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Loi nha xu~t ban

Gido trinh h6a h9C hftu ca dztr;Jc bien soan thea chuang trinh hod hoc hitu cd do B6 Gido due va Baa tao ban hanh. cho nh6m

.. II. ill

ngdnh III va cac nhom nganli co lien. quan.

Sdch gOln 5 chuang: hai chuang d6u (do GS. PTS. Trdn Quoe San. truang DHSP - DHQG Ha N9i viet) la dai cuang vi hoti hitu cd va hidrocacbon; ba chuang con 19,i (do GS. TS. D<£ng Nhzt Tai truang DHKHTN - [)HQG Ha N9i viet) d€ cQ_p den cdc dan xurft eua hidrocacbon va hap chdt di uong,

Mq.c du chuang trinh hoa h9C hilu ca nh6m nganh. III rat han. che" v€ thai luang (tang so" 3 don V? hoc trinh. ki cd ph/in. bai

, ,

t~p), gicio trinh nay dzlt;lc bien soan. theo tinh than nang cao ve

miit co sd li thuytt va phuang phdp nghien. cuu, nhiini pluit trie"n tu duy cua sinh oieti va v~n dung tot nhftng hilu bitt Ina sinh oien. da duac h9C trong chuang trinli h6a h9C· d{li cuang va d~t n€n mong hod hiiu co cho vi~c hoc hod sinh hoc sau ·ndy. Nhitng

ph/in. InC! rQng them duac in bang chit nho at tham hluio. Sau In6i bai cua tling chuang diu co mqt sc/ bai t/j.p; t6 hap ttit cd nhitng bai tap nay se pluin. tinh. nhitng yeu c6u co ban cua chuang trinh. h6a h9C hftu ca.

Gido trinh nay dztr/c dung lam. tai li~u hoc t~p cho sinh uien; ngoai ra co thl dung [run tai li?u tham khdo cho gido vien phd thong trung h9C va hoc sinh cdc IClp nang khitu vi hoa hoc.

Nha xtuit ban rdt mong nluin. duoc nhitng y kitn dong gop v€ n9i dung vd hinh thuc cua cuon sach. nay.

Nha xutit ban nHQG n« N9i

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. Chuong I

DAI Cl1dNG VE HOA HOC Hitu CO

? ~

1.1 MO.DAU

1.1.1 Hop chat hfru eo va hoa h9C huu ca

1. Khai ni~1ll v~ hgp.chai hUll cd va hoa hoc hfrueo

.

Cacbon la 11l9t nguyen to h6a hoc rat d~c biet: cac nguyen .

tit cacbon co th~ ket h9P vdi nhau va vdi nguyen ta cua nguyen to khac tao nen khoang muoi trieu hgp chat khac nhau, fly.la nlnrng hop 'chat cua eacbon. Trong khi do, cac nguyen toh6a hoc con lai trong bang h~ th5ng tuan hoan chi co th€ tao nen chimg g€in lTIqt trieu hop chat khong chua cacbon.

. .

Nhiing hap cluit eua cacboti (trit CO, CO2, cdc mu6z

cacbonat .. .) duoc goi la h'lP chfit hiiu ca.

Ngdnh h6a hoc ch.uyen. nghien ctiu. cdc hop chat hitu ca. tuc 18. cac hop chat cua cacbon, duac g9i lit haa hoc hitu ca.

2. LuQ'c s-t:t p hat tri€n cua hoa hoc him ea

..

Loai ngltoi· biet dieu che va su dung cac san phAm huu co a dang khong t.inh kbiet hoac h6n h(Jp da tu ra'tlau (duoug rnia, giam, pham nhuom, tinh datl,v.v.4.), song mai t6i giua the ki XVIII mdi tach dlt(jc tit thuc vat va dOng v~t mot s6- ch·at him co nrcng doi tinh khiet (axit xitric, axit tactric,

11 re ,. v . v . 4 4 ) 4

DAu the ki XIX boa hoc hun co tach ra tit h6a hoc n6i chung, 'va trd

- . .

thanh mot nganh khoa hoc dQc lap. Ngttdi ta goi la h6a ·hrjc hiiu cd .

(Beczeliuyt, 1806) vi hoi d6 chi }Jiet. co cac chat huu cd thien nhien. tOO: tai

r • ...... •

I)

trong co th~ dOng v~t, va thuc vat. Vi the. thai bay IDa da xuat hif)l1 mOt quan 11i~m duy tam gQl 18 "thuyer lue song", thea d6 cac chat huu co chi co th~ sinh rH trong co th~ SOllg nho c6 mot luc huyen bf nao d6. Quail niem nay chi t6n .t~i dltQC vai chuc nam, vA da bi bac bo bdi cac cong trinh Wng hop hang loat

hop chat hiru cd xuat phat tu cac chat huu Cd khac hoac tit cac chat vo co, nhu Wng hQI) axil. oxalic (1824), ure (1828)~ chat bee (1854)pv.v ... Cung voi nhung thanh tun ve t6ng hop hun co, tit giUa the ki XIX da hinh thanh thuye]. Call tC;10 h6a hoc (1861) va quan niem dau tien ve h6a hoc l~p ih.§ (1874).

Biroc sang the ki XX, trong hoa hoc huu co da hinh thanh thuyet electron ve cau true phan t.it va khdi dau thai ki phat tri~n manh me cong IlghieI) httu co (nhien lietl, diroc phAm, l)hAm nhuom, polime.v.v ... ).

Sau dai chien the giai 1~11 flhit hai, cung" voi 8t.1 phat trri~n vU bao ella boa hoc lap th~, cua thuyet electron ve cau true phan tit va co che' phan Ung, la su tham 11h~1) cua toan hoc, cd hoc, vat If hoc .. ~ rV30 h6a hoc huu co va S\J tham llht)1) san fQllg cua hoa hoc hfru co VaD cac nganh sinh hoc, y diroc, nong

II

llghiep,v.v~ .. va dac biet 18 su phat trien cac phircng phap vat Ii nghien cuu

chat hOO co cung cac phep phan tich va tang hop htru co hien dai .

.

Hien nay h6a h9C hiru co dang d thoi ki phat tri~n rnanh me

11ha1 va co vai tro rat quan trong trong ITIQi nganh kinh te quoc

,

dan. Cac chat hiru co C6.111~t khap noi, ngoai cd th~ song ta gap

chat htru Cd trong thuc pharn, duoc pharn, pham nhucrn .. chat deo, to sci, cao "su, rnl pharn, bt)t gi~t, chat phong trir dich hai, chat kich thich tang trudng. thuoc n5, nhien lieu.v.v ... Trong the gidi quanh ta, dau dau cling co bong dang hop chat hiru co.

Nho co h6a h9C htru co nguoi ta moi hi~u ducc sau siic cac chat tao nen ce th~ S611g va ball chat cac qua trinh dien ra trong co th~ song. Vi v~y h6a hoc lnru co 1il co Sd cua cac nganh trung ginn nhu hoa sinh hoc, hoa diroc hoc, v.v ... Hoa hoc hiru co khong con la mQt men hQC Inc ta thuan tuy nhu truce day, Ina til Iauda trd thanh mot men hoc co suy luau, vua Ii thuyet vua

...

thuc nghiern.

6

~

3. Phan loai hgp cha't hfru ea

,

Co th~ phan loai cac hop chat hfru cd thea hai each chfnh

sau day:

a) Phfm loai t han h hidrocacbon va ddn xuat ella

III

hidrocacbon

Hidrocacbori 13. .nhfing hop chat hiru cd duoc cau tao chi bbi hai nguyen to' C va H.,

Cdc ddn ~~dt eua hidrocacbon chua trong phan ttl khong nhirng ,C va H. Ina ca nhirng nguyen to' khac nhu N;' 0, S, v.v ... D6-la nhfing hr;IP chdt co nhom. chaco

Nhom chuc 18. nhom nguyen ~u (hoac nguyen tit) quye't dinh tinh chat h6a hoc ct~c trung cua ea day hop chat co cung mot loai llh61TI chuc trong phan ttl (goi 1:1 chuc hoa hQC). Thi du

~ ~

-"O:H 1ft nhom CllUC ancol, ~COOH III nh6m chtrc axit, -~NH9 la

" ...

11116111 clnrc amin.

"~

Khi phan tit chi c6 mot nhom chuc duy nhat ta co hap cluit

I "

dan. chile (thi du: CH3CH20H, CH3COOH ... ). Nell co hai hay

nhieu nhorn chuc dang nhat trong phan tu~ ta co lutp chdt da

" "

cluic (thi du: HOCH2CHOHCH20H. HOOC- CH2- COOH, ... ).

" " " " " " !

Trang truong hop co hai hay nhieu .nhom clnrc khac nhau trong

" ' "

'phan tu. ta co hap ,chat, tap _ cluic (thf du: H2NCH2COO'H~

HOCH9CHOHCH=O,.~.). '

~

b) Phan Ioai theo machcacbon '

..

Hidrocacbon va datI: xuat cua hidrocacbon d~u co" th~ dude

..

phan loai thea mach cacbon (mach ho va mach vong, mach no

...

va mach khong no, ... ).

....

- .... .... -

-,.

Cac h«;ip cMt hUu cd

Hop chat khong yang (hay hdp chat mach hd)

Hcp ch~t yang

(hay hop cha't mach vong)

Hop chat no HQp chAt khong no

(mach CaCbOI) chi (mach cacbon co

co lien ket don) lien ket .boi)

HQp chAt d6ng yang HQP chAt dj VOJlg (trong vong chi co C) (ngoai C, trong yang con co nguyen tit khac nhu O,N ,8. ~.)

Vong no

Vong khong' no VOllg thorn

, OJ yang no Di vong khong no Dj vcng thom

4. Ngu5n h«1p chKt huu ca

a) Trong thien. nhie11: co nhieu nguon hop chat hiru co rat phong phti. D61a: d~u mo va cac khf thien nhien (chua chii. y~u III cac hidrocacbon) , than dit (cung cap nhua than da dina hidrocacbon thorn, phenol, v.v ... ), cac san ph~m dQng-thQc vat (cung cap gluxit, lip it , protein, tecpen, ancaloit va rat nhieu san pham khac) ...

b) _ Trong phong thi nghiem. va trong cong nghi~p ngtfbi ta co th~ Mng hop hang trieu hop chat hiru co khac nhau, xuat phat tit cac chat huu co va vo co; trong d6 co nhi~u san ph~m

8

cong nghiep duoc san xuat tren co sd cac ngu~n nguyen li~u

thien nhien neu d tren. ·

1 .. 1.2 Phudng philp tach bi~t va tinh che chat huu ea.

H~u het cac hoa chat eo trong thien nhien hay mdi digu che trong-phong thi nghiern. d~u b trang thai h8n' hop vdi thanh phan khac nhau. ,D~ khao sat diu true va tinh chat cua mdt

I •

chat hiru cd bang thuc nghiern va d~ sit dung trong thuc ti~n

nguoi ta thuong phai tach chat do ra khoi han hop, nharn tinb che no thanh mot chtit tinh khiet hay la chat nguyen clult.

1. Cac phudng p hap thong thuCing a) Chie't

, Nguoi ta dung ~9t, dung moi thfch _ hop (ete, benzen,

.

nude, ... ) co kha nang hoa tan t6t ch~1 htru cd can tach tit rndt

h6n hop long hoac riin viii cac chat khac sang dung dich trong dung moi do. Sau khi du6i dung moi ra khoi dung dich se thu etude chat can tach. ~ '.

. .. - .

, .

. Thi du: khi di~u che anilin bang phttdng phap khiL nitrobenzen

co mQf phan nho anilin tan trong ril1oc;d~ tach anilin d6 ra khoi ntltlcJ ngudi ta lAc ki dung dich voi ete,- anilih a~ tan trong ete hon 'trong nude se chuy~n sang dung dich ete. Tach dung dich ·~tera' va chung

duoi ete di se thu dude anilin, ..,. · .

.. .

..

. - .

~ :.... J I •

I • I .'. I·... • .' I

_ .Hi~l!, nay, co nhung dV~g :~\1 C;~ phep chi~t.lien t\lC.,,·

... .'-.. • I ..

<....

.

I of'.. .

.. p -:.. p.. ... 1'; ... I I: :. ',. ...._ . r~ I . ..r-, r . I .' : .r.. .! ~ I": .......

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-

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b)K:'Ittinh' '.:- .,;:".'; . r • . '"'~','." ':,", •• .•

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chat (chii y~u la cac ch~t:r_£n} trong mQt dung ~O\ thich hQP,. va

,

su khac nhau ve dQ tan cua met chat trong mot dung. moi d

. , "

nhiet do khac nhau.

• •

Ngttdi ta hoa tan mQth6Ii. hopran trong ffiQt dung moi thieh liQP bltng . each dun n6ng va lac, sau d6 lee n6ng d~ loai bo tap chat khong tan roi lam lanh. Khi ay chat' it. tan hen se tach ra trirdc a dang tinh th~ sach va duoc lay

ra b~g each Ioc, 'I'hf du axit benzoic CSH5COOH la mQt chat rAn tan .nhieu trong mroc nong va rat it tan trong mroc nguQi. Dfi tinh ch~ .ngUoi ta dun axit nay trong mroc d~ diroc dung dich bao hoa nong; dem IQc nong neu can, rai d~ nguQi cac tinh th~ axit tinh khiet hen se tach ra,

-

c) Chdng cat

Phuong phap Hay dua tren su khac nhau vg nhiet d~ soi cua cac chat khac nhau d mdt ap suit nhat dinh, Nguoi ta dung nhiet (dun nong) d~ chuyen h8n hop chat long sang pha hoi va thu chat long d khoang nhiet dQthich -hopbang cachcho hoi ngung tu. Ba ki~u chung cat thong dung IS.:

- Chung cat thdang

. . .

Khi tach mQt. chat long co nhiet dg soi khong cao ra khoi cac chat khac

co nhiet dQ sci khac xa ta co th~ chirng cat bang each dan ¢an nhA"t gQi la chung cat thirong. Thi du: dun soi mroc sinh heat trong bmh, nttO'c se boc thanh hoi, da.n hoi l11.tdc qua b¢ phan lam lanh dg hoi nude ngimg dong thanh

ntioc tinh khie't hen, con "lai trong .blnh la cac chat kh6 bay hdi. - :. - .

...

- Chung cat phfm doan

Phuong l)ha}) nay dung d8 tach h6Il hop long gam cac chat c6 nhiet dQ soi each nhau khong nhidu lam, rilld tnQt dung cu gQi la C9t ·cat pI-tan aO{Ll1. gan li~n hoac lap them vao binh cat, Chat nao c6 nhiet dQ soi thap hen se bay hoi truoe r5i ngirng tv. va dUQC lay rieng ra, tiep thea den chat nao co nhiet do

I 'I .'

soi cao hon. Thi du: dun hOll hop gom benzen va toluen trong binh c6 liip cOt

c~t phan dean, benzen sebay hoi va thoat ra trude, sau d6 den toluen .. ".

10

..

Doi voi nhung char co nhiet dQ soi cao va de phan huy b nbiet. dQ soi cua 110, ngtfdi ta chung cat dudi tip sudt tluip d~ ha nhi~t d¢ soi va tranh su phan hllY.

...

- Chung c5t bang each cho lc3i cuon thea hdi nliac

(~6 Ilhullg chat htru co sui a nhiet de) soi rift. cao va rat it tall trong rl\1(jc~ song co th§ chf(jC ehting eat (5 d<;lng h6n heJp vdi hoi rnrdc a nhiet dQ soi cua Illine.

-- ,. "-

each t,iell hanh: cho mot dong' bci nude nong di vao han hop cae chat Call

tach ra, hoi nuoc se lam cho m<)t. vai thanh phan cua hOn hop bay hoi thea hoi

....

nuoc. Thi du chirng c~t. anilin, t.inh dau thuc v~t; V4 v ...

~

2. Ph tidng philp sac lei

Nguyen t.~c: ticSl1 hQIJ cae chat ·c~rl tach va dung moi dUQc dung lam pha d91l·g a th~ lOllg hoac khi, Pha (l(nlg t.httdllg xuyen t.iel) xuc vdi pha tlnh 18. mot chat ran co diQl1 tich be mat r~t. km, hoac m<)t chat long trang.Ien be mij,t ch~t ran, khien cho cae thau h l)h~ll cua hOll hop co f,l)'c do chlly~n dich khac nhau se t.ach ra kho! nhau.

Pha11 loai: 'T'(-1 phan hiel. hai loai chinh Ii%. s~c kf hap phu va sac ki phan .

bo.

- Sde lei J,iip phu dua thea slj khac nhau v~· h~ sO hap phu cua cac

chat, Pha tinh lit m()t chat ran, pha CiQl1g 1a chat. I011g hoac chat khi. Sac kf

hal) phu co t h& c6 cac dang: sac kf cot, sac kf 101) mOllg, sAc ki khi,

- S&.C' ki p luin. b6~: pha tlnh lit chat IOIlg, pha doug_ la chat. long hoac

.. '" '" ... . ~ ... ...

chat khl. Sac ki 1)hal1 ()O co t.he Iii. sac ki CQt, sac kf 1(1) mong, sac ki gia)~, sac

kf kht.

Sdc hi c9t t.hirong g~l) la loai rna pha tinh la m<)t chat rci11· nhtt alumin

,

(~~1203)' silicagel (8i02. IlH20) dliQC cl~t. trong mot ong tlh~ng dltng (cQt); l)ha

clQng 18 dung dich chua hOll hop C~11 tach trong dung moi thfch h<)l).

sac hi gic£y: t.httdng l)ha tin h la llUOC dinh vi tren gii!y.

sac ki lilp m,ong: pha t:inh 18 ldp mongchat hap phu nhtt silicagel trang tren m{tt ball thuy tinh hose ban nhorn: pha dt)ng 18. dung dich chua h5n hQp

l,l~ .

e~n tach 'dircc d1.'ia vao bAng each nhung hoac nho giot, chat long di chuy~n

llho tae dung mao dA11. '

sat.: lei khi: pha (tOllg la mor chat. kht, con pha tinh co th~ la chat ran boac chat. IC)llg.

, , ,

1.1.3 Phan tich nguyen to va thiet l~p cong thuc phan t-li

I • I.

1. Phan tich dinh tinh nguyen to

Phan tfch dinh tinh nguyen to' nharn xac dinh cac 10~i nguyen to co In~t trong hop chat hfru co. Nguyen t~c chung 18. chuyen cac nguyen to trong hop chat can khao sat thanh cac chat VO co den gian r6i nhan ra cac san pham nay dua VaG 111~Ullg tinh chat dac trung cua chung,

a) Xac d irrh cacbon va lridro

DUll noug chat hiru co vdi C:uO (chat oxi hoa) d§ chuyen cachon thanh CO2 va hidro thanh H20 rai nhan ra CO2 bang nuoc voi trong (tao thanh ket tua tr5.11g CaC0;3) va nhan ra H20 bang CuS04· khan (bQtCuS04 mau trang chuyen thanh

[C] + 2CllO

(hQP chat hiru co)

..

CO2 + 2Ctl

2[H]

(hop chat hUu co)

+ CuO

t

C02 + Ca(OH)2

• C~C03 ~ + H20 --......iI .... CuS04~5H20

12

b) X3.c dinh nitd

~

Dun nong hop chat hiru. co vdi Na se .sinh. ra NaCN. De

. nhan ra ion CN( "(chua nito) ta cho them Fe2+ va Fe~+rdi axit

~ _

hoa nhe, neu co CN(-) se .sinh ra ket tua mau xanh darn rat dac

• • 9

trung cua Fe4[Fe(CN)6]a:

Na + [C] ,.+. [Nl (hQP chat him co)

----....I! .. _. NaCN. _

Fe2+ + 6CN(-) ..___ _ _.. ..... [Fe(CN)(1]4- .

+~+ ~-

4Fe'·· .. + 3[Fe(CN)6] --~. Fe4[Fe(CN)6]3 ~

c) Xac ·dinh halogen

. .

. . ~ . .. .

. Dot In9t bang giay lee tan} chat hiru co chua halogen va

. .

ancoletylic (nhien lieu) se sinh ra hidro halogenua, Ta nhan ra

I • • • •

hidro halogenua. bang dung dich AgN03 (sinh ra ke't' tua AgHal)

sau do xac nhan AgHal bang dung dichamoniac (hoa tan ket

I • ... •

tua):

' •.. : _ ,[H~l] +

[H '

] .. ,

..

. .L_., _, . HHal

,

(hop chat hiru co)

(hQP chat hini co hoac ancol .. ~.)

,_

.... •• .. _" I • • " I. ~'- f . _.

- :r .. .._..I. I'"

'. .... :

. ., !.

" ........ I

...

-I ...- .1· - .-. _

.: - t ... "I" ~ I ....... - _. I ", i" • .. i'" - • .. - "I'" ;.. "I~ III. -I· ~ ,... • r • r - • •• - • .. I

1- _I I -:. ~ I·. - - • -4 - I I. I: ••• I.. • • ~ .... I • • • I I 1 III I ~. • I • • - .1

_. ... ... • .. r _4... _ . .. _ ." r I •• r . ...or _. .. .1 '_I • ... or I _ .... i... -:: _. . _I ... or '--::..'_ • __ __ I" ~ I •••• I • .. ._

,. tap

• t"._ '.'~~ ,. .;"',.,..--~.~._ - ,'~ .. , ; _J t Yj"-~.·~-; . _ t~. _ . .

~. • ' ,- l ~.. • " ~ l ... - \ ~.. ,. .--yo" ~-.r: ~. -, • J)' -. 1.., I . r «: /.. • ~ \ • r •. ~ ."'1: • . ~.. ., - _ •. _ ..

