My PhD dissertation - Institut Fresnel

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96 31 P NMR settings: It is known that the Nuclear Overhauser Effect (NOE) causes change in the integration intensity during 1 H decoupling. Thus, all spectra were recorded in a 1 H-nondecoupling mode. Furthermore, pulse delay time must be long enough to allow complete relaxation of the nuclei and thus quantitative measurements. Hence, a typical experiment based on the progressive saturation [ , ] and saturation recovery 233 234 was applied to the phosphonium salts in order to determine the minimum spin-lattice relaxation time T1(min.). To insure complete relaxation of all nuclei considered, the experimental relaxation time T1(exp.) was then set to 5T1(min.). The effective NMR settings used were data points 32K, spectral width 19000 Hz, pulse width 12.0 µsec (pulse angle 90°), pulse delay time 30 sec, and number of FID accumulation 256. In order to evaluate the standard error on the measurements, a calibration was performed by recording several spectra, in the conditions described above. Twelve sample mixtures of di-tert-butylmethylphosphine oxide and dibutylmethylphosphine oxide were prepared by accurate weighting in ratios ranging from 48.7 : 51.3 to 99.3 : 0.7. The accuracy of the 31 P-NMR quantification was hence checked for ratios close to 1 : 1 mixture, as well as extreme 99 : 1 cases, by comparing the theoretical ratios to thoses obtained by NMR integration of the peaks (see Figure 10 – 14 for typical examples). Each sample of phosphine oxides mixture was recorded three times and an average integration value was used to obtain a linear regression with a good correlation factor (r² = 0.99): Theoretica l ratio = 1.01× Experimental ratio - 0.50 Theoretical ratio: (48.7:51.3) Experimental ratio: (48.0:52.0) Figure 10. Calibration 31 P-NMR spectrum of a (tert-C4H9)2P(O)CH3 / (C4H9)2P(O)CH3
97 Theoretical ratio: (50.3:49.7) Experimental ratio: (51.0:49.0) Figure 11. Calibration 31 P-NMR spectrum of a (tert-C4H9)2P(O)CH3 / (C4H9)2P(O)CH3 Theoretical ratio: (94.0:6.0) Experimental ratio: (93.4:6.6) Figure 12. Calibration 31 P-NMR spectrum of a (tert-C4H9)2P(O)CH3 / (C4H9)2P(O)CH3
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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
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 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 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,
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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