CHUYN 3: DN XUT HALOGEN - ANCOL PHENOL

A. KIN THC TRNG TM DN XUT HALOGEN

I. KHI NIM, PHN LOI, NG PHN V DANH PHP 1. Khi nim v phn loi Khi thay th nguyn t hidro ca phn t hidrocacbon bng nguyn t halogen ta c dn xut halogen Bc ca dn xut halogen: chnh l bc ca nguyn t C lin kt trc tip vi halogen X. Ty thuc vo gc hidrocacbon m ngi ta chia dn xut halogen thnh dn xut no, khng no v thm. Ty thuc vo kh nng tham gia phn ng th halogen (X) bng nhm OH, ngi ta phn lm 3 loi chnh:
Dn xut ankyl halogen:

CH3Cl, C2H5Cl, CH2Cl2, .....

( Nhm 1) (Nhm 2) ( Nhm 3)

Dn xut anlyl halogen, benzyl halogen:

CH = CH CH2Cl, C6H5 CH2Cl, CH3 CH =CH CH2Cl, .....

Dn xut vinyl halogen, phenyl halogen:

CH2 = CH Cl, C6H5 Cl, CH3 CH = CH Cl, ..... 2. ng phn Dn xut halogen c ng phn cu to (ng phn mch C v ng phn v tr halogen) v c th c ng phn hnh hc. 3. Danh php Tn thng: CHCl3: Clorofom Tn gc + chc: CH2 = CH Cl: Vinyl clorua CH2 = CH CH2-Cl: Anlyl clorua C6H5 CH2 Cl: Benzyl clorua C6H5 Cl: Phenyl clorua Tn thay th (IUPAC): Tn thay th ca dn xut halogen gi theo hyrocacbon tng ng (coi halogen nh mt nhnh) Ch : Khi trn mnh chnh va c dn xut halogen va c lin kt pi th nh s th t C trn mch chnh u tin lin kt pi, sao cho v tr C c lin kt pi l nh nht) II. TNH CHT VT L iu kin thng, cc dn xut halogen c phn t khi nh nh CH3F, CH3Cl, CH3Br l nhng cht kh. Cc dn xut halogen c phn t khi ln hn thng th lng, nng hn nc. Cc dn xut halogen hu nh khng tan trong nc, tan tt trong dung mi khng phn cc nh hirocacbon, ete, ... Nhiu dn xut halogen c hot tnh sinh hc cao, chng hn nh CHCl3 c tc dng gy m, C6H6Cl6 c tc dng dit su b, ... Trang 1 CHBr3: Bromofom CHI3: Iodofom

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III. TNH CHT HA HC 1. Phn ng th nguyn t halogen bng nhm OH Phn ng vi H2O nng
Dn xut nhm 1 v 3 khng phn ng vi H2O mi nhit

Dn xut nhm 2 phn ng vi H2O khi ung nng

t CH2= CH CH2 Cl + H2O CH2 = CH CH2-OH + HCl
0

Anlyl Clorua
t C6H5 CH2 Cl + H2O C6H5 CH2 OH
0

+ HCl

Benzyl Clorua Phn ng vi dung dch kim

Dn xut nhm 1 v 2 tc dng c vi dung dch kim long nng. Trong nhm 2
phn ng d dng hn nhm 1.
t RX + NaOH ROH + NaX t CH3CH2Br + NaOH CH3CH2OH + NaBr t CH2 = CH CH2 Cl + NaOH CH2 = CH CH2 OH
0 0 0

+ NaCl

Dn xut nhm 3 khng phn ng th vi dung dch kim k c khi un nng 2. Phn ng tch hirohalogenua PTTQ: (i vi dn xut halogen no, n chc, mch h)
C2 H5OH CnH2n+1X + KOH CnH2n + t0

KX + H2O

C2 H5OH CH3 CH2Cl + KOH CH2 = CH2 + KCl + H2O t0

Ch : Quy tc Zaixep: Khi tch HX ca dn xut halogen th u tin tch X vi nguyn t H C bn cnh bc cao hn lm sn phm chnh Khi tch HX ca dn xut halogen thu c 1 anken duy nht (khng tnh ng phn hnh hc) th dn xut halogen l no, bc 1 hoc i xng. 3. Phn ng vi kim loi Mg (mi trng ete khan)
t RX + Mg R Mg X
0

