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Volumn , Issue 12, 2008, Pages 1877-1881

A novel method for the synthesis of N-alkoxyamines starting from nitroxide radicals and ketones

Author keywords

N alkoxyamines; Peroxides; Piperidines; Polymer light stabilizer; Radical reactions

Indexed keywords

AMINE; COPPER; HYDROGEN PEROXIDE; KETONE DERIVATIVE; N ALKOXYAMINE DERIVATIVE; NITROXIDE;

EID: 48349147502     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1078526     Document Type: Article
Times cited : (18)

References (35)
  • 4
    • 3042616491 scopus 로고    scopus 로고
    • Matyjazewski, K, Davis, T. P, Eds, Wiley Interscience: Hoboken
    • (c) Hawker, C. J. In Handbook of Radical Polymerization; Matyjazewski, K.; Davis, T. P., Eds.; Wiley Interscience: Hoboken, 2002, 463-522.
    • (2002) Handbook of Radical Polymerization , pp. 463-522
    • Hawker, C.J.1
  • 10
    • 3542996292 scopus 로고    scopus 로고
    • Compare also: Bertin, D.; Gigmes, D.; Le Mercier, C.; Marque, S. R. A.; Tordo, P. J. Org. Chem. 2004, 69, 4925.
    • (e) Compare also: Bertin, D.; Gigmes, D.; Le Mercier, C.; Marque, S. R. A.; Tordo, P. J. Org. Chem. 2004, 69, 4925.
  • 15
    • 48349135186 scopus 로고    scopus 로고
    • See also ref. 5
    • (b) See also ref. 5.
  • 16
    • 33846287580 scopus 로고    scopus 로고
    • (a) Nesvadba, P. Chimia 2006, 12, 832.
    • (2006) Chimia , vol.12 , pp. 832
    • Nesvadba, P.1
  • 17
    • 48349114635 scopus 로고    scopus 로고
    • See also ref. 3a
    • (b) See also ref. 3a.
  • 21
    • 48349112248 scopus 로고    scopus 로고
    • General Procedure for the Synthesis of N-Alkoxyamines Prostab 5198™ (2.50 g, 14.5 mmol) was dissolved in 4-heptanone (18.5 mL, 132.2 mmol, and 30% aq H2O2 (10 mL, 97.1 mmol) was added dropwise. Upon cooling to 10 °C, CuCl (100 mg, 7 mol, was added. The reaction mixture was stirred overnight at r.t. to give a greenish solution. A peroxide test conducted at this stage indicated no residual H2O2. EtOAc (80 mL) was added and the two phases were separated. The organic phase was washed successively with 10% ascorbic acid soin, H2O, 10% Na2CO3 soln, and brine. After drying over sodium sulfate and removal of the solvent, a green-brown oil was obtained. The product was purified by column chromatography on SiO2 (hexane-EtOAc, 15:1) to afford 1.75 g (60, of 1-propoxy-2,2,6,6- tetramethylpiperidin-4-ol; off-white solid. 1H NMR 400 MHz, CDCl3, δ
    • +.
  • 22
    • 48349116685 scopus 로고    scopus 로고
    • Commercial Product of Ciba Inc
    • Commercial Product of Ciba Inc.
  • 23
    • 48349097064 scopus 로고    scopus 로고
    • TEMPO works equally well. This method should also be applicable to other nitroxyl radicals
    • TEMPO works equally well. This method should also be applicable to other nitroxyl radicals.
  • 25
    • 84932727448 scopus 로고
    • and references cited therein. See also
    • (b) See also: Kirillov, A. I. Zh. Org. Khim. (Engl. Transl.) 1966, 2, 1048; and references cited therein.
    • (1966) Zh. Org. Khim. (Engl. Transl.) , vol.2 , pp. 1048
    • Kirillov, A.I.1
  • 26
    • 48349099829 scopus 로고    scopus 로고
    • Dussault, P. Reactions of Hydroperoxides and Peroxides, In Active Oxygen in Chemistry, 2; Search Series, Chapman and Hall: London, 1995, 150.
    • Dussault, P. Reactions of Hydroperoxides and Peroxides, In Active Oxygen in Chemistry, Vol. 2; Search Series, Chapman and Hall: London, 1995, 150.
  • 27
    • 48349131322 scopus 로고    scopus 로고
    • General Procedure for the Synthesis of N-Alkoxyamines Using Solvents Prostab 5198™ (8.6 g, 49.9 mmol) was added to toluene (100 mL, followed by 1-methoxyacetone (11.0 g, 2.5 equiv) and CuCl (125 mg, 2.5 mol, The mixture was stirred well while adding 30% aq H2O 2 (17.8 mL, 3.5 equiv) over a period of 1 h. The reaction mixture was stirred at r.t. overnight. Workup: as reported in ref. 8. Yield 8.89 g (82, of 1-methoxymethyl-2,2,6,6-tetrarnethylpiperidin-4-ol, off-white solid; NOCH 2OMe/NOMe ratio, ca. 13.5:1. 1H NMR (300MHz, CDCl 3, δ, 4.01 (m, 1 H, 3.82 (s, 3 H, 1.89 (dd, J, 14.2,3.6 Hz, 2 H, 1.82 (br s, 1 H, 1.67 (dd, J, 11.0, 3.6 Hz, 2 H, 1.21 (2 s, 6 H, 1.15 (2 s, 6 H, 13C NMR (75 MHz, CDCl3, δ, 103.1 (s, 63.5 (2q, 60.1 (t, 56.9 (p, 48.6 (2s, 33.7 (2 p, 21.5 (2 p, IR neat, 3239, 3005, 2972, 2933, 1467, 1363, 1343, 1245, 1148, 1
    • +.
  • 29
    • 48349097053 scopus 로고    scopus 로고
    • General Procedure for the Synthesis of N-Alkoxyamines under Acidic Condition144, 116, 56, 36s Prostab 5198™ (25.1 g, 145.1 mmol) was dissolved in 2-butanone (105 mL, and 30% aq H2O 2 (50.0 mL, 485.3 mmol, ca. 3 equiv) was added over 10 min. Upon cooling to 5 °C, CuCl (0.71 g, 7.2 mmol, 5 mol, was added and the temperature was kept between 10 °C and 15 °C After 15-30 min, the pH of the reaction mixture was slowly adjusted to ca. 3.2 using 1 N HCl. The brownish solution was stirred overnight at r.t. while keeping the pH value at around 3.5 using a dosimat. A green homogeneous solution was obtained after 12 h. Workup: as reported in ref. 8. Yield: 22.9 g (114 mmol, 78, of 1-ethoxy-2,2,6,6- tetramethyl-piperidin-4-ol, solid, NOEt/NOMe ratio, ca. 9:1. 1H NMR (400 MHz, CDCl3, δ, 3.93 (dddd, J, 14.4, 11.6, 5.6, 3.6 Hz, 1 H, 3.77 (q, J, 9.6 Hz, 2 H, 1.81 dd, J, 14.4, 5.6
    • +.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.