mat phang chua true lien ket lam ffi~t phing doi ximg, cluing duoc goi la obitan 7t. Obitan 1t rna mat d~ electron duoc tang cuong b vung gitra hai hat nhan a hai phia cua true lien ket goi lil obitan 7t lien ket (ki hieu lil 7t1k, hoac la n) va tao thanh lien ket 7t.

Lien ket 7t duqc taothanh do su xen phu ben, kern hii'u hieu han su xen phu true, nen kern ben han lien ket c, no de bi dUt fa trong phan ling hoa hoc. Hai nguyen tii hoac nh6rn nguyen til lien ket voi nhau bang lien ket 1t thl khong quay diroc W do quanh true n6i hai hat nhan lien ket vi su quay d6 se lam mat su xen phii ben, lam pha va lien ket 1t. Chinh vi v~ y, hai nguyen tir lien ket doi v6i nhau (mot lien ket o va mot lien ket 7t) tao ra mot b\> phan cirng nhac cia phan tir, Chinh do la mot trong nhtrng nguyen nhan lam xuat hien d6ng phan hinh hoc b cac hop chat c6 lien ket dOi (xem chuang I, muc §4.II).

2. Stllai hOO obitan

a) Khai niem lai hod obitan

Nhu tren dii thay s'! xen phu cac obitan cua cac nguyen tir khac nhau c6 the dan toi tao thanh lien ket giua chung, MOi lien ket duoc dam bao b&i s'! ghe~ doi cua hai electron d¢c than c6 spin trai dau. Co nhieu tnrong hop, 6 trang thai co ban nguyen tu khOng co du so electron d()c than can cho sl!' tao thanh phan tir voi cau true khong gian nhat dinh, vi vay nguiri ta cho rang cluing phai chuyen sang trang tMi kich thich voi nhieu electron d¢c than han trangthai co ban. Thi du, cau hinh electron cua nguyen til C d trang thai co ban va trang thai kich thich duqc trinh bay d hinh 1I.2a.b.

56

H H H
.i. .i. .t, j_ _1_ H 11 11 11
11 2px 2Py 2pz .i. 2px 2py 2pz It
E 2s2 Kfch thich 2s +4H'
-
.tl. .tl_ J1
Is2 Is2
a) Ceo ban b) Ckich thCch CH4 gia dinh Hinh 112. a) Cd trang thai co hom; b) Cd trang thai kich thich c) phan hi: CH.t glli. thi~t (kh6ng dUng voi thuc ~

Nell nguyen ttt C kich thfch dung ngay 4 obitan voi 4 electron d¢C than cua minh xen phu vcri 4 obitan S cua 4 nguyen tu H thi se tao ra mot phan ttt CH4 gia dinh nhu a hlnh II.2e. 0 phan tu gia dinh nay e6 1 lien ket C-H tao thanh tir electron b obitan 2s eua C, trong khi d6 3 lien ket C-H kia lai tao thanh tit 3 electron b obitan 2p. R5 rang lien ket C-H d rmrc nang hrong thap han phai khac biet so voi 3 lien k€t con lai, Nhung thuc te lai cho thay rAng 4 lien ket C-H b metan la hoan toan giong nhau. D6i v6i nhieu nguyen t6 khac ciing g~p nhtmg mau thuin tirong nr,

£M khAc phuc nhUng mall thuan d6, nam 1931, L. Pauling dii de ra khai niem lai hoa cac obitan trong mot nguyen tiro Theo quan niem d6, cac obitan khdc nhau trong m(Jt nguyen tit co the t6 hap vai nhau de tao ra cae obitan mai, gi6ng nhau, thich hap cho su tao thrum lien ket, D6 la su lai hoa obitan. S6 obitan moi tao fa bang 56 obitan tham gia t6 hop. M6i obitan moi do d6u mang mot pharr dac tinh cua tung obitan tao ra n6 vi the diroc goi Ht obitan lai hoa, Can nho rang su lai hoa khac 51.! xen phil a ch8 n6 xay fa giita cac obitan khac nhau trong cung mot nguyen tit, con su xen phu xay ra gitra cac obitan cua cac nguyen tit khac nhau.

Cac obitan lai hoa a mot nguyen ti'r tuy huang ve cac phirong khac nhau nhung c6 hinh dang nhunhau, cling b mot mire nang hrong nhu nhau, do d6 khi xen phu vui cac obitan gi6ng nhau cua cac nguyen tir khac thi se tao ra cac lien ket urong dirong nhau.

-b} Lai hod s/

Kitu lai boa sp3 la Sl,I t6 hop cua 1 obitan 5 va 3 obitan p tao fa 4 obitan lai boa sp3 gi6ng nhau ve hlnh dang, kfch thuoc, nang hrong va huang ve b6n dinh cua mot tu dien deu rna tam la h~t nhan nguyen tit. Vi the kieu lai hoa nay con diroc goi la lai hoa tu di~n (hinh II.3a). Khac voi obitan 5 c6 dang hinh cau va obitan p c6 dang hinh qua ta

57

doi (56 8 nci) (xern hinh IL3a). obitan lai hoa co dang qua ta doi lech ve mot phia (hinh II.3b). Sv don mat d¢ electron ve mot phfa lam cho kha nang xen phu cua obitan lai hoa 100 hem cua obitan chua lai hoa, Tinh toan cho thay, neu coi khit nang xen phu cua

obitan 5 Ia 1 thi kha nang xen phu cua obitan p la 1.73 con cua obitan lai hoa Sp3 lil 2,0. TI1,Ie cua cac obitan lai hoa sp3 khong vu6ng g6e voi nhau nhu true cua cac obitan 2px' 2py, 2pz rna tao voi nhau nhlmg goc bang 1090.28' (lam tron thanh 109,5°) .

....

, ,

lai twa

b)

a)

Hinh 113. a) Lai hoa tt! dien (sp3) ; b) M()t obitan sp3

Lai hoa sp3 g<]i.p a nguyen ti'r C no, chang han cr metan (hlnh II.4a), etan (hinh II.4b) ... 6 phan ti'r metan, 4 obitan sp3 cua C giong nhau ve hlnh dang, kich thuoc va b cling mot mire nang hrong, lai xen phu voi 4 obitan 5 cua 4 nguyen tu H, vi the 4 lien ket C-H cfing hoan toan nrong duong nhau. 0 phan til etan, m6i nguyen til C sir dung 1 obit an sp3 d6 tao lien ket C-C, con 3 obitan sp3 thi xen phu voi 3 obitan sella 3 nguyen

til H de tao ra cac lien ket C-H. Cac goc hoa tr] HeR va HcC b rnetan va etan dell bang 109,5°. Nguyen til N a amoniae (hlnh Il.dc) hoac a nhom amino (-NH2), nguyen tir 0 trong aneol, ete cling a trang thai lai hoa sp3.

a)

58

b)

c)

Hinh 114. 5,! hinh thanh cac lien ke't cr ; a) d metan; b) d etan; c) d amoniac

c) Lai hod s/

Ki€u lai hoa sp2 la su t6 hop cua 1 obitan s va 2 obitan p tao ra 3 obitan lai hOG s/ giong nhau va huang ve 3 dinh cua tarn giac deu rna tarn Iii. hat nhan nguyen tit. Vi vay, kieu lai hoa sp2 eon duoc goi la lai hoa tam giac (hlnh 11.5). Obitan sp2 cung co hlnh qua ta doi lech, kha nang xen phu nrong d6i cua nola 1,99, hoi nho han cua obitan sp3 .

..

lai hoa

H1nh 0.5. Lai hoa tam giac (sp2)

Tr1:1c cua 3 obitan Iai hoa Sp2 cung nam tren mot mat phang va hop voi nhau mot goc 120°. Con mot obitan 2p khong tham gia lai hoa, tI1J.c cua no vuong goc voi mat phang chua true cua 3 obitan lai hoa sp2. Thi du dan gian nhat ve lai hoa sp2 13. tnrong hop cua nguyen tit B trong cac hop chat BF3, (RO)3B, ... a cac hop chat nay, 3 obitan sp2 voi 3 electron doc than cua B tao lien ket c voi 3 nguyen tir khac, eon mot obitan 2p cua no khong co electron nao, nen duoc goi la obitan trong va nguoi ta eo the ve hoac khong ve no tren hinh (hlnh 11.6).

a)

b)

Thf d1:1 quen thuoc ve Iai hoa sp2 Ia phan ta etilen, CzH4 (hlnh II.7). Trong phan tu etilen, 2 nguyen nr C deu a trang thai lai hoa Sp2. Moi nguyen tu C dung 2 obitan Sp2 d~ tao lien ket voi 2 nguyen ta H va 1 obitan sp2 de tao lien ket c v& nguyen tu C kia. a moi nguyen tir C eon 1 obitan 2p khong lai hoa chua 1 electron doc than, true cua

59

chting song song nhau, cluing xen phtl ben voi nhau tao thanh lien ket 1t (hlnh II.7a). Electron 0 obitan 1t goi Ill. electron 7t. Theo thuyet MO, sir t6 hop 2 obitan p da hlnh

'"

thanh fa obitan 1t (lien ket, hinh 1l.7b) va obitan 1t (phan lien ket), Nhu vay, lien ket

giua 2 C 0 etilen diroc dam bao boi 1 lien ke't CJ va m9t lien kef st, do d6 goi fa lien ket d6i. Tit viec xem xet su lai hoa ella C trong etilen, cluing ta thay ducc cau true khong gian cua n6: Toan be:> 6 nguyen tir trong phan til deu nam tren cung mot mat phang, goi

la mgt phJng phan til; Cac g6c hoa tri HcH va HCC deu gAn bang 120°, Obitan 1t nam o hai phia d6i ximg nhau qua mat phang phan tir (hinh II.7b) ; Hai nh6rn =CH2 khong the quay tv do quanh true C-C duoc vi nhu vay se lam mat su xen phu ben cua hai obitan 2p, nghia Ill. lam dli1 lien ket 1t.

a)

b)

Hinh 117 a) SI! hinh thanh lien k€t don va d6i d etilen b) Obitan 1t lien ke't d etilen

c) Lai hOG sp

Kieu lai hoa sp la 51! 16 hop cua 1 obitan S voi 1 obitan p tao raZ obitan lai hoa sp gi6ng nhau, e6 ehung true d6i xirng nhirng huang ve hai phia ngiroc nhau cua true d6. Vi vay, ki~u lai hoa sp con goi la lai hoa dUOng thang (hlnh II.S). Obitan lai hoa sp cling c6 hinh qua ta doi lech, kha nang xen phu wang d6i ella n6 Ut 1,93, nho hem so voi obitan sp2 va sp3, Ian hem. so v6i obitan 2s va 2p.

lai hoa

a)

Hinh II.8. a) Lai hoa dttong thing (sp); b) Cac obitan d nguy~n tlt C lai hoa sp (Csp)

60

Trong Boa hoc BUu co, lai hoa sp thirong g~p a cac hop chat e6 lien ket ba hoac lien ket ddi lien. Thi du : a phan tiI axetilen H-C""C-H, rn6i nguyen tiI Csp dung 1 obitan lai hoa tao lien ket voi 1 'nguyen tiI H, va 1 obitan lai hoa khac tao lien ket o voi nguyen ni Csp kia. o rnoi nguyen tu C con 2 obitan 2p khong lai hoa (obitan p thuan khiet) rna true cua cluing vuong g6e voi nbau va vuong g6c voi true lien ker, Hai obitan 2p c6 true song song nbau (0 hai nguyen til C) lai xen phu voi nhau tirng ddi mot tao thanh 2 lien ket 1t. Nhu the, lien ket gifra hai nguyen tu C 6 axetilen duoc dam bao b6i 1 lien kit a va 2 lien kit n; d6 180 lien ket ba (hinh II.9a). 6 lien k€t ba, mat do electron 1t phan b6 deu 0 ell 4 phia cua true lien ket, cluing hop vci nhau thanh dang gan gi6ng nhu hlnh tru (hinh II.9b).

a)

b)

H1nh Il9. a) SI,1 hinh thanh phan ttr H-C "" C-H ; b) Lien k€t 1t d phan ttr H-C == C-H

111- TiNH CHAT CllA LIEN KET CONG HoA TRI

. . .

1. Nang luqng cua lien ke't c9n9 hoa tr]

Mot trong nhiing tinh chat quan trong cua lien ket cong hoa tri 180 d¢ ben cua lien keto D¢ ben cua lien ket duqc danh gia bang nang hrong lien kef. Lien ket cang ben thi nang hrong lien ket cang 16'0 va nguoc lai,

Hay xet phan irng sau :

A-B + nang hrong -) A" + B'

Trong phan ling nay, nang luong dung d~ phan cAt lien ket A-B khien cac electron lien ket diroc chia d6ng deu cho A va B. D6 la st,T phan edt dong li. Ngtroi ta goi nang luang cdn thiet at phdn edt dong li mot mol lien ket fa nang luqng phan Ii lien ket.

Nang hrong phan li lien ket ducc xac dinh dira vao entanpi cua cac phan ilng hoac dira v800 phirong phap pho dao dong ... Nang Iirong phan li lien ket phu thuoc tnroc het

61

vao ban chat hai nguyen ta tham gia lien ket va vao d¢ boi lien ket giiia chang (dan, doi, ba). Chang han, nang hrong phan li lien ket C-H nho han lien ket O-H ; Nang hrong

•

phan Ii lien ket dan nho han lien ket doi; nang luqng phAn Ii lien ket doi nho han lien ket

ba. Ngoai fa nang ltrong phan li lien ket con phu thuoc cau tnic hai phan phan tir c6 chung lien ket bi phan cat.

