You are on page 1of 406

.

.,.:':' "

+.... _r ...

.....

r -

..... -- ..... _.-



LliLh.j,,'i ' l"U' NGUyiN THI THANH .. DUONG VAN TUt

. ~ .

vu nAo TRANG .. H6 CONG XINH

· ;;U:5""Jf r t:L~a -111

.,'

,tI,.

... ..

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

r''''~

Chu bien: HoANG TRONG Y~M

. .

co

•••• •• • •••• .._. • • • ~ •• - __ _. ...... I _. _ _. - I - I.' - •• - - - .._ .........

:'. ',,' ' '·fiiHA 'xu AT ,BAN;KHOA~HQC' vA: J(f THU~ T < ~. ': "',

" ;-.- . .: . - .'. .-., .. - "~ U 1· .: NOli~_~~· 1009 . ~ ~~_!~~ .... ' ~~ ~ .. ' ..

-- RA . 77 ....- ..- - 'I~'..' . .: - 'l ... ;r.'

, ,."

HOA'HOC H



-

T!PHAI

TAU Vf~N tJlt.DAN llI>:',. . '. PHOHG DOC .

..

". .... Q d. =B ,Ut..-it

..........

- .. . ..



, .

. - . i

.~ .. - - - .

-

T ":,' ' .. : ~ .' ...1 • • .. _~ • ':. • I

• It· I.;· .:.:. _ ... ~

,

.., -. oS • • ., i-

.... p. ~; • _. I... ~

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

-. ~~ ~ . .. ~ r.' . t- . -;

".,_ ... ... . . _ ... .,.1 ..

~.~~ • .'(,.,-:.II', ..... - ........ ~

f ""' l

~. ~ .. J.~~~t!i '-; ,., . .J!' ,

... ,,""""'" • _J-

.. ; " .... :::-... 1, ~ ..

i- • ~

I •• : •• ;" .. ~ j.'~ ... ' .~;}

. ~ - 'L' r.'- "r J:

·1 It:· .. I· .. ~ -.. .. .. ~....... _. f

- ,

.".

.,. .. _

, ': ..-' "

.. - .- •• 1 • _ ..

- ~,

I' ...... O("~.... - '. ~

~. -:. . ~ ~_1. 'i...... - I ..... • .:

I I .. I • f . .. ~

. . -. .

J... ...... ....

. . .... -

I.... • .. ~ _ I ~_

~ ~

• • r- .. •

t:.

L

e

. ...

-.., . ..:.

.;:.....;... .~~, I ""':

. . ,

~ •• _' ..... 'IIi

,

i

t 1

.. - p -...- .. II

. '

•• I _ ....

,

.,. - . +

r +-. .,

~ 1 <

t

-

.' .

. .. .

• • - • ... - I P"

.1.:

:to ,

,

t» ~ -

I PI.: .... .

'.' ,.- '. ,,' .

, .

. .

. ·.~I .....

..... - ,

PGS, PTS. TO BANG HAl

NGUrtN 1Hl NG<X; KI·nffi PHAM ,.V AN NffiN

. .~

, ., T~N:VAN CAM

• .. • I I

Chju trdch nhlfm Xll4t bdn:

Bien tQp :

Chi bibi· ... '......:i'.. .' .:...,;-

... .-.



., -~ l. ~ .,~,

- .. I.:. .. ~

..... I II

. ~

"I _ ...

Vi bia :

HlfONG LAN

. ..

_ A;f 5 - 547

~MA·SO ... - ;; ........ - --.:~~- '-41-:'33 - 99

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

~ . ~Kif · :19· .. "..... .

• r- ... ... • .... :..

.. _ .• .. ... I. I.... . ... .• .. ..

.... .. .. ... .. PI! .. I..·

- (. ... 1.. .. ... ·1... I. I ... !I- .. _. ~...... L

-. ...... ~.. 1 "p rJ ..." •• __ .. I .... ...._ :

.. PI... _.... 1 ... .-

.'.~ .

,

...

. . ' .......

, . .,..~ ~ ~ ~.

. I .1....·..:.. .... -.. -r" .. ..: . - ..

~ _... ~ ~ '- - j ..t..;- ",. •

.::r ... " • .r .. .. . P. I

... ~I.j. • .._ ... p. ..

... I ... p .. , • ... .... - "IiI- ... tf

•• -.4"t -r.-" ....... 'I":~"" - ..........

1:1. _ ........

. ~

:. .

L ~

'.,1

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

... :-".,.,.,~~ .-. ...,,_.....,..;. ••. _ A.

NHA Xl}AT BAN·.J(H(~~A'Ltl'()C VA K Y THl JAT

. .

70 - TrAIl Hung D~() - Ha Noi

In 1000 cu6n khO'14,5 x 20,5 em. T~j Co slJ in 16 Hang Chuoi, Nha in DHQG Ha N¢i. Gia'y phep xui't ban sO 41-33-16/9/99. In xong va nop htu chi~u thang 10/1999.

'.

, , "\III.

LUI NOI OAU

Co the nol, phan IOn cac thanh qua trong h6a hoc hl1u co deu gAn fien voi su phat trii$n cua Iy thuyet h6a h9C n6i chung va 19 thuyet h6a hoc huu co n6i rh~ng~

~ -

Neu nhU truoc day h6a hoc hIJu co chi ~a mOt man hoc, mot linh

vue mang tfnh tiep nhan, thl ngay nay can chuy~n-mon- hoc nay thanh mQt rnon hoc mang tlnh Sl-JY dil~n.

Xuat phat ttl quan di~m do, cac tac gia cua bC) sach nay da d~ cap d9"n nhOng quy lutH cO ban c6 lien quan den h6a hQC rnlu co, vol mong muon chuyen tal tdi ban doc 1L1~ng kie"n tfu~(c sau hen, gan gui vbi thuc te hon

BO "H6a Hoc Htlu COli nay gam 4 tap, vOi noi dung nhU sau:

T@p I nau len nhung khal nil~m, nhang quy lu~t co ban cua hoa hoc hilu co nhtl Iy thuye't ve lien ket, cac hi~u Ung, khai ni~m ve IUong tu hLlu co, tac nhan va cac 'o~i phan ling huu co VIV~.

TLr phan Iy thuyet nay ap dl,mg V80 phan chuc huu co d~ dl,l doan loai phan ling, kha nang phan ling, huong phan lJng, co che p han lin 9 huu co,

Tap II va III trlnh bay cac chlrC huu co baa gOm cac hop chat htlu co mach hd, cac hop chilt hL1u co mach vong (k~ ca di vong).

Trang hai t~p II va III neu len phuonq phap dieu che, tfnh ch&t Iy, h6a cua cac chuc, co ehA cua phan ling htJu CO, d~c bi~t IUu y den cac phan ling hilu co tao nen cac san pharn h6a hoc (htlu co) phuc Vl,J cho nen kinh te qu6e dan.

Cac hie gia da buoc dau ap dunq nhang khal ni~m, nhl1ng quy

l··~·'

... .

lu~t co ban ve IV thuyet htlu co de cho ngtJdi doc suy luan dllc;1c huang phan On9, su tuonq tac ghJa cac chat trong phan ling huu COl

Tron"g tap IV trlnh bay cac phuonq phap v~t Iy dg xac dlnh cau true cac hop chat lulu co, xac dinh cac chat trong h6n hOP cac hQP chat tnlu co,

Cudn IIH6a hoc htlu co" nay co th§ dung lam tili lieu hoc tap, tham khao cho sinh vien, nghien cuu slnh nqanh hoa, cac nqanh co lien quan den h6a h9C va cac can bQ him vi~c trong linh vue htlu co cunq nhu cac finh vue h6a hoc khac,

Chung toi mong nhan dLlQc va xin chan thanh cam on nhLlng y kien don 9 gop cua ban doc.

Chu bien



GS. TS. HOANG TRQNG rtM

..

2

-

MUCLUC

. ~

Chuang 1.~H.YDROCACBON

17

1.1 .. 7 ~ Ch:lt tieu bien: Metan CH4

1.2. ALKEN

1.2.1. Day d6ng ding etylen 1 .. 2.2.. Cach goi ten

1 .2 .. 3 - DOng phan

1 62~4. Phuong l'hap dieu che' 1 .. 265 ~ Tinh cha:t vat 19

..

1.2 .. 6.. Tfnh ch~t hoa hoc

I

17 17

18 18 22

" 26

28 40

" 43 43 43 45 46

" 50 52 68

69 69

70 71 74 75

" 83

84 84

~ Ll , ALKAN

1 '" 1.1 6 Da Y dong ding metan 1.1.2.. Dong phan

F -1 .. 1.3. Cach goiten

1 .. 164.. Phuong phap dieu ch€ 1 .. 1 .. 5.. Tinh chat v~t ly

1 .. 1 .. 6. Tfnh chat hoa hoc



" ...

1 .. 2_7 . AIken tieu bieu

1~3. ALKIN

1 .. 3.1_ Day dOng ding axetylen

1 .. 362.. each goi ten - Dong phan 1.3 .. 3.. Phuong phap dieu che

1 .. 3 +4.. Tfnh ch~t v~t 19

163.5. Tinh ch(t hoa hoc



1.3.6. Chat tieu bieu

1.4. ALKADIEN

1.46 1. au tao electron ciia h~ thong n6i dOi lien hop

3

..

..

1.4.2.. cae phuong pbap dieu che butadien

.

1 .. 4.3. Tinh chit cac hop chAt c6 n6i dOi lien hqp

1 .. 4.4. Cao su

88 89

94

Chuang 11. nAN XUAT HALOGEN;.CUA HYDROCACBON M~CH HO

~ ,.",

2.1. DANXUATMONOHALOGEN ALKAN

2.1 .. 1.. each goi te:n

:: ~ 1 62.. DOng phan

2 .. 1.3. Phuong phap di~u che 2 .. 1.4. Tfnh chat lSi h9C

26 1 .. 5. Tfnh chat hoa hoc

..

96 96 97 98

-101 101

A ~ ~ A

2.2~ DAN XUAT HALOGEN ellA HYDR()(~A(:BON KHONG NC) 125

2.2 .. 1 vinytnatogenua 125 _

2.2 .. 2 Allylclorua 126

~ ~ ~

2.3. DAN XUAT DIHAL(_)GEN (~lJA HYDR(~)(~A(~BON N(~) 128

2 .. 3 .. 1 Phtrong phap dieu ch€ 128

2.3.2.. Tfnh chd"t chung ella dan xufft dihalogen 129

2 .. 3.36 Cac ch!it tieu bien 130

ChUC1ng Ill. Al,COL - ETE

3 .. 1. ALCOL 132

3.1 .. 1. each gQi ten 133.

3.162. Monoalcol no 134

3.1 62.1- Phuong phap dieu ch€ 134

. 3 .. 162.1 a. Phan ling dung xuc lac axit H2SO4 134

361.2_lb6 Thuy phan dan xuat halogen RX 135

3.1 .. 2.1c .. Khir aldehit, xeton hoac ete vong 136

361.261 d. Tac dung hop chat co magie v6i aldehit, xeton

hoac ete vong 137

4

,

3.1.2 .. 1 e. Dieu che' alcol tir este

3 .. 1 .. 2 .. lf. Dieu ch€ alcol tit CO va 82 3.1 .. 2.1 g. Phuong phap len men

361.2.2. Tinh chit 19 hQC cua monoalcol no 3.1.2.3 . Tinh chat hoa hoc



138 139 139 140 141 141 142

3 .. 1 .. 2 .. 3a_ Tinh axit

3 .. 1 .. 2 .. 3b .. Ph3.n Ung este hoa

3 .. 1 .. 2.3c. Phan ling loai mroc (dehydrat hoa) 3 .. 1 .. 2 .. 3d. Phan trng oxy hoa

3 .. 1 .. 2~4. Gici thieu mot s6 monoalcol no

. ...

a .. Metanol CH30H

b. Etanol CzHsOH

c. Pentanol CSH110H

3 .. 1 .. 3. Alcol no hai ch(tr: r diol)

3.163 .. 1 each gQI lell

361.3.2.. rnuoug pnap di~u che'

3.1 .. 3.2a. Thuy phan dan xu{lt dihalogen

.

143

146 147

,

147 149 149 150 150 150 150

, 361.3.2b. Oxy hoa hydrocacbon c6 n6i dtli 151

3 .. 1.3 .. 2c. Khir hoa khong hom tOM hop cha:t xeton nha

h5n h6ng magie 151

3 .. 1 .. 3.2d .. Dieu che tit aldehit 151

3.1 .. 363. Tfnh chi"t hoa hoc 151

. ...

3.1.3~3a .. Tfnh axit 151

3.1.3-3b. Ph3n trng vCri ret, 152

3 .. 1.3 .. 3c. Phan tmg oxy hoa 152

3.1.3 .. 3d. Glycol tham gia phan ling loai mroc 152

361.3.3e. Glycol phan ling v6i axit hiru co tao este 153 .

3.1.4. Alcol no ba chile 153

3.1 .. 4 .. 1. Phuong phap dieu che' 153

3.1.4.1a. Thuy phan chat beo 153

3.1.4.1 h. Tdng hop tit propylen 154

- ..

3 .. 1 .. 4 .. 2 .. Tinh chat boa hoc



154 154 155 155 155 155 156 156 156 159

161 161 161 162

J

3.1 .. 4 .. 2a. Tfnh axit

3.1 .. 4 .. 2b. Tac dung vOi Pel5 3 .. 1 .. 4.2c. Phan Ung oxy boa 3 .. 1 .. 4.2d .. Phan ling loai mroc

3 .. 1.462e.. PhWt rmg voi axit AN03 3.1.4.2f. Phan tmg tao este

3 .. 1.4 .. 2g. Len men glyxerin

3.1.5. Alcol khong no don chirc 3 .. 1 .. 6+ Thiol va thioete

3.2. ETE

3 .. 2 .. 1. each goi ten

3.2.2.. Phuong phap di~u che ete 3.2 .. 3. · Tfnh chat hoa hoc



, ~

ChU011g·W. ALDEHIT VA XETON

4.1. Cach goi ten

4 .. 1 .. 1. each goi ten aldehit

4 .. 1 .. 1 .. 1. Ten thongthirong 4.161.2. T@n qu6c tl (IUPAC)

..

4.1.2. each goi ten .xeton

~ .. 1 .. 2 .. 1. T~n thong thtrong ~

. 4.1.262. Ten qu6c tt! (IUPAC)

. ~ ,...,

4 .. 2. DIEU CHE ALDEHIT, XET()N

164 164

-

164

lQ4

I .

.

4.2.1 6 Oxyhoa hoac dehydro hoa alcol

4.2.2.. Thuy phan dAn xu!t gem-dihalogen

165 165 165

1651

. ..--,

'16~ 167

167 168 168 169

. .

'4 .. 2 .. 3~ Nhiet phan mu6i canxi cua axit cacboxylic

4.264.. Nhiet phan axit cacboxylic

4.2.5. Hydrat hoa axetilen va d6ng dang cua n6 4 .. 2.6.. Oxy boa 1,2 .. glycol

6

4.2 .. 7 6 Ozon hoa olefin 169

. 4.2 .. 8.. Cac phirong phap d~c biet dung dieu che aldehit 169

, ~; ~

4.3. TINH eHA T L Y HOC 170



4.4.1. Phhl trng khir 171

464~2. Phan ling oxy hoa 17I2

4_4~3.. Phan tmg cong hop 174

464.4. Phan ling Cannizzaro 179

4 .. 4.5. Cac phan ling hoa hoc co sir tham gia ella lien ket

C-H 0 cacbon a 180

4.4.66 Phan trng v(ri PCls tao hop chat gem .dihalogen 184

.....,.".; A,~ .".. ;.?

4.5. MOT so HQP (~HAT ALDEHIT, XET~)N NO TIEU BIEU. 184

46561 ~ Formaldehit (metanal) HCH() 184

4_5_2. Etanal CH3CHC) 185

4~5 .. 3_ Axeton CH3-CO-CH3 186

4.6. HQP CHAT DICACBONYL (DIALDEHIT, DIXETON) 186

4 .. 661. CLdicacbonyl 186

4 .. 6.2~ B .. dicacbonyl 187

4.7. ALDEHIT, XET()N KHONG N() 188

4 .. 761.. Gi6i thieu 188



467_2. Vai hop chit tieu bieu 190

4 .. 7 .. 2~ 1. Acrolein 190

4 .. 7 .. 2 .. 26 Xeten 190

'A K

Chuang V. AXIT CACBOXYLIC VA DAN XUAT .

5.1. AXIT MONOCACBOXYLICVA DAN XUAT 192

. 5 .. 1 .. 1.. Cac phuong phap dieu che 192

5 .. 1 .. 1 .. 16 Thu y phan hop chat nitrilo 192

5.1 .1 62 _ Thuy phan este cloanhydric hoac amit ella axit 19~

..

7

5 .. 1 .. 1 .. 3 .. Oxy hoa cac hQP chtit hiiu co khac nhau nhir alcol,

aldehit.xeton, aiken 193

5.1 .. 1.4. Tac dung cac hop chat C(1 kim v6i dioxyt cacbon 193

5.1.165.. TOng hop v6i malonat este · 193

5 .. 1 .. 1 .. 6. TOng hop v(ri este axeto axetat va xyan axetat 194

5.1.1.7. T6ng hop tic oxyt cacbon 195

5 .. 1.2.. C(u tao cua nh6m cacboxyI

5.1.3. Tfnh ch~t v~t 19 cua axit cacboxylic 5 .. 1 .. 4.. Tinh chit hoa hoc cua axit

...

195 196 197

5 .. 1 .. 461. Tfnh axit cua axit hiiu co 198 5.1.4.2.. Phan irng xay ra 6' nguyen tu cacbon cua nh6m cacboxyl 199 5 .. 1 .. 4 .. 3. Phan Ung decacboxyl hoa axit ~ 202 5.1.4.4. Phin nng ~l:{ nguyen tit cacbonC, ciia axit cacboxylic 204

561 .. 4.5 .. Phan ling oxy hoa 205

5.1.4.6. Phim ring tao thrum axit v~ nitryl 206

5.1.4.7_ Phan ling loai mroc tao thkoo_ll~hydrit 206

5.1.5. Gioi thieu mot s6~aXitf·tieu bien, ~ 206

.. .. I _ __... - _

561.5 .. 1 .. Axit formic 206

5 .. 1.5 .. 2. Axit axetic 208

5.1 .. 563.. Axit palmitic va stearic 209

. 5.1 .. 6+ Dan xuat chirc cua axit cacboxylic

5 .. 1 .. 6.1. Halogen anhydrit ella axit (axyl halogenua) 5.1.6.2. Anhydrit axit

5.1 .. 6.3.. Este

5 .. 1 .. 6.4. Amit

5.1.6 .. 5.. Arnidin

5 .. 1 .. 6 .. 6.. Axit hydroxamic

,

5 .. 1 .. 6.76 Hydrazit va azit cua axit

5 .. 1 .. 6.8.. Nitryl va izonitryl

210 211 212 213

2.1r9' 223 224 225 226· 228

229

5.1 .. 6.9 .. Hydroperoxyt va perox~ axit 5.2. AXIT MONOCACBOXYLIC C~HlJA NO

8

5.2 .. 1. Cac phuong phap dieu ch€

5.2 .. 2.. Tinh chat chung cua axit monocacboxylic khong no 5.2 .. 3. Mot s6 chat tieu bi~u

...

5~2.3.1.

5.2.03~2.

Axit acrylic

. J"-

Axit metacrylic (ce-metyl acrylIc axit)

229 230 233 233 234 234

235 235 237 237 238 238

5.2 .. 3 .. 3.. Axit oleic

5.3. AXIT DICACBOXYLIC NO

5 .. 3.1.. Cac phirong phap dit!u che

5 .. 3~2.. Tfnh chtft chung cua axit dieacboxylic 5.3.2.1. Tinh axit

5 .. 3 .. 2.2. Phan ling decacboxyl hoa

5 .. 3~2.3. Tach niroc tao thanh anhydrit n¢i phan tir 5.3.2.4. Phan ling the' b nguyen tU cacbon Co: (TOng hop

malonic este)

5.3.3.. Dan xutft cua axit dicacboxylic .5 .. 3 .. 4.. Gioi thieu mot s6 chtll tieu bien

. "

5 ... 3.4.1. Axitoxalic

5.3 .. 4402- Axit adipic

239 241 244 244 245

A

5.4. AXIT DICACB(_)XYLIC KHONG NC)

5.4 .. 1. Dit!u che

5.4 .. 2. Tfnh cha:'t

5 .. 4.3.. Anhydrit maleic

II' -;:;: """".,. .

5~5. CAe DAN XUAT ellA AXIT C:ACBONIC~

5.5.1.. nan xuat halogen eua axit cacbonic

5 .. 5 .. 1.1.. Photgen

5.5.1.2.. Diphotgen

5 .. 5 .. 2.. Este ella axit cacbonic

- 5.5.3. Dan xuat Iuu huynh C,'Ul axir cacbonic 5 .. 5 .. 3.1. Sunfua cacbon .

5.5 .. 3.2.. Axit xantogenic

5.5.4.. Dan xuat chua nitocua axit cacbonic

246
246
247
2lSU"
251
251
251
253
253
254
254
255
256
i
}
9· . ...



. ..

.. I. ..

I

. I ..

.. loP.

.. -

.......... -

• • r

• •• _ ". r

• I.". •

, ,

I ..

. .:- .

6.'"1 a HOP eRA T NITO



.. 6.1.1. each gci ten . : .' - ..'.

·6.1.2. Cac phirong phap dieu che 6.162 .. 1. Nitro hoa cac parafin

259 259 260 260

.. 661.2.2.. Dung mu6i nitrit tac dung v{ri dln·'·xuat halogen

hay alkyl sunfat 261

6 .. 1.2 .. 3. Dung nitrit natri hay nitrit kali tac dung vOi dan xuAt

, " cc-halogen cua axit cacboxylic

6.1.2.4. Oxy h.o~ amin

6.1.3. Tum ellat v~t Jy ,

.. 6 .. 1. 4.. Tlnh chat h6a hoc



6 .. 2 .. 268. Tit axit cacboxylic va axit nitohydric .

261
262
262
263
263
263
264
264
264
265
265
·266
266
266 ......
267
268
. 268
268
268
268
269 6.1. 4_16 Tac dung voi kiem

6.1.4.26 Phan ling y(1i axit vb co manh va d~ d~c . 6~ 1. 4 .. 36 Tac dung vai axi t nitro

6 .. 1. 4.4. Tac dung vai. axit v(j f~i"

6.1. 465.. Philo ling khir .

661.4.6_ Ngirng tu voi aldehit

6.2. AMIN

~ .~.2.1- each goi ten

6.2.2. Phuong pht!tp dieu che

6.2.2.1.. Tit dAn xuat halogenua alkyl yai amoniac 6 .. 2 .. 2626 Dieu che amin bac I tit amit axit



6~2..2.3. Tu fait axit

6 .. 2.2 .. 4. PiliP. ling thuy phan izonitryl

6~2.4.S. Iglit nhtmg hop chfit hiru co c6 chua nita

6.2.2.6. Die\! cht amin bang each khir va alkyl hoa dOng thai 662.2.7 - Til amoniac va alcol

- ,

10

6.262_9. Phin Ung Leicart

6.2 .. 3. Tinh ch·(t v~t ]9 coo c3C amin 6.2 .. 46 Tinh chit hoa hoc cua amin



6.2.4 .. 1_ Tinh bazo

6.2.4 .. 2. rae dung cu~ axit nitro HNC)2 6_2.4.3_ Tao amit the



6.2 .. 4_4. Phan iing oxy hoa

6.2.4.5. Tic dung cua halogen 662_4.6.. Tao izonitryl

6.2.56 MOt s6 amin tieu bieu



6 .. 2 .. 5-1. Metylarnin

6.2.562- Dimetylamin 6.2.5.3 - Trimetylamin

6~2.5_4.. Bazo amoni th€ bac b6n

. ...

6.2.5.5. Nitryl va izonitryl

662 .. 5 .. 6_ Amino aleol

269 269 270 270 271 272 272 272 272 273 273 273 273 273 275 279

Chuang VII. cAe H<)P CHAT co NGUytN_T6

7 -1. HOP ellA T co MAGIE

+

... ..

7 .1 6 1. Phuong phap dieu che

7.1.2.. Tfnh ch«t cua hop chat CO' rnagie

7.1 62.1. Phan ling voi hop ch!t c6 hydro linh d¢ng (H ~A) 7.1.2.2.. Phan ung the

7.1.2.3. Ph3.n ling cong

7 .1_2.4.. Phan ling vci oxy

7 .2. c~Ac HOP eRA T CHlfA unr HUYNH

. '

283 283 285 285 286 286 290

290

7 .2.1. Nh~ xet chung 290

7 .2 ... 2- Thiol 292

7 .2.2.1. Trang thai ttl nhien va cac phuong phap dieu che 292

7 .. 2 .. 2.2. Tfnh ch:ft cua thiol 293

762.3+ Thioete (alkylsunfua)

762.3.1. Cac phuong phap dieu che' 7 ~2 .. 3 .. 26 Tfnh chat ella thioete

7.2.4 'Axit sunfenic, sunfinic va sunfonic

294 294 295 296

7.3. cAe HQP CHAT CHlfA PHOTPHO, ASEN, ANTIMON,

BISMUT 298

7 ~3.1 ~ 7.3.2 .. 7~3.3~

Giai thieu chung

CAe phirong phap di~u che photphin, asin, stibin, bismutin

~

Tinh ch~t chung ciia cac dan xuat hiru co chua photpho,

298 299

asen, antimon.bismut

7.3.4. Mot s6 tinh chat rieng 763.461. Photphin

7 .. 3 .. 4.2. Asin

763.463. Stibin

7.3.4.4. Cac hop chfft htru co ciia bismut

,

7 .4t c~Ac HOP t~HA T co SILI(~



299 302 302 303 304 305

305 305 307 308

7 .. 4.1 ~ Khai niem chung

7 .4.2. Dieu che cac hop chat silan hiru CC1

~

7.4 .. 3. ~Tfnh chatcua cac hop chat silan

Chuang VIII. HYDROXY AXIT (OXY AXIT)

..



- .

8.16 MONOHYDROXY MONO(_~A(~B()XYLI(: AXIT

8.1 .. 1 6 Cac phirong phap dieu che

8.1.2. Tfnh chftt cua monohydroxy monocacboxylicaxit 8.1.3. Gioi thieu mot 56 chat tieu bi~u

• •

. 8.1.361. Axit glycolic (hydroxy axetic axit)

8 .. 1.3:2. Axit lactic

8.2. POL YHYDROXY M()N()(:A(~Bl)XYLI(: AXIT

312 312 314 318 318 319

320

. .

8 .. 3. AXIT HYDROXY P()L Y(~A(~B()XYLI(:

321

12

8 .. 3.1. Axit malic (axit hydroxy succinic ) 8 .. 3 .. 2. Axit tartric

863-3. Axit xitric

321. 32·2 324

....