•••••••• r • I. I _ .. I I ...... III. I I . ~.. .. • I __ ... • I -. II _ ....

~ -. _. ... ...._J.......... ......... .. ~ ...... _.. ....... ... _ .. \.....,. . .-.... -..)........: ~ _}..J .. 1_ .. 1........ ••• - • .JI-_ - ~~. I .. ~ •• • • .; ".J . _. . .. _- II .IfJ. ~.... •

....__ "T" • - ...! .. ._.

J.13

~.. ~

~ ,_

2. Ph an t ich djrrh htqng nguyen to

Phan tich d111h .htong nham xac dinh thanh phil.u % v~ khoi hrong cua cac nguyen to trong hop chat hiru co. Nguyen tiic

.,

chung 13. chuyen hoan toan cac nguyen t6 trong InQt hrong can

nhat dinh ella chat hiru cd thanh cac chat vf co don gian, sau d6 xac dinh khoi lucng (hoac thS tich d6i voi chat khf) cua cac san phfiul do, r6i tinh thanhphan % cac nguyen ta.

a) D!nh ltic;ing cacbon va h'id ro

Nung 11611g 11.lQt luong Call chinh xac a mg hop chat 11Utt co

.

voi CuO (lay du) trong dong khi oxi. Khi CO2 va hoi nude sinh

ra dllQC hap thu h03.11 toan va rieng re bdi nhung binh chua cac chat hap thu thich hop duoc Call truoc va sau khi thf nghiem

?

[thi du dung Mg(CI04'2 hoac H2S04 dd ... de hap thu H20, dung

NaOH ... dg hap thu CO2], GiS. sa trong thf nghiern sinh ra In mg CO2 va In' mg H20, ta t111h:

12n1col

me = 44

12nlco . .100

%c = 44~

I

2m H20

liB = 18

2m~2o.l00 %H=----

I·Sa

b) Djnh lli<jng nitd

DUll nong mdt luong can chfnh xac a mg hop chat hiru co

. !) ~ '"

vci CuO (lay dtt) trong dong khi CO2 de chuyen het nita trong

hop chat thanh khi nita va d§.n vao " nito ke''' (dung cu thu do khi nito) chua dung dich KOH dd (d~ hap thu CO2 va H20). GiS.

14

....

sit thu dUQcV ml khf nito, do b nhi~t~t,-ap suat khi quy~n p,

ap suathoi litlocb§.o hoa t. ta tfnhduoc: . _. -

. . . ·28 .... p~f 1 -

mN2 = 22400'V·760· t

. 1+273 .

. .

mN .100 %N=-.-2_-

a

c) Djnh higng halogen

Sau khi phan huy Infru chat huu co chang han b~ng oxi hay axit nitric bO'c khoi, cac halogen dl1qc chuyen thanh AgHal d~ d111111uQng.

d) Dlnh hi<1i1g oxi

. .Thollg thuong ham 111~ng .oxi ·trong mQt hop chat hiru co duoc xac dinh gian tiep bang each lay 100% t:riJdi tang sO % eua

~

cac nguyen t6 khac co trong hop chat. Tuy v~y t khi can thiet

ding co th~ xac dinh true tie'p bang each ehuyen oxi trong mau chat thanh co r3i dinh hrongCf) dua theo phan irng:

,

, . -

. . .

3. XRc d irrh phan tit khol . .

a) Cac ph~dng -phap thong t~tidng

- Doi vdi cac chdt khi hoac chdt long di bay hoi, ta co th~ xac dinh ti khoi hoi d eua: chat do so vdi mQt khi don gian nat) do (thi du hidro, oxi, khong' khi. ... ) "roi tinhM theo bi~u thflc:

r • • _ 'I •• •

-

. d~ . m.(g) chat huu Cd: __ ·M_(_g) __ m' (g) khong khi ..

,

-. ----It- M =29d 29 (g) ...

.

In va In' t5.11 IU(1t la kh6i luong. cua cling mot th~ tich khi hoac

. .

hoi (V) chat hiru co va .khong .khf trong di~u kien nhu nhau; khdi

hrong cua 1 ,lit khong khf d dktc lit 1,293 gam,

Tuong tu nhu vay ta c6 ea~ bi~tl thtre:

. , ...

d= M MH2

. M

_. ·d··=-'-

. Mo·· .

2 .

M=2d

"

va

. I

-s . M=32d

- Doi vdi chat ran hoac chdt long khong b.ay hoi ngtldi ta co th~ do dQ giam nhiet de? dong d~e ~t (phep nghiem lanh) hoac dQ tang nhiet dg sci ~t (phep nghiem s6i) cua dung dich (chua m gam chathfru co trong p gam dung.moi) so voidung mei nguyen ehat,.r5i tfnh ·M thea bi~u thuc:

...

. M = .K. ml000 .: '. . p.At

L

,

... , . ' .....

K Ia hang s611ghi~ln lanhttrong phep nghiem lanh) hoac hang

sCi nghiern soi (trong phep nghiem soi). K chi phu thul}c VaG ban

chat cua dung moi. ..

Phep nghiem lanh dtiQC dung rQng rai hen phepnghiern soi.

" - - I "

b)Phlidng phap p~6k~oi hiqng (khoi ph6)·. .

.. " - ... - "

, •• ..-, _ "'10 • , ,

Khi r.ho·c~c~p·h"an t~ h,UUCddf qua may khoi phS, chung blphii va thanh

Lilli.. ..." - "

', I

~.: ~ ~ - r.." ..

..• . , . l~;'

... ~ of' • • ....... ., ...

"I • ~, ~ - : rl r .... ; ~ .:."'l.. •

"II " " I L __

, . .

.,

- ......... -

I - "r"

" ... I"" I.

" - - I ....... I

:

16

....... • - I ..

~~ ...

... " .......

tWIg manh (t,htt011g la cac ion duong) do bi va d()p manh bdi m¢t dong electron vbi toe dQ 1011. Chi rat·it phan ·til: di qua diroc mot each nguyen ven. Tren kh6i ph6 do cua mot chat c6 r~t nhieu· pic (mg vdi cac manh khac nhau, v6i khOi hrcng mol khac nhau va ham lttQng 'khac nhau (th~ hien d vi trf va cinmg dQ ella pic), Pic ling vm. khat lUQng mol cao ·nha't (cudng dO thuang rat r.hap) cho biet khoi hrong mol ciia chat huu co dt1Qc khao sat. Thi du khoi ph6 ella axeton (kf hieu ·X) co dang nhu sau:

..

cirong d¢ ~~ urong d6i

I

..

. . . , . ~ ,. -

U l~_ 20 30 40 _50 60 7~ kh6i hrong tuong doi

Hinh 1.1 Phd khoi luring eua axeton.

Ti~ll phan 16}] nhat tl(jtlg ling vdi mot phan til nguyen ven chi bat di mot e lectron lA X(+) c6 khoi Itt<./ng molla 58 gam. Ta suy ra M = 58.

4.. Thi~t l~p cong thiic phan tl:i

Sa u khi aa phan tich nguyen to va xac dinh phan tIt khdi ella hop chat huu co ta co th€ thiet l~p cong thuc phan tit cua no thea lllQt trong ba each ph6 bien sau day:

. . .' .- .

a) L~p cong thiic don gian nh~t r6i den cong thiic phan

. - .

tlt

-

Gin sa eo hop chat chi chua C. H va o. Khi dot chay a gam

chat nay sinh ra meo va 1nH 0 . Theo cac bi~ I' tiHh -da neu

'2 . 2~..... ..

.. . 'A. _,." ~.-

d tren ta tfnh dUQC lnc~ 1nH va 1no QdU $ Qt\1t1'!&¥.. :~~tltQc %C, PRONG DQC ._ 1

..

-17

, .

, ~

%H va:: o/dO):: Deinchia diicr'~~rl{tQng'~~y. cho ~lioI lu~ng IDe1

. : T I r • .... '_ ~-' I ,'I : '_ r I I I l I --:- I r : I ~. - ,I --: ... • _ ,I ~ I : } I I I·. ~ I..' • ~. 1- • .; . •

~lgltyeli'b1' wql~~'_(t~g>~'~6~ chia, ,cl}p:' ~dc _ s~ chung' ),on .n.liat_:_ta' s~

dli(jC ti l~ ve so Iuong .nguyen tit ella _ cac nguyen 1:6. trong : phan ti1.-~db d'6 l~p dtroc cong thttcdon ginn 11h11t. Tircongth(1c nay va

• I r • • I . I I'" .

. II) . ., -,' ... - .... ' . .,.,

phantit kllOi tao "de· dang tun ra ·cc)ng 'thtrcphantir.

Thi d u: Dot chay hOa11 toan 0.090 gam hop chat chua C. H. o cho 0~130 gam CO~ va 0,054 gam H20. Ti ~kh6i 'hoi cua chat nay so vdi hidro bang 30. Hay thiet IQ_p cong tlntc phan tit

Giai: 1nc = 12 . 0,130 : 44 = 0.036 (g)

In~ll = 2 . 0,064 : 18 = O~006 (g)

• "I •• 1 •• _,

ln6= 0,'090 .; (O~036 + 0,006) = 0,048 (g)

. . ','

C : H :0 = .0,03-6 : 0,006 : 0,048 ~ 1 : 2 : 1

12 1· 16

Cong thuc den gian nhat Ifl CH')O .

. . ~ ...

,- ...,. ..

_ • I r _ I

,

M = 2 ~ 30 = 60

. . "

. (CH~}O)'1 = .60 ~ n = 2 .

.;j ., . .

. . .

. ~,V ay eo 'c6ng th ftc phan tti (CH20)2 hay la C2H40 2'-

b) Dua vao khoi hidng cac SaD phAm dot chay va M rna

. .. ~

. - .

khong qu.a cong thuc ddn: gian ~hat "

:0..

DQ_t cong tlnrc cua hop chat lil CxHyOz' Thea sd do:

. '_ .

. . [()J.. y

- ·:-C.xJf¥O_z~~~_"'· .• ' xC02'"+ 2 H20 .

_J r : .. ..:.. ~.. r- • I I I' I': • .;. : ••

r. ... ~ r". ... :

, '

. ...-

_. I, '. .. ~~ :- :~

I .. I. ,,~ Ir

.' ...... _ . it ...... '1

"I ., " _

- -- . .. ..

- - .

18

• - ..... II__.. ........... _ •

.......... • .............. r· .....

44x 9v M
" ......
ta co : - -
-- -

III (:,c ,~) In. tl?,() a
., 44a

M.lnH 0

va v = 2

~ 9a

Ttl d6 ta co :

M.11I·('O.;

.,

X=

z duoc suy ra tit x. y va M,

-

~ . . .

Ap dung phuong phap giai nay vao thf du tren ta cung tim

duoc x =2. y = 4. z = 2 va cong thuc phan tit C2H40Z"

c) Dlla vito t.h an h phiin o/r cac nguyen tova M, khong qua

,

cong thuc d o'n ginn nhat

Thanh phan % cite nguyen to' (Huh dltQC thea die bi~u thuc d5. hoc) ti l~ vci.khoi luong lnoi nguyen to'trong phan tit. Ta co:

.'.

12x _ y' _ 16z' _ 12x + y+ 16z _

---_ - - _--

%C· %H . %0· 100 ··100

··M~%C

Suy ra : x = :

12xlOO

M.%H· y = 100 ~

·M.%O

Z= :

16xlOO·

Ap dung phuong phap giai nay vao thf du d trentacung tim ra coug' thuc phan tu C~H"102'

... -

.. .. .. •••• .. .. .. ".., - / ,. • -.... • I I -.' I •

• '''p .' ill • _. I I • I. I • I. I ...: • P I I' I

. . _ . _' _ .- I·.. " _. "I 1_ ... _' ~.. . r ....... • _'.

B .... III '" .. .

Q 'L tan f' ~ . - . - -:. . ••

- ~ .. ,'_r" ~ ,. . . . . - . .. ' ...... - ... ~ . , - , . .. . , ... \. . -~ !. ., . r r ~. • ~ t - '.:

•• 1, ~ .. ~ ....:. I _ I. • .. ~_.... ...... II' '.. .' •• 1 p •• I' • _ I _' - ." • - I: T I ~_.... .. ..

. .

1.1 a) t-lc1~·· neu djnb ughla: ch~t. huu co, hoa hoc huu co, hidrocaCb·bnt goe hidrocacbon, goc t.V do, dAn XitatieiuH1id~d€8cDorl'"··";~'~ '"',: T. :

"i ":~~ .9)~eho caH!Gijng:thitc.':J1P~ liQe ~~u~day: :CHaCL~);';Coc}t:t~a);reaC2 (C);· :L~L,~~ Ct.«tt)(~);;B21:j6 (~K:;"~li3<"~<¥>U (f);~,~H3+C~H3 ~); ,CgfriSPH·;(:l!I);

(1\9

~ _.

CH3CH:t (1-): HOCH2CH~NH2 (K). Hay chi' r5: hQ'P'c~at httu edt

hidrocacbon, I1h6m chaco

11>2 a) Nguyen tac chung cua phep phan tich h6a hoc cae nguyen to trong hop

chat hiru co 13 gi? Minh hoa bang 2,thi du cu th~.

,

b) Adrenalin la mot homon. Tron dell 18,3mg adrenalin vdi bot CuO (lay,

du) rai nung n6ng thi dircc 1,27.ml khi nitc (do a 27°C va 750mrnHg). Neu dot chay hoan toan CiiIlg hrong adrenalin nhu v~y trong oxi thl thu

. ... - . ..

. '. . - ...

duoc 39,6mg CO2 va 11,7mg H20. Tinh thanh phan % cac nguyen to.

. .

1.3 a) C6 mot chat. hiru co khong tinh khiet la~l tu nguon thien nhien, Hay neu cac buoc thuc .. nghiern va tmh toan d~ thict l~p COIlg thuc phan tit

~ r I • ..... • •

eua hQI) chat. do.

- .

bW) Phan tich dinh hrong lO,5mg hop chat A (chi chua C,H,O) thu duoc

. - .

30,8mg,CO? va 4,5mg H90. Hoa tan .1,03 gam A trong 50 gam benzen

..J iIIIIII

r6i'xacdluh nhiet dQs6i cua dung dich thi th~y ts = 80,356°C, trong khi

benzen nguyen chat c6 ts = 80,Ioe. Xac dinh cong thuc phan tit cua A, bie't hlil1g s011ghiem soi trong .trttong hop nay la 2,614

'"

1.4 Nen nguyeu tac ella mot viti phrrong phap tinh che hop chat hfru co:

a) Chat ran;

b) Chat, long.

,,'" ~ ,/IIt,? ""~_

1.2 CAU TRUe PHAN TU Hdp CHAT HUU co

1 .. 2.1 Cau true electron. Lien ke't cong hoa tri va lien ket

. . ..

",t

yeu

1. Lien ket o va lien ket 1t

.. Lien ke't h6a h9C quan trong va phd bien nhat trong hop chat hun co 18. lien 'klt ·c9ng hod ·tri. Lien k~t nay dude hinh

20

J

thanh bang slj xen phil cdc obitan nguyen ill (AO) tao nen obitan

ph/in. tii (MO) chung cho ca .hai nguyen tit tham gia lien keto C6 hai ki~u xen phil chinh:

a) Xen p h u tl~':1C

MO co true dol xung trung vdi true noi hai hat nh3.11 nguyen tit lien ket:

.,

s s

p

p

s

p

- "

_ :r-

FIinh 1.2 Obitan a

,

Do la nhung MO ben vung, du:q,c goi Ja MO cr. Lien ket cong

. .

hoa tri dUQC hinh thanh bang su xen phu true nhu tren duoc goi

.

la lien kdt 0'. Lien ke't o tucng .doi ben, Hai nguyen tit noi vdi

nhau chi bang lien ket 0" thai thi co kha nang quay quanh true lien ket Ina khong lam mat su xen phu (thi du H -H, H3C-CH~

do do co kha nang xuat hien van d~ cdudang d hop chat httu co

.. . - . - . .

(xem 1.2.2).

,

~ '. .

, b)'Xen phu ben

- .... • I • • .. I I

Vung xen phii nam b hai ben true noillai hat .nhan nguyen

tit lien k~t nell MO tuong 'dot kern bgn. D6'fa MO 7t, vA li~n ke't

t ,. 1..... l- A-I... ~ ... ~ S ' oil ~·liA , k~t th' 1: ~ k:{.t kA. b ~

UdDg'Un:g' a . ·,.e·n "ro:¥. -lle."- 0 VOL:· en\ e, (J.- ~ 1 AJ.;t::nl ~ :n;'. .. -~m.~. en~

. . .

H · ;'\.... A.~ , III nh bX. "·Ii" k'" (._ At li"'" k'<t

. ~l~~n tU:AO:l~~l~, au "~ngctnQ~:.: EW-. et.1t vamot .ien. e.

,q)~kh~~gJh~ 9U~y' tq .doquanh tl'\1rc ,n9i, hai .. h~~nha~ flugc vi

.__ _. -..... . .. .... .!. _.' - _ .. r,' • ,.. ... t I Ir. ; L • .. }I ~ ~ ", ~ -, • I ~ I ... I - ) ~.,. l ~ I I _.

nhuthe' s~ vi phamsu xen phil cuc.daicua hai.AO, do d6: co" kha

-. • <4r -... I .. r. t- I I' I r" .. I {'... I • ••••

na:ng' xuathi~n ad~g phan-~t~h, ·ii9C;~r'cac. 4QP . chat' c6 hai.' 'd8i

'I:, "f - . ~ ,- I ~ F ,.- , ~ -+

- 11 .11 ~ .. "".I·,I II '" .~ •• ' .t-.: r'i :1 .. ,.., .. , ......

C C C N ( 1 2 2) ~ ... 1" .., ,.. - 'J '

_ = . = .,... . xem ... . ~ . . ~ I - •• ~ _.. !. :". .""i' ~ j , Jo. ... ~..\. ~"~ .. - _. . ' .

1- .

.. '

.. 21

, ~ , .__

. '. '

. . . ...

.1- I

I I • • ..

. • I ,... .-:-~ :'1 . ~.. .

; • ,. ~:..:,. - ':::'.J . .

. ~. .

... ., I.

i .

: . - .,. r. r- I· .. I ~ ~ ~

. . . ~ . .,., ~ ). .. ~ ~ .

-

- I·

. ~ .. _.

. " -. "", .... : ~. . ~ .'. .. . ........... .. , .

. .. ....... ', . - - r- .- ~

II • • • .. I • I .. 'I", ••

..... •• 1 ...... rI~ .... ) ." _ .~.~ Ij.. _

. ...... ~ . . ... ..

. . ; ! _ I,' ~ ". ~ ,''I. ~ • 1 :". - ;- • i 1 ... . ~: .. ~-. . ~

... of. .. ~ t. _ ~ .. • .t.r I, I... oJ _-... • .1'" ./ ... .. j = ...

~ .

~ : - . ~ ~ ~. : .. ~ .~; I, i.. .. _ t ..

.. - '''.. ~ ~ .... :" r.> _," ' ..

.-.

.- • I

~

• ~ r- ...

. • = I ......_

. . ,,~ "p'.. p

.. I" I I, I "I ~ :

. ; _. ~ .... - _. ... ~

~

... ·f··, ~ 'f T r . .

I • • •

._ _. .., _.. '. .

, . . ".

. .

.. I' I ••••

. . . .' .. - - .. ~

..

.. -. 'I' -

. ... .. .

. ' .. -

. ~ .. ~.---;~ ." ~.; . ~. Hinh·l.~3 Obitan-r: ~-

~ • -., ~ . 1!f' .. ,. - ~ .. :.. .. ;:,.- ; - .... ~ - ~,~ . ~ ~ .... ~.~ _ ~ . ~ ; . _ ~,-:", y _ • _;-. ~

.. , ..' 'I. ", '1"'"_ •• :; .. - .. 'I '._ .~~ ... ~ -

. _-. -y"-- 'I.

..•.. ~ .

..... ~

- • • ..... - .'1 I • _'

., .'

I··

, ,

2. S111ai hoa obitan va cac lien ke't don, doi, ba ,

oj '.. .., , '. ";. . . . • - . (- ~.

d trang thai co ban nguyen tit cacbon co cau h111h electron:

.. -

.. .

. .

J ....

»,

a traug. thai lien, ktt nang .Iirong .cao.vmdt- electron 2$

chuy€n. eh6 sang obitancon t~oug 2pz. dodo cacbon co cau hinh electron 1111U :salt:

.., .

Khi ay co su to hop giira obitan 28 vdi 111Qt so obitan 2p. goi

, ~

In sl! lai hod obitan. Cac obitan mdi hinh thanh diroc goi 19.

obitan. lai hod. Caebon co ba ki~u lai hoa:

a) Lai hoa sp:J hay Hi lai hoa tu 'di~n: M~t obitan 2s t6 hop vdi ba obitan 2p tao thanh bon obitan lai hoa Sp3 dang uhat (hinh 1.4).' True ella cac obitan lai hoa Sp3 tao nen nhimg g6e

'"'-'109°28' va huong ve bon dinh cua 1110t hinh tit dien dgu Ina trong tarn in. hat nhan nguyen tv C :

22

......... - ..

. .

....... ....1 •.

3 Sp .

2.s

2PF ... ;

Z ~ ..

" -, 2 p .... y

Cac obitan - sp". se xen phil true v8iAO cua cac nguyen tl1 khac tao thanh uhimg lienketc. Thi du: ....

. ~

-,

. ~

.-

. ...

- .

1....·- ...