Thi du: Nang hrong phan li lien ket C-C b butan nhu sau

. .

CH3 -CH2 -CH2 -CH3 ----40 CH3 -CH2 -CH2 + CH3

Llli::; 357 kl/mol

. ,

CH3 -CH2 -CH2 -CH3 ----40 CH3 -CH2 + CH2 -or,

tlH::; 346 kl/mol

Nang hrong phan li lien ket C-H thtr nhat a mot s6 phan tir lil nhu sau

tlH ::; 435 kl/mol

,

CH2=CH-H ----40 GI2 =CH + H'

CH=CH - H ----40 ill =C' + H'

tlH ::; 453 kl/mol

tlH = 500 kl/mol

Nang hrong phan li lien ket C-H thu hai khac voi lien ket thu nhat, tlnr ba khac voi thu hai. , . VI the nguiJi ta thuong lay rno: gia tri trung binh cho d. phan tir, thi du d6i voi nhom metan:

CH4 ----40 C + 4H

Llli::; 1659 kl/mol

Nang luong phan Ii trung binh cua lien ket C-H b metan lil 1659: 4 ~ 415 kl/mol, Nang hrong phan li trung binh cua lien ket C-H a ankan la 410 kl/mol,

De su dung rong rai hem, nguoi ta con tinh gia tri nang luang phdn li lien kef trung binh cho timg loai lien ket a cac hop chat khac nhau va goi la nang luang lien kef trung binh hoac doikhi dan gian chi la nang lirong lien ket. Trong bang 11.2 cho cac gia tri nang hrong phan Ii lien ket trung blnh d6i voi nhUng lien ket thuong g~p.

Tat nhien gia tri nang hrong lien ket trung binh khong rmg dung voi mot hop chat, tham chi mot lienket C\1 the nao ca, tuy vay no co the dung diroc trong nhieu muc dich, chang han nhu d~ so sanh d¢ ben cua lien ket, de so sanh d¢ ben nhiet dong cua cac tieu phan khac nhau, hoac tinh gan dung hieu ung nhiet cua phan irng. .. Khi doi hoi sl! chinh xac cao, ta thirong sir dung nhii'ng gia tri hieu dinh them cho m6i lien ket a cac cau tao khac nhau.

62

Bang 11.2. Nang lu~ng phOn HUen ket trung binh. kJ/mol

Lien kef Nang luang Lien kilt Nang luang Lien ket Nang luang
I
-C-H 410 CI-H 425 C-F 425
I .
""C-H 435 Br-H 362 C-Q 325
I
~C-H 502 I-H 295 C-Br 270
= C - H (thorn) 456 C-C 351 C-I 240
I
-O-H 431 C-O 359 C=C 614
N-H 385 C-N 316 C=O 736
S-H 367 C-S 235 C=N 627
Si-H 319 C-Si 334 Co-C 811
F-H 564 Si-O 370 <:EN 899 Thi dt! 1: Dua vito cac s6li¢u da cho trong hang 11.2. hay cho biet lien kel dan C-C hay lien ket doi C=C ben han? Lien ket nao co kha nang phan irng cao han. vi sao?

Gidi: Ve t6ng the thi lien ket doi bin hon lien ket don vi nang IUQl1g cua no 16'0 hOO (Ec--c = 614 > Ec-c = 351 kl/mol). Mot each gan dung, ta co the coi nang Iirong cua lien ket doi lit t6ng cua nang hrong lien ket cr (Ecr) va nang hrong lien ket 1t (En). tlic lit Ec=c = Ecr + En. Neu lay Ecr = Ec-c ::: 351 kl/rnol thi En ::: 614 -351 = 263 klIma!. Lien ket 1t co nang Iirong nho han. yeu hon lien ket o nen de hi pha va trong cac phan ling hoa hoc, VI the, lien ket doi co kha nang phan trng cao hon.

Thi du 2: Vi sao khi cong rnroc vao axetilen, ngtroi ta khong thu diroc etenol rna thu diroc axetandehit ?

Gidi: Biernang .hrong phan li lien ket va nang luong tao thanh lien ket tit nguyen tit co tri s6 bang nhau nhimg ngtroc dau nen ta co the tinh diroc ~.H(hlnh thanh) phan tit tir nguyen tit (mot each gan dung).

[:~C=<H] l\. H
CHEC-H + HOH ----40 ---)0 H -c-c.'
Ii' '\)
C=C 614 C-C 351
3 =C-H 1305 C=O 736·
C-O 359 3 C-H 1230
O-H 431 =C-H 435
6H(hlnh Ihanh)' kllmot : -2709 -2752
63 Axetandehit ben han etenol vi nang hrong hlnh thrum ciia n6 Am han etenol khoang 43 kl/mol.

Thi d~ 3: Trong dung dich nuoc, metanal t6n tai hau nhu dum dang metadiol. Vi sao khong th~ tach duoc metadiol ra khoi dung dich ?

Gidi: Tfnh entanpi cua phan irng :

+

H-O-H

8H(hlnh thanh)- kl/mol :

2 c-o: 718

2C-H: 820

2 O-H: 862

-2400

c=o

736

2 =C-H 870 -1606

20-H: 862 -862

8H(phiin LIng), kl/mol = -1606 --862 - (-2400) = - 68 kl/rnol.

Neu co lap metadiol fa khoi dung dich, n6 chuyen ngay thrum metanal va nu6c vi phan Ung d6 duoc 19i v~ mat nang hrong (toa nhiet) khoang 68 kl/mol, Do c6 nang luong hinh thanh Am hon.jai tao nhieu lien ket hidro ben vm mroc nen metadiol Ia dang chii yeu t6n tai trong dung dich,

2. D{) dili lien kit

£)9 dai lien ket la khodng each can bang giiia hai hat nhdn cua nhiing nguyen lU lien kit WR nhau. D¢ dai lien ket duqc xac dinh bang cac phuong phap thuc nghiem nhir plnrong phap nhieu xa tia X, phuong phap phd vi song, ...

D¢ dai lien ket phu thuoc ehll yeu vito bin. chat cua lien ket, tuc lit phu thuoc bin chat ella hai nguyen tu tham gia lien ket, trang thai lai hoa vit kieu lien ket (don, doi, ba) gifra chung, Ngoai ra n6 con bien d6i chut it tuy thuoc vao phan con lai ciia phan tir. Vi the, trong nhtmg tnrong hop khong ca.n su chfnh xac cao, ngiroi ta thuong dung d(J dai lien ket trung blnh, tuc la gia tri trung binh dQ dai cua mot lien ket nhat dinh a nhieu hop chat khac nhau.

Bang II.3 Iiet ke d¢ dai lien ket trung binh cua cac lien ket thuong g~p trong Hoa hnu ca. Tnroc kia d¢ dai lien ket thuong diroc tinh bang A, ngay nay sir dung h¢ do

luang qu6c tC SI tfnh thee om (nanomet) hoac pm (picornet): 1 A = 1O-'nm = 102 pm (tinh thea pm thuan 19i vi it phai dung den s6 thap phan sau dau phay),

64

....... '4, ......

,"1>'

Bang 11.3. D9 dol trung binh euo mC)t so lien k~t thuong gQP

lJtj dai trung binh Lien klt lJ,j dai trung binh
Lien klr
A nm pm A nm pm
I
-C-H 1,09 0,109 109 C-N 1,47 0,147 147
I
=C-H 1,08 0,108 108 c-o 1,43 0,143 143
I
=C-H 1,06 0,106 106 C-F 1,38 0,138 138
O-H 0,97 0,097 97 C-CI 1,76 0,176 176
N-H 1,04 0,104 104 C-Br 1,93 0,193 193
P-H 1,43 0,143 143 C-I 2,14 0,214 214
S-H 1,34 0,134 134 c=o 1,23 0,123 123
Si-H 1,46 0,146 146 C=N 1,30 0,130 130
I I
-C-C- 1,54 0,154 154 C=C(thom) 1,39 0,139 139
I I
I
-C-C= 1,51 0,151 151 C=C 1,34 0,134 134
I I
I
-C-C= 1,46 0,146 146 N=N 1,25 0,125 125
I
=C-C= 1,42 0,142 142 C=C 1,20 0,120 120
=C-C= 1,37 0,137 137 C=N 1,16 0.116 116 GiiIa d¢ dai lien ket va nang hrong lien ket co m6i lien he chat che: dr) dai lien ket cang nho thi nang luang lien ke't cang lim. Chimg han, cac so lieu a bang 11.3 va 11.2 cho thay:

DQ dai lien ket

: C-C > C=C> C=C

I

-C-H > =C-H >=C-H

I .j

I

-C-H < =C-H < =C-H

I I

Nang hrong lien ket : C-C < C=C < C=C

Nhu vay, khi hai nguyen tit lien ket voi nhau, d¢ dai lien ket cang nho thi lien k€t giiia chung ding ben vtrng.

5· HHHC1

65

3. Ban kinh cQng boa t'1

Phdn dong gop da m6i nguyen tlf vao d¢ dai lien ke't cong hOG Iff giiia chung goi Iii . ban kinh ct)ng hoa trio Neu xac dinh dircc d¢ dai lien ket Iii d, thi ban kfnh cong hoa tri r duoc tinh theo cac bieu tlurc sau:

dAA = 2rA dAB = rA + rB

(1) (2)

Bang II.4 sau day cho biet ban kfnh cong hoa tri trung binh cua mot 56 nguyen til 0 cac trang thai lien ket khac nhau .

.

Sang 11.4. Bon kinh cc}ng hoolrj trung binh cue m9t so nguyen til thlJang gQP

Nguyin ta Ball kinh c911g hod tri Nguyen ttf Ball kinh cong hoa tri
(liill kit) A nm pm (lien kef) A nm pm
Csp3 (dan) 0,77 0,077 77 H (dan) 0,37 0,037 37
Csp2 (doi) 0,67 0,067 67 F (dan) 0,64 0,064 64
Csp (ba) 0,60 0,060 60 Cl (dan) 0,99 0,099 99
3 0,70 0,070 70 Br (dan) 1,14 0,114 114
Nsp (dan)
Nsp2 (d6i) 0,60 0,060 60 I (dan) 1, 13 0,113 I 113
Nsp (ba) 0,55 0,055 55 Si (dan) 1,17 0,117 117 I
Osp3 (don) 0,66 0,066 66 S(dem) 1,04 0,104 I 104
Osp2 (doi) 0,55 0,055 55 P (dan) 1,10 0,110 110 Qua bang II.4 ta thay him kinn cong hOG tri thay do'i thea trang tluii lai hOG CIla

nguyen tit va dQ boi ella lien ket ma no tham gia. Thi du:
Nguyen n'r (lien ket) : Csp3 (doli) Csp2 (d6i) Csp (ba) J Nsp2 (d6i) Nsp (bat
Nsp (doli)
Ti l¢ obitan s (%) 25 33 50 25 33 50
Ban kfnh (pm) 77 67 60 70 60 55 sa di nhu v~y mot mat III do obit an s nno gon hon obitan p (trong cung mot lap) nen nguyen tir a trang thai lai hoa nao co ti It; obitan s cao han se co ban kinh cong hoa tri nho hon, Mat khac, str ~p trung mat d¢ electron (c va n) giira hai nguyen tu lien ket doi hoac ba voi nhau di Him giam II,lC day giira hai hat nhan, khien chiing lai gan nhau hon. Vi vay rna lien ket ba ngan hon lien ket doi, lien k€t doi ngan hen lien ket dan (xem bang 11.3).

Tit cac gia tri ban kfnh cong hoa tri trong bang 11.4. co the uac IU(Jng gun dung gia tri cua nhtrng d¢ dai lien ket khong ghi trong bang 11.3. Thf du;

66

I I
Lien ket =C-C- ==C-N- -C-N=
I I I I I
D¢ dai (tinh), pm 67 + 77 = 144 67 + 70 ~ 137 77 + 60 =: 137
D¢ dai (do), pm 151 143 Can chu y rang, cac gia tri cho a bang Il.4 dtroc tfnh tit d¢ dai lien ket trung blnh nen chung lit ban kfnh cong hoa tri trung blnh, cluing co th~ sai khac so voi ban kfnh nguyen tu, nhat 1ft tnrong hop cac nguyen tit co d¢ am dien Ion. Changhan, ban kinh nguyen til ella C lit 77 pm (xac dinh tit kim cirong), ban kfnh cong hoa tri cua C a cac hidrocacbon no ding dung bang 77 pm, Ban kinh nguyen til cua F Ia 71 pm (xac dinh til F a th~ ran) con ban kinh cong hoa tri trung binh cua F trong cac hop chat chi III 64 pm. (Ban kinh nguyen tit chinh la ban kinh cong hoa tri hoac ban kfnh kim loai ella don chat).

4. GOc lien ket

Goc gitra hai lien ket cong hoa tri a cling mot nguyen tir goi lit goc lien ket hoac goc hoa trio Tren ca sa quan niem ella Liuyt ve lien kct cong hoa tri, Thuyet "Su day cua cac cap electron hoa tri" (VSEPR) dii giai thfch thoa dang sl! khac nhau ve d¢ 160 ella cac goc lien keto Sau nay, Thuyet "Lai hoa obitan" ding dii thanh cong trong viec giai thich g6c lien ket. Ca hai thuyet tren deu dua vao nguyen tac Ia cac c~p electron hoa tri (lien ket hoac chua lien ket) co xu huang dAy nhau ra xa.