Chuang IX. ALDEHIT AXIT V A XETON AXIT

9~2. XET()N AXIT

9 .. 2.1. ccxeton axit (axit pyruvic)

.

327 .

327 328

328 328

9.1. ALDEHIT AXIT

9.1.1., o-aldehit axit (axil glyoxylic) ,

9~ 1.2.. ~-aldehit axit

9 .. 2 .. 2. J3-xeton axit (axeto axetic axit va este cua no) 330

9.2.261. Cac phuong phap dieu che axeto axetat etyl 330

96262_2 - Tinh chilt cua axeto axetat ety I 331

9.2.2.3. Sir dung axeto axetic este trong t6ng hop xeton va

axit beo 333

Chuang X GLUXIT (HYDRAT(~A(:BON)

10.1. MONOSACC:ARIT

10 .. 1.16 can tao cua monosaccarit



10.1 .. 2 .. Hoa lap the cua monosaccarit

lO~ 1.3 .. C~U tnie dang vong cua. monosaccarit

lO~1.4 .. MQt s6 ph~n ling quan trong cua monosaccarit 10.1 .. 4 .. 1. Tac dung vci pbenylbydrazin

1 O~ 1.4.2 .. Phan ling oxy hoa

10~1.4.3. PhAn Ung khil hoa

10 .. 1.4.4. Tac dung voi axit HCN

10.1 .. 4.5. Tac dung vm dung dich kiem _ 10.1 ~4.6 .. Tac dung v6i anhydrit axit

, .

. 10.1.5. Gim thieu mQt 86 mono saccarit thuanggtp

. .

340
340
342
346
353
353
355
356
.
. ,
358
.358
,.. 359
359
I . 13

- ,. ... 106195619 Pentoza 359
10.1.5 .. 2. Hexoza 360
10.2. OLIGOjSACCARIT 362
10.2.1. Giro thieu chung - 362
1062 .. 26 Saccaroza 363
10.2.3 .. Maltoza 365
10.2.4. Xellobioza 368
10.2 .. 5. Lactoza 369
lO~3~ POL YSACCARIT 371
1063916 Tinh bot 371
...
1 0.3 .. 2. Xelluloza 377 Chuang XI. AMINO AXIT • PROTIT

11 .. 19 AMINO AXIT . 380

1161916 Gim thieu chung 380

11.1 .. 2. Cac phtrong phap dieu che amino axit 382

1191 .. 2 .. 1. Di~u ch~ a-amino axit 382

11 .. 16292. Dieu ch€ ~-amino axit 383

"..

1191 .. 293 .. Di~u ch~ aminaxit c6 nh6m -NH2 (1 cac vi trf y, 8~ 006._ 384

11.1936 Tfnh chat ciia amino ax it 384

1161.3619 Tinh axit ~ bazo 384

· 11916392 .. Cac phan ling cua nh6m cacboxyl 386

11 .. 1 ~3.3. Cac phan Ung cua nh6m amin "387

11.1 .3.4 .. Phan tmg xay ra vOi sl;t tham. gia dOng thai cua eel. hai

nh6m axit va amin '-

11.1.4 .. Hoa lap th~ cua amin axit

. ,

388
3"89
~ .
390
390
..
391
391
392 11.29 PROTIEIN 116291. Phan loai

...

I 162 .. 2 .. cru tnic protit

1192 .. 2.1 .. Cau true hac mot

• •

11 .. 2.2 .. 26 C~U tnic bac hai



14

11 .. 2 .. 2~3 .. cau tnic bac ba



398 398 398 400 401 401 401

11.2 .. 3. MQt sO tfnh chat cua protein 11.2 .. 3 .. 1. Cac tfnh chat chung

11.263 .. 2. M¢t 86 phan ling tao mall ella protein 11 ~294.. Gioi thieu mot s6 protein

11.2.4.1. Gi6i thieu mot s6 protein don gian 11 .. 2 .. 4 .. 2 .. Gi6i thieu mot s6 protein phirc tap

,

, '

- +

l:i

"

.~

-

,

.. -

Chullng I

HYDROCACBON

Hydrocacbon 13. ten goi chung cua cac hop ch~t hiru co trong thanh phan phan lti chi chua hai loai nguyen to Ia cacbon va hydro .. D6 la nhirng hQP chat hiiu co don gian nhat.

Tren co sO cau tao hoa hQC, co th~ phan chia cac hydrocacbon thanh nhiing loai chfnh sau day:

Khi mach cacbon trong phan tit 13. mach ha, co cac loai hydrocacbon no We alk an , hydrocacbon chua no chua lien ket dOi nrc alken, hydrocacbon chua no chua lien ket ba nrc alkin. Khi mach cacbon 18. mach yang, c6 cac loai hydrocacbon vong no trrc xycloalkan,

hydrocacbon yang chua no chtr , hydrocacbon

...... .....

yang chua no chua lien ket b · ,N-4r~~ on thorn chua

nhan benzen trong phan tic co .~,,~

p

....

1.1. ALKAN

,

/

·-·-·-J2.U_Yl'~.~'_.

...,....__ ........

1.1.1. Day dong dAng metan

Alkan thuoc loai hydrocacbon mach ho, trong phan tu chi co cac lien ket dan C-C va C-H diroc goi Iii hydrocacbon no hoac parafin, cluing co cong thrrc phan tu la CnH2n ... :-

Khi n= 1, ta co hydrocacbon no don gian nhilt CH4, goi Iii metan; n=2, ta c6 elan C2H6 ; n=S, co propan C3H6; n-4, co butan C~HI0' v,v .. .,

Nhir vay, m6i khi n tang them mot dan vi-ta dtroc mot hydrocacbon no moi, chi khac chat dirng tnroc no mot nhom metylen CH2•

'L

'Joan b¢ cac hydrocacbon no mach hb khac nhau trong thanh phan phan tit bOi mot boi 56 cac nhom metylen, hop thanh day dong dang metan,

17

-

'\

1.1.2. BOng phan

:oat diu tirbutan C4HlO xu«t hien d6ng phanve mach cacbon:

n- butan

CH3-CH-CH2-CH3 I

CH3 izobutan

.Khi n=5, pentan CSH12 c6 ba d6ng phan: -~

n- pentan

CH3-CH-CH2-CII3

I .

CH3

izopentan

neopentan

n=6, hexan CJi14 c6 nam d6ng phan; n=7, heptan ~H16 co chin dang phan; n=10, deean C1oH22 c6 75 dong phan; n=12, dodecan C12H26 co 355 d6ng phan; v. v ...

. .

Nhu vay, khi 56 nguyen tit cacbon trong phan ,tit tang len, s6 d6ng

phan c6 the c6 ~ita cac .. hy _ no ~~ 1Ang len ra:t nhanh .

.. - "1P. • "I ~ .. ' ~ .. ..

"I ....... ~,. "." t ; .. ~ • rIJ.t "I :....

-:a.I~ •. , •• _.- .

1.1.3. each ~gQi teQ ," ,,- - _- -, _; - -

_.. I_ I 'I' I .'

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

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

, ... 'I

1.1.3.1. Ctict giliT!n_tl6ng thuang ~ _

Theo each goi ten tA6ng' th~t,~l5If c;h«'t d'u day d6ng dang mang

ten goi co tfnh chit ijch"sir:'-' _ - :" .,. __ w .. ~·-

CH4 metan

~~ etan

~Hs- propan

-

,

~ ~

-

• I

, C4H 10 butan

Tn d6ng ~ng thtl 5 trO di, ten m6i chat xu~1't phat til ten chit s6 Hy Lap nrong ling vOi s6 cacbon trong 'phan. tit:

CsH12 pentan
CJi14 .. .heixan
~H16 heptan
CaH18 actan 18

..

..

4H20 nonan

C1oH22 decan

v.,.v ....

Khi bOt di mot nguyen tit hydro tu m6i phan tir alkan se thu duoc mot g6c hydrocacbon no nrong iing, cac g6c hydrocacbon no co ten goi chung la alkyl. Ten cu thi m6i g6e xuat phat tu ten cua alkan nrong ling, nhung d5i duoi an thanh yl. Thf du:

metyl ; C2Hs- etyl

co hai dong phan 13:

CH3-CH2-CH2-

n- propyl

i CH3-or~ I CH3

izopropyJ

/ ... /)

- .~ ..... -. J

........ • J

~ .

..'

V f du: C*H9 c6 b6n dong phan ..

1.1.3.2. each so! len hop Ij

Theo each goi ten hQP 19, mu6n goi len mot hydrocacbon no co mach cacbon phan nhanh, ngum ta chon mot nguyen tir cacbon co bac cao nhat trong cau tao phan til, nrc 13. nguyen tir cacbon n6i voi nhieu cacbon khac nhat lam cacbon trung tarn mang ten metan. Lan Ittqt goi ten cac g6c xung quanh nguyen tit cacbon d6 theo thrr tlr. goe nho tnroc, g6c 100 sau, cu6i cang lit chiC metan. Thi du:

CH3-CH-CH3 I

CH3 trimetyl metan (con 9Qi Ja zobetan)

.. _". '.

~___..._" e " - ~~.. ~ ••.•

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

~Cli-CH2~ CH2-CH3 .~.

. ~ -.~ ..

·.1 CH2 ./' matyl etyJ n-propyl' metan

I .: r

I

'·-CH3 .' .

. 1.1.3.3~ each gt)i ten thea IUP A·C

• • • I •

NAn11892,HQi .nghi Qu6c te"·c8R nha hoa hoc a Genevedf quy dpth

• • • I I I P _ • • • • • I ••

• . '.. ..' I : . .' • I ~ .'

19

....

mot h~ thong ten gQi cac chtfi--hOU ca. Do la danh phap qu6c W Geneve CIa dtrqc sir dung rong rai trong thOi gian dai, NAIll 1954, xuat hien danh phap qu6c te rom goi la danh phap IUPAC "International Union Pure and Applied Chemistry", co nghla lit "Hoi nghi Qu6c t~ ve Hoa hQC thudn tuy va Hoa hQC Ung dung", Ye thuc chat, danh phap IUPAC khong phai hoan toan rnoi, n6 chi sua chua, b6 sung va hoan thien them nhirng quy tac cua danh phap Geneve cho phil hop vOi tinh hmh phat trien cua hoa hoc hl1u co hien dai, Do do, danh phap IUPAC ngay cang diroc sir dung roug roo hem so vci danh phap Geneve.

D6i vci hydrocacbon no, urc aIkan, danh phap IUPAC de ra mot s6

,

nguyen tac nhir sau:

.,.

1 .. Gi u nguyen ten goi cac alkan thang khong phan nhanh thea cac ten

goi lich sir va ten gQi xuat phat tit ten chit 56 Hy Lap .



2 .. Giir nguyen ten goi mot 56 alkan co cau tao izo hoac neo nhu mot

so alkan sau day:

(CH3)~CH-CH3 (CH3)~CH-CH:-CH3 (CH3)4C

(CH3)~CH-CH~-CH1-CH3

izobutan

izopentan

neopentan

izohexan

3. D6i v6i cac alkan philo nhanh khac, tnroc h~t phai chon mach chinh. Mach chfnh 13. mach cacbon dai nhat, Thf du, trong alkan sau day:

mach chfnh nam trong khung cham gem 6 nguyen tir eacbon.

4. Hirong danh s6 thu tV cacbon trong mach chfnh duqc chon lua sao cho cac s6 chi vi trf cac mach nhanh 18. nho nh«t. Neu khi danh 86 thu 111

. . . . ..

dau nay va dtiu kia cua mach chinh, ta duqc cac s6 khac nhau thl phai so sanh chiing va s11p xep thea thir nr tang d~~ Cac s6 trong mot day diroc

20



coi 18. nho nhtit, khi trong day do co s6 tnroc Qh6 han so vQi s6 luang irng trong day kia, Thi du:

2,3,5 nho han 2,4,5; 2,7,8 nho hem. 3,4,9;

Nguyen lac tren diroc ap dung kh6ng phu rhuoc ban chat cac nh6m the .. Thf du:

..

6

5 4

3

2 1

CH3-CH-CH~-CH -CH-CH3

r - I ,

CH3 CHa CH3

2J3~5-trimetylhexan (khong doc 2,4,5- trimetylhexan)

..

5. Neu trong mach nhanh lai co nhanh nho thi cling phai danh s6 thu nr trong mach nhanh bat diiu tit nguyen til' cacbon dfnh vao mach chinh (mang 86 1, co hoa tri nr do). Thf du:

54321

CH~-CH~-CH -CH-CH-

~ - I

CH3

1-mety Ipentyl

.,

6. Khi goi ten alkan phan nhanh, co the goi ten cac nhanh hoac theo

trinh nr ABC hoac thea trinh nr tang dan tfnh phirc tap ella nhanh, cuoi cung hi ten ciia alkan tuong ling v6i mach chfnh, Thf du: .

CH3CH3 I ,

He - CH -CH2-CH2-CH3

13 12 11 10 9 8 7 .. 6 . 5 ..4 3 2, 1

CH3-CH2-CH2-CH~-CH2-CHi-CH-CH2iH-CH2-CH2-CH2-CH3 .

CH / "

CH3 CH3

, .

7 -(1 f2-dimetylpentyjl~5:izopropyltridecai1

. .

•• • I 1

• • I .,jl.

.

r _ ." ••••

......

~ ~ -

21

..

~ -L-t~4-.Phmmg pmip dlEu the : _. ; .

1~1~4.1. Phuong phdp giii nguyen m~h cacbon "

• ~ • I I

" ""

-~ . - ..

f J"

,

" ) -

. .

Trong phirong phap nay, e6 the dung cac chlt d'u.la. cac dAn xuat khac 1 nhaucua hydrocacbon, nhu cac dAn xuat halogen, cac alcol va c6 the ca cac axit la. nhirng chat ra-t kh6 _ khir. Tac nhan khir 130· axit _ icx:Ihydric

Ill, thirong dung axil iodhydric d~c (~ 80%) Ct nhiet dQ 180 + 200°C va co mat photpho do. Phin ii'ng thirong tien hanh trong 6ng thuy tinh han kin. Khi dun nang, HI bi phan ly thanh hydro nguyen tir rom sinh co khll nang khir manh:



2HI ) 2H + I,

- -

Ban d:l:u chuyen qua san pham trung gian 13. dan xuat iod va chat nay lai hi khir a nhiet dQ<cao hem thanh hydrocacbon no. Thf du, d6i v6i alcol : lIla trinh khlr dien ra nhtr sau:

+

HI HI

- ...... ) R-I

+ HOH

R-OH +

R-I

- ....... ) R-H + [,

-

Vi du:

..

alcol n-butylic

n-butan



s'! co mat cua photpho do trong h6n hop phan lam tmg tang cuong kha nang khtr hoa cua HI~ Photpho tac dung vm iod tao ra photpho

..

triiodua va ch~t nay khi tac dung vci H~O 1e;U tai t<;10 HI:

2P + '3I~

...

2PI3 + 6H20 "> 2H3P03 + 6HI

Ngoai tac ohm HI cung c6 the dung nhieu tac nhan khac cho hydro rom sinh nhir kent hoac hOn hong natri clura HCl~

Khit hydrocacbon chua no

Trang phirong phap nay, cac chat dau 13. nhtmg hydrocacbon chua no, co chua lien kt!t d6i hoac lien k~t ba trong phan tlr~ Tac nhan co the 13. cac ch~t khu khac nhau, nhir HI, nhung b day co .the dung hydro phan tit tren

22

xuc tac c6 hoat tinh cao nhir kim loai platin va paladi, Khi c6 m~t cac kim loai nay, phan tmg khir co th! ti~n hanhde dang ngay a nhiet dQ thuong.

Phan ling khir hydrocacbon chua no bang hydro c6 mat chat xiic tac

xay ra nhu sau:· .

"I .,

R-CH=CH-R· + Hi

R-C ""=sC-R' + 2H2

'''I' • I •

,

1~1.4,.2. Phuong phdp tang mf!Ch cacbon

. ..

~ .

a~ Tong hap hydrocacbon tilCO l'a H2 '

TOng hcphydrocacbon tlt CO va H2 tren cac ch~t xiic me Co, Fe do Fischer .: Strop phat hien tir nam 1926 thea sa "£t6 sau;

. . .

- tren xuc tac Co 18m chat mang:

.~ .

. nCO + .. (2n + 1 )H1 ) ~H1n+i + nH20·

n<xJ + 2nH2 ) CnH2n

"'I '. •

- tren xuc lac Fe lam ch~'t mang: "

'2nCO + (n + 1)H2

--.) ~H2n+2 + nCO,

.

. ,

~ . nCO + nH2 ) CuH2n + nC02

.

Trong tnrong hop sir dung H2 cua ruroc, phan tmg tdng"" hop

hydrocacbon theo phirong trinh sau:

(30 + l)CO + (n + l)H20 -) ~H~n+2 + (2n + 1)C02

3nCO + nH20 . )0 CnH2n + 2 nCO 2

Qua trmh tao thanh hydrocacbon true tiep tit CO2 va H2. dugc tien hanh thea phirong 'trinh sau:

3nC02 + (3n + 1)H2 .) ~H2n+2 + 2nH20

3nC02 + 3nH2 ~ ~H2n + 2nH20

Cac qua trmh tren deu phat nhiet ..

. . ., . .- -

!JJ-IR = - 39,4 kcal/mol (d 227°C)

'.:t~ .~

. AHR = - 48,9 kcaVrOOl (C, 22JOC) . .

3CO + H20 .) (-CH2-) + 2C02

!lHR ~ - 58,4 kcatmol (d 227°C)

Trong qua trrnh t6ng hQP hydrocacbon thea Fischer - Strop con tein tai mot s6 san pharo phu nhu cae aleol, cac .aldehit (~H2n+lOH,

~1I2n+l<:I10). ~

Phan rmg phat nhiet nen thl~t hi tie'n hanh phan ling phai dam bao viec

thoat nhiet bang lay nhiet ra khoi phan rmg. . .

Cac chat xuc tac cong nghiep cua phan ling nay tlnrong Iii Ni, Fe, Co, .Ru.

Tnroc Chien 'tranh' The gioi Tha 2, mroc DUe san xu~t nhieu loai hydrocacbon thea plnrong phap tdng hop Fischer - Strop. D€n nay tren th~ gioi eon hai mroc san xuat hydrocacbon til' CO va H2 la Cong hoa Nam Phi (dung xuc Me Fe) va Cong hoa Lien bang .. Nga (dung xuc tac

Co-MgO lam chat mang). .

. .

, -

Bang 1-1. S" phan b6 san phaID t6ng hQP h.ydrocacbon tit co va H2

khi co mat ella chat xuc me Fe .

oil

"

Qua trinh Chat xuc tile Fe 100p Chat xuc tao Fe trong
co dinh dieu ki~n tang soi~

..
Nhiet ee -c , 220+ 240 320 + 340
. . .,
". ~ 26 22 .
Ap suat~ atm
,
~O 1 ~7 3
-
SLJphAn bO % (theo tr9ng hJQT1Q) 7
..
san ph§'m T6ng hydrocacbon Olefin TcSng r-ydrocacbon Olefin
C1 7,8 - 13.2
.
-
C2 3,2 2.3 10tC , 43
C3 6,1 64 16,2 79
C4 4,9 51 13*2 76
Cs + e" 29,8 50 ~ 33~4 70
C12 + G20 14.7 40 5,1 60
Cao hon C20 36.2 15 ,
- -
Cac alcol, xeton 2~3 - 7.8 -
.
Cac axit - - 1 JO - 24

.J~~'" •• -- ..........

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

...... '\

, '" '

... b~, Tong hap . Wurtz. _ .. ~

__ ..... __ . __ . .

.- - ...... '1"-- .I.'- .'_

Tac dung cua natri kim loai vOi cac dan xu~t halogen .gS ... tao ra

hydrocacbon no do hai g6c cua dan xuat halogen k~t hop lai, nhir v$.y

mach cacbon tang len gap doi: .

R-X + 2Na + X-R ) R-R + 2NaX (hieu sua:t 80%)

Thf du:

. .

~H5-I· + 2N.a + I~Hs - ...... ) C2Hs~Hs + 2NaI

Neu dung hai loai din xuat halogen co g6c alkyl khac nhau, se thu duoc hOn hop ba alkan khac nhau:

R-X + 2Na + X-R'

R-R'

_ _')o R-R + 2NaX

Thf du:

...



~

CH3-CH2-CH3.

C~H5-I '+ 2Na + I-CH3-__...) CH3-CH2-CH2-CH3· +~ 2NaI

. . . CH3~3 , C~ ,-C2H4

, .

, ,

- -

Phan rmg t6ng hop Wurtz c6 Y' ngbia quan trong khong nhiing trong

dieu che hydrocacbon no v6i diu tao xac dinh, rna' con dung. de cluing minh cau tao nhieu hgp ch~t hUu co khac nhau.

.' _ ~.' . _

Theoquan niem hien nay, phan iingWiirtz tien hanh theo co che' g6c.

TUC1.ng tac cua dan xu~t halogen vm natrikim loaitnro; he"t tao g~ tudo

. .- " . ,. :

R , sau d6 tao ra hydrocacbon no do su ke't hop eua hai g6c ~ do:

R-X +Na

. \ ' . _. R~~+ ·R~

._.. .... 'I' • • _

. "c. T6ngh{1p~Kolbe:·'.'

_ _..,> .,R· + N aX

. ,

- ...... ) R~R·,

. .

... 1 .. ~ ..

I" . _ ~ + .

. .

.L '

~-

. ..

L

. . '.' .'

, . -

,

• '.. .. 'I

Khi dien phan dung dich mu6i natri cua axit monocacboxylic, r cation kim loai nam seJdi'v! rJhiacatot,:ihu ~ electron ~Ja.oguyen~t4natri

...JIt," h~ ~ .• ~~ A.:. H-· .A- .... "", - ..... ~~ .. N OH.a ~ l.! .nhA:n.n ],1.,( l.x7A..:r.... ~-lt ... 1\..1~ ··~UUl·lg~·~I'·VUl'··· 2~J ~o 'mann a .. 'va.' gtiU:.l"'a.v&.&C.J~:~~~~ :~."~

am~Jr gdC~ axi t~: dj;'ire' i"hN_:~anoti'm«t electron ~~ ra ~g6c- tI1 ~ ;R£()(t.,

.-

:25

d6ng thai g6c nay khong b&!, thoai phan thanh g6c R· va khf cacbonic, Hai g6c ~ do R· ktt hQP vdi nhau tao thanh hydrocacbon no. R -R. Sa de qua trlnh nhu sau:

CJ catot

+9

-e

.. .

R-COO·

HzO -+- NaO" + H2

• '

R· + CO2

+

R· + R· , ~ R-R .

, ...

- ..

Vi du, tit mu6i natri cua axit axetic CH3COONa se thu dugc etan; tit

mum natri cua axit propionic CH3CH2COONa se thu dugc n-butan,_y~v'-~: .. D6i vCti cac axit chua til 2 d~n.l8 cacbon trong phan nr, phan ling Kolbe

cho hieu su«t 50 + 90%.

. .

1.1.4.3. Phuong ph6.p gidm macb cacbon

Khi c«'t khan mu6i kiemhoac kiem the; cua axit cacboxylic v6i voi toi, xut, Sf! thu du(1C hydrocacbon co mach cacbon giam di mot nguyen ¢ so

v6i axit cacboxylic: .

-

R-COONa + NaOfl ) R-H + Na2C03

Bang phirong -philp nay, c6 th~ di~u che duQC metan CH4 tit .axetat

natri, etan C2H6 til propionat natri V.v... '

..

1.1.5. Tinh chat v,t Iy

Ttl' metan tm butan, b6n chat d3u cua day d6ng . dAng . lJ nhiet dQ thtrong Iii nhiing chat khi. Cac d6ng ding trung bmh til pentan tra di c6 mach cacbon th~g Iii nbimg cha't long. Cac dang ding cao honla nhirng ch~t rhI.

. ~

Nhiet dt) soi cua cac alkan tang dAn khi mach cacbon tang len. Cac

alkan c6 mach cacbon phan nhanh co diem soi thap han cac alkan d6ng phan co mach cacbon khong phan nhanh (n-alkan), S6 nhanh cang nhieu,

26

..

A

. " ~'

, .

• . r.

n-pentan

f soi == 36J 1QC

izopentan

., ~ntali

'''~I'''.

-, .J ••••• ~_ ••• -. {Os·ai=27,~C. '_ . ~.sOi=9 .• ~~~. -. ·

Nhiet d¢ nong chay cua cac hydrocaebon no mach _ thang tang ~-d4n

trong.daydong' ding.,: " . ,: ,'.'..,

, -

. - '

- -Ty ldi6i· ella cac hydrocacbon no-o nhiet d() soi eua chURg bAt ~ tang

nhanh, rOi saudo cham dfut: -~ 0,416 d6i voimetanden O,78··dtSi HOi 'cae

alkan cao. . ~ -: . - e-» • ~. • - • : •• ~ •••

.

Cac alkan khong tan trong nttCtc. Trong alcol cac alkan thip· de 'tan~

cac alkan cao kh6 tan. Chung d~ tan trong ete, trong cac hydrocacbon

. . .• -', 'r .. . . .oj • • -. • • •

khac va trong cac dan xuat halogen.. ., ~ ~. - . - ... . . r.. . -

, .

Hang s6 vat 19 ella mot s6 alkan c6 cho trong bang 1-2-. .. - ,

. . ,

.. '

Bang .1-2~ Hang s6 v4t It CU~ mt)t, sO alkan ~

• ....ifI •

, "

J • .'.'

Nhiet do NhiAttdo-- .., . ~ ;~ ~Chtso.
• -
. ,
• .. .. ..
Cong thirc Ten 99i n6ng chilYI ...... Ti khoi khuc xa
SOl J
.
.. ~c °C +
.
, - -
~
"'
CH4 metan -184 ~161~5 O.J4150 -
.
• ·CJ-164°C
.
- . . ,
C,H3-CH3 etan - , Ol5610 _. - I -
- :.172 -883
- -
- ...
.
• . - - '_. c,-1'~C ~
-
- . . . I
-
. -
CH3-CH2-CH3 ~. . . propan ~189,9 -42~ t7·- O~5853 ~ ~ ~ .. .
- - . - ,
-
- " ~
- ..
- . - . ., 4415~C ~
- I
- -{1
-
CH3-CH2-CH;2-C H3 ~butan +
-1·35,0 -O~6+ -O~3 , .OJ600 -
, ,
(CH3)2CH-CH3 izobutan -
-1450 -10,2- O~6030 -
,
CH3-CH2-CH2--C H2-C H3 n-pentan -13116 +36~2 O~6260 1.3570
(CH3hCH-CHz-CH3 - izopentan -1605 28,0 0,6197 1 t3550

(CH3kC(CH3)2 .. neopentan -20 ,9,5 015910 -
-
CH3-(CH2)4-CH3 n-hexan -943 6910 O~6603 1 ~3750
I'
~izbh~a~ . _.
(Ct;-l3hCH-CH2-CH2-CH3 ~ - 6O~O -0 i 5640 1 ~3720
-
I !
. • of"

_'-., Trongph6 hdngng~!cuaaJk~ t4n s6daod()ng hoa utcua cac.lien ket C-H nam trong khoang tir28S0 den 3000 em", Cac dns6 daodeng hoa tri ella lien ktlC-< tbmng ye'u va tbay:dOi. Cac nh6m metyl (CH3-) va metylen (~2-) thuongcc nlnmg dao d¢ng bien dang d,ctnmg ella

C-H til 1400 ctc!n 17()O cm ". .

