giáo trình Bài giảng Phenol

PHENOL -OH liờn kt trc tip vi nhõn thm o 1,36A 109 o Danh phỏp OH OH -Naptol Phenol Nhng hp cht khỏc c gi nh dn xut ca phenol hay naptol OH Cl OH o-clorophenol CH3 m-metil phenol (m-cresol) OH OH OH OH CH3 CH3 phenol o-cresol CH3 m-cresol p-cresol OH OH OH OH OH Tờn thụng thng O2N NO2 OH OH catechol resorcinol OH hydroquinone OH OCH3 NO2 OH picric acid OH CH(CH3)2 H3C CH2CH CH2 eugenol Thymol -naphthol -naphthol Tờn IUPAC OH OH OH CH3 Cl Br OCH3 4-methoxyphenol Cl 3-bromo-4-chlorophenol 5-chloro-2-methylphenol OH OH OH OH OH 1,2-benzenediol 1,3-benzenediol OH 1,4-benzenediol Lý tớnh So sỏnh lý tớnh ca phenol v ciclohexanol Phenol 43oC 181oC 9,3 - núng chy - sụi - Tớnh hũa tan nc g/100g nc, 20oC - Ka 1,0.1010 Ciclohexanol 25,5oC 161oC 3,6 1018 Ngun k ngh 3.1 T benzen SO 3H H2SO4, Cl (1) NaOH, tan chaớy (2)H Cl2, FeCl3 OH NaOH, H2O 350oC, 315 Atm 3.2 T isopropil benzen hoc toluen O2 CH3 C H CH3 H2O, H CH3 C OOH CH3 OH + CH3 C CH3 O C ch: (1) +H CH3 C O-OH CH3 (I) CH3 C O-OH2 CH3 (2) + H 2O CH3 C O-OH2 CH3 (3) CH3 C O CH3 CH3 C O CH3 C O CH3 CH3 (II) xaớy õọửng thồỡ (4) CH3 C O OH2 CH3 C O + H2O (II) CH3 OH (5) CH3 C O CH3 OH CH3 C O CH3 H CH3 (III) CH3 C CH3 + O OH Cú th giai on (2) v (3) xy ng thi, s chuyn v nhúm phenil giỳp nc tỏch Ph CH3 C O OH2 CH3 CH3 C O Ph + H2O CH3 Ngoi ra, Toluen cng cú th b oxid húa bng oxigen ca khớ tri vi xỳc tỏc mui Cu2, Mg2 CH3 + O2 Cu 2 , Mg OH 5.2.5 Nitroso húa OH NaNO2, H2SO4, 7-8oC OH NO p-nitrosophenol hiu sut 80% 5.2.6 Ghộp cp vi mui diazonium OH N2Cl + HO N N 5.2.7 Carbonyl húa - Phn ng Kolbe ONa O + C 125oC, 4-7 Atm OH COONa OH H COOH O C ch: O O C O O CO2Na H OH COONa 5.2.8 Phn ng Riemer Tiemann S to thnh aldehid OH CHCl3, NaOH, H2O O CHCl2 O CHO HCl OH CHO 70oC Clorurbenzal to thnh u tiờn, nhng b thy gii dung dch kim Phn ng Riemer-Tiemann: phn ng th thõn e trờn vũng phenoxid rt phn ng 5.2.9 To thnh eter CH2Br + OH NaOH, H2O benzilphenileter bromur benzil OH + CH3OSO2OH3 sulfat metil CH2 O NaOH, H2O OCH3 + CH3OSO3Na anisol Trong mụi trng kim phenol nm di dng ion phenoxid, nú l mt tỏc nhõn thõn hch tỏc kớch trờn halogenur hoc sulfat alkil bng phn ng th SN2 Do halogenur aril khú cho phn ng th thõn hch, nờn khụng th s dng phng phỏp tng hp Willamson ny iu ch alkil aril eter, ngi ta thng húa hp tỏc cht, nhng halogenur aril khụng c s dng CH3CH2CH2Br + NaO CH3CH2CH2 O CH3CH2O Na + Br thổỷc hióỷn õổồỹc khọng thóứ thổỷc hióỷn õổồỹ Phenoxid c iu ch t phenol cũn halogenur alkil cú th iu ch t alcol Eter aril phc hn cú th c iu ch bng phng phỏp tng hp Williamson vi mt epoxdid (thng l epoxid etilen) c s dng thay th halogenur alkil OH + CH2 O CH2 H hoỷc OH OCH2CH2OH 2-phenoxietanol Xỳc tỏc