..... ~.. • -- - 1.. ....

I ••• _

. " .. _..... ..... .

. .

- H .

-- ~

_~r-' • '_'.

. . -.

Hinh 1.5 Cdc obitan a trong phan. tit CH4 va Cfll6.

- • I •

I ~.' .. ,

• :;. r_ I I - .. • - I,

• r •• I {'. : r-. _ ~

.. -

I ~ . _

, ,

.: I I' r I \. I ~ •

. ..}

- I' I

23

. - . .. .

\ Sp2

\

sp2

Hinh 1 .. 6 Su lai hod Sp2.

, .

. Cac obitan Sp2 se xen phu true vdi obitan cua cac nguyen til khac tao thanh cac lieu ket cr. Con lai ffiQt obitan 2p chua lai hoa co true thitng g6c vdi mat phang chua ba obitan Sp2 se dung

d~ xen phu ben voi obitan ~p cua nguyen ta khac -tao thanh lien kgt 1t (x. thi d~ d hinh. 1.7),

H

H

H ·

(a)

(b)

Hinh 1.7 St: hinh thank lien kit a (a) va lien ktt n tb) trong

phdn tit etilen.

- . c) Lai hoa sp hay 13. lai hotidudng thJ.ng: MQt obitan 2s t5

I {' ".

hop vOi motobitan 2p tao thanh hai obitan lai hoa sp dang nh§1 co

. ,

.... .... ..,.

true dOl rung cung nam tren In9t dUdng thang (hinh 1.8):

24

.. ._

Hinh. 1.8 81/ lai hexl SPA

Cac obitan sp se xen phu true vdi obitan cua hai nguyen tit khac tao thanh hai lien ket 0'. Con lai hai obitan chua Iai hoa 2p

~ . . ~

co true doi xung thang g6c vdi nha u va cung thang goc vdi true

- 9

doi xung chung cua hai obitan lai hoa sp, se dung de xen phu

ben vdi obitan chua lai hoa cua nguyen tli khac tao nen nhfmg lien ket 7t (x. thi du d hinh 1.9).

. . ~

H-C===C-H

H H

'C=c=c .....

H'" ..... H

12

H

a)

b)

Hinh 1.9 811 hinh thanh. lien ktt a (a) va lien ktt 1l (b) trong cdc pluiti tii CH'-CH (axetilen) va CH2=C=CH2 (anlen).

3. Lien·ket h'idro

a) Lien ket hidro duoc hinh thanh gina nh6m XO- +- HcS+ phan cue va nguyen tit Y:O- mang cap electron tu do nho iUdng

. 25

tac tinh dien yeu (20-25kJhn.ol):

_

. - .-

_-/. __ • ..:, •• - I

s 8+ 0-.

J"., _ __ ." • - .....

X • H ••• Y . ,--,.I.

\., .J\. J'

V Y

Lien ket Lien ket ('Qng hoa tri hidro

,. phan·c~c.··· - . . .. , .' ..

I • • •

(j" day x cungnhu y. tlntong in. oxi. nito, flo. Lien k~t X - H ding

phan cue va khd nang nhucng electron cua Y cang 1011 thi lien

_ ~

k~t hidro cang ben virng. ' . .

..

b) Nguoi ta phanbiet hai loai lien ket hidro:

Lien lIef, hidro lien pluin til:: D6 la lien ket giuaXe-H va Y thuoc ve hai phan tit rieng re (giong' nha u hoac khac nhau). Thi du:

4

. ,

,

Q-H···O-H

/ /

C6:H5. eR3

_'

", - "-

Lien ket hidro ruii pluin tit: D6 13. lien kel giuriX~ H- yaY cua

.

~ ..

.~

26

.-.

0, H

c) Su co mat cua lien ket hidro gay anh hucng d6i khi rat

quan trong den Huh chat cua h9P chat hitu co:

. .

- Lieu ket hidro lien phan tit lam tang manh nhiet d<} soi va

uhiet dQ nong chay so voi nhirng chat co phan tit khoi tuong ducng 1118. khong co lien ket hidro hoac chi c6 lien ket hidro llQi phan tii. Thi du:

. --

- ..
,
'H1P chat' M-(g/lllOI) t8 (OC ) tnc (DC)
CH:3CH~-OH 46 78 -
~. -
.-
'CH.;-O.:.CH·1 " ·'46 ·.~24 -
.
v ~
-
~ -
CHa-SH 48 6 -

. .
p-N-02-C6tI4-0H 139· - 114
-
- .
.. . 139
' o-NO~~C(}H,r-OH , - . . .. 44
. ., { . .'. _ .. - , .
. .
. _. - -

-:-, ~>~ Sr.t 11i11:h. thanhlien ket hidro "giua chat tan vadung 11lOi

.

lam tang .manh d~'ftalitrol1g dung -moi do. Nb61U chuc co kha

nang tao lieli :ke:{nldrb ~ vdi dung "lnoi -cangtang tht dQ tan ella

.. ,

chat cang ldn, trai lai goc hidrocacbon cang ldn ct(> tan cua 'chat

. ~

.. • ~. ""-r " .. - I. " • _. -.... ": .... .r r I. r -

..'" I -.... _" ~ ._

27

HQP chat M (g/mol) ! D(} tan (g/lOOg
H2O)
'C2H5-OH 46 C()
n-C4Hg-OH 74 I 7,4
..
n-C6H13-OH 102 0,6 r
C6H1206 (glucozo) 180 83,0
.. 86 0,01
n-C6H14
60 •
CHsCOOH ·00
HCOOCH3 60 30 Chu Y rang ngoai lien ke't hidro ra; giua cac -phan ti1 hop chat hau co con co th~ co cac luc lien k~t y~u khac nhu hjc hut

. .

hrdng cue gifra cac phan ttl phan cue, luc hut Van de Van, V.v ...

1.2.2 Cau true khong gian. Dang phan l~p th@ ,

1. Khai ni~m v~ cau true khong gian va cac cong thuc mo til. Call true khong gian

a) Ngay tu nam 1874, Le-Ben va Van-Hop da de ra gia

.

thie't eho r~llg trong phan tic hop cha1 hfru co bO'n hoa tri ,eua

nguyen tii cacbon no huang vg bon dinh ciia ffiQt tli dien, tuc 13. trong khoug gian ba chieu, chu khong n~m tren InQt mat phitng. Gia thiet d6 da duoc xac nhan va giai thfch nho hoa hrong ttt va cac thuc nghiem h-hoa hoc, D~ mo t3. cau, true khonggian cua ' phan ttl tren rna.t ph!ng giay ta co th~ dung cac cong thtrc thich hQp nhu phO'i canh, Niumen, Fisd ... ,

b) Trong cong thitc ph6i canh phan tu dUQC rna ta trong ,

28

khong gian ba chieu: cac net gach lien binh thuong ( ) bi~u

,di@n lien ket c§ng hoa tri nam tren mat phang giay; cac net

gach gian doan (~---- hoac IIIH' ) Inc ta lien ket hudng v~ phia sau tdgiay. t(tc 13. xa dan nguoi ,quan sat; trai lai cac net gach d~nl ( 1 hoac .) chi ro nhung lien ke't huang v~ phia

truoe td giay hay latien toi gan .ngudi quan sat. Thi du:

..

H I

",r"" C

H- ,

I H H

hoac

H H H H
-,
-, .
I;"H
hoac H .,11111 C
H·--C
C
• /
-,
./
H H
H
CH3-CH3 -

Co lllQt dang nfra cua cong tlnrc phdi canh thuong chi dung

eho cac phan tit co lien ket C-C In trung tam. Theo each bi~u di~n nay, phan tit duoc quan sat ttt eben trai noi gan nguoi quan sat; nguyen tii: C dircc h111h dung d giao di~rn cua cac lien ket; con -chinh lien ket C-C dUQC rna tii b~ng mQt dUdng cheo ttl trai sang phai va xa dfln ng11di quan sat.-Thi du etan:

H H

H

... , ,

H ·-R

H

, ( 'I'ai rnci nguyen -tit cacbon, H '6 ben phai lit gAn nguoi quan sat, H a ben trai la xa, con i-I d tren duong' thing dang lao d gifta cling vdi C) ...

c) D~ bi~u di~n bang c6ng thltc Ni umen , phan tii dl1\fC nhin theo doc true lien ke't giira hai nguyen tii C trung tam; dung mot vong tron d~ bieu thi cac nguyen til d6 dangche khuat nhau. Nguyen tii C thu nhat d gan nguoi quan sat co ba lien ket gii\p nhau d tam cua yang tron va tao nen nhimg gee

120°. Nguyen hi C thu hai bi che khuat nen ba lien ke"t xuat phat tiI tam cua vong tron chi 16 ra tu chu vi cua yang tron do. Thi du etan:

..

H

H

H

H

H

d) Khi l*p c6ng thite chieu Fiso, nguci ta d~t phan tit sao cho cac nguyen tlf hoac nhorn nguyen tii n6i vdi C rna d ben phai

, .

'. .

va ben trai nguci quan sat a~u huang ve phia nguoi quan sat;

• "I • •

sau d6 chieu phan tu Ien mat phftng giay, Cong thuc mdi thu

,-

duoc chinh lit -cong thuc Fisd. Trang cong thuc nay, ban lien ket

• - '. • I

cua nguyen til: C trung ta m duoc rna ts. bang hai net gach bmh

thuong va thing g6c vdi nhau (nguyen tit c riarn d giao .di~m) du ding cac lien ke't bi~u thi bAng duong narn ngang d~u huang

? ..

ve phia truce td giay (le ra duoc bieu thi bang .) con cac

lien ket bi~u thi bang ducng thang dung huang v~ phia sau t21

'} ~

giay (Ie ra duoc bieu thi bang 1111" ). Thi du eR3-CHOR-COOH:

30

" .

COOH

eaOH

COOH

-

.:. chien

,',' H~C ,"OR .. H

viet li~n

.·OH ... H~~OH

-

-

...

• • •

· .

.

CH:1

,

CH:3

C6ng thuc Fiso

C6ng thuc phoi canh

2. Dong ph an hinh hoc

.' ..

. Dong phan Irinh hoc lij. loai dang phan khong gian (hay d611g phon li?p th~) gay Hell bdi su phan be; khac nhau cua cac nguyen hi hoac nhom nguyen tit a hai ben 11l9t bQ phan "cung nhac' nhu noi doi, vong no. v. v ... Thf du:

.

~,

I ....._

H H

\ I.

c-c . I \

CH;{· CH;l

, .

"

va

H CH3

. .\ /

c-c / \

. CH:3 .. H

tJ~anS-Bllten-2

H

H

'H

CH~~

I r I •

IJi€u Ili¢n cdn. va dil d~ xuat hien dang phan hinh hoc la:

, ' . - Phan tit phai co liell ket d&i (mot hay nhieu lieu ket d6i) hoac

- . . .. . - - ~. . .

vong 119 (lll)lt xiclopropan, xiclobutan ... ) coi d6 Ill. h9 phan "citng

• I,., • .. • I .

. .I -.'.'. 'I "I' ...... ~- ..... _ .. " • .:... I

nhac' ciU_l_trd SlJ quay t\1 do cua hai nguyen tu b bQ phan do.

~ - _ _I ...... • • ~ ! .... .. ... _., ... ~ _ ~-._ . ." .·r

• .1'

.31

- 0 lu6i nguyen tit cacbon cua lien ket doi va d it nhat hai nguyen til cacbon cua vong no phai co hai nguyen tit hoac nhom nguyen tit khac nhau.

Neu lu&i nguyeu tit cacbon noi tren chi co mot nhorn the

"

(xem hai thi du neu 0 tren) ta d~ dang ap dung danli phdp cis-

trans: hai 11h6111 the (thi du eR3) d cung met phfa Ia dang phan cis; nguoc lai khi chung d hai phia khac nhau ta co dang phan

'trant';.

Trong trucng hop Inoi nguyen ttl cacbon noi tren co hai nhom t1~e. kh6 ap dung danh phap cis-trans. ta phai dung danh pluip Z-E. Thea danh phap nay. trudc het ta chon cho In6i nguyen tit cacbon mot nguyen tit hay nhom nguyen tit tuong aoi

\

hon cap, dua thea S\1 cao hen v~ so thil h.i Z cua nguyen to' (thi

du -CHa ' > -H: -Br > -CI~ -OH > -NH2 ... xem them. trang 35). sau do xem xet vi tri kh6ng gian cua hai 11h61n the hon cap d hai

,

nguyen tit cacbon: neu chung a cung mot phia ta co dang phan Z

;-

(tu tie'ng Due Zusammeti co nghia 13. "cung"), trai lai neu chiing

b khac phia nhau ta co d6ng phan E (chu cai d§.u cua Entgegen co nghia 13. "doi"). Thi d \1: .

~ /CH3

C-C

/ \

CH3 H

CI Br

\ /

C-C

B! 'I

(Z)-1,2-Dibrom-l-clo- (E)-l\zobenzen ... 2- iotetilen

vi -Br > -Cl va -I > -Br

Hai chat dong phan hinh hoc cua nhau co nhieu Huh ch~t khac nhau, dua theo do ta co th~ nhan dang dang phan, Thong thuong dang phan trans b~l1 hon d6ng phan cis, va co nhiet dQ

(E)-Bllten-2 vi -CHa >-H

32

nong chay cao hen uhung .lai soi d nhiet dQ thap hon, Till du trans/cis-buten-2 co tn(~( (Ie) In. -106/-139 va ts< °C) In 0,9/3.7.

3 .. Dong p h an Quang h9C

Co nlnmg chat hiru co co khii nang lam quay mat phang cua anh sang phan cue mot g6c a. 11aO d6. D6 Iil. nhirng chift quang haat va tinh chat d6 ducc goi Iii tinh quang hoat,

1\ nli «a 1I.g pluin. c~ic: l~ R 11 h sal1g ch i c6 dao dQllg t.ren m(jl. mat I) h~llg

"OJ-

uhat dinh, no k hac vdi auli sci1~g tltzlChl.g co dao dQIlg tren moi mat phang

t.h ~ llg goe voi 1J h uon g t.ruvcn (.t. hi 17,fL 1.10).

A

0:

A'

D 1.1 II g di ell La ng

cllat quang kinh hoat

Hil11, 1.10 All.I,. ~cil1,g pluin. c¥c va· sd ad pluin. eVe ke~

.B

Anh sang

l)h:i 11 Cl.tc

B

~ ~

Tinh quaug hoar diroc NRC dinh bang ct§ quay clfc riel~g [u] thea bieu

.t.h lie:

, . .

t.r()']ig (16 Cl 1ft g6~ (}llAY do (l.lt<jc trel1 ma~~ (goi la pluin 'c¢c he) dOl voi dung dich

.'

chat quang hoat e(j l)e da~~·d(i Htlh sal1g IJhall .clJc di (1l1H la I dm chua a gam

c hRl. ·l}11Al1 g hoa t l rong V m 1 d t 111 g die h. {)hC1) do a drroc th tic hi~11 d 11 hiOt (lQ t vdi 811h SHllg (;0 l}tioc s611g )" (tlltt(511g llgttdi ta dung anh sang D cua dell hoi nat ri 00·'.· = 589;311m).

Dien kien xuat hien tmh quang hoatIa.phan tit co y(u to" _khong trung v~( -sinli (chirali,ty). Khi co yeu.t.o nay nlQt pharr tit

'v~:~~Jl~· .~9.ni. cU,~ .. 1'9._·~~1~911'g. th~Jong .khi~i vao nhau .b~l1g cae

_ - . 1 r . - - ...... ...." .A. J ....... _ ... '.. "I .{ ... _. ... _. .. .. _ ~ • • .. • _ I I ... _ • .... •

- .

phep - tinh ti~n va -quay, tttdllg t\t 'nhu 'quan h~~ giu·a hai ban tay

cua InQt nguoi btnh thudng. . ~ . . . .

Yeu to khong trung vat-anh quan trQng va ph5 bi~n nbat la

I I I ..

• - oF \ * r • - • - r ,. .- ~ f'".... r ~ • ~

nguyen tit cacbon bat dol. ki hieu C .~ DO i~ nguy'ell tit cacbou 116i

'*

. vdi bon.nguyen tit .hay nhom nguyen til khac nhau C abed (a ~

. -b *- c =d). TIll du: _. .. _. -

-. ~

,

COOH I .

H-C*-OH I

CH3

. ~

-

CH=O·

I H.O-C*-H

, I

CHa)OH-

-

. Br

[ H-C*-F I

CI

Khi trong phan to: co 1119t nguyen tIt -C*, phan tit co th~ ton

- .

tai d hai dang dCii xtrng nhau qua .mat phang-gucng va khong

~ 'I,,: . , .. ~, . ..,

tIle long chap vao 1111all duoc: met dang lam quay mat phang

, .

a1111 sang phan cue sang bell phai .1119t g6c +0.0. con dang kia Hun

quay sang ben trai _0.°, b61a hai chdt dot Quang hay enantiome. Hai chat uoi quang la truong hop di~n hinh eua dang phan

. Quang hoc: cluing co cac tfnh chat li-hoa thong thuong gioug nhau, chi khac nhau d dau cua [ex] va heat tinh sinh hoc, Thi du:

I

eRO: eRO

I

CH=O' . I .: - I CH-Q II C : C III

HO--+--H == HOCH.)-,Ilj " ~ / \·CH~_~.OH== H----+-OH

, - H:H

CH.)OH HO i· OR CfuOH

~ I

I

(-)-- Glixerandehit

2;3

[all)::: -8, 7cP

(+)- Glixerandehit [o.]~ ::::+8, 70°

.. ~ .

Ti).p hop hai chat d6i ·qllang vdi s6 mol 11ht1 nhau duocgoi In

bic'n the" raxemic. Do 5\1 btl trir ve [a]. bien th~ raxemic khong co

34

50%(+)- Glixerandehit + 50~b( .... )- Glixerandehit = (±)- Glixerandehit

D~ phan biet hai chat doi quang ta co th~ dung cac dau (+)

va (-) nhu tren (dua theo dau cua goc quay a), hoac da co thoi dung cac ki hieu d (xuat pha t tit dextrurri nghia la ben phai) va I (xuat phat tir Iaeuurri nghfa In bell trai) va 11i~11 nay dung rat ph6 bien trong hoa hoc gluxit cac kf hieu D (am chi nhom OH d nguyen tit C'" -clloi cung huong v€ ben vphai trong cong tlnrc

. phang d tren) va L (khi nhom 'OR d6 hudng ve ben trai). Ngoai ra nguoi to. rat hay dung cac ki hieu R va S 1111~ se neu duci day.

D~ goi ten cau hinh cua 111qt dang phan Quang hoc thea he danh phap R}S truce het uguoi ta siip xep bon nguyen ta hoac

* ' ~ .. '

nhom .nguyen tll de. theo· trinh tu gialll dan dQ hon cap

• II,.. •

a>b>c,>d dua thea S\1 giarn so thu tl_t··Z, cua nguyen ttt true tiep

* ~ ..

Hoi vdi C (goi In nguyen ttl d YOng I) nhu d d6ng phan h111h hoc,

. '

,

Neu nguyen t11 d vong I gioug nhau (thi du cung In. C) thi xet

ct~ll so th(t tu cua nguyen tit d vong II. Thi du:

• I '. ..

-

. ,

. . -CHz-Br. >_ -CH.t·~Cl .> ·~~H2-0H· '.> -C?H.2~~1l3 > ·-CH~rH

..

~ .

. . . . .

: '. ]{hi" ay nhirng nguyen tit rnang .. nol dai hoac lloi ba dU<;ic coi

nhu tuong duong hai hoac ba ngtiY~l1 tit mang noi don. TIll du:

.

, .

. ~ I

, .

.

<,

C = 0 nrong dtrong

. ,/ - . ~ .,., ~., . ,

H' , ,. . . :. '. .

• '. • I.. • .. I. • .. _ _ •

• • • I. -

I. ,

. ,

. . . .

. • I

. .. ..

.

. '.

." I - •

>

-

I ... !

• ~ I

. 1. . :" •.

, ~o, !c

- , .

....... OR

.>.- ~- CH20H

I

I

.. . Jr' .. ' ~. • . P • I - ..

• ,',. .: -.. • ~.. I • ..

. ;;

..

,

I

Sau.khi da SO sanh'dQ hon cap ,ihay c> b > c >.d ta nhin

* I

. phantu thee dochuongC ;_ -d.rietttMy thit t\l a > b: > C di. theo

chieu kiln: d5ng'h6 ta li6i:r&ng phan tit cO cdu hinh. R (tit Latin Rectus nghia la"phai"). trai lai ueu trinh t1:t d6 nguoc vdi chieu kim dang h5 phan tit co cctu hinh S (tu Latin Sinister nghla 18:

"trilT').Thf du CH20HCHOHCH=O c6 -ORCa) > -CH=O(b) > -CH90·H(c) > -H(d)

-

(R)-Glix·erandehi t

-. eRO (b) ~ 1 ~

.l~·l,_+ --- --THC - H

... q 1[11

HO··,,'I' ,(d)

. (0) \__ ,

CH~OH (c)

(b) CH=O

...

;'

hay la H. ORCa)

ttl

(d) CH.)OH

. ~

Chu .Y rallg tr011 eong t htn: Fiso rna d a dttdng 118m ngang thi trlnh t\1 az-boc trRi chicll kim (i()llg ho mdi I~ R, COIl trinh tt,t thee chien kim d511g ho 1(1~ Iii S .

36

SO' luong dong phan quang h9C phu thuoc vao so nguyen tit

~ , "*.

C trong phan ttt. Neu co n nguyen tit C khac nhau se co 2n

....

dOllg phan quang hoc.

