Hey, Psyloxy !

[element 109]

I'm pretty interested in a post of yours not so long ago, "hey, bromosafrolers..", to which no-one replied. You say:

  R-Cl + K-Phtalamide --> R-Phtalamide + KCl

R-Phtalamide + 2H2O --> R-NH2 + Phtalic acid

Seems pretty do-able, will be in the library this afternoon to look up K-phtalamide.

All the info you got on this is very much appreciated.

And for the R-Cl: isn't it easier to make not-chlorosaffy from saf with HCl/PTC ? I believe Chem Guy has info on this.

PS I couldn't check my hushmail yet (slow thing using older netxplorers)

[psyloxy]

Hey E 109!

Osmium replied to it a few times.
All the info I have on this is what I've posted here. I've just seen it in two books I've bought to learn general org. chem. They do not deal with special things so this can only be a hint into the right direction.

I don't know at all, if it works. I don't have a lab, sadly. But I know that to replace a secondary halogen you need a good nucleophile. I know NH3 is just a so-so nucleophile. And I know that the most expensive of my books sez K-phtalimide is a very good nucleophile. So all I can do with this info is combinig it and say: "Why not give it a try, the theory looks good". I also still have no library access but I will have in 2 weeks. I hope then I can give/get more refs and such.

Im not very up to date when it comes  to Cl/Br/I-Safrole but have a look at this:

Al2O3 with H2O on it's surface + COBr2 -->
Al2O3 with HBr on it's surface + CO2
(also works with SiO2 and PI3/SOCl2)

this Al2O3 with HBr on it's surface reacts with alkenes to the halo-alkane with CH2Cl as solvent in 20min and 99% yield.

Here's the ref: Kropp, P.J., K.A. Daus, M. W. Tubergen, et al., J. Am. Chem. Soc., 1993, 115, 3071. Surface-mediated reactions. 3. Hydrohalogenation of alkenes.

Have fun and please report any dreams  you may or may-not have dreamt.

--psyloxy--

[Rhodium]

COBr2 sounds vile, considering the fact that COCl2 is phosgene...

[CHEM GUY]

Is the HBr anhydrous?  What percentage water?

Al2O3 is pretty easy to obtain.  If the reaction can proceed with 48% HBr on the Al2O3 this is a huge improvement on the procedure that requires 7 days to halogenate with 48% HBr.

[element 109]

First we must find a viable way to get haloalkanes in good yields. CHEM GUY, earlier you talked about HCl + any not-so-sol Q-A-S.

[psyloxy]

Rhodium: then there's still SiO2 and SOCl2 or PI3 left...

CHEM GUY: I suggest reading the ref. I for my part have no clue on the whole thing.

--psyloxy--

[CHEM GUY]

I will certainly try, but if you posted the article I would be much more likely to get to it in a reasonable amount of time.

Also, element 109...

You are talking about the addition of HCl to safrole (or the like) with a Quarterny Ammunium Salt.  I don't remenber talking about that recently.  I think the last time I posted about that specificly was at least a year ago.  I don't really have a lot of info on that specifically, but I'll try to answer any questions you have about it.

------------------
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If you are in violation of any law by reading this leave now.

[psyloxy]

CHEM GUY: I'd love to post it here but the problem is that I don't have it laying around. I took this ref from a book I read.

--psyloxy--

[element 109]

CHEM GUY: i'm sorry, i meant a year ago (in an old threath).

How much Q-A-S is added per quantity of HCl ?
Is it just left at RT ? How long ? Yield ?

If you could answer any of these questions i would very much appreciate it.

Psyloxy: i look up K-phtalimide in the Merck but it only lists phtalimide and K-diphtalate
How would phtalimide add the the Cl/Br/I ?

[psyloxy]

E 109: K-phtalimide can easily be made from phtalimide and KOH.

--psyloxy--

[element 109]

phtalimide + KOH --> K-phtalimide + H2O ?

Sorry if these questions sound stupid, but i want to understand first before i start dreaming things.

[CHEM GUY]

I read that article.  It seems that they use a saturated sloution of HX in CH2Cl2.  Without the the silica or aluma in the mix nothing happens really, but once the silica or aluma is added the reaction proceeds quickly.  The product in a markinokov addition.

The problem here is that you need a saturated solution of HX in CH2Cl2.  There can be water, but the article suggests that the water should be minimal or none exsistant.

The advantage is that you can use HCl which is much easier to get than HBr or HI.  Disadvantage is that you should keep the water content very low. 

BUT, since the aluma and silica are added as anhydrous one might beable to get away with a larger excess of aluma and or silica to get rid of some of the accidental water content.  Alas, straight muractic acid won't work, but one could always add NaCl into a pop bottle of muractic acid and use the HCl gass that evolves to pump into a CH2Cl2 solution.

I wounder if CHCl3 would work in place of CH2Cl2?