acid bin epoxid thnh epoxid proton húa cú hot tớnh cao Xỳc tỏc base bin phenol thnh cht thõn hch mnh hn ú l ion phenoxid OH + CH2 CH2 O chỏỳt thỏn H haỷch yóỳu epoxid proton hoùa hoaỷt tờnh cao O + CH2 CH2 thỏn haỷch maỷnhO H -H O-CH2CH2OH OCH2CH2OH OCH2CH2O H 5.2.10 P vi formaldehid: polimer phenol-formaldehid OH OH H hoỷc OH CH2OH C H OH, H OH CH2 OH C6H5OH, HCHO OH CH2 CH2 OH OH OH OH (n + 1) + nHCHO OH CH2 n Trong trng hp thc hin phn ng d formaldehid, s to thnh nha cresol trờn nhõn benzen cũn cha thờm nhúm CH2OH gi l nha cresol OH n OH + (n + 1)HCHO OH CH2 n CH2OH Nha cresol l dõy di nờn d núng chy v tan c dung mụi Khi nha ny c nộn di ỏp sut cao v nhit cao, dõy di cú th kt hp to thnh polimer cú lng cao hn, cú cu to li khụng gian ba chiu gi l nha bakelite, khụng núng chy v khụng tan bt k dung mụi no, c s dng lm nhng vt liu thay th g, hay lm bng mch in t CH2 OH CH2 HO CH2 OH CH2 CH2 OH CH2 CH2 CH2 C ch Xỳc tỏc base: O H C O + H O H CH2O O H2O CH2OH Xỳc tỏc acid: OH + H H OH C OH H CH2OH OH H2O CH2OH 5.2.11 S C v O-alkil húa chuyn v claisen dung ONa hổợu cổỷc + CH2=CH-CHBr Bromur alil Phenoxid Na dung OCH2CH=CH2 Phenilalil eter O H CH2CH=CH2 khọng hổợu cổỷc OH O CH2 CH2 200oC CH2 O H CH2CH=CH2 CH2CH=CH2 o-Alilphenol OH CH2CH=CH2 5.2.12 Phn ng ca liờn kt CO OH + CH3Br O CH3 + HBr Br + CH3OH OH OH NO2 + PCl5 khọng phaớn ổùng NO2 Cl PCl5 NO2 NO2 5.2.13 Oxid húa phenol OH O O O O [O] Vi 2, 4, 6-triterbutil phenol, s oxh vi s hin din ca butadien to thnh sp cng vi butadien Me3C OH CMe3 CMe3 PbO2 C6H6 Me3C O Me3C CMe3 CMe3 O CMe3 Me3C CH2=CH-CH=CH2 O O CH2 CH CH CH2 Phenol b oxid húa bi CrO3 cho sn phm benzoquinon OH O CrO3H CrO3 H H O OH H2CrO3 - H2CrO3 O O HO H OH O p-Benzoquinon [...]... 4,6-dibromo-2-metilphenol o-cresol OH Br OH Br2, CS2, 0oC Br OH Br + 3HBr + H2SO4 Br 2,4,6-Tribromophenol OH OH + Br o-Bromophenol Br p-Bromophenol saớn phỏứm chờnh 5.2.2 Nitro húa OH HNO3 NO2 Phenol OH NO2 NO2 2,4,6-Trinitrophenol (acid picric) Mun cú mononitro phenol, phi dựng HNO3 loóng nhit thp, nhng hiu sut thp (sn phm ng phõn c phõn ly d dng bng s lụi cun bng hi nc) OH o HNO3 loaợng, 20 C Phenol OH... clorur acetil p-nitrophenol NO2 acetat p-nitrophenil O O C C2H5 OH C2H5COCl Phenol OH AlCl3, CS2 propionatphenil OCOH3 OH O C C2H5 + o-hidroxi pheniletilceton C O C2H5 p-hidroxi pheniletilceton 5.2 Phn ng ca nhõn thm OH OH H Y I Y II H O O H Y Y III IV H 5.2.1 Halogen húa OH + Br2, H2O Phenol Br OH Br + 3HBr Br Tribromophenol OH CH3 + Br2, H2O OH + Br2, H2O SO3H acid-p-phenolsulfonic Phenol CH3 + 2HBr... 5.1.1 Tớnh acid Phenol l acid mnh hn nc, nhng yu hn acid carboxilic Phn ln phenol cú giỏ tr Ka khong 1010, trong khi giỏ tr Ka ca acid khong 105 Do ú, s