Nhu da biet, true cua cac obitan lai hoa sp3, sp2, sp l~p thanh cac g6c tuong ffi1g la 109,5°, 120°, 180°. Tuy nhien, cac g6c lien ket dung bang cac goc Iai hoa chi g~p a mot s6 rat it phan til can d6i hoan toan (nhir CH4, BF3, CzH2, ... ).6 dal bo phan cac phan tir khac, goc lien ket thuong sai khac viti d¢ so v6i goc lai hoa. Dieu do lit hien nhien bOi VI b cac phan til nay cac nguyen nr tham gia lien ket rat khac nhau, mat dQ electron a cac obitan lien ket hoac chua lien ket cilng khac nhau. Hinh II.lO chi ra goc lien ket a mot s6 hop chat don gian,

Trang nhimg tnrong hop thong thirong, dua vao goc lien kei co tM suy ra trang thai lai hoa. Chang han, a phan tir (CH3hN, goc lien kel CNC do diroc lit g~n 110°, gan vci lai hoa til dien (109,5°) han 1ft goc giira cac obitan 2px' 2py, 2pz cua N khong lai hoa (90°). Nhu vay, nguyen tu N a trirnetylamin a trang thai lai hoa Sp3. Goc' Cae a (CH3hO 1ft 111 ° ciing chirng to nguyen ttr 0 a phan ti't do thuoc ki~u lai hoa sp3.

Ngoai nhimg tfnh chat ke tren, nhirng tfnh chat khac cua lien ket cong hoa tri nhu sl! phan eire lien ket, su lien hop va str phan cat lien ket..; se hin IUQ1 duqc trinh bay b cac phan tiep theo,

67

H "'-;, /CH3 H·._ /CI {i::/ /CH3
;CJ1110 -;,~ ) oJ 1110
C 1120
H'" "CI
H CH3 CH3
H" /H .H
H" /H 1800 ",'
C=C 1220 /H c::---.. ~ H
C=C L/ ,,~ =C-C
L/ "H o - \.j
H -1200 C=C 1090 \
H -1200 H/ "H 1010
H 1220 -«,0 CI" ©r;OO
,,~
C=O H -C ) 1210 1140 ~C = a
H/ <,
OH CI
Hinh 1L1O. Coc lien kl1(t d mot s6hqp chert don gian 5. SI! philn ct[.c va SI! phan cl!c hoa lien ke't c~mg hoa tIi

a) Momen luling cue ella lien ket va cua phdn til

Khi hai nguyen tiI eo dQ am dien khac nhau lien ket voi nhau, doi eleetron dung chung bi lech ve phia nguyen tiI eo d¢ am dien Ion hen lam eho no mang mot phan dien tich am (-q). eon nguyen tit co d¢ am dien nho hon thl mang mot phan dien tich duong (+q). Lien ket do goi la lien ke't cong hod tri phdn cue. Hai dien tich --q va +q hop thanh mot ludng cue dien, khoang each I giira cluing goi la d¢ dai luang cue, Diem dat cua dien tich -q va +q khong phai la tam cua hai nguyen tit lien ket, rna HI. "trong tam" cua dien tieh am va dien tich duong, Nhir vay, a lien ket cong hoa tri phan cue cung nhu a phan nr phan cue, "trong tam" cua dien tich am va "trong tam" cua dien tich duang khong trung nhau, D6 chi mot luang cue, nguoi ta dung mui ten co chieu til eire dtrong den C\IC am, thi du:

H-Cl -J..--).

H-C ~

C-Cl ~

C-Li ~

D6 dac tnrng eho dQ Ian ella mot luang eire, nguoi ta dung mot dai hrong goi Ia momen luang cue u, co gia tri bang tich ella dien tich q (thea don vi dien-tich e, bang

4,8.10-10 dan V! tinh dien) voi d¢ dai I cua luang cue (tinh bang A, lA = 10-10 m):

J..l = q.l

Don vi de do momen luang cue thea cong thirc tren goi la Dobai, ki hieu 1a D (lAy ten Nha V~t H - Hoa hQC Ha Lan, P.Debye, 1884 - 1966).

68

D6 d~c tnrng cho su phan cue cua lien ket, nguoi ta dung momen ludng Cl_(C ella lien kef tfnh thea gia tri d¢ am dien re cua Paolinh :

J.lA-B = <EB- reA (B Am dien han A)

Vay, mornen IUOng eire cua lien ket phu thuoc vao su chenh lech v~ dQ am dien giua hai nguyen tu lien ket. Tir gia tri rnomen IU5'ng eire cua lien ket, theo thuyet lien ket hoa tri (VB), nguai ta tinh diroc mire d¢ ion cua lien ket fa % boi cong thirc sau:

D¢ ion (%) = 1 ,6J.l + 3,5,u2

Gia tri )..t va d¢ ion cua mot s6 lien ket va nhorn lien ket thong thuong diroc ghi b bang 1I.5. Cac gia tri tinh toan nay UIt nhien co sai lech so voi gia tri thuc nghiern.

Bang 11.5. Momen Iuong CI!C va de;, Ion cue m9t so lien ket tinh theo Ii thuyet

Lien ket J.i (0) D¢ ion (%) Lien ktl j.J(D) oo ion (0/0)
C-H 0,35 6 -CONH2 3,40 -
O-H 1,24 25 C-N 0,49 9
N-H 0,84 16 C""N 3,44 -
F-H 1,78 39 C-F 1,43 30
CI-H 0,96 18 C-Cl 0,61 11
Br-H 0,76 14 C-Br 0,41 7
I-H 0,46 8 C-I 0,11 1,8
C-O 0,89 17 C-S 0,03 0,5
C=O 2,25 - -S02- - 4,25 - Bier rnornen IU5'ng eire, dua vao phep t6ng hop vecto ta co the tinh dtroc gan dung rnornen luang eire cua phan ti'r dan gian, Nguoc lai, neu bang thuc nghiem xac dinh dtroc mornen luang cue cua phan ti'r, dua vao quy tac phan tich vecto cung se xac dinh duoc morn en luang eire cua lien ket, Bang I1.6 dAn fa rnomen hrong cue cua mot so phan til dan gian xac dinh bang thuc nghiern.

Mornen luang eire Hi mire do d¢ phan cue va la mot tinh chat quan trong cua lien ket va cua hop chat, bbi vi tirong tac hrong cue - hrong cue 13. mot trong nhilng yeu t6 gay nen lire hut gifra cac phan tir, til do chi ph6i cii tinh chat vat If va tfnh chat hoa hoc cua hop chat (xern muc §2.I.l).

69

Sang 11.6. Momen Iliang eve (thl!e nghi,m) cue mQt s6 phOn tu don gian

Hap chd: J1(D) Hf/p chi;'r f.-/(D) Hop chdt J1(D)
* 1,81 1,29 1,35
Me -F Me-NH2 C6HjF
Me-O 1,97 Me-SCN 3,34 C6HjCl 1,75
Me-Br 1,79 CHF3 1,60 C6HjBr 1,70
Me-I 1,60 CHCl3 1,00 C6 Hj-I 1,70
Me-OH 1,70 CHBr3 1,00 C6HjN02 4,00
Me-OMe 1,30 CHI3 0,80 o-C6H4Cl2 2,50
Me-SH 1,26 MeCOF 2,96 m-C6H402 1,72
Me-SMe 1,46 MeCOCI 2,71 p-C6H4C12 0,00
Me-SeMe 1,32 MeCOBr 2,45 o-OC6H4N02 4,63
Me-N02 3,40 MeCHO 2,68 m-OC6H4N02 " 3,40
Me-CN 4,00 MeCOOMe 1,77 p-CIC6H4N02 2,60 * Me = g6c metyl CH3

b) D9 phdn cue hod eua lien kef va eua phdn tif

Electron hi tieu phan tich dien co khoi lirong rat nho be (hau nlur khong dang ke so voi hat nhan), du dil tham gia lien ket cluing van co mot mire d¢ linh dong dang ke. Vi the, khi mot lien ket (hoac mot phan nr) chiu tac dung ella dien twang ngoai (gay ra boi mot ion hoac mot luang eire) thi se xuat hien mot luang cue cam irng cong them vao lu5ng eire san co nham lam giam b61: tac dung cua dien tnrong ngoai. Ngiroi ta goi do la sf! phdn cue hod lien kel (hoac phan til).

De dac trung cho kha nang bi phan eire hoa, nguoi ta dung khai niern d¢ phdn cue hod. Cac nguyen til (hoac ion) nho kho bi phan cue hoa han cac nguyen til (hoac ion)

1&1 boi vi cac electron cua no bi hat nhan gifr chat han, do do: .

- D¢ phan eire hoa cua cac nguyen tu (hoac ion) trong cling nhorn thi lang tu tren xu6ng duoi boi vi kich thiroc nguyen tu cang 1&1 thi lap vo electron cang d~ bi bien dang do tac dong cua dien tnrong ngoai,

- D¢ phan cue hoa giam tic trai sang phai trong mot chu ki boi vi dien tich hat nhan tang dii giii chat electron han.

- Nguyen tu trung hoa d~ bl phan cue hoa hon cation nhung kern bi phan eire hoa han anion nrong irng.

TIl[ du : D¢ phan cue hoa ella cac lien ket C-X se lang theo thtr nr C-F < C-Cl < C-Br < C-I. D¢ phan cue hoa ella lien ket It Ian hem. cua lien ket cr.

70

Su phan eire hoa cua cac lien ket se dong gop phan minh vao su phan cue hoa chung cua phan nr. D¢ phan cue hoa cua phan tir (kf hieu a) anh huang den ca tinh chat vat If va tinh chat hoa 119C cua phan t11 (xern muc §2.I.l). D¢ pharr eire hoa cua phan tir lien quan den mot hien tirong quen thuoc la su khuc xa anh sang cua hop chat rna dai hrong dac tnrng cho n6 lit chi 56 chiet suat n. Nguoi ta do chi s6 chiet suat bang mot dung cu dan gian goi Ht khuc X;,I ke, Tir chi s6 chiet suat n co the tinh duoc dQ phan cue hoa trung blnh a cua phan tir theo phirong trlnh Lorentz-Lorenz:

3M (n2 -1)

a=--x---

41tNd (n2 + 2)

M : khoi hrong phan tir ; N : s6 Avogadro; d : ti kh6i cua chat; n : chi 56 chiet suat.

Gia tri a d6i v6i mot so phan tu dan gian diroc dua ra a bang 11.7, a do co dua kern gia tr] rnornen luang cue cua phan 111 d~ d6i chieu va pharr biet 51! phan cue hoa v6i. su pharr cue ella pharr tu .

Bang 11.7. £)9 phon cue hoa trung binh cuo m9t so phOn tli don gian

P}Ulll tIt -24 3 fleD) Phd" ttt aJIO-24 em3 fleD)
a/IO em
He 0,2 0,00 H2O 1,48 1.84
H2 0,79 0,00 NH3 2,21 1.48
N2 1,76 0,00 CH4 2,60 0,00
CO 1.95 0,11 CH3Cl 8,26 1,97
CO2 2,65 0,00 CH202 6,48 1,58
HF [0,51] 1,78 CHCl3 12,61 1,00
HCl 2,63 0,96 CC14 10,1 0,00
HBr 3,61 0,76 CH)OH 3,23 1,70
HI 5,45 0,46 C6H6 10,36 0,0 DQ phan cue (tinh ra j.l, D) va do phan eire hoa (tfnh ra a/l0-24 cm3) co the bien d6i theo huang nguoc nhau. Chang han, trong day HX theo chieu tang s6 tlur nr, dQ pharr eire giam con dq pharr eire hoa lai tang. Nhln chung, phan tir cang IOn thl d¢ phan cue hoa cang IOn. Phan tir co nhieu electron 1t thi d¢ phan eire hoa cfing Ian. Giai thich duoc dieu do, cluing ta co the van dung de til cac hop chat dan gian trong bang 11.7 suy luan cho cac hop "chat phirc tap han. Ching han, co th~ cho rang dq phan cue hoa cua cac

metyl halogenua CH3X se tang theo trat ur F < Cl < Br < L Dieu do giup ta hieu duoc nhtrng quy luat chi ph6i phan trng hoa hoc ella chung.

71

§2. cAe LIEN KtT ytu

d nhiet d¢ thuong, da s6 cac chat hfru co a the long hoac ran, Dieu do clnrng to co t6n tai nhirng luc hut nao do giiia cac phan tiro 6 the ran, luc nay gifr cho cac phan tir b nguyen trong su sap xep trat nr cua rnang tinh th~ phan tiI. 6 th~ long, lI!C nay gifr cho cac phan til a trang thai chuyen dong hon don, nhung khong den mire chuyen dong hoan toan tu do. 6 the khi, khoang each giiia cac phan tu kha 1&1 den mire iuc hut gifta chung tro nen khong dang k~ va cac phan tir chuyen dong mot each 11,1' do.