4. Cau dang

Xet phau tit CH;rCH;) ta thay rang lien ket C-C duoc hinh thanh do su xen phil true cac obitan spa, do do In6i nhom eR3 co . th~ xoay xuug quanh true lien ket do tao nen vo Vall dang hmh hoc khac nha u voi the nang- khac nha u. Nhitng dang khong gian do duoc goi In. nlnmg cdu. dang cua etan, trong so do co hai Call dang d~c trung nhat:

MQt Ia dang ehe khudt~ dang nay rtft khong b€n vi cac nguyen tli hidro thuoc hai cacbon khac nhau d rat gall nhau va d5y nhau.

Hai Itt dang xen ke, dang nay ben nhat vi cac nguyen tit hidro d xa nhau,

H H
H
H I

-
-
H H - H
H H H HR,

Dang che khuat
R,
H H H H

-
-
-
H
H H H
.
Dang xen ke "H'-" 37

~ - ~

so can - dang xen . ke' (b~ii) va sO caUd(illg' che khuat (khong

bell) cua mot chat c6 th~ ~lhi€u' hen, Till du, l1~Uilllm phail. tll1'CH3 - . - ~CH2 _aCH~ _.tCH;j dQC thea true lien ket 2C - 3C ta'tha'yco hai cau '.

~

dang xen ke men nuni va hai cau dang che khuat (x. 2.1.1). Cau

dang ella cac hop chat vong no kha plnrc tap (x. 2.Ll).- I' " .

Bili t~p

1.5 Ban charcua lir.~ll ket CQllg hoa t,rj la giY Hay trtnh baybanghinh ve theo quanniemhien dai.su hinh t.hanh C_A.C lien ket C()11g hO.H tri trong mOl 1) hA 11 l,ti sal I (1A)·: ~

. ,

1,,6 H) B~11 eh·~t CUR lie11 k€l hidro IH gi? Nell thf du minh hO~4

.

b) Trin h IJRj- IJHllg e()llg t.huc Call L~O liell k6t hidro giiJa cac }JhRI1 LU .

trone t rlitjllg hop: motanol: axii axet.ic: dung dich 11hp11{)1 t.rong (~tA_1101_

CI-l~,~-(~ l' 12-() 1-]: HO-(~li~-Cl-l~-O H.; CH3-0-C fi.2-(~ [{2-0 I I~ (~1"1 ;{OC H ~-(~ ]i20(~ H :J; ortILo-l~'(~6r-r.:1 o I~I: para-l~C()Ii4 0 tTl:

1- I l~: f i ~) 0: 1·140) S; f i 10) N (~ l-i~) - (_; 1-1 !.) 0 11

o.J w _;- ...; .....

I.A a) Vi{{t. l!Ollg t.hue Call - _l rue cac (tOllg l)hall hill h hoc (11 ell co) trong m6i trtidllg hQl) S}1 '-1 :

C I-i ;3-C J 1 =C, 1".[ -(~}-I~-3 (1\) (C H :3)~(:=(; 11-( ~ H ~~ (B) (~Ii :3-(~ l l =(; 1 l+C 6 f 15 (C) rli~-1-r;=('-rf)lI5 .. (J))

CII3-Cli=Cli-CH=Cf-i-Cli8 (l~)

C H ~3-(~ 1'1 =C H -C 00 H (I~')

1, I-Di merylxic 10 hexan «;)

1 ,2,-.D i met ylxiclohoxan

(li)

38

1)) (~hiXl 11 HO (ltroi (fa)· co t.h~ e() (t{)llg 1) han tll_l ang hQC? So ItfQ11g d011g phan lR bao 11 h ieu?

C 11 ~~: I· f BrC ~ I t :J (i \)

C tl ~3r.l-I Br(~ 112.~~!i ~3 (13)

CpH;lCHBr-(~HBrC1-f3 «»

Cli3CHOHCOOH (E)

HOOC-CH')-CH(NH.)COOH (F)

6tttI ....

HOOC·-CHOH-CHOH-COOH

(G) (H)

1.10 (~Atl dang (3 gl~t Viet .. eOllg r.huc . Call dang b6Il .cua cac phan tit etan: l)rOl)211: lnuan: isopentan: I.z-dicloetan.

'" ...... ~...." ",.~" ~ ,,? .,

1.3 KHAI NIEM VE MOT SO PHUONG PHAP PHO KHAO

. .,

~ A..' , ,." .,

SAT CAU TRUe PRAN TU.

Iloa hoc hutl co hi~n nay dang slt dung ngay cailg rOng rai cac phuong 11l181) v~t If (l~ l)hAl} t.ich va khao sat. Call· true .chat huu cd, Nhimg phirong 1) hal) nay (;6 II hiel} \ ru .di~m:

- Co kha 'nang CUIlg dell) nhtrng thong tin phong phu va chfnh xac ve Call t.ruc phan tv;

. "' . . ... . - -

- C6 the phan tich din h nnh ·va ea dinh luong trong nhieu trirong hop;

. .

- Chi t.Oll Ili<jtlg : rat. ·llho chat m~ll va nhieu khi con thu hoi dUQC chat

- Cho ket qllH r~t mall le:

- Co t.h8 .ghi 'dtfcjc ket qt18 llhd cac thier hi tt;! dOng hoa, v. v ...

Ngoai nhimg phuong phapxac djnh .cae ·hang, 66· ,·v(it :u; thong

. ~,

thinmg, n1Rc nhiet de> n6ng chay (tne), nhiet dQ soi (ts>, chiet su~t (n),

dQ:qtiay cue (ct}~'inol1leh: !-lmng cue ().ly:' ... -va nhung phirong phap rna

"I" .- .. -'.. . .,... .. ~ ... r·..... I • •

'. • I .. • •••• '\~ _'I~ ",I "'''', _. • _.

thi6tbf chuaduoc ph6 'bien'rQng rAi -a tanhu phan tich' 'tia 'X, khOi

• I _..- I' _ _

~Ir': '1, ~".l~'·· r . ' .. r," ,'. "p ... _,' I p!, .. : .. -

ph8:.:.rigitai tahay 811 d(iiig W'h® cac-phltCfiig'phap 'ph6~eleCtXon,'ph6' -

dao dOng va ph5 cQng hl1dng tith~t ri1iiit~:" <' ..,. :: ..

39

"

1.3.1 Kha i l1i~ln v~ quang ph6 di~n tit

Khi cho cue bite XQ- dien tit (cac ria lIang ngoai, tit 11gOQ.i va khu kien ... ) di qua char 11 Ull co se XU)" l"a su hap thu mot phan hay tcan phan eric tia eta, tuy theo nang hrcng hue xa va cau true hop chat h1"1\1

~ ~ ~

co. Nang lucng duoc hap thu co tile kich thich su chuyen nang lucng

e 1 ectron t it mire thap len nine cao (phd electron) va cung co th~ gay uen 511 duo dong (ph6 dao dqug) va su quay (ph5 quay) cua cac nguyen t11 va nhom nguyen tU:. Salt day 13. mot so vung pho vci budc S611g ?~ (nm) va so song v (em -1) tuong ling:

t 1 I· .1 .
i ! I I
tIOl1 t1 11 o oa i KJla Tir naoai
o e .. e .
- kien
.
. -
.::- gatl xa
X~l trung uan
e :Ii'.

j.." 11ID

800

400

200

___ A~ ~~ ~J~ ~~ ~J

V V ~ V

Pl16 quay PI16 dao dong

?

PlIO electron

.)

1.3.2 Phlidng ph ap phi) aleotron

Ph5 electron (tit ngoai va kha kien) co nguon goe 13. su chuyen mite nang luong electron tit trang thai lien ket len trang thai phan

, ,

""

lien ket hay la trang thai kich thich (trang thai najr duoc ki hieu bang

- dau * ghi a g6e tren cua 1\:1 hieu electron):

40

Nang luong

~~
j ~ ~ ~
. * I * 0'-0'*
I'-Tr. .
Jt-1[ ()*

Il

Pl16 electron duoc dac trung bang hai dai hrong chinh: vi tri cua cue dai hap thu (i.max' nm) va cuong de) hap thu (E): nhimg dac trung nay thuong diroc th~ hien tren mot dirong eong hap thu (x. hinh. 1.11).

n-x*

200

250

.300

Hinh 1.11 Dztdng cong luip tliu. eua axetoti va 3-pen.tenon-2.

811 kich thich cac electron (J l~at kh6 khan, doi hoi nang luong cao nen chi xuat hien eve dai a vung tfl ngoai xa vdi i.max I'at nho «200nm) vdi xac suat l~at thap (e l~at nho), Trang khi d6 cac electron 7t d~ kfch chich hon nhieu nen thucng bi~u hien a vung ttl ngoai gin (200-40011m) hoacvung kha kien (400-750nm) VCJi E l"at Ian. Con cac

41

-. .

chuyen nnrc n ~1[ tuy ·C6--j~~1~a~ khong nho, song E l~ rat nho. Nhirng he

lien hop voi nhieu noi d6i deu co i~lIlax km va e cling Ion. Thi du i·umx(nm)(e) cua nlQt so _ hidrocaebon khong no: CH2=CH~ 180nm (10.000): CH.)_:_CHCH=CH~) 217nm(21.000)~ CH~)=CHCH=CHCH=CH~)

....t - _ 4ttJ

258nm( 35. 000) ~

1.3.3 Phlidng phap phil h6ng rigoat

Vung hong ngoai diroc khao sat bAng cac may thong thirong co sO'

song tir 500 eln - 1 den 5000 em I . .

..

Pha h5ng ngcai cua mot hop chat ducc ghi mot each tu dQng dudi

dang mot gian do, tai d6 co cac cue dai hap thu (cac eve dai) ung voi nhimg dao dQng d(tc trimg cua mot nhom nguyen tit hay mot lien ket nhat dinh (XA hinli 1.12).

C-H

~2()(} ·~O()() . 2800

1700 1500

1300

1100 -1

V> Ctrl .

.

Hinh 1.12 Phd hdng ngoai ciia axeton CH3COCH3"

42

Sau da~'" lfl gia tr] dao dong dac trung cua mot so lien ket:

C-H ankan 2960-2850 em - 1 C=o and-xet. 1 740-1 700cm .... 1
C-H anken 3050-3020 C=O xet.khong 1685-1665
no
C-H aren 3100-3000 ·O-H ancol
C-H ankin -.,3300 khDng lien kei hidm 3650-3590
C=C ankin 2260-2220 05 lien ket hidro 3590-3200 (IQng)
C=C anken 1680-1620 O-H • 3OCO-- 250:) (lvng)
axit
C=C aren 1600-1450 Can cu vao pho do hong ngoai (do may tu dQng ghi) doi chieu vdi cac dao dong dac trung cua cac lien ket, ta co th~ nhan ra su co mat cac lien ket troug phan tit.

1.3.4 Phtidng p h ap ph5 c<}ng hl.tdng tit proton

Hat nhan cua nguyen tit 1 H va mot so nguyen tit khac nhu 1 aC, 1 !)F, ... co momen tit. 'Neu .d:j._t proton ching han trong tit trucng khong

d6i thi rnomen tit CUD. no co th8 dinh hirdng' cling chieu hay nguoc chien vci tu truong. Do 13. vi spin hat nhan co tinh chat luong tit vdi

; "..,-'" 1 +"'" 1/ ' 1/

cae so udng tu + ~ va - ~~

~ . .

~ ~ . -

De ChUYE!ll proton til: trang thai nang htQ'ng thap len trang thai

• • • I • _ I

nang hrong cao can cung cap cho proton nang luqng aE = yhHJ2x,

. .

trong do y va h la nhtmg hang so, H 13. cltOng dQ tit tn1dng.

. - .. ...

• ~ • • ~ • I

Trong phuong phap ph6 cQng hltGng tu hat nhan ciin'g nhu cac phuong phap phd' khac dua tren s~ hap thu cac tia di~n tit ta co bi~u thtrc ~E=hv, tit do suy ra v=yH/21t .

. .

. ~

D~ nhan diroc tm hieu hap~th\l eQng httang·tu hat nhan . phai gill

- ...) .

eho v khong dr5i va .cho H bie'n,:thien, nhd d6 ~h$.n dltqC dlta~g cong

I • "I' I. oJ. .., I

hap thu, tit do thu dltqc,DA\}ng,d~i htQng co ban .eua ph6 cQng. httang

• "I • •

. ... .. '_. .. ... .

~ .

tit hat nhan 13. r19 ch.uyen dich. hoahoc () (ppm trong tieng. Anh hay pt

trong tieng Viet nghla lit pluin trieu) va hdng so'ttldng tac spin-spin J (Hz)" 'I'ren hmh 1.13 ghi ph6 cong hirdng tu hat nhan cua etanol.

100

. I
~
~ ..
-
- j
! 1
~ I
)
... __ .L - J~ r r .... .J l j ~ _ole_" L..
~ _. ..... - I -- ... """1JI I""""
..........L. ................. 1 ......... ,.. • ! b"~ I .1 .• ~ ... ...........!... .......... _ 1 J. ..... -~ j_ ._ I J L ...... .L ~ 6,0

ZoO

1.0

Hinh. 1.13 Phi} c9ng hzidng tit proton. cua etanol.

Dg chu.y€'n dich, hoa hoc 0 duoc xac dinh bang quiing each giua

. ~

tin hieu cua nh6m nhirng hat nhan dltQC khao sat va tin hieu cua chat

lam chuan (thirong dung la (CH:l)4Sitetrametylsilan,vigt tAt TMS), 0 lit dai luong co tinh dac trirng. Thi du (5 (ppm hay pt) ciia proton trong lU9t so nh6m cua phan tit hun co nhu sau;

R-CH:~ 0,9 AiH 7,3
1,3 ROH ....
R-CH~)-R 0
...J
R;3CH 1,5-2 PuOH 7
RC=CH 2,5 RCH=O 9,7
.... RCOOH 11
R,)C=CH~) 0:
*'tttI - 44

Dua V3.0 8 ta biet duoc loai proton nao c6 mat trong chat ducc khao sat.

.... .. ....

Hiing ~~a tuang tac «pin=spin J ducc xac dinh bang quang each

giira cac VQ_C}l ke nhau cua mot tap hop, n6 d~c trung cho tuong tac gina nhi1ng hat nhan cua dang proton hoac hat nhan khacnhau. Thi du J(Hz) ella 1119t so doi P110tOll":

Ha H, C ........
.......... C .......... /C 12-15
'H
12-15
,./ 'Hb
H, H ,
<, CH / .,
CH 6-8 /C C' 4-12
<,
/" -, Tit tri so J thu duoc ta co th~ rut ra ket luan v~ vi tri tuong doi cua cac hatnhan co tucng tac voi nhau.

1 .. 4 HIED UNG CAD TRue

1.4.1 Sl;f phan -c¥clien ket 0. Hi~u ling cam iing 1. St! phan ct:j.c lien ket 0'

Khi hai nguyen tit hoan toan dong nhat lien ket vdi nhau,

"

lien ket d6 kh6ng phan Cl~C. Thi du: H-H. CI-Cl, CHa-CH~. Trai

,

lai neu hai nguyen- ttl - d6 khong d611g nhat va eo dQ anl dien

khac nhau thi lien ket gina chung se phan C\1C ve phia nguyen tit cua nguyen to' 11aO co dQ am dien 1011 hon lam xuat hien met

. ·dffli anl'(S--) VD., 111qt dfiti duong (o+):Thi du :

" . .

~ _.- "

"" ,

.. \ ~"'_

_ ~

I "

8+ 8- -, (5+.

H .. Cl , H3C ..

s-" CI

" 45

M UC (l() phan cue duoc danh gia mot each dinh lUQ11g bang momen luang cLte ciiell ~ v(jj thu llby\1)·{~11 ]~ Debai (ki hi()11 D)~ J.I. ella liell kct.. C211g 1011 chung t ,(') SLit 1 J h ;.111 t! t! e . e H 11 J.!" m t:\ll h. T h f (I 1.) :

H-H . O~OOD H-Cl 1,08D H-Br O,7SD

CHJ-H O,OOD

CH~~-Cl 1, S6D CH3-Br 1,78D

Th 1_J:e frl J.l k hon g chi 1) h l) thuoc d it511 tfch (1 a Ilt611g cue (ga>· ra bai s t.1 I) h All cue: m H COIl 1) h \l r.h ll()<~ tIltH]} g cHe h l gi aa ha i trong tam (ti011: ~=(11.

81,t phan cue cua cac lien ket cr In nguyen 11h5.n chu yeu cua 1119t loai anh hucng qua lai giita cac nguyen tit va 11h6111 nguyen tlt trong phan til: goi lit hieu ung earn ung.

2. Hieu ling cam ung

. Khi thay the mot nguyen ttt H trong phan ttt CHa-CH2-CH:3 eJl = 0) bang nguyen t1.1 clo ta duoc 3CH:r 2CH2- lCH2CI (u = 1,8D)- Lien ke't C-Cl hi phan cue ve phia CI Hun xuat hien ft d CI va 8+ d 'c. do mang dien tich 8+ nen 'c lam cho lien ket 2C _le hi phan cue thea (tuy d rmrc dQ yeu hen), va de'll hrot .2C lai HUll cho lien ke't ;3C - ~C cimg phan cue (tuy d mire dQ con yeu

. ,

, .

hen nita):

H

I

0·"

I

H

H

1

c •• ,. Cl

I

H

H

H-C ~

I

H

S\"i phan Cl~C Ian truyen theo doc true cac lien ket a 1111.1t vay duoc goi In s\1 phan cue earn {tug hay In hi~u itng cam ling. ki

hieu bang chit I (tu Inductive Effect)_'

Nguyen tit clo gay nen hieu ung cam ung bang each keo

46

-

electron hay hut electron ve phia no, ta noi rang clo dii gay hieu llrtg cam. Ultg tim. (ki hieu -1) va clo la rndt nhom. hut electron,

. . Hieu ung cam ungam co dQ manh tang theo dQ 8.111 dien cua nguyen tit hay nhom nguyen tit gay nen hieu (tug d6. Thi du:

~I < -Br < -Cl .< -F

~NH~) < -OR < -F .

-

-CH=CH2. < -C6H5 < -C=CH

Ngoai hieu ung -I con co hi~u ung +1 goi Itt hieu. ?Lng cam

. .. ~

Ilng,dild11.g~ .. D6 ltt hieu irngcua cacnhom day electron (so vdi H).

r ,I • •

Thf du cac goc hidrocacbon no. clning co hieu ung earn (tug

~. . I

ducng tang theo bac cua goe:

-CH;~ < -CH2~CH:3 < -CH(CH:3)2 < -C(CHa)3

Hieu zing cam. ung co dijc dicln la guim. rtit nhanh khi mach. cacboti keD' dai. Thi du co Y CHj3 CH2 a.CH2COOH, neu dua mot nguyen tit do vao vi tri ex. se lam cho tinh axit tang 92 15.n. nell dua clovao vi trl'(3 thi chi Iamtangf lall~ cond vi tri 't chi tang gap dOi.

, 1.4.2 'Sl/phan elj-c cua iien k~t 1t. Hi~u iing lien 'h<!p

• • I. ,I •

1. St;l phan etf.e cua lien ke't 7t

Lien ket 1t giita hai nguyen tit dang nhat thi du CH2=CH2 thuong' khong phaii cue. 'I'rai Iai, lien ket 7t giua hai nguyen tit

r r

c6'·dQihn di~n~].dlac nhau lai IUD!! luon phan.cuc v~ phfa .nguyeu

tit cua nguyen to 11aO ~6 dQ am dien Idn hen. Thi du 8+CH2=Oo-,

;':. ~ ··S\fllhAll etfC:crm~lieri ket. x dltcjC~me,taJb~ng~:mt3i-ten··cong.va··cllng dttQc .: -··~nh:.gia .ln6t.:. ~:h-. djnh ·.lllQ1-tg. bal)g mornenhrdng cue. Thf 'du; .... _ .

r: .;:: .: ,.:' 1 ~ .: : ~·c:H·.)·~d rr.; ~ .::; 0;000·' ,; . , ., CHo)=O· J.1. = r 2 ·27D '

•• r ...... .., ',_ ~,

• • :.. ~~. .- .....: I" I I • ; I • .. i .r I. - _ I' I -~. • • r • I • ..

. 'r. ~' ... l~I"" ~I.'" ,', I. _1:1. . . L'

..

.- 47

. 2. H·~ lien h~p vah ieu ung lien hgp

Khi trong phan tit co hai (hoac nhieu) lien ket 7t d each nhau bang 1119t lien ket don o thi cac obitan p c6 th~ xen phil nhau kh6ng nhimg tao thanh hai MO 1t rieng re Ina con tao thanh mdt MO chung cho cD. phan tlt Ta goi do la SlJ lien hop (x. hinli 1.11).

H

CH.) I

~ /c~ H

. C CH~)

I -

H

(a)

...

H H H H

H

(b)

(c)

Hinh 1.14 Con .. [;{ th.uc cdu. tao (a), slj hinh thanh. hai MO 1f rieng re (b) va MO J[ chung cho toari phati til butadien (c).

He cac lien ket 7t xen ke voi cac lien ke't o d~ tao thanh MO

• •

1t chung cho cD. phan tit duoc goi Ii h~ lien h.ap, Neu thay the

...

111Qt 11116111 =CH~) trong phan tit tren bang =0 thi 11~ lien 11QP

-

. ~ ~ ....

luon luon phan Cl;(C ve phia =0 Ina ta c6 the bien thi bang cac

l11Ui tell coug:

0+

s: ~ &-

CH~J-CH-CH 0

......

