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Gii thiu Khi thay th nguyn t hyro ca nguyn t cacbon no trong phn t hirocacbon bng nhm hiroxi s cho ancol cn khi thay th nguyn t hiro trong nhn benzene bng nhm hiroxi thu c phenol, thay th nguyn t hiro trong nhm hiro ca ancol v phenol bng gc hirocacbon thu c ete. Ngoi ra, khi thay th nguyn t hiro ca nguyn t cacbon cha no trong phn t hiro ca nguyn t cacbon cha no trong phn t hyrocacbon bng nhm hiroxi thu c enol: CH3CH2OH (ancol) CH2=CHOH (enol) C6H5CH2OH (ancol thm) C6H5OH (phenol)
Ty theo s nhm hiri trong phn t, ta c dn xut monohiroxi (monoancol, monophanol,), dn xut ddihiddrooxxi (iol v ipheol),.v dn xut polihiroxi (poliol, poliphenol). Th d: CH3OH (Monoancol) C6H5OH (Monolphenol) CH3-CHOH-CH2OH (iol) C6H4(OH)2 (iphenol
II. NH TNH MU TH xantogenat Hydro linh ng Este ha Xeri nitrat (NH4)2[Ce(NO3)6] Iodofom ALCOL (Bc 1,2) <10C CH3CH(OH)R PHENOL POLYALCOL ENOL
Oxi ha bng HIO3 Oxi ha bng HIO4 Oxi ha bng KMnO4 (K2Cr2O7) Lucas (ZnCl2 + HCl) ng (II) hidroxit ng (II) axetat Acid boric St (III) clorua Acid nitr Phtalein Tetrazoli
C2 C7
OH cnh nhau
polyphenol Bng 1: Cc mu th nh tnh hp cht c cha nhm OH. 2.1. Mu th xantogenat (xantat) nh tnh ancol bc 1 v bc 2 Du hiu: To cc xanat c mu vng hoc khi thm dung dich molipdat to phc mu tm, hoc phn ng vi ng sunfat to kt ta nu, hoc lm mt mu I2.
ROH CS2 KOH SK S C OR SK S C OR I2 S C OR 2 S KI
Vi thuc th l Na kim loi, dng pht hin cc hp cht c cha hydro linh ng (nhm OH, SH, NH hay alkin u mch) Du hiu: to ra kh hidro
ROH Na RONa [H]
V d:
CH3OH Na CH3ONa [H]
2.3. Mu th este ha Thc hin phn ng este ha (+acid carboxylic/H2SO4 hoc axyl halogenua/NaOH) ri nhn bit este to ra bng mi thm, c im chy r rt hoc bng mu th acid hidroxamic. V d:
(CH3)2CHCH2CH2OH CH3COOH CH3COOCH2CH2CH(CH3)2 H 2O
Mi du chui
OH CH3OH COOH OH COOCH3 H2O
O C O
H 2O
Thuc th xerinitrat dng nhn bit cc alcol, phenol; cc acid, aldehyd, ceton c cha nhm OH. Du hiu nhn bit l to dung dch hoc kt ta mu , nu hoc xanh nu.
ROH (NH4)2[Ce(NO3)6] (NH4)2[Ce(NO3)5(OR)] HNO3
V d:
C6H5OH (NH4)2[Ce(NO3)6] (NH4)2[Ce(NO3)5(OC6H5)] HNO3
2.5. Mu th iodofom L dung kch KI/I2 dng nh tnh alcol c cng thc CH3CH(OH)R
I2 I2 KI NaOH KI3 HOI NaI
OH R CH CH3 OH 3HOI HI R C CH3 OH R C CH3 O H2O
R C CH3 O R C Cl3 O
3HOI
R C Cl3 O
3H2O
NaOH
RCOONa
CHI3
Phn ng c th nhn bit bng tinh th iodofom to ra c mu vng m v im nng chy hong 1190C 2.6. Oxi ha bng HClO3 Mu th c th nh tnh c cc alcol t C2 n C7, phenol v mt s hp cht polihidroxi. Phn ng to ra I2 lm mu dung dch chuyn sang nu.
