In this thesis the results of an investigation of the chlorination of cyclopentanone and cyclohexanone in the solvent carbontetrachloride and catalyzed by hydrogen chloride are described. ... Zie: Summar

Maatman, Hendrik

University of Groningen

   University of GroningenThe chlorination of cyclopentanone and cyclohexanoneMaatman, HendrikIMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:1980Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Maatman, H. (1980). The chlorination of cyclopentanone and cyclohexanone. s.n.CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 12-11-2019s -l$t\RYChlor ina ted  ke tones  are  use fu l  in te rmed ia tes  in  the  syn thes is  o f  var ious:: ' ;ani.c products. Al icycl ic f ive- and six-rnembered r i .ngs with a carbonyl group:l i Ï  an important role in the synthesis of cornpounds based on natural products.- : . lo r ina t ion  o f  ke tones  are  subs t i tu t ion  reac t ions  in  wh ich  one,  o r  more ,: i . : roqen a tom o f  the  o-carbon a tons  is  rep laced by  ch lo r ine .  Dur ing  the:eec t ion  hydrogen ch lo r ide  is  fo rned,  wh ich  ac ts  as  a  ca ta lys t ;  there fore  these:e :c t ions  have an  au tocata ly t i c  na ture .  Because there  is  more  than one reac t ive: . . ' . l rogen a ton  a t  the  o-carbon a tons  these reac t ions  show a  low se lec t iv i t y  to: :e  rpnoch loro  produc t .  Para1 le l  w i th  the  ch lo r ina t ion  reac t ion ,  an  undes i red: r - ' : c  ca ta lyzeda ldo l  condensat ion  o f  the  parent  ke tone takes  p Iace .  Ch lor ina-: : . rns  on  an  indus t r ia l  sca le  a re  most ly  car r ied  ou t  in  carbonte t rach lo r ide  as< c l v e n t ,  i t s  a t t r a c t i v e  p r o p e r t i e s  b e i n g  i t s  i n e r t n e s s ,  t h e  h i g h  s o l u b i l i t y  o fs :3 r t ing  mater ia l  and produc t ,  and i t . s  re la t i ve ly  low a tnospher ic  bo i l ing: 'J r nt .I n  t h i s  t h e s i s the  resu l ts  o f  an  inves t iga t ion  o f  the  ch lo r ina t ion  o fcyclohexanone in the solvent carbontetrachloride and cata-ch lo r ide  are  descr ibed.  A l though the  ha logenat j -on  o f  a l i -aqueous so lvents  i s  one o f  the  most  s tud ied  sub jec ts  o f: r -c lopentanone andi r ' :ed  by  hydrogen:.: .rat i .c ketones in|h ) ' s ica l  o rgan ic  chern is t ry ,  no  de ta i led  in fo rna t ion  is  ava i lab le  as  to  the: r lo r ina t ion  in  apo la i r  apro t ic  so lvents .  In  Chapter  2  the  mechan is rn  o f  the:h lo r ina t ion  o f  ke tones  in  po la r  so lvent  i s  descr ibed as  presented  in  theI  i  t e r a t u r e .Chapter  3  conta ins  the  resu l ts  o f  an  inves t iga t ion  o f  the  k ine t ics  o f  the;hlorination of cyclopentanone and cyclohexanone and their monohalogenated prod-: : ; t s  ca ta lyzed by  hydrogen ch lo r ide  in  carbonte t rach lo r ide .  Sorne o f  the  resu l tsa r e :-  the  k ine t ic  o rder  in  ch lo r ine  is  zero ,-  the  k ine t ic  o rder  in  hydrogen ch lo r ide  is  approx i .na te ly  one,-  the  k ine t ic  o rder  in  ke tone and nonoch loro  ke tone depends on  the  ke toneconcentrat ion, and varies froÍn almost 2 aI Iow to I at higher ketone concen-t r a t i o n s .I leasurements  o f  the  k ine t ic  i so tope e f fec ts  show tha t  th is  var ia t ion  cannotbe  exp la ined by  a  change in  the  ra te  l im i t ing  s tep .  The var ia t ion  in  the  ordero f  t h e  k e t o n e  c a n  e x c e l l e n t l y  b e  e x p l a i n e d  b y  a  s e l f - a s s o c i a t i o n  o f  t h e  p o l a rke tones  in  the  apo la i r  so lvent .  