Synthesis and chemistry of 1,3,5,7-tetranitrocubane including measurement of its acidity, formation of o-nitro anions, and the first preparations of pentanitrocubane and hexanitrocubane

Journal of the American Chemical Society

Volumn 119, Issue 41, 1997, Pages 9591-9602

  Lukin, Kirill A ^a   Li, Jianchang ^a   Eaton, Philip E ^a   Kanomata, Nobuhiro ^a   Hain, Jürgen ^a   Punzalan, Eric ^a   Gilardi, Richard ^b  

^a UNIVERSITY OF CHICAGO   (United States)

^b NAVAL RESEARCH LABORATORY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CUBANE DERIVATIVE;

DRUG SYNTHESIS; MEASUREMENT; PH; REACTION ANALYSIS; REVIEW; X RAY CRYSTALLOGRAPHY;

EID: 0030703631     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970552q     Document Type: Review

References (65)

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42. 10
43. We can find no definitive evidence in the literature for metalation e.g., CH → CLi) assisted by an ortho nitro group. Ortho metalation of aromatic nitro compounds is usually unsuccessful; electron transfer is the dominant process instead (Seebach, D.; Colvin, E. W.; Lehr, F.; Weller, T. Chimia 1979, 33, 8). However, ortho-lithiated nitrobenzenes (thermally unstable) have been generated by metal-halogen exchange at temperatures below -100 °C (Köbrich, G.; Buck, P. Chem. Ber. 1970, 103, 1412; 1970, 103, 1420
44. We can find no definitive evidence in the literature for metalation e.g., CH → CLi) assisted by an ortho nitro group. Ortho metalation of aromatic nitro compounds is usually unsuccessful; electron transfer is the dominant process instead (Seebach, D.; Colvin, E. W.; Lehr, F.; Weller, T. Chimia 1979, 33, 8). However, ortho-lithiated nitrobenzenes (thermally unstable) have been generated by metal-halogen exchange at temperatures below -100 °C (Köbrich, G.; Buck, P. Chem. Ber. 1970, 103, 1412; 1970, 103, 1420
45. We can find no definitive evidence in the literature for metalation e.g., CH → CLi) assisted by an ortho nitro group. Ortho metalation of aromatic nitro compounds is usually unsuccessful; electron transfer is the dominant process instead (Seebach, D.; Colvin, E. W.; Lehr, F.; Weller, T. Chimia 1979, 33, 8). However, ortho-lithiated nitrobenzenes (thermally unstable) have been generated by metal-halogen exchange at temperatures below -100 °C (Köbrich, G.; Buck, P. Chem. Ber. 1970, 103, 1412; 1970, 103, 1420
46. When deprotonation β to a nitro group does occur (e.g., in β-nitro ketones because of the carbonyl group) elimination of nitrite and olefin formation follows immediately (Ono, N. In Nitro Compounds. Recent Advances in Synthesis and Chemistry, Feuer, H., Nielsen, A. T., Eds.; VCH Publishers Inc., 1990, p 86).
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50. We are grateful to Drs. Ravi Shankar and Gene Wicks for these experiments.
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52. For example: (a) Lukin, K. A.; Li, J.; Gilardi, R.; Eaton, P. E. Angew. Chem., Int. Ed. Engl. 1996, 35, 866. (b) Lukin, K. A.; Li, J.; Gilardi, R.; Eaton, P. E. J. Org. Chem., in press.
53. For example: (a) Lukin, K. A.; Li, J.; Gilardi, R.; Eaton, P. E. Angew. Chem., Int. Ed. Engl. 1996, 35, 866. (b) Lukin, K. A.; Li, J.; Gilardi, R.; Eaton, P. E. J. Org. Chem., in press.
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60. We examined the literature, briefly, to see if more recent results might have rendered obsolete traditional values for van der Waals radii, particularly the value for aliphatic carbon. A recent, massive review (Rowland, R. S.; Taylor, R. J. Phys. Chem. 1996, 100, 7384) examined close contacts in 28 000 suitable crystal structures. The analysis pointed out inaccuracies in a few of the still-used 1948 Pauling vdW values (Pauling, L. The Nature of the Chemical Bond, 2nd ed.; Cornell University Press: Ithaca, NY, 1948; pp 187-193) but generally supported the 1964 tabulation of Bondi (Bondi, A. J. Phys. Chem. 1964, 68, 441). This gives a carbon van der Waals radius of 1.7 Å and an oxygen radius of 1.52 Å).
61. We examined the literature, briefly, to see if more recent results might have rendered obsolete traditional values for van der Waals radii, particularly the value for aliphatic carbon. A recent, massive review (Rowland, R. S.; Taylor, R. J. Phys. Chem. 1996, 100, 7384) examined close contacts in 28 000 suitable crystal structures. The analysis pointed out inaccuracies in a few of the still-used 1948 Pauling vdW values (Pauling, L. The Nature of the Chemical Bond, 2nd ed.; Cornell University Press: Ithaca, NY, 1948; pp 187-193) but generally supported the 1964 tabulation of Bondi (Bondi, A. J. Phys. Chem. 1964, 68, 441). This gives a carbon van der Waals radius of 1.7 Å and an oxygen radius of 1.52 Å).
62. We examined the literature, briefly, to see if more recent results might have rendered obsolete traditional values for van der Waals radii, particularly the value for aliphatic carbon. A recent, massive review (Rowland, R. S.; Taylor, R. J. Phys. Chem. 1996, 100, 7384) examined close contacts in 28 000 suitable crystal structures. The analysis pointed out inaccuracies in a few of the still-used 1948 Pauling vdW values (Pauling, L. The Nature of the Chemical Bond, 2nd ed.; Cornell University Press: Ithaca, NY, 1948; pp 187-193) but generally supported the 1964 tabulation of Bondi (Bondi, A. J. Phys. Chem. 1964, 68, 441). This gives a carbon van der Waals radius of 1.7 Å and an oxygen radius of 1.52 Å).
63. Chu, S. C.; Jeffrey, G. A.; Sakurai, T. Acta Crystallogr. 1962, 15, 651.
64. Hirotsu, K.; Kamitori, S.; Higuchi, T.; Tabushi, I.; Yamamura, K.; Nonoguchi, H. J. Inclusion Phenom. 1984, 2, 215.
65. Eaton, P. E.; Nordari, N.; Tsanaktsidis, J.; Upadhyaya, S. P. Synthesis 1995, 501.