RCH2OH 5HI HIO3 2HIO3 3I2 RCOOH 3H2O 3H2O 2HI
2.7. Oxi ha bng HIO4 Dng HClO4 oxi ha polialcol to thnh aldehyd
CH2OH(CHOH)n+1CH2OH nHIO4 2HCHO (n+1)HCOOH nHIO3 H2O
CH2
OH OH
Tm hng 2.8. Oxi ha bng KMnO4 (K2Cr2O7) L mu th dng phn bit alcol bc 1, bc 2 hay bc 3 da vo s thay i tc nhn phn ng. Nhn bit alcol: un nng vi dung dch KMnO4 (mi trng trung tnh H2O), mu tm ca dung dch mt i v xut hin kt ta en MnO2. Nhn bit alcol bc 1: Lc vi K2Cr2O7 (mi trng acid :H2SO4), dung dch t mu vng cam (Cr2O72-) chuyn sang mu xanh l cy (Cr3+) Alcol bc 1
3 R CH2 OH [O] [O]
Aldehyd
16H+
Acid
3 R COOH 4Cr3+ 11H2O
2Cr2O72-
(vng cam)
(xanh l cy)
Nhn bit alcol bc 2: Lc vi dung dch KMnO4 (mi trng acid :H2SO4), dung dch chuyn t mu tm (MnO4-) chuyn sang khng mu (Mn2+) Alcol bc 2
R' 5 R CH OH 2 MnO46 H+ [O]
Ceton
R' 5R C O 2 Mn2+ 8 H 2O
(tm)
(khng mu)
Nhn bit alcol bc 3: : Lc vi dung dch KMnO4 (mi trng base: NaOH), dung dch chuyn t mu tm (Mn2+) sang mu xanh (MnO42-) Alcol bc 3
[O]
Hn hp acid carboxylic
2.9. Mu th Lucas (ZnCl2 + HCl c) Dng phn bit cc alcol bc 1, 2, 3 da vo tc to alkyl clorua (sn phm phn lp) khc nhau: Alcol bc 3 phn ng nhanh, gn nh ngay lp tc
R' R C OH R
''
R' HCl
ZnCl2
R C Cl R''
H2O
R' R CH Cl H2O
Alcol bc 1 (tr anlyl alcol) i hi thi gian di, c th cn phi gia nhit.
R CH2 OH HCl
ZnCl2
R CH2 Cl
H 2O
Nu ch dng HCl c th ch c alcol bc 3 sau 5 20 pht. 2.10. Mu th ng (II) hidroxit Cc polialcol (c nhm OH gn vi cc C cnh nhau) to phc mu xanh lam vi thuc th Cu(OH)2 V d phn ng ca glycerol vi phc ng (II) hidroxit:
CH2 OH CH OH CH2 OH + Cu(OH)2 + HO CH2 HO HO CH CH2 CH2 O CH O CH2 OH Cu H O CH2 O CH H HO CH2 + H 2O
2.11. Mu th ng (II) axetat Dng nh tnh cc enol da trn s to phc rn mu xanh da tri hoc xanh nc bin Phn ng tm ngoi sch 2.12.Mu th acid boric
Dung dch hn hp ca mui borat v thuc th phenolphtalein c mu hng do s thy phn ca mui borat. Khi thm polialcol vo dung dch hn hp ni trn, polialcol to phc vi borat to thnh phc acid mnh hn acid boric, lm mt mu hng ca phenolphtalein. T ta pht hin c polialcol.