The va lue  o f  the  assoc ia t ion  cons tan t  cou ldbe de tern ined by  neasur ing  the  f reez ing  po in t  depress ion  o f  so lu t ions  o f  cyc lo -L47pentanone in carbontetrachloride. The kinetic nodel as developed for thech lo r ina t ion  o f  the  unsubs t i tu ted  ke tones  can a lso  be  used fo r  the  ch lo r ina t ionof the nonochloro ketones.In the reacti ,on nechanisn the hydrogen chloride acts as an acid catalyst,and the ketone both as a base catalyst and as a substrate.This holds for the parent ketone as well  as for the nonochlorinated ketone.The unsubsti tuted ketone also reacts as a base catalyst in the consecutivechlorination of the monochloro compound. The contribution of this reactiondeternines to a large extent the selectivi ty of the chlorination to the nono-chloro ketone. Furthennore, i t  could be establ ished that, even at low fract ionalconvetsions of the parent ketone, the three possible isorneric dichloro compoundsare already forrned. At fract ional conversions as low as 5% of the ketone theselectivi ty to the nonochloro compound does not exceed 86% in the chlorinationof cyclopentanone and 81% in the chlorination of cyclohexanone. This is causedby a very rapid chlorination of the monochloro product by a hitherto st i l11it t le understood mechanisrn.Chapter 5 also contains the kj-netics of the aldol condensation of theketones catalyzed by hydrogen chloride. The order in hydrogen chloride is 2 andin ketone 1.5. CyclohexÍrnone appears to be much more reactive than cyclopenta-none in the aldol condensation.In an industr ial reactor, the chlorine wil l  be added as a gaseous conpo-nent. The product hydrogen chloride usually is poorly soluble and wi-11 desorb.Before the chlorine can react in the l iquid i t  has to be transferred from thegas to the l iquid phase. The rate of absorption can be enhanced by a chernicalreaction relat ive to the rate of purely physical absorption.In Chapter 4 the inf luence of an autocatalyt ic reaction with sinultaneousdesorption of the catalyst on the absorption of a gaseous Íeactant is described.Calculat ions carr ied out using both the penetrat ion and the f i lm nodel showedthat due to this type of reaction the absorption ratL can be twice as high asdue to the corresponding reaction without auto-catalysis. This is nainly causedby the local ly high concentrat ion of the catalyst in the reaction zone.Experiments carr ied out on the chlorination of cyclohexanone in a st irred cel lconfirn the calculated enhancenent of the absorption rate.In Chapter 5 the experinental results of the chlorination in some gas-l iqu id  reac tors  a re  descr ibed.  The ch lo r ina t ion  is  car r ied  ou t  in  a  t r i ck lebed reactor, with gas and l iquid in concurrent downward f low, both in the gascont i -nuous  and the  pu ls ing  f low reg imes,  and in  a  mechan ica l l y  s t i r rcd  gas-l iqu id  contac tor .  Us ing  the  k ine t ic  resu l ts  as  p resented  in  Chapter  3 ,  conputc r148calculat ions urere carr iero f  the  se lec t j -v i t y ' to  th rwith the experinental onrexperinents in the tr ick.gas continuous f low regirpulsing f low regine. In5-8eo hi.gher than predict,the choice of a suitablepentanone on an industr i iis found to restr ict thecalculat ions were carr ied out for these reactor types. The calculated valuesof the selectivi ty ' to the monochloro compound are in reasonable agreenentwith the experirnental ones. I t  should be mentioned, however, that for theexperinents in the tr ickle bed reactor, the calculated selectivi t ies in thegas continuous f low regirne are closer to the experinental values than in thepulsing f low regime. In the latter regime the experirnental select ivi t ies are5-8% higher than predicted. Final ly, some considerations ale given concerningthe choice of a suitable reactor system for the production of 2-chlorocyclo-pentanone on an industr ial scale. The production of large quanti t ies of heatis  found to  res t r i c t  the  poss ib i l i t i es  ser ious ly '149

The chlorination of cyclopentanone and cyclohexanone

