My PhD dissertation - Institut Fresnel

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70 deuterochloroform (CDCl3) unless otherwise stated, at 400 MHz, 101 MHz, 162 MHz and 376 MHz respectively, and with a Bruker DPX-400 spectrometer. The chemical shifts δ given are relative to the signal of tetramethylsilane (δ 0.00 ppm) for 1 H-NMR and 13 C-NMR, and to trichlorofluoromethane (δ 0.00 ppm) for 19 F-NMR. For the 31 P-NMR spectra, a 85% solution of phosphoric acid was used as an external standard (δ 0.00 ppm). Variable-temperature 1 H-NMR studies were performed in perdeuterated tetrahydrofuran, chemical shifts referring to the residual signal of the non deuterated tetrahydrofuran (δ 3.58 ppm). The absolute values of the temperatures were determined by means of a methanol probe [ , ] 223 224 . Coupling constants (J) are given in Hz. Coupling patterns are described by abbreviations: s (singlet), d (doublet), t (triplet), q (quartet), quint (quintet), m (multiplet), symm. m (symmetrical multiplet). Composite patterns (dd, dt for example) are arranged according to decreasing coupling constants. Optical rotations were measured on a Perkin Elmer polarimeter 341, specific rotations being indicated at the mentioned wave length (nm), concentration (g/100 mL), and solvent. Mass spectra (Finnigan 4000 or Nermag R 10-10 spectrometer) were obtained by chemical ionisation at 95.3 eV and at a source temperature of 100 °C in an ammonia atmosphere. The numbers given in the parentheses indicate the intensities relative to the base peak (100%). Elemental analyses were performed by the laboratories of I. Beetz, (D-96301 Kronach) or Solvias (CH-4002 Basel). The expected percentages were calculated using the atomic weight numbers listed in 2000 IUPAC recommendations. X-ray diffraction analyses were performed with an Oxford Diffraction/Kuma diffractometer having a kappa geometry and a CCD KM4CCD/Sapphire detector for 44 and 45 and with an IP mar345 for 43. The software Crysalis RED [ ] structure was resolved and refined with SHELXTL version 5.1 226 . [ ] 225 was used to determine the crystallographic data. The If no literature quotation is associated with a compound, it means either that it had not been previously described at all or without sufficient characterization. The literature search was performed with the aid of Chemical Abstracts, Beilstein Crossfire and Scifinder and covers the period from 1900 up to February 2005.
2 The Preparation of Phosphines from Triethyl phosphite 2.1 Triarylphosphines 71 General procedure for the preparation of triarylphosphines: At -75 °C, butyllithium (0.15 mol) in hexanes (0.10 L) was added to a solution of a bromo- or iodoarene (0.15 mol) in tetrahydrofuran (0.30 L). Triethyl phosphite (8.7 mL, 8.3 g, 50 mmol) was added at -75 °C and the suspension was stirred at 25 °C until Gilman color test I [ ] 227 did not show the presence of any organolithium reagent. The volatiles were evaporated and the crude product was crystallized from ethanol to afford the desired compound. Tris(4-methoxyphenyl)phosphine (1): Prepared from 1-bromo-4-methoxybenzene (28 g, 0.15 mol); colorless needles; m.p. 129 - 131 °C (ref. [80] m.p. 129 - 131 °C); yield: 17.5 g (99%). 1 H NMR: δ = 7.2 (m, 6 H), 6.87 (dd, J = 9, 1 Hz, 6 H), 3.80 (s, 9 H) ppm. 13 C NMR: δ = 160.5, 135.2 (d, J = 21 Hz), 134.1 (d, J = 11 Hz), 114.1 (d, J = 7 Hz), 55.2 ppm. 31 P NMR: δ = - 9.5 ppm. MS: 352 (100%, M + ), 138 (48%). Tris(2-methoxyphenyl)phosphine (2): Prepared from 1-bromo-2-methoxybenzene (28 g, 0.15 mol); colorless needles; m.p. 208 - 210 °C (ref. [81] m.p. 209 - 210 °C); yield: 17.4 g (99%).