Lire nrong tac giiia cac phan tiI tuy rat nho so voi hrc lien ket gitta cac nguyen tiI trong phan tiI nhirng cluing cling co nhflng d~c diem chung Ia a mot khoang each can bang nao do thl luc hut se chiem uu the, nho hem. khoang each do thi Il_IC day se phat huy Hie dung. Mat khac, ve ban chat (nhu se thay sau day) thi life tuang tac gii1a cdc phan ttl ciing tirong dong mot phan nao d6 voi luc lien ket hoa hoc, VI vay, ngiroi ta goi cluing la cac lien kef yeu. Lien ket yeu phd bien nhat giila cac phan tir Ia lien ket Van de Van rna ta vAn thuong goi Ia life hut Van de Van (Van der Waals). Cac lien ket yeu khac thtrong g<)p Ia lien kef hidro, lien kif cho nhan 6 phia: ehuye'n dien tich, ... Chfnh nhii'ng lien ket yeu nay giup ta giai thich duoc nhtrng tfnh chat vat If nhu nhiet d¢ nong chay, nhiet d¢ soi, tinh tan, ... cua cac chat hitu ca. Cling chinb nho nhUng lien ket yeu nay rna cac phan tir tiep c~n voi nhau de dan toi cac phan irng boa hQC. Sau day ta se xern xet 2 trong s6 cac lien ket do.

_ J

I· LIEN KETVAN OE VAN

1.Khiti ni~m vi lien ke't Van de Van

Nhu da: biet, lien ket ion diroc dam bao boi hrc hut tinh dien gitra cac ion trai dau, Ltrc luang tac do tl l~ thuan voi dien tich q va q' cua 2 ion va ti l~ nghich voi blnh phirong khoang each gitra cluing :

I

F - q.q

. 2

r

(1)

Lien kef Van de Van (Johannes Van Der Waals, Nha V ~l If Ha Lan, nguai giai thich ban chat Co hoc hrong tir cua lien ket Van de Van) cling co ban chat tinh dien nhung Ia mot Ioai lien ket yeu gifra cac phan tir, n6 diroc dam bao boi Iuc hut giiia cac luang cue

72

hoac luang cue cam ung (ki hieu lil p va p' tuong img). Lire nay giam rat nhanh thea khoang each :

(n> 2) ,

(2)

Lien kei Van de Van thuong duoc goi la luc hut Van de Van. Lire lien ket Van de Van a cac hop chat hiru co chu yeu g6m 3 loai : Lire wang tac luang cue - luang eire, luc wang tac luang cue - luang cue cam irng va hrc wang tac luang eire cam irng - luang cue cam ling.

a) Luc tuang tac luang cue -Luiing cue

Phan tir hop chat hiru co co cau tao tit nguyen tu cua cac nguyen t6 co d¢ am dien khac nhau, VI the trong phan tir luon eo nhfrng lien ket phan eire lam cho phan tic trb thanh mot luang eire (trir tnrong hop cac lien ket phan cue tao ra cac momen luang cue trier tieu IAn nhau), Thi du:

8+ 8- 8+ 8- /Cl /Cl
H-C C-Cl H - C,II'" Cl Cl- C ,II',. Cl
Cl Cl
~ ~ ~
fllk -:I: ° fllk -:I: 0 fl-:l:O fl=O Gia tri momen luang cue cua mot so lien ket da: dircc liet ke a bang Il.S, cua mot s6 phan tir dan gian diroc trlnh bay a bang 1L6. Cac luang eire lucri co xu huang sap xep sao eho cac cue trai dau lai gan nhau. VI the tuong tac gitra cluing goi Ia tuang lac dinh huang. Lire tirong tac luBng eire - luang eire diroc tinh thee cong thirc (2) voi n=4. Luc nay ti I~ thuan voi d¢ Ian cua luang cue p va p', vi vay cac phan tic co cac lien ket phan cue manh lam eho phan tic phan eire manh se nrong tac voi nhau rnanh. Chang han, tirong tac luang cue - luang eire a diln xuat halogen Ian han, d6ng thai kh6i hrong phan tir va d¢ phan cue hoa cilng Ian han iJ hidrocacbon, tam cho nhiet d¢ soi, nhiet dQ nong chay cung cao hon. Cis-dicloetilen phan eire nen soi iJ nhiet dQ cao han trans-dicloetilen:

fl = 1,89 D

fl = 0,0 .

b) Luc luang lac luiJng cue - luang C/fC cdm ung

Dum lac dong cua dien tnrong (cua ion hoac cua mot luang cue), mot lien ket khong phan eire hoac mot phan tir khong phan cue se tra thanh phan eire tarn thai, tue la

73

trong phan tiI dii xuat hien mot luiing cue cam ung - no dii bi phan eire hoa (xem muc 1.5). Luang eire cam trng nay tuong tac voi luang CI!C co dinh boi mot hrc phil hop voi cong thirc (2) voi n= 6. Tuong tac nay can duoc goi Ia tuang rae edm ttng. De biet diroc lien ket nao de bi phan cue hoa c6 the xem a muc § LIII.5.

c) Tuong tac luting cue cam ling -Lu/ing cue cam ling

Dei voi khi hiern hoac nhtrng chat rna phan tiI khong c6 lien ket nao phan eire nhu Hz, N2• °2"" va nhimg phan tiI khong phan C\!C nhu CH4, CCl4, ... thi lien 'ket Van de Van gifra chung duoc dam bao bci nrong tac lirong cue cam img - luang cue cam (mg. Ta co the hinh dung urong tac nay, chang han trong tnrong hop khi hiern, nhu sau : Ve tong the thi nguyen tu khi hiem khong phan eire nhirng vi cac electron luon luon chuyen dong nen 6' mot thai diem nhat dinh bat ki, trong tam dien tich am va dien tich dtrong khong trung nhau, do d6 sinh ra mot luang eire nhat thai. Luang eire nay tac dong toi cac electron cua cac nguyen nr ben canh lam xuat hien mot luang cue cam mg. Luong cue cam irng nay lai lam xuat hien mot luang cue dun ling khac, Cu nhu vay, moi nguyen tii nhat thai deu co the tro thanh mot luang eire cam ung, tuy khong phai la hang dinh va khong co chieu co dinh vi luon thay d6i, nhirng chung van urong tac voi nhau.

Lire urong tac giira chiing ti l¢ nghich voi r6 (cong thtrc (2) voi n:::o 6). Tuong tac luang eire cam ling - luang cue cam irng con diroc goi la luang lac khuec]: tan, duoc Nha V~t li hoc ngiroi Due la Fritz London neu ra nam 1930, nen can duoc goi la luc London.

L\1e khuech tan tuy yeu nhung co mat 6 bat kl ticu phan nao du 13 ion, IUOng cue hay khong phan cue, Lire khuech tan sinh ra tu wang tac cua cac hrong eve cam ling nen no phu thuoc VaG d¢ phan cue hoa (xern a muc §l.III.5), dong thai n6 phu thuoc vao s6 hrong electron trong phan til. 56 electron trong phan tu lai - phu thuoc vao s6 Iuong nguyen til trong phan til, vi vay phan til cang 100 thi hrc khuech tan cang Ian. Chinh lire khuech tan da dong vai tro quyet dinh trong lien ket Van de Van gifra cac phan tir kh6ng phan cue, va giup giai thfch VI sao khi khoi hrong phan til tang thi nhiet d¢ n6ng chay, nhiet dQ soi noi chung deu tang.

D6i voi cac chat hiru co nguyen chat, tire Iii cac phan tir dong nhat thi bao gia cling co tUC1Ilg tac khuech tan, con tUC1Ilg hl.c dinh hirong va cam irng thi chi co khi trong phan tir co nhfrng lien ket phan eire lam eho phan til tro thanh phan cue,

Ve mat dinh luong, neu nhu nang luong cua lien ket cong hoa tri vao co hang tram kl/mol thi nang luong cua lien ket Van de Van t6i da chi den hang chuc, CI,I tM, nang Iuong cua moi hop phan trong d6 nhu sau :

74

Tuang tac Luong eire - IUOng cue

Luong eire -Tufmg eire cam irng

Luong eire cam irng - luang cue cam irng

2. Ban kinh Van de Van

Nang luang, kllmol 5-;.-25

2-;.-10 0,05+40

Khi do khoang each giira hal hat nhan nguyen tu clo (dung clo a trang thai ran) nguoi ta thu duoc hai gia tri khac nhau nhu chi fa a hlnh II. l Ia, Gia tri nho han la khoang each gitta hal nguyen til clo lien ket voi nhau trong mot phan tiro D6 la d¢ dai lien ket (nhu da n6i a muc §2.III.2) rna mot mra gia tri d6 13 ban kinh cong hoa tri (muc §2.IU.3). Oia tri IOn han HI. khoang each giiia hai nguyen !l( clo khong lien kit do, fd khodng each Van de Van, mot nira khoang each do diroc goi 13 ban kinh Van de Van.

V gy, ban kinli Van de Van ta mQl m(a Hwang each ngdn nhdt giiia hai hat nhdn dong nhdt khong tham gia lien ke't vai nhau. Dol voi mot nguyen tir, ban kinh Van de Van luon IOn han ban kinh cong hoa tri nhirng no cling giam dan trang mor chu ki va tang dan trong mot nhorn nhir ban kinh cong hoa tri (hlnh 11.11 b).

a)

F
71
147
CI
110 104 99
190 185 180 b)

Hinh 1I.11. a} Xac dinh ban kinh cong hoa tri va ban kinh Van de Van l16i voi do d the'r.in

b) Ban kinh nguyen tlt (rwr) va ban kinh Van de Van (rvDV) cua mot vainguy~n tlt, pm

Hai hat nhan cua hai nguyen tii lien ket vci nhau kh6ng th~ lai gAn nhau han tcing . ban klnh cong hoa tri cua cluing, vi hie d6 lire day giira hai hat nhan se thang lire lien ket. Hai hat nhan cua hai nguyen tir a hal phan tir khac nhau se khong the: lai gan nhau han tcing ban kinh Van de Van cua chting. Nhir v~y, bin kinh Van de Van giup ta hlnh dung duoc kfch thiroc cua phan nr, bier duoc khoang each khong gian toi thieu rna cluing chiem giCi'. Bang II.g diln ra ban kfnh Van de Van cua mot s6 nguyen nr thuong gap.

75

Bang 11.8. Ban kinh Van de Van cua m9t so nguyen til

Ball kinh Ball kinlt Ban kinh
Nguyen ttl Van de Vall Nguyen til Vall de Vall Nguyen til Van de Vall
A pm A pm A pm
-H 1.24 124 -N 1.55 155 -Se 1,90 190
-c 1.65 165 =N 1,55 155 -Te 2.06 206
=c*} 1,77 177 '=N 1.60 160 -F 1,47 147
,=C 1.78 178 -p 1,80 180 -CI 1.75 175
-0 1,52 152 -As 1,85 185 -Hr 1,85 185
=0 1,50 150 -$ 1,80 180 -I 1,98 198 (*) mot rnra be day cua nhan thorn,

Neu so sanh cac gia tri trong bang 11.8 voi bang n.4 ta thay co mot diem b~t tlurong HI. 51! bien doi ban kinh Van de Van cua C, 0, N a cac trang thai lai hoa khac nhau khong dong dieu vcri 51! bien d6i ban kinh cong hoa tri hoa tri cua cluing. Co Ie nguyen nhan 18. do b cac lien ket 1t mat d¢ electron khong tap trung vao vung gifra hai hat nhan lien ket nhu a lien ket o, mat khac con phai ke den vai tro cua cac cap electron a cac obitan p khong tham gia lien ket nira.

3. Hinh d~g cua philn t.t

Nhu tren dff thay, phan tir co cau true va kich thuoc xac dinh. Chlnh cau tnic phan tir quy dinh hinh dang cua chung. Rat nhieu tinh chat Ii hoc, hoa hoc va hoa sinh cua cac chat phu thuoc vao hinh dang phan tir cua cluing. VI vay, Hoa hoc htru co hien dai 'fat chu y den viec xern xet hlnh dang cac phan tfr tu don gian, nho be den phirc tap, khong 10 nh ir phan tiI AND, enzim, ...

a) M6 hinh phdn til

De thay diroc r6 rang moi chi tiet ve hlnh dang phan tir, nguOi ta xay dung rno hinh phan tiI. Thong dung nhat Iii mo hinii qua cdu - thann nifi (mo hinh "rong") va mo hinb kilb! "ddc " , ngoai ra can co mo hinlt mgt dt) electron .... Hay xern thi du 2 mo hinh phan nr etan o hmh n.12.

a)

b)

H'mh 1112. Phan hi C2~

<1) M6 hinh y'Ud cau • thanh noi : b) M6 hinh khoi d<?c

76

M6 hinh qua cdu - thanh n6'i :

a mo hmh nay cac nguyen tu duoc nrong tnrng bang nhtmg qua cau ho~c nhtrng kh6i da dien co mau thtrong theo quy uac sau: C den, H trang, 0 do, N xanh, ... Cac lien ket cong hoa tr! duoc nrong tnrng bang nhfrng thanh n6i voi d¢ dai ti l~ voi d¢ dai lien keto a cac qua diu (hoac khoi da dien) co khoan nhtmg 16 dinh vi sao eho khi lap cap voi cac thanh n6i thl goc giua cac thanh noi dung bang goc lien ket (goc hoa tri), Cac lien ket b¢i thuong duoc bieu dien boi cac thanh noi hlnh eung (hlnh II. 13). Mo hlnh nay cho ta biet su phan b6 trong khong gian cua cac nguyen tiI trong phan til, eho biet goe lien ker va d¢ dai lien ket, con kfch thuoc cac qua cau (hoac kh6i da dien) thl khong bat buoc phai ti l~ voi kich thiroc cac nguyen nr.

a)

b)

Hinb Ill3. M6 hinh phan h1 etilen (a) va axetilen (b)

M 0 hink khot dt}ic :

6 mo hinh kh6i dac, moi nguyen tiI duoc nrong tnrng bang mot qua cau cat vat. Ban kinh cua qua cau tl le voi ban kinh Van de Van cua nguyen ui. Khoang each tit tarn den mat cat vat ti l~ vci ban kinh cong hoa tri cua nguyen nr. Cac ban kinh cua qua cau vuong goc voi cac mat cat vat lap vci nhau nhtrng goc bang goc lien ker (hlnh 11.14). Mau sac cua cac qua cau ciing duoc quy uae nhu d6i voi 0 rno hlnh qua cau - thanh noi.

