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S  0t ``  X*  0 `   Z*  0ȩ `   Z*z  bA޽h @ ?Parchment ̙33 Default Design 0 zr@ ( )   0`% <7   P*    0* v 7  R*  d  c $ ?Em    0,  :xy  RClick to edit Master text styles Second level Third level Fourth level Fifth level!     S  6 <K   P*    6 v K  R*  H  0g彖 ? ̙3380___PPT10.3-Ri 0X(   $+ X X 01 <7   X*  X 0D7 v 7  Z*  X 6X: <K   X*  X 6`| v K  Z* H X 0g彖 ? ̙3380___PPT10.3-q 0L0 P _(    0 -ROUTES TO PHENOL A guide for A level students\(2 (26f<f  0 sKNOCKHARDY PUBLISHING&Ff J   C "A  KTRE` ; H    0"`>B 2008 SPECIFICATIONS<G$G   B  s *޽h ? ̙33y___PPT10Y+D=' = @B +  0L0   `  (  [  0T30P{ INTRODUCTION This Powerpoint show is one of several produced to help students understand selected topics at AS and A2 level Chemistry. It is based on the requirements of the AQA and OCR specifications but is suitable for other examination boards. Individual students may use the material at home for revision purposes or it may be used for classroom teaching if an interactive white board is available. Accompanying notes on this, and the full range of AS and A2 topics, are available from the KNOCKHARDY SCIENCE WEBSITE at... www.knockhardy.org.uk/sci.htm Navigation is achieved by... either clicking on the grey arrows at the foot of each page or using the left and right arrow keys on the keyboard (2 2(2 2   75,   0k BPHENOL (2$fjB  BD)@0A  6Pp@ 0 0jB @ BD)@X@  6X0@ 0 0dB  <D?x x   0@)`  OKNOCKHARDY PUBLISHING(2B  s *޽h ? ̙33y___PPT10Y+D=' = @B +  0L0    (0 g (  jB   BD)@0A   6Pp@ 0 0jB  @ BD)@X@   6X0@ 0 0  6tAh   CONTENTS Prior knowledge Synthesis from benzene Reactions of the OH group Reactions of the ring Benzene diazonium chloride - preparation Benzene diazonium chloride - reactionsr0}2 (33ff,~ "   <? `@ 0 0  B? p@e 0 0  B? x@ 0 0  B? yz @s 0 0  B? ij @z 0 0  B?0 H@^ 0 0 ' 0 BPHENOL (2$fB  s *޽h ? ̙33y___PPT10Y+D=' = @B + 0L0 p pz(  pp p 0P  Before you start it would be helpful to& know the functional groups found in organic chemistry know the arrangement of bonds around atoms recall and explain electrophilic substitution of aromatic rings2*(2 2*  dB p <D)@0A p 0Pp@ 0 0dB p@ <D)@X@ p 0X0@ 0 0  p 0 BPHENOL (2$fB p s *޽h ? ̙33y___PPT10Y+D=' = @B + 0L0  (    0` BPHENOL (2fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *Ԍ?*  TStructure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid h@ 3.  m   @`R   C *A phenol2g5/n  VA޽h ?Parchment ̙33y___PPT10Y+D=' = @B + 0L0  R( RE- L   C $A  bdc1g   0( BPHENOL (2fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *|?*  @HStructure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid Preparation You cannot put an OH group directly onto a benzene ring by electrophilic substitution, so phenol has to be synthesised in a multi-stage processI@7l 3&   K  @`R   C *A phenol2g5/n  VA޽h ?Parchment ̙33y___PPT10Y+D=' = @B +  0L0 '    (  L  C $A  bdc1g   0 BPHENOL (2fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *?*  @HStructure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid Preparation You cannot put an OH group directly onto a benzene ring by electrophilic substitution, so phenol has to be synthesised in a multi-stage processI@7l 3&   K  @`   0P!>?9  Step 1 - Nitration of benzene reagents conc. nitric acid and conc. sulphuric acid (catalyst) conditions reflux at 55C equation C6H6 + HNO3   > C6H5NO2 + H2O mechanism electrophilic substitutionp@f38 33         3&     @`B   ZD3>?*   H8>?j. E1((23R   C *A phenol2g5/n  VA޽h ?Parchment ̙33y___PPT10Y+D=' = @B +|  0L0    ! (  L  C $A  bdc1g   0> BPHENOL (2fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *x<>?