Trng i hc Khoa hc T nhin Thnh ph H Ch Minh Khoa Ha Chuyn ngnh Ha Hu c

Seminar K thut Hu c

PHN NG HYDRAT HA V DEHYDRAT HA

H v tn sinh vin: Ng Th Chu Ng MSSV: 0914148 Gio vin hng dn: Tn Hong Nm hc: 2011-2012

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1. i cng. 1.1. Hydrat ha. 1.2. Dehydrat ha. 2. Cc phn ng hydrat ha. 2.1. C ch phn ng. 2.2. Phn loi. 2.3. Hydrat ha mt s loi hp cht. 2.3.1. Hydrat ha cc hp cht olefin. 2.3.2. Hydrat ha acetylen. 2.3.3. Hydrat ha cc hp cht cha nhm C=O. 2.3.4. Hydrat ha cc hp cht cha nhm C=N. 3. Cc phn ng dehydrat ha. 3.1. C ch. 3.2. Cc phn ng dehydrat ha ni phn t quan trng. 3.2.1. Dehydrat ha to ni i C=C. 3.2.2. Dehydrat ha to ra hp cht vng. 4. Ti liu tham kho. 3 3 3 3 3 4 4 4 5 6 6 7 7 7 7 7 8

1. i cng.
Cc phn ng hydrat ha v dehydrat ha u c ng dng rng ri trong k thut hu c v trong ha sinh. Rt nhiu nguyn liu ca ngnh cng nghip c iu ch bng phn ng hydrat ha hoc dehydrat ha. 1.1. Hydrat ha. Nu trn mt cht no xy ra qu trnh cng hp ca phn t nc th ta ni l qu trinh hydrat ha. Bi v phn ng cng hp ch c th xy ra trn cc hp cht cha lin kt nn phn ng cng nc ny (hydrat ha) cng thng ch c xy ra vi cc hp cht cha lin kt CC, C=C, CN, C=N, C=O. 2.2. Dehydrat ha. Qu trnh loi ra mt phn t nc t mt phn t no c gi l dehydrat ha. Dehydrat ha xy ra bng phn ng tch loi nc. Phn ng dehydrat ha l qu trnh ngc ca phn ng hydrat ha. Ta c th chia dehydrat ha thnh hai nhm: + Dehydrat ha ni phn t: phn t nc loi ra t mt phn t. + Dehydrat ha ngoi phn t: phn t nc loi ra ly t hai hay nhiu phn t ging nhau (ngng t cng loi) hay t cc phn t khc nhau (ngng t khc loi). y ta ch xt n phn ng dehydrat ha ni phn t.

2. Cc phn ng hydrat ha.

2.1. C ch phn ng. Khng th vit c mt c ch phn ng hydrat ha tng qut m ch c th lit k nhng phn ng ca nhng hp cht c th cng hp c vi nc. i vi cc tc cht khc nhau th c ch phn ng hydrat ha cng khc nhau.
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2.2. Phn loi. Cc phn ng hydrat ha c phn loi da trn loi lin kt a (lin kt i hoc lin kt ba) ca tc cht. Theo cch phn loi ny ta c hydrat ha cc hp cht cha lin kt CC, C=C, CN, C=N, C=O. 2.3. Hydrat ha mt s loi hp cht. 2.3.1. Hydrat ha cc hp cht alken. Hydrat ha cc hp cht alken l phng php cng nghip sn xut alcol.

CnH2n + H2O

hydrat ha dehydrat ha

CnH2n+1OH

Phn ng cng hp nc vo hp cht alken c xc tc bng acid proton (thng s dng acid sulfuric). Di tc dng ca proton, carbocation c hnh thnh. Ty thuc nng acid s dng trong phn ng m alcol c sinh ra bng hai con ng: hoc carbocation tc dng trc tip vi nc to thnh alcol (xc tc acid long nng thp) hoc carbocation tc dng vi hydrosunfat anion nh l mt tc nhn thn hch to ra sn phm trung gian l hydrosunfat alkyl (xc tc acid nng cao) sau thy phn ester ny c alcol.
H+

C C

C C H
H2O

HSO4

C C HO3SO H

C C HO H

H H

C CH OH alcol

Hydrat ha c acid sulfuric long lm xc tc l qu trnh hydrat ha trc tip, cn trng hp s dng acid sulfuric c lm xc tc th do c s hnh thnh hydrosulfat alkyl trc khi to ra alcol nn c gi l hydrat ha gin tip. Vn tc phn ng c quyt nh trong giai on to ion carbonium. 2.3.2. Hydrat ha acetylen. Vic cng hp nc vo lin kt ba CC c tin hnh trong acid sulfuric long c xc tc l thy ngn (II) sulfat. Sn phm l cc enol, sau khi hnh thnh lp tc h bin v dng ceton bn hn. T acetylen th acetaldehid c to ra cn t cc ng ng ca acetylen th to thnh cc ceton tng ng.
H2SO4 HgSO4