I I ,

I

, I

-

Ban kinh CHT

cuaC .

, , ,

~

I ,

, ,

~

Ban kinh CHT Ban kfnh Vf)V ella C

a)

b)

H1n11 Il14. M~t eM cua mo hinh phan t& kh6i d~e. a) C2H4; b) C2H2

77

Nhin vao mo hlnh pharr til kieu kh6i dac, ta khong thay duoc cac lien ket (don, doi, ba), do dai cling nhu goc lien ket. Tuy nhien, mo hinh khoi dac lai 1.1 mo hlnh gan dung nhat so voi hinh dang thuc cua phan tl1. C6 the n6i no 1.1 ban sao, phien ban cua phan tl1 thuc. VI the, ngay nay khi nghien ctru tinh cha] cua cac chat, nhat Ia nhtrng tinh chat hoa sinh, nguoi ta rat hay dung mo hinh phan til kieu khoi dac, Mot s6 mo hin"h khoi d~c se duoc thay a cac muc sau.

b) Anh huang cua hlnh dang pluin tlr den nhiet d¢ nang chdy va nhiet d¢ soi

Chung ta da bie] cac chat co khoi luong phan 1U cang Ian thi nhiet d¢ soi va nhiet d¢ nong chay cang cao. Vay d6i voi cac chat dong phan thl nhiet do soi va nhiet do nang chay cua cluing co nhu nhau khong ? Hay xcm truong hop n-pentan va neopentan a hinh II.l5a.)

t~c - 16,5°C

t~ 9,4°e

t~c - 129,8°e

t~ 36,1°e

(1)

(2)

Hinh II. 15a cho thay phan nr neopentan co dang gao vci hlnh cau, con phan tir n-pentan thi gan voi hinh trong, hlnh tnrng hay hlnh banh day.

Vi sao neopentan co Ilhi¢t d¢ nang chdy cao han n-pentan ?

o trang thai tinh the, cac phan til sap xep theo mot trat 1\1' xac dinh, Phan til neopentan co dang hinh cau, co tinh d6i xirng cao d~ sap xep chat khit theo cit 3 chieu hon la nhiing phan tir n-pentan kern d6i xirng, Cang sap xep char khft thi khoang each giira cac phan tu cang nho va Il!C hut Van de Van cang Ion, do do can nhiet do cao hon de thang diroc luc hut do moi khien eho chat chuyen sang the long.

Vi' sao neopentan co nhiet d{J soi th{i'p han n-pentan ?

o the long, cac phan tu khong con sap xep tr~t nr nhu a the ran, chung chuyen dong nrong d6i han don, Khi nhiet d¢ gan voi nhiet d¢ soi, khoang each trung ·blnh giira cac phan tt'r neopentan va n-pentan tnr nen bang nhau nhirng dien tich tiep xuc cua chung thl khac nhau. Vi voi cling mot the tfch nhu nhau, hlnh cau se co dien tich be mat nho nhat do do, phan til neopentan co dien tlch tiep xuc voi cac pharr tu khac nho hon, lire Van de Van nho han so voi phan tii n-pentan, Vi the, neopentan co nhiet d¢ soi thap hon so voi n-pentan,

78

4. 51! dAy Van de Van va hi~u ung khong gian

a) 51/ dely Van de Van va cdu dang ctia phdn lIe

Khi hai phan tir hoac hai nh6rn nguyen tu trong mot phan tu lai gan nhau han khoang each Van de Van giua chung thl SC xuat hien mot luc day chung ra xa nhau. D6 fa S 1/ day V an de Van. Chinh su d& y Van de Van q uyet dinh cac cau dang ben cua phan lU dong thai cling gay fa nhimg anh huang den tinh chat li - hoa hoc cua chat rna ngiroi ta goi Ia hieu ling khong gian. n~ xern xet SI! day Van de Van, can sir dung ban kinh Van de Van (bang II.S) hoac tot han lit xay dung rna hlnh phan tu kieu khoi dac. Thi du, mo hinh 3 cau dang cua butan diroc trinh bay a hinh II.ISh.

Nh6 han t6ng ~ .. ban kfnh VDV

(1)

(2)

(3)

Hinh IU5b. M6 hinh 3 oi'u dang cua n-butan. (1) anti; (2) syn ; (3) che khuat hoan toan

Nhln vao rna hlnh phan tu butan ta thay: 6 cau dang anti khong c6 cap nguyen tir H nao xarn pham vao khoang ban kinh Van de Van cua nhau, tuc la khoang each gilta chung deu bang hoac Ian han t6ng ban kinh Van de Van cua chiing : 6 cau dang syn co mot cap nguyen tir H (rnoi nguyen lU H a mot nhom CH3) xam pharn vao khoang ban kinh Van de Van cua nhau, CI,I the la khoang each gifra cluing nho han tong hai ban kinh Van de Van; 6 cau dang che khuat hoan toan c6 toi hai cap nguyen tir H (moi cap a mot nhorn CH3) "chen Ian, xo day" nhau vi khoang each giira cluing nho hon tong hai ban kinh Van de Van. Chfnh vi cau dang che khuat holm toan kern ben nhat, cau dang anti ben nhat nen n-butan ton tai chu yeu a cau dang anti (xem hinh IV.ISb).

Cling chinh do II!C day Van de Van rna cac nhom the Ian dinh vao vong xiclohexan dang ghe khi a vao lien ket equatorial (e) thi ben hon so voi khi a vao lien ket axial (a). (Khi a lien ket axial n6 bi 51,1' day Van de Van voi hai nh6m the (hoac hai nguyen tir H) khac cilng a vi tri axial nhu no).

b J nu« ling khong gian loai I

Gilt su ta cho trimctyl bo (Me)B) vao mot hon hop darig phan tir g6rn trimetylamin (CH)hN va tritert-butylamin (t-C4H9hN thi se thu duoc san pharn nao la chu yeu, Hay xem xet cau true phan til cua chung a hlnh II. 16.

79

a)

b)

c)

HiOO Il16. Cau true phan b1 trimetylamin (a), trimetyl bo (b) va tritert-butylamin (c)

(dl.1ong vong cung net dtit ve thea ban kinh Van de Van)

Nhu da thay b muc §2.II.2, nguyen tu N trong phan tu trirnetylarnin a trang thai lai hoa sp3, co mot obitan sp3 chua mot cap electron chua lien ket, Con nguyen tii B a phan tu Me3B thi b trang thai lai hoa sp2 co mot obitan 2p trcng, thuoc loai thieu hut electron VI xung quanh no moi c6 6 electron. N61u6n co xu huang "Iffy them" 2 electron niia cho dung quy tde bat tif. Mu6n vay, nguyen tit B phai lai gan nguyen tit N cua phan tu trirnetylarnin sao cho obitan trong ella no xen phu voi obitan chua cap electron chua chia cua N de hinh thanh lien ket N ~ B rna doi electron dung chung la do N cung cap, VI the lien ket do diroc goi la lien ktt cho - nhan. Ket qua la hinh thanh phan tit rna dien tfch

am dircc chuyen tir N toi B. Nguoi ta goi do Ia phuc chuyln dien rich. 0 phirc nay, nguyen tu N c6 di¢n tfch hinh thirc la 1 +, nguyen tit B rnang dien tfch hinh thuc la 1-.

o phan nr tritert-butylarnin, do co t6'i 9 nhom CH3 xoe ra tu phia (hinh II.16e) an ngfr 16i vao, tuc che chan 16i tiep can cua phan ur Me3B v6i obitan chua e~p electron chua lien kei ~ua nguyen til N. Vi the lien ket gnra hai nguyen tit B va N rat kh6 co the hinh thanh va phirc chuyen dien tich se rat It co xac suat tao ra. Ngtroi ta noi nhom tert-butyl da gay ra hieu U'ng khong gian loat 1 V~y, hi¢u ung khong gian loai 1 La hieu ung eua cdc nhom thi co kich tlutilc km lam cdn tra Sf! fiip cq_n eua cac trung tam phdn ung a phdn ttl cac chat thorn gia phdn ung.

Nguyen nhan gay ra hieu img kh6ng gian loai I lit do hrc diy Van de Van. Vi the khi xern xet hieu iing khong gian loai I, ngoai viec clni y den cau tnic cua phan tu thi dieu quan trong lit phai chu y den ban kinh Van de Van cua nhirng nguyen tiI hoac nh6m nguyen tir a gan trung tam phan irng,

c) Hinh dang phdn ttt va hoc tiep nhan

Dt co duoc tuong tac hoa hQC, cac trung tam phan irng phai tiep xuc ven nhau du d~ sap xep lai cac lien ket hoa hoc, Muon vay, dau tien cluing ph iii tiep cdn vai nhau sao

80

cho viec hinh thank lien kef Van de Van la thudn loi, dong thai trann duac luc ddy Van de Van giiia cluing. Nguyen tile nay hien nay rAt diroc quan Him trong cac nganh Hoa sinh, Hoa duoc.

Chang han, trong thiet ke cac heat chat lam diroc lieu, nguoi ta rat chu y tci hinh dang cua phan tir, Bai vi rat nhieu cong trinh nghien cuu da cho thay cac phan ti'.r hoat chat khi vao trong co the se den nhtrng hoc tiep nhan (receptor site) rna 6 do no phat huy tac dung, Nhiing hoc tiep nhan nay c6 6 cac dai phan tiI nhu enzim, AND, ... Quan he gifia phan ttl heat chat vci dai phan tiI tiep nhan giong nhir la chla khoa va <5 khoa:

Hinh dang cua chla khoa phai phil hop voi 6 khoa thl moi phil huy diroc tac dung, Thf du a hinh 11.17, cac amin c6 cau tao rat khac nhau nhirng c6 chung mot nhom cau true in d<i\.m tren cong thirc phil hop voi mot kieu hoc tiep nhan nao do rna 6 day chung tac d(>og vao de the hien hoat tinh cua rnlnh,

OR

HO

OH

Histamin (chat gay di rmg)

Adrenalin (hornon tuyen than)

Triptarnin (ancaloit tlr cay xiem gai)

Serotonin

(0 vo nao, nr duy)

HOc phan (mg

Mescalin (chat gay ao giac)

Melatonin

(hornon tuyen tung, d6ng h6 sinh hoc tren nao)

H6c Hen k§t VDV

6 - HHHC1

Hinh [117. M¢t s6 amin co hoat tinh sinh hoc cao va so d6 h6c ti€p nhan chting

81

Nguoi ta cling da chimg minh diroc rang nhieu qua trlnh hoa sinh trong co th~ co lien quan t61 cac enzim hoat dong thea kieu "chla khoa" va "6 khoa" nhu diroc trlnh bay b so d6 tren,

Y nrong ban d~u ve cac hoc tiep nhan da co tit giifa the kl 20, trong thuyet "Hoa lap th~ ve mui", Theo thuyet nay thi hinh dang va tinh phan cue cua pharr tiI (clnr khong phai thanh phdn phan nr) quyet dinh mui so b¢ cua eMit. Thuyet nay cho thay moi quan he giira hinh dang phan tir va mui, Co 7 mui co ban nrong irng v6i 7 I01:\i hoc tiep nhan a co quan khtru giac, Bay hoc tiep nhan nay co hlnh dang khac nhau nhu hlnh tnrng, hinh ong, hlnh pheu .... Phan tir eo hlnh dang va kick tluroc phu hop voi hoc tiep nhan nao thi khi 19t vao hoc tiep nhan do se t1:\O tuong tac v6i dai phan tir tiep nhan lam phat sinh cac xung than kinh truyen ve nao bo. Bay mui co ban la mui long nao, mui X1:\ huang, mui hoa, mui bac ha, mui ete, rnui hat tieu (rnui cay) va rnui thoi. Hai mui eo ban cu6i cimg co lien quan nhieu den tinh pharr eire han Ia hinh dang cua phan tiro Ngiroi ta dua ra nhieu din cluing minh hoa eho nhirng gia thuyet tren. Thi du : cac phan tu campho, hexacloetan, xiciooctan, ... co thanh phan rat khac nhau nhung deu co dang giong voi hlnh tnmg nen deu co mui giong long nao,

A ..f

II - LIEN KET HIDRO

1. Ban chit lien ke't hidro

Nguyen tir hidro chi co mot electron, khi tham gia lien' ket doi electron dung chung lech han ve phia nguyen tir cua nguyen t6 co d¢ am dien 160 khien n6 tre nen gan nhu mot "proton tran". VI the no co kha nang tien 11:\i rat gan vo electron cua mot nguyen tir am dien khac do lire hut tinh dien giira cluing. Khi do mot lien ket yeu diroc hinh thanh,

nguoi ta goi d6 13 lien ket hidro. Nhtrng ion nhu u, Na+, ... khong the hlnh thanh lien ket kieu luang tl! nhu the duoc boi VI vo electron cua nguyen tir da ngan can cluing 11:\i qua gj,n vo electron cea cac nguyen tir khac.