Kh nng phn ng: RI > RBr > RCl

CO2 Ch : R Mg X + R COO Mg X HCl R COOH + MgXCl

ANCOL
I. KHI NIM V PHN LOI 1. Khi nim Ancol l nhng hp cht hu c trong phn t c nhm OH lin kt trc tip vi nguyn t C no. CT chung: CnH2n + 2 - 2k - x(OH)x hoc R(OH)x (Trong k l s lk pi + s vng, x n )

Khi k = 0 ta c ancol no: CnH2n + 2

- x(OH)x

hay CnH2n + 2 Ox hoc R(OH)x hay hoc ROH

Khi x = 1 ta c ancol n chc: CnH2n + 2

- 2kOH

Khi k = 0 v x = 1 ta c ancol no n chc: CnH2n + 1OH hay CnH2n + 2O hoc ROH

Bc ancol l bc ca nguyn t C lin kt trc tip vi nhm OH. Th d: Trang 2

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CH3 CH2 CH2 CH2OH: CH3 CH2 CH(CH3) OH: CH3 C(CH3)2 OH: 2. Phn loi

ancol bc I ancol bc II ancol bc III

ru l s ml ru nguyn cht c trong 100 ml dung dich ru. Ancol no, n chc, mch h (CnH2n+1OH): V d: CH3OH . . . Ancol khng no, n chc mch h: CH2 = CH CH2OH Ancol thm n chc: C6H5 CH2OH Ancol vng no, n chc: OH xiclohexan Ancol a chc: CH2OH-CH2OH (etilen glicol), CH2OH-CHOH-CH2OH (glixerol) 3. Mt s trng hp khng bn ca Ancol Ancol dng: R CH = CH OH (ancol bc 1 c OH lin kt vi C khng no) R CH = CH OH R CH2CHO (anehit) Ancol dng: R CH2 CH(OH)2 (ancol c 2 nhm OH lin kt vi 1 C ngoi cng) R CH2 CH(OH)2 R CH2 CHO (anehit) + H2O Ancol dng: R CH = C(OH) R (ancol bc 2 c OH lin kt vi C khng no pha trong) R CH = C(OH) R R CH2 CO R(xeton) Ancol dng: R CH2 C(OH)2 R (ancol c 2 nhm OH lin kt vi 1 C pha trong) R CH2 C(OH)2 R R CH2 CO R(xeton) + H2O Ancol dng: R CH2 CH(OH)3 (ancol c 3 nhm OH lin kt vi 1 C) R CH2 CH(OH)3 R CH2COOH (axit) + H2O II. NG PHN V DANH PHP 1. ng phn: Ch c ng phn cu to (gm ng phn mch C v ng phn v tr nhm OH). Th d C4H10O c 4 ng phn ancol CH3 CH2 CH2 CH2 OH; CH3 CH(CH3) CH2 OH CH3 CH2 CH(CH3) OH; 2. Danh php: Danh php thng: Ancol + tn gc + ic Danh php thay th (IUPAC): V tr nhnh + tn nhnh (nu c) + tn H.C tng ng + v tr OH + ol
4 3 2 1

CH3 C(CH3)2 OH Th d: C2H5OH (ancol etylic)

Th d: C H 3 C H(CH 3 ) C H 2 C H 2OH (3-metylbutan-1-ol) III. TNH CHT 1. Tnh cht vt l Tan nhiu trong nc do to c lin kt H vi nc. tan trong nc gim dn khi s nguyn t C tng ln. Ancol c kh nng to lin kt hiro vi phn t ancol khc v vi H2O nn n c nhit si cao hn so vi hidrocacbon, dn xut halogen, ete, andehit, xeton v c este. 2. Tnh cht ha hc a. Phn ng vi kim loi kim 2R(OH)x + 2xNa 2R(ONa)x + xH2 Trang 3

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Mui R(ONa)x d phn ng vi H2O ti to li ancol R(ONa)x + xH2O R(OH)x + xNaOH b. Phn ng vi dung dch axit ( phn ng este ha) Phn ng vi axit v c C2H5 OH +
t H Br C2H5Br + H2O
0

