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CC BY-ND-NC 4.0 · SynOpen 2017; 01(01): 0121-0124
DOI: 10.1055/s-0036-1588574
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New Facile Synthesis of Adamantyl Isothiocyanates

Vladimir Burmistrov 
,
Dmitry Pitushkin
,
Gennady Butov*
This work was supported by the Russian Fund for Basic Research (grant number 16-33-00172) and by the Ministry of Education and Science of the Russian Federation (base part of state assignment for 2017–2019; project no. 4.7491.2017/BCh).
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Publication History

Received: 20 July 2017

Accepted after revision: 29 August 2017

Publication Date:
15 September 2017 (online)

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Abstract

A series of adamantyl isothiocyanates containing different substituents in the nodal positions of adamantane or spacers between the adamantane and isothiocyanate group have been synthesised by using the reaction of the corresponding adamantyl amines with phenyl isothiocyanate.

Key words

adamantane - isothiocyanates - amines - thioureas - metathesis

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588574.
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  • References and Notes

  • 1 Butov GM. Burmistrov VV. Danilov DV. Pitushkin DA. Morisseau C. Hammock BD. Russ. Chem. Bull. 2015; 64: 1569
    Crossref
  • 2 Venkatraj M. Messagie J. Joossens J. Lambeir AM. Haemers A. Van der Veken P. Augustyns K. Bioorg. Med. Chem. 2012; 20: 1557
    CrossrefPubMed
  • 3 Lakouraj MM. Ghodrati K. Monatsh. Chem. 2008; 139: 549
    Crossref
    • 4a Kodani SD. Hammock BD. Drug Metab. Dispos. 2015; 43: 788
      CrossrefPubMed
    • 4b Lee KS. S. Liu J.-Y. Wagner KM. Pakhomova S. Dong H. Morisseau C. Fu SH. Yang J. Wang P. Ulu A. Mate CA. Nguyen LV. Hwang SH. Edin ML. Mara AA. Wulff H. Newcomer ME. Zeldin DC. Hammock BD. J. Med. Chem. 2015; 57: 7016
  • 5 Takeda K. Tsuboyama K. Takeura M. Chem. Pharm. Bull. 1989; 37: 2334
    Crossref
  • 6 Nam KD. Han M. Yoon J. Kim E. Cho S. Hahn H. Bull. Korean Chem. Soc. 2013; 34: 271
    Crossref
  • 7 Sasaki T. Nakanishi A. Ohno M. J. Org. Chem. 1981; 46: 5445
    Crossref
  • 8 Stetter J. Wulff D. Chem. Ber. 1962; 95: 2302
    Crossref
  • 9 Scattolin T. Klein A. Schoenebeck F. Org. Lett. 2017; 19: 1831
    CrossrefPubMed
    • 10a Burmistrov V. Morisseau C. Lee KS. S. Shihadih DS. Harris TR. Butov GM. Hammock BD. Bioorg. Med. Chem. Lett. 2014; 24: 2193
      CrossrefPubMed
    • 10b Burmistrov V. Morisseau C. Danilov D. Harris TR. Dalinger I. Vatsadze I. Shkineva T. Butov GM. Hammock BD. Bioorg. Med. Chem. Lett. 2015; 25: 5514
      CrossrefPubMed
    • 10c Butov GM. Burmistrov VV. Danilov DV. Pitushkin DA. Morisseau C. Hammock BD. Russ. Chem. Bull. 2015; 64: 1569
      Crossref