Lien ke'l hidro hi mQI loai lien kil yell duoc hinh. thanh' khi nguyen tli hidro dd tham gia lien ket cong hod tri vai nguyen Iii eLla mQI nguyen l{/ tim di¢n mann Iai tuang tac voi mot nguyen Iii tim dien khac co c{ip electron chua lien kit (chua chia). C6 the bieu dien su tao thanh lien ket hidro nhu sau:

AX-H ... VB

X, Y thuong la F, 0, N (a Y co it nhat 1 cap electron chua chia). A va B 13 phan con 11:\i cua phan tir,

82

Lien ket hidro khong phil hop voi hoa tri cua hidro, vi vay trong nhieu nam ngtroi ta cho rang n6 c6 ban chat tinh dien. Nhung khi tinh toan ki cang, nguoi ta nhan thay n6 cling c6 ban chat ca hrong tu nhir cac lien ket khac gitta cac phan tiro Phan tfch nang hrong cho thay, lien ket hidro cling c6 dac tnrng cong hoa tri ro rang. D6 la lien k~t 3 tarn (X, H, Y) diroc dam bao boi hai cap electron, mot cap electron a lien ket X-H, mot cap electron chua chia a Y. Khoang each giira hai nguyen tu X va Y trong lien ket hidro X-H ... Y nho hem nhieu so voi tong han kinh Van de Van cua chiing, dicu do cho thay hai c~p electron d6 khong phai la rieng re, khong day nhau rna da co nrong tac trao d6i, chung khong dinh V! rna hop thanh obitan chung cho ca. 3 nguyen tu lien keto Tuy nhien, nguyen tir H van lien ket hflt d6i xirng voi X va Y, mot ben lien ket manh, mot ben lien ket yeu mac du su khac nhau la khong 1611 Him va thay d6i tuy tirng Wang hop cu the.

2. D9 b~n etia Ii~n ktt hidro

D¢ ben cua lien ket hidro phu thuoc nhieu yeu t6. Lien ket se manh nhat khi 3 nguyen tir X, H, Y nam thang hang. D¢ am dien cua X va Y cang 100 thi lien ket hidro cang manh vi the lien ket hidro yeu dan thee chieu F> 0> N > G, Br, S > P. Ngoai ra lien ket hidro con chiu anh huong bOi phan con Iai ella phan tiro Nang hrong cua lien ket hidro a mot s6 he dii duoc xac dinh nhu ghi trong hang 11.9.

Sang 11.9. Nang IUQng cua lien ket hldro (, mc}t so h •• kJ/mol

\. Niing Niing
Lien kef Hl*) Lien kef H¢(*)
luang lltqng
O-H ... O Phenol-Dioxan (CQ4) 21,0 N-H ... N Anilin-Piridin (~H12) 14,0
O-H ... O Metanol (CCI4) 39,0 N-H ... O=C 2-Piridon (CCI4) 18,0
O-H ... O=C Niroc- axeton (CCI4) 10,5 N-H ... O N-rnetyl axetamit (CCI4) 15,0
O-H ... O=C Axit axeric (khf) 30,0 N-H ... O Anilin- THF (Ce;H12) 12,0
O-H ... F Phenol- Floankan (CCI4) 9,0 N-H ... S NCNH-H ... SBu2 (CCI4) 15,0
O-H ... N Metanol-DMFA (CCI4) 15,5 N-H ... N 2-xianoetanol (CCI4) . 0,6
O-H ... N Metanol-Piridin (CCI4) 38,0 O-H. . .I 2-iodophenol (CCI4) 3,0
O-H ... N Phenol-NEt3 (CCI4) 35,0 O-H ... O Axit 2-rnotOoKibenzoic (CCI4) 14,0 (*) DMFA: Dirnetyl fornamit ; Cifl12: Xiclohexan ; THF: Tetrahidrofuran

Cac s6 lieu trong bang 11.9 cho thay, nang hrong cua lien ket hidro nho hem rAt nhieu so voi nang hrong cua lien ket cong hoa tri (bang 11.2) va Ian hem khong nhieu so voi nang Iuong cua chuyen dong nhiet a dieu kien thirong (- 3 kJ/mol). Chinh vi vay a trang thai long, su hlnh thanh lien ket hidro Iii thuan nghich, su d6t lien kt!t hidro co the

83

xay ra a ea hai phia cua nguyen tu hidro (ca phia lien ket manh va ca phia lien kel yeu han). Bang clnrng la khi cho metanol van "rnroc nang" (D20) roi chung cat thi se thu diroc metanol va "metanol nang" (CH)OD), "nude nang" va d. "nude trung blnh" (HOD) hin mroc tlnrong, Dieu do diroc giai thich nhu a SO' do hlnh II.I8.

CH3 -0 - H CH3 - 0 - 0 0-0-0

-

Hinh IL18. So d6 sir tao thrum va dlit lien ket hidro d dung dich metanol trong "nude n<}ng"

Tinh chat dac biet tren cua lien ket hidro khong nhtrng giup giai thich su trao dOi proton trong dung dich rna con giup giai thich nhieu qua trlnh hoa hoc va hoa sinh phtrc tap khac,

3. Uen kef hidro lien phan tit va n9i phan tit

Trong SI! tao thanh lien ket hidro, AX-H ... YB, hop phan AX-H dua nguyen tu hidro vao lien ket nen diroc goi la hap phdn clio hoac chdt cho, hop phan YB dira cap electron chua chia fa d~ "tiep nhan" nguyen tii H phan cue nen duoc goi la hap phdn nhan hoac chill nhan. SI! phan chia nhu vay cho thay co sl! nrong dong voi luang tac axit - bazo, va thuc ra 51! tao thanh lien ket hidro thuong Iii khoi dau cho phan tmg axit - bazo, Thi du, ave trai trong can bang sau CH)COOH la chat cho, NH) lit chat nhan, con

ave phai thi NH4 + la chat cho. CH)COO-Ia chat nhan :

H, H,+

H-N···H-O CH3 ~ H-N-H"'O CH3

H/ "C/ H/ 'C/

II II

o 0

Lien kitl hidro rna hap phdn cho va hap phdn nhdn a hai phdn tit (khacnhau hoac gicfng nhau] goi la lien ket hidro lien phon tii. Thi du:

CZH5 <,

O-H· .. O-H ... !

C2H5

C,H5"",,- rR.

- ... O-H ... NQ

84

Lien kit hidro rna hap phdn cho va liap phdn nhdn deu J cling mot phtin tlt goi lil lien kei hidro nlJi phdn tu. Thi du.

CH CH CH

3,~ ~C/ 3

II I

0. 0 "'H/

De tao duoc lienket hidro noi phan nr, hop phan cho va hop phan nhan phai 0 hai vi tri sao cho H c6 the tie'p cdn vai obitan chua doi electron chua lien kef Clia Y, khi do tlurong tao ra vong 5, 6 hoac doi khi 7 canh (xcm thi du tren). Lien ket hidro noi phan tii thirong ben han lien ket hidro lien phan tiI. Vi vay, neu hai hop phan eho va nhan trong mot phan tlt da tao thanh lien ket hidro noi phan nr thi cluing khong tham gia vao lien ket hidro lien phan tiI nira.

,

4. Anh hlldng cua lien ke't hidro den tinh chit v~t li

Phan tir khoi M, momen luang cue 1-1, nhiet d¢ nong chay tnc, nhiet d¢ soi ti; va d¢ tan trong mroc s (tinh bang s6 gam trong 100 gam ruroc) cua cac chat dliU tien (trir elan) - trong mot s6 day d6ng dang (eo phan tiI kh6i hon kern nhau kh6ng nhieu tam) duoc dan ra d bang II. 10 diroi day.

Bang II. 10.Tinh chat vc;.t Ii cue m9t val hQp cheSt ddn gion

GIrGI3 CH2=O GIrNH2 CHrOH CHrF CHrOCHJ GIrCI
M.dvC 30 30 31 32 34 46 50,5
j.l,D 0 2,33 1.31 1,70 1,81 1,30 1,97
°c -172 -92 -92 -98 -142 -138 -98
tn.:,
~, °c -89 -19 -6,7 65 -78 -24 -24
s, g/IOOg 0,007 -40 ratt6t vo han 0,25 7,6 0.4 .0 muc §2.1 cluing ta dii thay rang khi phan tiI kh6i tang, momen luang cue cang IOn thi nhiet d¢ soi va nhiet dQ nong chay cang eao. Trong bang II. 10, etan vira eo phan tii kh6i thap nhat vira khong phan cue (u = 0) nen co tnc va t, nho nhat. The nhung d6i voi nhiing hop chat con lai thi su bien doi ~c va ts lai kh6ng tuan thea quy luat do. Chang

85

han, CH3F, CH3Cl vira co phan tit khoi Ian han vira co momen luang cue Ian han nhung lai co tnc va ts t~ap han CH3NH2 va CH30H, ... Nguyen nhan lam cho tnc va ts cua CH3NH2 va CH30H cao han so voi nhieu chat khac trong bang la do a trang thai long va cit trang thai ran cluing tao diroc lien ket hidro lien phan til':

CH3 CH3

'\. '\.

O~H ... O-H ... O-H ... . /

CH3

CH3 H... CH3

-, '\. -,

N-H ... N-H ... N~H ...

/ / /

... H CH3 R ...

Cac phan til' CH2::;:O, CHrF, CH30CH3 chi co mot hop phan nhan rna khong co hop phan cho, con a CHrCI khong c6 hop pharr cho cling nhu hop phan nhan nen a trang thai nguyen chili cluing khong tao diroc lien ket hidro. Ngoai fa, can luu y rang klch thuoc va hlnh dang cua cac pharr tiI cflng la mot trong nlnrng yeu to anh huang den

tnc va ts. Nhu vay, neu phan til' khoi, momen luang cue, hlnh dang pharr tit khong khac nhau nhieu thl chat nao tao duac lien ktt hidro lienphan tit, chdt do co tile va ts cao han so viti chat khong tao duac lien klt hidro lien phdn tli.

Bang 11.10 con cho thay cac chat tan tot trong mroc la CH2::;:O, CH30H va CH3NH2.

Nguyen nhan la do cac chat nay tao duoc lien ket hidro ben voi ruroc : Ch.1ng han lien ket hidro cua CH30H voi mroc da diroc bieu dien a hlnh 11.18 ; CH2::;:O va CH3NH2 khi tan trong mroc co phan irng voi nu6c:

CH2::;:O + H20 ~ CH2(OHh CH3NH2 + H20 ~ [CH3NH3tHO-

Ca chat dtlu IAn san pham cua phan irng deu tao diroc lien ket hidro ben voi nuoc.

Han ntra, cac chili CH30H, CH3NH2, CH2(OH}z vira co the d6ng vai tro chat cho, vira co the dong vai tro chat nhan khi tao lien ket hidro v6'i nu6'c. Nhir vay, nhilng chdt tao lien ktr hidro ben viti nhau thi tan rot vao nhau.

Lien ket hidro noi pharr til' anh huang den Inc' ts va dQ tan khong giong nhu iien ket hidro lien phan hr. Trong nhiing chat d6ng phan hoac nhiing chat co cau tao nrong II! nhau, chat nao tao lien kef hidro noi phan tit thi co tllC' ts thdp han, d(J ran trong dung moi phdn cue thdp han, d¢ ran trong dung moi khong phdn cue cao han so viti chdt tao lien ktr hidro lien phan rit. Thi du:

86

......-H. H'" H'"
6-) a"""- a"""-
r6l p .. ¢
, N~a
N~
a .,?N"
a a···
Lien ket hidro NQiphantir Lien phan tir Lien phan tiI
loc, DC 45.7 97 115
ts, DC 214,5 194 (70 mmHg) 279 (phan huy)
Tan trong lOOg H2O 0,21 g 1,35 g 1,60 g
Tan trong benzen lanh nong nong §3. SI/CHUYEN DICH M4T DO ELECTRON is

.... ,. ",,'-

PHAN TtfHIJP CHAT HIRJ CO'

Electron Ht tieu phan linh dong nhat trong phan tir, du chua tham gia lien ket hoac da. tham gia lien ket no deu co th~ bi dich chuyen bci anh huang nrong he; cua cac

nguyen tir trong phan tiro .

Thuyet Dich chuyen electron xuat hien tit nam 1920, tnroc thai kl phat tri~n cua Thuyet Obitan phan til (khoang 1950). -Dan gian va de hieu, no da. giup giai thich da s6 cac dii' kien thuc nghiem co lien quan den cau true, tinh chat va kha nang phan ling cua cac hop chat htru co, vi vay no da. diroc <ip. dung rong rai cho den nay. SI! dich chuyen mat dQ electron duoc phan thanh hieu ling cam ung, hieu ling truang, hieu ifng lien hap va hi¢u ung sieu lien hap, diroc goi chung la hieu ung electron .

.A. rtf' ., (I'

I - HI~U UNG CAM UNG

1. Him cha"t va d~c di~m

Hay xet thi du ve anh huang ella nguyen tir clo den Iuc axit trong day sau: .

