Sciencemadness Discussion Board

Chlorotoluene

Waffles SS - 16-6-2011 at 08:21
Quote:








What is easier and best method for chlorination of Toluene?

[Edited on 16-6-2011 by Waffles SS]

entropy51 - 16-6-2011 at 08:44

Diazotization and Sandmeyer using CuCl performed on the appropriate isomer of toluidine. Dissolving metal reduction with Fe/HCl on the appropriate chloronitrobenzene will also work, but I prefer the Sandmeyer route.

gsd - 16-6-2011 at 11:46

Browse these threads:

http://www.sciencemadness.org/talk/viewthread.php?tid=11698&...

http://www.sciencemadness.org/talk/viewthread.php?tid=13196&...

gsd

Waffles SS - 16-6-2011 at 11:53

Thanks but i am looking for chlorination not Diazotization.
I am looking for easier method of toluene chlorination
I think simple bubbling a chlorine gas in toluene (with some acetic acid) lead to chlorotoluene but i think the temp and time of reaction is very important(higher temp may lead to dichloro toluene)

gsd - 16-6-2011 at 15:44

Quote: Originally posted by Waffles SS  
Thanks but i am looking for chlorination not Diazotization.
I am looking for easier method of toluene chlorination
I think simple bubbling a chlorine gas in toluene (with some acetic acid) lead to chlorotoluene but i think the temp and time of reaction is very important(higher temp may lead to dichloro toluene)


Please quote a reference.

AFAIK direct chlorination of toluene leads to substitution in side chain not nucleus.

gsd

Waffles SS - 16-6-2011 at 21:42

Dear gsd,
Thanks but your first link cause error and seems doesnt exist "The item you requested could not be found."
and your second link contain lot of patent and link and i dont know which one is about chlorotoluene

gsd - 16-6-2011 at 21:54

@ WSS

look for the post which gives "Attachment: Preparation of o-Chlorotoluene.pdf (85kB)
This file has been downloaded 9 times"

This link still worked fine for me.

In the second link, look for DJF90's post "Attachment: Oxidising chlorination of toluene.pdf (231kB)
This file has been downloaded 19 times"

gsd

Waffles SS - 16-6-2011 at 22:10

Dear gsd,
There is no djf90 post on second link
Second link is"Wanted References and Needed Translations(6)" page 5
and first link is"Wanted References and Needed Translations (5)" that cause error
:(

Waffles SS - 16-6-2011 at 22:15

Quote: Originally posted by gsd  


Please quote a reference.

AFAIK direct chlorination of toluene leads to substitution in side chain not nucleus.

gsd



Quote:


Chlorination of toluene with chlorine without catalyst requires a polar solvent as well such as acetic acid. The ortho to para selectivity is low

J. L. O'Connell, J. S. Simpson, P. G. Dumanski, G. W. Simpson and C. J. Easton (2006). "Aromatic chlorination of ω-phenylalkylamines and ω-phenylalkylamides in carbon tetrachloride and α,α,α-trifluorotoluene"


gsd - 17-6-2011 at 07:23

check DJF90 post in Wanted References and Needed Translations(6) page 5

you can also utfse to locate the post given names of poster and article.

gsd

redox - 17-6-2011 at 09:38

When you do this reaction, you may want to keep light out of the reaction vessel, as the free radical chlorines would react to form benzyl chloride.

not_important - 17-6-2011 at 10:05

Note that the reference with acetic acid is using glacial acetic acid as a solvent/diluent.

Old school method is to use a Lewis acid catalyst when the aromatic nucleus is not strongly activated. Plenty of examples of that around, in most practical org synth lab books since 1890 or so.

All of these methods will give a mixture of o-, p-, and often m- haloaromatics, plus not uncommonly a small amount of polyhalogenated material. If you want a specific isomer then the diazotization and Sandmeyer reaction on the proper toluidene is a much better route; again old trad org synth.


Waffles SS - 17-6-2011 at 23:29

Thank Dear Not_important,I am so happy to see your post again
The price of final product is very important for me,my final goal is preparing cheap M-cresol. i want to chlorination of toluene(0.6$/kg) to Para and ortho isomer and then separate para isomer.after that i will hydroxylation of Para-chlorotoluene to M-cresol and P-cresol.I think toluidine is much more expensive that my final product by this method.
Quote:

For example, treatment of para-chlorotoluene with sodium hydroxide solution at temperatures above 350 ºC gave an equimolar mixture of meta- and para-cresols (hydroxytoluenes)
http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/benz...


Preparation of chlorotoluene by oxidizing chlorination of toluene
http://www.sciencemadness.org/talk/files.php?pid=213135&...



benzyne1.gif - 1kB

[Edited on 18-6-2011 by Waffles SS]

Kemoterapia - 20-8-2016 at 18:25

I can't access to this link?

http://www.sciencemadness.org/talk/files.php?pid=213135&...

Somebody can reupload the file or give an alternative link?

Thanks in advance :)

Waffles SS - 20-8-2016 at 18:55

Quote: Originally posted by Kemoterapia  
I can't access to this link?

http://www.sciencemadness.org/talk/files.php?pid=213135&...

Somebody can reupload the file or give an alternative link?

Thanks in advance :)


Attachment: Preparation of chlorotoluene by oxidizing chlorination of toluene.pdf (231kB)
This file has been downloaded 527 times

Kemoterapia - 21-8-2016 at 04:24

Quote: Originally posted by Waffles SS  
Quote: Originally posted by Kemoterapia  
I can't access to this link?

http://www.sciencemadness.org/talk/files.php?pid=213135&...

Somebody can reupload the file or give an alternative link?

Thanks in advance :)


Thanks a lot WafflesSS! Is exactly the paper from Neftekhemiye that I was looking for.

I post this yesterday in late night and after few hours I get the answer.

Have a nice day!