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The efficiency of ferrocene as a catalyst for significantly more efficient in the absence of the inhibition of methamphetamine synthesis water. Further investigation is required in is remarkable. Ferrocene is in the lowest order to sort out the details of the chemistry common oxidation state of this compound. occurring with these compounds. Oxidation to the ferrocenium ion occurs at mild potentials, but this process is not likely One of the principle problems encountered to play a role in a reducing environment. To with the Fe(II) and Fe(III) coordination the best of our knowledge, reduction of compounds we have studied has been their ferrocene has not been reported in the lit- insolubility in anhydrous ammonia. Com- erature. pounds that are insoluble in anhydrous am- monia are expected to be incompatible with Reduction of ferrocene probably results in a the ammonia distribution infrastructure. large structural reorganization, for example, partial or complete cyclopentadienyl disso- ciation. Such a process is likely to be criti- cal to the catalytic function of the compound by opening up accessible coordination sites necessary for the stabilization of intermedi- ates in the proton reduction mechanism. 4 Conclusions At the present extent of our investigation, Figure 4. Structures of the organometallic we have identified two potentially viable compounds discussed in the text. additives for anhydrous ammonia, each capable of inhibiting methamphetamine synthesis. The first, 1,1,1,2-tetrafluoro- 3.5 Organometallic Compounds ethane, cannot be removed by the simple distillation of the ammonia. Furthermore, we have estimated and experimentally veri- funded under Navy Contract N00024-98-D- fied that each molecule of this compound is 8124. capable of scavenging ca. eight electrons. A 6 References high electron scavenging capacity is neces- sary to minimize the amount of additive [1] Hargreaves, G. Clandestine Drug necessary to inhibit the reduction reaction. Labs Chemical Time Bombs FBI Law En- forcement Bulletin April 2000, 69, 1-6. Ferrocene is another additive that is poten- tially useful as a methamphetamine synthe- [2] Cazenavette, G. J., III DEA Congres- sis inhibiting ammonia. This compound ap- sional Testimony before the House Judiciary pears to be highly efficient at catalytically Subcommittee on Crime, February 25, 2000. scavenging solvated electrons. It does not appear that the additive can be defeated by [3] Carey, F. A.; Sundberg, R. J. the addition of excess lithium metal. In Advanced Organic Chemistry Part B: order to defeat the catalyst, a cryogenic Reactions and Synthesis , Third Ed., distillation is required. A cryogenic distilla- Plenum Press, New York, Ch. 5, Sec. 5. tion of ammonia is difficult, dangerous, and requires additional equipment and supplies. [4] Corcoran, J. J. DEA Congressional The increased level of difficulty is expected Testimony before the House Judiciary Sub- to reduce the number of untrained chemists, committee on Crime, August 8, 2000. i.e., the majority of the clandestine chemists, capable of carrying out the synthesis. The [5] Ely, R. A.; McGrath, D. C. Lith- additional step will require additional time ium-Ammonia Reduction of Ephedrine to to carry out the synthesis. The additional Methamphetamine: An Unusual Clandestine equipment necessary to conduct the distilla- Synthesis J. Forensic Sci. 1990, 35, 720- tion will decrease the portability and the 723. ease of concealment of the clandestine laboratory. Finally, the acquisition of the [6] Parker, S. Ammonia s New cryogenic supplies necessary to perform the Cachet , U.S. News Online, 9/27/99. distillation will increase the exposure of the clandestine chemist to surveillance. [7] Amshel, C. E.; Fealk, M. H.; Phillips, B. J.; Caruso, D. M. Anhydrous In summary, the addition of either inhibitor Ammonia Burns Case Report and Review of is expected to both decrease the number of the Literature Burns 2000, 26, 493-497. clandestine laboratories due to the increased level of difficulty and increase the probabil- [8] National Drug Threat Assessment ity of detection of the laboratory operation. 2001, The Domestic Perspective , National 6 Acknowledgments Drug Intelligence Center, U. S. Department of Justice, October 2000. The authors would like to acknowledge the support and technical inputs from Dr. Albert [9] Bennett, D. Stealing Anhydrous Brandenstein and Mr. James Petrousky of Ammonia , Delta Farm Press, Vol. 57, No. ONDCP/CTAC, and from Dr. Haddad 19, May 12,2000. Dubbleday and Mr. Richard Mellor of SPAWARSYSCEN. This work is being [10] Hwu, J. R.; Wein, Y. S.; Leu, Y.-J., Calcium Metal in Liquid Ammonia for Selective Reduction of Organic Com- pounds , J. Org. Chem. 1996, 61, 1493- 1499. [11] Rabideau, P. W.; Marcinow, Z. The Birch Reduction of Aromatic Compounds , Organic Reactions 1992, 42, 1-334. [12] Sun, G.-R.; He, J.-B.; Pittman, C. U., Jr., Destruction of Halogenated Hydro- carbons with Solvated Electrons in the Pres- ence of Water , Chemosphere 2000, 41, 907-916. [13] Chai Kao, C.-P.; Paulaitis, M. E.; Yokozeki, A. Double azeotropy in binary mixtures of NH3 and CHF2CF3 Fluid Phase Equilibria 1997, 127, 191-203. [14] Koelle, U., Transition Metal Catalyzed Proton Reduction , New J. Chem. 1992, 16, 157-169. [15] Baxendale, J. H.; Fielden, E. M.; Keene, J. P. Proc. Roy. Soc. Ser. A 1965, 286, 320-336.
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Dobre pomysły nie mają przeszłości, mają tylko przyszłość. Robert Mallet De minimis - o najmniejszych rzeczach. Dobroć jest ważniejsza niż mądrość, a uznanie tej prawdy to pierwszy krok do mądrości. Theodore Isaac Rubin Dobro to tylko to, co szlachetne, zło to tylko to, co haniebne. Dla człowieka nie tylko świat otaczający jest zagadką; jest on nią sam dla siebie. I z obu tajemnic bardziej dręczącą wydaje się ta druga. Antoni Kępiński (1918-1972)
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