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Volumn 47, Issue 23, 2008, Pages 4436-4439

Efficient solvent-free syntheses of [2]- and [4]rotaxanes

Author keywords

Dihydropyrimidines; Host guest systems; Interlocked molecules; Rotaxanes; Solvent free synthesis

Indexed keywords

BALL MILLING; CONDENSATION REACTIONS;

EID: 46749115177     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200800530     Document Type: Article
Times cited : (55)

References (36)
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    • a) Molecular Electronics: Science and Technology (Eds.: A. Aviram, M. Ratner), New York Academy of Sciences, New York, 1998;
    • (1998) Molecular Electronics: Science and Technology
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  • 10
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    • The production of tight-binding ion pairs during the stoppering process is believed to lower the yields of several rotaxane syntheses; for examples, see a S. J. Rowan, S. J. Cantrill, J. F. Stoddart, Org. Lett. 1999, 1, 129-132;
    • The production of tight-binding ion pairs during the stoppering process is believed to lower the yields of several rotaxane syntheses; for examples, see a) S. J. Rowan, S. J. Cantrill, J. F. Stoddart, Org. Lett. 1999, 1, 129-132;
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    • Ed, K. Tanaka, Wiley-VCH, Weinheim
    • b) Solvent Free Organic Synthesis (Ed.: K. Tanaka), Wiley-VCH, Weinheim, 2004.
    • (2004) Solvent Free Organic Synthesis
  • 15
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    • The corresponding [2]rotaxane was synthesized in 85% yield from the film obtained after evaporating a solution of all three components. This elegant approach takes advantage of bringing the reactants together to generate the film, and thus may not be classified as a true solid/solid reaction. Directly grinding the three individual solids together gave the [2]rotaxane in only 11% yield; see A. Orita, J. Okano, Y. Tawa, L. Jiang, J. Otera, Angew. Chem. 2004, 116, 3810-3814;
    • The corresponding [2]rotaxane was synthesized in 85% yield from the film obtained after evaporating a solution of all three components. This elegant approach takes advantage of bringing the reactants together to generate the film, and thus may not be classified as a true solid/solid reaction. Directly grinding the three individual solids together gave the [2]rotaxane in only 11% yield; see A. Orita, J. Okano, Y. Tawa, L. Jiang, J. Otera, Angew. Chem. 2004, 116, 3810-3814;
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  • 25
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    • When using the immediate solvent evaporation method (ISEM, that is, dissolving 1 (38 μmol, 2-H·PF6 (38 μmol, and 3 (76 μmol) in CH3CN (0.5 mL) and then evaporating the solvent under reduced pressure, we found that the [2]rotaxane 4-H·PF6 was also generated in the resulting thin film. According to 1H NMR spectroscopy, the reaction was finished after 5 h with a maximum yield of 64, as determined from integration of the signals of the interlocked and free macrocycles see the Supporting Information, By using the ball-milling approach, the same mixture gave a yield of 87% after 1 h of grinding, as determined by integration of the 1H NMR signals. These results show that the yield of 4-H·PF6 from the ball-milling reaction was higher. For details of the ISEM approach, see A. Orita, G. Uehara, K. Miwa, J. Otera, Chem. Commun. 2006, 4729-4731 and
    • 6 from the ball-milling reaction was higher. For details of the ISEM approach, see A. Orita, G. Uehara, K. Miwa, J. Otera, Chem. Commun. 2006, 4729-4731 and Ref. [5].
  • 29
    • 53549085233 scopus 로고    scopus 로고
    • We did not detect any signals for 4-H·PF6 in the 1H NMR spectrum of a ball-milled equimolar mixture of the solid dumbbell 5-H·PF6 and the macrocycle 1, which suggests that it was unlikely that this [2]rotaxane was generated through slippage
    • 6 and the macrocycle 1, which suggests that it was unlikely that this [2]rotaxane was generated through slippage.
  • 33
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    • 6.
    • 6.
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    • +, see a M. C. T. Fyfe, J. F. Stoddart, Adv. Supramol. Chem. 1999, 5, 1-53;
    • +, see a) M. C. T. Fyfe, J. F. Stoddart, Adv. Supramol. Chem. 1999, 5, 1-53;
  • 35
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    • for a discussion of the complexity that can arise from ion pairing in this recognition system, see b
    • for a discussion of the complexity that can arise from ion pairing in this recognition system, see b) W. J. Jones, H. W. Gibson, J. Am. Chem. Soc. 2003, 125, 7001-7004.
    • (2003) J. Am. Chem. Soc , vol.125 , pp. 7001-7004
    • Jones, W.J.1    Gibson, H.W.2
  • 36
    • 53549113715 scopus 로고    scopus 로고
    • The [4]rotaxane 8-H3·3PF6 could also be generated by dissolving DB24C8 (50 μmol, 6-H3· 3PF6 (13 μmol, and 3 (50 μmol) in CH3CN (1 mL) and then evaporating the solvent under reduced pressure. According to 1H NMR spectroscopy, this ISEM reaction required 5 h to reach completion; the yield was 52% based on integration of signals of the aromatic protons of the interlocked and free DB24C8 moieties (see the Supporting Information, By using the ball-milling approach, the corresponding reaction afforded the [4]rotaxane in 82% yield (1H NMR spectroscopy) after 1 h. The yields of the isolated [4]rotaxanes from the ISEM and ball-milled approaches were 50 and 78, respectively; thus, the latter approach was superior
    • 1H NMR spectroscopy) after 1 h. The yields of the isolated [4]rotaxanes from the ISEM and ball-milled approaches were 50 and 78%, respectively; thus, the latter approach was superior.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.