Phn ng vi axit hu c
t R OH + R COOH R COO R + H2O
0

c. Phn ng tch nc Tch H2O ca 1 phn t ru no n chc 1700C xc tc H2SO4 c nng. to thnh anken:
H 2SO4 , 170 C CnH2n+1OH CnH2n + H2O
0

Tch H2O ca 2 phn t ru no n chc 1400C xc tc H2SO4 c nng to thnh ete

H 2SO4 , 140 C 2ROH R-O-R + H2O
0

Ch : Di tc dng ca cht ht nc mnh nh KHSO4, etilenglicol v glixerol b mt nc to thnh axetanehit v propenal

4 CH2(OH) CH2(OH) KHSO CH3CHO + H2O 4 CH2(OH) CH(OH) CH2(OH) KHSO CH2 = CH CHO + H2O

d. Phn ng oxi ha Oxi ha khng hon ton

Ancol bc 1 khi b oxi ha bi CuO/to cho ra sn phm l andehit

t R CH2OH + CuO RCHO + Cu +
0

H2O

Ancol bc hai khi b oxi ha bi CuO/t cho ra sn phm l xeton.

t R CH(OH) R + CuO R CO R + Cu + H2O
0

Ancol bc III kh b oxi ha bi CuO/to

Oxi ha hon ton CnH2n+1OH +
3n t0 O2 nCO2 + (n+1)H2O 2

e. Tnh cht c trng ca ancol a chc c t hai nhm OH lin k tr ln

Ha tan c Cu(OH)2 iu kin thng to thnh dung dch mu xanh lam. Phn ng ny dng nhn bit ancol a chc c t hai nhm OH tr ln lin k nhau.
CH2 OH CH2 OH HO CH2 HO CH2 CH2 OH HO CH2 CH2 OH HO CH2 CH OH + Cu(OH)2 + HO CH CH O Cu O CH + 2H2 O

IV. NG DNG V IU CH 1. ng dng

t Sn xut caosubuna: 2C2H5OH C4H6 + H2 + 2H2O. Trng hp C4H6 ta c caosubuna
0

Ln men gim: C2H5OH + O2 CH3COOH + H2O

m gi '

2. iu ch
iu ch t anken tng ng:
H 2SO4 , t CnH2n + H2O CnH2n+1OH
0

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 Thy phn dn xut halogen ca hydrocacbon no trong mi trng kim

t CnH2n + 1 X + NaOH CnH2n + 1 OH + NaX
0

Cng H2 vo anehit hoc xeton iu ch C2H5OH t tinh bt, xenluloz

+H 2 O (C6H10O5)n C6H12O6 t 0 , xt
enzim C6H12O6 2C2H5OH + 2CO2

iu ch etilen glicol t etilen 3C2H4 + 2 KMnO4 + 4H2O 3C2H4(OH)2 + 2MnO2en +2KOH iu ch glixerol i t anken tng ng l CH2=CH CH3 hoc thy phn lipit
t CH2 = CH CH3 + Cl2 CH2 = CH CH2Cl
0

CH2 = CH CH2Cl + Cl2 + H2O CH2Cl CH(OH) CH2Cl + HCl CH2Cl CH(OH) CH2Cl + 2NaOH CH2(OH) CH(OH) CH2(OH) + 2NaCl Glixerol
t T CH4: 2CH4 + O2 2CH3OH , 200 atm , 400 C T CO: CO + 2H2 Zn CH3OH
o

V. GII TON ANCOL 1. Phn ng vi kim loi kim.

2R(OH)x + 2xNa 2R(ONa)x + xH2 Mui R(ONa)x d phn ng vi H2O ti to li ancol R(ONa)x + xH2O R(OH)x + xNaOH Ancol + kim loi kim: da vo t l: n Ancol : n H 2 ta suy ra s nhm chc OH Khi ni ancol + kim loi kim d ch xy ra phn ng gia ancol v kim loi nhng khi ni dung dch ancol (c ru) phn ng vi kim loi kim d th c thm phn ng gia H2O vi kim loi kim. Bo ton khi lng:

m Ancol + m Na = m R 'n + m H 2

V d 1: Cho 1 lt cn 92o tc dng vi Na d. Cho khi lng ring ca ru etylic nguyn cht l 0,8 g/ml. th tch kh H2 c ktc l
A. 224,24 lt B. 224 lt C. 280 lt D. 228,98 lt