ARTS repository - University of Groningen

   University of GroningenThe chlorination of cyclopentanone and cyclohexanoneMaatman, HendrikIMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:1980Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Maatman, H. (1980). The chlorination of cyclopentanone and cyclohexanone. s.n.CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 07-06-2022s -l$t\RYChlor ina ted  ke tones  are  use fu l  in te rmed ia tes  in  the  syn thes is  o f  var ious:: ' ;ani.c products. Al icycl ic f ive- and six-rnembered r i .ngs with a carbonyl group:l i Ï  an important role in the synthesis of cornpounds based on natural products.- : . lo r ina t ion  o f  ke tones  are  subs t i tu t ion  reac t ions  in  wh ich  one,  o r  more ,: i . : roqen a tom o f  the  o-carbon a tons  is  rep laced by  ch lo r ine .  Dur ing  the:eec t ion  hydrogen ch lo r ide  is  fo rned,  wh ich  ac ts  as  a  ca ta lys t ;  there fore  these:e :c t ions  have an  au tocata ly t i c  na ture .  Because there  is  more  than one reac t ive: . . ' . l rogen a ton  a t  the  o-carbon a tons  these reac t ions  show a  low se lec t iv i t y  to: :e  rpnoch loro  produc t .  Para1 le l  w i th  the  ch lo r ina t ion  reac t ion ,  an  undes i red: r - ' : c  ca ta lyzeda ldo l  condensat ion  o f  the  parent  ke tone takes  p Iace .  Ch lor ina-: : . rns  on  an  indus t r ia l  sca le  a re  most ly  car r ied  ou t  in  carbonte t rach lo r ide  as< c l v e n t ,  i t s  a t t r a c t i v e  p r o p e r t i e s  b e i n g  i t s  i n e r t n e s s ,  t h e  h i g h  s o l u b i l i t y  o fs :3 r t ing  mater ia l  and produc t ,  and i t . s  re la t i ve ly  low a tnospher ic  bo i l ing: 'J r nt .I n  t h i s  t h e s i s the  resu l ts  o f  an  inves t iga t ion  o f  the  ch lo r ina t ion  o fcyclohexanone in the solvent carbontetrachloride and cata-ch lo r ide  are  descr ibed.  A l though the  ha logenat j -on  o f  a l i -aqueous so lvents  i s  one o f  the  most  s tud ied  sub jec ts  o f: r -c lopentanone andi r ' :ed  by  hydrogen:.: .rat i .c ketones in|h ) ' s ica l  o rgan ic  chern is t ry ,  no  de ta i led  in fo rna t ion  is  ava i lab le  as  to  the: r lo r ina t ion  in  apo la i r  apro t ic  so lvents .  In  Chapter  2  the  mechan is rn  o f  the:h lo r ina t ion  o f  ke tones  in  po la r  so lvent  i s  descr ibed as  presented  in  theI  i  t e r a t u r e .Chapter  3  conta ins  the  resu l ts  o f  an  inves t iga t ion  o f  the  k ine t ics  o f  the;hlorination of cyclopentanone and cyclohexanone and their monohalogenated prod-: : ; t s  ca ta lyzed by  hydrogen ch lo r ide  in  carbonte t rach lo r ide .  Sorne o f  the  resu l tsa r e :-  the  k ine t ic  o rder  in  ch lo r ine  is  zero ,-  the  k ine t ic  o rder  in  hydrogen ch lo r ide  is  approx i .na te ly  one,-  the  k ine t ic  o rder  in  ke tone and nonoch loro  ke tone depends on  the  ke toneconcentrat ion, and varies froÍn almost 2 aI Iow to I at higher ketone concen-t r a t i o n s .I leasurements  o f  the  k ine t ic  i so tope e f fec ts  show tha t  th is  var ia t ion  cannotbe  exp la ined by  a  change in  the  ra te  l im i t ing  s tep .  The var ia t ion  in  the  ordero f  t h e  k e t o n e  c a n  e x c e l l e n t l y  b e  e x p l a i n e d  b y  a  s e l f - a s s o c i a t i o n  o f  t h e  p o l a rke tones  in  the  apo la i r  so lvent .  