C OH C OH HO HO HO C HO C C O C O O C O C
B OH
H+
3H2O
2.13. Mu th st (III) clorua Pht hin phenol v enol da trn s to phc mu ca cc cht ny vi Fe3+
6ArOH FeCl3 [Fe(OAr)6]33H+ 3HCl
a s cc enol v mt s phenol khc cho phc mu . 2.14. Mu th acid nitr Dng nh tnh cc phenol c v tr octho v para t do nh xy ra phn ng Libecman (phn ng mu indophenol) cho mu t xanh da tri n ty vo hp cht cn nh tnh
OH
OH
+ HONO NO NO
H2O
H2SO4 + C6H5OH
OH
H2O
OH
OH
HSO4-
NaOH O- Na+
2.15. Mu th phtalein nh tnh cc phenol da vo s to co phtalic c mu dc trng, thng s dng bng anhidrit o-phtalic V d: xc nh cch phenol ngi ta thng dn alhidrit o-phtalic vi cc phn ng nh sau:
HO H H
+
O C O C O
C O
mu hng 2.16. Mu th tetrazoli C th s dng mui tetrazoli nh tnh poliphenol da vo s bin i mu ca dung dch thnh tm hoc xanh ty vo luoij mui tetrazoli c s dng. V d mui 2,5-diphenyl-3-o-tolyltetrazoli c nhy rt cao
R'' C N N N R 2H+ (Polyphenol) R'' C N N NH N R R' HX
3.1.1. Phng php axyl ha bng anhiric axetic - Trong piririn: Trong trng hp ny piriin va ng vai tr dung mi va lm vai tr xc tc
O O (CH 3CO)2O N N C O N C O
N
C CH3
CH3
CH3
CH3COO-
C O
CH3
ROH
ROCOCH3
H2O
CH3COO-
H+
CH3COOH
HClO4
O
NH4
ClO4
NH4
CH3 CH3
C C
O O
C O
CH3
CH3COOH
C O
CH3
ROH
ROCOCH3
H+
ClO4-
H+
HClO4
Phng php ny ng dng cho cc ancol bo bt 1, bc 2, glicol v c phenol. Trong etyl axetat v HClO4 lm xc tc:
O CH3 CH3 C C O O H+ CH3 CH3 C C O O CH3 C O CH3COOH O
CH3
C O
ROH
ROCOCH3
H+
Tc nhn oxy ha ny rt mnh cho php xc nh cc ancol bc mt, bc hai v phenol, k c cc ancol v phenol c n ng khng gian ln m cc
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phng trn khng cho php xc nh. Tuy nhin, nhc im ca cc tc nhn axyl ha dng axit pecloric lm xc tc km bn, thng phi chun b mi khi tin hnh chun b mi khi tin hnh phn tch andehit axetic v ancol atylic ko lm i mu qu tm Cc phng php trn y ngi ta xc nh lng anhiric axetic d bng cch cho thy phn v chun kim Thuc th : AgNO3/NH3 , phenolphthalein. Kim tra xem phn ng ca pridin vi ancol kt thc cha dng thuc th AgNO3/NH3 th anhiric axetic cho kt ta Ag cn ancol khng c . Chun kim nh lng axit axetic sinh ra. Nng ng lng axit sinh ra bng vi nng ng lng ca ancol do
N NaOH
3.1.2. Phng php axyl ha bng anhiric propionic Trong phng php ny lng d (C2H5CO)2O xc nh bng cch cho tac dng vi aniline v sau xc nh aniline d bng cch chun vi HClO4 trong mi trng axitaxetic. Phng php ny cho php xc nh ancol bc ba, cc poliancol (polihiroxipropilenglicol, polietilenglicol. Phng php xc nh lng thuc th d bng thy phn anhirit axit n axit v chun kim khng thch hp i vi cc ancol bc ba v cc poliancol (thng cho kt qu cao) do cc este chng d b thy phn. Phng php xc nh lng d anhirit axit nu trn trnh c nh hng ny 3.1.3. Phng php axyl ha bng anhiric trong piriin
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Anhiric phtalic este ha yu hn anhiric axetic v propinic nn phn ng i hi lu hn (1-2 gi 1000C). CO O CO COOR COOH
ROH
H2O
Lng thuc th d xc nh bng thy phn v chun kim.Trong mt s trng hp c th tch ring sn phm este axit v chun kim. Phng php ng dng xc nh ancol bc 1, bc 2, v glycol Phng php ny c u im so vi cc phng php axyl ha nu chhoox anhiric phtalic khng phn ng vi phenol nn c th xc nh ancol c mt trong phenol. Phng php axyl ha bng anhiric phtalic vi s ci tin cng c th ng dng xc nh cc ancol bc 3: R3COH + C2H5MgBr