Li gii:
1 lt cn 92o cha 920 ml C2H5OH v 80 ml nc S mol C2H5OH l S mol H2O l PTP: C2H5OH + Na C2H5ONa + 16 mol H2O + Na 1 H 2 2 8 mol

920.0,8 = 16 mol 46

80 = 4,444 mol 18

NaOH

1 H 2 2 Trang 5

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4,444 mol

2,222 mol

Th tch kh H2 thu c (ktc) : (8 + 2,222). 22,4 = 228,98 lt

p n D

V d 2: Cho 15,6 gam hn hp hai ancol (ru) n chc, k tip nhau trong dy ng ng tc dng ht vi 9,2 gam Na, thu c 24,5 gam cht rn. Hai ancol l
A. CH3OH v C2H5OH C. C2H5OH v C3H7OH B. C3H7OH v C4H9OH D. C3H5OH v C4H7OH

Li gii: t cng thc phn t chung ca 2 ancol l R OH

Ta c

R OH + Na R ONa + 1/2 H2

BTKL mHiro = 24,5 (15,6 + 9,2) = 0,3 gam nHiro = 0,15 mol

n ROH = 0,3 mol M ROH = R + 17 =

15,6 = 52 R = 35 0,3

hai ancol l: C2H5OH (M = 46) v C3H7OH (M = 60) V d 3: Cho 18,0 g hn hp hai ancol gm mt ancol no n chc v mt ancol n chc c mt lin kt i trong phn t c s mol bng nhau tc dng ht vi Na thu c 4,48 lt H2 ktc. Xc nh CTCT hai ancol. Li gii: t CTPT chung ca hai ancol l R OH.
Ta c: 2 R OH + 2Na 2 R ONa + H2

S mol hn hp ancol = 2nHiro = 2.

4, 48 = 0, 4 mol 22, 4

M = 18 = 45 c 1 ancol c phn t khi nh hn 45 Hai ancol l CH3OH: 0,02 mol

0, 4

ROH: 0,02 mol

mAncol = 32*0,02 + (R + 17)*0,02 = 18 R = 41 CTCT CH2=CHCH2OH 2. Phn ng tch nc

Tch H2O ca 1 phn t ru no n chc 1700C xc tc H2SO4 c nng. to thnh Anken
H 2SO 4 , 170 C tng ng: CnH2n+1OH CnH2n + H2O
0

Khi tch H2O ca Ancol 1700C xc tc H2SO4 thu c An ken Ancol no, n chc.

Nu ch thu c 1 anken duy nht Ancol no, n chc l Ancol bc 1 hoc i xng.

m Ancol = m Anken + m H 2O

( Bo ton khi lng)

n Ancol ( p / u ') = n Anken = n H 2O ( Bo ton nguyn t)

nCO2 ( 't A) = nCO2 ( 't B )

0

Tch H2O ca 2 phn t ru 1400C xc tc H2SO4 c nng to thnh ete

H 2SO 4 , 140 C 2ROH R-O-R

H2O k(k + 1) 2

Khi tch H2O ca k phn t ancol khc nhau 1400C xc tc H2SO4 c s to ra

phn t ete, trong c k ete i xng.

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 mAncol = mete + mH20 (Bo ton khi lng)

nete= nH20 = nAncol phn ng (Bo ton nguyn t)

V d 1: Khi thc hin phn ng tch nc i vi ru (ancol) X, ch thu c mt anken duy nht. Oxi ho hon ton mt lng cht X thu c 5,6 lt CO2 ( ktc) v 5,4 gam nc. Xc nh CTPT, cc CTCT c th c ca X Li gii:
Loi nc thu c anken nn X l ancol no, n chc: CnH2n+2O Theo : S mol CO2 l 5,6 : 22,4 = 0,25 mol S mol H2O l 5,4 : 18 = 0,3 mol