The va lue  o f  the  assoc ia t ion  cons tan t  cou ldbe de tern ined by  neasur ing  the  f reez ing  po in t  depress ion  o f  so lu t ions  o f  cyc lo -L47pentanone in carbontetrachloride. The kinetic nodel as developed for thech lo r ina t ion  o f  the  unsubs t i tu ted  ke tones  can a lso  be  used fo r  the  ch lo r ina t ionof the nonochloro ketones.In the reacti ,on nechanisn the hydrogen chloride acts as an acid catalyst,and the ketone both as a base catalyst and as a substrate.This holds for the parent ketone as well  as for the nonochlorinated ketone.The unsubsti tuted ketone also reacts as a base catalyst in the consecutivechlorination of the monochloro compound. The contribution of this reactiondeternines to a large extent the selectivi ty of the chlorination to the nono-chloro ketone. Furthennore, i t  could be establ ished that, even at low fract ionalconvetsions of the parent ketone, the three possible isorneric dichloro compoundsare already forrned. At fract ional conversions as low as 5% of the ketone theselectivi ty to the nonochloro compound does not exceed 86% in the chlorinationof cyclopentanone and 81% in the chlorination of cyclohexanone. This is causedby a very rapid chlorination of the monochloro product by a hitherto st i l11it t le understood mechanisrn.Chapter 5 also contains the kj-netics of the aldol condensation of theketones catalyzed by hydrogen chloride. The order in hydrogen chloride is 2 andin ketone 1.5. CyclohexÍrnone appears to be much more reactive than cyclopenta-none in the aldol condensation.In an industr ial reactor, the chlorine wil l  be added as a gaseous conpo-nent. The product hydrogen chloride usually is poorly soluble and wi-11 desorb.Before the chlorine can react in the l iquid i t  has to be transferred from thegas to the l iquid phase. The rate of absorption can be enhanced by a chernicalreaction relat ive to the rate of purely physical absorption.In Chapter 4 the inf luence of an autocatalyt ic reaction with sinultaneousdesorption of the catalyst on the absorption of a gaseous Íeactant is described.Calculat ions carr ied out using both the penetrat ion and the f i lm nodel showedthat due to this type of reaction the absorption ratL can be twice as high asdue to the corresponding reaction without auto-catalysis. This is nainly causedby the local ly high concentrat ion of the catalyst in the reaction zone.Experiments carr ied out on the chlorination of cyclohexanone in a st irred cel lconfirn the calculated enhancenent of the absorption rate.In Chapter 5 the experinental results of the chlorination in some gas-l iqu id  reac tors  a re  descr ibed.  The ch lo r ina t ion  is  car r ied  ou t  in  a  t r i ck lebed reactor, with gas and l iquid in concurrent downward f low, both in the gascont i -nuous  and the  pu ls ing  f low reg imes,  and in  a  mechan ica l l y  s t i r rcd  gas-l iqu id  contac tor .  Us ing  the  k ine t ic  resu l ts  as  p resented  in  Chapter  3 ,  conputc r148calculat ions urere carr iero f  the  se lec t j -v i t y ' to  th rwith the experinental onrexperinents in the tr ick.gas continuous f low regirpulsing f low regine. In5-8eo hi.gher than predict,the choice of a suitablepentanone on an industr i iis found to restr ict thecalculat ions were carr ied out for these reactor types. The calculated valuesof the selectivi ty ' to the monochloro compound are in reasonable agreenentwith the experirnental ones. I t  should be mentioned, however, that for theexperinents in the tr ickle bed reactor, the calculated selectivi t ies in thegas continuous f low regirne are closer to the experinental values than in thepulsing f low regime. In the latter regime the experirnental select ivi t ies are5-8% higher than predicted. Final ly, some considerations ale given concerningthe choice of a suitable reactor system for the production of 2-chlorocyclo-pentanone on an industr ial scale. The production of large quanti t ies of heatis  found to  res t r i c t  the  poss ib i l i t i es  ser ious ly '149

English

University of Groningen Research Database

  
 University of Groningen
The chlorination of cyclopentanone and cyclohexanone
Maatman, Hendrik
IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from
it. Please check the document version below.