R3COMgBr CO O CO
R3COMgBr
HCl
+ C2H6
COOR COOH MgBrCl
Sau tch sn phm este axit v chun kim. Axyl ha bng axitaxetic kt tinh vi xc tc BF3
BF3
CH3COOR [BF3OH]H
H2 O
Nh s to phc bn ny phn ng xy ra n cng v xc nh H2O to ra bng thuc th Fise: 2H2O + SO2 + I2 H2SO4 + 2HI
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im cui chun c xc nh bng phng php biampe hoc khi xut hin mu h phch. Phng php c ng dng cho cc ancol bc 1, bc 2, v c ancol bc 3. Cc phenol v ancol phn ng th yu. Tuy nhin ngi ta cho rng cc kt qu i khi thu c chnh xc i vi ancol bc ba khng phi bng phn ng este ha m bng qu trnh ehidrat hoa cng to ra mt phn t nc. 3.1.4. Phng php axyl ha bng 3,5- initrobenzoyl clorua
O2N COCl O2N ROH O2N O2N COOR HCl
Phn hy lng thuc th d bng dung dch NaOH. Sn phm este khng tan trong nc c tch v xc nh nhm NO2 bng chun vi TiCl3. Phng php ng dng cho ancol bc 1, bc 2 v glycol. Tin hnh th nghim: - Cn 0,5 gam cht kho st. - Thm d 3,5 ddinitrobenzylclorua hoc cloanhirit ca antra quinon- cacboxylic trong benzene hoc ete - 3 ml pirin, 24 h Xy ra s este ha (ru bc nht hoc bc hai). Este ha bc 3 cn phi un si 1 gi trong bnh lp sinh hn hi lu - Lc vi NaOH 50% - Dng axit HCl 1:1 ui thuc th d v anhiric i khi to thnh - Ct dung mi, kt tinh lai este bng t du ha. Este kh tan tinh ch bng NaOH sau kt tinh ta thu c phn cn.
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N acl no
mete s = M ete . a c l V no s
Lng thuc th d em thuy phn v chun kim (natri cacbonat vi ch th metyl da cam).
O O.SO3 H2O H2SO4 O O
Phng php c ng dng xc nh ancol bc 1, 2, 3, poliancol, ng. Lng HBr d c xc nh bng chun vi natri axetat trong axit axetic kt tinh v ch th tinh th tm.
N a ncol =
3.1.6. Phng php xc nh hiro linh ng Nguyn t hiro trong nhm hiroxyl kh linh ng, v vy xc nh n c th s dng phn ng vi thuc th Grinha ROH + CH3MgI CH4 + ROMgI
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ROH + LiAlH4
4 H2 + LiOR + Al(OR)3
Thu v o th tch to ra (CH4, H2) c th thu c hm lng ancol. Hm lng hiro hot ng (A%) trong ancol c tnh theo cng thc
3.2. POLIOL Ngoi cc phng php axyl ha, xc nh H linh ng, nhm OH glycol (nhm OH cnh nhau) cn c phng php xc nh c trng ring m cc monoancol v poliancol c cc nhm hyroxyl cch nhau mt hay nhiu nguyn t cacbon 1,3 dihiddroxixipropan, pentaerit C(CH2OH)4 khng c. l phng php oxi ha b gy bng axit peioic HIO4 (phn ng Malaprade) CH2OH (CHOH)n- CH2OH + (n+1) HIO4 (n+1)HIO3 + 2HCHO + HCOOH + H2O T phn ng trn ta thy sn phm oxi ha hai nhm CH2OH l hai phn t fomanehit v tiu tn Mt phn t axit peioic, cn i vi mi nhm CHOH th to thnh axit fomic v cng cn mt phn t axit peiodic; ng thi ta cng thy axit fomic c to ra khi phn t c nhiu hn hai nhm hiroxyl cnh nhau, th d glixerin cho mt phn t axit fomic
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Nu nguyn t H gn vi carbon c thay th bng cc gc th s to ra anehit khc, th d: CH3CHOH-CH2OH + HIO4 CH3CHOH-CHOHCH3 + HIO4 CH2OH-CHOH + HIO4 HIO3 + CH3CHO + HCHO + H2O HIO3 + 2CH3CHO + H2O + H2O HIO3 + HCHO + ROCH2CHO + H2O