1.1.6. Tinh chat hoa hoc



Trong c«u tao .phan til ella cacalkan chi c6 hai loai lien klt: C-C va C-H,.d6 lA .nhtmg lien k~t cong boa tri hau nhir khOng phan cl}'c~· Khi nang phan l'rr:lg cua cac lien k€t nay thap, Tuy nhien, nhitng nghien em. men'dAy da chUng minhrang, cac alkan chi tro d6i'v6i cac lac nhan ion nhu cac ·bazo, cac axit vO CO trung binh vacac ch«t oxy hoa trong dung dich nttOc. Trai lai, chang phan ling nrong dol de dang vm cac tac nhAn

c6 khci nang phan rmg cao va vOi cac goc tl! do. .

1.1.6.1. Cdc phan Wag thu~c lien lli C-H Phan Ung the'

Q. Toe dung viti halogen

Khi cho metan tac dung v6i flo; hoac v6i clo rOi cham lira se xay ra

... - - ..

..,., .. .

phan ling phan huy metan:

CH4 + 2F2 - .... ) C + 4HF CH4 +.~ 202 _---) C + 4HQ

Trong dieu kien c6 arm sang xuc tac, ho~c a nhiet dO cao, cho clo hoac brom tiep xric vOi metan se xay fa phan ling thS' nguyen til hydro trong metan bang nguyen tit halogen. Neu du halogen, phan trng th~ ti~p tuc ~en.ra chotoi khi the' he't hydro cua metan:

,

·CH4 + Cl2 ). CH3-0 + HO

• •

... -

matyl elorua

· metylen clorua

..

--..) CHCl3 + HO

cloroform

28

., .

.. '~ CC4 + --HO

.

.. • .. I .. _~'" _ r'. I .. I

- . .. ~ :_.' .. .': JlI= If _ I .

_ caebon tetraclorua, .. ,. . .'

'I. -. .' - - • '.

. . .. ~.t - .,.,... . .. . .. I • • '. I I I • .'" ~ I" -~ '" •

- . N1:t1r)~y"khi clo hoa metanco 3.r¢..s~g".xUc,ac .s,s ~1:\'~ hl)nihQp

b6ri' san-' pham: metyl clorua~' metylen . 'clorua," clorofonn ::vl·· cacbon

tetraclorua. ca b6n chat do deu .lit nhiing chA't co nhi~lj"dng'd1;ing 'ti6ng ,.

cong nghiep, ~

V e mat co che' phan (mg, phan .\hlg clo hoa metan lit phan U'ng the' g6c (SR) a nguyen tic cacbonno.. D6-1am¢t chu6icac phan t'rng day chuyen

n6i tiep nhau. . _- ~ : .~. ,

_ I • '. •• .~ • • • " .r

Tnroc h~t lit giai doan khoi mao, a giai doan nay nho rae dung cua

anh sang, phan tit clo phan ly thanh hai nguyen tir-clo:-· . .

- ,

...

. ~ . ...,

, . -

, .

. ,

, ...

- ....

a I. . C1 .. .hv .; ·2'" C1.

L. __ -, . > .

• •

I

.. ,

....... .

• e» •

Tiep sau lagiai doan phat trien, day 13. giai doan chi! yeu ella qua trinh phan -ung, trong d6 nguyen tir clo vOi mQt electron ~ do, hoat d¢ng nhir '

mQt g6c tl! do, tan cong vao mot lien ket C-H cua metan tao ra g6c tl1 do

•• - I

metyl CH3• = -

H

f . .

H-C-H + O· I

H

·H I

- ..... ) H----C- + HO

f

·R

, . .

G6c t1}' do metyl CHs- tac dung tiep voi phan tit cIo tao thanh metyl

clorua va nguyen tit 0- :

,.

• • •

CH3 + Q:O ~ CH3G + O·

Nguyen tit clo co the tAll cong vao phan tlr metylclorua moi tao thanh, cho mQt g6c nr do We IS. eH2er , r6i thanh metylen c1orua:

..

CH3Q + cr ') C'H2Cl + HG

.

-

. CH2Cl + 0: 0" • ) CH202 + 0-

Phan rmg ell' the tilp dien tm khi tao thanh san pham the- hom toan ca b6n nguyen tit hydro IS. cacbon tetraclorua C04-

Giai doan cu6i cung cua qua trtnh phan rmg the- g6c la giai doan tat

..

29~

m~ khi cae g6c t\l' do _tel hgp:'l~ vdi _ nhau _ de ..., _ th8nh phan tlr va khong con hliili thanh 6C nr do nim~

g . A .. , ..

. . .

__ Ph8n ~ clo hoa cacd6tig ~g cua metan b the kbi nhu etan.propan, butan, ciitig ~_ ~_ m¢i h~ pgp ~~u san pharo phUc tap, Thf du, _ d6i v6i

propan, ta c6 th~ _~p sa d6 'sari: _ _. _ _ -: __

,..

·_::c~

-CH3-CH2.:_c}i20

• '~:CL~ _

. ;~ .

..

..

, .

..

_ ... rl

v e mat kha nang phan ling the: g6c cua cac nguyen tit hydro cr cacbon co b~c khac nhau trong phan tit alkan, nguOi ta nhan thay c6 qui luat dinh huang sau day: pharr tmg dien fa vai t6c dl) Ian nha':t d6i vOi nguyen tir H

\ lJ cacbon bac 3, r6i d~n H ~ cacbon bac 2, va yell nha:t ct6i v6.i H b cacbon bac 1 .

...

• ',I _ • .' •

C6 th~'giai' thfch kha nang phan irng- the khac nhauciia cac nguyen tir

H a cac bac cacbon khac nhau dua vao trang thai nang hrong -va d¢ ben cua cac g6c tl! do trung gian hlnh thanh, Phan rmg theo _ co che g6c tit

. - . - ~ -

izopentan c6 th~ hinh thanh mQt s6 g6c tl! do, ~ du:

, '

.... • I •

H

.. -

H

H

..

..

I

n

30



Phan tfch so sanh ve hieu Ung sieu lien hop giira cac electron cr ella cac lien k~t C-H vm electron nrdo trong ba g6c t1! do tren, c6 tb~ nit ra nhan xet; trang thai nang hrong cua g6c (III) 13. thap nhit, do ~6 su lien

hop cua 8 dOi electron 0" vm electron t1! do, nen Mn nhat va d8hlnh thrum

. nhat; sau d~n g6c (TI), co s1:1 lien hgp cua 4 dOi electron cr voi electron tu , do, va ,cu6i cung Hi. g6c (I), chi c6 st}' .lien hop cua 2 d()i electron 0' vOi electron.nr do. Do d6, ta c6 tr~t t1! sap x~p vi dQ ben va Icha' nang hmh thanh g6c t11 do nhir sau: b~c 3 > b$c 2 > bac 1 ~

- .

, - Phan rmg clo hoa neu tic!n hanh qua manh liet thuong gay ra n6, d~ tranh dieu do, ngtrci ta thuong cho du alkan hoac pha loang bang khi

nito, hoac cho cac khf vao mQt dung moi long. ·

, - P.bin l1ng brom hOaaikM tien hanh JUOng tu phan ling clo hoa,

. .

nhtmg thuc ~ ·y~u hC1D.· va it duqc ap. dung hon,

. ... . .. .

.. Phin t1ng iod h04: aIkan 18 qua: trlnh thu~ nghich:

, ',' R~H +- I ' ~,·.;~t~,'·, R~I + HI

. .. 2 ".~~t.... ... .

.. .

I' I 0"' I • ..

... Trong di~u'ki¢n th~>pfian ling c6 khuynh ,httdng chuyen ve

phfa tnfi tai 6)0 alkan.-Mu6n c~6' phan ling chuyen dich v~ phfa phai de , tao ra dan xua:t iod c~dUng ritQt chat oxy hoa rnanh, nhu axit iodic mOl c~angh~, de tach HI ra khOi hOn hop phan tffig:

5HI + m03 ~ 3H20 + 312

Phlm ling flo hoa tryc tiepcac alkan bi han ch€ do phan img xay ra ra-t , rnanh liet, giai ph6ng HF~ CF4 va cac san pham phan huy khac, va thUbng , ket thuc bang s1! n6. Nguyen nhan co ban cua phan ling th€ flo rnanh liet

13. do nang hrong tao thanh ella HF va cua lien k~t C-F ritt cao:



C-H. + F2 ~ C-F + HF + 103 kcal/mol

. trong khi phan iing clo hoa chi giai ph6ng 23 kcal/mol,

I

b. T tic dung vOi axit nitric

Alkan khong phantrng v6i axit nitric ,d~c b nhiet dO thuong. Khi nang cao nhiet dQ, HN03 ·d~ se oxy hoa cham . cac alkan, be gay cac lien k~t

C-C va cho san phAm chinh 18. axit cacboxylic.

, Tuy nhien, neu dung axit nitric loang, tien hanh phan ling lJ nhiet d<)

31

.......

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

.. ,~ ... ~ ... 1 ~:.:._- .. _ . ::;; . ..: ... '.: r"_. .... 'i·r•· .. ~. '- •. r,'Il"

cao va 'p su«t cao thl c6 .. ~'ru.~ flo! -ditQC cac aIkan.· so- 46 churig nhu

_ -. • .' •••• • : 'I • • ._ ... •

sau: _ - ..

~ _ _

r.. _... • . _. . . '" 'I

.~. '. I

~.

-

R~H.+ . HNO~ l1oing) . 11.0~140~~;. ~NO-· + H~ O ..

. 3 \~ ~psu(t. _' 2 . . 2·

.

. Pbim Ung nay do ~f.l~Koriovaiov pilat minh va nghien cuu chi tie't van

nam 18,88 - 1 ~94; da: fuu dlllJC ~tt qua t6t $4't (hieu suat ten . 50% va hgp

. ... -. .

chat nitro tinh khiet), khi nitro hoa bang HN03 loang 12,5% (d = 1,075)

6 110 + 140°C trong cac 6ng han kin.

c. T ac dung vdi axit sunfuric

. .-

.

Ciing nhu v6i axit nitric, cac alkan khong phan irng voi axit sunfuric

d~c b nhiet dQ thirong. Cac alkan co mach 6 + 8 cacbonkhi dun nong voi axit sunfuric b6c kh6i (oleum 15% S03 tu do) se bi sunfo hoa tnrc tiep

tao thanh alkan sunfoaxit, Vf du: .

..



_- .

COHl'; + HOS03H ) C6H13-S03H + H20

.. . . .

Trong thuc te, ngiroi ta -thtrong khong sunfo hoa 'trgc tiep bang H2SO4

. .

. .

d~c rna hay dung phan img sunfoclo hoa, hoac sunfooxy hoa.

Sllnfoclo 110a

-

Khi cho S02 va clo cung tac dung len alkan b 20 + 30~C c6 chieu sang

.• I .... .

. . _

bang den tit ngoai, hoac co chat khoi mao 13. rnotperoxyt, se thu diroc san

.. ? . .. . .

pham alkan sunfoclorua:



R-H + sO,a~

- -

.

. 1107140°C

hoac peroxyt

De tranh tao ra nhimg sanpham phu nlur R-Q, ngiroi ta dung du SOl' thirong vOi ti l~ 2: 1. KID thuy phan dan xuat .alkan sunfoc1orua c6 mach cacbon kha dai (> 1 0 cacbon) bang N aOH, ta se· thu dugc· cac mu6i sunfonat IA nmmg chfft co tac dung tay rita t6t. Vi vay, phan tmg sunfoclo

.: ,

hoa cac alkan co y nghia tlnrc t€ trong san xuar nguyen lieu xa phong .. Xa

phong alkan sunfonat thtrong goi til meczolat:

32

Sunfooxy hod

Khi cho S02 va oxy vrn tY l~ dAng phan tit, tac dung voi alkan c6 mach 6 ~ 8 cacbon b nhiet dQ 20 + 30°C, dong thbi chieu sang bang den tir ngoai, se thu diroc alkan sunfoaxit:

R---H + S02 + O2 ) R-SOJH

Qua -trlnh sunfooxy hoa ciing - co the tien hanhkhi c6 mat anhydrit

axetic nhung phai tiin harm lJ nhiet d(l45°C va ap suat IS + 18 at. .

1.1.6.2. Cdc phdn ftng thutjc lien ket C-C

a. Dot chdy \'Q O~')~ hod .

(j nhiet dQ thuong, oxy va cac chat oxy hoa khac, ke ca nhimg chat oxy hoa manh nhtr axit cromie va kali permanganat deu khong eo tac

dung v6i cac hydrocacbon no.. .

o nhiet d(l cao (khi cham lira d6t) hydrocacbon no chay trong khong khi (uit nhien, ding chay trong oxy nguyen chat) toa nhieu nhiet va phat sang. Phuong trinh phAn ling d6t chay hom tOM nhu sau:

2~H2n+2 + (3n + 1)02 ----.) 2nC02 + 2(n + 1)H20 . + 2Q Vfdu:

...

~ CH4 + 202 } co:! + 2H20 + 210,9 kcal

. Vi nhiet hrong phan ling d6t chay sinh fa kha Ion, nen cac alkan diroc dung lam nhien lieu r~t t6t.

Tuy nhien, trong nhtmg dieukien ·nht: nhang thfch hop, co the thirc hien phan ung oxy hoa alkan bang oxy khong khi, hoac oxy nguyen chat va se thu ducc nhUng hop eMt hw' co chrra oxy nhir alcol, aldehit, axit cacboxylic, v.v ... Vi du khi oxy hoa metanbang khong khi dttOi"ap suat

thirong a nhiet dQ 400 +. 600°C~ ven xuc tac la cac nita oxyt se thu duqc aldehit formic, con khi dum ap suat 150 at va a 400°C, san pham chi! yeu

18. metanol. Oxy hoa etan bang khong' khi CJ 280°C, dum apsuar 100 at, se thu .~~ mQt ~On hop CH30E;, GzHsOH, ~H3CHO cung hrong nb6 CH3~H. Khi oxy hoacac a1kan cao q ther!n,b~g.khOng khi.CI 100 + 130°C c6 m.~ kho~g 0,3%· KMn04, sa ~ay.ra s\l M giy lienket C~c va

.. -. . -. I '. -

..

33

...

. ~ ..

. cho cac axit beo ~ao. cae, J#ti ~g tren d~u duQc ap d1!Jlg trong cOng

nghiep san x~~t rna nhan tao, ~A' phong, . v.v... .. f· _

h. Cracking

• -= ,

CrackingIa qua trinh be' gay mach eacbon_ dai thanh mach ngan hem.

PI:tlm Ung cracking da:u rno la chuyen be gay cac phan tit hydrocacbon co khOi hrong phan tircao thanh hydrocacbon c6 khOi luC}Ilg phan tir thap, tang hieu su,"t ella san pharo nhe (xAng,· dau diezel, vv ... ) va tang chat Iirong ella san phAm nhien lieu. Cracking bao gorn cac loai sau:

- cracking nhiet;

- cracking xric tac:

oil

- cracking veti hoi mroc;

,- cracking duOi ap suA't hydro (hydrccracking). '

hi. Cracking nhi~t

Cracking nhiet dum ap suat cao se dieu che duqc benzin; dum ap suat thap, nhiet d¢ cao (nhiet phan) se thu duqc khf chua Iirong IOn olefin va

hydrocacbonthom. ·

Cracking dum ap suat cao, nhiet dQ 470 + 540°C, ap suat 40 -;- 60 at, voi nguyen lieu 13. ligroin cho d€n goudron, benzin c6 chi s6 octan

khoang 60 + 70, se cho san pharo chua nhieu olefin, do vay can phai che hoa tiep OOu reforming v.v._. -

Co che cracking nhiet co thi trinh bay nlur sau:

...

Cac g6c nay c6 the phan huy thanh cac g6c nho hon, cac olefin va hydro. Cac g6c hinh thanh k6t hgp voi hydro tao thanh parafin, hydrocacbon no, ciing c6 the ke't hop voi phan tit nguyen lieu ban d~u de tao thanh hydrocacbon no va g6c moi:

CnH2n+2 + R· ) RH + CuH·2n+J

Day 18. phan img day chuyen thee co che tao g_6c, phat trien mach va ca.t mach. Qua trmh cracking gorn day phan tmg n6i tiep, song- song, urong tmg vm phirong trtnh bac 1 v6i hang sO t6c dQ phlm tmg:

34



..

k=(Xln a

't ,a-~'·

· k - hang s5 van t6c phan ling ;

ex ~ ltrong nguyen lieu tinh bang mol tren don vi th~ tich phan ling ;

- ,

x - s6 mol phan huy trong m¢t don V! thm gian r,

~ s6 mol cua chat ban dafJ di qua thiet bi xuc Me trong mot Clan vi

thoi gian, ,

Phuong trmh tren dap rrng ducc d6i v6'i su phan huy tnroc h~t parafin, olefin cao va dealkin. Nhirng olefin thap co kha nang trung hop hoa nen tha bac phan trng thirong cao hon mot. Van t6e cua qua trinh cracking nhiet bieu dien theo phuong trlnh sau:

. a a

k=...c_ln -~

t a-x

P - hang 56 dac tnmg cho rmrc dQ dimg, phu thuoc vao loai nguyen lieu, dieu kien phan ung: J3 nam trong khoang 0 -of- 1.

St! phu thuoc gifra hang s6 k va nhiet d¢ dircc bieu dien hOi phuong

...

trtnh Arhenius, tlr d6 tfnh diroc nang Iuong hoat hoa 53 +·58 kcal/mol

(nguyen lieu dau hoa, gazoin); 65 + 70 kcal/mol (Iigroin); 70 + 98 kcal/mol (hydrocacbon thorn); 60 + 65 kcal/mol (parafin va naphten) .

..

h2. Cracking a nhiet dq cao, dum ap sudt

Muc dfch chinh cua dang cracking nay 1a san xuat cac khf hydrocacbon cAn cho cong nghe hoa hoc va cac hydrocacbon thorn, Qua

trlnh lien harm b 650 + 700°C, ap suat g~ vOi ap suat khf quyen, san pham tao thanh bao g6m 500/0 khi, khoang 50% nlnra, trong d6 chua khoang 10"" be nz en , 6% toluen, xylen, naphtalen, antraxen, ..... Trong

-thanh phan khf chua khoang 30% hydrocacbon chua no,

Ben canh hai loai cracking tren, trong cOng nghiep con tien hanh . qua trlnh cracking nhiet Ct ap su«t tM"p. Muc dfch cua qua trmh nay la

di6u che' c6c, hydro, 60 + 65% Hi. phan doan benzin, dau hoa, gazoin va khi. Nguyen lieu la goudron, phdn c~ cua cracking, bitum.

b3.· Cracking xuc lac

..

Qua trtnh nay c6 su tham gia cua xiic lac, cho ta san pharo c6 eMt

35

luong cao va tang hieu suat cua phan 6l;tg (tang san pham), Benzin c6 chi

- -

s6 octan khoang 85 dung lam nhien lieu cho 616, phan doan dau hoa -

~ I •

gazoin dung lam nhien lieu cho dQng ca. diezel hay tuabin khf. Khi

tlnrong chua hrong 16'11 hydrocacbon no vakhong no C, + C4•

Ch«t xnc lac duqC sir dung tnroc day la aluminosilicat chtra 10 + 15%

~

oxyt nhom, c6 M mat rieng hang tram m2jgam va kfch thiroc 16 cua xuc

.tac 50 + 100 A.Hi~n nay tren the' gi6i nguoi ta s~ dung cac loai zeolit Y hay ZSM c6 hoar tfnh (d¢ hoar dQng) cao, tao duqc nhieu san phAro co eMt hrong.

..

Qua trmh cracking xric tac thuCmg xay ra q nhiet d¢ 450 + 520°C, ap

su«t I -:- 2 at, thOi gian tiep xtic (nguyen lieu vOi xuc tae) khoang vai giay. Ph3n rmg c6 rn~t cua chat xiic tac tmrong xay ra nhanh va phrrc tap han cracking nhiet, Nhieu loai phan irng xay fa trong qua trmh nay nhu phan ling d6ng phan hoa, loai hydro, chuyen nhom alkyl, de alkyl , polyme hoa ... nen de dang tao c6c tren be m~t chat xuc taco Do do viec tim cac cha:t xric tac it tao thanh c6'c tren be m~t, d6 dang hoan nguyen trb thanh mOt yeu c~u dip thiet, N gay nay, trong cong nghiep, van de nay v~ co ban di d11QC giro quyet, .

. Cracking xiic lac la mot qua trinh phtrc tap, d~ng hQC cua qua trinh co

the bieu dien dum dang phuong trinh phan ling thti bac 1: .

V ln 1 ::: AV V + a.

o 1 P 0 ...

-)' .

v 0 -. ~i tfch nguyen li¢u~ cho vao thi~t bi phan rmg tren m.,t the tfch

chtt xuc .tac va don vi thbi gian; ·

. ,

}~ - d¢ chuyen hoa.

. -

" a va J3 -mhtmg gia tri tY l¢ vci hang s6 toe dQ phan l1ng; ex. va f3 trong phuong trtnh nay co y nghia v~t 1Y.

. Phan-ung cracking xnc tac ti.6t hanh thea co che sau:

Dqa theo 19 thuyet ion cacboni thi ti'r hydrocacbon no c6 the hinh thanh do st! phan huy phan dr. tao thanh olefin, olefin klt hop v(ri proton

chuyen thanh ion cacboni (axit Bronsted hay axit Lewis). Vi du:

<.

36

.

.

. .

Ion cacboni lac dung vdi phan tit hydrocacbon tao thanh phan til mcSi

va ion cacboni rom:

+ +

CH3-:-CH-CH2-CH3 + R-H ) Cli3-CH~2-:-CH3 + R 2

f' .

. Rl

R, va R2 Ia cac g6c hlnh thanh tit phan tl:r hydrocacbon,

Ly thuyetion cacboni th~ hien a phan tmg phan chia mach cacbon, con ap dung veri cac 'dang bien hoa khac trong qua trinh cracking nlnr phan iing dOng phan hoa, alkyl hoa, trung hop hoa, phan rmg pharr b6 I~

hydro.i. .

, .

- . Hieu sua:'t cua che hoa Ian 1 ella cracking xnc tac dat: .. khf the, (tirC, +

C3): 6 + 9%; butan - butylen (phan doan) 6 + 9%; benzin (soi d~n'205°C)

30 + 40%; gazoin xtic tac 45 + 550/0 va c6c 3 .;; 6%. Tri so.octan cua _ etxang: 76 7- 82. Cac khi cua qua trinh cracking xuc tac thuong dung lam

nguyen lieu cho tOng hop hiiu ca. .

. I

b4.. Cracking vai hoi nude

Cracking vci hoi ruroc thuong thu ducc cac olefin nhe can cho t6ng hop hoa dau. V u viet cua qua trinh flay so vm qua trinh nhiet phan Ut san pham. ccc hoa it, hieu suat olefin tang, d~c biet khi sir dung cac chat xuc tac (niken oxyt tren magie oxyt). Nhiet d~ eiia phan irng trong khoang

650 + 800oe. 'San - pham chu y~u; la etylen, ciing thu duQC propylen, butylen, butadien, axetylen nhung voi hrong ft. San pham hydrocacbon

khong no cao dung d~ sarrxuat nhira chiu nhiet. .

, .

ss, Cracking dum tip sudt hydro (hydrocracking)

I • • •

Qua trtnh nay dung de ch€ hoa cac da:u mo va cac phan doan dau trung va eMu nang chua nhieu hru huynh va nhira; nhUng d§u nay khong . the che hoa bang con dirong xiic clc diroc.

Hydrocracking ti~n hanh dum ap suat hydro 30 + 140 at, nhiet dQ 350 + 4500C. Cac chat. xuc tac thubng dung - Ut cac oxyt hay sunfit molipden, niken, molypdat coban tren cac cha:t mang c6 tinh axit.

Nhiing phan ling co ban cua qua trmh nay la hydro hoa rna yang cUa cac hydrocaebon vong voi su tao thanh izoparafin, dong phan hoa va cat

. . .

cac phan tir parafin cao thanh cac hydroeacbon c6 mach nhanh, c6 s6

nguyen ttY cacbon it hem, phan huy cac hop chA:t btu huynh thanh hydrocacbon va khf 82S .



NgUOi ta sir dung apsua; hydro de ngan ngira s,! tao thanh coc tren

xtlc taco Hydrocracking lam tang san phim phan doannhe lam nhien lieu

. _I I

cho dOng co (benzin, diezdt, nhien lieu phan hrc). '

b 6., Reforming xUc lac

Qua trmh reforming _ xuc tac bao g6m d6ng phan hoa, de hydro. d6ng vong, hydrocracking.

DOng phan hoa cac a1kan thea co eh~ cacbocation, chuyen cac atkan mach thing sang cac alkan mach nhanh, tao thanh nhien .lieu c6 chi s6 octan cao ..

.

- Dehydro boa dong- yang 13 su chuyen n-alkan thanh hQP cMt vong

thorn, tang chi s6. octan cua nhien lieu: ·

CuH2D+2

)

Phan lhlg nay thu nhiet, vi v~y hang s6 can bang tang khi tang nhiet d¢. cae giai doan chuyen hoa cua dehydro boa d6ng yang nhu sau:

. Alkan -+ xycloalkan ~ xycloalken -) hop ch«t thorn Hydrocracking cho cac san phAro. alkan tha'p han. Vi du: -

. .

~ ....... ::-~ CH3-CH2-CH2-CH2-CH3 + CH4

H2 -

......__--t---~~~ CH3-CH2-CH2-CH3 + CH3-CH3



It

Qua trlnh nay con dugc goi lit su phan.huy hOi hydro.

D6i vcii cac xycloalkan thi c6 the xay ra ~c qua trlnh - sau: dehydro hoa de chuyen thanh cac hydrocacbon thorn; ddng phan hoa, hydro hoa pha va vong; hydrocracking. Vf du; .

dehydro hoa

, . _ ..
..... _
, . - . .
_
~ _
.
.
,
dong phan hOB ,
. ,
....
.....


. ,
, hydro hoa
..... .
_ ~ ...
r pha v6vong
- .'
_ .
...
__....
hydrocracking,
....
.....
....
...,.... •

.'"

, . + . 3H2 ~

...

..

'. I ....

• •• ~ - I I. ••

C1l3-CH2,~2-CH2~~2~CH2-CH3

. . I._ _ .

J

. . _

+ <lit. "", "!'

... . ... ~ -:. _

- - - -. . ..

. -. .. .

