The Vespiary

The Hive => Chemistry Discourse => Topic started by: Vibrating_Lights on June 30, 2002, 11:13:00 PM

Title: Hypo chlorination of safrole
Post by: Vibrating_Lights on June 30, 2002, 11:13:00 PM
Is there a procedure to make a 2hypochlorite from safrole or isosafrole?(RCH2-O-Cl). Apoun treatment with a base would yeild the ketone +Hcl?
Vl_
Title: Chlorination of alkenes in the presence of water ...
Post by: Osmium on July 01, 2002, 01:12:00 AM
Chlorination of alkenes in the presence of water produces the chlorohydrins (R-CHCl-CHOH-R). When basified they will produce the epoxide/glycol which can be converted to the ketone.
I'm not fat just horizontally disproportionate.
Title: Do you have any references one can look up for ...
Post by: sYnThOmAtIc on July 01, 2002, 12:25:00 PM
Do you have any references one can look up for that procedure?
Title: Good luck
Post by: Chromic on July 01, 2002, 12:26:00 PM
Good luck getting this technique to work. I never got anything other than inconclusive results. The general idea is to have safrole in 10% NaOCl and slowly drip in HCl. Then isolate the chlorohydrin, treat with hydroxide in alcohol to get the epoxide, and then distill or rearrange to get the ketone.

I'm starting to get the sense that to use bleach as an oxidant, you need an appropriate catalyst.
Title: What about
Post by: PrimoPyro on July 01, 2002, 01:41:00 PM
using dry Ca(OCl)2 has this ever been tried? Is the HCl addition crucial to the reaction?
Title: I think so?
Post by: Chromic on July 01, 2002, 02:11:00 PM
It seems so. Bleach and alkene just sit in a biphasic mixture, happily spinning away. Maybe over many, many hours a reaction would take place? With a bit of hydrochloric acid, HOCl is formed... and hypochlorous acid is a much more active reagent than NaOCl.
Title: can we say
Post by: foxy2 on July 01, 2002, 05:41:00 PM
phase transfer catalyst

I wouldn't bother trying without one.
Those who give up essential liberties for temporary safety deserve neither liberty nor safety
Title: What are molar ratios one should use for the ...
Post by: sYnThOmAtIc on July 01, 2002, 09:36:00 PM
What are molar ratios one should use for the clorination(xxmol safrole, xxmole 10%hypo soln, xxmole hcl; xxmole   ?%naoh/etoh soln, xxmole chlorohydrin? Any heat applied or time allowed for conversion to chlorohydrin? Then what percent hydroxide/ethanol and how should the interaction occur to get epoxide? Afterward extract organic right to distill? Ok so this epoxide rearrangement has been verified to happen when it is distilled with out vacuum? I remember a long thread about it but I dont remember anybody getting ketone from it in any dream. This sounds about as easy and rewarding as the mdp2pol only problem is getting it to work eheh.
Title: Generate the Cl2 externally.
Post by: Osmium on July 02, 2002, 12:52:00 AM
Generate the Cl2 externally.
I'm not fat just horizontally disproportionate.
Title: What about ring halogenation when using X2
Post by: Vibrating_Lights on July 02, 2002, 02:26:00 AM
When using X2 Is there not the chance of halogenation of the ring?  Is there need to protect the ring structure. Perhaps protect from UV Light would help minimize this. The dihalo compound would definatly need purification to seperate the ring structure substituted hydrohalohydrans.  If not then dosage level will be off in relation to the % analog compounds.
Vl_ ;)
Title: Good idea
Post by: Chromic on July 06, 2002, 02:53:00 PM
Foxy, yeah, I should have been using a PTC when I ran the experiments. If I was to do it again, that would be the way to go...