Phn ng c tin hnh trong mi trng axit yu, trung tnh hoc kim yu nhit nhit phng. Sau phn ng ngi ta xc nh lng axit peioic (hoc peiopat) d, hoc lng anehit to thnh, cng nh axit fomic to thnh. 3.2.1. Xc nh HIO4 d 3.2.1.1. Phng php ioua-tiosunfat Khi phn ng kt thc, ngi ta thm KI v axit sunfuric vo hn hp phn ng . Khi iot thot ra t lnaxit axit peiodic d cng nh t lng axit ioic to ra phn ng : HIO4 + 7HI HIO3 + 5HI 4 I2 + 4H2O 3I2 + 3H2O
V c chun tiosunfat. Do vy, tnh hm poliol cn phi xc nh lng iot thot ra t m lng nht nh axit peiodic (peiodat) trc v sau phn ng oxi ha peiol 3.2.1.2. Phng php asenit Trong phng php ny ngi ta kh lng axit peiodic d bng natri asenit trong s c mt ca natri bicacbonat hoc hn hp m n iodat HIO4 + Na3AsO3 + NaHCO3 Na3AsO4 + NaIO3 + H2CO3
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Lng d asenit sau c chun ngc vi iot Na3AsO3 3.2.2. + I2 2HI + Na3AsO4 Xc nh fomanehit
a.1) Phng php th tch Hn hp sau khi thm KI v H2SO4 tr ph HIO4, HIO3 v chun lng iot thot ra bng natri asenit th chun fomanehit bng hipioit sinh ra thm NaOH v I2 vo hn hp phn ng: NaOH + I2 NaOH + HOI HCHO + 2NaOH a.2) Phng php so mu Thm Na2S vo hn hp sau khi oxi ha ph cht oxi ha, sau xc nh fomanehit bng phng php so mu vi axit cromotropic (dung dch cha anehit c un nng 10 pht nhit 600C vi axit cromotropic trong axit sunfuric 72% cho mu tm, v o mu bc sng 570nm) 3.2.3. Xc nh axit fomic - Trng hp s dng axit peioic lm tc nhn oxi ha ngi ta c th xc nh s nhm cacboxyl to thnh (s phn t axit fomic) bng cch chun kim vi ch th metyl (sau khi tr lng axit peioic cng c chun ): i vi glycol l glixerin 1, critrit 2, aonit 3, mannit 4 nhm - Trng hp s dng mui peioat lm tc nhn oxi ha th khng cn phi tr lng axit peioic 3.4. Phenol 3.4.1 Chun trong mi trng khng nc Do phenol c tnh acid yu nn chun trong mi trng nc s cho kt qu khng chnh xc. HOI + NaI H2 O NaOH +
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V d: trong mi trng baz (C2H5)4NOH c tnh baz tng i mnh s gip cho phenol th hin tnh acid r rng, quan st c bc nhy, do cho kt qu khch quan hn. C6H5OH + (C4H9)4NOH C6H5O-[C4H9)4N]+ + H2O
T phn ng: lng C6H5OH phn ng bng lng (C4H9)4NOH Xc nh nng C6H5OH: V (C4H9)4NOH x N(C4H9)4NOH N (C6H5OH) = V H OH) (C6 5 3.4.2. Phng php brom ha Phenol cha nhn thm vi nhm th loi mt nn tc nhn brom c th dng brom nguyn t trong hn hp bromua-bromat v acid clohidric, lng bromua ly d m bo kh ha hon ton bromat cng nh gi brom trong dung dch. V d: 5KBr + KbrO3 + 6HCl
OH Br + 4Br2 + H2O Br OH Br Br + HBr Br Br Br OH Br + Br2 (2)
(N)
(1)
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Lng brom d c xc nh bng phng php iot, thm KI vo hn hp sau phn ng v chun lng iot thot ra natri tiosunfat vi ch th h tinh bt. Br2 + KI I2 + Na2S2O3 T phn ng: Lng C6H5OH = lng Br2 phn ng (1) = lng Brom ban u - lng Br2 phn ng (3) = lng I2 phn ng (4) = lng Na2S2O3 phn ng (4)
V S O x NNa S O Na2 2 3 2 2 3 (N) N = C6H5OH V H OH C
6 5
I2 + KBr
(3) (4)
NaI + Na2S4O6
3.4.3. cc phng php so mu 3.4.3.1. phng php so mu bng phn ng ghp i (azo ha)
OH OH + H
ArN
NCl N N Ar
+ HCl
Phn ng ghp i xy ra v tr para nhanh, cn v tr octo xy ra chm . Cc phm mu azo thng c mu v o bc sng 500 nm khi dng tc nhn azo ha l p-nitroanilin iazo ha, ngoi ra c th s dng acid sunfanilic iazo lm tc nhn azo ha. Thng c mu v do bc sng 500nm.