Qua trlnh de hydro thirong dung chat X uc tac kim loai hay cac - h6n

hop oxyt cua cluing, qua trtnh d6ng phan .hoa 'dttngcac chat xuc tac la axit-bazo, qua trinh -hydro hoa dimg cacc{:htft xuc tac kim I()~ (die ch!'t dung cho hydrocracking da trinh bay ophtin hydrocracking). TY l~ giira cac phan ung tren phu thuoc vao cac y~u t6 hhi~t dQ va dt?ng hoc, cling nhir hoat tfnh cua cac chtit xiic lac ..

..

Cac ch~t xric tactlnrong dung- trong cong nghiepla cac cha':t xuc tac da chile nang nhir Pt/y-A1203 ;0 Pt + nlvle v611t:tQl1g nho /y:-Alz03, trong do Me la cac kim loaiquyhoac kim loai chuyen tiep. .: . _ .

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

. .

Trong qua trinh reforming.cac hop cht{t chiradi nguyento N, S, 0

hydro hoa tao t~~ NH3,H2S~ ~20 va cac .hydrocacbon nrong jmg. Amoniac va sunfuahydro l_amng~dQc cac ch~t xtic tac Pt,·Vi v~y nguyen lieu cua qua trinh reforming phai duqc lam sach hydro va khong

diroc chira qua 0,05 % luu huynh va 10-40/0 nita. . . - . ,

Nhln chung, cac c(}ng 'do~ ttdng'-nhii may .lcchoa daunenco qua trtah reforming .~.cha:t luong nhien lieu moi cao -va tao duqc cac

nguyen lieu cho ea qua trinh hoa d~U:_ ' .

39

ibJt Dehydro cdc parafin .~-~

. . •• _:..... . ..... - ".. I

... Dehydro cac nilara(m cO ~ s6 cacbon fir C1('~·+ C14' thanh .cac . a-olefin.

Cac san pham tao ra nay tie'p tuc alkyl hoa cho nguyen lieu san xuat ch«l: tdy nia trlng hop (detergent): .

.. _ ._-

. CH3-(CH2)s-CH2-CH3

..

, .

. ...

'."

a-olefin .

, ,

Thong thubng trong cong nghiep, hrong n-parafin chuyen thanh

olefin vao khoang 10 + 15~. Qua trmh c6 dl)'chQn lQC cao, de'n 90% tao

•• • - "I I • • 'il " ..

thanh a-olefin va khoang 10% olefin c6 n6l d()i kh~ng"o ngoai cung,

. .

1.1.7.Clult tieu bi~u: Metan CH4'

Trong VQ Trai Dl't co nhieu vung chtra khi thien nhien, metan 13. thanh phdn chfnh cua khf nay, c6ldii ·ct~t tm 99%, trung binh ciing tm 97 ~

+.98% .. Metan cting c6 trong khi diu rna (39 -;.. 85%), trong cac rna than <fa (3,5 + 1,5%). HOn ilQp·metan va khongkhf khi gW lira se nO manh, d6 13. nguyen nhan . cua nhiing vu nO Kay ra trong cac ham. rno than. Metan eiing chiem m¢t tY l~ dang ke trong khf thap (g6m 50% H2, 30% C~, 8% CO; 4% cac hydrocacbon chua .no, 2% CO2 va 5% N2) thu duqc khi chung than da (than beo), Metan cUng tao thanh do su phan huy ytm khf.cac.bid¢~g thl1c v~t dum·lac dung eua cac vi.khuan a day ao h6 tao ra "khf bun ao" (Volta, 1778) .

.60

Cac vi khuan tham ra qua trinh nay c6 a trong . chat thai ho~e trong

bun. MQt s6 dang vi khudn nay c6 the dung ngay ca hydro phan tit, mot s6 dang We dung hydro tit cac hop char hiiu CO (gluxit, protit) trong



qua trinh len men chiing. cae nghien ctru qua trtnh sinh hoa nay da dan

Wi nhieu phit minh moi,

Metan ciing co the tao thanh khi khu khf eacbonic:

..

1.1.7.1. Phlldllg phdp dieu chI

_

a. T 6ng hap metan

, _

Metan c6 ilie"dugc tdng hop bang· each hydro hoa CO. a ap suru: thuCmg va nhi~t dQ 230 + 150°C tren ch«t xiic tac Ni, CO,'Fe~· Ph8n 1lng

ti~ri hanh theo ·SCl do sau: .. ~ . . ,

..

(1)



+

!lHR ::: - 49,3 kcaUmol (d 25°C) .1HR = - 51;3 kcal/mol (ii 2~JO~)

Fe) ca, .;..-C02' ~R = - 60.8 kcal/mol (d 2~7"C)

(2)·

...

~

-- ...... , CH4 + _ 2HzO

(3)

.

_ :Y-IR = - 39,5 kcaUmol (d 25°C)

+

Theo tfnh toan tren co sa nhiet dQng,· S\! tao thanh CH4 vOi t6c d¢ 16n khi nhiet dl} khong cao han 550°C. Tang ap su~t ·c6 8nh huOng dirong

d~n qua trinh tao thanh CH4• A.p suat rieng phm cua co lam giam su tao thanh CH~. T6c _d() cua phan ling metan tang khi tang tY 1~ HJCO.·



Cac qua trinh c6 the xay ra rUU! sau:

)

4( CO2 + H2

JJ-iR = - 9~5 kcalJmol (d 22?OC) ·

~ .

(4) .



200 . -- ..... ) C .. + . CO2

(5) .

,

• !YIR;:: - 32. keal/mol (22roC)

Khi tang nhiet dO til 250°C den 80Qoe, t6c dQ cuaphan ling (4) tang

khong nhanh, nhimg t6c dQ cua phan Ung (5) tang nhanh. _ ~

. '

. .

Hoar d() cua xuc tac metan hoa khong em phu thu(}c vao kim Ioai, rna,

con ph\! thuec vao chat mang va qua trmh di~u ch! chat xiic tac.· .,

Phan rmg tOng hqp metan c6 t~ quan trong ttong viec bao v~. moi tnrong, vi khi chay nhien lieu trong cac dQng CCI se 'hinh thanh raCO, ·phcii bien chung thanh C~ sau d6 ddt chay (khf CO lakhf doc),

41 .~'.

-

b. Thuj phdncacbua kim 10000i



Thf du:

..

,.

- ~

. .. ...

- "

: ~ ~

nh~c~~-" ".

I .. • _... ..

. " "

:. "I P

p " -

Ngoai cacbua nhom cling, c6 th~ thuy phan cac .caebua kim loai khac

nhu cacbua berili, thori, urani, mangan, ... - ·

" "

e.t» tit cacbon disunfua, hydrosunfuava d6ng kim Ioai

..

"" "

• .... I, I •

. "

• r I _ • _

Day lit m.,t phim ling C9 Y nghia lich sir. Bang each cho hOn hop khf

hydrosunfua va hoi cacbon sunfua di qua dOng 'nung do, se thu duqc khf

metanva d6ng (I) sunfuai.. .'_ , .. .',

..

d. 'f) i tit axetat natr i ~d va i toi, xu: ' -, ", ,.'

• • • - I

Dun nong hOn hop natri axetat v~ voi toi, xtit, co the ~~u ch€ diroc

khf elL. Phuong phap nay .co the dung trong phong thf nghiem de di~u ch~ hrong $0 metan: """ : "

.

" ,

CH3COONa + NaOH

"" .

" ..

.

". -

"" ,

.

,,' I

" ' t

1.1.7.2. Tinh chiit va ltng dung "

Metan IA khi khong mau, khong mui, It tan trong mroc, chay vm ngon lira xanh nhat, toa nhieu nhiet (8560 kcal/nr'). -VI vay hrong Ian

metan dl1QC dung lam nhien ii~u.-·' '

· Khi d6t metan trong di6u kienkhong du khong khf trong nhtmg thiet hi dac biet se tao ra cacbon b dang-bot than min:

" "r

.. . -"

ClL +" O2 ---.") C +" 2H20

.. .

. .. .. . ... .

BQt than nay la nguyen lieu co gia tri dung lam ch~t dl)n trong san '

xu~t'· cao ·su.. "" " ~' - " "

Khi cho metan va hoi mroc di qua xric tac niken- 6 850ClC, se thu dircc hOn hophydrova cacbon oxyt dung lam nguyen Iieu tdng hqp:> . ~

- I ...

..

42

Cho hOn hqp nay di qua xuc tac sAt oxyt a 400°C, cacbon oxyt chuyen hoa thanh khf CO2, tach kill CO2 ra, hydro con Iai c6 the dung trong tdng hop amoniac va trong nhieu tmg dung khac,

Metan cling dugc dung lam nguyen, lieu tOng hop axetylen, dung dieu che' cac dan xua:t clometan, axit xyanhydric, ...

1.2. ALKEN

~ ~ ,

1.2.1. Day dong dang etylen

.

AIken 18. cac 'hydrocacbon chua no mach ha c6 chua mot lien k5t dOi

C--C trong phan tiro So voi thanh phan cac phan tit alkan co cung s6 nguyen tu cacbon nrong Ung, aiken luon luon c6 It hon hOO nguyen tiI

hydro. Cong th«c phan til chung eua alken 1.8. ~H2n voi n ~ 2. Khi n = 2~ ta co chat d1iu tien ella day d6ng ding goi 13. etylen ~H4; n = 3, c6 propylen c;llt;; n = 4, co butylen C4Hg; v.v ... TA't ca hop thanh day d6ng

7 ,~ , ,

dang goi la day.dong dang etylen.

1.2.2. each gQi ten '

Cach goi ten thong thuang hay ten lich sit cua.cac alken xuat phat tit

• • I •

ten goi hydrocaebon no nrong irng nhimg thay duoi an bang duoi ylen:

etan - etylen; propan - propylen; butan - butylen; pentan - pentylen hoac

, '

amylen.

, ,

each goi ten hop lj coi cac alken nhu cac dan xuat cua etylen, bang

each thay the' cac nguyen tu hydro cua etylen bOi cac g6e hydrocacbon khac, Vi du, each gQi hgp 19 m(\t s6 ddng phan cua butylen:

, ,CH3-CH2-CH=CH2 ' ,etyl etylen

. .",

CH3-CH=CH-CH3 ,di~etyl etylen doi xling

.' 'I

.. '

I: .

dimetyl etylen kh6ng dcSi x(fng

" ,

1'k,_.II I' • '.

Cach gt;Ji ten thea lUPACj ~ thl cac alken co tan quoc t~ ella cac alkan wang dng nhungdOi duoi sit thimh en, ,Yi trf CU~ lien ke't dOi duqc IcY .. hieu bang met chii' s6. Viec danh s6 machcacbon thea tr~t tv' oj' c14u mach g4n n6i ML,Qic ehi's6 vi~ltu6c tennhanh vA ten mach.chmh. Vi

du: '-, ~ , · - ': ' s , :', ' ..... - -, ,~

: .

I "'_'

:43

+

. . .

I . _.... . -i. 'It...... . - .. rr-. Ii: . t-

• , . r- . _".b ,..: . .'. » ~'r CH3: >... ·.1 . ,:-. _: •.. : .:. " ~ ~ ~ _ ;'. ... :.~.,

' ..

. ;.:. ~~ .... : ' v _. ~ . .' -6· ~ .. - ~5"1~" ··~r ··4··: -r , ... > . 3·· . 2~;' . - 1· i" .~.. .'.~" ... - .. ' -.::. . .. J. ~ +, .- • - -.- -

_ . .. _., . ._ r..... I. • ..

. " .. ". .' r... '. I .:.. ... I' _ ... ~

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

.... ""1"'" r ... - ,. _ r- '. • I ...&. ~ • _. J ." .' ".r I • I" - -... ... ..' I': I' • •• 'I , .... •

~ CH -CH:...cH ~CH =·CH.:..cH · ._" ~ .~ ,r. _ .. :-".~ .. -;. ", .: -

.- .. _ .. _ , ..... 3 .. ~ 1 . J

_'" .. iJ _ L '. __ 'I 'I I • I ..' - 1.)1 -.&. t I 1. '" 'I .... "I .,. 1"- ..' _. __ r

~~'. . ~m·9tyt-2-tlex'en· ~ .. . "', . ~ ~."< : .. ' _.

• • I ._

cae g6c hydrocacbon cht1'a lieid~efdoi'c6 d~oi enYl-~·vi~:ti s6m~h cacbon trong g6c bAt dttu til nguyen til cacbon c6 hoa tri tlJ-OO.o.1hi du: .

. ,.

I • I, . .

r- .'

; ,

. ..... . "

43 21 4321

. .. - . .

. CH3-CH = CH-CH2- cH;~CH~Hi--CH2-

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

. -. " - 2-buteny' J '. - • • ~:.) 3-bl.rtenyl

... - . - . -.

M~t s6 g6c .alkenyl ~6.~ ten goi thong ·iiur~g ·du~· sir dung - phd Dl~n

han. DolA cac g6c vinyl, alyl, izopropenyl: · ·

.., - ," :-

. CHi=CH-

eH3 I

eH, ='CH- '

-

'! -

. ..

, ,

." .. J.

. .

. . r

vinyl alyl· izopropenyl

Ten goi cua mot s6 alken don gian xem b bang .] -3 ..

Bang J -3. Ten gQi mt)t so aIken don gian

Cong ~hCtc CBU tao

Ten Ifch sli T~n hop 15'

thong thllCJng .

..,. '~ .

Ten quoc t~ IUPAC

CH3-CH=CH2 CHiC,H2CH!::CH2 CH3CH=CHCH3

CH3-C=CH3 . I

CH3· ·

CH3C H2Cl-I2C H =C H2 · CH3CH2CH=CHCH3

..

CH3-CH-CH!::CH2 .- I

CH3 •

CH3-C=CH-CH3 I

CH3

CH2=C-CH2-CH3

. J

CH3

44

etyten propylen

a-butylen ~ ... butYren

etylen

. metyf etylen

_ etyt atylen dimetyl etylen doixUng

dimetyl etylen

izobutylen

-

khong d6j xltng

propyl etylen metyletyl etylen

dOl xung lzopropyl etyJen

a.-amyJen p-amilen

a-izoamylen

p-izoamy len

trimetyl etylen

metyJetyr etylen khong d6i xCtng

-

eten propen t-buten 2-buten

2-metyl-1-propen

1-penten 2-penten

3-metyl-1-buten

2-metyl-2 .. buten

2-metyl-1-buten

.. . L2.3. IlOng phan

- ... . ..

·I'.2.3~I .. fJfJng phlin··cdu tao ;

- - - ..

N gam d6ng pharr vernach cacbon nhir d6i vOj alkan, cac alken con c6

cac d6ng phan ve vi trf ella lien k€t doi, do do s6 d6ng phan G«u tao cua aIken nhieu hon cua alkan c6 cimg s6 nguyen tit cacbon. Vi du, buten C4Hg c6 3 dOng phan, trong khi d6 butan C4H10 chi co 2 d6ng phan; penten CSHIO c6 5 dong phan, trong khi pentan CsH12 chl c6 3 dong phan; hexen C6H 12 c6

12 dong phan, trong khi hexan CJI 14 c6 5 d6ng phan.

56 nguyen tit cacbon trong phan tit cang tang, thl su chenh lech v~ s6 dong phan cau tao gifra aIken va alkan nrong irng cang nhieu,

1.2 .. 3 ~2. Bo'ng phan hinh h ,!C

51:1" co mat lien k€t doi trong alken lam xuat hien mot loai dOng phan lap the, d6 Iii d6ng phan hlnh hoc. Dac diem cua loai d6ng phan nay la

_ hai nhom dinh a hai cachon mang n6i doi a cung ve mot phfa hoac khac phfa d6i voi n6i doi, thuc chat 13. b cung phia boac khac phfa d6i' vdi m~t

phang 1t ella lien ket doi. Khi hai nhom the' b cung phfa ta co dang dong phan cis; khi hai nh6m the a khac phfata c6 .dang.dong phan trans. Vi

du, 2-buten cho hai dang d6ng phan cis - trans nhu sau:

H H H CH3

'C=C/ 'C=C/

/ <, /"

-H3e CH3 H3C H ..

cis-2 .. buten

trans-2-buten

.,

~ ..

. , .

..

. .... '.

• L

.

.. ~6j

..

. -

FIt, .:. h 1 1· - - ... . ...'" . -. -:..:. .. : ,. -. ~ ......

n . ~ . - .. " _..;. -. - .. ~..... .

• I : ,. , '! •.•.

. 45



.. ,

- '. -II -. • •• .,.

Nguyen nhan t6n tai hien tuQllg dOng phAn cis~:.-:tranS'UPaCh6·cac

_ nh6m lhe- khong the quay t11 do xung quanh',lien:,ke\~:,nmr'xung qaanh lien-ke't·dqn, y),lcQi quay nhu the' lien ktt dOi se lli pM ,v~. . _ .

. .. . .

• • - 'I • •

. Cic ddngphan cis +transco tfnb ch«t v.t 19 va.hoa hockhacnhau

nhu caic' ddrig phan thOng tbutfng. Ta c6 the tbly rosl! ldu1c. ohau ve Iy tinh,giita ~c ddrig phAn-cis =trans trong tri.ti»lg·hqp cua dicloetylen;

·0 a

-" / /c=c"

H H

c is-d ic I oety len

. .

"H . a

-" - /

... C=C· / ... -,

a H

. trans-2- dictoe~len

, Nhi~t d" soi, °CJ 760 mmHg . 60,2 48,3

. . Nhi~t d(i n6ng ch8y I °C -80,5 ~ ~ --50

d~S 1,289 1.265

Moman h.long ct!C (D) 1 J89 . ... 0

.. V! hoa tfnh, ta thay ra S,! khac nhau trong vfdu giira axit maleic (cis) va axit fumaric (trans). Khi dun n6ng, chi c6 axit maleic moi co the

chuyen thanh dang anhydrit: .

H-C-COOH H-C-CO HOOC-C-H

150aC I"

- I -H20 ' /0 II

H-C-COOH H-C-CO ~ H-c-eOOH

axit maleic

anhydrit maleic

axit fumaric

Bang phirong phap nhieu xa tia Roentgen va mot s6 plnrong phap 19 hoa khac, ngirci ta da xac dinh direc, khoang each gifta hai nguyen tu elo

trong cac dong phan cis - trans cua dicloetylen. Trong d6ng phan cis, khoang eachdo bang.3,22 A, trong dong phan trans, khosng each do b~g 4,27 A.

,

N6i chung, d~ng'-trans ben hon dang cis, do & trang thai nang hrong

thap hon. .

. 1.2.4. Phuong phap dieu che 1.2.4.1. Tach H20 ra khoi alcol no

Khi tach H20 ra thai alcol no, se thu diroc aiken. C6 the tien hanh

vi~ tach H20 bAng hai phtrong phap: ·

46

• Dun. n6ng alcol vm .axit manh, nhu axit sunfuric hoac axit

, .

.. .

photphoric, hoac vOi· kali sunfat axit, Axit se nrong tac vrn. alcol, tnroc

he-t tao fa este (este V() CO), sau d6 este bi phan huy se cho aiken. Sa d6 chung nhir sau:

R -:-CH2-CH2-OH + H2S04 d~c dun n6ng R -CH2-CH20-S03H + H20

R-CH2-CH20-S03H ) R-CH=CH2 + H2S04

Vi du dun n6ng aleol etylic vOi H1S04 dac (j nhiet d(? tren 170°C se thu diroc etylen: .

1.1.. ••

......... v,



CH3-CH20H + HOS03H·· . ) H20 + CH3-CH10S03H

.CH3-CH20S03H , CH2=CH2 + H2S04

'. .

Phan Ling nay dung de dieu che cac alken co s6 cacbon thap trong

cong nghiep, Dac biet la d6i voi cac alcol. bac 2 va bac 3, phan irng loai ruroc bang H2S0~ cho hieu suat r~t cao.

D6i v6i cac alcol bac cao, tlurong co san phtim phu kern theo cho cac alken dong phan, do SI! tach H10 thea cac lurong khac nhau, cung co the co sir di chuyen nOl doi trong olefin dum tac dung clla H2S0~ .

• . CJ?,o hoi.: aleol ell qua xuc tac ran nhu nhom oxyt (),-AlZ03), alumit osilicat, thori oxyt (zeolitX, Y, ZSM), b nhiet dQ 300 + 400°C, se

. .

t~.J-iill¢t phan tit H10 ra khoi phan tif alcol va ta thu diroc alken, Hieu

,~·'J~swlt phan ung d~t lUi gfut hieu su~t 19 thuyet. Phan irng co th~ tien hanh

lien tuc va c6 th€ sir dung trong cong nghiep. So dO. chung cua qua trmh nay nhir S au:



R-CH-CH-Rr

[JH"~J

300 + 40aoC

Phan til H20 diroc tach ra de dang nhat tit cac alcol bac 3, r6i d~n cac alcol bac 2; cac alcol bac 1 ben viing hon ca, kh6 tach H20 nhrft. Phan til H20 diroc tach fa dac biet de dang fir cac alcol bac 2 va bac 3· c6 chua rih6m phenyl b ben canh cacbon mang nh6m :OH. VI. du:

C6Hs-CH-CH, r;t:--t-;

LOH _!!J

phenyl metyl cacbinol



• ••

------+) C6HS-CH = CH2 + H20

styren

. 47

t

..

Khi tach H20 bang cac phuong phap tren, co the xay ra Sl! di chuyen lien ~~t doi, lien ket dOi co the a vi trf khac vci vi trf dir kien tircong thtrc CU~ aleol ban dtiu. Vi du, khi tach H20 til aleol n-butylic· c6 mat H2S04 (hoac ZnCl2) se thu dtroc m¢t h3n hop chua hrong 2-buten nhieu

?

hon han hrong l-buten:

- 2-buten

1 ... buten

1.2.4.2. Tach hydro halogenua tit cdc ddn XfttU monohaiogen no Cac dAn xuat monohalogen no, dac biet ladan xuat bac 3; khi nrong lac vm cac dung dich bazo manh nhu KOH, Na9H trong alcol va dun n6ng, se bi tach mot phan tlr hydro halogenua cho alken nrong ling:

,CH·

I 3

R-C-CH2 r~ .~- r l2' HJ

Cac din xuft tratogen b,"c 2 ~ tach HX kh6 hon dan xust bac 3. Ngo8.i tac nhan III dung dich KOB trong aleol, - co the tach HX ra lchoi ·dAn xuat halogen b!ng each cho hoi dan xuat halogen di qua d&t set 1\Ung d6, ~ canxi oxytbari oxyt nung do. -

So sam, khs" nang tach IfX cua cac dAn xutit clo, brom, iot, flo -ta co

trmh nr sao: ·

durig dich KOH~ alcol

~



R-I > R-Br > R-Cl > R-F

.

..

.

D6 13 do nang lirong . lien ket cua cac lien ket O-X khac nhau (nang

hrong lien k€t cua C- I 13. 51 kcal/mol, cua C-Br 13. 68, cua C-O 13. 81,

cua C~F la 11.6 kcal/mol). _.

• I

. ~}' !de Zaitxep

. . .

Khi tach RX ra khoi dan xui1"t halogen, X se _ k6t hop vm nguyen tit

hydro <fifth van nguyen tic cacbon l:J lien ben canh c6 bac cao hon.' Phan

ling tach HX di!n ra theo co che' E, va E2• - ..

Truong hqp E1:

48

nhanh

E9 R-CH2-CH-CH3 + X-

R~CH=:CH-CH3 + H+

.~

(I)

R-aI2--CH-CH3

. - - ,



e .

R-CH2--CH~CH3

R-CH2-CH=CH2 + H+ (II)

....

T6c dO phan (mg dugc xac dinh bbi giai doan cham, nhtr v~y tOe d()

cua qua trinh nay . chi phu thuoc vao nong d¢ alkyl halogenua

[R-CH2-CHX-CHJ], nghia Ia t6c dQ phan trng thtrc cha:t do tOe dl) tao thanh ion cacboni .. ·

.

Truong hop E2:

Trong co che £1 co th~ hinh thanh thee SO do sau (xem them a muc halogenua alkyl):

,.

"0- + H-C-t-X . ch~m ).. H.,O + -t -t-x nhanh) . 'c--c ..... + x-

I J - . I I -' ,.

,:·'l = [R -XJ [HO-]

Giai doan tach proton Iii giai doan cham, trong qua triRh tllang -tac RX v6i HO-.

-

Quy tae t6ng quat

Khi tach HX ra khoi dAn xuat halogen, se thu diroc olefin c6 s6

nguyen tir Ho., d6i voi lien ket dOi Ian nhat, Thi d1:l:' .

~

CH3

.... " ,.

/CH-CH2iH-CH1-CH3

CH3 X

-HX·

)-

CH3 .

" .

/ CH-CH1-CH=CH-CH3

CH3· (s6 Het = ?) '.

CH3 ' .

. '" . '

./ C~-CH=CH-CH2-CH3

CH3 (s6 Het :: 3)

1.2.4.3. Di tit ddn xulit dihalogen

. .

. Tuong tacgiii'a cac dan x:uat dihalogen co hai .halogen dfnhvao hai

~A9

-.. -

,



- ..

. - .......

"_ .

cacbon lien nhau v6i bot kern trong dung dich axit axetic, se tach hai

halogen tao ra alken. Phan ling nay tmrong dung de tach cac alken ra khoi cac hydrocacbon khac. So d6 chung cua qua trinh nhusau:

R-CH-CH-Rr + Zn _" ----+) R~CH=CH~Rt +" ZnX2

I I

x "x "~""

1.u.4.4. Decacboxyl hoa axil chua no

" "

Khi dun nong cac axit chua no, nhom cacboxyl bj tach de hon cac

~ -

axit no, tao fa alken. Vf du, til axit xinnamic tao fa styren: "

dun n6ng

.

CO2 + C6Hs-CH~H2

styren

C6HS-CH=CH-COOH axit xinnamic

. ... ..

1.2.5. Tinh chat v~t Iy

Bit cha':t dau tien ella daydong dfing b nhiet d() thirong la cac chat khi, cac aiken _ trung binh 13. nhiing ch~t long, cac alken _ cao hOO III nlurng cha:t ran, Nhiet d¢ soi ella cac alken gfut v6i. nhiet d¢ soi ella .cac alkan co cling s6 nguyen tir cacbon trong phan t-Lt. Ty kh6i cac aIken hoi cao bon ty khOi cua cac alkan nrong ung.

Tfnh chat v~t ly co y nghia quan trong cua aiken la dq khuc xa phan tir MR. MR co tinh ch~t cong tfnh, nghia Ul dq kluic xa phan tir bang t6ng s6 d¢ kluic xa cua cac nguyen tir co trong pharr til a:'y. Cho nen MR cua cac alkan bang tong s6 d¢ khuc xa cua cac nguyen til C va H eo trong thanh phan phan tit. Tuy nhien, trong tnronghop cac alken, tri s6 MR xac dinh bang thuc nghiem (theo cong thirc Lorentz - Lorenz) IOn hon tri s6 tfnh thea 19 thuyet dira vao de? khuc xa nguyen tit. Do d6, d6i vCti cac alken co mot dai luqngb6 sung the hien 51! .co mat n6i d6i

" "

trong phan tit, ky' .. hieu bang daul=Tri s6 F dol VOl mot lien ket doi bang

1,7 + 1,9 (xem bang sau) ..