Axit:

x, (25DC) -5 1,54.10

1,39.10-3

CH3-CH2-CH2-caaH CH3-CH2-CH-CaaH I

Cl

87

CH3-CH-CH2-COOH I

CI

8,9.10-5

CH2-CH2-CH-COOH I

Cl

3,0.10-5

Nguyen tir do lam tang hrc axit cua axit butanoic, khi nguyen tit do ding a gan nhom cacboxyl (COOH) hrc axit cang tang. VI sao vay ?

a rnuc § 1.III.5 da cho thay lien ket giira hai nguyen til co 0(> am dien khac nhau Ia lien ket cong hoa tri phan ,,=1'C, mat o¢ electron bi lech ve phia nguyen tit co o¢ am dien Ian han, nguyen tiI co 00 am dien kern han do hi thieu hut electron nen se mang mot phan dien tich dirong (0+). SI! phan cue a lien ker C-Cl kh6ng chi c6 dinh a lien ket do rna Ian truyen theo mach lien ket cua phan tu lam xuat hien cac dien tfch dirong a cac nguyen tu khac cho den t~n nhom cacboxyl. Tic dung nay lam tang cirong str phan q1'C

cua lien ket O~H, lam 6n dinh nhom cacboxylat (-COO-) do do lam tang It!C axit:

0+

CH3 -CH2 -CH~COOH

"-

Clo-

0+ 0+

CH3 -CH~CH2 ~COOH J-

Cl

0+ 0+ 0+

CH2 ~CH2 ~CH2 ~COOH

"-

CI

S,! dicb chuyln mdt d¢ electron doc theo mach. lien kef a trong phan til gay ra bdi Sf! chenh. [¢ch ve d¢ am di¢n nhu tren duac goi fa hieu ling cam ung, kf hieu bang chii' I (Inductive Effect) va duoc chi bang mi1i ten thang huong ve phia nguyen tir co d(> am dien 160 han.

Trong thf du tren, khi nguyen til Cl a vi trf a so voi nhom -COOH thi lam tang K, len 90 tan, a vi tri ~ thl lam tang K, len gan 6 Ian, con a vi trf y chi lam tang K, len gan 2 Ian, Nhu vay, dfJc dilm ella hieu U'ng edm ung fa gidm rat nhanh khi scI lien ktl rr rna no phdi truyen qua tang len.

2. Phan lO{li

Trong thi du tren, nguyen til Cl gay ra hieu irng cam ling bang each "hut" electron ve phia mlnh, ngtroi ta noi rang no gay hieu ung com ung am, ki hieu la -1. Nhiing

88

nguyen tll co d¢ Am dien 16n han C khi dinh voi C deu Ia nhilng nhom hut electron tuc la nhom gay hieu irng -1. D¢ 100 cua hieu U'ng cam irng am tang thea d¢ am dien cua nguyen tu hoac nhom nguyen tll gay ra hieu irng do:

-I < -Br < -CI <-F

-NH2 < -OH < -F

DQ am dien cua nguyen tll b cac trang thai lai hoa khac nhau tang theo ti I¢ electron strong obitan lai hoa (xem muc § 1.111.3) theo trat ttl sau :

Vi the, cac nhom khong no deu la cac nhorn hut electron theo hieu irng cam irng, nrc la nhorn co hieu irng -1. va do lon cua hieu irng -I cling tang theo d¢ am dien cua cac nhom do:

-C=C < -C=N < -C=O

Neu viec thay nguyen tu H thanh nguyen tu Cl dii lam tang hrc axit cua nhorn -COOH thi viec thay H thanh cac nhom ankyl lai lam giarn hrc axit cua no. Thi du:

-4 1,72.10

CHrCOOH -5 1,76.10

Axit

H-COOH

-5 1,34.10

-6 9,4.10

Nhu vay, cac nhom ankyl khong "hut" electron nhu clo rna lai "day" electron.

Ngiroi ta noi rang, cluing gay hieu ung cam ung duang (kf hieu +1) va duoc chi boi mui

ten thAng, thi du CH3~' CzH5~' ... D¢ manh cua hieu trng +1 cua cac nhom ankyl tang theo mire dQ phan nhanh cua cluing:

II - HI~U lING LIEN HQP VA SIEU LIEN HQP

1. S,! lien hqp 1t-1t

Khi cac lien ket boi (doi hoac i?a) b each nhau dung mot lien ket dan thi tao thanh mot he lien hop, trong do cac electron 1t b lien ket boi nay xen phu voi cac electron 1t b lien kei boi khac. Vi vay, ngiroi ta goi do la S~( lien hap x-n: Thi du:

89

Lien hop :

CH2 = CH - CH = CH2

Khong lien hop :

CH2 = C = CH - CH3

c o

CH2 = CH - C == C - CH3

CH2 =CH-CH2 -C= CH CH2=CH -CH2-CH=O

Trang muc § 1.11.2 da xet su tao thanh lien ket dan, lien ket boi thea quan diem cua thuyet VB (thuyet Lien ket hoa tri). De gilli thich S1! tao thanh lien ket a cac he lien hop cling nhir nhieu tinh chat cua he lien hop thl thuyet MO (thuyet Obitan phan nr) to fa thich hop va hiiu hieu han. Ta hay xet tnrong hop dan gian Iii. butadien. Thee thuyet MO, bon obitan 2p a bon nguyen tiI C lien nhau co the xen phu voi nhau. Su t6 hop 4 obitan

2p do dan toi 2 obitan phan tic lien ket Xl' 7t2 va 2 obitan phan tic phan lien ket 7t;, x:.

*

Obitan 7t2 la obitan bi chiern cao nhat (HOMO), obitan 7t3 la obitan khong bi chiem

thap nhat (LUMO). Hinh dang va nang luong cua cluing diroc trlnh bay a hlnh II.19.

7t3 (LUMO)

7t2 (HOMO)

E = - 1255 kJ mol-1 (- 300 kcal rnor")

Hinh Ill9. Cac obitan 1t d buta-l,3-dien

90

Cac mCtc nang IlI9ng (kJ/mol)

E

-t+- -1255

+750

-- +345

-t+- -960

Hinh 11.19 cho thay 0 trang thai co ban, mat de) electron 1t khong chi tap trung 0 giira hai nguyen tir CI-C2 va C3-C4 rna con tap trung a giira hai nguyen til C2-C3. Noi

mot each khac, obitan phan tir 1>6n nhat la obitan 1t] bao trum ca 4 nguyen tir C, electron 1t diroc chuyen dong tir do trong d. he do, vi the rna no duoc goi HI. he lien hop 1t-7t. o cac phan tu rna cac lien ket boi (j each xa nhau tir hai lien ket dan tro len thi cac obitan p

. khong the xen phu voi nhau diroc, khong tht tao ra obitan 1t chung cho ca phan tu nen khong tao thanh h~ lien hop duoc.

2. Slllien hcJp 1t-p

Khi mot lien ket boi (doi hoac ba) b each mot obitan p dung mot lien ket dan thl tao diroc h~ lien hop 1t-p. Thi du:

Lien hop :

..

CH2 = CH - CI

Khong lien hop :

CH2 = CH - CH2 - CI

OF

Trong cac cong thtrc a hang tren, mac du cac cap obit an p da xen phil ben voi nhau tao ra lien ket 1t, nhirng obitan 1t do lai b ngay sat obitan p cua cac nguyen til Cl, F hoac C ben canh, do do chiing lai xen phu tiep voi nhau. Ta goi do Ia su lien hr;p it-p, Thuyet MO khong xern xet rieng re tirng lien ket nhu vay rna coi cac he lien hop tren la nhimg he gem n tarn lien ket, moi tarn co mot obitan p. Xet tnrong hop n = 3, t6 hop 3 obitan p

dan tui 1 obitan lien ket 1tj, mot obitan khong lien ket 1t2 va mot obitan phan lien ket n; rna hlnh dang va muc nang hrong cua cluing diroc th~ hien b hlnh H.20.

Hlnh H.20 cho thay su tao thanh MO la gi6ng nhau nlnrng so electron a cac MO thi

+ .

khac nhau d6i voi cation anlyl CH2 = CH - C H2 (a), g6c tv do anlyl CH2 = CH - CH2 (b)

va anion anlylCH2 = CHCH2 (c). Sb di nhu vay VI trong s6 3 obitan p dong gop vao he lien hop, a cation anlyl co mot obitan p trong (khong co electron), con b anion anlyl thl co mot obitan nguyen tir chua 2 electron p.

Nhu vay, chuyen dong trong tnrong lire ba hat nhan cua he lien hop a cation anlyl co 2 electron, b g6c anlyl co 3 electron, con b anion anlyl thi co 4 electron (hlnh 11.20).

91

~ ~ ~
, ~ -'
~ . -
Hinh danq obitan l.oai obitan a) b) c)
-<......:: .....
~~®)H :n:; (Phan lien ket)
H7~~'\~ (LUMO)
~"?\ ~~~i
"'tl"-· ....
~~ ..
~~:~'~ ~
~'>""";.~~' 0 ~H
'P'IIJ-,.. ... _"'lrl'~ + -t+-
..... "'-~ .... 7t2 (Khong lien ket)
H~ ~t~·'1'
. 'H r;'__~1
'11:':' _-: (LUMO) (HOMO) -t+-

(HOMO)

+ .

Hinh 1120. Cac obitan rt d cation CH2 = CH-CH2' g6c CH2 = CH-CH2'

anion CH2 = CH - C H2 va s~ phan b6 electron d chung

3. Hieu (mg lien hdp

. .

Nhu b tren da thay, cac electron 7t hoac p khi tharn gia lien hop thi khong con khu tni rieng b mot vi tri nao, rna chuyen dong trong roan h¢ lien hop. Tuy nhien, mat d¢ electron b cac vi trf khac nhau la khong nhu nhau, rna khac nhau tuy theo ban chat cua cac nhorn nguyen tiI tharn gia lien hop, Khi cac nhorn nguyen tiI lien hop voi nhau thi

mat d¢ electron 1t hoac p cua cluing bi thay doi, bi chuyen dich. Ngiroi ta goi do la hleu ung lien hop, ki hieu la C (xuat phat tit Conjugation effect).

Thi du : 0 phan tit 1,3-butadien, hieu irng lien hop da lam cho mat d¢ electron 7t dich chuyen tu lien ket doi den lien ket dan C2-C3, hau qua la lien ket doi Cl=C2 va C3=C4 tro nen dai hem lien ket C=C a he co lap, con lien ket dan C2-C3 thi ngan han

mot cluit so voi lien ket dan blnh thirong. 0 phan tu propenal (CH2=CH-CH=O), nguyen tu 0 co d¢ am dien 100 gil! chat electron rt han so voi nguyen tiI C nen ket qua ella 51! lien hop a day la mat d¢ electron 7t d6n v6 phia nguyen tii 0 lam cho no mang dien tieh 0- con nguyen tir C3 thi mang dien tich 0+. Hieu irng lien hop a hai thi du tren diroc minh hoa duci day va dtroc bieu dien bang miii ten cong :

92

Khi tham gia lien hop, nhom nao "hut" electron rt hoac p ve phia mlnh thl diroc coi la co hieu {mg lien hap am, ki hieu la -c. Cac nh6m gay hieu ling -C la cac nh6m c6 lien ket boi vai nguyen nr co d¢ am dien lon, hoac cac nhorn mang dien tich 1 + voi obitan p tr6ng.

ru d(1 :

-C=N- -C""C-, -C""N,

I '

-s=o

+

-CI

Nhiing nh6m nguyen tl1 nao khi tham .gia lien hop rna "day" electron toi nhom khac thi duoc goi la nhom co hieu ung lien hap duang, ki hieu la +C, Cac nhorn gay hieu ung +C thuong la cac nguyen tl1 c6 1 hoac I cap electron p chua chia (ll! do). Vi cac electron nay chua tham gia lien ket nen rat linh dong; du nguyen tl1 mang cluing co d¢ am dien Ian hay nho thi bao gia chung cung dich chuyln tai cluj kem linh drug han (nrc la tai cho c6 cac electron n, hoac cho co obitan tr6ng).

Thi du:

8-

F~O-

8-

M(Jt nhorn the hien hieu ling -C hay +C con tuy thuoc vao luang quan voi nhorn lien hop voi no. 6 cac thi du dum day nh6m C=C va C6Hs khi thi the hien hieu irng -C, khi Ihi the hien hieu rrng +C.

8~ ~-

CH2 =CH - CH2

+C

-'C

+C

-C

6 cac thi du tren cluing ta thay rang khac voi hieu irng cam ling. hieu LIng lien hap gay ra SI! phan bo' xen ke- dell ddn cac vi tri "giau" va "ngheo" electron Jr. Nhorn gay hieu irng +C lam xuat hien cac vi tri "giau" electron (ki hieu 6-) xen ke voi cac vi tri khong giau electron. Nhom gay hieu img -C lam XU;}t hien cac vi trf "ngheo" electron (ki hieu 0+) xen ke vci cac v] tri khong bi ngheo electron. Tac dung nay Ian truyen trong toan mach lien hop, khac voi hieu irng cam ling, no khong hi gidm khi keo dai macn lien hap, thi du:

0+ t::::\ 0+ ~ 8+ 8-

CH 3 - CH = CH - CH = CH - CH ,[(j

93

Hieu ling lien hop chi phat huy lac dung khi s1,I lien hop (nrc su xen phu ben) cua cac obitan 1t voi 1t hoac P duoc dam bao (xern rnuc 1,2 d tren), Mu6n vay, cac nguyen tir tham gia van he lien hop phai cling nam tren rnQt mat phang (dong phang) de dam bao cho true cua cac obitan p tham gia lien hop song song voi nhau. Trong thi du sau day, a

phan tir A nh6m -N02 nam tren cling mat phang chua vong benzen nen phat huy duoc hieu irng lien hop toi tan nh6m -DH ; Con a hop chat B, do hai nh6m -CH3 dii chiern giU mat khoang khong gian khien cho nhorn -N02 khong the nam tren mat phang cung voi vong benzen duoc, su lien hop giira chung bi vi pham, VI the hieu irng lien hop cua nhom -N02 khong anh hirong toi nhan benzen va nh6m -DH:

° :H CH3

~N:v.=:OH (A)

° ~

J.:l/ CH3

Ker qua lit 19c axit cua A Ian hon rat nhieu so voi B. Nguai ta noi a hop chat B dii xay ra hieu ung khong gian loai II : hieu trng khong gian lam vi pham tinh dong phang ella he lien hop,

4. Hi~u itng cqog httdog, hi~u itng mesomer va hi~u itng Hen hyp D~ giai thich su dich chuyen mat d¢ electron a he lien hop thea quan diem cua thuyet cong hmrng, ngiroi ta dung thuat ngu hleu trng c(mg huang (Resonance effect, ki hieu R) hoac hieu U'ng mesomer (Mesomeric effect, ki hieu M) thay cho thuat ngtr hieu irng lien hop va bieu dit~n chung boi su dich chuyen cii cap electron 1t hoac p tir vi tri nay sang vi trf khac (thea chieu mtli len cong nhu khi bieu dien hieu ling lien hop), Khi d6 se tao ra cac cau tnic gi6i han (muc §l. 1.3). Thi du diroi day so sanh each bieu dien hieu irng lien hop (C) voi each bieu dien hieu irng cong hirong hoac mesomer:

8+ 8-

Hieu ling C : CH2 =~ CH ro

+ -

Hieu tfug R CH2 -CH = CH - 0

(hoac M):

Tuy each thuc bieu dien sir dich chuyen mat d¢ electron c6 khac nhau, nhimg ket qua thi nhu nhau, nrc la cung chi ra diroccac vi tri nao giau electron (0- hoac dau -), cac vi tri nao ngheo electron (0+ hoac dau +) trong he lien hop. Nhu vay, hieu ling lien hop,

94

hieu irng cong hireng. hieu irng mesomer chi la ten goi khac nhau cua cung mot hien nrong, VI the co the van dung cac each bieu dien do sao cho thich hop vci tung d6i tuong ClJ the.