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Thc hin th nghim: Ha tan cht kho st trong dung dch natri hydroxit 15%. Dng a thy tinh r mt vi git dung dch thu c ln giy lc. Cng bng cch vi git dung dch p-iazobenzensunfonic vo st cnh cc git trc cho cc dung dch thm c vo nhau. Da vo mu xut hin ch hai dung dch tip xc suy lun v s c mt ca nhm phenol.
OH
+ NaOH
ONa + H2O
ONa
ONa +
ArN
NCl N N Ar
+ HCl
S dng thuc th: acid p-iazobenzensunfonic. iu ch dung dch ca hp cht diazo t 0.1 gam acid sunfanilic trong 5ml nc v 0.5 ml natri nitrit 10% trong nc 3.4.3.2. To phm mu antipirin Trng hp tin hnh phn ng trong nc th o mu bc sng 510 nm khng chm hn 30 pht, nhng nu chit phm mu vo CHCl3 th nhy hn v bn hn (3 gi cha b thay i) v o mu bc sng 460 nm. Trong mi trng kim yu khi c mt kali ferixyanua to thnh mu . V d: Vi phenol th rt nhy, nng xc nh ti thiu l 2.10-4%
H3C H3C N N C6H5 C NH2 O
+
OH
N O
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S dng thuc th: Dung dch 4-aminoantipyrin 2% trong nc, dung dch amoniac 2N, dung dch kali ferixyanua 2%. Thc hin th nghim: Thm 0.3 ml dung dch 4-aminoantipyrin v 1ml dung dch amoniac vo 50 ml dung dch cha phenol c trung ha trc. Sau kho trn u, thm 1ml dung dch kali ferixyanua ri lc mnh. So snh mu thu c vi mu thang chun c chun bi tng t. 3.4.3.3. To phm mu indophenol Khi trn 0.5 gam cht kho st vi mt git anilin, 5 ml nc v 2 ml dung dch clorua vi th lc u s xut hin mu tm bn, sau khi thm nc amoniac vo th dung dch chuyn thnh mu xanh chm. V d: vi monophenol phn ng xy ra nh sau
X O X NCl + OH pH = 9,1: 9,5 HCl O X X N OH
S dng thuc th: Borac, dung dch 19.1 gam borac trong 1 lt nc (pH = 9.4), ru pha long, N-clorimin-2,6-icloquinon. Qu trnh th nghim tin hnh nh sau: thm vi git N-clorimin-2,6icloquinon vo 10-15 ml dung dch gm 1-2 phn trng lng phenol kho st trong 1000 phn trng lng nc hoc ru pha long. Lc dung dch xut hin mu xanh xm ca idophenol, c bit sau khi thm mt vi git dung dch borac. 3.4.3.4. To hp cht nitrozo
+ H2O
OH
RC6H3
O NH4OH/ ruou
RC H 6 3
+ H+
NO
N O
Phn ng i hi 35 50 pht, sau kho thm NH4OH/ ru vo 1 gi hoc lu hn v o mu bc sng 420 nm. 3.4.4. phng php sc k 3.4.4.1. Sc k kh Cc phenol bay hi c th xc nh bng sc k kh trc tip. V d: tch hn hp phenol, cresol cng nh cc dn xut th ca phenol c th s dng ct tch mao qun thy tinh chu nhit PTE - 5QTM cha pha tnh l poli (5% diphenyl/ 95% diphenylsiloxan) di 15 m x 0.53 mm (ng knh trong) vi chiu di mng pha tnh 0,5 um ; chng trnh nhit ct 650 n 1800 vi tc nng nhit 100C/pht, gi 5 pht; kh mang He; tect FID 3000C; lng bm mu 1 ul theo ch khng chia dng. Kt qu thu c sc k vi th t nh sau: phenol, 2-clophenol, 3metylphenol, 3-bromphenol, 3-metylphenol, 2-nitrophenol, 2,4-dimetylphenol, 2,4-diclophenol, 4-clo-3-metylphenol, 2,4,6-triclophenol, 4-nitrophenol, 2,3,4,6-tetraclophenol. 