*  @HStructure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid Preparation You cannot put an OH group directly onto a benzene ring by electrophilic substitution, so phenol has to be synthesised in a multi-stage processI@7k 3&   K  @`x   0R>?9  bStep 2 - Reduction of nitrobenzene reagents tin and conc. hydrochloric acid conditions reflux equation C6H5NO2 + 6 [H]   > C6H5NH2 + 2H2O mechanism reductionp@#f3" 3 3         3    @`B   ZD3>?    HT>?  E2((23R   C *A phenol2g5/B  s *޽h ? ̙33y___PPT10Y+D=' = @B +d  0L0 s k   (  L   C $A  bdc1g   0d^> BPHENOL (2fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *x>?*  @HStructure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid Preparation You cannot put an OH group directly onto a benzene ring by electrophilic substitution, so phenol has to be synthesised in a multi-stage processI@7k 3&   K  @``   0>?9 P Step 3 - Diazotisation of phenylamine reagents nitrous acid and hydrochloric acid (use sodium nitrite) conditions keep below 10C equation C6H5NH2 + HNO2 + HCl   > C6H5N2+ Cl + 2H2O reaction type diazotisation@&f3: 33            3Z       '  @`B   ZD3>? P   HԚ>?2  E3((23R   C *A phenol2g5/B  s *޽h ? ̙33y___PPT10Y+D=' = @B +  0L0 #    ( ACHEM\bd L   C $A  bdc1g   0> BPHENOL (2fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *\>?*  @HStructure phenol is an aromatic alcohol with formula C6H5OH the OH group is attached directly to the benzene ring it is an almost colourless crystalline solid Preparation You cannot put an OH group directly onto a benzene ring by electrophilic substitution, so phenol has to be synthesised in a multi-stage processI@7k 3&   K  @`   0v?9  Step 4 - Substitution of diazo group by OH reagents water conditions warm above 10C equation C6H5N2+ Cl + H2O   > C6H5OH + N2 + HCl reaction type hydrolysis / substitution@*f3 33           3Z  K  .  ,  @`B   ZD3>?*   Hv?r6 E4((23R   C *A phenol2g5/B  s *޽h ? ̙33y___PPT10Y+D=' = @B +  0L0    ( w   0$> "PHENOL - REACTIONS OF THE OH GROUPV#(2 f 3f3 dB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *v?. u Water phenol is a weak acid it dissolves very slightly in water to form a weak acidic solution it is a stronger acid than aliphatic alcohols the ring helps weaken the O-H bond and stabilises the resulting anion C6H5OH(aq) C6H5O(aq) + H+(aq)   @3ffff fffffff&    @`FF  j   tT @  #  *B   TDfV?@@B   TDfV?@tT @  # F jB   TDfV?@@B  TDfV?@B  s *޽h ? ̙33y___PPT10Y+D=' = @B + 0L0   (    0t'v "PHENOL - REACTIONS OF THE OH GROUPV#(2 f 3f3 dB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *dJv?.  nxWater phenol is a weak acid it dissolves very slightly in water to form a weak acidic solution it is a stronger acid than aliphatic alcohols the ring helps weaken the O-H bond and stabilises the resulting anion C6H5OH(aq) C6H5O(aq) + H+(aq) NaOH phenol reacts with sodium hydroxide to form a salt - sodium phenoxide it is ionic and water soluble C6H5OH(aq) + NaOH(aq)   > C6H5O Na+(aq) + H2O(l) .@3ffff fffffff3h ffffffffff fff    =   9      @`FF  j   tT @  #  *B   TDfV?@@B   TDfV?@tT @  # F jB   TDfV?@@B  TDfV?@B  s *޽h ? ̙33y___PPT10Y+D=' = @B +Q 0L0 `X`(   ` ` 0$uv "PHENOL - REACTIONS OF THE OH GROUPV#(2 f 3f3 dB ` <D)@0A ` 0Pp@ 0 0dB `@ <D)@X@ ` 0X0@ 0 0( ` s *̯v?. nWater phenol is a weak acid it dissolves very slightly in water to form a weak acidic solution it is a stronger acid than aliphatic alcohols the ring helps weaken the O-H bond and stabilises the resulting anion C6H5OH(aq) C6H5O(aq) + H+(aq) NaOH phenol reacts with sodium hydroxide to form a salt - sodium phenoxide it is ionic and water soluble C6H5OH(aq) + NaOH(aq)   > C6H5O Na+(aq) + H2O(l) Sodium phenol reacts with sodium to form an ionic salt - sodium phenoxide hydrogen is also produced this reaction is similar to that with aliphatic alcohols such as ethanol 2C6H5OH(s) + 2Na(s)   > 2C6H5O Na+(s) + H2(g)d@3  fffff fffffff3h ffffffffff fff3 ffff!ffffff fff    =   9    P       @`FF  j `  tT @  `#  *B  ` TDfV?