Trang truong hop co mot nguyen tit luang cap electron chua lien ket hay con tu do (con goi In. electron n) noi vdi mot nguyen tt1 cacbon mang lien ket 1t ta cungco he lien hop tuong tu 11h11 tren, song 6 day electron n chuydn dich ve phfa lieu ket 7t theo

48

chieu mui tell congo Thi du CH2=CH-CI:

H

1

hayla

. '

H

Hien tuong phan cue tren 11~ lien hop nhu tren duoc gQi 13. hi~u itng lien htJp. va ki hieu b~llg chit C (til Conjugation

Effect). Nh6111 -CH=O gay nen hieu (tng lien hop bang each keo electron ve phia 110 (hay 1a hut electron) ducc coi 18. nhom gay hieu. ung lien hop am ( ki hieu - C ). Nguyen tit clo trong thi du tren gay hieu (tug lien hop bang each chuyen dich electron ve phia lien ket 1t thi Qlt<jC eoi 1ft nhom gay hi~u ilng lien hcJp ducng ( ki hieu +C ).

.. .

Xet theo dQ manh cua hieu ung - C ta co:

>c=o > >C=NH >

(vi trat t\l de> am dien 0 > N > C)~

Xet theo Q(> manh cua hieu {tng +C ta co:

-F> -CI > -Br->-I

(vi kich thuoc nguyen tit va do d6 kich thudc obitan n tang ttl F den I). .

-NH .. J > ~O·H > -F

tJ

(vi dQ ain di~ntang tit N dell F).

..

49

Chu y rang hi~,j_ zmg zi~1i h</p" g&ri: :nhri . k'hong gid:m khi

mach. lien lutp keo dai. ._ .. _.~. _ '.~ . I

• ~ • ,"'I,.~ (

.-''''--..

~ .

. .

.. ,

. .

. .

3. Hi~u: un,g sieu·.lienhqp

., .

. - ... ~

." .

.....

.. ....

Khi d vi tri a dOl voi nguyen tu cacbon mang lien' kgt 1t co cac lien ket Ca-H nguoi ta thay duong nhu eo sir lien hop gina cac Cn-Ii va .C.=C~ Thf du:

n --CH---CH9

.....

Ta noi rang' nhom CH3 da gay hi~u ung sieu. lien h<Jp driy

. ....

electron tam ki hieu bang +H (ttl Hyperconjugation Effect). Hieu

ung +H se yeu di khi giam so lieu ket Ca-H:

~1.4.3 Hi~u ling k.hfmg gian

D6 1ft hieu ung. cua cac nhom co kich thudc Ion ( - CHa. -C2H5' v.v ... ) Hun can tres mdt vi tri hay lllQt nhorn chuc 11aO d6 tuong tac vdi tac nhan phan ung (x. thi d¥- 1) hoac lam giihn hieu ung lien hop cua 1ll9t nhom khac (x. thi du 2).

Thi du .1: Trong phan tii 2.6-dilnetylquinon dudi day co hai ( 1)

nhorn C=O song chi C = O'tham gia phan ling vdi NH20H. con (~)

C == 0 khong phan ling duoc, vi hai nhom bencanh da gay hieu

ung khong gian can trb NH20H den gftll:

50

(1) 0-,-

eR3 (2) 1-0

eR3

Thi d,j_ 2: Phenol la mot axit yeu, neu dua nhom -N02 VaG vi tri para se 13.111 tang manh tinh axit vi nhom nay gay hieu ltng -C va -1. Tuy nhien, neu (j" cac vi tri ortho d6i vdi nh6m

-N02 co nhirng nhom -eRa thi tfnh axit chi tang it vi hai nhom

-eRa da gay hieu ling khong gian, lam giam su lien hop do do

giarn hieu (tng -C ella -NO 2' .

OR

OH

OH

CH3 CH3
N N
c ~O
jj\~
o ~ ,
0' 0
pKa 9~98 . ., 7~16 . 8,24 Bai t~p

.'. . .

1.11 a) Hieu Ullg cam Utlg la gil! Nell d?c diem quan trong nhat etia hieu ung ·

.. ". ~ .. ., . . .

cam ling. .. ".' _" _

b) SAp xep cae nguyen La va nh6ni-hguyen tutheo chieutang 'dAn ella

r

hieu 1lng cam ang~am trong mOl·day sau:

• ". I • ~_

. ..

r I. ._

F'· ~l . B ._ I _ ,

~ . .

... --. ........- .......

. . .•. , I ':. "II _., ~ _ f_...· ,~ ,

, '

~_

5·1

c) Sap xep theo chieu tang dAn ella hieu ung cam ling dirong:

..

. -

1.12 a)Hi~tl lllg lien hill) 13 gi.'? Neu dac di~m quan trong nhat ella hieu img

. .-

lien hou.

b) Sal) Xel) thea chieu tallg d~ll cua hieu Ung +C trong m6i day sau:

c) Sap xep thee chien tang dcin ·c~a hieu Ung -C trong mBi day sau:

1.13 a) Cho ba hop chat chua oxi CH3-OH; C6H5-0H~ H-COOH. Hay cho biet nguyen 11h~Jl eua tinh axil. trong m6i trltdng hop. So sanh tinh axit ella ba chat. do. (~iai thtch.

b) Cho IJa hop chat.. chua nito : NH3; CH3-NI-I2; C6!-I5-NH2. So S811h tinh bazo eua chung, (~iai t.htch.

a) Cho He] lac dung YOl CH3-CH=CH-CH2-CH3 sinh ra chu yeu ]a . dong phan CH3-CHC1-CH2-CH:rCH3•

b) Nitro hoa dong dJng ella benzen

+

Nell R 1R (~l,i;) t.ht ti 1<3 ha i dOllg phan ortho : para ia 1,4 song lletl R la Crl (C J-13)~ t.hl t.1 It) do chi ballg Ot5.

52

?,It 4~ "til _'

1.5 PHAN trxc eUA H(jP CHAT HUU co .

..

..

1.5.1 Phan loai phan ling huu cd C6 ba loai chinh:

..

1. Phan ling the

Phan (tug the duoc kf hieu bang chit S (xuat phat til Substitution co nghla 13. "su thay the") 18. phan ung trong d6 mot nguyen ttt hay nh6111 nguyen tit trong phan tl1 duoc thay the bang nguyen tir hay nhom nguyen tii: khac. Thi du :

CH;)-H + CI-C1 -4 CH3-CI +. HCI

Phan ung trung ngung thuc chat 1ft nlnmg phanung the' n6i tiep 1111 a 11.

2. Phan -ling c9ng

Phan ung CQl1g duoc ki hieu bang chit A (xuat phat tit Addition c6 nghia lit "su cQng hop") la phan -ang trong d6 hai phan tV: ket hop vdi nhau tao thanh lTIQt phan tir mdi, Thi du:

..

CH,)=CH9 + Br-Br ~ Br-·CH9~CH9-Br

w ~ "*ttl -.J

+ H-H --) CH3-OH

,

Phall itng trung 'UIP co ban chat 18. phan tmg c9ng nhieu

. . -

lUll.

3. Phan (tng tach

,

. -

Phan "ltng tach dU(JC ki hieu bang cha E (xuat phat tu

53

~

Elimination co nghia lit "su tach bo") 13. phan ung lam cho hai

nguyen tit hay 111161n nguyen tit hi tach ra khoi met phan tit Ina khong co nguyen ttl hay nhom nguyen tit nao thay thevao. Thf du:

..

CH2=CH2 + H2 CH2=CH2 + H20

Crackinh thuc chat la mot loai phan ung tach.

1.5 .. 2 Cac ki~u ph an ciit lien ket cQng hoa tri va cac ti~u phan trung gian kern b~n eua p han ung

1.. Sl! phan cAt d6ng Iy. Goc cacbo tt! do

Trang phan irng hftu co. lien ke't cong hoa tri C-X (X c6 th~ In H. C. L v.v ... ) co th~ bi phan -c£t sao eho In6i nguyen tit lien ket sau khi bi drrt ra v!n con giu duoc Inqt electron. Ta goi d6 18.

; ,

slj pluin cat dong ly. TIll du :

H. , :

H-CL~~IH

, ~

H t

Ph an tit metan

+ cr'

..

H J

H-C· + H;CI I

H

Goc tl1 do metyl

·CH;j co chua met electron dQc than tu do nell duoc g9i lit gac tT! do metyl. Ngoai ·CH3 ta con biet nhieu goc cacbo tl.! do

khac nita nhu CHa-·CH2• (CH3>2·CH , C6H5·CH2• v.v .... rna ta

co thS ki hieu ehung Iii R-.

Cac goc tu do thucng rat khong b~l1 va chi tan tai trong khoang thoi gian rt(t ugan (chang han ·CH3 chi t6n tai trong vai

. ,

54

phan nghin giay). Tuy vay df} bell tuong d6i cua cac g6'c tv do

. - . .

phu thucc vao cacnhom nguyen ttl noi vdi nguyen tit cacbon

mang dien ttl tlJ do: cac nhom gay hieu trng lien hop hoac sieu

. . .

lien hop lam tang dQ ben cua goc t\t do, vi chiing lam giai toa

best mat do electrontu do. TIll du:

... .. ..

·CH:J < ·CH2CH3 < ·CH(CH3)2 < ·C(CH3)3 ·CH2CH2CH3 < ·CH2-CH=CH2; ·CH2-C6H5

Cac goc tu do R· thuong co cdu true phdng, ttrc 1a ba lien ke-t xuat phat ttt C· d~u 1151n tren mot mat ph~ng,

Tat cn. nhimg phan (tug .xay ra vdi su phan c~t dong ly lien ket deu duoc goi la phan. itng c!6ng ly.

~

2~ 811 phan cat d] ly, Cacbocation va cacbanion

-

Khi xay ra phan ling hiru co, lien ket C- X co th~ bi phan ciit

ve mot phia nao d6 sao eho cap electron lieu ket thuoc hAn ve ITIQt trong hai nguyen tit vonlienket voi .nhauI'C hoac .X). D61a nhirng kiiu ph/in. edt dj ly.

a) Sf! phiin erit dj ly 11 phia nguyen t(t C se sinh ra ffi9t

. - . .

cation Ina dien tich duong ehuye'u d nguyen til cacbon, nen ta

gQi 13. cacbocation, kf hieu bang R(+). Thf du:

oil

.'.

. o~ 5-

0.. CH3 ":'·C~ •.. Br

I I

CH;3 .

(+). .. (-) .

----. ·CHa-CH'-t Br .

.. ... ,.' (.. .. .. ' .. J . :....:.

en,

( .

r _

- .

_ '.1 _. .'. .... :r-:

ISOpl·OP)71 bromua

- • I • ..

.. _: ., ~ I .- .:. ~. _ •

....

r . .Cation isopropyl

_. . , . L .II .' •

~.. . r

~ - 1 . '

4

- '. .

• I,

-5-5

- ~

. • Tltcn1g h~ gOc: titdo/'cacbocatidn cung'kh()lrg,bgn; 'song:d:Q

b~n' tuong doiena cacbocationse tihig:len'khi:'c6 m~t eacnhorn

• I • • • •

the dffy electro 11 'lam · giai' toa bdt di~ri. tfch d tldng:'" , " '

(+)CH:3 < (+)CH2CHg < (+)CH(CH~)2 < (+}C(CH~)3

(+)CH CH CH (+)CH . C (+) . .

2 2 3 < 2-CH= H2, CH2-C6H5

I)

Cacbocation cung co cdu true phung. tuc 13. ba lien ket xuat

, '

phat til C(+! d~u narn tren mot mat phang .

b) S,!phan ctit d# ly a phia nguyen tii X se tao thanh 1119t anion Ina dien tich am chu yeu d nguyen tit cacbon, nen ta

...

goi If! cacbanion, ki hieu bang R<-). TIll du:

: '. NH;~ long (-) (+) ,

2 (C6H5)3C-:H + 2Na ... 2 (C6H5hC Na + H2

I 1

Cacbanion cung khong bell. D9 b~n tuong doi cua cacbanion se tang len. neu co 11h6111 the hut electron co tac d\111g 'phau tan

dien tfch am:

..

Khac vdi R· va R(+). cacbanion c6 cdu true hinh tluip ; chimg 111ljC nao tuong tu nhu amin bac ba.

" ;

Tat cD. nhtrng phan ung xay ra vdi 81.1 phan cat di ly lien ket

deu duoc goi 13. pluin zeng di [y.

56

+

1.5.3 Ph an ling electrophin va phan ling nucleophin Trong mdt phan ling di ly. cac ti~u phan hoa h9C tuong tac vdi nhau nho ai luc ella chung ct6i vdi electron hoac doi vdi hat 11113.11 nguyen tt1.

1 .. LOQ.i ti~u phan co ai luc doi vdi electron duoc goi la chtit electrophin. Do la nhung ion duong nhu R(+). H30(+). (+)N02•

Br(+). . ... hoac nhirng phan tit c6 chua nguyen tit thieu hut electron do SlJ phan cue manh cua cac lien ket nhu SOs. ICl, ....

. Nhirng phan ling xay ra gina phan til: chat. huu co vdi chat electrophin d giai doan cham duoc goi 18. phan itng electrophin. TIll du:

2 .. LOQ.i ti~u phan co ai luc doi vdi hat nhan nguyen ttl duoc goi Ia ch{ft nucleophin. D6 1ft nhimg anion nhu RH. HO(··). C2H50(-l. I( l ••••• hoac nhiing phan tit co cap electron chua lien

.. .. ..

ke"t d~ nhuong di 1111u NH3• H20 .. C2H50H. v.v ...

Nhfmg phan ung xay ra giua phan tit chat huu co vdi chat nucleophin d giaido~n cham duoc goi 1a pluin -ling nucleophin, Thi du:

. ."

-;

57

1.5.4 Khai ni~m ve ca che p han ling

Trong lllQt phuong trinh phan irng 116a 119C thong thuong chi trinh bay cac chat dUll va cac chat cuoi cua phan Ullg Ina khong neu r6 qua trinh do diel1 ra 11111t the 113.0. qua nhimg budc trung giau ra sao. tuc lil khong eho bie't co che phan ung. Thi du:

..

CH2=CH~ + HBr ---). CHa-CH2Br

chi In 1119t phuong triuh phau ung, COIl co cile cua no da trinh bav d muc 1.5t3.

..... .

Co th~ noi ca ehe' phan itng h6a hoc liz eon dUdng chi tiet rna h~ cdc chfit phcii di qua dl t qo ra san ph6m. Con

duong do phan anh cac buoc cc ban cua phan ung, each phan cAt lien ket va each hinh thanh lien ket mdi, ... cung nhimg dir kien khac v~ phau ung.

Co che' cac phan ung huu co rat da dang va thircng phtrc tap, Co ba loai co che' chinh:

1. Ca che' gifc tu do: Trong cac phan (tng thea cd che gac tu do thuong c6 su tham gia cua cac g6c tl;1 do. D~ ki hieu cho

. ;

nhimg phan (tng theo co che nay nguoi ta ghi chtr R (xuat phat

tu Radical nghia la"g5cU) vao g6e duoi bell phai cua ki hieu phan ling. Thi du:

S n In phan irng the' theo co ehe goc. Ch:ing han, cIa h03. CH4 trong digu kien chien sang.

All 13. phan uug cong thea co che goc. Chang han, cong HBr vao CH,)=CH~) co mat Hi)O.) .

..." w .. - ....

2. Co ehe' electrophin: D6 III nhirng phan ung eo su tham gia ella tac nhan electrophiu. D~ ki hieu cho nhirng phan Ullg

, '_

58

..

nay nguoi ta ghi chu E ben canh ki hieu cua phan ung. Thi du:

AE 13. phan ung ccng thea Cd che electrophin. Ching han, cong HBr (khi kh6ng co oxi hoac peoxit) vao CH2=CH2 (x. 1.5.3).

OJ! r

S E lit phan ling the' thea co che' electrophin. Chang han,

brom hoa benzen nho chill xuc tac FeBr3 sinh ra tit Fe va Br2·

T h'~" .... " nhf h" #' 1'" B (+) h 'W

rong p an ung nay tac an p an ung a r oac

6+ 6-

Br .... Br . FeBr:J.

3. Co che~ nucleophin: Tac nhan phan ling 13. nhimg chat nucleophin nhu H20, C2H50H, v.v .... Nguoi ta dung them ki hieu N d~ phan biet vdi cac co che khac, 'I'hi du:

AN 1ft phan ling cong thea cc che' nucleophin. Chang' han, cong HeN vao CH3CH=O (x. 1.5.3).

S N 19. phan ling the thea co che' nucleophin baa g6m cac phan ling: the; nucleophin mQt giai doan-ludng phan t11 SN2 (thf du CH3Br tac dung vdi NaOH d~m d~c trong nude); the nucleaphin hai giai dean-don phan t11 SNl (thi du tert-C4HgBr tac dung vdi dung dich ki~m loang trong nude); the' nucleophin thee ki~u c9ng r3i tach d axitcacboxylic va din xuat SN2[CO] (thi du este hoa va thuy phan este).

Elva E2 la nhiing phan img tachnucleophin don phan tit va luang phan tii (thi du CH3GHBrCH3 tac dung vdi dung cijch

. .' '-

KO H trong ruou) song rit hiem co phan ung tach thea co che"

g6c t~ do hoac cc che electrophin, nen ngUdi ta di den gian hoa

khongghi theln ~liu N.-··

I :r • .

~ I' • 'I I I. .' J ... II : : : . ".

• ~. J •. ~. . .. - .

~

, '

.... .'

, . \

I P I .r

• <

.. ' .

"'-n....-. h-K ~ ~.\.' t"" b·~ .,.. A /fIW At" h b'

- ~, " .: :. ~ 'Z·n1.1n-g Cd~~ c e .~C1l}. ··;III-IC V=<i- re\l leU.':(j- tren:·se um;sc rIn ay

trong cac chuong II ·va ~II~ . '

Bili t~p

1.15 Nell djnh nghla vA cho thi d\l minh hoa VB phan iillg the, .phan ling tach,

. . -

... . - .,

phan ((Jig ei)11gt phan UIlg oxi hoa-khir, phan img dong ly va phan img di

l~· ~

1.16 Hay" S~lJ XCI) moi phan U11g sau daj" V80 mot. loai thich hop k~ a tren:

a) CH2~CH2 + H1 b) CH2=CH2 + HI c) CH:J-CH:~ + C12 d) CH~J-CH:3

p, t

-----1 .. _ CH3-CH3

H:/> .. CH3-CH2I as

_._,... CH3-CH2Cl + HeI

t, xt

-----I .. ~ CH2=CH2.+ H2

e) CH;~-CH2-Bl~ + KOH f) CH:.~CH2Bl~ + KOH

g) CHa-CH=O + HeN

l;2};5l)H

--__.....,jJ .. - CH:z=CH2 + KBr + H20

H?CJ .. CH3-CH20H + KBr

------.oj .. -- ~ CH3-CHOH-CN

1.17 a) Ii a)~ djnh nghla: cachocation, cacbanion, goe· cacbo t.t_t do.

CI-la(+l, CH:3CHz(-fi, CH3CH(+JCH3, (CH3hC<-t1

. .

.(~ t-l ;-3' (~If;3·C 112, (~Ii 3 ·(_~H o H3l (CH3)sC· CI-18CH2(-J, CF'aCHz(-'. CC13CH2<-1

1.18 (~o the lJht411 Ullg 114 gl~? I-iRj· minh hoa bl%llg GO che cac l)hall Ung sau:

Ct-I,'1 + (~~2

---iI') C}-laC1 + Hel

60

Cll.s=C ~·L) + rlBr

- .;

·C.l-l ~3-(:Ii=O + HeN

(~Ii3-CI-12Br CH3-CH_OH-CN

. _

1.6 DANH PHAp Hap CHAT HUu co

Trude kia, khi 11lOi tun ra 111Qt so hrcng it oi chat hiru co nguoi ta dat eha lu<3i chat 111«$t ten thuong thea nguon gO'c tim ra chat eta 110~C 1119t tinh chat vat Ii nao d6 cua chat, rna khong theo mot h~ thong 11300 ca. Do 18. ten thudng, Sau nay. khi ~a tim ra rat nhieu chat hiru co khac nhau, nguoi ta tim each goi ten cac chat hiru co thea nlnrng h~ thong 11h5t dinh, D6 18. cac ten h~ thong. Giiia hai loai d6 co loai dauh phap trung gian g9i 1a ten nita h? th{/ng chi dung mot vai yeu to' h~ thong.

Hien nay. nguoi ta ua dung each goi ten b~ thong do IUPAC III de ra goi In. danh pluip thay the: MQt s5 h~ danh phap it dung hen (danh phap goc-clnrc, daub phap cong.v.v ... cung duoc dua

.

.,-

vac cac quy tile danh phap IUPAC.

1.6.1 Dan h p h ap hidrocacbon va goc hidrocacbon

.

, 1. Hidrocacbonno mach hi1 va g6c hoa tri m(}t

a) Hid rooacbon no rnaoh hCi k horig co n'harih

, BOn chat dfiu co ten nita h~ thong va deu t~n cung bhng duoi ~ an. Ten cac dang, d&~lg cao hen d~u' gO,Ill: mQt "phannen"

d~ chi s6 luong nguyen ttl cacbon (11), nhu pent- (C5)~ hex- (C6), hept- (C7) .. .. va'phfill dllOi 1a - an. Ten ch:ll-ng·:'ankan.

" .. .. . .