Document Version
Publisher's PDF, also known as Version of record
Publication date:
1980
Link to publication in University of Groningen/UMCG research database
Citation for published version (APA):
Maatman, H. (1980). The chlorination of cyclopentanone and cyclohexanone s.n.
Copyright
Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the
author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).
Take-down policy
If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately
and investigate your claim.
Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the
number of authors shown on this cover page is limited to 10 maximum.
Download date: 10-02-2018
s -l$t\RY
Chlor ina ted  ke tones  are  use fu l  in te rmed ia tes  in  the  syn thes is  o f  var ious
:: ' ;ani.c products. Al icycl ic f ive- and six-rnembered r i .ngs with a carbonyl group
:l i Ï  an important role in the synthesis of cornpounds based on natural products.
- : . lo r ina t ion  o f  ke tones  are  subs t i tu t ion  reac t ions  in  wh ich  one,  o r  more ,
: i . : roqen a tom o f  the  o-carbon a tons  is  rep laced by  ch lo r ine .  Dur ing  the
:eec t ion  hydrogen ch lo r ide  is  fo rned,  wh ich  ac ts  as  a  ca ta lys t ;  there fore  these
:e :c t ions  have an  au tocata ly t i c  na ture .  Because there  is  more  than one reac t ive
: . . ' . l rogen a ton  a t  the  o-carbon a tons  these reac t ions  show a  low se lec t iv i t y  to
: :e  rpnoch loro  produc t .  Para1 le l  w i th  the  ch lo r ina t ion  reac t ion ,  an  undes i red
: r - ' : c  ca ta lyzeda ldo l  condensat ion  o f  the  parent  ke tone takes  p Iace .  Ch lor ina-
: : . rns  on  an  indus t r ia l  sca le  a re  most ly  car r ied  ou t  in  carbonte t rach lo r ide  as
< c l v e n t ,  i t s  a t t r a c t i v e  p r o p e r t i e s  b e i n g  i t s  i n e r t n e s s ,  t h e  h i g h  s o l u b i l i t y  o f
s :3 r t ing  mater ia l  and produc t ,  and i t . s  re la t i ve ly  low a tnospher ic  bo i l ing
: 'J r nt .
I n  t h i s  t h e s i s the  resu l ts  o f  an  inves t iga t ion  o f  the  ch lo r ina t ion  o f
cyclohexanone in the solvent carbontetrachloride and cata-
ch lo r ide  are  descr ibed.  A l though the  ha logenat j -on  o f  a l i -
aqueous so lvents  i s  one o f  the  most  s tud ied  sub jec ts  o f
: r -c lopentanone and
i r ' :ed  by  hydrogen
:.: .rat i .c ketones in
|h ) ' s ica l  o rgan ic  chern is t ry ,  no  de ta i led  in fo rna t ion  is  ava i lab le  as  to  the
: r lo r ina t ion  in  apo la i r  apro t ic  so lvents .  In  Chapter  2  the  mechan is rn  o f  the
:h lo r ina t ion  o f  ke tones  in  po la r  so lvent  i s  descr ibed as  presented  in  the
I  i  t e r a t u r e .
Chapter  3  conta ins  the  resu l ts  o f  an  inves t iga t ion  o f  the  k ine t ics  o f  the
;hlorination of cyclopentanone and cyclohexanone and their monohalogenated prod-
: : ; t s  ca ta lyzed by  hydrogen ch lo r ide  in  carbonte t rach lo r ide .  Sorne o f  the  resu l ts
a r e :
-  the  k ine t ic  o rder  in  ch lo r ine  is  zero ,
-  the  k ine t ic  o rder  in  hydrogen ch lo r ide  is  approx i .na te ly  one,
-  the  k ine t ic  o rder  in  ke tone and nonoch loro  ke tone depends on  the  ke tone
concentrat ion, and varies froÍn almost 2 aI Iow to I at higher ketone concen-
t r a t i o n s .
