05-17-02 01:48
No 309640
March's 5th edition page 869, ...............Hurtley Reaction
ArX + CH3COCH3 ----?-----> ArCH2COCH3 + ArCH2CHOHCH3
?=liquid amonia containing Na or K
X= Halide
The text goes on and says that it also occurs under UV-light when K or Na are omitted.
At least that's how I read it.............
(Hive Addict)
05-17-02 02:42
No 309659
Do you think the liquid ammonia could be replaced by an amine ?
So whats the ammonia doing? acting as an solvent ?
Don't cry for me I'm the cleaner
(Stranger)
05-17-02 04:07
No 309708
There is a reference to this reaction Rossi, R.A.:Bunnett, J.F. J. Org. Chem., 1973,38,3020; Bunnett, J.F.: Gloor, B.F. J.Org. Chem.,1973,38,4156;1974,39,382.
I haven't had a chance to study it clearly that's why I posted it so the bees can work on it along with me.
(Hive Prodigy)
05-17-02 08:12
No 309811
Great find! But next time, if you would be so kind, copy the entire passage. Upon my looking up this reaction in my copy of March's 5th, I read some additional good info that you did not cite. Here is the entire passage word for word:
Arylation at a Carbon Containing an Active Hydrogen
(uninteresting paragraph)
* * *
"The reaction on unactivated halides can also be done with copper halide catalysts (the Hurtley Reaction), and with palladium complex catalysts. Compounds of the form CH3Z can be arylated by treatment with an aryl halide in liquid ammonia containing Na or K, for example (it gives this specific example):
ArX + CH3COCH3 ==NH3/K==> ArCH2COCH3 + ArCH2CH(OH)CH3
The same products are obtained, although in different proportions, when Na or K is omitted but the solution is irradiated with near-UV light. In either case other leaving groups can be used instead of halogens (e.g., NR3+, SAr) and the mechanism is the SRN1 mechanism. Iron(II) salts have also been used to initiate this reaction."
OrgSyn V, 12, 263; VI, 36, 873, 928; VII, 229.
And other ref's for many of these statements contained in the passage can be supplied by request, and one of us can type them later.
PrimoPyro
Vivent Longtemps La Ruche!
(Hive Bee)
05-17-02 11:17
No 309867
http://orgsyn.org/orgsyn/prep.asp?prep=c
Shure thing, yield is not great in first step, lead is toxic and not enviromentally friendly, some reagents are not quite OTC at the first shot, still... if you take benzo-1,3-dioxole as aryl and ethyl acetoacetate as beta-dicarbonyl, then potential product looks like useful one.
(Official Hive Translator)
05-17-02 11:43
No 309875
This is a variation of the so-called 'Drone's enolate synthesis' - the article he compiled on this route can bee found on Rh's site.
To my knowledge, noone has tried it yet, but it's very tempting.
One thing that the synthesis needs to bee investigated/twitched, as there currently exist no 'fully OTC' variation - but the liquid ammonia will surely work.
The closest-to-OTC would bee using UV light - BTW, i have a HyperLab post somewhere in which a guy tells how to make one oneself - real easy (he doesn't know what the energy of such a source would bee, though)
Antoncho
(Newbee)
05-17-02 16:00
No 309926
I was reading your comment but I wasn't able to connect it to the reaction at hand, however on section 13-3 of the afore said text March's 5th edition , there is a section of Aryl substrate to carboxylic acids and their derivatives , aldehydes, and ketones, where lead is indeed called for . I wasn't able to see hoe the reaction you quoted relates........perhaps I'm short sighted.
Perhaps you misread the reaction as I read it it doesn't involve any lead and only benzyl chloride , acetone, and K or Na. And as quoted "same product obtained when neither K or Na are used but solution irradiated with near U-V light. There are many OTC approches to benzyl chloride , I see no problem with acetone or a U-V light. I could be wrong in my assessment but this is a forum on the practice of chemistry, a trial an error endevour.
(Newbee)
05-17-02 16:03
No 309930
Not sure what ammonia does but less sure if it can be substituded for an amide. I'm still looking for the refrences to better understand the mechanism and how it works and what can be substituded, as I know where you want to go with that.
(Newbee)
05-17-02 16:26
No 309939
Thank you for the head's up on the enolate article , I found it very educational and promising. I had no knowledge of the good work drone did on the subject.
Hence to answer many of the questions I recommend the reading for those interested on this method:
../rhodium /p2p.eno
(Hive Bee)
05-17-02 18:38
No 309979
Dear Java, my comment was related to OS link, that was provided, rather than directly to your post.