O [CH2 CH OH ] CH3 C H

HC CH

H2O

R C CH

H2O

H2SO4 HgSO4

[ R C CH2 ] H

R C CH3 O

Nghin cu c ch phn ng hydrat ha acetylen trong acid sulfuric long c xc tc thy ngn (II) sulfat, trc ht acetylen to phc vi mui thy ngn, phc ny tc dng vi nc to ra hp cht thy ngn hydroxyl, cht ny li b nc thy phn to thnh vinylalcol (dng enol ca acetaldehid) v sau l acetaldehid.
CH CH HgX
+

CH CH HgX
+

H2O

HC CH HgX OH

H2O H
+

H2C CH OH

HgX(OH)

X=

HO

O H3C C H

HSO4

Acetaldehid l cht lng c nhit si thp (si 20,160C), c mi hc, tan tt trong nc, alcol, ete. 2.3.3. Hydrat ha cc hp cht cha nhm C=O. Aldehid phn ng vi nc cho hydrat ca aldehid.

R C

O H

OH
+

H2O

R CH OH

Cn bng trong phn ng trn ch yu chuyn dch v pha tri, do vic iu ch v phn lp c hydrat n nh ch c th thc hin i vi nhng aldehid cha cc nhm gy hiu ng cm v hiu ng cng hng. V d ngi ta c th phn lp c cloral hydrat dng tinh th n nh.

Cl OH Cl C CH OH Cl
Cloral hydrat trong y hc c s dng lm thuc ng, v l nguyn liu quan trng sn xut cloroform. 2.3.4. Hydrat ha cc hp cht cha nhm C=N. Lin kt C=N thng tm thy trong cc dn xut ca cc hp cht oxo, nh imin, oxim, bazo-Schiff, trong cc hydrazon hoc trong cc hp cht d vng. Vic thy phn cc dn xut ny c mt ngha quan trng khi mun quay tr v hp cht carbonyl, trong hydrat ha l phn ng u tin to ra mt hp cht khng n nh v tip tc b thy phn. Hydrat ha lin kt CN ca nitrin s to thnh amid. Phn ng ny c ngha quan trng trong vic iu ch ure.

H2N C N

H2O

H2O/H2SO4

H2N C

OH NH

H2N C NH2 O ure

3. Cc phn ng dehydrat ha.

3.1. C ch. Cc phn ng dehydrat ha ni phn t c th chia thnh hai nhm: + Nhm to ra hp cht c ni i. + Nhm to ra hp cht vng: thng loi nc ra t cc nhm th c khong cch tng i xa nhau nm trong cng mt phn t, kt qu to ra vng 5 hoc 6. 3.2. Cc phn ng dehydrat ha ni phn t quan trng. 3.2.1. Dehydrat ha to ni i C=C. Trong cng nghip phn ng dehydrat ha alcol thnh alken hoc diol thnh dien l quan trng nht. T cc alcol khc nhau, di tc dng ca acid sulfuric v nhit cao, alken c hnh thnh. Sau y l c ch ca qu trnh dehydrat ha etanol thnh etylen.
H2SO4
+ +
+ -H

C2H5OH

C2H5 OH2

CH2 CH2 H

CH2 CH2

3.2.2. Dehydrat ha to ra hp cht vng. Trong nhng phn t c cha hai nhm chc ging nhau hoc khc nhau, khi ng vng s c th loi ra mt phn t nc to ra phn t n nh hn. Phn ng loi ny thng c ng dng trong iu ch cc hp cht d vng. V d nh phn ng iu ch furfurol t pentoz:
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HO CH

CH OH

CH2 CH2 CHO OH HO

-3 H2O

CHO

Furfurol l cht lng khng mu, lu trong khng kh s chuyn sang mu nu v b nha ha, si 1610C, tan trong nc 270C l 8,7%, vi nc to thnh hn hp d bay hi c im si l 97,9% c thnh phn furfurol chim 18,7%.

4. Ti liu tham kho.

1. Michael B. S., Jeny M. Marchs Advanced Organic Chemistry Reactions, Mechanisms and Structuve, 5th Ed. John Wiley & Sons, Inc. New York. Chichester. Weinheim. Brisbane. Singapore. Toronto, 2001. 2. Graham Solomons T. W.: Fundamentals of Organic Chemistry. John Wiley & Sons, Inc. New York. Chichester. Brisbane. Toronto. Singapore 1986.