I leasurements  o f  the  k ine t ic  i so tope e f fec ts  show tha t  th is  var ia t ion  cannot
be  exp la ined by  a  change in  the  ra te  l im i t ing  s tep .  The var ia t ion  in  the  order
o f  t h e  k e t o n e  c a n  e x c e l l e n t l y  b e  e x p l a i n e d  b y  a  s e l f - a s s o c i a t i o n  o f  t h e  p o l a r
ke tones  in  the  apo la i r  so lvent .  The va lue  o f  the  assoc ia t ion  cons tan t  cou ld
be de tern ined by  neasur ing  the  f reez ing  po in t  depress ion  o f  so lu t ions  o f  cyc lo -
L47
pentanone in carbontetrachloride. The kinetic nodel as developed for the
ch lo r ina t ion  o f  the  unsubs t i tu ted  ke tones  can a lso  be  used fo r  the  ch lo r ina t ion
of the nonochloro ketones.
In the reacti ,on nechanisn the hydrogen chloride acts as an acid catalyst,
and the ketone both as a base catalyst and as a substrate.
This holds for the parent ketone as well  as for the nonochlorinated ketone.
The unsubsti tuted ketone also reacts as a base catalyst in the consecutive
chlorination of the monochloro compound. The contribution of this reaction
deternines to a large extent the selectivi ty of the chlorination to the nono-
chloro ketone. Furthennore, i t  could be establ ished that, even at low fract ional
convetsions of the parent ketone, the three possible isorneric dichloro compounds
are already forrned. At fract ional conversions as low as 5% of the ketone the
selectivi ty to the nonochloro compound does not exceed 86% in the chlorination
of cyclopentanone and 81% in the chlorination of cyclohexanone. This is caused
by a very rapid chlorination of the monochloro product by a hitherto st i l1
1it t le understood mechanisrn.
Chapter 5 also contains the kj-netics of the aldol condensation of the
ketones catalyzed by hydrogen chloride. The order in hydrogen chloride is 2 and
in ketone 1.5. CyclohexÍrnone appears to be much more reactive than cyclopenta-
none in the aldol condensation.
In an industr ial reactor, the chlorine wil l  be added as a gaseous conpo-
nent. The product hydrogen chloride usually is poorly soluble and wi-11 desorb.
Before the chlorine can react in the l iquid i t  has to be transferred from the
gas to the l iquid phase. The rate of absorption can be enhanced by a chernical
reaction relat ive to the rate of purely physical absorption.
In Chapter 4 the inf luence of an autocatalyt ic reaction with sinultaneous
desorption of the catalyst on the absorption of a gaseous Íeactant is described.
Calculat ions carr ied out using both the penetrat ion and the f i lm nodel showed
that due to this type of reaction the absorption ratL can be twice as high as
due to the corresponding reaction without auto-catalysis. This is nainly caused
by the local ly high concentrat ion of the catalyst in the reaction zone.
Experiments carr ied out on the chlorination of cyclohexanone in a st irred cel l
confirn the calculated enhancenent of the absorption rate.
In Chapter 5 the experinental results of the chlorination in some gas-
l iqu id  reac tors  a re  descr ibed.  The ch lo r ina t ion  is  car r ied  ou t  in  a  t r i ck le
bed reactor, with gas and l iquid in concurrent downward f low, both in the gas
cont i -nuous  and the  pu ls ing  f low reg imes,  and in  a  mechan ica l l y  s t i r rcd  gas-
l iqu id  contac tor .  Us ing  the  k ine t ic  resu l ts  as  p resented  in  Chapter  3 ,  conputc r
148
calculat ions urere carr ier
o f  the  se lec t j -v i t y ' to  th r
with the experinental onr
experinents in the tr ick.