Anyway SWIM thinks that some look at recent advances in palladium catalysis might make wonders with this enolate arylation problem.
(Official Hive Translator)
05-17-02 19:13
No 309994
I remember having an article about that rxn being made in some common solvt, catalyzed by PdCl2 and some weird stannic methoxide-thing......
Any other suggestions?
Uh, guess a self-made UV source would sound a lot better for the most
.Damn it, it's so simple - why noone even attempted to try this over the past years?!
Antoncho
(Chief Bee)
05-17-02 19:28
No 310000
Everybody at the Hive always wait for someone else to try something out first. It usually takes about two years for a new excellent idea to take hold, and about as much time for people stop using a stupid or unnecessary procedure.
(Stoni's sexual toy)
05-17-02 22:38
No 310063
Many bees still don't know what an A/B is, although me and others are preaching it since 1997!
I'm not fat just horizontally disproportionate.
(Chief Bee)
01-06-04 12:44
No 480727
(Rated as: good read)
A Principle for Establishing a Carbon Chain on an Aromatic Ring in Place of Nitrogen, Oxygen, Fluorine, Sulfur, Chlorine, Bromine, or Iodine Functionality
Roberto A. Rossi, J. F. Bunnett
J. Am. Chem. Soc. 94, 683-684 (1972) (../rhodium/pdf /arylation.na
A major leaving group effect on chemical events after the group has left:
Reactions of acetone enolate ion with halobenzenes and related substrates provoked by solvated electrons
Raymond R. Bard, J. F. Bunnett, Xavier Creary, Michael J. Tremelling
J. Am. Chem. Soc. 102, 2852-2854 (1980) (../rhodium/pdf /arylation.k-
The Hive - Clandestine Chemists Without Borders
(Active Asperger Archivist)
01-06-04 19:18
No 480768
Osmium, I've taken quite a large amount of time trying to prepare several documents to the effect of teaching a few of the newbees some acid-base chemistry. However, they just don't bother to read them. I've had several "students" who have excelled with the slightest amount of tutilage, but they made the effort to read the links I provided and research the topics I suggested. Unfortunately, the majority here still only want to make a buck- they don't want to learn.
In any case, here is some basic acid base chemistry and related links for the practical application of those ideals.
Post 398337 (Aurelius: "Compilation of Acid Reagents", Chemistry Discourse)
(would it be considered beneficial if began including general chemistry tutorial links within my digests? or perhaps creating an entire digest devoted to particular general chemistry concepts within our site?)
Act quickly or not at all.
(Chief Bee)
02-01-04 22:50
No 485886
(Rated as: excellent)
The following data is from a monograph about aromatic substitution via the SRN1 pathway.
From: Aromatic Substitution by the SRN1 Reaction
R. Rossi, et al.
Organic Reactions, Vol. 54, pp. 56-67 (Tbl 2) and 263-269 (Refs) (../rhodium/pdf /archive/srn1
It so happens that the monograph lists several pages with different reaction conditions where acetone enolate has been used to alkylate almost any aryl halide there is.
Almost all of them uses either K or Na(Hg) in NH3(l) or in DMSO with UV irradiation. A few of them manage to get decent yields in DMSO using ambient light, their trick is to use an aryldiazonium salt instead of an aryl halide.
Here is Drone's original proposition: Post 122752 (dormouse: "what happened to my enolate review?! -drone 342", Serious Chemistry)
Here are a lot of references on the SRN1 reaction collected: http://w3.uniroma1.it/centricnr-csmr/enp
General procedures, using either DMSO or anhydrous ammonia as solvent, with reaction mechanisms:
The SRN1 reactions of 1,8-diiodonaphthalene
Robert K. Norris and James A. McMahon
Arkivoc (RR-819C) pp. 139-155 (2003) (http://arkat-usa.org/ark/journal/2003/R
The Hive - Clandestine Chemists Without Borders
(Hive Addict)
08-09-04 19:04
No 524447
Here are posts articles needed in this thread , that compliment the flow of this method.....
http://www.basf.com/inorganics/pdf/bulle
Post 459094 (java: "Re: Novel easy preparations of Iodobenzene.....", Novel Discourse)
Post 395155 (pHarmacist: "iodobenzene 86–87% yield", Chemistry Discourse)
Post 391612 (pHarmacist: "Synthesis of Iodobenzene/Chlorobenzene in one pot", Methods Discourse)
Post 455083 (ning: "Questions about drone's enolate p2p synth", Newbee Forum)
Just hold on to the thread...that keeps us going
http://www.chiapaslink.ukgateway.net/