3.4.4.2. Sc k lng cao p V d: tch hn hp phenol, xilenol,cng nh dn xut th clo v nitrocuar phenol c th s dng ct tch SUPECOSIL LC8 di 15 cm x 4.6 mm vi iu kin sc k sau: pha ng 1% acid acetic/metanol: 1% acid acetic/H2O, chy theo ch garien 35 : 65 n 100 : 0 (20 pht), ri i ngc li
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35 : 65 (20 pht ); tc dng 1,5 mm/pht; nhit ct: 300C, tect: UV, 280 nm. Kt qu c sc k nh sau: phenol, 2-ntrophenol, 2,4-dinitrophenol, 2nitrophenol, o-clophenol, 4,6-dinitrophenol, 2,4-dimetylphenol, 4-clo-3metylphenol, 2,4-diclophenol, 2,4,6-triclophenol, pentaclophenol. 3.4.5. Phng php vt l Nhm OH khng hp th trong vng t ngoi, tuy nhin phenol c th c xc nh bng phng php t ngoi o trc tip. S hp th phenol trong vng t ngoi tun theo nh lut hp th LambertBeer Nhm OH hp th mnh trong vng hng ngoi V d: o phenol trong dung mi CCL4 , di sng 2.7-2.84 um 3.5. Enol 3.5.1. Chun bng brom. Phng php nh lng enol da trn kh nng phn ng tc thi ca enol vi dung dch brom trong ancol: C O 3.5.1.1. Chun gin tip p dng cho cc enol cn bng trong h xeto-enol Nguyn tc: trn dung dch cha hn hp xeto-enol lm lnh xung 00C vi mt lng dung dch brom trong methanol ly hi d, sau lp tc ui brom d bng dung dch b-naphtol trong ancol. Kh dn xut c brom ha c CH Br 2 C O CH Br + HBr
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enol bng cch un nng nh bng dung dch natri ioua trong ancol v chun lng iot thot ra bng dung dch tiosunfat: V d:
C O
C O CH Br 2HI 2
CH
Br2
C O
C O
CH Br
CH2
+ HBr
I2
Thuc th: Brom : Dung dch 30 gam brom trong 1 lt ru metylic Dung dch natri iodua 20% Ru etylic Dung dch 15 gam b-naphtol trong 100 ml ru Dung dch natri tiosunfat 0.1N Tin hnh th nghim: Trn trc tip khong 0.3-0.6g cht kho st vi 30 ml dung dch brom c lm lnh ti -100C. Lc hn hp mt lc v loi ngy brom d bng cch thm vo vi mililit dung dch b-naphtaol. 10-15 ml dung dch natri iodua 20%, hn hp trn ni cch thy nng 350c trong 10 pht, ri lm ngui ngay bng nc ti nhit phng v chun iot thot ra bng dung dch natri sunfat 0.1N ti mt mu iot (khng cn thm cht ch th) Khi hm lng ca enol c xc nh theo cng thc:
E=
VxM 2 x a x 100
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a: lng cn (g) M : Trng lng phn t 3.5.1.2. Chun trc tip Ch p dng cho cc enol t do Ngi ta s dng dung dch brom trong metanol bo ha natri bromua trnh s bay hi ca brom lm thay i chun ca dung dch brom trong ancol. Hin tng: tin hnh phn ng ti khi xut hin mu ca brom bn trong 15-30 giy. V d: Vi thuc th dung dch brom 0.1N trong ru, ru, dung dch natri tiosunfat 0.1N. Tin hnh phn ng: u tin, iu ch dung dch brom tron ru c nng khong 0.1N v xc nh chun ca n bng dung dch natri tiosunfat 0.1N. Sau nhanh chng chun dung dch cha 1-2g hn hp xeto-enol trong ru lnh (00C) bng dung dch brom ti xut hin mu brom bn trong 15-30 giy. Ngay sau khi kt thc chun kim tra li chun ca dung dch brom. C O CH Br2 C O CH Br + HBr
