My PhD dissertation - Institut Fresnel

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98 Theoretical ratio: (96.1:3.9) Experimental ratio: (95.7:4.3) Figure 13. Calibration 31 P-NMR spectrum of a (tert-C4H9)2P(O)CH3 / (C4H9)2P(O)CH3 Theoretical ratio: (99.3:0.7) Experimental ratio: (98.6:1.4) Figure 14. Calibration 31 P-NMR spectrum of a (tert-C4H9)2P(O)CH3 / (C4H9)2P(O)CH3
99 To illustrate the experimental method for the quantification of the phosphine oxides resulting from alkaline decomposition of phosphonium halides, a detailed protocole is given for tributylneopentylphosphonium iodide degradation: Tributylneopentylphosphonium iodide (0.40 g, 1.0 mmol) was suspended in butanol (5.0 mL) and a 6.0 M aqueous potassium hydroxide solution (1.0 mL) was added. Triisopropylphosphine oxide (0.13 g, 0.76 mmol) was immediately added as internal standard. The reaction mixture was then heated at 110 °C in a thermostated bath until no trace of starting phosphonium remained. The gases formed during the decomposition were bubbled into a solution of bromine (0.2 mL, 0.5 g, 3 mmol) in chloroform (5.0 mL). After the gas evolution ceased, the bromine solution was treated with a sodium sulfite solution, phases were decantated. The organic layer was dried with sodium sulfate and the presence of brominated adduct was immediately checked by gas chromatography (30 m, DB-1, 70 °C). Cyclohexane (20 mL) was added to the reaction slurry and the solvents were removed under reduced pressure. The residue was dissolved in diethyl ether (15 mL), dried with sodium sulfate and evaporated to dryness. 31 P NMR experiment was directly run on the crude mixture without any further purification (See Figure 15). Yield: 98% according to triisopropylphosphine oxide (internal standard). This experiment was repeated three times in the same conditions to afford an average phosphine oxide ratio by comparison with the spectra of each individual original phosphine oxide. The average tributylphosphine oxide/dibutylneopentylphosphine oxide was calculated of 17:83. Figure 15. Alkaline decomposition of tributylneopentylphosphonium iodide with potassium hydroxide in a butanol/water (8:2) mixture at 110 °C
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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
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3.2 Alkyl Carbanions Stabilities in
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3.3.1 Mechanistic Discussion on the
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25 The assumption reported by these
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27 However, in the eventuality of a
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29 To prepare tertiary phosphines b
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31 Table 4. Mixed tertiary alkylpho
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33 were comparable to those obtaine
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35 led to the formation of di-tert-
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37 depending on the alkyl substitue
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39 4 A Novel Access to Atropisomeri
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41 Since the homocoupling of the ha
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43 Few other attempts to selectivel
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45 The second phenol ether 36 was f
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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 92 and 93: 70 deuterochloroform (CDCl3) unless
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 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,
Page 142 and 143: 118 [ 70] J. Drowart, C.E. Myers, R
Page 144 and 145: 120 [117] S.T. Graul, R.R. Squires,
Page 146 and 147: 122 [170] B.H. Lipshutz, F. Kayser,
Page 148: 124 [212] M. Schlosser, in Organome
Page 152: O P 27i: p. 30, 80 C 9H 21OP P 26b:
Page 156: P P P O 2: p. 11, 59 3 P O O O 11:
Page 160: Nom Maurin Prénom Michaël 129 Cur
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My PhD dissertation - Institut Fresnel

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