Ht;1P chat MR MR Tri so
- , " ~" theo Jy thuyet thl/c nghi~m F
..
Amylen CsH,o " 23109 24.83 1,74 /
Hexylen CeH12 27r70 w 2Q~61 1 ~91
~ " ,
- .
-
Octylen Cati16 36t94 38~75 1 ~81 50 "

Hang so v~t 19' cua mot 56 alken co cho trong bang 1- 4.

Bdng /-4. Hang so vat Iy ella mot so aiken

Nhi~t d9 n6ng Nhiet do sol, Ti khoj
. .
Cong thCtc Ten 9qi chay t~c .sc t"_ • °C d20
:"'II 4
CH2=CH2 etylen -169,4 -103~9 O~566
: d-120 )
-.. 4
CH3-CH=CH2 propylen -185~2 -47 a O~609
I'
(d:7 )
CH3-CH2-CH=CH? 1-buten -130~O ~5 0 O~668
J
(d~ )
CH3-CH=CH-CH3 cis .. 2-buten -139~O +3 5
t
trans-2-buten -105 +1,0 Ot635
CHJ
<, izobutylen -6jO
/C=CHz -140
CH~
.
CH3-CH2-CHz-CH!::C H:2 1-penten -138~O , 29~g O~640
(0200C)
CH3~CH2-CH=CH-CH3 2.penten --139 36J4 0,651
CHJ-CH-CH=CH2 3 ... rnetyl-t- -135 25*0 O~648
I buten
CH3
CH 3-C H2-C::C H2 -124 38J4 Ot668
"2~inetyr-2-
r
(d:3 )
CH3 buten Nhir vay, bang each so sanh d" khuc xa phan nr MR thuc nghiem voi dO khuc x~ phan llr MR tfnh thea 1y thuyet, e.91h6 khang dinh slJ co mat

hay khongciia lien kit dOi trong phan (\r., . .', .

" ,

Ph6 hong- ngoai cuacac alken cho vach hap lh\l gmL1650 cm ', d~c . . tnmg cho dao ~ng hqa.Jri::cua):i~n ~e't doi C=C. Tuy nhien, cirong dO va . vi trf cua vach nay con phu thuoc vao cau ·t~o phan tit cua aiken; n6 thay

,

~

"" 51

..,

doi v6i dQ phan nhanh b lien ket doi va v6i su c6 mat cua lien k~t chua

no thtr hai lien hop v6i lienket doi thii nh~t.

1.2.6 .. Ttnh chat hoa hoc



1.2.6.1. Ban chat, dq.c dilmcua lien klt doi C=C



Nhir da trtnh bay tnroc day, lien ke't doi C=C diroc tao nen bOi hai

nguyen tit cacbon a trang thai lai tao sp", nrc Ia kieu lai tao tam giac,

Trang lien ket doi co mot lien ket 0' do sir xen phil true cua hai electron lai tao va ID¢t lien ket 7t do su xen phil ben cua hai electron p~ Tat ca cac nguyen tir n6i voi hai nguyen tll' cacbon mang nrn doi deu nam tren cling mot mat phang vai hai cachon do, va goc hoa tri a m6i cacbon mang n6i d6i bang 120°. Hai true caa hat electron p song song vci nhau tao thanh

m~t phang 1[ thang g6c v6i mat phang noitren. Thirc chat cua lien ket 7t



,

tao thanh la orbitan lien k€t 1t c6 mat d¢ electron baa phil ca phia tren va

phia dum hai nguyen tic cacbon mang n6i doi.

~ ;

Lien ket doi co d¢ dai lien ket bang 1,34 A, ngan han so veri lien ket

don (1,54 A). Nang hrong lien ket doi c=c hang 145,8 kcal/rnol, trong

khi d6 nang hrong lien ket don C-C bang 82,6 kcal/mol; gift thiet nang Iirong lien ket 0' lon han nang hrong lien ket 7t bang 145,8 - 82,6 = 63,2

~

kcal/mol, Nhir vay nang IUQl1g lien ket o ICm han nang hrong lien ket rt,

dQ chenh lech vao khoang 20 kcal/mol, dieu nay gi3.i thich tfnh chat kern

ben cua lien ket 1t va kha nang phan trng cao cua lien k€t doi. Thirc vay, so v{ri alkan, aiken co kha nang phan irng 16'11 hon nhieu. Ole phan ling cua aIken thuong ttJ-p trung vao lien ket doi, do d6 n6i doi diroc 'coi la trung tam phan ling cua cac alken.

Cac phan irng quan trong nhelt'd6i voi alken la phan trng cong, phan ling oxy hoa va phan ling trimg hop .



1.2.6.2. Phan ·Nng ciJng

Cac phan tmg cong dac tnrng nh&'t d6i voi alken la phan ll"ng cong vao lien kt!t doi. Trang cac phan ling nay, lien k~t dlJi thuc chat Iii lien

k€t 1t bi be gay va k~t hop voi hOO nguyen tit hoac hai nhom nguyen tu moi tao ra hop chat no. Sa d6 chung ciia phan Ung cong vao lien ket doi

52

nhir sal!":

" c/ ..,C= "

::c-cc I I Xy

So v6i viec be gay mot lien ket don C-C trong alkan, vice be gay lien

ket 1t trong alken d~ dang hon nhieu. Thf du: '

+

x-v

)

- )

CH,-CH~

I - I - r

Sr Br

2CH3-Br

jJ-I = -27 kcal,

hieu suat 85%

~ = -7 kcal

.. D6 13. do nang IUQ11g lien ket 7t nho hem nang hrong lien ket cr.

Kha nang' phan (mg cao cua aiken so 'ire alkan con co th~ giai thich la do trona lien ket doi ella alken mat do electron dtroc trw rang hem

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

trong lien, ket don trong aIkan. Cac electron trong cac lien k€t doi bi dfty.

ra xa do sue day nhau cua chiing. Do do, nhftng vi trf cua lien k~t doi co mal do electron bang voi ch6 co mat do electron nhir the cua lien .ket

.. . ....... . .

don thi b xa true lien ket han (hinh 1-2).

<, ..... :.:.:.::: .. : ... -.. /

"" t.'- --4

-- C -':'.------- ... ----~ .. C .

\: ..... ...-f

" _---_....,., "-

/ _----_.... <,

--- ....

~.... .....,

, _---- ,

<; c,~;_..--- ~ ~

"' C ~-----~ C

__..,,- ~-==:. ~~ ~

_..-- <--, ----.... /1

, _-_ .... - ~

' _ . _,

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

a) .

b)

8r Vung co mat d¢ electron Hinh ')·2

cao (, lien kat don C-C

b. Vung co m~t dg electron cao a lien kat doi C=C

a .. C 91Zg hydro (hay hydro hod)

Ket qua phan U'ng cong hydro vao alken cho ta alkan tirong (mg. Sa d6 chung cua phan rrng cong hydro vao aiken nhir sau:

~c-c~· I I""" HH

Vi du, phan ling etylen khi cong hydro tao thanh etan. Day la phan ling phat nhiet (M! = -30 kcal). Binh thtrong, mot hOn hop hydro va

53~· _

..

. ..

, •

..

etylcn ben vtrng vo han 0 nhict d<) 200°C. Cac alken cling khong the cong dtroc V(Ji hydro men sinh, nhir bang kern lac dung vOl axil, hoac natri trong aleol. Tuy nhien, co th6 cho hydro phan tir a trang thai khl, co mat XUC lac nhir niken kiln loai, cong VaG lien ker dOi ella aiken.

Dang h(1t niken hoat d()ng manh Iii "niken Renei", dieu ch€ lit -h(Jp kiln niken nhom .. Khi chc hoa hop kim nay vrn dung dich NaOH, dung dich siS hoa tan nhorn 06 lai niken b trang thai hQt nho filt min, de hoc chay. Nikcn Rcnci hinh thanh thea phan (rug:

2Ni-AI + 20H- + 2H~O

PUc hat mang , 2N+ 2AID - "')H

7' I + ~ + _"'t .,

- -

Pi/chat mane IA cac chat xiic tac c() hoat tfnh manh,

"'- ..

Cac hop L:hal cua hru huynh, photpho, ascn Iii nhfrng chat dgc lam mat kha nang hoat d(lng ella cac xuc tac hydro hoa ngay (J nhfrng nong

do nho. . '



Phan (mg xuc lac bao gom nam giai doan:

- Khuech tan cac chat lac dune trcn he mat chtll xuc tac.

• L ~

- Hap phu cac chat (tac nhan),

- Phan ling tien hanh trong I(lp hfip phu.

- Nha hap phu cua san phtim phan ling.

- Khuech tc'in sanpham khoi be mat chat xuc taco

Toe 00 chung cua .phan (eng quyet dinh hOi giai doan cham .. D6i v(n phan rrng x iic lac t·hl giai doan hffp phu va giai dean phan rrng t r{_}ng lop

hap phu .ia quan trong. ~

Co chc hydro hoa alken khi co m~t cac chat xiic lac kim l( iai - chat mang co the dtlQ't;" giai thfch nhu dmJi day.

Su hap phu hoahoc etylen tren be mat kim loai chuyen ticp (Ni, Pt, Pd V.V •• 9) kern thea 51! tach hydro theo phirong trinh sau:

4Me + C:H~

---) Me~C~H~ + 2MeH

_. ... -

Hydro hjp;:phl} hoa hoc nhanh chong tac dung ven etylcn d8 tao thanh elan :theo·;p~ '~anh:

,M ~H

. I I

Me-Me +

54



..

,Khi dung, cac kim loai chuyen tiep, phan ling c6 tht1' bac 0 d6i vOi etylen va thir bac 1 d6i v6i hydro.

b~ Cong electrophyl (AE) VGO aiken

Cac tac nhan phan ling nhir cac halogen (ell, Br1) 12), cac hydro halogenua (Hel, HBr), .cac axit hypohalogenic (HOCI, HOHr), ruroc, axit sunfuric, dell eo the cong direc vao n6'i doi cua aiken cho cac hop chat no nrong img. Qua trinh c6 the dtroc bieu dien bang sa d6 chung nhir sau:

+ Br2 \.. -C-c-
7
I I
.Br Br
+ HOCJ .'\. -C-C-
,
r r
a OH
<; C.,......,.... + H2S04 -c~c-
. C '\..
7
»> <, r 1
H OS03H
+HCJ· '" -C-C-
,
I r
.. H CI . -c-c-

r I

H OH

..

Cac phan rrng tren co nhiing dac di~m chung v~ mat co che, d6 Iii co ch€ cong electrophyl (nrc co che cong ai ·di~n tir, ky hieu AJ, VI cac tac nhan deu 18. electrophyl.

Khi tac nhan electrophyl tien l~ gan phan ur alken, trong phan tir aiken co sir di chuyen mat dQ electronrt cua lien k€t dOi,Jam phan eve

hoa lien kt!t doi: .. , _ . .

S+ 0-

R,C=CR,

... -

Co che' ccng electrophyl tien hanh qua hai giai doan, b giai doan I, tac nhan electrophyl s~ ket hop vm cacbon mang n6i dOi giau electron 1[

hon, tao ra ion cacboni. Sau d6 i:J giai doan Il, ion cacboni se k~t hop veri phan con lai cua lac nhan tich dien am:

Giai· doan I:



J + ~

X -c -c-........ + Y"

1

GiOO doan n.

..



I + X-C-C"""-+ v:

I "

I I X-C-C-y ~

j f

Sl! xuHt hien ion cacboni trong giai doan I ella co che' dff duqc lam sang to trong phan ilng cua etylen v6i brom trong dung dich mroc c6 .. chua cac anion khac nhir Cl , N03-. Trang dieu kien nay, san pham tao

thanh ngoai Br-CH2-CH2-Br, con eo cac san pharo cong cua cac ion Cl", NO) - voi ion cacboni trung gian:

)-

+

Br-CH2- CH2 + Br-

Br-CHz-CHz-Br Br-CH2-CH2-CI

Br-CH2-CH2-N03

Co che phan trng nay doi hoi dung moi phan eire, vi trang thai

· chuyen tiep va cac san pham cua giai doan I eo dien tfch ion, trong khi

~ 06 tac nhan lai khOng phan eire:

s+ ~ +

::::c= C;::: + Br-Br ):;C=C-----Br-=---Br ~:::C -C-Br + Br"

Trang thai chuyen tiep nay chi c6 the tao thanh trong dung moi co kha nang ion hoa rAt manh nhir mroc, alcol.

Cac halogen cong vao n6i dOi cua alken mot each de dang tao ra dan xuat dihalogen, san pham co hai halogen dfnh b cac nguyen tit cacbon canh nhau, Vi du:

6 •

-______...~ O-CH2-CHz-Q 1,2 .. dicloetan

56

+



Trang 56 cac halogen, phan ling cong cua clo manh liet nhat, kh6 nhat 18. d6i voi iot. Phan irng nay thirong dung de nhan biet n6i doi (lam mat mau dung dich brom) hoac dung de dinh hrong p6t doi bang dung dich bromo Ngoai ra, cling c6 the dung de tach alken ra khoi h8n hop voi cac hydrocacbon khac.

Cac hydro halogenua (HQ, HBr, HI) cong vao lien ket doi cua aiken eho cac dan xua:t monohalogen. Phan tmg xay ra de dang nhat d6i voi

"-

hydro iodua, kho nh~t d6i vrn hydro clorua .. Thi du: .

CH2=CH2 + HI ) CH3-CH2-I

etyl iodua

Tile dung cua cac dung d~ch rurcc clo hoac brom v6i alken cho san pham 13. cac halogen hydrin. Trong tnrong bop nay, tac nhan hoat dong , 1a axit hypocloro hoac axit hypobromo. Thi du:

CH2=CH1 + Hoa ) HOCH2-CH2C1

· etylen clohydrin

Tac dung cua aIken v6i axit sunfuric se tao ra alkyl sunfat axit. 1hf du:



---~) CH3-CH2-OS03H· etyl sunfat axit

Phan irng dung de tach alken khf ra khoi h8n hop vOi cac khf khac va 13. giai doan trung gian trong viec dieu.ch€ alecl tIT alken,

..

~

c. Cdc quy tdc dinh huang trong phdn ung cong )laO aIken



c l . Quy tac Macconicop

Trongphan ling cong cua mot rae nhan khong d6i xung (nhu HX

....

chang han) vao mot alken khong d6i xirng (hai cacbon mang n6i d6i co

bac khac nhau), nguyen tu hydro cua HX se tan cong vao nguyen til cacbon cua n6'i doi chua nhieu hydro hem (eaebon bac thap), con X se tan cong vao nguyen tit cacbon con lai cua n6i doi chua it hydro hon (cacbon bac cao), Thi du:

propylen

izopropylen

5·'

- Gidi thich theo trang thai tinh

Trong phan tir propylen, do tic dung day electron cua nh6m metyl vephfa lien k~t dOi lam cho lien klt nay tra nen phan eire, mat dQ electron

1t dich chuyen ve phia nh6m CH2 (cacbon bac thap) lam cho nhom nay mang mQt phan dien tich am (0-) vi giau electron han, 'con nh6m metin CH (cacbon bac cao) mang mot phan dien tfch duong (8+)~ Do do, sir phan b6 mat dl) electron trong phan tit propylen co the bieu dien nhu

sau:

..

H H H.

Khi cho H+CI- tac dung v~ propylen, phan cation cua tac nhan (We proton H+) se tan cong vao cachon mang dien tich am (0-), con phan anion cua tac nhan (0·) se tan cong vao cacbon mang dien tfch dtrong

(5+).

- Gidi thich theo tr~l'lg thai dong

Vi phan ling dien ra thea co che cong electrophyl (A E) nen giai doan quyet dinh toe d¢ phan (mg Iii. giai dean cua H+ tan cong vao phan tir propylen. C6fhe giathiet c6 hal qua trlnh dien ra nhir sau:

+ CH3-CH=CH2 + H+- ....... ~ CH3- CH-CH3

(I)

cr ) CH3-CH-CH3 (1)

I -

a izopropyl clorua

+

CH3-CH=CH2 + H+ - ..... ~ CH3-CH~- CH2

(ll)

n-propylclorua

.Trong qua. trinh (1), H+ tan .cong vao nh6m CH2 tao ra ion cacboni trung gian (1); con trong qua trinh (2), H+ ta:n cong vao nh6m CH nen tao ra ion cacboni trung gian CIT). Phan irng xay ra thea qua trinh nao Iii phu thuoc vao nang hrong va dO ben cuaion cacboni trung gian, Dang ion cacboni co nang IUQTlg cang thap va c6 dQ ben cang 1<10 khi dien tfch dirong a nguyen ttl cacbon cang diroc giai toa; ctieu do xay ra khi dien

..__,_ - ... -

tfch dirong b nguyen til cacbon lien hgp v6i cang nhieu electron (j cua cac lien ket C-H. Ion cacboni c6 d¢ ben cang IOn thl cang de hmh thanh,

So sanh dac diem cau tao ella hai ion cachoni (1) va (Il), ta nhan thay ion (I) co nang hrong thap han ion (II), VI trong ion (I) co sir lien hop

cua dien tfch dirong v(ri 6 lien ket CJe-H' con trong ion (II) chi co su lien hQP voi hai lien ke't O"c H- Do do ion (I) ben hon va de hinh thrum hem ion (II)~

Dieu nay giai thfch tai sao trong phan irng cong cua propylen voi HCl" tao thanh chu yeu Ia san pham izapropyl clorua,

Tren co sO giro thich thea trang thai d()ng v~ su phan b6 mat d\J electron ella phan tit chua phan irng, co the phat bieu quy t~c

Macconicop nhtr sau: +

"Tac dong cua mot tac nhan khong d6i xirng (HX chang han) vao mot aiken khong d6i ximg, phan cation cua rae nhan (H+) se tfu cong vao nguyen til cacbon mang n6i d6i giau mat d¢ electron tich dien tim, con phan anion se ket hop vOi nguyen tit cacbon cua noi doi tfch dien duon 2.: 11 +

'-

'M~t khac, tren co sa giai thfch theo trang thai dong, co the phat bieu .

...

khai quat quy tac Macconicop nhir sau:

"Phan img cong electrophyl vao aIken se dien ra chir yeu qua dang ion cacboni trung gian co d¢ ben IOn nhat",

c2. Phdn ung cong khong theo quy ldc Macconicop .

Hau het cac phan img cong vao alken d~u tuan thea quy t~c Macconicop. Tuy nhien, trong mot s6 dieu kien rih{(t dinh, phan ling cong vao aIken .chok& qua trai voiquy lAc Macconicop,

NAIll 1933 Kharat nhan thA:y rang, khi cho HBr c(?ng vito alkyl bromua, n~u loai tro su c6 m~t cua peroxyt bang each ,cho them-mot Itrqng Ma ,thM .cMng oxy bOO. vao h6rihW phim t1ng, thl phan .m.g cong diM -:r. :bB1fitJltMllg7'::~.d() ~, theo. quy tic MaccOQic()p; ;nhung neu _ 11&1 hQp _tbtg; cO-·sin peroltyt'-~'cb01nem: pem.xyt mlIi V80, fI't~ s!' di&l;f:;i .t,di ,d· qay ticiMiaCc~~ vdi M(:,d¢ nbanti:" " '

• r

, .

59

-

,

CH2=CH-·CH2Br + HBr alyl bromua

ch't ch6'n oxj· hoa chAm



CH3~HBr~CH2Br (c9n9 binh thU'ang)"

I, • •

......._ ro_x_it __ ...... BrCHi-CH2-CH2Br .

nhanh

(c~ng kh6ng binh thuang)

Co the dung cha:t chong oxy hoa runt hydroquinon; con peroxyt xuc tac cho phan U'ng b~t thirong c6 the dung perox yt benzoyl chang han, Ngoai tnrong hop alyl bromua ngtroi ta nhan th~y phan tmg cong bat thirong vci HBr co mat peroxyt con dien ra voi cac alken. Thi du, phan ling cong HBr co mat peroxyt van propylen se tao thanh n-propyl bromua, hieu suat phan ling dat tCri. 80%:

chat chOn oxi hoe

Br

I CH3-CH-CH3



izopropylbromua

perox t

n-propyl bromua

Ta goi anh huong cua peroxyt gay ra phan trng trai vdi quy ta.c Macconicop nay 13. hieu img peroxyt hoac hieu lIng Kharat. Phan ling dien ra thea co ch€ g6c nhir dum day:

Tnroc het, peroxyt phan ly tao cac g6c ur do mdi dum tac dung cua nhiet (giai doan khoi mao):

R~-O-R. .. ) 2 R-O· jJ-f = + 35 kcal

..

Cac g6c t1;I do RO· c6 th~ tac dung vci hydro bromua thee hai each:

. ROH + Br' .jJ-f = - 23 kcal

R-O· + HBr

ROBr + H·

.11-1 ~ + 39 kcal '

ve m~t nang Iirong, phan iing tao .~a ROH va nguyen tlr bromthuan lqi hon, Nguyen tit brom se tan cong vao aiken tao ra mQt gee tl! do moi, r6i g6c ur do nay lai tac dung vOi. HBr tao fa n-propyl bromua va ng~yen

tit brom. \..

60

..

Giai dean phat trien mach:

CH3-CH~CH2 + Br2

- ........ ) G:H3-C·H-CH2-Br :Y-I = - 5 kcal/mol

.......--- ...... ) CH3-CH2-CH1-Br + Br· ~ = - 11 kcal/rnol

aiai doan ta.t mach:

• •

R" + R· ~ R-R (R = nguyen tit hoac g6c)

So sanh hai g6c t1! do trung gian co th~ tao ra:

CH3-C·H-CH,-Br va CH3-CH-CH~·

- 1-

Bf

(I)

(II)

v« mat nang hrong, goc (I) ben hon g6c (In, do s6 luong lien k€t C-H lien hop vOi electron nr do trong g6e (I) lA nam nhieu han so vOl trong g6c (II) la mot. Vi vay, gee (I) d~ hlnh thanh han g6c (In.

N6i chung, kha nang tao thanh va dQ ben cua cac g6c nr do giam thea trinh tu:



g6c bac 3 > g6c bac 2 > g6c bac I

dieu d6 giai thich s,! hrnh thanh san pham n-propyl bromua khi cong HBr vao propylen co m~t peroxyt.

"

',c3 .. QU)' uic Zaitxev - \1 acnhe

Tirong lac cua mot lac nhan khong d6i ximg HX v6i mot alken, trong d6 hOO nguyen tit cacbon mang n6i doi co cling bac, lien ket voi hai g6c

alkyl khac nhau, thl phan anion x~ cua tac nhan se k~'t hop voi cacbon cua n6i dOi (n6i voi it nh6m alkyl hem). Vi du:

H

~ CH3-CHz-CHziH-CH3 X'

K~t qua phan Ung dUQC giai thfch bang hieu ling sieu lien hop cua cac g6c alkyl. Trong hieu ling sieu lien hop, khci nang dciy electron cua cac g6c alkyl ngtroc v6i trong hieu tmg dim iing.

61

..

Hieu ling cam ling (+1) cua cac g6c giam theo trtnh t¥ sau:

...

(CH3)3C- > (CH3)2CH- > CH3CH2- > CH3-

Hieu ling sieu lien hQP cua cac g6c giam thee trlnh tu sau:

CH3- > CH3-CH2- > (CH3)2CH- > (CH;)3C-

....

Do do, trong 2-penten, mat dl) electron 1t lech ve phia C3 lam cho mat d¢ electron 6 C3 giau len va tich dien am. Khi tac dung voi HX, proton se tan cong vao C, , ket qua 1A phan anion X- se ke't hop vao C, mang nhom metyI.

1.2.6.3. Phdn Ung oxy hoa

Cac hydrocacbon chua lien k~t doi nhay cam hon nhieu d6i vOl cac chat oxy hoa. Khi dieu- kien tien harm phan ling tac nhan oxy hoa khac nhau thi san pham phan tmg tao ra cling khac nhau.

.. - .. . - . . ..

- Nho tac dung cua kali permanganat trong dung dich trung tfnh hoac

dung dich kiem, lien ket doi cua aiken se k€t hgp vm hai nhom

hydroxyl, nhtr khi cong v6i hydro peroxyt HO-OH, tao ra 1,2-diol:

...

R-CH==CH-R + 2 [OH] ~) R-<fH-CfH-R

. OH OH

(40745%)·

Phan ling nay dung trong phan tfch d~ nhan ra n6i dOi~ Cho alken tac

~

dung vm dung dich kali pennanganat trong moi tnrong Idem (thuoc thir

Bayer) dung dich se mat mau, ·

r- .",. .'

""

o dieu ki~n manh li~t hon, nhir trong dung dich axit va dun nong, se

xay fa phan ung be g~y phan tir b chO nm doi tao ra hai axit caeboxylic.

- Axit cromic.duoc sir dung rong rai de oxy h6a lien k€t doi ~o~c dum dang dung dich CrZ03 trong axit axetic d~ ~, c6 mat H2S04 hoac khong, hoac dum dang dung dich natri hoac kali bicromat, Phan ling be gay lien ket d6i tao ra xeton hoac axit cacboxylic, Sl! tao thanh xeton chrmg to sq co mat nhom R2C:=, con su tao thanh axit cacboxylic

. .

chirng to S1! co m*t nhom R -CH= :

R2C=CH-R + 3 [0] . _ ___.) R2C=O + R-COOH

Nho phan rrng nay co the xac dinh vi tricua lien k{!t dOi trong alken.

- Peraxit hiru co, nhir axit perbenzoic, axit peraxetic, v.v .... oxy hoa



62

--

cac aIken tao rtl a-oxyt:

~c = C~ + R-C-()--OH --> "-.C-C~ + R-COOH

.- -...... If ~\/'

o 0

a-oxyt

Axit peraxctic dung trong phan LIng nay du(1i dang dung dich trong axil axctic, dU(_1C t6ng hop tic hydro peroxyt va anhydrit axetic.

Dun n6ng (flU i nhict dt) cao, dang Ie duoc aIken oxyt, ta I ai thu diroc san phAm thuy phin cua no, 1UC diol:

,c-c...-+ H.O ~ \ /" ~

()

OH I I --) -c-c-

H6 I

- OX)I h6a etylcn den axetaldehit (sir dung trong cong nghiep).

Etylen bi oxy h6a den axetaldehit trong dung dich Hel pha loang chua clorua Pd va u6ng~ Thuy phan nhirc chat nay cho ta axetaldchit va kim I oai Ptl:

..

) CH3-C-H + Pd + 2H:!+ + 2CI~ tJ

o

Pt1 + 2CuCI; = ...... ===-,... 2CuO + PdCl~

D~ co CuCI~, ngiroi ta oxy hoa CuCl trong khong khf hoac oxy:

2CuCI + 2HCl + 1/2 0 .. - ...... ) 2OJC1., + H~~O

- -

Phiin ling lbng quat:

C_~H~ + 1/2 0_""" - ...... ) CH)-C-H II

o

dung xuc lac PdCI~~ Cu01 trong dung dich HCl.