• ~. - .. I, • I : -' •

. ,

',! IJ,V . .P ~C: ?~~~t. p~H 1. tit Int_~n'!',tio1lpl .U~~i~n of.Pure, a!~d Applied Chemistry c6

- ·nghia 18. H iep· hQi qt16c' tt· hoa hoe co Dali ~va ~un g a·\111g. _

61~

1

11 Tell 11 Tell 11 Tell
1 Metau 8 Octan 15 Pentadecan
2 Etall 9 Nonan 16 Hexadecan
3 Propan 10 Decan , Heptadecan
17
4 Blltall 11 Undecan 18 Octadecan
- Pentan 12 Dodecan 19 Nonadecan
o
6 Hexan 13 Tridecan 20 Icosan
7 Heptau 14 Tetradecan 30 Triacontan Khi tach 111Qt H d dftu mach cua ankan ta duoc g6c 110 hoa

.

tri 1119t eo ten xuat phat tll ten ankan tuong img, chi d6i duoi

- an thanh duoi -yl. va goi chung 13. ankyl, Thi du: CH3- metyl,

. CH:3CH2CH2CH~CH~- pentyl.

b) Hidrocacbon no mach n.harih

..

Theo danh phap thay the cua IUPAC each gQi tell ankan c6 mach 1111al111 1111li sa 11:

- Xac dinh mach chinh. d6 In mach cacbon dai nhat va co

• I •

nhieu nhanh hon (khi phai Iua chon gina hai mach dai b5.l1g

nhau),

- Danh so cac nguyen ttl cacbon tren mach chmh xuat pha t tit dfru 11aO gan nhanh va eho so chi vi tri nhanh la nho nhat.

~

."

- G9i ten cac nhanh (duoc coi nhu nhtmg nhom the) cung

. - ~ I

voi cac so chi vi tri ella nhanh (dQ_ t truce ten moi nhanh) r6i den

ten mach chinh tQ.l1 cung bang -an.

Neu co tir hai mach nhanh trd len thi gQi ten chting theo

62

thir tu bang chir cui. Trang truong hgp eo hai, ba. bon ... mach uhanh dong nhat thi dung cac tiep daungu di-, tri-, tetra- ..... TIll du:

..

i

6' 5 4 :3 :2 1

CH3-CH2-CH~ - CH ,- CH2-CH3 3-Metylhexan

, . I

eRa

CH:3

~t ~1 I 2 1

CH3-CH2-CH C - CH2-CHa 4-Etyl-3,3-dimetylheptan

7 6 51 I

CHa-CH2-CH~ CH:3

Muon g<;d ten cac goe ankyl hoa tr] mC)t co mach nhanh. uguoi ta chon mach dai 11h3:'t co chua hoatri tl1 do Hun mach chinh r6i danh so tu nguyen ttl cacbon mang hoa trl tlJ do roi goi ten thea trinh tu da gc).p d ankan mach nhanh. Thi du:

4 3 2 1 .

CH:3-CH-CH2 -eH - 1,3-Dhnetylbutyl

- I I

. C'H3 . eR3

Chu y r&llg cac qui t~c cua IUPAC vftn cho dung ten thirong ella mdt sO ankan co ~ n11a11h lit isobutan (CH:03CH. isopentan

(QHS>2CHCH2CHg. neopentan (CHg)4C' va .cua cac goc, ankyl 'co nhanh : -la. isopropyl _ ~(1-1netyletyl)~: : sec-butyl ; (l-metylpropyl). isobutyl (2-1netyl-propyl).' tert-butyl (1', t;;.diinetyletYl).· 'isopentyl (S-metyl-butyl). neopentyl (2.2-dimetylpropyl). tert-pentyl (1,1-

dimetyl-prcpyl). .' .: . I· . , • I' I , .. ,

. . .

. . ~ .

. ,-

I • - "

-

_. _ .

..... -

- .

• • r • I

• I" '.' I

63

~

2. Hidrocacbon khong no machho va gO'c hoa tri mQt a) Ten cua hidrocacbon co mot, hai, ba .... noi d6i xuat phat hl' ten cua ankan tuong irng chi thay duoi -an bang -eri (neu co 1119t noi doi). -adien (hai noi doi), -atrien (ba noi doi), .... kern theo so ell} vi tri cua cac 110i, doi do *) • Mach chinh la mach dai

... ..

1111at va c6 chua nhieu 110i d6i nhat, duoc danh so sao cho co cac

"

ell} so 11110 1111at. TIll du:

..

·1 ;~ :2 1

CH·)-CH·)-CH=CH~) Buten-l hoac Lbuten hoac but-l-en

• I '""'" _ • ..

C. J ;~ ~ 1

CH~)::::CH ... CH~)-C=CH9 2-Et~~lpentadien-l,4

- -- I ~

CH~-CH3

b) Ten cua hidrocacbon c6 chua 115i ba cung xuat phat tit ten ella ankan tuong ung chi d6i -an thanh -in (lnt$t noi ba), -adiin. (hai noi ba), -eniri (1119t n6i d3i va InQt Hoi ba). v.v ... Thi du:

CH:~ C C-CH:z-CHa Pentin-2

CH==C-C=C-CH:~ CH=C-CH9-CH=CH.) Penten-l-in-4

~ .....

Pentadiin-l,3

c) Tell cua goe khong no hoa trj lUQt co duoi -enyl (chua noi doi) hoac inyl (chua noi ba) .... cung vdi chi so v~ vi tri cua lien l{Eit kep, Thf du:

CH:~-CH=CH- Propen-I-yl

.... , .-.

ChU. Y rang cac quy tac ella IUPAC Vail eha dung cac ten

thuong: etilen (eten). axetilen (etin), isopren (2-1netylbutadien- 1.3)~ vinyl (etenyl), anlyl (propell-2-yl)'A~ ...

~ I 'I'll (.~ 0 (111 ~. d i 11 h e U H J LJ I) A (:, cA 11 dB 1. e h i s6~ (h ay 1 oc all t) ng a y t rude ph a n dircc chi d i 11 h 1 )() 1 chi so (1 ()_ r I' h i ( I ~ cA 11 viet: I) II r- 2 - e 1 \ ; 2 -c t Y 11 Je 11 ta -1 ,4 - die 11, ]JT'()1)t-1.11- l-()] ~

64

3. Hidrocacbon \Tong va goc hoa tri mi}t

a) Tell ella hidrocacbon 110 va khong 110 don vong duoc 1111111 thanh ttl ten cua hidrocacbon mach hes tuong ung bang each them tiep dau ngu xiclo-.

Qui t&c nay cung ap d\111g cho cite goc hoa tri mot, Thi du:

I

Xiclopropan Xiclohexan Xiclopenten Xiclohexadien-l,3

4-Met)~lxiclohexyl Xiclopenten-2-yl-l."_ .

b) Ten thuong cua nhieu hidrocacbon thorn v§.l1 duoc dung; cac chat d6ng d~ng duoc coinhu nhfmg dfrll xuat the. Thf du:

8 1 8 9 1
'J .J
- -
;J 7
() 3

5 ·"1 - 10 4 6 4- 3
0
..
-!"
.
Benzen N aphtalen ., . .Phenantren .
Antraxen CH:3

l-E tjrl-4 - propylbenzen (p-Et:ylprop)~lbenzen)

Toluen (Metylbenzen)

1,2- Dimet:yl-3- propyl benzen

• •• - I •

Chu y rang khi chi co hai nhom the d cac vi tri 1.2 hoac .1.3

65

~ r

hoac 1.4 c6 the thay cae chisd do 1~11 ltiQt bang' :0- tortho-), In-

tmeta-), p- tpara-),

'I'en.thuong cua 111Qt so goc thorn Vall duccdung. Thf du:

CB3

Phenvl

....

p-Phen)rlen

1.6.2 Danh phap cae ddn xuai.cua hidrocacbon

1. Danh phap thay the

. a) Quy tac ch ung

- Xac dinh fa nhcm chuc trong phan tit thuoc loai .chi duoc goi tell duoi dang tiep dfru ngft (c~c nhomloai A) hay thuoc loai co th~ goi tell d.110i dang tiep aau ngu hoac tiep vi ngu tuy

truong hop (nhorn loai B).' ·

- Neu la hop chat tap chuc thi can xac dinh them xem nhorn 11aO lit 11h6n1 chuc chmh d~ goi tell dudi dang tiep vi ngu; cac nhom chuc khac trong phan tit chi duoc goi ten duol dang

" "

tiep dftu ngu vatheo trinh tu bang chu cai.

- Xac dinhmach chinh, d6 -1ft mach dai nhat Ina chua 111101n

... . ..

chuc, Neu la hop chat tap clute thi d6 lit mach .chua 11h6111 clute

" -

chinh, "

. "

- Danh so mach chinh tu dftu nao g5.n nhom chuc va nh6111

clnrc chinh. . . . -. , :-. ...

66

" . - Doi voi hop chat don clnrchoac da clnrc chua nhom loai A

- .

thi goi ten nhom clute (dang tiep dau ngti) cling vdi so chi vi tri

tren mach, r6i den ten mach chinh. Neu hop chat chua nhom loai B thi goi ten mach chmh truce rBi de'n ten nhom chile (dang tiep vi ngir) cung vdi so chi vi tri cua no tren mach,

. .

. .

-:- D6i vci hop chat tQ.P chtrc, can neu ten truoc h€t 13. cac

nhom chuc ij' dang tie'p d:§.u ngu thea trinh t\t chu cai, cung vdi cac s'o chi vi tri cua chung trong mach, r6i de'n ten mach chfnh, va cuoi cung In ten cua nhom chuc chinh d dang tiep vi ngfi cung voi so chi vi tri cua 110 neu cfrn thiet,

. .

b) Cac nh6m chi dtigc goi ten dlioi dang tie'p ddu ngii

(nh6m loaiA)

- Tie'p da U ngu
Loai IlQP. chat Nh61n .. . .
-
....,.. .; Floro- (hay flc-)
Dan xuat flo ~F
Dall xufit clo -
-CI Cloro- (hay clo-)
Dan xuat brom -Br Bromo- (hay brorn-)
HQP chat nitro so -NO Nitroso-
H 9P ella t ni tro _:.NO" Nitro-
.J
-
"
Ete ~·OR,~ R-oxi- (metoxi-, etoxi- ... )
.... ~ Tlll du:

1 » ·3 4

CHs--CHCl-'CH2- eR3

43 » 1

< CH;:r "'CH2- CH2- N02

CHg-O-CH2-CH;J

2-Clobutan

1- Nitropropan Metoxietan

6.7··

c) Cae nl10m .~~ t~n: ·iI·d':rigiti«p'~·dtu riga va~ titp ,,-j "DgU

• r

• I' - • .I'

(nhomloai B)'; .: ~;;,". 2 ~ :._> ... :: : .i _'. :,.: i ";' i~. .:: ~: .: i. . - . ~,

- - r" -

• - • I -.-

.' ... .. - "

r '. _' .. ' ". •

. .

t . . .

, .

_ .. ~:_ I}L_ .... r. I' • "

., .. .

, .

: .. - / : ~ ~

~ '. ~ .

r !. .

.. - +

. .

• .. . : ..

- , .

~. , . ,

,

~

. '. . ."

.~.

, I .. ~ 'I-

I •

, L.

.... I .. _. .

" ...

......

Axit cacboxylic -:.COOH I .Cacboxi- ~ ' .. .Axit·~.~- cacboxylic

- r -COOH, _r:- - Axit .... oie

.. I • -

-

~C09R . ~-oxicacbollyl~ R. cacboxylat

-COOR - R oat

Este

....

Allllt

r - - - ,
. - Cacbarnoyl- ' ... , cacboxarnit
-
-CONH~)
- -
-CONH~) - ~ ., ~. amit
-
-CH=O FOlllyl- ... ~, cacbandehit
, - ... ~ .. , .. - al
~CH=O· OXO_·L : .: . -
. , - ,

>C=O Oxo- , .... 011 ,
-OR Hidroxi- ~ ••• A 01
. -
Amino- ...
-NH~) or , .... II' t aIDlll ..........
Andehit
..
,_
Xeton
Ancel
- .
A III ill ... .. Clui thich.: Nhiing nguyen- til. C (in- d(i1n) til/fie tinh. trong ten CUra

, "

mach. chinh, kll.ong tin-It tr·ong ten, citra tiep diiu. ngit

hay tiep vi ngii.

,r

~

CH;rCH2-CH20 H CH,:r-CH;N~2-CH3

, ~.

(CH3):tCH-CH2'CH=O .

(CH:3)2CH-CO-CH;3

Propanol-I Pro panamin- 2

_. . .

3-Mety1,butallal

- .

3 - Mety lbu tanon- 2

. :

CH;3CH2CH2CH2CH2COOH Axit pentancacboxylic-I

hay axit hexanoic

68

-- __ . --- -

d) So sarih dQ tiu tien cua cac nh6m chitc trong ten eua

• t

cac h9'p chat t~p chiic

.. -'II • "I

.. Theo qui t&c IUPAC. nH]C uQ uu tien cua eac nhorn chuc

• • • I • • •• _ '.' _ •

giam thea thit tu sau: -COOH > -S03H > -COOR > -CONH2 >

--CH=O > >c=o >, -OH > -NH~) > ~OR > -R .

. . -.

. . .

Trang phan tit hop chat tap chuc, nhom chile chinh la nhom

co do Ul1 tien cao nhat. TIll du: ..

.. . ~

:{ 2 1

CH9-CH -COOH-

I r: I·~·

OR NH9

Axit 2-amino-·3-hidroxipropanoic (vi ·-COOH la nh6m uu tien cao nhat)

-

1 ~ ~3 ·1 5 6

CH:i~C~C=CH ---CH -CH2 3-Clo-6·-hidroxi-5-.metylhexen-3-on-2

II I I I· (vi >C=O la nh6m chuc chinh)

o Cl en, .O.H ,

- .

, .

2. Danh philp goc chuc.. '-

......

. .

. . .

Loai danh phapnay thuong chi dung cho nhimg hqp chat

hiru cokhong phuc .tap. Theo danh phap nay; ten ella hop chat

bi'tu cd g&lllhai b-QPh~-llchinh IiI 'ga'c va nh6m-chue:.~,' .. .. ,- - ·

R-(~O-R Diankyl xeton

R-CO-Hal Axyl halogenua

. :

'. - H <II) chat, - : -. ·(~olig tj}uc.: '

, _ chung .~ -

- . 'Te11 chnng

., ..

CH3- Br metyl bromua

, C2"~5r9~f .ancol etylic ..

- ~ -..... . .......

. G2~5r9-:-.C;2~5· ~i~~yl~ete'. ' CH3-CO-~H5 etyl metyl xeton

CH3-CO-Cl axetvl clorua

..

.

R-Hc-\"I

~ - ;

Dan xuat

halogen

Ancel. .

Ankyl halogenua

R-OH

~t

~ Ancel ankylic

- ~ • I .' •• .'. ..-

- - I I ... I ... I

- I ..._

-. .

.. ....... I'. .r

r : ..il _ ••

..

- . . .

,

-

Diankyl ete __

~ :..... '-...:. • p

.. ' - .....

.... -:..,.. ~~..... .... '_

l~-O-R

I _ -

. ~ ~. ._

~

- .' 't' .. .. -.

Halogenua l axil.

69

... r . 1

,;1 I ........ 1 1 •• 1 • I· • •• •••• .,.. ". •• l . +

• '._ • !I' I I. .• .,. ~ • • ~ . I'" .. . 4 ~ .... • ,. •• • r _ _, ... _., _ _~ ,

". '- -3.'Danhlihap·flilfitng-'- - -',-,.;',,' ~,.,; ~.:_1. .. ' :>". ,,'.:

, , ~~

I ... t .>.. ,.

. .. .. -I -... ... [ .. ~ .. ·.1· "... "I ~. r

..... r- .~... I" ~:" "r":' .. j..1 ; ~L ~ _ • ..:. 1 ...

, .. ..:r.. ,

Doi vdi hidrocacbon va nhieu din xuat don chuc cua

hidrocacbon . cac ten thiuang tUdngdOi it ' dung, ~ song -dQi' ~di cac , Ioai h® - chi'tkiia~, riha't Ih' h~p chat t~p ;chuc; va - h<;11> chat' dj

vong, danh phaji thudng'l~i dU(jc dung"phc5 bi~n"hdi1, cac Ioai danh phap khac. _Sau, day lA n;lQt.so thf.du: :.

, , ,

... -J" . . . .. =. •

, 1

a) Axit cacboxylic va gocax"l : Ten thirong' ciia axit cacboxylic thuong eo nguon goc lich sit

Axit

HeOOH CH3COOH CH3CH2COOH

CH3(CH2)lSCOOH HODe-eOGH HOOC-(CH:04-CQ'OH

• •

CHa(CH016CO- -co-co ..

-CO-(CH2l4-GO-

Ten (-ic --+ -yl hoac

-oyl)

Fomyl Axetyl Propionyl

Stearoyl Oxalyl Adipoyl

. . .

b) Andehit: Ten thuong cua andehit xuat phat tu ten

thuong cua axit tuong ung b~ng each thay "axit -ic" b~ng

"- andehit ".

T~n

Goe axyl

..

H-CH=O Fomandehit CH3CH2CH=O Propionandehit

Axit fomic .Axit axetic Axit

HCO'CH3CO·~

propionic Axitstearic

./

Axit oxalic

,

Axit adipic

CH3CH=O Axetandehit C6H5CH=O

70

Benzandehit

c) Hidroxiaxit va goc axyl:

. "

aoc axyl

Ten

1/ • 1

~-lC --+ -oy )

Ax it

HOCH2COOH Axit glicolic HCH2-CO-
,/
CH:~CH(OH)CO.OH Axi t lactic CH3CH{OH)-CO~
CH~OHCH(OH)COOH Axn glixeric CH2OHCH(OH)CG-
o-HOCnH,1-COOH Axi t sa lixyl ic o-HOC6H4-CO- Glicoloyl Lactoyl Glixeroyl Salixyloyl

d) Aminoaxit va goc axyl:

Goc axyl

Ten

(- in ---+ -yl)

Axit

H'2NCH~COOH Glyxiu ...

C·HaCH(NH~)CQ.O·H ~, . .Alanin (CHi)2CH~(NH;)COOH Valill HOCH2CH(NH2)COOH Serin

H2NCH2-CO~· CHaCH(NH2)-CO-

, I

(C~J2CHCH(NHJCO-

Glyxyl Alanyl Valyl Seryl

, ,

"

e) H{Jp chfit dJ vong:

.. ,

.-

N H

. ~ '. .

, '

I: -. .. .. . '-'1 .1'. _ .' • ~ • •

. Furan _ Thiophen Pirei Piridin

: .... ~; ~..' It" . .' : _ . II ~ ..' I . .. ~ • . - •

. . -'. - . ". I.. " .. .. . .. ~. .

, .

, ....

• • • I I •

F • ,

Indol Qtl in olin

r" • • • - .. ~; .. • _

. -.. ., . - .

.. , '.. I I • I: ..

,

• I /.. ,I • : r '.' • "I

• • •• I • •

.......

{' . ~....

~.' .

I .... .. _ • •

1

...

. Ii· ....

I. r •

. -

, ,

• •• 1-'

.. i I

".

.. ... ..... .. - .-

r--r. ~ 1

.. .

71

_. . ... .....__. - -.'

-NH: I

~-

._0 ... N-

·H

. .

D -....., - ",. . ....... - .... ,

. , .. "I.. ' .. NH'~ . · ... - ~ ";. '. l ... ~ .f'....... ':: I .... . 7 ......

... . .•.. ~ .. _~.... 2...1' . ,', ~ · II. ·r.· 'NH~}~ ~

_ NH _ - CH!1 - - - . - - - ----,- ~- CH 3 -

_ .-? ~- _ ',_; I _ N IN_:{

o N______ _ _0 ~N"T . OJ-N

H - -. - _H ,- - - -- - - H- --,.--

. 0

Uraxin ,

Timin' .

Xitozin

5':'MetylXitozin : .

. , .

,

, ,

, I .

1 .. 19 a) Ml1611 gQi tell mOt, ankan mach nhanh thea danh l)ha}) thay t.he cua IlJI)A(~ t·~ phai lam gt? Nell mQt. t~hi du de minh hO$6

. . .

~ - ..... ~.. . . .,

.... -.,... ~ . __ . '. __ . . ... - .,

b) Neu ten cac hidrocacbon sau day dua thea cac quy tac cua I UPr\C :

eH3 CH3 CH2CH3 CH2CH3

.CH3-CH=C(CHiJ2 . (CH3l2CH--C=CH CH2=CH-CH=CH-C Hi

. .

1.20 Cho biel. tell cua cac hQ}) chat, san day thee danh phap goe-chuc va danh

phap thay the ella IUPAC :

(CH3)3C-Br (q~~];J )a(_~-O 1-,1

CH3-CH.)-O-CHQ-CI !.}-CH3

~ -.III...tI

(CH;3)2CH~(~O-CH2-CH3

. -

CrI~~Cli~r.I-l~ .... Nfi2 .

... -.... . -

CH3-CH(N H2)-CH2-CH3

. . _ ..

11021 a) Nell lell IlJPA(~ ella cac chat. sau:

Axit axetic (_~H;3COOH Axit oleic CH3(CH2)7CH=CH«(~H2)7COOH

Alanin CH3-(~H(NH2)-COOH Serin HOCH2-CH(NH2)-COOH Lysin Ii ~)N(~fi 9CI-I9CH'J(~H9CI-I(NH') )COO H

...J .w ~ 4<It#'" ~

1922 Axil glutamic GO tell he IThOllg la axil. 2-amillOI)elltandjoie v~ co ba goe axyl t~el1 12 glutamoyl, (X-gilltamyl vA y-glutamyl. Vie~t COl1g t.huc Call tao cua HXjL va ba goc 116i ~Tell.