ion húa to thnh ion phenoxid d hn s to thnh ion alcoxid R OH alcol O H H + RO ion alcoxid O OH O H + I phenol II ion phenoxid Vỡ cú tớnh base, oxigen cú th cho in t vo vũng iu ny c xỏc nh bi s phõn phi in t trong c cu V, VI, VII ca phenol v VIII,... loóng nhit thp, nhng hiu sut thp (sn phm ng phõn c phõn ly d dng bng s lụi cun bng hi nc) OH o HNO3 loaợng, 20 C Phenol OH NO 2 OH + o-Nitrophenol NO2 p-Nitrophenol 5.2.3 Sulfon húa OH 15 - 20oC H2SO4 SO3H acid-o-phenolsulfonic 100oC 100oC OH SO 3H acid-p-phenolsulfonic 5.2.4 Alkil húa v acil húa Friedel - Crafts OH + CH3 CH3 C Cl CH3 OH HF CH3 C CH3 CH3 OH OH + CH3(CH2)4COOH OH resorcinol ZnCl2... OH + H2 O ONa Na + H2 Tớnh acid: phenol < H2CO3 : C6H5ONa + CO2 + H2O C6H5OH + NaHCO3 So sỏnh tớnh acid ca 1 s phenol : OH NO2 > pKa OH OH > NO2 NO2 7.15 OH OH 10.08 8.4 7.23 OH > > CH3 10.14 CH3 CH3 OH OH OH 10.28 OCH3 > > OCH3 9.65 OCH3 10.21 9.98 OH OH OH Cl > > Cl 8.48 9.02 Cl 9.38 5.1.2 To thnh ester: chuyn v Fries Ar OH RCOCl hoỷc (RCO) 2O Ar'SO2Cl Thớ d: OH Phenol RCOOAr Ar'SO2Ar OCOCH3 + (CH3CO)2O... khọng thóứ thổỷc hióỷn õổồỹ Phenoxid c iu ch t phenol cũn halogenur alkil cú th iu ch t alcol Eter aril phc tp hn cú th c iu ch bng phng phỏp tng hp Williamson vi mt epoxdid (thng l epoxid etilen) c s dng thay th halogenur alkil OH + CH2 O CH2 H hoỷc OH OCH2CH2OH 2-phenoxietanol Xỳc tỏc acid bin epoxid thnh epoxid proton húa cú hot tớnh cao Xỳc tỏc base bin phenol thnh cht thõn hch mnh hn ú l ion phenoxid... th thõn e trờn vũng phenoxid rt phn ng 5.2.9 To thnh eter CH2Br + OH NaOH, H2O benzilphenileter bromur benzil OH + CH3OSO2OH3 sulfat metil CH2 O NaOH, H2O OCH3 + CH3OSO3Na anisol Trong mụi trng kim phenol nm di dng ion phenoxid, nú l mt tỏc nhõn thõn hch tỏc kớch trờn halogenur hoc sulfat alkil bng phn ng th SN2  Do halogenur aril khú cho phn ng th thõn hch, nờn khụng th s dng trong phng phỏp tng... C CH3 O 2-Metil-4-hidroxi-acetophenon 25oC OH (CH3CO)2O CH3 OCOCH3 AlCl3 CH3 160oC CH3 OH O C CH3 4-Metil-2-hidroxi-acetophenon saớn phỏứm chờnh 5.2.5 Nitroso húa OH NaNO2, H2SO4, 7-8oC OH NO p-nitrosophenol hiu sut 80% 5.2.6 Ghộp cp vi mui diazonium OH N2Cl + HO N N 5.2.7 Carbonyl húa - Phn ng Kolbe ONa O + C 125oC, 4-7 Atm OH COONa OH H COOH O C ch: O O C O O CO2Na H OH COONa 5.2.8 Phn ng Riemer... hch mnh hn ú l ion phenoxid OH + CH2 CH2 O chỏỳt thỏn H haỷch yóỳu epoxid proton hoùa hoaỷt tờnh cao O + CH2 CH2 thỏn haỷch maỷnhO H -H O-CH2CH2OH OCH2CH2OH OCH2CH2O H 5.2.10 P vi formaldehid: polimer phenol- formaldehid OH OH H hoỷc OH CH2OH C H OH, H 6 5 OH CH2 OH C6H5OH, HCHO OH CH2 CH2 OH OH OH OH (n + 1) + nHCHO OH CH2 n Trong trng hp thc hin phn ng d formaldehid, s to thnh nha cresol trờn nhõn