S mol ancol = 0,05 mol n = 5. Vy CTPT X l C5H12O

X c 4 CTCT ph hp: CH3 CH2 CH2 CH2 CH2OH CH3 CH(CH3) CH2 CH2OH CH3 CH2 CHOH CH2 CH3 CH3 CH2 CH(CH3) CH2OH

V d 2: un nng 12,90 gam hn hp X gm 2 ancol no, n chc, bc 1, l ng ng k tip trong H2SO4 c 140oC thu c 10,65 gam hn hp Y gm 3 ete (h = 100%). Xc nh cng thc phn t ca hai ancol. Li gii:

t CT ca hai ancol l R OH
BTKL mnc = mancol - mete = 12,9 - 10,65 = 2,25 (gam) nnc = 0,125 mol 129 = 516 hai ancol l: C2H5OH v C3H7OH 025

nancol = 2nnc = 0,25 (mol) M

ancol

V d 3: Cho hn hp hai anken ng ng k tip nhau tc dng vi nc (c H2SO4 lm xc tc) thu c hn hp Z gm hai ru (ancol) X v Y. t chy hon ton 1,06 gam hn hp Z sau hp th ton b sn phm chy vo 2 lt dung dch NaOH 0,1M thu c dung dch T trong nng ca NaOH bng 0,05M. Xc nh Cng thc cu to thu gn ca X v Y Li gii:
Ta c: nNaOH ban u = 0,2 mol; nNaOH d = 0,1 mol nNaOH p/ = 0,1 mol CO2 + 2 NaOH Na2CO3 + H2O 0,05

0,1

Theo X, Y l sn phm cng nc vo anken ng ng k tip nn X, Y l ancol no n chc, ng ng k tip: Cn H 2 n + 2O :

Cn H 2 n + 2 O +

3n O2 n CO2 + ( n +1) H2O 2

1,06

Ta c n Ancol =

14 n + 18

1 0,05 1, 06.n .nCO2 = _ = 0,05 n = 2,5 18 + 14.n n n

Cng thc ca X, Y l C2H5OH v C3H7OH 3. Phn ng oxi ha

Oxi ha khng hon ton: CnH2n + 1 OH + CuO CnH2n O + Cu + H2O

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Xt ancol no n chc ta lun c: nO (trong CuO) = nancol = nanehit hoc xeton =

Oxi ha hon ton: CnH2n+1OH + 3n t0 O2 nCO2 + (n+1)H2O 2

mCuO mCu 16

Khi t chy ancol X nu thu c nCO2 < n H 2O

Ancol X no, mch h: C n H 2 n + 2 O x v n X = n H 2O nCO2

t chy hp cht hu c X gm C, H, O thu c CO2 v H2O. Nu t l nO2 = 1,5.nCO2

CTPT X dng: CnH2n + 2O (ete hoc ancol no, n chc h)

V d: Cho m gam mt ancol (ru) no, n chc X qua bnh ng CuO (d), nung nng. Sau khi phn ng hon ton, khi lng cht rn trong bnh gim 0,32 gam. Hn hp hi thu c c t khi i vi hiro l 15,5. Gi tr ca m l A. 0,92 Li gii:
Gi CTPT ca ru CnH2n+1OH:
o

B. 0,46 x mol

C. 0,32

D. 0,64

t Phn ng: CnH2n+1OH + CuO CnH2nO + Cu + H2O

mcht rn gim = mCuO mCu = 16x = 0,32 x = 0,02 mol

Y M .1 + 18.1 Hn hp hi: c t khi so vi H2 l 15,5 nn ta c: Y = 15,5.2 M Y = 44 1+1 H 2O
Mancol = 44 + 2 = 46 m = 46.0,02 = 0,92 gam 4. Ln men tinh bt, xenluloz V d 1: T mt tn khoai cha 20% tinh bt, bng phng php ln men ngi ta iu ch c 100 lt ru etylic tuyt i c khi lng ring l 0,8 g/ml. Tnh hiu sut ca qu trnh phn ng Li gii:
nH 2O ,t S qu trnh iu ch: (C 6 H 10 O5 ) n + nC 6 H 12 O6 xt 2nC 2 H 5 OH + 2nCO2
o

