HANGIN' IT ALL OUT, CHEMISTRY-WISE

You are in your second or third year of doctoral studies. You must submit a really hot original research proposal or your Committee will skin you alive (thereby having nothing to steal for their own grant funding applications). We both know anything worth thinking about has already been thought. Here we go...

Research was once a giddy serendipitous stroll into the unknown. Somebody threw in money and men of genius did fabulous things with remarkable frequency. Polymerized methyl methacrylate was horrible glue for glass, Plexiglas remaining as the panes fell away. Methyl cyanoacrylate made awful Plexiglas because the glass mold held tight - Super Glue. Almost everything wonderful short of the laser was uncloaked in part by accident. Had somebody made Jello with sodium fluorescein or Rhodamine G and zapped it with a flashlamp, so the laser, too.

Business management requires a business plan. No MBA dares toss a farthing until every niggling variable is discounted cash flow/return on investment parameterized in multidimensional economic space. PERT charts! Not a ha'penny flows from Federal coffers until a savant's grant proposal is riskless, reaching for the least publishable bit from the most infinitesimal incremental extension of the most non-controversial beaten to death precursor. (Compare with War on Drugs' funding, Project Head Start, or Homeland Severity. State terror sells.)

Uncle Al ventures into the lab to play puddly games. You don't learn sex from a book, you confer with a brothel's real world professionals. Chemistry or sex, remember safety precautions.

1. 1,4,7-triazacyclononane is readily made via N,N',N"-triethylenediamine tritosylamide in DMF with NaH at reflux and very slowly adding a DMF solution of ethylene glycol ditosylate, then deprotecting in concentrated sulfuric acid. Nitrosate to the mono-nitroso adduct, followed by intramolecular nitrogen lone pair attack on the tethered nitrosyl to give the hydroxylamine. See hydroxylaminesulfonic acid in Reagents for Organic Synthesis, Vol. 1, Fieser and Fieser. Stir the bicyclic hydroxylamine in oleum to get the O-sulfonic acid without sulfonating the nitrogens, then hydrolyze in base to get the central nitrogen bonded to the third peripheral nitrogen:
   1. The central nitrogen lone pair sticks WAY out in space, the whole tricyclic arrangement being fiercely rigid, but...
   2. the peripheral nitrogens exert massive inductive electron withdrawal, and...
   3. since it is all bridgeheads, there can be no pi conjugation and back donation.

   You thus synthesize an amine nitrogen bound only to aliphatic amine nitrogens that has no basic properties, no Beta Effect, and cannot invert. Kewl.

2. Place highly dispersed graphite or carbon black in the unremarkable adamantane reaction medium of AlCl₃ slush, then bubble in isobutylene. Will the graphene edges alkylate and solublize the graphite in organic media, or will the graphene structure go all higgledy-piggledy with tertiary alkylation? That last looks like a decorated two-dimensional diamond.

3. Proton Sponge is 1,8-bis(dimethylamino)naphthalene. Its chemical mirror is Hydride Sponge, 1,8-bis(dimethylborono)naphthalene. We have tetracyanoquinodimethane (TCNQ). Mix the pi-acids in a suitable solvent resistant to oxidation and absent of nucleophiles, then titrate in the base. The trigonal dicyanomethylene group of TCNQ is chelated by Proton Sponge resulting in a stable (intermediate, not transition state!) pentacoordinate carbon. Negative charge shuttles, aromatizes the ring, ending up as distal dicyanobenzyl anion where it is chelated by Hydride Sponge. You thus get two - count 'em - two stable pentacoordinate carbons, cationic and anionic, with massive charge separation (lotsa debyes)! It has non-linear optical properties if you derivatize the Sponge endcaps for asymmetry (re chiral allenes).

   J. Am. Chem. Soc. 119 11502 (1997) A Charge Density Analysis of Cationic and Anionic Hydrogen Bonds in a "Proton Sponge" Complex

   Lets do another one. Creativity is so easy! Look up Sargeson's sepulchrates and sarcophogates.

4. Cook tris(ethylenediamine)Co(III) with nitromethane and base as per literature to an excellent yield of the cobalt(III) sarcophogate with "para" nitro groups. Reduce to amino groups, (cobalt oxidation state thereafter is up to you - the metal ion isn't going anywhere).

   Make high molecular weight (Indian rope trick, or whatever) Redox Nylon with aromatic or aliphatic bis(acid chlorides). Imagine capacitor or battery plates where the construction material was electroactive. Industrial redox (hydrogen peroxide synthesis for wood pulp bleaching), boiler oxygen scavenger... You need not use cobalt, but start there for obvious reasons. Redox Nylon is the world's best ion exchange fabric - 100% active sites and strong. You get massive non-linear optical effects, too - Co(en)₃³⁺ is easily resolved into enantiomers to furnish chiral centers. Nylon makes high tensile heat-resistant oriented thin films.

The world is bursting with money and short of clever ideas. It desperately needs discovery and original thought. What stands in our way? Only the folks whose job it is to help us. Government and management exist to destroy money and suppress thought. They work!