  • 11 Burmistrov VV. Butov GM. Pitushkin DA. Russ. J. Org. Chem. 2015; 51: 1795
    Crossref
  • 12 Satchell DP. N. Satchell RS. Chem. Soc. Rev. 1975; 2: 231
  • 13 Habib NS. Rieker A. Synthesis 1984; 825
    Article in Thieme Connect
  • 14 Turkevich NM. Agaev KA. Steblyuk PN. Sementsiv GN. Khim.-Farm. Zh. 1982; 16: 1068
  • 15 Sbei N. Haouas B. Chebbi M. Smida YB. Arfaoui Y. Boujlel K. Benkhoud ML. J. Sulfur Chem. 2017; 38: 152
    Crossref
  • 16 Burmistrov VV. Pitushkin DA. Dyachenko VS. Sdvijkov DV. Kirilov SS. Rasskazova EV. Butov GM. Izvestia VSTU 2016; 4: 68
  • 17 General Experimental Procedure: To a solution of amine (5–10 mmol) in p-xylene (10–20 mL) was added phenyl isothiocyanate (2 equiv) at room temperature. After heating to reflux for 3 h, the reaction mixture was cooled to r.t. and conc HCl (1–2 mL) was added. After stirring for 1 h, the precipitate was filtered off, the filtrate was concentrated in vacuo and the residue was purified either by crystallization from EtOH (for solid compounds 5, 7, 8, 11) or by column chromatography (for liquid compounds 3, 9, 10).Analytical Data for Compound 3: Yield: 80%; yellow oil; MS (EI): m/z (%) = 221 (5%) [M]+, 163 (100%) [Ad]+; 1H NMR (500 MHz, CDCl3): δ = 2.17 (s, 1 H), 1.81 (s, 2 H), 1.62 (dd, J = 13.0, 12.0 Hz, 4 H), 1.32 (dd, J = 16.0, 12.5 Hz, 4 H), 1.15 (s, 2 H), 0.87 (s, 6 H). 13C NMR (125 MHz, CDCl3): δ = 129.92 (s, 1 C, NCS), 59.75 (s, 1 C, C-NCS), 49.88 (s, 1 C, Ad), 49.61 (s, 2 C, Ad), 42.26 (s, 1 C, Ad), 41.89 (s, 2 C, Ad), 32.58 (s, 1 C, Ad), 29.90 (s, 2 C, Ad), 29.62 (s, 2 C, 2CH3). Elemental analysis calcd for C13H19NS: C, 70.54; H, 8.65; N, 6.33; S, 14.48; found: C, 70.59; H, 8.67; N, 6.29; S, 14.44.Analytical Data for Compound 9: Yield: 78%; yellow oil; MS (EI): m/z (%) = 221 (15) [M]+, 135 (100) [Ad]+. 1H NMR (500 MHz, CDCl3): δ = 3.51 (t, J = 7.5 Hz, 2 H, CH2-NCS), 1.96 (s, 3 H), 1.67 (dd, J = 32.0, 12.0 Hz, 4 H), 1.54–1.49 (m, 10 H). 13C NMR (125 MHz, CDCl3): δ = 128.99 (s, 1 C, NCS), 43.89 (s, 1 C, CH2-NCS), 41.88 (s, 3 C, Ad), 40.19 (s, 1 C, Ad-CH2), 36.79 (s, 3 C, Ad), 28.38 (s, 3 C, Ad), 27.54 (s, 1 C, quaternary C in Ad). Elemental analysis calcd for C13H19NS: C, 70.54; H, 8.65; N, 6.33; S, 14.48; found: C, 70.50; H, 8.66; N, 6.33; S, 14.45.Analytical Data for Compound 10: Yield: 86%; brown oil; MS (EI): m/z (%) = 221 (12) [M]+, 163 (8) [Ad-CH(CH3]+, 135 (100) [Ad]+. 1H NMR (500 MHz, CDCl3): δ = 3.35 (q, J = 6.5 Hz, 1 H, CH), 2.03 (s, 3 H), 1.74–1.46 (m, 12 H), 1.27 (d, J = 6.5 Hz, 3 H, CH3). 13C NMR (125 MHz, CDCl3): δ = 128.50 (s, NCS), 63.68 (s, 1 C, CH), 38.22 (s, 3 C, Ad), 36.90 (s, quaternary C in Ad), 36.72 (s, 3 C, Ad), 28.17 (s, 3 C, Ad), 15.13 (s, 1 C, CH3). Elemental analysis calcd for C13H19NS: C, 70.54; H, 8.65; N, 6.33; S, 14.48; found: C, 70.51; H, 8.66; N, 6.32; S 14.45