Xc nh nng : Lng enol tham gia phn ng bng lng brom tham gia phn ng. Nenol = N Br x VBr 2 2 Venol
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3.5.1.3. Chun khng nc Cc enol th hin tnh acid r nn c th chun chung trong mi trng khng nc:
RCH C OH CH3 + CH3ONa RCH C ONa CH3 + CH3OH
Ch thi c dng l timolphtalein Xc nh nng : Lng enol tham gia phn ng bng lng natri menolat tham gia phn ng.
Nenol = NCH ONa x V ONa CH3 3 Venol
3.5.2. Phng php so mu Cc ng phn cis-enol (ca hp cht b-icacbonyl) c kh nng to phc chelat (phc vng cng) cho cc mu c trng: vng, , chm, tm, i khi mu lc. Da vo c th xc nh cc hp cht cis-enol:
R'' C R" R C C COR OH R' R C C O O H
FeCl3 C C R O O FeCl3
+
R'
HCl
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3.5.3. Phng php vt l C th xc nh chnh xc hm lng enol da vo s hp th trong vng t ngoi nh s c mt trong h lin hp n-pi trong phn t nu nh bit ph ca dng cuae enol tinh khit. Cng c th dng ph hng ngoi nh lng enol. c bit cc nhm enol to c vng cng ni phn t (cis-enol) th quan st c nhng dch tn s ca nhm hydroxyl rt c trng. IV. KT LUN Nu pht hin c cc nhm hyroxyl bng cc phn ng ni trn th thng sau ngi ta xc nh s cc nhm hyroxyl theo phng php iu ch xc este tng ng . Tt nht nn %hm lng cc nhm hyroxyl theo kt qu chun lng kim d sau khi x phng ha dn xut axyl trong bnh x phng ha. Cng c th, sau khi thy phn cc gc axetyl v benzoyl, ct cc axit bng li cun hi nc v chun lng axit . Vic xc nh hyro hot ng rt c li cho s nh lng cc nhm hiro-xyl. Cn khng nh trc trong trng hp ny khng cha cc nhm l cht kho st khng cha cc nhm khc c cha nguyn t hyro hot ng. Xc nh nhm hyeroxyl bng cch iu ch cc dn xut th tng ng . Thun li l cc dn xut th cha halogen, nitow, lu hunh, . Trong nhu trng hp c th xc nh hm lng nhm hyroxyl theo kt qu phn tch cc nguyn t cc cht . Vic xc nh s nhm hyroxyl trong cc hp cht ch cha cacbon, hiro v oxi da vo kt qu phn tch cc nguyn t cc este ca axit axetic v benzoic (ngha l theo hm lng cacbon v hiro) l hon ton thiu tin cy, v s khc nhau gia hm lng ca cacbon (%) trong cc mono-, i-, v polyester rt nh. C th thy iu trong cc viduj di y. Cc dn sut th mono-, i-, v triaxyl ca trioxibenzen C6H3(OH)3 u c cng thc chung
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(C2H2O)n v c cng thnh phn (%), nhng hm lng nhm axetyl khc nhau .
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