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Synthesis and Crystal Structures of N-Aryl-N-methylaminocyclohexanols

Abstract

N-Aryl-N-methylaminocyclohexanols 1012 were synthesised and their crystal structures were studied by X-ray diffraction. Compound 10 crystallizes in the monoclinic space group Cc with cell parameters of a = 13.7366(2) Å, b = 13.7234(2) Å, c = 26.9057(5) Å, β = 93.0900(5)°, V = 5064.70(14) Å3 and Z = 16. Compound 11 crystallizes in the trigonal space group \(P\bar{3}\) with cell parameters of a = b = 25.4429(4) Å, c = 9.6417(2) Å, V = 5405.27(16) Å3 and Z = 18. Compound 12 crystallizes in the monoclinic space group P21/n with cell parameters of a = 9.9511(2) Å, b = 11.5777(2) Å, c = 20.5968(4) Å, β = 95.5037(9)°, V = 2362.04(8) Å3 and Z = 8. All three structures were characterised by arrays of hydrogen bonding interactions and these crystallographic studies revealed conformations of 1012 which gave valuable information into the mechanism of the reaction during their formation.

Graphical Abstract

Crystals of (RS,RS,RS)-3-[N-methyl-N-(4'-methoxyphenyl)amino]cyclohexane-1,2-diol, (RS,RS,RS)-3-(N-methyl-N-phenylamino)cyclohexane-1,2-diol and (RS,RS,RS)-2-fluoro-6-(N-methyl-N-phenylamino)cyclohexan-1-ol were synthesised and their structures were studied by X-ray diffraction.

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Notes

  1. 1.

    The relative configuration within 3 was established by single crystal X-ray diffraction analysis of a derivative [25].

  2. 2.

    The solvent volume was chosen to ensure a final concentration of 0.1 M wrt the substrate, taking into account the volume of HBF4·OEt2 and m-CPBA solution added.

  3. 3.

    Freshly prepared from titrated m-CPBA and dried over MgSO4.

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Acknowledgments

The authors would like to thank Syngenta for a CASE studentship (A. J. C.) and Ajinomoto Co., Inc. for funding (W. K.).

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Correspondence to Stephen G. Davies.

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Cresswell, A.J., Davies, S.G., Hewings, D.S. et al. Synthesis and Crystal Structures of N-Aryl-N-methylaminocyclohexanols. J Chem Crystallogr 43, 646–654 (2013). https://doi.org/10.1007/s10870-013-0460-8

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Keywords

  • Amino alcohol
  • Hydrogen bonding
  • Olefinic oxidation
  • Dihydroxylation
  • Hydroxyfluorination