5. Hi~u itng sieu lien hqp

Ngiroi ta nhan thay ding, nhom -CH3 va cii cac nhom ankyl khac khong chi dan thuan la nhom day electron thee hieu irng cam img (+1) rna khi a vi tri a. so voi mot lien ket boi hoac mot obitan p no cling the hien mot chut luang tu nhu hieu irng lien hop cua mot lien k;et boi. Ngiroi ta cho rang, cac lien ket C - H i:J vi tri lien hop voi lien ket boi hoac voi nguyen tu chua obitan p da the hien hieu ung sieu lien hop, ki hieu la H (Hyperconjugation), bieu dien boi mui ten congo Nguyen nhan cua hieu irng sieu lien hop, thee thuyet Cong huong, la do co su lien hop cr - 1t hoac cr - p khi electron cr 0 vi tri lien hop voi obitan 1t hoac p. S,! lien h9P do lam dich chuyen electron cr vao he lien hop,

Nho hieu 6n.g sieu lien hop, ngiroi ta moi giai thich diroc vi sao cac tieu phan chua nguyen tu C, bA"t ke mang dien tich duong (cacbocation), mang dien tich Am (cabanion) hay mang electron doc than (g6c cacbo ttl do), deu tro nen ben vftng han khi i:J vi tri a. so voi no co cang nhieu lien ket C - H. Chang han d¢ ben ella cacbanion trong day sau lang thee so lien ket C - H sieu lien hop :

S6 lien ket C - H lien hop :

o

3

<

<

Cacbanion:

Neu cho rang nhorn CH3 chi gay ra hieu img cam irng duang (day electron) thi khi co cang nhieu nhom metyl d¢ ben cua cacbanion se cang giam chir khong tang nhu a day tren, 6 thi du tren, mtli ten cong chi su sieu lien hop chu khong chi chicu dich chuyen electron.

95

Chinh hieu ling sieu lien hop cua nhom -CH3 dii lam bing momen lirong cuc-cua h¢ lien hop sau_ so voi tinh toan theo quy uie cong vecto :

11 (0) tinh : 11 CD) do :

H0cH=~CHIO 3,26

3.67

r» CH3 - CH2 ;_ CH2 - CH == 0

2,54

2,57

Cac nhorn ankyl thirong gay hieu ling sieu lien hop dirong (ki hieu +H) va d~ Ian cua hieu ung do bien d6i thee trat tl! ngiroc voi tf~t ur ve dQ Ian hieu ung +1 cua chung :

Hi~u Ung +1

-CH3 < -CH2CH3 < -CH(CH3h < -C(CH3h

-CH3 > -CH2CH3 > -CH(CH3)z > -C(CH3)3

Hi¢u ung +H

Ngiroc voi lien ket C - H, cac lien ket C - F khi a vi tri lien hop thl gay fa hieu ung sieu lien hop am (ki hieu -H). Thi du nhorn -CF3 tam cho mat dQ electron a cac vi trf 0, pella nhan benzen ngheo hem so voi a vi tri meta:

1 6 _

§4. PHAN ((NG HUU CO

o muc §3 cluing ta dii xem xet hieu irng electron, tire HI. cac hieu trng lam dich chuyen mat dQ electron. tam bien d6i lien ket trong phan ta hop chat heu co nhung khong pha va phan tlr, cling khong hlnh thanh phan tlr moi. o muc nay chung ta se xem xet su bien dlSi cac lien ket trong phan tu a mire phi va lien ket eli, hlnh thanh lien ket moi duoi tac dung cua cac dieu kien va tac nhan phan ung din tci tao thanh phan tiI maio £)6 la phan ling hoa hoc cua cac hop chat htru co, noi gon la phdn Ung hiiu co.

Sir pha va va hinh thanh lien ket trong phan tiI hilu co co the xay fa thee kieu phan cue goi la phdn ung phdn cue (Wc phdn ung di Ii) hoac thee kieu khong phan C\!C, nhu phan (rug voi. Sl! tham gia ella go'c tu do hoac phdn lmg lrJp vong dong btl. goi chung la phdn ung khong phdn cue (tire phon Img dong li).

96

.~.::-'

, ....

<l>' ,

I - PHAN ONG PHAN eve (PHAN ONG D! LI)

1. Cacbocation va cacbanion

Dum. hie dung cua cac dieu kien phan Ung nhat dinh, nhtrng lien ket phan cue trong phan tiI co tht bi phan cAt khong dong d~u : nguyen tll' co d¢ am dien IOn hen chiem c~p electron dung chung va tro thanh tieu phan tich dien am, con nguyen tit voi d¢ Am dien nbC, hem thi tro thanh titu phan tich dien dirong. S,! phan cat lien ke't khong dong d~u nhu the' goi la sl{ phan edt di li, va phan ling duoc goi Ia phdn Ung di ii hay phdn ung phan cuc :

(CH3hC ~r - (CH3hC + Br- (1)

~ +- - - +

(C2HSOOC)zCH - H + NaOC2HS - (~HsOOC)zCH Na + C2HS - OH (2)

(3) .

Cation (CH3hC co mot nguyen tu C mang dien tfch quy udc 1+ vi the no diroc goi Iii. cacbocation, ki hieu R+, Anion (CzH500ChCH- co mot nguyen tiI C mang dien tlch quy ucrc 1- nen no diroc goi Iii. cacbanion, kf hieu la R-. Khac voi cac ion vO co, cacbocation va cacbanion la nhilng tieu phan rdt khong ben. cluing chi sinh ra tuc thoi trong qua trlnh philo img roi bi bien d6i ngay thanh cac hop chat ben han. Vi the' chang thuoc loai cac tilu phdn trung gian trong phan Ung hnu co, £>¢ ben cua cacbocation va cacbanion phu thuoc VaG cau tnic cua cluing : nhirng yeu t6, nhung hieu (Jog electron nao lam giai toa (giam bot) dien tich dirong hoac Am 0 nguyen tu cacbon thl se lam cho cacbocation va cacbanion ~n hon, Vi the d¢ ben urong d6i cua cluing dUQc sAp xep chang han nhu sau :

+ + + + + +

C{)HsCH2 > CH2 = CH - CH2 > (CH3hC > (CH3hCH > CH3CH2 > CH3

C1;HsCH2 > CH2 = CH - CH2 > CH3 - CH2 - CH2 ; (C:iHsOOC)zCH > C2HsOOcCH2

Cacbocation ding nhir cacbanion, neu cang kem bEn thi thai gian sdng cang ngdn nen cang it co xac suat chuyen hod theo huang tao fa san phdm mong dai, nguoc lai, neu ding ben thi cang co mc sudt lan dl chuyln hod thea huang tao ra san phdm mong dai. Vi vay, phdn ung hilu ca se uu tien xay ra theo huirng tao ra tilu phon trung gian ben vilng hem. Thl du :

7 - HHHC1

97

+_I,'

CH2~CH-CH3+H ~

+

CH3-CH-CH3

ben hem

CH3-CH-CH3 I

CL

san pham chinh

+ C{-

CH2 - CH2 - CH3 -- TH2 - CH2 - CH3

kern ben hon Cl san ph~m phu

2. Tile phan electrophin va tile nhio nucleophin

Trong phan img cua mot chat hitu co voi mot chat v6 co, ngiroi ta goi chat htru co Hi chdt phdn ung, con chit vo co lit tac nhdn phdn iing. Trong phan img cua hai chat hiiu co voi nhau thl thong tlurong ngtroi ta coi chat don gian hon lit hie nhan phan irng, chat con

lai lit chat phan irng, Thi du, trong phan irng (3) 0 muc 1.1 vira neu, (CH3hC ;;: CH2 la chat phan ling, HCI la tac nhan ; Cl,1 th~ han 0 giai doan tlnr nnat cua phan img do tac nhan phan img la H+ ; chat phan irng 13 (CH3hC;;:CH2 ; 0 giai doan tlnr hai tac nhan

+

phan irng HI. ci" con chat phan irng lit (CH3h c. 6 phan trng (2) chat phan irng hi

(~HsOOChCHz, tac nhan phan irng CzHsONa rna cu th~ hen la C2H50- .

+

Cac cation nhu cation kim loai, cacbocation, N 02 ... luon c6 khuynh huang thu

nhan electron d~ 6n dinh, cluing co ai lI.(C viti electron. Cac phan tiI co cac nguyen tu mang dien tfch quy u6c dirong 1&1 nhu S03' hoac co nguyen tir thieu hut electron so voi guy tac bat tiI nhu BF3 (xern muc § 1.1.2) cling co ai luc len vai electron. Cac cation va cac phan tir do diroc goi 13 char electrophin (ira electron). Khi chat electrophin dong vai tro tac nhan phan irng thl n6 duoc goi III tac nhdn electrophin.

Cac anion nhu halogenua, cac bani on, ." va nhimg phan tir trung hoa co cac electron 1t

.. .....

nhu anken, aren ... hoac co cac cap electron tl! do nhu N H 3, H20, R N H 2 , .. , luon co ai

luc cao viti di¢n tich duang nen duoc goi 13 cac chdtnucleophin (ira hat nhan). Khi chat nucleophin d6ng vai tro tac nhan phan Ung thi n6 diroc goi la Me nhan nucleophin. Thi du :

Chat nucleophin + Tac nhan eiectrophin - San pham
(Tac nhan nucleophin) (Chat eiectrophin)
(CH3hCH;;: CH2 H+ +
+ - (CH3hC
C6H6 + (CH3hC+ - C6HSC(CH3h + H+
(C6H5hN: BF3 +
+ - (C6H5hN --+ BF3
+
CH3NH2 + CiJH5CH2Br - C6H5CH2NH2CH3Br -
98 Chit electrophin va tac nhan electrophin tlurong duoc ki hieu la E+, chit nucleophin va lac nhan nucleophin thuong duoc ki hieu la Nu -. Chung luon c6 xu huong k€t hop voi nhau :

~+

Nu + E --7 Nu - E

Trong nhtmg dieu kien nhat dinh, mot phan tiI hoac mot ti~u phan Nu - E c6 th~ bi pharr cat di li tao ra chit nucleophin va chit electrophin :

N0 E --7 Nu - + E+

Cach ki hieu nhu tren hoan toan c6 tinh chit quy uoc boi vi khong phai moi chit nucleophin deu 13. anion, khong phai moi chit electrophin deu la cation, mat khac cung mot chit trong phan ling nay 13. chat nucleophin nhung trong phan ung khac lai la char electrophin.

II - PHAN ONG KHONG PHAN CVC (PHAN ONG D6NG LI)

1. Phan itog Vdi sf!. tham gia eua gae tf!. do

Lien ket trong phan tiI huu co c6 th~ duoc phan cat mot each dong deu d6i v6i hai nguyen tiI tham gia lien ket : moi nguyen tiI chiern 1 electron tlr c~p electron dung chung va tr6' thanh ticu phan. mang 1 electron doc than. SI! phan cat lien kel dong deu nhu the goi la sl{ phdn edt dong Ii. Ti~u phan mang electron doc than diroc goi la goc tl! do va

tlurong diroc goi dan gian la g6c, ki hieu la R·. Thi du ;-

CI tCI

hv --

20'

(CrIa g6c nr do)

CH3 t H + cr -- CH3 + HCl

(CH3 g6c metyl)

CH3 - CH2 t CH2 - CH3

C6HS - C - 0 t 0 - C - 4HS

11 II

o 0

. G6c tl;t do la mot loai tilu phan trung gian, tlnrong khong ben va co thai gian s6ng ngan, Chung se tra nen ben hon (thai gian s6ng dai hon) neu electron doc than duqc giai tea nho hieu ling lien hop hoac sieu lien hop, Vi the d¢ ben nrong d6i ella mot s6 g6c tl! do diroc sAp xep nhu sau :

99