72

Chlidng 2

-HIDROCACBON

2.1 HIDROCACBON NO

Hidrocacbon no ia nhimg hidrocacbon nia {rong phan tit chi co nlnrng nguyen tit cacbonno Csp3 va .do d6 chi co nhitng lien ke't . don, Co hai loai: hidrocacbon 110 mach hb goi 18. anhan, cong

thuc chung CnH2n+2 (11::::1) va hidrocacbon no mach vong goi la xicloankan cong tlnrc chung CnH2n (n?;3) d6i vdi xicloankan don

...

yO~lg. '

2 .. 1 .. 1 Cau true phan tli 1. Ankan

Phan tit ankan chi conhirng nguyen til Csp3 vdi goc hoa trj --109.5') do do mach cacbon thuong la ziczac va tOn tai chit y~u a dang xen ke. vi do In nhimg dang b~n (x. hinh 2.1).

Cac lien ket C-C va C- H trong ankan khong phan cue hoac chi phan C\"lC rat yeu. Nanghrong cua cac lien ke't do thay d6i thea bac ciia nguyen tu cacbon. song noi chung hi Ion (khoang 350-400kJhnol). Vi v~y h§.u het cac phan (tug ciia ankan

. thuong xay ra theo kisu nang ly •.

_.73

H

H H

·R.· 'H

H H

H

H H

ca, H

H CH3 H

,..

~ r· • , anti syn

.. CH~~-CH 2~CH3· .. . ... . ... ,;. .~ ~' ~. ~-,; ... J

CHa-CH2-CH2-CH3

Hinh 2.1 Cfiu dang xen he cu.a 1n9t sO''' ankan.

2. Xicloankan

. .

Xiclopropan va xiclobutan 13. nhimg vong kern ben. Do g6c

ccc bi ep nhieu so voi g6c binh thirong (109,5°),'lien ke't C~C

, .

. , '.,. . . . ....

trong phan ta xiclopropan chang han dligc' hinh thanh bang

. .

each xen phu b InQt bell (x, hinh 2.2): chinh vi v~y lien k~t nay

kern ben. Ngoai ra, neu nhin theo doc lien ket C-C ta thay cac nguyen tit hidro d vi tri ehe khuat nhau, ye'u to' do cling gop

L

phan lam eho vong kern ben.

. .

Hinh 2.2 Sij hinh thanh. lien kit cong trong xiclopropan .

Xiclopentan va xiclohexan lit nhirng vong bell. Vong xiclohexan c6 dang ghe' nen cac g6c lien ket tu dien v~n diroc

74

baa dam con cac nguyen tit hidro luon luon d vi trf xen ke. Dang thuyen tuy v~n darn hac gee lieu keto song co mot so nguyen tit hidro d vi tri ehe khuat (x. hinh 2.3) nell dang thuyen khong ben.

a

a

e

e

e

a

a

Hinli 2.3 Cilu dang eua xiclohexan ..

2.1.2 Tinh ch3:'t v~t 1j1

1. Giua cac phan, tii ankan chi co luc hut Van de Van nen cac chat dati day dong dAng 13. nhung chat khi (tit metan den butan), nhirng chat sau lit long (tit C5 den Cuv hoac r~n _(tit C20 trCs len). N6i chung, khi phan tit. khoi cua ankan tang len thi nhiet dQ soi va nhiet d9 n6ng chay cling tang thee (x.bang 2.1). S~ phan nhanh Jam cho nhiet dQ soi giam di (x. thi du ve cac pentan a bang 2.1).

-

2 •. Cac ankan d~ll nhe hen DU.CfCt Khoi 111Qng rieng cua ankan

tang thea mach cacbon, song gidi han roi da Ia O,8g/ml.

3. Cac ankan dell khongtan (hoac rat it tan) trong nuoc. Ngtroc

~ ~

lai cluing de tantrong nhieu dung moi hiru co, hoa tan duoc chat beo.

• I • + .

. Bang 2.1 Hdng s()" uqi Ij cua mot so' ankan.

C13ng thuc Ten o- a d
t11c C ts C
phan tit .
CH4 Metan -183 -162 0,415
- ..
C2HS Etan -183 -89 .. 0,561
. , .
.
- ~
C;"Hfj . ·Propa·n ... - ... 188 .'~:'
-42 0,585
C.-lH 1 () Blltan -138 -0,5 0,600
C,.lH10 2-Met)"lpl"opan (Isobutan) -159 -10 0,603
C5H12 Pentan -130 36 0,626
-
C5Hi2 2--Met)t>lblltan (Isopentan) -160 28 0,620
C5H 1'2 2, 2-Dimet)~lpropan - . 9,5 -
(Neopentan)
CgH18 . Octan . -57 126 0,703
CloH2~ Decan -30 . . '174 0,730
-
, ,
C~~()H4'~ Icosan 37 343 - 0,778 2.1.3 Tinh chat boa hoc

..

So vdi cac loai hop chat hitu co khac. ankan co kha nang

.. . -0), -

phan ung rat kern. o dieu kien thuong, ankan khong tac dung

. vdi axit. bazo, chat oxi hoa, kiln loai hoat dQug, v.v ... vi the . ankan con co ten In parafin (tit tieng Latin parum a,ffinis co

ughia 1a it ai luc).

Cac phan (tug hoa h9C cua ankan thuong chi xay ra khi dun nong, khi chien saug hoac co Inc)t cac chat khoi mao va xuc tile. va hau het theo co che d6ng ly. .'

., ·7·6

...

1.. Ph an ling thif hidro bang halogen

Phan (tug chi' xay ra voi clo hoac brom, trong dieu kien chien sang. Iot khong phan tmg. con flo chi gay phan dng 116.

a) So dc5 ph'an Utig

r ..

. .

- hv

R.-H, + x.) .. R-X + HX

...

TI1l du: .

(~12 . e12 Cl2 C12

CH4 -..:HCI'" CH:~CI .. CH2Cb.... .. CHCh .. CC14

-·He1 -lie} -He}

Motyl clorua

Metylen clorua

Clorofom

Cacbon

. tetraclorua

-

b) Co che p hari ung

_ Co che the goc tl;t do SR:

- Khoi Il1aO phall ung:

11V •

x.) ------1..... 2X

-

• t •

X + R : H

I

R· + X· t X

. . .

X· lai tiep tuc tac dung vdi R-H nhu tren, qua trinh dUQC

. .

l~p lai n Ifill (neu RH la CH4 n-lOOOO).

. - T£t mach theo cac hudng sau:

, '

·77

• x· X~)
x'~ + ...
4l1li
R· + x· .. R-X
It+ R· .. R-R c) Kha nang pb an ling va huang p han iing

Khi halogen hoa cac dang d:ing cua etan eo th~ sinh ra mot

hOll hop dan xuat monohalogen cua nhau. Thi du:

.

Ti Ie % cac san pham d6 phu thuoc VaG so luong ni cac

. . .

nguyen tV: hidro cung 1119t loai, ttrc lit lien ket vdi nguyen tit

cacbon bac i (bac I. bac II hay bac III)~ va phu thuoc kha nang

phan ling ri cua nguyen tit hidro d cacbon bac i d6. Thuc nghiern cho thuy ri cua phan ling 0 100°C 11h\1 sau:

Clo 110a

• •

Brom hoa :

Ta th5y bac cua cacbon caug cao tht kha nang phan ung ella H cang 1011 vi cacbon bac cang cao se eho goc tu do bac cao ben hen. Su khac nhau ve ri trong phan ling brom hoa ra ret

~ .

h611 trong phan ling clo hoa,

Gina t1 l~ phau tram ai cua san pharn the-voi ni va ri co Illdi quan 11~ 111111 sau:

78

a. % = _l_O_O_'i._n_i

I. ~ r.n. ~ l I

Trang thi du ve do hoa propan d tren n[=6: nll=2~ r[=l~ rII

~ ~ .

==4 .. 3. Ap dvng bien th(tC.6 tren . .ta tinh duoc: .

, "

.. '"JI

San pham A : aj% ~ 41 %

San pham B : all% ~ 59%

-

Neu brorn hoa propan. ta thu duoc h~u nhu chi InQt san

phiiIn CH:1CHBrCH:1.

d) Ph an ullg cua xicloankan vai halogen

Xiclohexan. xiclopentan, ... ". tile dung voi halogen tuong t~t, ankan, ngliia la cho san pham the. 'I'hi du:

hv

+ Br~) •

-

Br

+ HBr

Tuy nhien xiclopropan lai tham gia phan ung CQllg - Ind vong .. vi voug nay kern ben. Thi du: .

I -_ ••

+ Br»

-

CC4

Ngoai phan itng cong brom, xiclopropan con d~ dang cQllg

. "

hidro, HBr. HeI. H2SO .. 1' ....

. ,

• • - -. I

• ..' ... r-,' I. • •

.

. ; .2. - :Ph~ ling tach. . ...

• • " • '.. I ... r I • " .r _

,

'I - _ I

a) Deh'idro boa hay Iataoh hidro

I • r. '. _ :

" "~ " """ ~ "~ " " """ "

Khi ~~111~4tlg'~1l~;~11 ... co mach n~An vdichatxuc tac (Cr203J

Cu. Pt, ... ) xayra phall (tng tach hidro tao thanh hidI'oCacbon

- "

79

khong no. Thf du:

~ I .! ...

. 'I. -.. = :'~ 'I

'I -. _.

,

,0

CH -CH xt, t

:~ :1 ...

I '

, , '

'. .... .

Khi nhiet phan CR.'I_ tuy digu kien phan irng co th@ thu

duoc 111l10i than 110aC 'axetilell:

~ ~ .

CH CH + 3H9

.."

Phan (rug tach hidro nhirng ankan co 5-7 nguyen ttl cacbon trong mach chinh co th~ dan tdi 8\1 dong vong hoac xa hen nita 1ft thorn 110a. TIll du:

C'R,) CH~)
0 0
/ - \ -
xt, t xt, t
CH~) CH:'1 .. ..
-3H2
\- -n,

-
CH~) CH;~

- :?

Crackinh In. qua trinh be gay mach cacbon ciia ankan de tao

- ,

ra lllQt 11011 l1QP 1111Ullg anken va ankan co mach cacbon ngan

hen. Qua trinh nay xay ra nho tac dung don thuan cua nhiet (500-700°C) goi In crackinli nhiet, hoac nho chat xuc tac d nhiet

d9 thap hen (450-500oC) .goi Itt crackinli -xuc'tcic. Thf du:

+

.' 80

CH4 + CH2=CHCH2CH2CHa CH3-CHa + CH2=CHCH2CH3 ........._... CH3CH2CH8 + CH2=CHCH3

CH :3C H2CH 2C H2 CH ~C H:J

,

Crackinh dtfiJt: dung trone cang 11ghiep datI mo d~ Chtly~n mazut va

{i iezen t.han h XH11g va khi crackinh, Ngoai crackinh ng110i ta con thuc hien

."

t.lllH trinh ludrocrackinli (crackinh dt1di ap suat hidro de tang IUQng nhien

-. -.. .. -._. ... .,

lie11 lOllg), va ·ritonl.illh (bie1) d6i Call true hidrocacbon mech thal1g sang mach

11 hanh, mach vong 110 va thorn) (l~ tang chat lU<1ng cua xang.

3. Phan ling oxi hoa a) Oxi hoa hoan toan: dot chay trong khong khi

...

. . .'

Khi co tia lira dot va dti oxi, ankan va xicloankan co th~

chay hoan toan sinh ra CO2, H20 va taa nhiet manh:

..

~, .

- I ,.

CnH~11+~' + 3n+l 0.) nhiet nC09 + (n+l)H2O·


2 - ...
Ankan
CnH211 3n 09 nhiet .. nC02 + .11H2O
+


2 -
Xicloankan Thf du: CH4 + 20~ ---.:; CO2 + 2H20 ~H = - 880kJ /mol

'.

Phan ung chay cua ankan dUQC ung dung rgng rai trong

cong nghiep va ddi song.

b) Oxi hoa khorrg hoan toan

Tuy thee di~u kien phan ung, ankan hi oxi hoa khong hoan toan cho nhirng san pham khac nhau trong cong nghiep.

81

z

_ ..

. .

I • _" : :

···CH·~··~·O~. ·~k~h6~.n~k~h~5_0~O_,OC_,'~,~_.i_._.~ .. ~~" co! + ~~~hld~),:

..

_ _

, dot:thieu ~ong khf 'c' + '2H29~Q~ than) ,

I I .

. .

.. 1.1 • ,.

.

. .

.. ', outan:

.. . .....

_. .

- Oxi hoa ankan cao: ,

. kh~ _ R.-COOH N OH

R.-CH9 O2 khong ~ 1 a

- +.

Rl=-6H9 xt: muoi mangan R'-COOH

....

R-COONa'-

+ (Xa phong)

Rr-COONa

-

-Oxi hoa xiclohexan;

. .

. . ~

~---~ .. Nilon-6 -----0

"-------~ .. Nilo.n-6,6

Xiclohexanon

82

.

2.1.4 Di~u che va itng du ng' hidrocacbon no 1. Di~u ch'

a) Trong COlIC ,&glti~p, metan va cac dong d~ng ducc lAy tit khi thien nhien, khi rno dAtI (khf (iOl1g hanh) tu dAu rno va san pham che' bign dau mo.

b) T,·ong pllOTtg thi ngl,i~n', co th~ dieu ch€ ankan ttt cac hidrocacbon khong 110 ttrong Ullg (x. 2.3), tit dan xuat halogen va tit xeton (x. chlid1~g 3),v.v .. ,

Ngiroi ia con c6 th~ diell che cac ankan thAp bang each nungkhan muoi nat.ri cua axit cacboxylic (C2+C.:,f) yai NaOH (d dang voi t6i xut). Thf du:

to .

CH;3COONa + NaOH --......i!.~ CH4t+Na:aC03

(rein) CaO

a) Nh ien lieu

..

Nho kha 11811g toa Ilhict. rat. cao khi dot chay, ankan dUQc dung rat T()Ilg rRi lam nhien li~ll

-- CrHC all kan khi, 11hat IH metan, dung lam nhien lieu chay may phat (ti~ll, nung gom SU, (tun 11 all , v .' v ...

- Cae ankau l()llg (xang, (Jatt hoa ) duoc dung cho dong co ma}1> bay, xe

may', at-o, may }lhat. (li~n, dun nau.v.v .

- Hall hop ankan raIl (parafin) dung lam nen, ....

b) Nguyen li~u c&ng nghi~p hoa hoc

TR't. ca l~HC loai ankan (khi, lOllg, ran) dell dUQC dung lam nguyen lit;u

"lI

t.rong t.Ol} g hop hfru co:

Til metan SRB xu at. ra eli3e} (dung trong t6ng hop hi1u co), CH2CI2• (~HCI3 va CC14 (dung mel), CF2C12 (chAt sinh 'han), HCHO (san xu~t chat (1 (~O )" C H =C 1- i (s all Xl18 taxi t axe tic. ~ . ), v. v ....

83

,. 'III

.'

Til etan ~~ :W~.f; ~L:q~o;r~~ ~ptPH?W'r~ ' .. · _. -:.. _", <: -: r c '

. _.... ~. ~ '-.-. .. J ..... r. • :\, .... " ....I;J. ... oJ ~ .t ~ 'J '.. ~ ) ,

, .. pi ~. ,~- _. ••.

Tit butan san xuat axit axetic. .. r

...... "";'" l .

,. ~ ,

~

._ - ,.- '1"1'

! ... ..... •

:.w. .• ) -. if • • :

:.. ir- .. -'_

, ' ., ~ ~

e , ~ ......

.~ - 'J "-_.

~ ... ~ ...........

'"

... • .rJ"

~.j ~J ~ '-L~. ., r~

. rn.........' . k (C C-.....t\.. ",." h.... .

; ·"I;~ :.l~~ac 11.~~1.1Irran _ ,25}+: ... ~t1tY ~B:n xuat xa P .Qng,· .. ~.~, .. ::' ._.

....

. ' ~

r •

• ' • ;" •• I, •• .. I • I ;.: • • I .. .: •• - • I • • I I • I ~. • I • 1. :.. .. _ . . '.. . I

. Tu xiclohexan dietl che axit adipic ( d~~ san xuat nilon-Bji ') va

. ~ ~ ~

caprolactam (de ·s·all· xuat capron 'h·ay 13 ·peClOll}.~ .: ~.: ~ i~· .. ..:,. ". : •. ' .. .: i .

.

I' .... - •

I. Fr'

. ..

. , .. . ,

..".. I ... ' I

,. .

2.1.5 Gi&i thieu chat tH~u bi~u

..

1., Met.an, CH4

Metan 18. chat kht khoug mau, khong mui vi, rat it tan trong mrcc.

Metan 1a thanh phan chinh c,ila khi.thien nhien va khi dong hanh (khi rna d~u» mat khac no lit t.hanh phanquan trong (chiem 20~30%) cua khi 10 CDC .

N goai each (lit~ll che hallg each nung khan CH3,CpONa v.oi v6i

, '

N aOH txem tren) met.an con ducc (tiell che thea cae each S811:

'"

......

to]

-- ............. CH4

Ni ·

CO + 3H·J 0 ... CH4 + H!P

- 200-400 C

~

Metan c6 rat nhieu mlg dung trong cong nghiep .va trong dai song (x.

2.1.4),

2. Xiclohexan, CoH12

., - _. .-

Xiclohexan IH chat long',' kh6ng-~a~-,'kh611g 'ta~~ trong nUdc.·du~e di~u che b·~ng each d611g YOllg l~~hexHll hoae hidro hoa benzen (if llhullg mrdc c6 dir ben ze 11) r

, . Xiclohcxanla mot nguyen lieu (~6ng ilghiep rat. quan troug, nhat Ia trong san Xllat m(}l. ~O loai to poliami t 1-\ hu ni 1011;· poclonr ... (a. 2~,1 ~ 3) ..

B3.i t*p

;.

2~1.· a) Vi6t- c61~g thuc .c~u tao v<)__._,gQi tell" cac ankan c6 cong thuc .phan ttt

.' .. .. '..: :- .' . . . . - .

. CI5H 12· ·DUll~·SO Lama chi r~ b~~ CU~ .t~g nguyen t.u cacbon. '.

b) Viet, COl1g thirc Call tao ella cac xicloankan co cong thtrc 'phan ttl C5H 10· ,

c) C6 bao nhieu goc t,lJ do.ung v:oi cQng thuc C4H9 ", 'So sanh 'dQ·ben tucng

.. --- -

. dol cua CHC.gOC t~ do do.·

2~2 ebb li~but'IHi phan ling v6i elo thea d Ii; mol 1:1' c6 chieu- siihg ta dUQc hon hQI) 2 SaIl })hAm hiru co va m()t chat khf A4

a) Viet phuong trinh phan llllg va co ch€ phan ling.

_. . .. '-

* ~

b ) So ssnh khoi luong :2 san ph~m hiru co, biet fang mot ~guyen tit

hidro a cacbon bac I I co kha Hang phan img cao hen 3- i~n' so vdi mot

nguyen tU hidro i.j cacbon bac I.. . . ,

2.3 'a) Trang thi ughiernneu a bal 2.2. d~ haP thu het 'khf A sinh ra cAn vua dun'g 1,6 lit dungdich NaOHl,25M. Tfnh khoih1Qng 2 san phAm huu cc.

. -

b -) Thel): clo '[~ll hrot bl3.ilg brorn, ior va flo. Viet phuong trluh phan iing

~ hO(4· hoc 116tl co ·XH~T ra.

. ....,.,

2.4 Crackin h 1a gl'! Khi crackinh »-octan sinh ra mot b'on hop san pharn. Hay

viet die phtidug trinh phan (tng tao thanh nhung san phAm d6. '

,

.. .

2.5 a) Khi oxi hoa 71,-butall.ballg oxi kh6ng khi (to,p,xt) thu dllQC mQt h6n hop

'. . . .' .

. axit ·caeboxylie trona do CI-I3COOH l8 thanh phAn chfnh. Viet cae

.. . - . . -' . .

phiroug rriuh l)hall mlg~

r ., I'

b) Nell (tot chay n-btlt311 ta se thu dircc gi? Vi€t phuong trinh phan Ung~ Neu mlg d\111g cua phan ullg nay trong doi song.

·85

'"

2.2 HIDROCACBON KHONG NO

Hidrocacbon khong 110 la nhimg hidrocacbon CO chua lien ket ct6i, 110ac lien ket ba. 110ac ca lien ke't doi lin lien ket ba

~ .

trong phan tl1.

Ta phan biet cac hidrocacbon co mot nO'i doi (a nken , CnH2n• n22). nhieu no! d6i ,(p6lien). InQt noi ba (ankin, CnH2n-2, n2:2) , nhieu n6i ba (poliin), c6 ea n6i doi l~n1l6i ba (ankeniu). Ngoai ra co nlntng hidrocacbon khong no mach yang, nhu xi clo a Ilk ell , }(i<:l()fll~l.~AA

2.2.1 Cau true phan tit 1. Anken

Phan til anken co lien ket doi~ do Ia t~p hop ciia lllQt lien ket 0" (do co hai obitan 'lai hoa Sp2 xen phil true vdi nhau tao

neu) va mot.lieu ket 7t (do co hai obitan p xeu phti ben vdi nhau;

~

x, hinh 2.4). Phan tli etilen co 6 nguyen tit (2C va 4H). tat eel

deu nam tren InQt mat phAllg chua true cua 5 lieu ket 0'. Dc} dai cua lien ke't cacbon-cacbon la 1,341\ (trong khi do trong etan

,

... 1\ A ....

bang 1,54A). Cae g6c HCCva HCHbang -'120°.