Page 1:
Various Facets of Organophosphorus
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III Remerciements Je tiens à remer
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3.3.6 Relevance of the Data Assesse
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VII Literature References 115 Compo
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IX Version Abrégée Les composés
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1 Introduction 1 The present thesis
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3 research groups in the field are
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5 However, this mechanism suffers f
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7 At first, a double bromine/lithiu
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10 Although the most frequently emp
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12 The preparation of the latter ph
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protected to its dioxolane derivati
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N (S)-14 1) NBS, THF, - 75 °C 2) -
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3 Alkaline Decomposition of Phospho
Page 41 and 42: 3.2 Alkyl Carbanions Stabilities in
Page 43 and 44: 3.3.1 Mechanistic Discussion on the
Page 45 and 46: 25 The assumption reported by these
Page 47 and 48: 27 However, in the eventuality of a
Page 49 and 50: 29 To prepare tertiary phosphines b
Page 51 and 52: 31 Table 4. Mixed tertiary alkylpho
Page 53 and 54: 33 were comparable to those obtaine
Page 55 and 56: 35 led to the formation of di-tert-
Page 57 and 58: 37 depending on the alkyl substitue
Page 59 and 60: 39 4 A Novel Access to Atropisomeri
Page 61 and 62: 41 Since the homocoupling of the ha
Page 63 and 64: 43 Few other attempts to selectivel
Page 65 and 66: 45 The second phenol ether 36 was f
Page 67 and 68: 47 The enantiomeric purity was chec
Page 69 and 70: 49 A second purpose of this derivat
Page 71 and 72: 51 substrates considered. In conseq
Page 73 and 74: 53 Single-crystal X-ray analysis of
Page 75 and 76: 55 To convert atropisomer Ia into I
Page 77 and 78: 57 This finally allows one to use t
Page 79 and 80: the steric bulk and charge delocali
Page 81 and 82: 61 To check the reproducibility of
Page 83: 63 Figure 9. Full lineshape analysi
Page 86 and 87: 66 suitably substituted dilithiobip
Page 89: Experimental Part
Page 94 and 95: 72 1 H NMR: δ = 7.32 (dddd, J = 9,
Page 96 and 97: 1 H NMR: δ = 6.96 (s, 3 H), 6.94 (
Page 98 and 99: 76 C21H21O9P (448.36) calcd. C 56.2
Page 100 and 101: 78 C12H12BrN (250.13) calcd. C 57.6
Page 102 and 103: 80 C13H13NO2 (215.25) calcd. C 72.5
Page 104 and 105: 82 3.1.1 Dialkyl-N,N-diethylaminoph
Page 106 and 107: 84 apparatus. The solution was adde
Page 108 and 109: 86 Di-tert-butylisopropylphosphine
Page 110 and 111: 88 13 C NMR: δ = 32.9 (d, J = 12 H
Page 112 and 113: 90 13 C NMR: δ = 41.5 (d, J = 61 H
Page 114 and 115: 31 P NMR: δ = 53.4 ppm. 92 C16H31O
Page 116 and 117: 94 13 C NMR: δ = 40.8 (d, J = 3 Hz
Page 118 and 119: 96 31 P NMR settings: It is known t
Page 120 and 121: 98 Theoretical ratio: (96.1:3.9) Ex
Page 123 and 124: 101 4 The Preparation and Racemate
Page 125 and 126: 103 extraction protocol with ethyl
Page 127 and 128: 105 extracted with ethyl acetate (2
Page 129 and 130: 107 (+)-(M)-Dimethyl-6,6’-dibromo
Page 131 and 132: 109 (+)-(M)-2,2’-Dibromo-6,6’-b
Page 133 and 134: 111 1 H NMR: δ = 7.2 (m, 20 H), 7.
Page 135 and 136: 113 2,2’-Dilithio-6,6’-bis(meth
Page 137: References
Page 140 and 141: 116 Conference Proceedings, Naples,
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118 [ 70] J. Drowart, C.E. Myers, R
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120 [117] S.T. Graul, R.R. Squires,
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122 [170] B.H. Lipshutz, F. Kayser,
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124 [212] M. Schlosser, in Organome
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O P 27i: p. 30, 80 C 9H 21OP P 26b:
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P P P O 2: p. 11, 59 3 P O O O 11:
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Nom Maurin Prénom Michaël 129 Cur
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