well someone has made the propionoxy ester freebased it with ammonia and it's insolublwe in petro ether so ether is called for.
Sonicator on the way so this xpeririment can conducted it's propionoxy ester is quite good one can only imagine what this tweak will do?

well godman jon does'nt have the software to open that up but they are fiesty now are'nt they?
a little air and atmospheric h2o and you got problems espescially in solvents like thf.
far more thermal btu's tha dynanmite.
jon thinks he"ll be doing this microscale.
with wet blankents and plenty of sand and fire retardardant clothing too.

from research the tert alyl lithiums are the strongest bases on book aryl lithiums may be slightlty different animals based on thier conjugation with the delocalized pi system but i think the pka for tert-butyl lithium was 2 enough to deprotonate anything espescially something enolizable as we were discussing this is going to to be an interesting expiriment.

much appreciated!!!

excllentread and they did metion it's pka value at 53 for tert butyllithium.
they also talk about organolithium's ability to induce anion catalyzed polymerizations which may be problelematic.
for example if the loperamide is esterified that incorprates an enolizazable proton but if it's left untouched then you have an even stronger base (an alkoxide)capable of inducing enolization of the dimethylaminde.

this is very informqtive on the subject of aklyl lithium induced polymerization

http://en.wikipedia.org/wiki/Anionic_addition_polymerization

hmmm intersting to note these initiators are used in conjugated pi systems most fequently as in this quote

"The most commercially useful of these initiators has been the alkyllithium initiators. They are primarily used for the polymerization of styrenes and dienes"
both conjugated electron rich systems


this is interesting
http://www3.interscience.wiley.com/journal/113343247/abstract?CRETRY=1&SRETRY=0
title: Electronic study of receptor binding of analgesic aryl moiety II: Prodine analogs

"The energy level of the highest occupied molecular orbital of the aryl moiety of these analogs may permit a charge transfer interaction between the aryl groups of the analgesic molecules and their receptors with the aryl groups acting as charge donors."
anything electron withdrawing like this pesky Cl would diminsh activity according to thier hypothesis and these are iraqi chemists so they know thier stuff working under saddam you would have to better know your shit!
or it's off to the woodchipper.

"can't wait to crack that p-chloro nut."

You are not going to like the nutcracker!

That tert butyl lithium route would be a very unconventional way to approach the dehalogenation, conventional methods would have you use something along the lines of Tributyltin Hydride with azobisisobutyronitrile as a catalyst for nearly quantitative yields.


Total Synthesis of Indoles from Tricholoma Species via Bartoli/Heteroaryl Radical Methodologies
A. Dobbs, J. Org. Chem., 2001, 66, 638-641.
DOI: 10.1021/jo0057396

Other methods(catalytic hydrogenation) selectively removing the halogen from chloroarenes generally uses more exotic catalysts than those, ie;

Dehalogenation of polychloroarenes with sodium formate in propan-2-ol catalyzed by RhCl(PPh3)3
http://www.rsc.org/delivery/_ArticleLinking/DisplayArticleForFree.cfm?doi=b102191p&JournalCode=NJ


Cross-Coupling and Dehalogenation Reactions Catalyzed by (N-Heterocyclic carbene)Pd(allyl)Cl Complexes
Oscar Navarro, Harneet Kaur, Parisa Mahjoor and Steven P. Nolan*

O. Navarro, H. Kaur, P. Mahjoor, S. P. Nolan, J. Org. Chem., 2004, 69, 3173-3180.
DOI: 10.1021/jo035834p

Hydrogenation and Dehalogenation under Aqueous Conditions with an Amphiphilic-Polymer-Supported Nanopalladium Catalyst
Ryu Nakao, Hakjune Rhee and Yasuhiro Uozumi*

http://www.hrhee-hanyang.net/board_file_img/Org.Lett.%202005,%207,%20163-165.pdf

There are many more floating around, Nickel(0)/Imidazolium Chloride Catalyzed Reduction of Aryl Halides and so on....
In the literature I have seen, there are no methods for dehalogenation using lithium, sodium or potassium metals unless using tert butanol to dissolve lithium or sodium in, to prepare the corresponding metal alkoxide (for example Sodium-tert-Butoxide) as done in the third paper referenced. I am sure if they could have they would have just dumped some butyl lithium in and been done with it, but as you can see very specific (but not impossible to get) catalysts are required to specifically remove the halogen and leave an aromatic ring with all other functional groups intact. There are many palladium type catalysts that are suitable I am sure a palladium chloride on alumina type of paper could be dug up, palladium chloride is very get-able!

edit;"which leads one to conclude perhaps such an animal does'nt exist?"

You want aromatic lithium compounds!
http://www.springerlink.com/content/v401204385567525/
They do exist, and for the record just because it is unconventional does not mean it will not work!

Conjugate addition of lithium ester enolates to 1-chlorovinyl p-tolyl sulfoxides: a novel synthesis of functionalized esters and lactones having a tertiary or a quaternary carbon at the ?-position
http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6THR-48N3HSM-C&_user=10&_rdoc=1&_fmt=&_orig=search&_sort=d&_docanchor=&view=c&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=d9d497da0adf06a1f316bd8bcb9b617a

Structure and Reactivity of Lithium Enolates. From Pinacolone to
Selective C-Alkylations of Peptides. Difficulties and Opportunities
Afforded by Complex Structures
http://infosee.ethz.ch/seebach/PULI/386_ACI_1988.pdf

"umm i think it's not so complicated"

That is indeed a much nicer procedure! I am sure I had a paper documenting a palladium chloride on alumina dehalogenation that was also very straight forward (cant seem to find it now).

"i rode the short bus to school and i  remember that"

Where I come from you guys get a special Blue bus!

Process for the debromination of 2-substituted-5-bromo-6-methoxynaphthalenes
United States Patent 5107013

http://www.freepatentsonline.com/5107013.html

Naphthalenes of formula ##STR1## wherein X represents COCH3, COC2 H5, CH(CH3)COOH, CH(CH3)COOR, CH(CH3)CN and CH(CH3)CONHR1, R represents alkyl and R1 represents hydrogen, alkyl or hydroxyalkyl, are debrominated by means of acceptors of bromine, like alkylarenes and alkoxyarenes, in the presence of Lewis acids.

All the compounds normally used as catalysts in the Friedel-Crafts reactions, like AlCl 3 , FeCl 3 , ZnCl 2 , TiCl 4 can be used as Lewis acids, even if the aluminum chloride showed to be particularly useful.

"and apparently via a dissolving metal reduction using calcium"
http://pubs.acs.org/doi/abs/10.1021/es010716%2B


When you post an ACS article could you either post the whole article or give us all a login we can use?  It's useless to most of us to have this kind of incomplete information.  I lost my ACS login ahwile back and no-one has stepped up with a good one yet.  Thanks.

oopsie i eat my words this is as good as it gets j. of appl. catalysis.

they say activated, or deactivated rings exhibit reduced reactivity.

very thorough.
explains kinetics, everything.
here it is w/o further ado.

and chemrox your reference even stated
"The cleavage of the carbon?chlorine bond on the aromatic ring bearing electron-donating group was difficult compared to the one bearing electron-withdrawing group."
in the case of calcium/ethanol dissolving metal reductions.

Have you got that formate yet? I'm eagerly awaiting your results.