" "

Nang luong cua lien k€t doi C=C biillg616 kJ/mol. 11ho hon

nhieu so voi nang luong ella hai lieu ket don C-C (2 x 348 = 69(.) k-I/mol). Dieu do chuug to r~l1g nang hrong cua lien ket 1t nho hen cua lien ket o, do d6 lien kat 1t kern b~n~

86

hay 19.

~

',' ..

j ..

(a)

-

- -.

. .

- .

, ,

-.

(b)

.,

- "~.: :;~. .-:

_1:11' I.:"

Hinh 2.4 MfJ hinh philn tiL etilen (a) va sf! hinh thanh. lien kef: "

- • 7. _ '.

(b).· .

Nguyen tit Csp2. co j§~alI}__~i~n lon~~d~~sp3. Hai nguyen tu:

C~p2 lien ket vdi nhau khong th~ quay t\t do duoc, do do co th~

xuat hien dong phan hinh hoc neu Inoi nguyen til Cs~ do noi vdi hai nguyen tis: hoac nh6111 nguyen tit khac nhau (x. 1.3).

2. Ankadien

L

Hai lloi doi trong ankadien co th~ lien nhau (thi du anlen

. . ..... - .

CH2=C=CH::!). xa nhau (tht du pentadieu-Ld CH2::::CH-CH2-

CH=CH2) 'hoac lieu. -. hop (till'- du . butadien-Ld - 'CH~i=CH-

CH=CH.,)~· .'. ,.' ~.. ... . , . ~ ... L. \ ••

~

". :. I

, ,

... • :.-... .. 'I • 1"'" ..

-

. .

, .

. .

-

. .' '. .. . ~ II; " . ~

Trong phan tit butadien-l,3 tat ca 10 nguyen tit (4C va "6H) va g'li(hiket;~(3 Cjc va:'6"C-H)' Mu'n~irt~tren rtlQt mat ~pha.l1g va t~ci'liEh~;11hullg·,g6c-"'1200'r(!;ac, obitanp lcliOhg ~Iihungxetl ~phu

ben voi nhau tao thanh lien k~t 7t giua C1 vdi C,s, 'vaJJg EVai, C:t.

~~w. ,_F,(n~,x~~, p!lQ. ~iH~· C2 ,_y~i, ~3 do d~ X\la.t hi~n obitan 1t, baa t~1ili1\~t-~'l:igu!ng{i \:~i{'flf cicllioo,(~.r,hirihj2.5)-. ::, o~! "" d ~~>:.: ..

. ::c.., .... l ..... Ll ~~~·.·· .. f ' -I j".~. 1 L -Y.~ ...... ~ '- ' ... -}L~ T ,_I ~ .' ..... ~ ~ ,rL ... ·1 .- ... ' ~ ~-.- "'- .. ; .- '. ._'.

, .f . J 1 .. l '- 1 < l ~... ~ "1-- ............ L. , ~ ~' r ~ ·.f + .. ~ !. L - .... ~ •• _, , . \ • • < • \",,;.. ~I"'; • ..L ,~ ~ ~. L • • , . •

_..} _....II - ., ~...... • - - I..... .......i. ..-.... ~ .._..... :- r ~ ~ "- ~ _. • 'I: I .. .i. ... " ".I .1 .... :. t. ).r ~ .. 'I • • • .:_ ... j. ' ~ ~.J. ~ ..:.;:... 4t.. pI. .. .;.-. • ~. ~ .... r ...

. - ..

..... f ~ L ~ , ,.. -,», • - 'L - •••

: .• . -:'" ~ .•. ~. r 0: . _., .,....... ,~.--. .. ~ ! •. ,- . :; i - Lr ',' • ..., ~. ,- L ~ ... • 1'. ~;;.

•.. ..J.. l i ! t 11 . • ~-. ~. .. - L ,[. • , , • , • • ~ , r L ••

. .......L - .• L. :r. ., .1. , ..., .... ~ : 1 ... L .• l _.. ' _ : . ; ,..;::. ;.. .:. ; , ~ _ . f .:... t .t. _ ... ~ .. ' ,~L ~ • .'

'_ ..... _. . _.

-

8~

--H·

H

H ..

"' ..

H

H

H (a)

H

(b)

. ,

Hinh 2.5 Si: xen phil cdc obitan p (hinh a) tao thanh. obitan 1t

chung cho loan pluin. til butadieri (hinh. b).

Hien tuong xell phu obitan nhu tren goi 13. lien hap, va do do butadien-Ld 18. mot dien lien hap .

. Ankadien liel1 h"p cUllg co cac Call d?ng khac nhau va cWlg co dong phan hlnh hQG, nell .nguyen til: Cs~ dAn 'ffili\ch noi v{ji hai nguyen til hoac nhom nguyen tit khac nhau (thf du CH3CH=CH-CH=CH2 c6 hai dong phan hiuh hoc, CH;jCH=CH-CH=€HC2H5 co 4 d3ng phan hlnh hoc),

3. Ankin

Phan tit ankin co mot .lien ket ba. do 18. tQ.p hop cua InQt lien ket o (do hai obitan lai hoa sp tao nen) va hai lien ket 1t (do 4 obitan p xen phil nhau, x. hinh 1.9).

. DQdai cua lien ket .esC chi bAng 1.201\ (ngtin hon C=C).

Lien ke't _Csp-H phan C\iC manh hon Cs~-H vi dQ am di~n ciia C:;p Ibn han Cs~. .

- .

, . . " "

Nang luong cua lien ket ba bang 813 kJ/mol, nbo hon nhieu

,

so voi nang luong cua ba lien ke't don (3x348=1044 kJ/mol); dieu

d6 cung chirng to lien ket 1t linh dQug.

88

2.2.2 Tinh cha't v~t ly .

H idrocacbon khong 110 CO nhieu tfnh chat, v~t ly nhu nhiet dQ soi, nhiet ([() 11{)llg chav, r.i k ho], t.inh I.H)1~.n4tttdl)g tu hidrocacbon no c6 cung SOllgll:fell 1 U (~H(~t)()11 VB cUIlg lJ() k hung cachon (x. bang 2.2)4

Bang 2.2 Hdng si/ v(tt lj cua 1n9t so' hidrocacbon khdng nOA

~

Cong tlnrc

d

Etilen (Eten)

Propen

Buten-I

trans- Buten-Z

cis-Bllten-2

Penten-l

Butadien - L3

Isopren

Pentadien-l,3 Pentadien -1, 4 Axetil.en(Etin)

Propin Butin-I

Blttin-2

CH~)=CH~)

...,; ~

CH2=CHCH3

, .

'CH2=CHCH2CH3 .

CH:~CH=CHCH3 ORseR,. CHCHa

CH~= CH CH2CH2CH3 CH2=CH-CH::::CH2. CH2=C(CH:0-CH=CH2 CH2=CH-CH=CIi.CH3 CH~)=CH -CH~)-CH=CH9

..I _ ....,

CH=CH

CH=C-GHa

-

,

-169 -105

·-1·S5 -48

.

-

-185 -6

-106 1

-13.9 4

...

-165 30

-109 --4,5

-120 ·34

-88 42

-148 26

·-82 ·-84

-103

-122

-24

-23 8,6

-

27

0~566 0~609 0,630 0,660 0,644 O~641 0,646 0,681 O~683 0.659

-

O~650 0.694

. r

(~6 mQI. sf; quy Ill~t. ve nhiet d<) soi va-nhiet dO nOllg chay;

89

- Aukou-I vi-l ankin-J e6 Ilhi0t. cto s6i t.hcIp hen ankan tl1dng ltng~

I • • •

, I' .--

-- Slj Chll}T~11 djch l1f{i (lei vA. ll(~)'i ba til d~ll mach vsophia trong lam tang 11 h iet. (to sc)i vii 11 h h}t (t.) 110llg C ha)~.

1> - l)Ollg 1)hHl1 trans ee) nhiet (to 11611g chay cao hen va nhiet dQ soi thaI)

....

h (j 11 d {) 11 g 1) h ~ 11 c i . ..:t •

2.2.3 'I'irih that· hoa hoc .

..

Su co mat cua lien ket 1t trong phan tit lam eho hidrocacbon khong no co kha nang phan (tng eao hen hidrocacbon no. Chinh

. . .

noi d6i va noi ba 13. nhung trung tam phan ung duoc coi 13.

1111UIlg 11h6111 CllUC.

.

1. Pb an ling c9ng hidro tren b~ mQ_t chat xuc tac kim

loai

Nhinig phan ung nay toa nhiet va chi xay ra khi co chat xuc tac nhu Ni, Pt. Pd, v, v ...

c~ H ~~ - C H :2 - C. II = (; 1-1 2 (4 5<}o)

(~ 1-] ~) - C H = C I-I - C H 2

....

. (48%)·

C 1-1 ~~·-c H 2--'·C H 2- C H· 3·

(6~b)

90

2. Phan ung_cf}ng electrophin

- .

a) An'kerr

- Sd de) phan ling:

~(\ 0/ &+:

_C C + X~ ..

/ "

8+ S- 8 + 8

X .. v . H .. Hal. H JIll OH, HOS03H, Br-Br, Br-Q

,

. - . ..
y
8 ... 'C 1/
y c
/r -,
X
........ : .

- Cd che' phan itng: Co che' AE - -

:,

~ 8+ +
~(\ 0 -, (+)/
/0: cham
,.y • C C"
C C +X! ...

/' -, , _y(-) / I .
I

X Y
-
, j
. -, ./ +i--) -, . 1/-·
hoac C----C C ··C-


/ "\ CDI " nhanh /-1· .,
\ I X
II ,
r ~ .. -X
(X = Hal) • .1' •• rTlnl' du-....· .

_ i_;.=;r.-.......--

• It

. . ~ .

.. ~ ..

4. ~ .. .. I '\ -

_ ". .... • .~. _. ,r .. I ~

.. J •

.. cbQtill:' (+) --Bl? . .. _. _:_

CH2=CH2 +)fBr II CH:3-CH2~ h' ,: hll CH:3CH2-Br .

· n' an

.. .. .. .

: .. I .. _

- ~.~.-

. .; ....:...'. '. ../ ..

• :. \ -: 4· Br

',.1 ... i" . ~. I' + .

. h ~ .~) -: · :. B f -) I

CH'J=CH.) + Br» C !!lW CH9-----CH" r .. CH,,-CH'J

... .. ... ''',: +,/ .. nhanh I'" ...

.. @ " ... ,. r :» _. .,.. -, ·Br· . ~.. . J .. ~"

~ •• ' ''I :1.. I. =I·~ _'.,

" I - ..- r.· .. L ' •• ..~ ., .. " j.' .~. . ... .,..

Br

..

..

_p" 'I •

Trong cac phan irng' cong d tren, n~u·a giaidoan sau co mat chat nucleophin nhu H20-, !(--). Cl(-l,v.v ... thi se sinh ra san p.h~nl

~

cong chat nucleophin d6: ...

", • l" "

•• I JJ ..

(+)

~ .. CH;{-CH2-OH2 .. CH3CHzOH

-H(+)

Nael

+" Br» .. CH~)---CH9

... " w , _

\, ®"/

... I , I

" J

Br

- Hliong cua phan ltng: .

Phan. lJ:ng C9ng Tn9t lac nluin. khong dOl xung (nhi: HeI, H2S04t HOB, lel, v.v ... J vdo m9t anken khong dOL xung

" .

(CH3CH=CH2 , CH3CH=CHCiH5 ... J se uu tien. xayra thea

" ,~

huang tao thanh. cacbocation trung" gian ben han. (Quy tile

Maccopnhicop). TIll du:

B (-) .

.....-..-.1r __ BrCH2CH 2Br(5,4%)

. Cl( -)BrCH?CH ';Cl( 46%)

4l1li ....

" "

(ben hen)

(95%) "

(kern ben)

(5~t,)

Thea quy luat tren ta co:

92

. - .

, ,

tt<+)

CH3-CH=CH~ + HOH ., CH3-CH-CH3

I

OH·

·CH~)=CH-·COOH + HBr---- ..... Br-CH~;-CH,)-COOH

.... ..... ....

. . ,

.

Kha nang phan ling ella anken:·

Khi thay t.he nguyen tit H trong etilen bang nhorn d~y

. · .lectron (CH;~, C2H~)" ... ) mat dQ electron d noi d3i se tang len va cacboca tion sinh ra cung ben hon do d6 phan img cong cling xay ra de dang hon, Trai lai. nhom the hut electron se Hun giam mat dq electron va cacbocation sinh ra cung kern bell; do d6 phan . (tng cong xay ra kh6 khan h<111. Vi v~y ta c6 trinh tl1 ve

"kha nang phan {tng nlnt sau:

, ,

CHi~CHCOOH < CH~:::CHCl < CH2=CH~ < CH2=CHCHa < CH~==C(CH:3)2

- Kha nang phan ung cuahidro halogenua:

Phan (tug cong HX vao anken se d~ dang neu HX co tinh axit 111~nh va X! I co tfnh nucleophin cao. Vi vf}.y kha nang phan ung cua HX giant theo trinh tu HI > HBr > HeI » HF.

. .

Chu Y TRlig 1 rong t.rlfdTlg h~i) cong ·f1Bt rna ·c6 m-?t 0,),· fl~)b .. ), ... l)h~]l

. . ~ ~ ~

Ullg xa):" ra .the() co chc goc AR thee) hirdng tao thanh goe trung gian ttrong doi

i"lCll hon: cho nen hli()11g C()llg All so trai vdi htiOllg c9ng AE a tren. Thf du:

Br' + CH;~CH=CH2 ~ CH:3·CHCH2Br (ben hon ·CH2CHBrCHa) CHa-·CH-CH~Br + HBr ~ CHs-CH2-CHgBr + Br", V.v ...

93

b) Ankin : ..

• ~ L

. . _.. -

. '

, -,

_.

., ,

~ . : .

. , .r . i :

....-osi.. ••. ._. ', ~

J .: ". j 2

t ~ : ~'

" .

..k.. .~

! .

Phan ltng cQng halogen va HX vito ankin cung tuong tv phan ,~~lg c~p: all~~ll v~: co,.Gb"~"ph~n Uij.g'i l;1U~~lg cua phan itng va anh huong cua 11h6111 the' den kha nang phan nng. So vdi

anken, thi ankin co kha nang !>pan. ~g t~~lap. hen i~i iffi~t:

,~, . _ _ .. . _ - . _ _ . _. -.' . _. .,,~ __ '. ,\., -. _ ~ _ .

. _....

CH .. ~C=G·H-.>. CH=CH > .CH=CCOOH

. _. . ~ _ _ . ,. . _ _ . _ . . .

. .... _.,

c) Anlcad ierr .

Ankadien co th~ cong halogen va hidro halogenua tao ra h611 hop g6n1 san pham cong i~2 va cong 1,4. Tuy thea tae nh3.11 . phan ung va nhiet dQ rna 1119t san pham nao do se chiem ti l~

. .

cab hen, Till du:

Br Br

ccng 1,2 I I

------- CH'r-CH-CH=CH9(20%)

~. -

1 2 3 4 Br» .

CH~)=CH-CH=CH·)" Br Br

~ ~ 40°C I I

cong 1,4 .

.....____---CH,)-CH=CH-CH~}(80%)

..... ......

3. Phan ling cqng .. dong vong (Phan itng Binxcr-Ando)

. K h i dun ll()11 g 1)11 t H (I iou- 1 ~;J v(ji e 1 ! len xR)· ra J) han ltI1g eQllg {l()llg t.hCii 1 (H) t han h von g x iclo h(~X(~11:

..... '

94

- _ _. _. - .~_ '_~'--------""'__

. ~CH2· CH

I +

CH

~CHi Dang s .. cis

- cua butadien

..

Etilen

CH . CH2

<, /' CH~

Xiclohexen

Phan Ul\g c(nl g-(l()llg voug t.rp.I \ ~(~ t.rci 11811 de dal1g hon lle\l (IVa VaG phan tll but.adien nhorn th6 dAy «Iecrron (-CH;~, -CH2CH~~, ... ) rna kh6ng elm trd SQ ell11)~411 Cittl1g' s-tran» S~llg Ci;:t11g' s-cis , hoac Olfa vao phan tll etilen nhorn tht~ hut e lectron (-C~()() H, .... C] {=(). H.).

4. Phan iing tritng hqp

Trung hop 18. qui trinh cQng hop lien tiep nhieu phan tit

. .

nho gi6ng nhau hay tuong tlJ nhau tao thanh phan tit co phan

tit khoi Ion (cao phan til:).

Chat dau tham gia trung h9P dU9C goi 13. monome, trong phan tit 1110nOlUe thuong phai co lien ket kep. San pham thu

,. . -

duoc la polime chua n rruit xich co btin Sil111 ra til n phan tit

monome. Neu n = 2710 polime duoc goi la oligome baa gaul dime (11 = 2), trime (n ::: 3). tetrame (11 = 4)~ V.V .•. ; n Ia h~ so" trung hap hay d9 tl~ung hap,

a) Anken

Cac anken va dall xuat co cong thuc chung CH'J=CH-R

~

tuong d6i d~ trung hop d dieu kien nhiet dQ va ap suat nhat

dinh co mat chat xuc tac, sinh ra cac polime tuong ung. Thi du:

95'

...

[- CH2 - CH2-J

. . II.

Polietilen (PE)

2-·:~ at.

II· (~1·1 =(~ll.)

. -

xl

I) · t ()

n.

(.: I I ;.~

Polipropilen (PP)

- .

b) Ankadien

Cac ankadien lien hop va don gian nhu butadien, isopren ... eo th@ tharn gia trung hop tao thanh polime dung lam cao SUo TIll dll:

Butadien

Polibutadien

·c) Ankin

Axetilen tharugia phan ung oligome hoa khac nhau tuy

.

theo dieu kien phan ung, Thi du:

Cl12C12, BOoC

---~.-. CH9=CH -C CH

dime hoa -

Buten-Ldn-B

3CH=CH

C ho~t tinh~ 60CPC trime haft

C6H6 Benzen

."

N goai ra, axetilen con' co the tham gia cac phan img

tetrame 110a4t· pentarne hoa va polime hoa.

~96

5. Phan ling the

a) Anken

.,

. d nhiet dQ cao (500-BOOoe) lUQt so anken dfiu day dang

d£llg co th~ tham gia pluiri U:ng th(bdi clo. Thi du:

CCl4 khi

C~H.)~CH9-Cl .. CH9==CH9 + CI~), .. CH2=CH -CI + H CI

,- - 0-250 - ~ .. 5000

Cl . Etilen Vinyl clorua

CC~ • khi

CI-CH~-CH -eH;] ... CH~=CH-CH3 + Cl2 •

I 0- 25° Propilen 5000

Cl

Anlyl clorua

b) Ankin

Do S \1 P han cue cua C s p «H cac ankin -1 co hidro linh d911g nen co th€ tham gia phan ung the' hidro bang kim loai. Thi du:

".

trang nga

6. Phan ling oxihoa

a) Oxi hoa hoan toan, Dot chay trong khong khi

Cungnhu hidrocacbon no, cac hidrocacbon khong no deu chay trong khong khi va toa nhiet L\H(C2H~ = -1423kJ/mol;

. ' .

r. r -:. •

;.1H(C;'H9'} ~; -l320kJ/mol.'· ';:: ;-~_. . _.

~ .;,,;

. . .

..

. ..

, _.

. ,

•• I 'I

, .,

.. . - . .. - .. .

b) Oxi b oa lchong hoan 'toan

- Dung dich KMn04 loiing nguoi bi mat mau bdicae hidrocacbon kh6ng no. nho d6 co th~ phan biet voi hidrocacbon

• '. I' •

110.

-Dung dich KMn04 dt;hn ag_c va nang oxi hoa 111?,uh lam dirt

...

mach li~li ke"t kep sinhra ·h6nhQp axit cacboxylic hoac xeton

hoac ca hai, tuy theo rmrc dQ the' cua nguyen tit cacbon khong 110. D6i vdi anken ta co sd d6:

, ,.

Rrt

/ O=C

'OH

R, .. R.II KM:n04.. R,-

,,/ ... 'C-Q +

C-----:-.C'H . /

. H'/' . . .. . R'

Thi du:

,. .

KMnO~1

CH8-CH:z-C=CH-CH2CHa ..

, . ,.1 .

CH3

3-Met)~lhexen· ... 3

...

CH·JCH~)-C=O

o - I

CH8

Butanon .. 2

+ O=C'-CH~)CH3

I -

O:H

Axit propanoic

_ •• • • r r

Dua vao cau tao ella cac san pharn oxi han ta co th~ suy ra

Call tao cua anken ball dall .

98

- Tac dung cua ozon, saudokhu bAng Zn.Sd dB phan (tug cua anken:

Anken

Ozonit

Xeton

Andehit

TIll du:

..

Ozonit

Zn

,

-----------.. CH3CH~)-C=O + Q=C-CH"CH3

kl1tt - I . I"

CH3. H

Butanon-2

Propanal

Phan ung Hay thuong duoc dung d~ xac dinh cau tao ciia anken..

- Oxi hoa nhe bang -oxi 'khong-khi tren h~ xtic tacPdC12- CU2C12. Phan ung nay duoc dung trong cong l1gm~p san xuat CHaCH=O tu CH2=CH2:

.1 ... _

2CH:9· CH·9~+·- 09

_ -tIooII " '/ _1IiIIIIII

. ,'. .

.. ,

99

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