Rapid fixation of methylene chloride by a macrocyclic amine

Journal of the American Chemical Society

Volumn 127, Issue 12, 2005, Pages 4184-4185

  Lee, Jung Jae ^a   Stanger, Keith J ^a   Noll, Bruce C ^a   Gonzalez, Carlos ^c   Marquez, Manuel ^b   Smith, Bradley D ^a  

^a UNIVERSITY OF NOTRE DAME   (United States)

^b LOS ALAMOS NATIONAL LABORATORY   (United States)

^c NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; DICHLOROMETHANE; FIXATIVE; MACROCYCLIC COMPOUND; QUATERNARY AMMONIUM DERIVATIVE;

ARTICLE; CALCULATION; CHEMICAL BINDING; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; DENSITY FUNCTIONAL THEORY; REACTION ANALYSIS; STRUCTURE ANALYSIS; X RAY ANALYSIS;

EID: 16244393066     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja042208g     Document Type: Article

References (18)

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6. 2. The energies relative to the sum of 1 plus methylene chloride are: 5 (-8.4 kcal/mol), 6 (-2.1 kcal/mol), and 7 (-38.0 kcal/mol).
7. 2. The energies relative to the sum of 1 plus methylene chloride are: 5 (-8.4 kcal/mol), 6 (-2.1 kcal/mol), and 7 (-38.0 kcal/mol).
8. N2 reaction of chloride anion with methylene chloride indicate that the nucleophile interacts with the two CH residues and forms a prereaction complex. Pagliai, M.; Raugei, S.; Cardini, G.; Schettino, V. Phys. Chem. Chem. Phys. 2001, 3, 4870-4873.
9. Ion-pair 2 crystallizes as a cofacial dimer in the solid state (see Supporting Information). However, calculations indicate that an unaggregated version of this conformation in solution is 2-3 kcal/mol less stable than conformation 7.
10. -1 at 298 K, (determined by NMR dilution experiments), which is substantially higher than the expected value for a quaternary ammonium chloride in DMSO. See, for example: Savedoff, L. G. J. Am. Chem. Soc. 1966, 88, 664-667.
11. (a) Menshutkin, N. Z. Phys. Chem. 1890, 6, 41-57.
12. (b) Abboud, J. M.; Notario, R.; Berrán, J.; Sola, M. H. In Progress in Physical Organic Chemistry; Taft, R. W., Ed.; Wiley: New York, 1993; Vol. 19, pp 1-182.
13. Swain, C. G.; Eddy, R. W. J. Am. Chem. Soc. 1948, 70, 2989-2994.
14. 3 at 298 K.
15. More studies are needed before the meaning of this kinetic isotope effect can be properly evaluated. However, it is worth noting at this point that the Menshutkin reaction typically exhibits an inverse secondary KIE. See, for example: Leffek, K. T.; Matheson, A. F. Can. J. Chem. 1972, 50, 982-985.
16. 3 with alumina and eliminate any residual HCl that otherwise inhibits the nucleophilicity of 1.
17. 1, is linearly dependent on the concentration of excess methylene chloride. For a detailed discussion of a related N-alkylation system that also exhibits simplified kinetics, see: Heemstra, J. M.; Moore, J. S. J. Org. Chem. 2004, 69, 9234-9237.
18. This information can be found on the Internet at http://www.epa.gov and http://www.osha.gov.