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Volumn 23, Issue 3, 2004, Pages 416-422

Organomagnesates from reactions of dialkylmagnesium compounds with alkali-metal alkoxides, potassium hydride, and other salts

Author keywords

[No Author keywords available]

Indexed keywords

AMMONIUM COMPOUNDS; ATOMS; BENZENE; CHEMICAL REACTIONS; LITHIUM COMPOUNDS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OXIDES; OXYGEN; POTASSIUM COMPOUNDS; SALTS; SOLUTIONS; STRUCTURE (COMPOSITION);

EID: 1142267469     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om030544k     Document Type: Article
Times cited : (18)

References (53)
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    • Richey, H. G., Jr. In Comprehensive Supramolecular Chemistry; Atwood, J. L., Davies, J. E. D., MacNicol, D. D., Vögtle, F., Eds.; Pergamon: Oxford, U.K., 1996; Vol. 1 (Gokel, G. W., Vol. Ed.), Chapter 21.
    • (1996) Comprehensive Supramolecular Chemistry , vol.1
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  • 4
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    • Ziegler, J.-C.1
  • 7
    • 1142277152 scopus 로고    scopus 로고
    • note
    • 2Mg, itself insoluble in benzene, was reported to dissolve in the presence of some alkali-metal alkoxide salts.
  • 9
    • 1142301444 scopus 로고    scopus 로고
    • note
    • 2Mg and KOPh in benzene or diethyl ether resulted in large amounts of precipitate; the remaining solutions had virtually no solute (analysis after hydrolysis found the solutions to contain no base, Mg, or K).
  • 10
    • 1142277149 scopus 로고    scopus 로고
    • note
    • 2Mg also were broad.
  • 14
    • 1142265081 scopus 로고    scopus 로고
    • note
    • 2Mg) too insoluble in benzene for NMR spectra.
  • 16
    • 0033667382 scopus 로고    scopus 로고
    • A recent review, including applications in synthesis
    • A recent review, including applications in synthesis: Screttas, C. G.; Steele, B. R. Appl. Organomet. Chem. 2000, 14, 653.
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    • Screttas, C.G.1    Steele, B.R.2
  • 20
    • 1142301445 scopus 로고    scopus 로고
    • note
    • 13C NMR absorptions of OMe are shown in ref 5.
  • 21
    • 1142265079 scopus 로고    scopus 로고
    • note
    • 2Mg are shown in ref 5.
  • 22
    • 1142289313 scopus 로고    scopus 로고
    • note
    • 2Mg H's indicates their stereochemistries to have a lifetime >0.002 s, setting an upper limit to the rate of any process that inverts the α-C of hexyl and hence exchanges these H's.
  • 23
    • 1142265086 scopus 로고    scopus 로고
    • note
    • 2Mg.
  • 24
    • 1142265087 scopus 로고    scopus 로고
    • note
    • 2Mg alone were stable.
  • 25
    • 1142265078 scopus 로고    scopus 로고
    • note
    • 2Mg-KOMe ratio is low, the positions of the two TMEDA absorptions are reversed compared to those of free TMEDA. The absorptions approach one another as the ratio increases, coincide at a ratio of ca. 2, and approach those of free TMEDA at higher ratios.
  • 26
    • 1142277157 scopus 로고    scopus 로고
    • note
    • 2Mg-KOR' preparations. Separation was sometimes not observed until after a sample had been sealed in an NMR tube, a procedure that involved submerging in liquid nitrogen, sealing, and then warming the NMR tube to ambient temperature.
  • 27
    • 0038389223 scopus 로고
    • note
    • This does not rule out exchange of sec-butyl groups, since exchange of RMg groups can be much faster than inversion. House, H. O.; Latham, R. A.; Whitesides, G. M. J. Org. Chem. 1967, 32, 2481.
    • (1967) J. Org. Chem. , vol.32 , pp. 2481
    • House, H.O.1    Latham, R.A.2    Whitesides, G.M.3
  • 28
    • 1142277150 scopus 로고    scopus 로고
    • note
    • 2Mg) in contrast to the single set of absorptions for 1:1 preparations.
  • 29
    • 1142265082 scopus 로고    scopus 로고
    • note
    • 2Mg led to precipitation. The only NMR absorptions were for traces of butane.
  • 30
    • 1142301446 scopus 로고    scopus 로고
    • note
    • 2Mg solution.
  • 31
    • 1142301449 scopus 로고    scopus 로고
    • note
    • 2Mg).
  • 32
    • 1142277151 scopus 로고    scopus 로고
    • note
    • 2Mg, and 18-crown-6 or TMEDA.
  • 33
    • 1142277154 scopus 로고    scopus 로고
    • note
    • 4NBr preparations having much lower concentration levels exhibited more than one set of absorptions and may have been homogeneous. Such preparations may merit further investigation.
  • 38
    • 1142277155 scopus 로고    scopus 로고
    • note
    • 2Mg.
  • 40
    • 1142265083 scopus 로고    scopus 로고
    • note
    • Analysis of a hydrolyzed portion of a similar reaction in diethyl ether also found total base: Mg:K to be ca. 3:1:1.
  • 41
    • 1142301450 scopus 로고    scopus 로고
    • note
    • 3MgK solutions to which TMEDA was added had only single sets of hexyl absorptions.
  • 42
    • 1142289312 scopus 로고    scopus 로고
    • note
    • 2Mg reactions also show only a single set of absorptions.
  • 44
    • 1142289310 scopus 로고    scopus 로고
    • note
    • 2Mg concentration in our experiments did not exceed that in previous work (0.20 M) and generally was lower.
  • 45
    • 85050539409 scopus 로고
    • note
    • 2Mg species provide any indication of permanent cis/trans relationships of R′ groups. Inversion at tricoordinate oxygen generally is rapid, although the barrier to inversion is higher in strained cyclic systems. Lambert, J. B. Top. Stereochem. 1971, 6, 19.
    • (1971) Top. Stereochem. , vol.6 , pp. 19
    • Lambert, J.B.1
  • 46
    • 1142265080 scopus 로고    scopus 로고
    • Schlosser, M., Ed.; Wiley: Chichester, U.K.; Chapter 1, Section 2.3.3
    • Schlosser, M. In Organometallics in Synthesis, A Manual; Schlosser, M., Ed.; Wiley: Chichester, U.K., 2002; Chapter 1, Section 2.3.3.
    • (2002) Organometallics in Synthesis, a Manual
    • Schlosser, M.1
  • 47
    • 0001436286 scopus 로고
    • note
    • 2Zn and KO-t-Bu that has structure 1 (Zn instead of Mg); one K-O distance (2.626(5) Å) is quite short, but of course this relationship is not likely to persist in solution. Fabicon, R. M.; Parvez, M.; Richey, Jr., H. G. J. Am. Chem. Soc. 1991, 113, 1412.
    • (1991) J. Am. Chem. Soc. , vol.113 , pp. 1412
    • Fabicon, R.M.1    Parvez, M.2    Richey Jr., H.G.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.