gas continuous f low regir
pulsing f low regine. In
5-8eo hi.gher than predict,
the choice of a suitable
pentanone on an industr i i
is found to restr ict the
calculat ions were carr ied out for these reactor types. The calculated values
of the selectivi ty ' to the monochloro compound are in reasonable agreenent
with the experirnental ones. I t  should be mentioned, however, that for the
experinents in the tr ickle bed reactor, the calculated selectivi t ies in the
gas continuous f low regirne are closer to the experinental values than in the
pulsing f low regime. In the latter regime the experirnental select ivi t ies are
5-8% higher than predicted. Final ly, some considerations ale given concerning
the choice of a suitable reactor system for the production of 2-chlorocyclo-
pentanone on an industr ial scale. The production of large quanti t ies of heat
is  found to  res t r i c t  the  poss ib i l i t i es  ser ious ly '
149


NARCIS 

   University of GroningenThe chlorination of cyclopentanone and cyclohexanoneMaatman, HendrikIMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:1980Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Maatman, H. (1980). The chlorination of cyclopentanone and cyclohexanone. s.n.CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 16-07-2023s -l$t\RYChlor ina ted  ke tones  are  use fu l  in te rmed ia tes  in  the  syn thes is  o f  var ious:: ' ;ani.c products. Al icycl ic f ive- and six-rnembered r i .ngs with a carbonyl group:l i Ï  an important role in the synthesis of cornpounds based on natural products.- : . lo r ina t ion  o f  ke tones  are  subs t i tu t ion  reac t ions  in  wh ich  one,  o r  more ,: i . : roqen a tom o f  the  o-carbon a tons  is  rep laced by  ch lo r ine .  Dur ing  the:eec t ion  hydrogen ch lo r ide  is  fo rned,  wh ich  ac ts  as  a  ca ta lys t ;  there fore  these:e :c t ions  have an  au tocata ly t i c  na ture .  Because there  is  more  than one reac t ive: . . ' . l rogen a ton  a t  the  o-carbon a tons  these reac t ions  show a  low se lec t iv i t y  to: :e  rpnoch loro  produc t .  Para1 le l  w i th  the  ch lo r ina t ion  reac t ion ,  an  undes i red: r - ' : c  ca ta lyzeda ldo l  condensat ion  o f  the  parent  ke tone takes  p Iace .  Ch lor ina-: : . rns  on  an  indus t r ia l  sca le  a re  most ly  car r ied  ou t  in  carbonte t rach lo r ide  as< c l v e n t ,  i t s  a t t r a c t i v e  p r o p e r t i e s  b e i n g  i t s  i n e r t n e s s ,  t h e  h i g h  s o l u b i l i t y  o fs :3 r t ing  mater ia l  and produc t ,  and i t . s  re la t i ve ly  low a tnospher ic  bo i l ing: 'J r nt .I n  t h i s  t h e s i s the  resu l ts  o f  an  inves t iga t ion  o f  the  ch lo r ina t ion  o fcyclohexanone in the solvent carbontetrachloride and cata-ch lo r ide  are  descr ibed.  A l though the  ha logenat j -on  o f  a l i -aqueous so lvents  i s  one o f  the  most  s tud ied  sub jec ts  o f: r -c lopentanone andi r ' :ed  by  hydrogen:.: .rat i .c ketones in|h ) ' s ica l  o rgan ic  chern is t ry ,  no  de ta i led  in fo rna t ion  is  ava i lab le  as  to  the: r lo r ina t ion  in  apo la i r  apro t ic  so lvents .  In  Chapter  2  the  mechan is rn  o f  the:h lo r ina t ion  o f  ke tones  in  po la r  so lvent  i s  descr ibed as  presented  in  theI  i  t e r a t u r e .Chapter  3  conta ins  the  resu l ts  o f  an  inves t iga t ion  o f  the  k ine t ics  o f  the;hlorination of cyclopentanone and cyclohexanone and their monohalogenated prod-: : ; t s  ca ta lyzed by  hydrogen ch lo r ide  in  carbonte t rach lo r ide .  Sorne o f  the  resu l tsa r e :-  the  k ine t ic  o rder  in  ch lo r ine  is  zero ,-  the  k ine t ic  o rder  in  hydrogen ch lo r ide  is  approx i .na te ly  one,-  the  k ine t ic  o rder  in  ke tone and nonoch loro  ke tone depends on  the  ke toneconcentrat ion, and varies froÍn almost 2 aI Iow to I at higher ketone concen-t r a t i o n s .I leasurements  o f  the  k ine t ic  i so tope e f fec ts  show tha t  th is  var ia t ion  cannotbe  exp la ined by  a  change in  the  ra te  l im i t ing  s tep .  The var ia t ion  in  the  ordero f  t h e  k e t o n e  c a n  e x c e l l e n t l y  b e  e x p l a i n e d  b y  a  s e l f - a s s o c i a t i o n  o f  t h e  p o l a rke tones  in  the  apo la i r  so lvent .  