Phan Ian cac aiken tac dung m(»t each de dang vOi ozon, ngay 0 nhiet df) thap, .lien ktt dOi hi be gay, tao ra san pham goi 13. ozonit. Phin -ungti~n hanh h.f!t slic nhe nhang so vm khi dung cac ch«t oxy h6a thong thuong va vi v~y duQC sir dung r"ng rAi de thi~t l.p cifu tao,

Ozonit til nhffng ~a:t long sanh nhir dau ho~c cha:t rAn vi} dinh hlnh, rA:t dt! nO va khong :th~ chun&·cat duqc.Ch6 h6a v6i nooc, ozonitse hi

, .

~~8 = -562 kcal/mol

I

63

phan huy thanh aldehit hoac xeton, tuy thea cau tao ciia aIken ban dau: . -0

/\

R r'--CH R 0 ) R.,C CHR . +H20 Reo R CT '0 H 0

2"""== - + 3 -, I ~ ::! = + - tl - + :2 2

0-0 xeton afdehit

De loai trtr mot s6 phan ling phu, nguoi ta thay the' giai doan thuy phan cu6i cung bang each khir, dung natri bisunfit, hoac tot han, dung hydro G6 xtic tac:

/0"

R1C CHR + H~ -~- R2C=O + OHC-R + H20

b-d -

. Thi du, khi ozon hoa izobutylen, ta thu dUQ'c san pharo 13 axeton va formal dehi t.

H3C,H3\ /0" .

C = ca. + 03 ---~~ C CH.,

/ - 1\ / ~

H3C H3C 0--0

~o

Phan ling ozon h6a cho hieu suat kha cao, d~n 60 -:- 70%~ 1.2.6.4. Phdn ting thi' u vi tri allyl va vinyl

.

Trong thoi gian g~ day, .: nguCri ta chu y tm m()t 56 phan trng cua cac

alken trong do lien ktt d6i van dttge duy tri. Trong tnrong hop nay,

nguyen tir hydro cua nh6m CH~ a V! trf a d6i vci n6i doi, thirong goi 13 vi trf allyl, dtroc thay the:

a

- CH = CH - CH2-

..

. .

Nguyen tir hydro nay ~6 kha nang phan ling ~c biet, the hien ro

. . .• r .

.trong nang hrong lien ket C-H cua no nho mot each bit thirong so vci

. . .

hydro dinh vao cac nguyen tir eacbon no khac (nang hnmg lien ket C-H

- . _. -

trong CH4 bang 102 kcal/mol, con cua C-H trong . allyl bang 77

. .

kcal/mol),

Nguyen til hydro (J vi- trf vinyl, nrc lit hydro dinh tnrc tiep voi cacbon mang n6i doi, tuy co nang hrong lien ket C-H IOn (104 kcal/mol) nhirng

64

-.~.

." J

trong nhtrng weu kien d~c biet vfu1 c6 the tham gia phan ung the.

Q. The~ a vi tri allyl

Trong nhtrng dieu· kien xac dinh, tac dung cua clo d~n alken khong tao fa dan XUllt diclo, rna cho san pham the kieu allyl thea sO'd6 sau:

-CH2-C=CH- + 0,

I ..

----+) -CH=C-CH - + Hel

J I.

Cl

Phan irng nay tien harm rat df dang d6i vci cac aIken phan nhanh, Vi du cIo hoa izobutylen ngay l:J nhiet dQ phong cho metalyl c1011la:

H3C"

/C::::: CH! + Cl2 - ...... ) CH2= <f-CH2Cl + HQ

H3C CH3 metallyl clorua

:3

. He a

.,. ? h ... -- .. 1 2 di 1 2 . 3 'c2/

San pham.p u la dan xuat , - IC 0- -metyl-propan: / "-1

H3C CH2CI

Th,!C chat, co sir di chuyen V! trf n6i d6i thea eo ch€ phan t1ng sau day:

~

. Tnroc het co phan ling cong binh thirong ella cation clo a+ van mot

cacbon mang n6i doi, sau do cation nay hoac se cong vOi anion cIo Cl" cho san pharn cong binh thirong, hoac se tach mot proton H+ cho san

, '

pham th~ allyl: .



.... .

- +.

. C1l3~ f ~CH2-a" .

. CH3 r



CH2=C-CH~-Cl

. J . . .

, CH3 (88." ph~m chfnh)



I : ~ ~

. .,

..



D6i vdi cac aIken khong phan nhanh, nhu propylen chang han, phan ling cho san pham the allyl tien hanh trong di~u kien kh6 khan hem:

500+600°C

CH3-CH=CH1 + O2 - r + Q .... CH2-CH=CH2

allyl cJorua

Nguyen tit hydro dfnh v6i cacbon mang n6i d6i (hydro vinyl) bang lien ket C-H co nang hrong lien k€t IOn han nhieu so v6i cac lien ket C-H khac (1 04 kcal/mol). D6 Iii do dQ "am dien kha IOn cua nguyen tic cacbon 1~ tao sp', Do do, viec thay th~ nguyen tii hydro vinyl bang halogen tien harm trong dieu kien kho khan, nhir lJ nhiet dO cao. Trong dieu kien thuong, tac dung cua halogen vci alken chi cho phan trng cong.

Phan ling the clo vao hydro trong etyJen tien hanh 0 nhiet dQ cao (200 + 600°C) cho san pham 13 vinyl clorua:

..

CH~~CH"\ + ci,

- - -

Phan ling nay dung trong cong nghiep san xua:t vinyl clorua lam nguyen lieu tong hop mot polyme co gia tri Hi polyvinyl clorua (PVC).

Hieu suat san pham phan Crng cIo hoa eo thf tang dat den:::: 90%, neu tien hanh phan ling (0 250 + 350°C) co m~t 0,5% oxy (oxy lam giam phan ling cong cia).

Co che' phan ling clo h6a etylen (; nhiet dl) cao cling Iii co che' g6c nhir clo h6a alkan:

t

CIL:,Cl

•• •

CH .. =CH~ + Cl·

- -

CH~=CH· + Cl: Cl

....

)

20-

CH~=CH· + H Cl

-

CH .,=CH -CI + Cl-

-

)

1.2.6.5. Phdn ung trung hap va telome hoa

Q. PI,al1 ung trung hqp ~

Mot trong nhirng phan ling quan trong bac nhit trong ky thuat hien nay cua cac alken va cac hop chat chua no khac Iii. phan tmg trimg hop, tao ra san pham 13. polyme ( cao phan nr ). Qua trinh trung hop toa nhiet rat ian; d6i v6i etylen la Ion nhat 1a 800 cal/g (trung hop 0 the khf), sau d6 IA izobutylen 228 cal/g (trung hop trong dung. dich).

66

'"

Sa dO chung cua phan mg. trung hop nhu sau:

nt\ ) (A)n

~

n - he s6 trung hop;

A - monome. - .

Thi du:



. potyetylen



. eH

T~3 . I q ~

n CH3-C =CH2 -- ....... i> -1f~CH2-

CH3 n

. .

izobutylen pclyizobutylen .

Tuy theo ban chat, d~c diem cua rnonome, tuy thea dieu kien tien hanh phan ling, qua trinh trung hop se xay ra theo co che khac nhau, cho polyme co cau tao khac nhau va h~ s6 trimg hop khac nhau. .

'•

h. Pllafl ittlg telome hoa

MQt trong nhtmg dang trimg hop d~ biet cua etylen Iii phan img telome hoa. Dum tac dung cua cacbon tetraclorua len etylen (j ap suat cao khi co mat peroxyt lam xric rae, se xiy raqua trlnh-trung hop etylen nhung chi cho duqc mot polyme c6 h~ s6 trung hop nhc>, .do s~ k~t .hop vOi phan tic C04 lam tat mach sam han phan tmg hung hop btnh thirong.

Qua trmh nay cung 13. mot chu6i cac phan ling day.chuyentheo C(/ .

~!g&: 9 • ~

o 0

II II

1. R-C--O-O-C-R

_ _........). 'R· +~. C02+ ·OCOR ------.) .. " R-Cl . +. .c ·ell: ' .... ', .

& •

• rJl .-,,; • .- ~.

··2'. "R r -._-+ . 00' .. "

. _ , ".~ 4

. "

.. .

3. CH2=CH2 + -CO)

-4.: ~CHl:_CH1-ca3 '< . .' ; .

-.'~ ~ ~;. ...~:. ~ ~- ..... !; . ~ ,~ , I· "..... ~. ,.. ~ . . _ .;.. ~ .~. .~.. ,~ , - .. .

• T"I •• r J. .. . I, .... I I' .. • l . . . • Ii.·.. I • '.. r 't . . ~ - • . ...2 ..

. ~ CHz-CI:t2"·- ~ . '-.... - ., .. - '" .. _.. ~:-. 7 .... ·' '.... . . ,-.:.. . ,

, .- "II .. ~ I I I r r . r ~ _ .... .,' .... .... ..... ..' .--.. - ... _

• • • • _ .....,.. I • 1. I,. : ~ ... ~... ~,.I i. r"... _.... I • _ • ,f!' _. I'

• -_. - . _ - - . ,,-! _. ..,. h. - ._-f .. " I. !., . . r·' ~ ,)i .... ,: ; P} _ .-. ,. : ,; ;,' t;',:, : c: ,

.~~f·'C;-~H' i'·;~Jca;:·'(;~·;' ~_..p...-~~ ';··:"-1lx~r ·.i: ..... r.oCI' "::. r-;--~··· ."- cu-·, ~. • ... .>', ...

.. ...., ~ ~ ... 'TW' .. ' . _"r.!II .i(Ctl ,·.1 .)~ reI ,~ .. ~. r.-.mI

- . '_ , . ... ~ .. '~ \"'1- 1 ~ t .~. ~ .... .•. ~,~ '+ ~ · ........ ~1 :

~ .- ~ :', :" : ~~ ,.po j . -: .: ~,~ ~ .... .: 'i::-.~;2 - ...... ~ , ,. ~ I~. :") ~ '.. - ~ r"·. _ . • ,2 t, , .2 ~ . 2 ~ . Y,. . ~

". ..',.... .t .. _ ~ .. ' ~ ~. .."... ,'. ,...,: ... :.' . r _ ' .., _ 1 n . ~..,.. - [ :.. . POi!' ,," ~ ~..".... ' _.

.... .. • • • - - ,..- • _ _.. ~ ,. .II. ,,_' :"'.. .~ ., ... .L p'.. ••• p ~ I • J I

-(ll) , . '" .. : - ,~_" -, ,.- \



-

Phan t1ng tdng quat c6 :th6bi~ dien ilhu' sau:, ';';; ~ ,',' , ",' _ , , " '

I. . . r

. '

" ,

, ~

nCH 2=CH 2 + CUt ! Cl(CFl2-CH~ca3

; • • -.. I'r •

trong d6 n ='1~ 2" -3,~~~ ,

1.2.7. Aiken tleu bi~u

M~t alken tieu bieu 13 etylen ~H~,- v6'i cong tht'rcC«U~:'

, -

H 'R

'c=c/ -. /: " '

H H

1.2.7.1. each die" che'.e.tylen

, ,Trong phong thlnghiem, ngam ta thuong di8u che etylen ttl aleol etylic bang, each dung H2S04 ~c trong pha long) ~c .bangcach cho hoi alcol di qua y -·AI203 crnhi¢tdl) cao; "

..

CH CH' 0' H " y-AI,03 • 350+600° C ) CH2=CH'2 + H20, 3-- 2-

, Trong cong nghiep, etylenco the thu diroc ti'rkhf than c6c va d~c biet ,Iii til khi cracking d'~u mo.

Ngoai ra cling c6the di~u the' etylen 'bang each hydro h6a khi axetylen c6 xric lac:

,

1.2.7.2. Tin'll c&I1t vd, 6:ng dung 'CUll etylen

. ~

o dieu kien thuang etylen l~ mot chit khf, hoa Iong a-105°C, khong rnau, khong mui, 'Mu nhu .khong tan trong mroc (0 'OOC, 100 the ncb

mroc .hoa tan 0,25 the tfch khf etylen). ", '

, L ,

Etylen 'co t4t ~ ca nhimg tinh chat h6a hQC nhu cac ~en khac nhu dB.

trtnh bay 6 tren. Trong khong khi, etylen chay v6i DgQJ1 lira' sang hon ngon Uta metan, tao thanh khf CO2 va hoi mroc, Hein '1iQp etylen va oxy 1ft hOn hop n6 manh vi phan ling d6t chay toa nhieu ohi~t~ Do docling co th~ dung hbnhgp etylen - OXY de cat, han kim 16~ nhu axetylen.

68

..

r • .

-

Khi k~t hop vOi nude; esylen tao thanh alcol etylic. ~ ling n~y co

the thirc hien nao H2S04 qua san pharo truag giaa.1a etylsunfat axil, hoac cling c6 thi cong tnrc tiep hoi mroc vao etylen nho xiic rae (nhir

A1203) a nhiet dQ 250 -;- 260°C va du(n - ap su~t 5H + 80 at. - " ,

Tac dung ella etylen VOl dung dich cIo trong nuae se tao thanh - etylen clobydrin va tir clohydrin co the dieu ch€ etylerr oxyt:

KOH CH

CH.,=CH2- + O2 + HOH ) CH.,-CH., ) CH")- 2

- J - f .. " /

La OH 0

etylen clohydrin San phfun phu ciia qua trmh la dicloetan.

Tac dung cua etylen voi benzen co xuc tac AI203 se tao ra etyl benzen, til etyl benzen se tao ra diroc styren:

etylen oxyt

ety! benzen styren

Styren dung san xuat polystyren va dung san ~uA't cao su tdng hop Buna-S.

Etylen trung hop tao thanh polyetylen cling 13. mot hop ch~t cao phan

tir co nhieurmg dung trong leY thuat va dbi song, -

Ngoai ling dung trong tong hop hihl co v6i rA't nhieu san pharo qui, etylen con dung de giam qua xanh vi n6 co tac dung kich thfchsu ho~t dQng cua cac men lam qua mau chin. Do d6, co the dung etylen de giarn ca chua, chanh, chu6i v.v ... " v6i nong dQ r1\t loang (1 the tfch etylen tren

1000 -T 2000 the tfch khong khf) a 18 + 20°C .. ' ·

1.3. ALKIN

_-1.3.1. Day dong' d!ng~axetylen

Alkin ciing 13. nhtmg hydrocacbon chua no mach ha, nhimg c6 chua lien ket ba trong phan tiro MOi phan tir alkin so vm phan tir alkan nrong Ung c6 It hem 4 nguyen tir hydro, do d6 cong tlurc chung cua alkin Ii

CnH2n•2, voi n ~ 2.·Khi n=2, ta duqc cMt d'u tiencua-day dong ding nay

69

,

• I

1~~H2''tuc axetylen; n =3, diroc metyl axetylen ~~-v.v ... T!t'ca h9'P-

thanh day d6ng- dang axety len. -

1.3.2. each gQi ten - DOng phan

Thee each goi ten hop Iy, ten goi cac hydrocacbon chua lien ket ba xuar phat ttl len cua axetylen, bang each goi ten goc alkyl b hai ben n6i

ba sau d6 them ten axetylen.Thf d1J.: ;

CH3-C=CH metyl axetylen

dimetyl axetylen

Theo each goi ten qu6c te (IUPAC), cac hydrocacbon chua lien ket ba goi chung l3. alkin, cluing d~u co duoi t~ cung bang in. Viec danh sO mach chfnh bilt dAu- tir nguyen tit caebon dAu mach gfin.li8n ket ba. Vi du:

..

1 2345 6 78

CH3-C = C-CH2-CH2-CH2-CH-C·H3

. . . I·

. CH3

Ten goi mot s6 alkin don .gian c6 chotrong bang 1-5. - Bang /-5. Ten goi ~9t ~6 alkin don gian

Cong thuc Ten llch sCi Ten h9P If Ten quae te (IUPAC)

CH=CH AxetYlen Axety~en· Eti"
CH=~":;'CH3 Anlyleri Metyl axetylen Propin
CH:C-C H2-C H3 Crotonylen Etyl axetylen 1-butin
_
C H,l-C=C-CH3 Crotonylen Dimety! axety len 2-butin
.
_ .
c; H3-C::!C-CH2-C H3 Valerylen Metyletyl·axetylen 2-p13ntin
: ·;H~-CH-C=CH . Valerylen lzopropyl axetylen. 3-mety 1-1 .. butin
. I ~
_
.
CH3 .
CH=C-CH2-CH2-CH3 Valerylen Propyl axetylen 1-pentin
, ~;
.. ~ . . • ,
,.
-- Cac goc hydrocacbon chua "lien k€t ba gQi chung·la alkinyl. Vi' du:

, .

. .... .

_ .

CH=C- etyny1. ~ -.

CH=C-CH2- ._ propiny) (con 9Qi Is R~oPacgyl)

70

'.

v~ d6ng phan cau tao, cac alkin nrong ttl cac aiken, ngoai cac dOng phan ve mach cacbon con co dong phan ve V! trf cQa lien ket ba. Nhung khac voi lien ket dOi cua alken, lien ket ba trong alkin khong tao ra dOng

.,.

phan lap the ..

1.3.3. Phuong phap diCit che 1.3.3.1. Di lit ddn xud: dihalogen

Cae dcin xuat dihalogcn no co hai halogen dinh b hai nguyen tu cacbon canh nhau, hoac cung dfnh vao'ffiQl nguyen tit cacbon (dan xuat gem-dihalogen) khi nrong tac voi dung dich KOH - alcol, se bi tach hai phan tit hydro halogenua, t ao ra lien ket ba:

R-CH-CH--Rt 2 KOH I alcol ) R-C:=C-Rt + 2HX

I J
X X
R-CH~-CHX~ 2KOH I alcol ) R-C=CH + 2HX

- - Nho' phan img tach hai phan tit HX tao fa lien ket ba, co th~ chuyen hoa lien ket d6i thanh lien ket ba. Vf du:

. , . .

, .



CH;-CH==CH, +'Br, --- .......... ) CH~"":'CH-CH., 2KOH/alc~1 , CH~:'_C=CH

. .' - - ... I I - 2H B r :J

Br Br propin

1 ~2-dibrompropan (rnetyl axetyten)

,

, ',Phan J.'rng tach hydrobromua co th~ tien hanh qua' hai giai doan, Vi du, d§.nxuat dibromphenyl dt! bi .tach mot phan tit .hydrobromua de bien thanh brornstyren; sau do lai tach ph an , tir hydrobromuathir haivgiai

doan nay kho .kI:t~ hon giai dean tnroc, tao ra phenyl axetylen: .. . ..

.. / . ~

. .

· ... e H ~CH-t;LJ· .. :+Br2. C' U -CH ~H. 2KO~/atcol \.

6 S ~.,., . .. ~ ) 6-' .i.e ~ '" t .' . .. 7 .

~ ~., ~, , . : ... .. ~ ~ 1 I - . - ..

. ~ .. ~ , ,. ' . Br ,~ B r~· .. ~ . '. . ' . ,'. ~ ~.. ; I

- ' ......

I ',,' : _ . . ... •

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

. .'

~ ~ .

,,'_,', .. I:::"

.. ~ _ J • . ., ~ , ~

. .

. . ..... , '. : ·1·~2-dibrotiipnenyletan

• J' : • _ .... 'I '. ( ~ _ -. • .... •

•• I • • I" •

. .

. ~.

. . ....-

_.

. - ..

"

, ~

- .. .

-

. .

• I • _

~ . .. .

.. '

• • I, .. •

'. : ...• ':. : :: .• ~r .: : .' • ~ : :. -.~ ., •• ;2 KOH i afeot· . . ~. i ,= :.:," ~:' .. ~' .: i ~ ~ ... : . ~I : ~. :~ _" :-. • ' •• ' •

: - -'··c.u -CH~· ... - ~ c J..I·~-CH_r.li ~'" .' .

'..... ~. . ~. ~ ".s ..... . . ~~ J ~1 ,: : . . ' .. ~.. .. : .: .. , ': ";. <: ~ r .6'" ~ ~ ~ .: ' .. ; ~ : : .. ~ : ~ .. : . . . . ~. .. ~ , ~ i: ~ ,~

'I r I -.. ... •

• r • - '. ~ - .. I .. l -. ,I .t&. - .. ~ .. ~ pf;t 'I ~Ien

•. ". .": . l , . ", •• : ., .1 .r.·L ..... ..:. _. ~ .... : .... ,.: " .. ,. ,. .. . • eMU a . I ~ •

.1''' .... 'I • • .r.F ~.. .lI . I. ~ " ~ __, r., .. I '. , :_. ~ , V '} . '.. ~ , .. r .' '!'

... • - ... • ... • ••• • ••• • _ - J .. ' _ ( .. ~ ."" ~ .....J : ~ '." '.', ,I

:-; .. -.... ~ r- .:

, ~.I. •. - ...

. .

,

. .

. ~. (~it- '\,.. ~ ~ r.'''' 'I I~' ~ • ..... _. , .I' _. .. ~'

, l' • 4.L ~ . .. 'I •• "

. -' .. ~ . 'I , _ '.' ''I....... .. J •

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

1.3.3.2 .. Bi tit ddn xutft tetrahalogen

Cho dan xuflt tetrahalogen co 4 halogen dfnh vao hai cae bon lien nhau tac dung vci bot-kern cung tao ra dugc lien ket ba:

X X

t I

R-C -C-R' + 2Zn

J I

X X

__ _____.) R-C=C-R' + 2ZnX.,

-- ,

1.3.3.3. fJie'u, cht dong ddng cua axetylen di tit axetylen

, NhO' kha nang co tht' chuyen hoa axetylen thanh dAn xuat co kim (dan xuat co natri), co th~ tong hop dUQ'C cac dong d~g cua axetylen , khi cho dan xua't nay tac dung v6i dan xuat halogen thea sa 06 sau:

CH=CH + Na

----) CH=C-Na

IR ) CH=C-R + NaI

Thf du, tit axetylen va etyl bromua, co the tong hop ra etyl axetylen:

CH3-CH2-B.f + Na-C=CH -- ------+) . CH3-CH2-C=CH + NaBr

. .

1 .. 3 .. 3.4. Dieu che~ axetylen



Trong day dong dfing alkin, axetylen 13. chat "~au tien, d6ng thoi ding dong vai tro quan trong nhat trong thirc te, nen duoc san xuat vci

')

qui mo 1911 trong cong nghiep .. Sau day trmh bay mot viii qua trinh ph6

" ...

bien.

a. Di tl~ call .. xi cacbua

Phuong phap quan tr9ng nhat va thong dvng nha:'t trong cong nghiep cung nhu trong phong thf nghiern 13. thuy phan canxi cacbua, fhtreng goi 13. dat .,den. Cho canxi cacbua tiep xuc v6i mroc, se giai phong khi axetyleri: .

esc + 2H.,O

- ...

_ _____...) HC=CH + Ca(OH)2

Trong cong nghiep, qua trinh thuy phan co the tien harm theo phirong phap uOt (co) hoac thea plurong ph~p kho (moi). Phuong phap u6t dung nhieu ruroc, phtrong phap kho dung it mroc hem, chi c~ IUQl1.g mroc bang l} 10 lirong mroc dung trong phuong phap trot, Trong 10 phan irng thea phtrong ph~p kho, ngiroi ta cho rnroc vao canxi cacbua, phan ling phat nhiet va lam tho toan kh6i nang len t61 115°C~ nacre du cling bay hoi chi con lai khoi voi ran. Hoi nude IAn VOl khfaxetylen bay ra se diroc ngirng tu Iai trong thap ngung,

72 .

Canx.i cacbua dircc dieu che til than eta va voi s6ng trong 10 dien b nhiet d¢ gan 2500°C:

CaO -+ 3C .. ) Cae; + CO ~}-f29a = + 111 keel/mol

,

Day Iii mot phan ling thu nhiet, doi hoi phai cung cap mot nang

hrong 16n~

Canxi cacbua la nhtrng tinh the ran. Mang hroi tinh the gom nhftng

...

ion Ca" va C ~ - (-C~C-); cac ion C? _ khong ben khi g~p ruroc, se lap

, ,

" urc chi em- liiy ion H+ cua phan nr H20 tao ra axetylen va cac ion OH-.

Axetylen dieu ch€ tu canxi cacbua thirong c6 chua mot hrong nho cac khi khac nhu NH3, PH3, A~H3' S(CH=CH~)2' vinyl axetylen v.v ... Cac tap chat nay co th~ diroc loaitrir bang each cho h6n hop khf oi qua

I • ••

dung dich kali bicromat trong axit sunfuric hoac qua cac dung dich oxy

h6a khac.: Axetylen dieu che theo phirong phap nay i6n nhieu nang

hrong, nen gia thanh cao. - - ;

b. Di fir khithien nhien (rH-J)

. - Cac phan irng quan trong trong cong nghiep d~ dieu ch€ ); san xuat axctylen Ia cracking oxy h6a nhiet va dien cracking metan (CH~).

• Qua trinh dien cracking' .

Cho CH4 di qua cac dien :CI:lC, dien the' mot chieu 8000 V, nhiet d¢ khoang khong gian phan Ung,.1_600oG,. t6c cit? dong khf 1000 m/s~ rmrc d¢ chuyen h6a CH4 vao_khpang'50%: "

, .'

'2CJt;--... ). -CH5=CH + 3H~"- !:J-f298 = 91 kcal/mol

Khf thoat ra lam lanh ngay, trong h6n hop khf Chua 13% axetylen theo the tfch, 45 %- hydro, - 1 % 'etylen V& cac khi .khac,

,

,'Ne-u dung 1000. nr'khf .thien nhien se thu dlIqc khoang300kg

" axetyle~~_2p~g etylen va 1 i 70 rrr' hydro. ' '-

, .-

I • • • .... • r I

~. .

• QU~J.tl,q11 cracking oxy h6a nhiet ",' ,-, ,

v6i tY'l~ cn.. 0;" =. 1 :' 0,65; phan U'ng tienhanh: theo-phuong 'trtnh

I __ ,

- s au .. ·, ,L',.::. "~ <...... • ' " " -L "- ,

• • _ .... " • • I •• • • .....:).. I '1 I • __

~ I I I I ...

6CH4 + 402 ~' • CH=CH + 8H2 + 3CO :.- CO2 + 3H20_"

: ~~\~,~ trong 10 ~ ~ho CH4 ~~ l?~y.,~qpa) kh~3.Q~)5000~, ,t6c dO khl diqua 10 rA't Ion, lam lanh nhanh se thu ~dugc hOn figp khi

"g6m 8% axet)ien;___54.5_%_ ~dr_Q~2.~_C.Q;__.1%_ CQ2.; 4~? 2£ __ ~f:l4~ __ O,2~

...

dorig" dang axetylen; 0,1% benzen va dong ding (0/0 thea the tfch).