@@B  ` TDfV?@tT @  `# F jB  ` TDfV?@@B ` TDfV?@B ` s *޽h ? ̙33y___PPT10Y+D=' = @B +  0L0 (   (  dB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0m  s *̩v?. ELECTROPHILIC SUBSTITUTION Ease the OH group is electron releasing it increases the electron density of the delocalised system it makes substitution much easier compared to benzene a p orbital on the oxygen overlaps with the p orbitals in benzene H@@3 f! f&    @`  0,v 'PHENOL - REACTIONS OF THE AROMATIC RINGV((2 f 3f3 X   C 0Aphenoxide1g 3 X   C 0Aphenoxide2ga @    < C6H5N2+ Cl + 2H2O notes nitrous acid is unstable and is made in situ from sodium nitrite C6H5NH2 + NaNO2 + 2HCl   > C6H5N2+ Cl + NaCl + 2H2O the solution is kept cold to slow down decomposition of the diazonium salt C6H5N2+ Cl + H2O   > C6H5OH + HCl + N2 n@`P@' 3    m32 3f3ffffff fffffffff fff3'ffffff ffffffffffffTfffffffff fffffff#     d   e        P     &    @`N  C &Abdc7ag.}B  s *޽h ? ̙33y___PPT10Y+D=' = @B + 0L0 -%0 (    0\| {DIAZONIUM SALTS - REACTIONSD(2f 3fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0*  s *)|?j_  Benzene diazonium chloride undergoes two main types of reaction SUBSTITUTION OF THE DIAZONIUM GROUP nitrogen (N2) expelled COUPLING REACTIONS nitrogen atoms are retained @Ht@H@3& ff ff&     @`N   C &Abdc7agT MB  s *޽h ? ̙33y___PPT10Y+D=' = @B +  0L0 @~(    0X7| ~DIAZONIUM SALTS - SUBSTITUTIOND(2f 3fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *X@|?jL  OH reagents water (HYDROLYSIS) conditions warm above 10C equation C6H5N2+ Cl + H2O   > C6H5OH + HCl + N2 use the only reasonably simple way to substitute OH phenol is an antiseptic and is used to make polymers  @gP{@3  f 33fffffffff fffffff m@N  &    @`L  C $A  bdc2glYB  s *޽h ? ̙33y___PPT10Y+D=' = @B +  0L0     (    0B| ~DIAZONIUM SALTS - SUBSTITUTIOND(2f 3fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *(?j 8OH reagents water (HYDROLYSIS) conditions warm above 10C equation C6H5N2+ Cl + H2O   > C6H5OH + HCl + N2 use the only reasonably simple way to substitute OH phenol is an antiseptic and is used to make polymers I reagents potassium iodide solution conditions warm equation C6H5N2+ Cl + KI   > C6H5I + KCl + N2  @gP@3  f 33fffffffff fffffff o3 33fffffffffffffftN  &    "    @`L  C $A  bdc2glYjB   BD?  B  s *޽h ? ̙33y___PPT10Y+D=' = @B +  0L0   P , (    0H| zDIAZONIUM SALTS - COUPLINGD(2f3fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0  s *$1?j0  n2reagents phenol and sodium hydroxide conditions alkaline solution below 10C equation C6H5N2+Cl + C6H5OH + NaOH   > C6H5-N=N-C6H4OH + NaCl + H2O (4-hydroxyphenol)azobenzene YELLOW use making azo dyes THE AZO GROUP P@?Pi8@3 33fffffff fffffffffffffff333Zr    Y  (  @`N  C &Abdc8ag0Fpj2   Bo?  * sR  C *Abdcazo2gd 4B  s *޽h ? ̙33y___PPT10Y+D=' = @B + 0L0  (  j2  Bo? , j2  Bo?^    0j I SOME AZO DYES (2fdB  <D)@0A  0Pp@ 0 0dB @ <D)@X@  0X0@ 0 0   s *3?j0*  (4-hydroxyphenol)azobenzene YELLOW 4-phenylazophenylamine YELLOW The first azo dye to be made methyl orange YELLOW IN ALKALI RED IN ACIDPi Pi33f3&j  >  @`j2   Bo? Z   C $A azomo"` `r^   C (AazoNH2g"`  \   C &AazoOHg"`j j2B  s *޽h ? ̙33y___PPT10Y+D=' = @B +` 0L0 og@(   X @  @ 0؍ i/ 2009 JONATHAN HOPTON & KNOCKHARDY PUBLISHING0(20f @ <̙?8x@= 0 0 @ 0ݍ ROUTES TO PHENOL THE END\(2 (26f<fJ @ C "A  KTRE` ; H H @ 0޽h ? ̙33y___PPT10Y+D=' = @B +r @|"~(O1;Fs=p7T"-8iu(MDD\sOh+'0T hp   No Slide TitleHOPTONJONATHAN HOPTON980Microsoft PowerPoint@Ј@@hNx@0GSg  )'    """)))UUUMMMBBB999|PP3f333f3333f3ffffff3f̙3ff333f333333333f33333333f33f3ff3f3f3f3333f33̙33333f333333f3333f3ffffff3f33ff3f3f3f3fff3ffffffffff3ffff̙fff3fffff3fff333f3f3ff3ff33f̙̙3̙ff̙̙̙3f̙3f333f3333f3ffffff3f̙3f3f3f333f3333f3ffffff3f̙3f3ffffffffff!___www(4'A x(xKʦ 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