Khi lng tinh bt:

20 .106 = 2. 105 gam 100 2.105 .n.2.46 = 113580. 24 g 162n 100.0,8.1000 .100 = 70% 113580, 24

khi lng ru etylic thu c l: Hiu sut ca qu trnh sn xut l:

V d 2: Cho m gam tinh bt ln men thnh ancol (ru) etylic vi hiu sut 81%. Ton b lng CO2 sinh ra c hp th hon ton vo dung dch Ca(OH)2 thu c 550 gam kt ta v dung dch X. un k dung dch X thu thm c 100 gam kt ta. Gi tr ca m l: A. 650 Li gii:
nH 2O ,t p / u ': (C 6 H 10 O5 ) n + nC 6 H 12 O6 xt 2nC 2 H 5 OH + 2nCO2
o

B. 550

C. 810

D. 750

CaCO3 : 5,5 mol Ca ( OH ) 2 CO2 + xt ,t o CaCO3 (1 mol ) + CO2 + H 2 O Ca ( HCO3 ) 2

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nCO2 = 7,5mol nTb =

7,5 162n.7,5.100 m= = 750 gam / a ' D 2n 2n.81

PHENOL
I. KHI NIM
Phenol l nhng hp cht hu c trong phn t c nhm OH lin kt trc tip vi nguyn t C vng benzen. CnH2n 7 OH ( n 6 ). Th d: C6H5OH (phenol), ...
Phenol cn gi l axit phenic, l mt axit yu (yu hn c H2CO3), khng lm qu tm i mu Khi nhm OH khng nh nhn m nh nhnh th hp cht khng thuc loi phenol m l ancol thm. Th d: C7H8O
CH2OH OH CH3 CH3 OH O

4 - metyl phenol P - metyl phenol P crezol

d
CH3

Ancol benzylic Khi nhm OH lin kt vi C ni i (chc axit) gi l enol

II. TNH CHT VT L

Phenol l nhng cht rn khng tan trong nc lnh nhng tan tt trong nc nng, etanol, ete, axeton... Trong qu trnh bo qun, phenol thng b chy ra v thm mu dn do ht m v b oxi ha bi oxi khng kh. Phenol c, khi tip xc vi da gy bng. Cc phenol l cht rn c nhit si cao do c lin kt hiro lin phn t tng t ancol.

III. TNH CHT HA HC 1. Phn ng th nguyn t H ca nhm OH

Tc dng vi kim loi kim to thnh mui phenolat 2C6H5OH + 2Na 2C6H5ONa + H2 Natri phenlot Tc dng vi dung dch baz (do nh hng ca nhn) C6H5OH + NaOH C6H5ONa + H2O Natri phenlot

Ch : Mui Phenolat gp axit d ti to li phenol

C6H5ONa + CO2 + H2O C6H5OH C6H5ONa + HCl C6H5OH + NaCl + NaHCO3

2. Phn ng th H ca vng benzen

Tc dng vi dung dch brom to kt ta trng (2,4,6 tribrom phenol (do nh hng ca nhm OH). Phn ng ny dng nhn bit phenol C6H5OH C6H5OH + 3Br2 C6H2Br3OH + 3HBr + 3HO- NO2 C6H2OH(NO2)3 + 3H2O Tc dng vi dung dch axit HO- NO2 to dung dich axit picric ( 2,4,6 trinitro phenol)

III. NG DNG V IU CH
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 ng dng:
Phn ln phenol c dng sn xut poliphenolfomanehit (PPF: dng lm cht do, cht kt dnh) Phenol c dng iu ch dc phm, phm nhum, thuc n (2,4,6 trinitrophenol), cht kch thch sinh trng thc vt, cht dit c 2,4 D (axit 2,4 iclophenoxiaxetic), cht dit nm mc (nitrophenol), cht tr su b, ...

iu ch: iu ch phenol ta c s sau:

C6H6 C6H5Cl C6H5ONa C6H5OH
= CH CH 3 ) O2 ( kk ); 2 ) H 2 SO4 Hoc C6H6 CH 2 C6H5CH(CH3)2 1 C6H5OH + CH3 CO CH3

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