Hien nay 6 cac ruroc tien lien sir dung phuong phap nay de dieu ch€ axetylen, d6ng thOi co the chuyen co va hydro thanh hydrocaebon

(nhien lieu) thea phan trng Fischer - Strop. ~

1.3.4. Tinh chat v~t Ii

Cac thanh phan thap eC2 + C~) lrong day dOng dAng alkin 13. nhimg

, chat kill khong mau, cac dong dc1ng cao hon 13. nhfrng chat long hoac ran. II khoi cua cac alkin cao hem so voi aiken luang irng. Cac alkin tan lrong ruroc nhieu hon cac hydrocacbon khac. Cac alkin co nhiet de) soi hoi cao hen so voi cac alken va alkan nrong rrng.

PhO hong ngoai cuacac alkin co dai hap thu b 2100 cm ", Ung v6i dao dqng hoa tIi ciia lien k~t ba C=C. Cac rnonoalkyl axetylen R-C=CH c6 dill. hap thu rnanh gan 3300 cm " d~c tnrng cho dao dong hoa tri ella

. .

lien ket C-H trong nh6rn ~C-H. Nhu vay su co mat cua nhom -C=CH

lrong phan 11i alkin co th~ nhan ra de dang nha phd h6ng' ngoai. Tuy

nhien, lien ket ba trong alkin ki~u R-C=C-RI lai kh6 phat hien do khong eo dai hap thu cua nhom =C-H gan 3300 cm'", va 51:1' hap thu ella

, .

lien ket Cae qua yeu kh6 nhan ra.

HAng s6 v~t 19 cua mot s6 alkin co cho trong bang 1-6.

Being 1-6. Hang so v~t Iy cua mot s6 alkin

Nhi~t d9 n6ng Nhiet do T1 khol
Gong thuc Ten 9qi •
ehily t~c. -c _. to QC
sor S J l1li
.
84
CH=CH axetylen - 81,8 -836 Of6200 d4
I

, ~ - 104,7 - 23J3 o 6785 d -27
CH3-C=CH proprn
~ 4
. 0
C2Hs-C=CH 1-butin - 13010 ·-86 0*6680 .d4
,
CH3-C=C-CH3 2-butin - 27J2 OJ6880(d 25°C)
iJ-C3HrCEiC H t-pentin -95 40,0 0,6882 d~5 .
-
- 0)7127 (17J?C)
CH3-C::C-C2Hs 2-pentin - 101 56JO
-
H3C
\ . 0
CH-C=CH 3-metyl-1-butin - 29J3 O~~854 d4
/ -
-
H3C . ~
~ 74

1 ~3.5~ Tinh chat hoa hoc



1.3.5.1. Ban chat ddc dilm cua lien kIt ba -C=C- -

..

Nhu da trmh bay a phan tren, lien ket ba Cec duQC tao nen blri hai nguyen tir cacbon 0 trang thai lai tao sp ; IUC Iii kieu lai tao dirong thang.

Trong lien kel ba co mot lien ket c do sir xen phil true cua hai .clcctron lai tao, con hai lien ket 7t do su xen phu ben eua hai cap electron p: Cac true ella cac electron p tao thanh hai mat phang thang g6c v6i nhau, giao tuyen cua hai mat phang d6 La dirong n6i tam hai nguyen tU cacbon.

,

Mac dQ lien k€t cua cac nguyen tit cacbon trong lien ket ba Ion han

trong lien kf!t d6i nen lam cho lien ket ba ng~ hem. D¢ dai lien ket ba

C=C bang 1 ,20 A~ trong khi do d¢ dai lien ket d6i C--c la 1,34 A va d¢ dai lien ket don C-C Hi 1,54 A. v« nang Iirong lien ket, lien ket ba c6

. .

nang hrong lien k€t bang 199,6 kcal/mol, lien ket ctOi co nang hrong lien

ket bang 145,8 kcal/mol va lien ket don c6 nang Iuong lien ket bang

82,6 kcal/mol. Mat dQ electron 7t t~p trung chit yeu b khoang giua hai hat nhan cua hai nguyen tir cacbon, nen khu V1fC ben ngoai ciia hat .nhan mat d¢ electron lai nrong d6i ngheo. Dieu d6 giai thfch kha nang 'phan ling kern ella Iien k6t ba so vOi lien k~t dOi trong cac phan rmg cong

electrophyl. ~

MQt diem dang chu y nita la cac nguyen tir cacbon b trang thai lai tao sp co dQ am ~er:t Ian han cua cacbon 100 tao Sp2, eon Csp2 lai co dO am

. . .

. .

dien 1611 hon Csp3:

Csp - > Cspl > C,p3 .

,

3- S+ .. .. a_:· B+

Ket qua Iii. trong lien k~t == C - H co sir phan eire manh: =: C -E-,H

lam tang rnomen hrang cue cua lien k~t va tang .kh~. nang tach hydro ra dUCli dang proton, thuc te' tfnh axit cua axetylen fa.' Ion hem ca so v6i

etyleii vaetan, '. - . l ; • ,;-.. " :' ., ... • ... .. . .:

... • I... • - .. .... r • - _ .... I ..;'" • • •

. ... I ~ .. • ~ ~ '. ~ • . .. . • ~ . . I I'.. • - .' • 1- r I • ~ p' • • .... .,,, •

_. "cae· plian lmg" cu'a· 'anon · 66 the Chi a . thanh l?~ ·19"~·~ "han .. tWl( ~9fig,

• . I • - -.,. ,. ' " ... "I

phan \1ng trung hop, va 46i vci nhUng alkin nhu R =-cac-H va' axetylen

thi c6 thMi,nrnm.g~ph8n·-tm~cua-nguy~:tlthydro dftii v6Lcilcbori mang

nllf:1 ba .-., . ,. - .............. ;. .. '. ''L' .

Ul • . . ~~ ~ ~-_. 4 •• ~. •• I _-. • •• _ .... "f""l : '\. .

• - I .._. I • ~ ' .. ~.. •

1.3.5.2. Phan ftng c9ng

Cac phan tmg cong vao lien ket ba dien fa qua hai giro doan: giai doan thu nhat chuyen n6i ba thanh n6i doi, va giai doan thtr hai chuyen nm d6i thanh nm dart.

a. Phdn ung hvdro hOG

So d6 phan irng hydro hoa lien k€t ba nhir sau:

I t

- C = C - + H, ~ -c = c-

....

~C=C- + H~ ). -C-c-

I I - I r .

Phan irng hydro hoa lien ket ba thtrong tien hanh v6i hydro phan tit

xuc tac kim Ioai (Ni, Pt, Pd) .. Mu6n dung ICP b .giai doan tao thanh nOt doi, ngllrn ta dUJ;1g xuc rae paladi tren canxi cacbonat, hoac paladi tren

silicagel o 200°C. Hieu smlt cua qua trinh dat tm 95%. '

b. Phdn ung cong halogen

Cling nhu phan irng hydro hoa, phan irng cong halogen xay ra theo hai giai doan. Vi du, khi cho brom cong vao axetylen, giai doan ddu se cho trallS-l ,2-di~romme.tylen, va giai doan sau cho 1,1,2,2- tetrabrommetan:

-

H BT f I

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

J r Br H

Br; )0 CHBr.,-CHBr,

- ...

He = CH + Br,



trans-1,2dibrommetylen

1 ,1 ,2,2-tetrabrommetan

D6i voi clo, trong dieu kien thirong, phan ung xay ra qua manh liet toa nhieu nhiet nen gay phan img huy. Trong dieu kien kg thuat, ngiroi ta thirc hien direc phan ung cong clo true tiep vao axetylen trong nhirng kh6i x6p~

c. Phdn ung cong hydro halogenua

Phan rrng cong hydro halogenua kh6 han phan irng cong halogen.

Tac dungciia hydro florua khan vao axetylen bat dAu cho vinyl fiorua, sau d6 cho Ll-difloetan:



HC=CH + HF

vinylflorua

1 J 1-difloetan

-

76

Trong ky thuat tdng bQp nhira polyvinyl. clorua (PVC), mu6n di~u che vinyl' clorua ngum ta cho axetylen tac .dung v6i hydro elorua tren

xuc tac thuy ngan clorua, Ct 120 + 150°C:

HC=CH + Hel

HgC!2 ) H2C=CH-CI

vinylclorua

d. P han ung cong nuac

Phan ling cong H OH vao axetylen va d6ng d~g cua no dUQ'c Kuserop nghien cU'U nam 188 1. Phlm Ung tien hanh bang each cho alkin di vao dung dich axit sunfuric 10311g c6 chua thuy ngan sunfat .dong vai tro xuc taco Phan - ting qua giai doan trung gian 13. dang enol khong ben nen n6 dOng phan hoa thanh hop chin cacbonyl thee so do chung nhu sau:

-C = c- + HOH. HgS°04 ~ -C = c-

I 6H

-- ....... ) - CH2 -C-

o 0 II ..

o

danq cacborwl

. . . .

Neu di tir axetylen, giai doan trung gian IA alcolvinylic khong ben,

va cu6i cung ta dtroc axetaldehit: 0 .~

HC=CH + HOH

------.) [CH2=CH-OH] alcol vinylic khong ben

--.) .CH3-CH=O aldehit .axetic

- .'

CH3-C=CH + HOH -~) CH3-reHl ·OH



proprn

------.) ··CH -C -CH .

3 II 3

o axeton

I - - .......... ) -c ~C-O

J r

. ; '.. . :. _: . ' tis -0 -S02. . . ,_ . ' .-

• • .... 'I • I • • I •• "I. • ....

. •. j ~. . ~ .

~,SaudQt:hgpcll«t ph'ttc My hi thUy phan{cho'hgp.ehft«toonyl v~··1~.

gi8.i ph6ng thuj' ngan: sorifat:~·: ~ : ::;:. : _ .: . -'.:: - .'. _ r . ":,:c - .. .: ":~' . - i, ; .:: . .

-:f~~~h?: . ':'-HH;~:: ;~ z-FfI=r~~~_ .~ ~·r~~:':_;-:-C~;!i;-:=" .• :;-;

Hg-O-S02 :< 0

Theo Kuserop, tnroc. htt thuyngan sunfat k~t hop v6i phan _tu alkin tao ra. mor hop chat phiic it tan:

- C s= C - + HgS04



Phan 11ng Kuserop co y nghia quan trong trong ley thuat, nho phan

6ng nay, xuAt phat til axetylen ciing nhu tit cac alkin khac, co th~ tong hop ra nhieu hop chat hfru co lam nguyen lieu trong cong nghiep hoa hoc .

..

e. Phdn Ung cong alcol \'Q cong axit cacboxylic ·

Tirong tu phan ling cQng HOH, dum Lac dung cua xt1c tac thuy ngan sunfat, hoac t6t hon dung xtic tac COs-COOH, BF3 va HgO, axetylen c6 the cho phan Ung cong v6i alcol tao ra ete vinylic, cong vOi axit cacboxylic tao fa este ella aleol vinylic, Vi du:

CH=CH + HOC2Hs _ _...) HlC=CH-O-C1HS etyl vinyl ete

alcol etylic

CH=CH + HOOC-CH3 axit axettc

- ..... ) H2C==CH-O-CO-CH3 vinyl axe tat

.

Cac ete vinylic, cling nhtr este vinylic, d~u. co the dung lam nguyen

lieu tOng hop polyrne c6 nhieu iiog dung trong ky thuat. .

f. T tic dung vai aldehit formic

Axetylen tac dung vm aldehit formic tao thanh butindiol 1-4 (ch«t lam bong khi rna niken):

.

CH=CH + 2HCHO xuc tac + HOCH2-{);;C-CH20H

Axety1en cling c6 the tac dung v6i aldehit (R-C-H), xeton (R-C-R)

- . H II

hay oxyt (CH2-CH2)]. 0 a

"cI

HQp cha:t butindiol de dang hydro hoa de tao thanh butandiol 1-4, d6 18. ban san pham quan. trong de san xuat polyetyleng!ycol, cung nhu di! san xuAt tetrahydro furan, anhydric adipic, butadien:

-

2H2 ~ HOCH2-CH2-CH2-CH20H Ni

78

...

-

butadlen

anhydric adipic

tet rahy d rofu ran

1.3.5.3. Phdn Ung trilngJt.tJP .

r

Q. Trung hap macn vong

Khi cho axetylen di qua 6ng nung do tm 600 -;- 8_OO°C, axetylen se trimg hop, cho mOt chAt nhtr nhira c6 chua san pharo chfnh l~ benzen (tm 28%), cling voi nhiing san pharo phu nhu toluen,pap~talen. va cac hydrocacbon thorn ngung tu khac, nrong t1! cac san pham· chung c~t

nhira than da: . . - -,

...


~CH /CH,\
CH CH ~ CH. CH
... .
III I . I
CH CH CH CH
'-CH 'cI' benz en . _,. .

Cac d6ng dang ella axetylen trung hop trong weu kien nhe nhang hon, dum rae dung xtlc tac ciia axit sunfuricdac, trong di~~ kien d6, metylaxetylen trimg hop cho trimetylbenzen d6i xtmg;



CH

I C-CH~

)

- .

. trirnetyl benzen d5i xUn.Q (mezitylen)

79



Theo Reppe, khi co chal xuc tat (CO)4Ni[P(C6Hs)3]2 (dieu che til tetracacbonyl niken va triphenylphotphin), lJ nhiet dO 60 + 70°C, axetylen se trung hcp thanh.benzen v6'i hieu su~t 80%.,

'. ..

Cungtheo Reppe, dum hie 'dung xuc lac ella niken xyanua b 20 at va "

60 -;- 70ve, axetylen trimg hop nhanh chong thanh xyclooctatetraen v6i hieu suat t6.i 70 4- 90%:

oil

CH==CH

CH CH

111 lit

CH CH

CH · -CH

/CH CH

en "rn

n u

CH eH

"CH=Ct!

... 3

b; Triing hop mach thang . .

• Dum tac dung xtic tac cua muoi dOng (1), axetylen trung hcp hai

phan tit (dime hoa) tao fa vinylaxetylen: .

H H

" , C--C-C=CH

/

H

HC=CH + HC=CH

)

..

vinyl axetyten

Phan irng nay co 9 nghia quan trong, vi tit vinyl axetylen, co the di8u che ra butadien-· CH2=CH-CH~H2 (cong hydro), va cloropren CH~=CH-Ccl=CH2 (cong HCl) la nhirng nguyen lieu trong tOng hop cao



• Axetylen cii-ng co the trung hop' ba phan tu cho divinyl axetylen

.

CH2=CH-C=C-CH=CH." hoac b6n phan tir cho 1,5,7-octatrien

1 2._ 3 45_Q 78

CH,=CH-C=C-CIf=CH-CH=CH2 ~.

-

• Khi co mat bot d6ng va v~t oxy b 200 + 250°C, axetylen trunghop thanh qll)t polyme (CH)u goi la cupren. DO Iii mot chat bQt vodinh hinh, kh6i luong phan tit ,at Ion, khong tan trong mroc va cac dung moi hiru co, thong thirong dung lam chat each dien.

80

...

. ~

~

. ,

1.3.5.4. Tinh axil ye~ . va phdn ling the' vOi kim loai

a. Tinh axit ,·eu

Nguyen til hydro dfnh vao nguyen tit cacbon rnang lien ket ba r~t linh dong, do vay cac alkin loai nay c6 tirih axit yeu va c6 th~ tham gia phan Ung the ven kim Ioai, Phan irng nay la phan ling d~c tnrng nhat cua cac . alkin co hydro dfnh vao cacbon mang n61 ba.

• •

. Trang axetylen HC=CH co hai nguyen tii hydro d~u dfnh vao cacbon

mang n6i ba. Axetylen co tfnh axil yeu han tfnh axit ella mroc, nhimg lai manh hon ella amoniac (tm 1013 Ian) va han tfnh axil cua etylen va etan

ft nhat t6i 1018 IAn (bang 1-7). "

Nguyen nhan tfnh linh dong cao cua hydro trong axetylen so vm trong etylen va trong elan la do dQ fun dien cua cac nguyen tir cacbon lJ trang thai lai tao khac nhau .. Cacbon lai tao !1]"J co ~¢ am dien IOn nhat, ke do la cacbon lai tao .'Ip2 va kern nh~t La eaebon lai tao Sp3:

CSP > Csp.:! > Csp3. -

D6 ia Vl a cachon lai tao sp ; trong orbital lai tao, ty l~ electron J; til electron co rmrc nang hrong thap cr gan nhan, chiem tm 50%" IOn hon han ty 1~ electron strong orbital lai tao sp' va ·Sp3. _ Do dQ am di~n cua

cacbon lai tao .. f\JJ lon, nen lien ket C-H cua cacbon mang lien ket ba phan eire manh, tang cuang kha nang proton boa cua nguyen tit hydro, cling nhu kha nang the v(Ji kim loai:

r--

B- 'I 6+

R-C=C(;I-t

L ......

Hang s6 phan ly K, ella mOt 56 char xem a bang 1-7.

b. Phdn ilng the~t'6i.kiin loa! kim,' \'0 kiint tht5

.

Khi cho axetylen di qUa natri kiM loai dun ri6ng. 0 ~t d() t500C

hoac di qua dung dich long natri amidua ·NaNH2)·SS t~-·ra dinxu«t"the'

natri axetylenua; , ,~', ~ , " r

~, ,

HC=CH + Na

":. HC=CH .'+ NaNH;! ~ HC=C~Na + NH3· ..

.... _ . _ r.. . I ~ .. •

I • - • .' _ ... or.- _ • - •

£>un ~_ . .. , .. _ .. ,~_., t4 ~g: 2200<: se tto· ra. ~ xu:~

..

Ht~-Na· + 1/2 82 ~', -.. .

81

dinatri axetylenna Na2Ca, C~ cacbua Ca~, thirc cheft 13 eanxi

axetylenua co clura ion t~~. " - .. - .

Bdng 1-7. Hing so phan Iy K. gao dung ciia mt)t s6 hqp chat

• I r- 1_ .. ... .

.

,- .

H9P chat

HCl04 .0

I CH3-C~H

~O CH3CH20H

CH5CH

2.10-5
10""4-
1 0-18
1 0-22 ...
10-35
-10~O
. < 10-40 NH3

CH2=CH2 . - ... I . -

.. CH3-CH3

c. Phdn ung the ·vOl cdc kim loai khdc.

- .

. .

Khi cho axetylen di vito dung dich bac nitrat trong arnoniac se tao ta

k!t tua bac axetylenua Ag2C2 mau xamr . . ,

- .

. .

HC-=CH· [Ag(NHa>z]+) Ag-C=C-Ag -J.. , . _.

Ciing nrong tl!, khi cho axetylen di qua dung dich d6ng (I) clorua trong amoniac, se tao fa ket tiia vO dinh hinh man do gach cua dOng

axetylenua ·Cu2C2• -

HG=CH [Cu(NH3b]+) . Cu-C=C-Cu -J..

Cac phan Ung vm muoi bac va mu6i d6ng dung de nhan ra axetylen va cling cO th~ dung de tach cac alkin co hydro dfnh b. cae bon mang n61

r

ba ra khoi cac dOng ding- khac,

Cac axetylenua dong va bac ben vimg d trong mroc. Chung chi bi thuy phan bOi axit manh, taitao fa axetylen. Dieu d6 chung to cac lien tei cacbon kim loai trong cac axetylenua nay mang tinh cha-t cQng__boa __ . tri nhieu hon vdi cac axetylenua kim loai - kiem, kiem th6. Cac axetylenuabac va dang, khikho r«t de n6 manh, gilU ph6ng kim loai va

eacbon, dong thoi toa ra mot nhiet hrong 100. Vf du:

Ag2C2.. ) 2C + 2Ag. + 87. kcal

VI khi bi va dap, cac axetylenua Ag, Cu nO manh nen ngiroi ta khong dung 6ng d6ng hay bac lam 6ng van chuyen khf axetylen.

1.3.6. Chat tieu bieu

Otat tieu bieu trong cac alkin 13. axetylen C2H2- co cong tlurc cau tao

. .

CH=CH- No Iii chat tieu bieu qUaIl. trong nhattrong day d6ng dimg

alkin.

Axetylen hay etin 13. mot ch~t khf khong mau, nguyen chat khong mui, nhe han khong khf, ft tan trong rnroc, 11 dieu kien thtrong, mot the tfeh mroc hoa tan diroc mot the tfch khfaxetylen, khi tip suilt tang len, dQ hoa tan cling tang theo. Axetylen tan nhieu hop trong cac dung moi hiiu co nhu aleol, ete, ?~C biet tan rilt nhieu trong axeton, dum ap suat thtrong, mot lft axeton hoa tan diroc 25 lit khf axetylen. Mu6n chuyen cho axetylen diroc nhieu va tranh nguy hiern n6, ngirci -ta cho axetylen

hoa tan trong axeton dum ap suat cao 12 +·15 at, dum ap suat nay mot 1ft axeton hoa tan dl1qc 300 lit' khfaxetylen. Bmh thep chua dung dich axetylen trong axeton khong nguy hiem so vOi axetylen long, nhat la khi dung them cac kh6i x6p vo co chat d~y trong btnh.

Axetylen Hi mot hop, chat khong ben ve mat nhiet dl)ng, no co the bi

. .

phan huy tao racacbon va hydro kern theo hien nrong nd. Phan ling n6

co the .khoi mao bang nhiet, bang thuy ngan funmirtat, hoac ~1! nO dum

ap suat cao. Phan rmgnd toa nhieu nhiet, Mr298 = - 54,9 kcal/mol, nhiet

dQ cua khf hie d6 c6·tbe len t6i hang nghin dQ. ,. ,

, Axetylen vhop ch(t thu ·nhi~t) vi v~y khi d6't chay, thoat rarnot

1 uqD.g , nhiet hrong l&t: Khi dung hOn- hop axetylea- oxy lam khf han, - c,at kim Ioai.niau, nlu6ri. han t61: thl phii ··sir d\}ng<khftra ; (argon) de oxy . khong n~ XUC tn.rctig'p':tten"be tft~t kim :1()~i: 'han.,i AX ety len ·cMy' trong

, .

khOng khf cho ta ngQn lira sang, tao ra C02'·-V~ ·H20:;· .. :' - : .. ~ -: - . ' . _ ...

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

... ~ :. - .~. ]·IC==CH ~ :.+ ·5/2 -02'; .. ) ... 'I)' ~2'CO ' .+~ H;O··· -.':j > -:, '. .': ~,._. <~ ~

- , 2 2

.. ~ r· \ .. ~ ~ ~ . r r~·. ~ • _ ... _ • - ~ -. ~ - ~. ~ r~ ..

~ . '_ ... .. ..- _ . _. ",; _ _ - : _ )'t ~ r. .. ~ ~ .r I -i ! ~..... .. - ~

, ., - + .-

L ... ...". II (- L f!'." ". I ifJ - • ,. ~. • r ... - I I. .... f ,.

I· -. •• 'I:r "Ii • .. r . . .. 'i. r • I • I •• ~ • • • • 'I ~ I "'I

' .. - ~288·=-315·kcarlmof~ r : ~~~ ..... , I .~ ..



83



1.4. ALKADIEN

Tuy theo Vi trf urong d6i cua cac n6i d6i trong mach cacbon, c6 the chia thanh ba loai polyen chfnh sau day:

- Polyen c6 cae n6i d6i each biet

Trong lo~ polyen nay cac n6i d6i nam xa hAn nhau, it nhat each nhau tir hai n6i dan lTd len; cac nOt dOi nay n6i chung khong anh huong gl d~n nhau, chting van duy tri nhimg tfnh cha:t cua lien ke't dOi nhtr trong alken, Vi du, hop chat squalen la mot polyen c6 cac nOt dbi each biet:

t

CH3-C=CH-CH1-(CH,-C--CH-CH ,) ~-CH.,-CH=C-CH3

f ~ - I.· _ .. - J

CH3 CH3 CH.3

.

- Polyen ~6. cac n6i d6i lien nhau

Cie n6i doi trong loai polyen nay 0 sat ben nhau, nguyen tit cacbon 0 giiia mang hai n6i d6i. Thf du, allen CH~=C=CH~.

. .

- Polyen co cac n6i doi lien hop (hay lUM phien)

.

Trong loai polyen nay, cac lien ket dOi nam each nhau bang mot lien

ke't don, H~ thong cac n6'i d()i each nhau m¢t lien kef. don nhu the gqi 121 h¢ cac noi don lien hop .. Vf du:

,

CHz=CH-CH=CH2 1,3-butadien

Trong ba loai polyen n6i tren, loai c6 cac n61 dbi lien hop co nhieu 9 nghia quan trong ve 19 thuyet va thuc lien. DUm day khao sat chit yeu

loai alkadien lien hop, '. '

1.4.1., Can tao electron cUa h~ thong om doi lien bqp

Phan tit 1,3-butadien co b6n nguyen tu cacbon b trang thai lai tao sp2.Chung lien kel vm nhau va voi cac nguyen tit hydro bang lien ket 0''cae lien ket 0' tao thanh do su xen phil ella cac orbital lai tao Spl ella cacbon (lien k!t C-C), va do su xen phu eua cac orbital lai tao v6i orbital s ella hydro (lien ket C-H).

Tift ca cac nguyen tit cacbon va hydro deu nam tren mot mat phang .

..,

o mOi nguyen til cacbon con mQt orbital (chiem bOi mot electron p),

84







chung co tru.~ thang goc v6i mat phang phan tit. B6n orbital p do hoa vaonhau thanh b6n orbital phan tlr (<PI' q>2, <P3, <1'4) 13. nhimg td hop tuyen tfnh cua cac orbital nguyen tit. Nang hrong cua chting tang len tir <PI dtn <p~. Orbital phan tir <Pl c6 nang IUQIlg thap nhat, co d¢ ben Ion nha:'t, phan b6 may electron 1t lJ ca 4 nguyen lii eacbon, tang ctrong lien ket giua 4

. ? ~

nguyen tir cacbon. Orbital phan tit <P2 co mat phang cat gitra cac nguyen

tir C:: va C3; no tang ctrong lien kef gitra C1-C2 va C3-C4, lam yeu lien kel C2-C3o Orbital phan lit <93 co hai m~t phang car, no tang cirong lien ket C2~C3 va lam yeu cac lien ket CI-CZ va C3-C4o Con orbital phan tir <p~ co cac m~t cAt giira tat ca 4 nguyen tit cacbon, n6 lam yeu di Hit ca cac lien ket C-C.

h)

oJ

. Hinh 1.3

a. St! tao thanh lien k't 0' trong phan tcr 1.3-butadien; b. SI! xen phu cac orbital· trong phan ,tlt 1 ~3-butadien

. . ,

~ .

o trang thai. Cd ban, phan til 1,3-butadien t6n tai vCri hai loai orbital

phan tiro <PI, <1>2 ben viing hem ca, cac orbital nay xac dinh ciu tao electron cua phan tit. Cac orbital co nang lirong cao «({)3., <&>4) chi co electron trong cac phan tic b trang thai kfch thfch.

-

Thirc tS' mat dQ electron 1t Ia Ian nhat gitta cac lien ket CI-C2 va

C3-~~' con lien ket C2-C3 khong phai hOM toan la Iien ket don 0', no eo mot mat d¢ electron 1t nhst dinh nen c6 dac tinh yeu ciia lien k€t doi,

85

..

II

E

..

~ .

o

~------.

...

o

t

Nut .

o

Q)

. ...