The va lue  o f  the  assoc ia t ion  cons tan t  cou ldbe de tern ined by  neasur ing  the  f reez ing  po in t  depress ion  o f  so lu t ions  o f  cyc lo -L47pentanone in carbontetrachloride. The kinetic nodel as developed for thech lo r ina t ion  o f  the  unsubs t i tu ted  ke tones  can a lso  be  used fo r  the  ch lo r ina t ionof the nonochloro ketones.In the reacti ,on nechanisn the hydrogen chloride acts as an acid catalyst,and the ketone both as a base catalyst and as a substrate.This holds for the parent ketone as well  as for the nonochlorinated ketone.The unsubsti tuted ketone also reacts as a base catalyst in the consecutivechlorination of the monochloro compound. The contribution of this reactiondeternines to a large extent the selectivi ty of the chlorination to the nono-chloro ketone. Furthennore, i t  could be establ ished that, even at low fract ionalconvetsions of the parent ketone, the three possible isorneric dichloro compoundsare already forrned. At fract ional conversions as low as 5% of the ketone theselectivi ty to the nonochloro compound does not exceed 86% in the chlorinationof cyclopentanone and 81% in the chlorination of cyclohexanone. This is causedby a very rapid chlorination of the monochloro product by a hitherto st i l11it t le understood mechanisrn.Chapter 5 also contains the kj-netics of the aldol condensation of theketones catalyzed by hydrogen chloride. The order in hydrogen chloride is 2 andin ketone 1.5. CyclohexÍrnone appears to be much more reactive than cyclopenta-none in the aldol condensation.In an industr ial reactor, the chlorine wil l  be added as a gaseous conpo-nent. The product hydrogen chloride usually is poorly soluble and wi-11 desorb.Before the chlorine can react in the l iquid i t  has to be transferred from thegas to the l iquid phase. The rate of absorption can be enhanced by a chernicalreaction relat ive to the rate of purely physical absorption.In Chapter 4 the inf luence of an autocatalyt ic reaction with sinultaneousdesorption of the catalyst on the absorption of a gaseous Íeactant is described.Calculat ions carr ied out using both the penetrat ion and the f i lm nodel showedthat due to this type of reaction the absorption ratL can be twice as high asdue to the corresponding reaction without auto-catalysis. This is nainly causedby the local ly high concentrat ion of the catalyst in the reaction zone.Experiments carr ied out on the chlorination of cyclohexanone in a st irred cel lconfirn the calculated enhancenent of the absorption rate.In Chapter 5 the experinental results of the chlorination in some gas-l iqu id  reac tors  a re  descr ibed.  The ch lo r ina t ion  is  car r ied  ou t  in  a  t r i ck lebed reactor, with gas and l iquid in concurrent downward f low, both in the gascont i -nuous  and the  pu ls ing  f low reg imes,  and in  a  mechan ica l l y  s t i r rcd  gas-l iqu id  contac tor .  Us ing  the  k ine t ic  resu l ts  as  p resented  in  Chapter  3 ,  conputc r148calculat ions urere carr iero f  the  se lec t j -v i t y ' to  th rwith the experinental onrexperinents in the tr ick.gas continuous f low regirpulsing f low regine. In5-8eo hi.gher than predict,the choice of a suitablepentanone on an industr i iis found to restr ict thecalculat ions were carr ied out for these reactor types. The calculated valuesof the selectivi ty ' to the monochloro compound are in reasonable agreenentwith the experirnental ones. I t  should be mentioned, however, that for theexperinents in the tr ickle bed reactor, the calculated selectivi t ies in thegas continuous f low regirne are closer to the experinental values than in thepulsing f low regime. In the latter regime the experirnental select ivi t ies are5-8% higher than predicted. Final ly, some considerations ale given concerningthe choice of a suitable reactor system for the production of 2-chlorocyclo-pentanone on an industr ial scale. The production of large quanti t ies of heatis  found to  res t r i c t  the  poss ib i l i t i es  ser ious ly '149

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The chlorination of cyclopentanone and cyclohexanone

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