. b)

Hinh t.4- Sa deS cac orbital cila 1,3-butadten.

a. Cac orbital nguyen tlt p trong phan tll 1 J3-butadien; b. Bon orbital phan tli

Bang cac phuong phap v~i ly hien dai, ngucn ta di xac dinh duoc de)

. .

dai cac lien k~t C-C trong phan tit 1,3-butadien~ d(}~<dm lien k~t C1-C2 va

C:J..:..C4bAng nhau va bang 1,37 A, I6n han dl) dai lien ket dOi C=C btnh thuCIJg (1,34 A); con dQ dai lien ke"t ~~ bing 1,46 A nho hon d¢.d8.i

-,

lien ke't don C-C binh thuong (1,54 A):

CH

eH

86

......

• > ..

..

Tuong tac cua electron 7t trong cac he n6i dl)i lien hQP nhu trong phan tit 1 ,3-buta~en, goi Ia s11 lien hop 1t ._ 1t. Sv lien hop nay lam cho phan tir tra nen ben viing 6n dinh va san bang cac lien ket,

Tuy nhien sir lien hop khong phru Ia nguyen nhan duy nhat lam thay d6i khoang each gitra cac nhan nguyen nr. DQ dai lien ket con phu thuoc

trang thai lai tao ella cacbon, VI vay su ngan lai cua lien ket don C2-C3 trong phan tir butadien 13. do ket qua ella hai yell to lien hop va lai tao,

Sl! lien hop ella cac lien ket 7t cua .phan tit chua phan ting, dac tnrng bang hieu tmg lien hop tinh. Co the bieu thi sir lien hop cac lien ket 1t trong I ,3-butadien bang cac mui ten cong nhir sau:

~ ~

CH"t = CH ~ CH T CH,

~ <::> -

hoac bang cac cham nrong tnrng sl! san d~u cac lien ket:

CHj---- CH ----:.CH ---=CHl

Dum anh lurong cua cac tac nhan, su lien hop dUQC. tang cirong va xuat hien hieu unglien hop dong (C~). Hieu ling lien hop tinh (el) con diroc ky hieu bang hieu ung M (hieu rrng mezome), hieu ling lien hop dong (Cd) con diroc goi la hieu ling E (hieu ling electrome). Ban chat hai loai hieu ling nay dong nhat, tuy nhien hieu rrng lien hQP dong Cd

. thtrong co y nghia quan trong hon. .

. .

Vi lien k~t C2-C3 co mat dO electron 1t nho nh~t nen kha nang quay

nr do hi han che, Ve mat cau tao l~p the, butadien e6 the tOn tai dum cac cau dang chfnh sau day: s-trans (a), s-cis (b); trong d6 dang s-trans (a) eo nang IUQl1g thA'p nhilt va ben vfrng nha't (hlnh 1.5)~

a)

b)

Hinh 1.5-. Cau d~ng ella 1,.3-butadien

a) d~ng s-trene; b) d~ng s-cis .

..

87

1..4.2. Cac phuong phap dieD che butadien CH2=CH~CH=CHl Butadien 13. mot trong nhtmg nguyen lieu quan trong nhat de tdng hop cao su nhan tao, da dugc weu che bang nhieu phuong phap khac

nhaUe .

1.4.2fil. Dehydro hoa xtic lac cdc n-buten va n-butan

Khi cho cac n-buten di qua xuc tac crom oxyt tren nhorn oxyt a nhiet d6 650°C, se thu dtroc butadien vOi hieu suat tren 70%:

. . ..

CH3-CH=CH-CH3 ) CH2=CH-CH=CH2. + H2

Do phan ling lam tang the tich, nen tien hanh trong dieu kien ap sua:-t thap se thuan 19i han. 1)6 tranh phan ling trung hop co the xay fa d6ng thoi, xuc tac diroc phil mot 16p cacbon mong, Xtic tac moi dac biet hoar dong 13. canxi niken photphat kep CagNi(P04)6, duqc hoat hoa b~ crom

oxyt, cho hieu suat 870/0. . .

Viec dehydro hoa n-butan· thirc hien qua hai giai doan, tnroc het, n-butan bi dehydro h6a trong dieu kien nhe nhang thanh cac 11-buten; cac n-buten dirge tach ra khoi hydro va cac hydrocacbon C3 va C2, sau do, cac n-buten bi dehydro h6a thanh butadien nhir di mO ta b tren,

J .4.2.2. Hi tit axetylen

Tit axetylen, c6 the dieu che dl1~ butadien bang nhieu each khac nhau: a. Trung ht!P. thanh vinylaxetylen r6i hydro h6a

HC=CH + HC=HC ) CH2=CH-C=CH Hi) CH2=CH-CH=CH2

6 .. Cong HOH qua axetandehit, qua aldol, qua butylen glvcol, rOl thanh butadien

HC=CH +HOH ~ CHleHO _ +KOH ) CH3-CHOH-CH2-CHO

-.....-.-. .) CH3-CHOH-CH2-CH20H ) CH2=Of..:.CH=CH2

- _I"-.

c. Cong focmandehit . thanh butindiol., qua

tetrahydrofuran, r6i thanh butadien (Reppe 1945)'

• - I -.. • ..

HC=CH +2HCOH) HOCH2-C=C-CH20H ~

butaldiol,

qua

) -H 0

_,~ 2 ~ CH2=CH-CH=CH2

o

88

d. Phuong poop Lebedep

-

Cho hoi etanoI di qua xuc tac g6m magie oxyt va kaolin voi mot

hrcng nho cac oxytsat, titan va kern d6ng vai tTO chat khoi mao. Hieu

suat butadien thu diroc tm 50 + 60% co chua khoang 100/0 buten .. Xric tac vita co tac dung dehydrat h6a, vita dehydro h6a. Phan ling co Ie tien hanh qua cac giai doan sau:

CH3-CH20H ) CH3-CHO + H2

2CH3-CH9 ) CHJ-CH=CH~CHO + H20

CH3-CH=CH-CHO + CHsCH20H ) CH3-CH==CH-CH20H + CH3eHO

I

---a.~ CH2=CH-CH=CH2 + H20

1.4.3. Tinh chat cac hQP chat co n6i doi lien hop

""

d nhiet dQ thirong butadien Ut mot chat khi, izopren va dimetyl

butadien itt nhimg chat long. -

.. Anh huong urong hi) cua cac nrn d6i lien hop th~ hien trong nhieu tfnh chat I y hQC, nhu trong quang phb tit ngoai, trong chi s6 khuc xa, gay ra IIS6 gia" moi trong d~ khuc xa phan tir, lam giam noi nang phan tit do do phan tit ben viing han. Ciing do anh huong lien hop nen chieu

..

dai cac lien ket C-C thay dOi: nrn dOi dai hem nili d3i etylenic binh

thtrong, con n6i don ngan hon n6i dan binh thirong.

• •

ve hoa tfnh, cinh huang lien hop the hien r5 C1 kha nang phan trng

cong tang len va d~c biet phan Ung cong 1 ,4. Loai phan rrng vao cac diiu mach khong gi6i han trong cac dien, rna con the hien trong nhieu hop chcit hiiu CeJ khac co chua h~ n6i doi lien hop. Ngoai ra, cac alkadien co noi d(}i lien hop con rat de tham gia phan img trung hop tao thanh cac polyme, thanh phdn chfnh cua cao ~u nhan tao.

--

..

1.4.3.1. Phan itng c(ing

Q. Cong brom

Khi cho butadien tac dung VOl brorn se thu dttqe san phfun cong 1,4-dibrombuten va mOt hrong nho 3,4-dibrom-l-buten 13. san pham phan irng cong vito mQt n6i doi:

89

_ .' ,Q:J2=GIi -CH=CHz ~ ~ Br 2

- ~ .. _II ) '''_''; • •

• - • ._ .... .. 'I" II.. I

- • \ ....., I I '. ~ • .. of. '. 1... _~. _i. '. ~ I. .... •

,_ • ,,_Br~CH2~Ctl~CH~H2-:-Br +

~ :.. • I • I • I I ~ I

•• P .r _ • 'I • r

. -

...... '

r . , ,

I I ...

1.4-dibrom 2-but~f1 ..

. .. -,'.

, 1

. . ,

..

3,4-dibrom 1-buten 7

-

- I

Cho butadien cong v6i clo trong dung dich cacbon disunfua ··se thu

diroc san pham cong 1,2 va 1,4 v¢i ty Ie bang nhau. - - ,

Tnroc day, Thiele da giai thfch phan (mg cong 1,4 bang thuyet hoa tri du (h6a tri phdn), Thiele cho rang, trong butadien mOi-nguyen tit cacbon , c6 mot h6a tri dir, cac h6a ttl du b C2 va C, ket .hQP vm nhau, con cac h6a tri du b C1 va C4 b trang thai nr do nen de ke't hop voi cac nguyen tit

khac cho san pham cong 1,4:

Br-Bt '

CH.,~CH-CH=CH~- ...... )CI Hz"':C;H-<;H-CH;l -----) CH,-CH=CH-CH2

- .. --. J :'\ ) ~ - I

I'\, ,I .. """ ~ ...

..... , I ...- I

-- I I

; ~ I ~ Br Br

Gia thuyet ella Thiele giru thich .. dugc phan img cong 1,4. nhirng khong giai thich duqc sir hlnh thanh san pham cong 1;2.

Thea quan niem hien dai, co che' phan Ung cong brom tien hanh thea hai giai doan, nhu khi cong brom vao mot lien ker dOi rieng biet .. Phan img cong brom 13. mot phan ling cong electrophyl, khi _cation Br" tien lai gar. butadien, se gay ra su phan eire trong phan tit butadien, va Br" t~ cong vao mot eMu cua h~ lien hop tao ra mQt ion cacboni trung gian:

s- ~ ('8- ., +

CH2=~CH CH CHi-Br - ...... ) CHz CH-CH CH2-Br-

Ion caeboni tao thanh co chua mot he g6m ba nguyen tit eachon, trong do hai cacbon lien ket bang -n6i doi, con mQt mang dien tfch dirong, do til cation allyl. Trong cation allyl ~o su phan h6 lai ,m~t d¢ electron 1t thanh mot orbital phan tlr~ baa trum ca- ba nguyen tir cacbon:

.....--.. + .5@_

CH2 ==' eH' CHeHz - Br ~ CH2hmm CU--· .. ··CH-CH2- Br

I

Sl}' phan b6 dieu hoa mat ~ electron 1t .nlur th~ lam cho 'cation allyl

co nang hrong thap hon cation co dien tich dirong ~p trung 0 met

90

eacbon, va do do no ben vtmg hon.

- Sau do. cation allyl tac ·d~ng voi anion Br'" hoac vao v~ trf 4 hoac vao vi trf 2 (khong the vao vi trf 3, VI tnrong hop nay khong tao duoc n6i doi):

ffi

.A..

r"--_"'" ----""

CHi ........ CH··· ...... 'CH ~CH"t---Br + Br

- -

---.) BrCH~-CH=CH-CH~Br

- -

Tnroc khi thiet lap can bang, cac san ph:1rn cong 1,2 va 1,4 de dang chuyen hoa Lan nhau. H6n hop can bang chua khoang 80% san pham cong 1 ,4~ Sir dong phan hoa lien hanh nho sir phan ly cua ion Br'", Trong sir phan -ly do, ca hai dan xuat dibrom d~u cung cho mot cation allyL, la san pham (rung gian cua phan ling cqng brom, la cation co nang hrong thap, ben vtrng hem ca.

Ty 19 san phfun cong 1,2 va 1,4 Cling con phu thuoc vao dieu .kien tien hanh phan img .. Trong dung moi phan cue nlur trong axit.axetic, (j

nhiet de) 4°C, ty If? san pham cong 1,4 dat t61 khoang 70 + 80'%:.

b .. C 911g hydro clorua

Cho butadien lac dung vm hydroclorua cling (~O fa hai san pharo cong 1,2 va 1 A~ nhung trong tnrong hop nay san pham cong 1.,2 dat lai

ty l¢ 75 ~ 80%, con san pham cong 1,4 chi chiem 1y 1~ 20 + 25%:

(f)

CI-CH~-CH:=:CH -CH]

.

20 -:- 25%

CH~=CH-CH-CH3·

.. I

75+ 80% Cl

c, Hvdro hoa

Phan rmg c(lIlg hydro van butadien tlurong tien hanh bang each dung hydro moi sinh do tiic dung ella kim loai voi dung moi proton nhir ruroc, aleol hose axite Khi l16 kim loai cho phan tit' butadien hai electron, d6ng

91

...

tho; chuyen thrum ion trong dung dich, 'phan tiI butadicn bi phan eire h6a va Ian 1l1Qt nhan hai proton ttl dung dich. Phan Ung hydro h6a tien hanh thea sa do sau:· .

0+ n n H+ 2e - ........ ) CH 2 = CH -CH = CH~ -----to) CH 2 -CH=CH ---CH3'

----------,..~ CH3-CH=CH ~CH3

••

Cac polyen co hai nhorn phenyl a hai dau mach {_l.r~ hydro h6a bang h6n hop natri trong etanol:

. ~ +2e

C~H5-CH=CH.-CH=CH--C6H5· .+2H+ C6H5-CH2~CH::CH -CHZ-C6Hs

1.4.3.2. Phdn tcng ctjngJ,4 khep vong: ling hap Diets-Alder

MOt trong nhtrng phan (rug thong dung nha':t trong t6ng hop htru co 13. phan ling cua mot h~ n6i doi lien hop v6i mot tac nh.in co n6i doi khac dB. diroc hoar h6a .. Tac nhan thtrong co chua lien ket d6i n6i· voi cac

nh6m hut electron nhtr -COOH, --CO--R, -CsN, v.v ...

. Ket qua phan irng cong 1,4 tao ra vong sau canh, con n6i doi (1 vi trf 2,3 ella chat dau. Phan irng thirong lien hanh khong can xtic tac, chi can

dun nang h8n hop phan rrng tm nhiet dQ 100 ..;. 120"C.

Tac nhan thong dung ia anhydrit maleic, co th~ t,~c dung vOi nhieu dien lien hQP khac nhau:

ACH", .".-

CH

r

CH .

'CH.)

-

+

. He-CO\ o

. He-cd

. ··co· / " o

aI

C6 nhieu tac nhan nhu acrolein, .crotonaldehit, axil acrylic, cac este

. .

va nitrin cua no, axirxinnamic C6HS-CH=CH-COOH, qui non, v.v ...

Cac alken don gian ciing co th~ dung lam tac nhan nh.rng hieu suat thap va phai tien harm. a nhiet dQ cao hon.

.' .

. .

D6i veri di,en lien hop, co th~ dung cac dan xuat ~i~ d6ng dfu-tg . cua

butadien co chua cac oh6rn metyl, phenyl, halogen; V.v ... Cac dien lien hop mach vong nhir xyclopentadien, xyclohexadien cq'ng' 'de dang' tham

. . . ..... ... . .....

•• -. I'

. ,

'92

gia phan ung Die1 s-Alder, tao fa nhirng - hopchat nhieu yang, co cac cau n61 khac nhau,

CH~ ~ -

CH

I

+

He-co" o HC-CO/

xycJopentadien

anhydric rnaleic

• CH~

. .

co

CO"b

Phan irna Dicls-Alder co hieu sual rat cao.

,.,_ 4

1 ~4& .. 1._1. Phdn Ung trung hop, dong lrung hap

Duoi lac dung ciia -XllC tac Na, butadien c6 thi trung hQ'P b vi trf 1,4 hoac 1.,2 thea s~a· do sau:··

..

CH~=CH-C·H=CH~

~ . .-

..

• r • p

... _. :

• • ..... I'

. .. .. ..

-CH,-CH-

, -- - ~ -]

eH

fI

CH,'

- n

. . ,

Tro~g; th1!c~te'thuCm.g x~y: -rad6ng thCritheo:·c.~ ~,'c~h: - __ - , _

(-r2~H)m) -:<~i~~=CH~H2-)n'~(CH~~~)~~CHt~~H~-CH2~)ni

· -CIt. I - .:, - -- - • - ' eli · , - -', -, ,

, · r - -' '-. - '- · -. , " r " -- • _.',.. -. - ,

"!' , , CR· ~~ .~, . --1 r : . ~ .£~, " .. . ,~, . . '. .. CH ~ _'.: . . ' .

- ; . • ,. . - .' ~ r _ ) -: .:;.. ~ _ . , ., .:.. - . I· - < ~ ~ • ,

- -

,I ...

93

'nt, n~, m., m~ l'as6'nguyeil dtrong; ~" ' .. 1 .!'; ;'. .

Rieng qua trlnh trung hop 1,4 co the xay fa. hai kha nAJig cong ci~ hoac tra liS .



tru ng hop cis 1,4

Butadien co kha nang dong trung hop vci nIt nhieu monome khac nhu styren (C5H5-CH·=CH~), acrylonitryl (CH~=CH-CN) tao ra cac san pharn co gia tri trong .th'l~.ti~n. Qua trinh xay ra thea S(1 do san:

. .

nCH:=CH-CH=CH~+ mCH~=<rH )( -CH:-.CH=CH.:...cH~- )n( -CH2-<fH-)m

X X

1.4.4. Cal) su

1 . .1 .. 4.1. Call su tit nhien

Cao Stl ur nhien la}r til nhua cay call SU. Cao su tJ! Dillen duoc coi nhu

..,.

Cal) phan tir cua izopren (CsHs)nv(li n Ia mot ~9 trung blnh, co the thay

d6i trong qua trinh che bien. Cao su C{) kha nanghap thu.hru huynh (co kha nang hru hoa) va tra thanh mot san phamco dg dan hoi va co kha nang chiu tac dung cua hoa chat.

Neu Cal) Sll hap thu 2.5+40o/~ hru huynh (so vrn trong hrong cao· su) tht ta dugc mot sail phfun cimg co de? each dien cao goi Iii nhua ebonit.

1 .. 4.4.2. CaD su nhdn tao



Dua tren cac monome nhir butadien, izopren, cloropren, styren, acrylonitryl, ... ngiroi ta tien hanh cac phan ling trung hqp d~ tao ra cac san pharn co tfnh ch~t nhu cao SUo Chang nhirng th(!~ rna con tuy theo yeu cau sirdung (cfut chiu nhiet.ichiu maimon, chiudau, ... ) rna ng.um ta sir dung cac monome trong qua trlnh trirng hQP va d6ng trung hop mot each hop ly. Vi du de tao ra cac cao su co eire, co kha nang chiu dau, Co d¢ bam dfnh cao, ngoai butadien, izopren nguCri ta thirong sir

94

dung cac monome khac nhir acrylonitryl, acrolein, ea. trong qua trtnh d6ng trung hop.

Tuy nhien, khong phai bat c~ mot ~~ac nao tren the gioi cling co co sa thiet hi h6a chat df tOng hop .cao su thea yeu ciiu tfnh nang, Me

dung ... ~ l1:uac ta, P~~:p!~(ph.~p bi€n r.tf~:- c~o-~.~~ t\1' ~en vAn la mot trong nhung phirong ·1tatJlIg'·chit ye'u -de tim ra .&cle' v~t Iieu thay the' cao

su lAng hop .. ~- . ~'.~ ~A- '. ... .... ~\. I,~~.~ :'. "7~.' . s-: ~ . ,_ ~ -r: - <:> , .' : '

U ":' t' ~ , .' .. I. . . .l . .. .... - .: ; 'J. .• , . • .:. - \1""'~

..

t

I ,

I • I •

.r .

J

• 'I ~.

~ :

.. (' ... /

• .... I ~ •

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

,. '. • I -' I ;

'. - .... -. ..

... ..:. .:, .. . ." _ : . ~ .

.

. '1';',"-

....... ....... - . • • . I... .. _ ~

. ;

- .. ; ..

.- ...

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

I. i = .. _ I. :

. " ..

..

" -

· ...... ,...

. ~ .

._'

r ..

.. .: • r-' ~ _',;' ... :

~ .

-

•• ' I ..

... \ J ,; ...

. "

,~~ ~~1 :. ;

I~' ...

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

. .. I

• I ...' •• • ...

- . ~

- .

, ,

.. ( . .

I

I" I

. ... ...

I .. .., •

I •

. .

- ~ .,

...

_ .

.

- .....

~ .

. ...,

._

. ..' ..

.~_I._,/""" -

,

.. ./'

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

t ...: ","-.

. : ' _; ._ . .i: ~ - '

-. .

I -- • • - .. -

..... I I,

. ..- .....

• ~ I' •

. ,

.' ..... . ..

r ~ ........ 1:1 • .:... • •• r . ..," .- .

..

~~ ; : ~

:. .....

~ .

..... ~..,

. - . - .

~ ·1 .. 1.1

.. .- ...

1-. j

.: ...... :: .. ...; I

..

• r

. ~ -

.

r::. .- ....

..

....

• r-,,:," ~ .,. •••

, .. I _. .... ••• _ ...

T

. .-

....

., . f" ... ~ :

. I ... ·.· ._ ", ~ • - ,... . . c,

.. ,

-

.. ·t - ..

• I ......... ••

/ .

--01' , r ••

..

...... I'" T-· • .f~ 7.

:.; )1 "!Ii. .

. .. - ....

...... ..

;. ...- I;. ... - ~I

. .. ", rI

1.. • ,

_. ,

.. .. ....

,.,

. "C.' !

. .._... .... -- ...

..

~ _.

- ,- .

. ~.~

. r

~ '. 'I • ~"... _. I.. :

~. ....

• I. I

.""",,= •

, -

..

I·· .

- . ~ .. . ... ~ .

. I - ... ~ .. -.

• 101 ~ .;., ~ _;_ ·rI: ~: . ~;. _ .!~.

, .

· ,~

,

."1 •

-

. ..

. .

••• ... - ... -; ~.'I 'I" ~ rr I

_. T'I. 'I ..

. . ,

r ~ •

...

. ".

I· II •

" /I

. ,

". .

~'

. , . ~

I· 'I ;!"~. • ( r....: -II - _.. .._. I .. ~ • .,.

.. '" r ~-.~ ~ ......... :1 ... _ .......

-

... '

. '

~ .

t

I ~.- ..... I·· .•.. - .. i" ..

• • I. .. .......

.

F .... .I' ...

I • r.. .

.... • ._ I. ..

• ( • r r. _ I • .po. I·

. I. 1 .. I:: . .: 1·1:

-. I

. .

: .. , ...

. ~

, , ,

- .....

...

.I' r. ~.

• • - I ." -~ r . I ••

• 1 ._. • •• ~ .. I .... ~

. .

. i. ~ .. ~ , . '

, ~

- I ... I· I of 1.1" ~ r·- --:: ..

• _- ::. I

I· • 'I •

I I.. • ••

_..J 11_. • ... r

. ~.

,

I ', ~ I •

- ..... .

...

, ... • I

I _ _ I·

... 'I'" .... .. .1 •

- . .. .. .

. : ,.1,.1,;-::

.... ~

- "'I _ "II ••

, . .

. ~ ~ ..

- -

I :.. L •• ~.. _ ... • _...J • L .....

-

.. .' ,. , -..,.

I I I _- ~...... :1 r

,

. i .r.. 1. ~ . I

I... . .. _ .. .::: ....... r·

: .._ .. e , ...

....... .. . • .' L •.

r. . _.

. - ~



, : / '

+ .

. ~

95

L _

. ~

, , .

..} ,I t

I _ I •

... : ... I

.' _:~ : • ... _: '. I _. I • '1 ~ ..

. .'

-

I .' •••

. .

.~ :" . r . ~ ~ 'J. ' -.' _- . ., '-./ :.. ~:'" : r-... i

~ iuamg.l] '. .. ". - ~ -: . . _ - _'.' _ _ ~'.. ,

, . ~ - , .. . ( ..

.

" .

. .

, .

.. -- .y ••••



.",.. .. ..... '. I...· ..

DAN }(UAT"HALOGE~t.-·.. .,'- :-

• .) •••• I '.. • _ • • ." .:... .. ' .... .. i,. • I .. • ~ _." = .. ' . 'I

ellA HYDROCACBON MACH He; -'-_



.... I. .

Khi thay th~ mot, hai hoac nhieu nguyen tit hydro trong phan tir hydrocacbon bang nguyen tir halogen, ta dugc dan xutit halogen;

R-H R-X

hydrocacbon dlan xuat haJogen (X = F. CJJ Br, f)

Tuy thuoc ban ch~t m6i lien ket cacbon - cacbon trong phan tlr, dan -

xu~t halogen diroc phan thanh halogen alkan, halogen alken, halogen alkin. Vf du:



CH=C-X

halogen alkan halogen aiken halogen alkin

Ngoai ra, dan xuar halogen cling dtroc phan thanh cac loai mono, eli, .... polyhalogen tuy thuoc so hrong nguyen tit halogen trong phan tu ..

;:: K

2.1. DAN XlTAT MONOHALOGEN ALKAN

Dan xuat rnonohalogen cua bydrocacbon no day atkan co cong thirc chung ~H2n+1X hoac R - X, trong d6 R la g6c alkyl, X Iii nguyen tit halogen (F, Q, Br, I).

2.1.1. Cach gQi ten

2.1.1.1. each glJi ten thong thuang

Dan xuat monohalogen cua hydrocacbon no duqc goi chung Iii alkyl



halogenua; nghia Hi goi ten cua.goc hydrocacbon (alkyl) r6i them vao

chit "halogenua'' nrong ling.

2.1.1.2. cae« gl!i ten theo IUPAC

each goi ten thea IUPAC dira tren nguyen d.c coi nguyen tit halogen

96

la nhom the' cua hydrocacbon, vi v~y vi trf va ten cua halogen dtroc d~t len cta.u, tiep theo Iii ten cua hydrocacbon nrong img.

Mot s6 vi du ve each goi ten thong tlnrong va each goi qu6c te cua mot s6 dan xuat halogen aIkan diroc trinh bay trong bang dum day:

. ..

Cong thltc

each Qqi ten thong thudng

each 9qi ten quae te

CH3CI CH3-CH2Br CH3-CH2-CH2-r CH3-CH-CH3

r Br

CH3-CH2-CH2-CH2CJ CH3-CH2-CH-CH3

I

CI

CH3-CH-CH2CI

I

CH3

CHa

t

CH3 .... C-CI

r CH3

metyr clorua

etyf bromua n-propyf iodua izopropyl bromua

n-huty I clorua sec .. butyl clorua

izobutyl cJorua

tett-butyl clorua

clo metan brom etan

t-ied propan 2-brom propan

t-clo butan 2-clo butan

1-clo-2-metyl propan

2-clo .. 2-metyt propan

2.1.2. Dong phan

Dan xu«t monohalogen a1kan c6 hai loai dong phan, dOng phan mach va d6ng phan vi trf,

- DOng phan mach:

Cac dOng phan mach We nhau ve cau tao ella mach cacbon. Vi du,

C4140 co 3 d6ng phan mach: .

CH3-CH2-CH2-CH2--CI n-butyl clorua '.

. ,

CH3·

I CH3-c-a·

r

ca,

·tert-butyl clorua

izobutyl clorua

9-7·

You might also like