My PhD dissertation - Institut Fresnel

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90 13 C NMR: δ = 41.5 (d, J = 61 Hz), 27.1 (d, J = 86 Hz), 26.7, 18.7 (d, J = 2 Hz) ppm. 31 P NMR: δ = 97.7 ppm. Dibutylneopentylhposphine oxide (27c) [81] : Analogously prepared from dibutylneopentylphosphine (26d; 5.0 g, 23 mmol) and 30% hydrogen peroxide solution (9 mL); colorless liquid; b.p. 113 - 118 °C/0.25 Torr; yield: 4.59 g (86%). 1 H NMR: δ = 1.7 (m, 6 H), 1.64 (d, J = 10.0 Hz, 2 H), 1.5 (m, 7 H), 1.16 (s, 9 H), 0.94 (t, J = 7.0 Hz, 6H) ppm. 13 C NMR: δ = 40.9 (d, J = 63 Hz), 31.5 (d, J = 7 Hz), 30.1 (d, J = 64 Hz), 24.3 (d, J = 14 Hz), 24.2 (d, J = 4 Hz), 24.2, 13.6 ppm. 31 P NMR: δ = 50.1 ppm. Dibutyl-tert-butylposphine oxide (27d): Analogously prepared from dibutyl-tert- butylposphine (26e; 10 g, 51 mmol) and 30% hydrogen peroxide solution (15 mL); colorless liquid; b.p. 95 - 96 °C/0.38 Torr; yield: 8.29 g (75%). 1 H NMR: δ = 1.6 (m, 8 H), 1.4 (m, 4 H), 1.17 (d, J = 14.0 Hz, 9 H), 0.94 (t, J = 7.4 Hz, 6 H) ppm. 13 C NMR: δ = 32.4 (d, J = 66 Hz), 24.8, 24.7 (d, J = 6 Hz), 24.5 (d, J = 22 Hz), 24.3 (d, J = 27 Hz), 13.7 ppm. 31 P NMR: δ = 57.9 ppm. C12H27OP (218.32) calcd. C 66.02% H 12.47% found C 66.01% H 12.43%. Butyldiethylphosphine oxide (27e): Analogously prepared from butyldiethylphosphine (26g; 6.0 g, 41 mmol) and 30% hydrogen peroxide solution (17 mL); colorless liquid; b.p. 93 - 94 °C/2.5 Torr (ref. [37] b.p. 160 °C/3.1 Torr); yield: 5.17 g (78%).
91 1 H NMR: δ = 1.7 (m, 6 H), 1.5 (m, 2 H), 1.4 (m, 2 H), 1.17 (dt, J = 15.6, 7.7 Hz, 6 H), 0.94 (t, J = 7.2 Hz, 3 H) ppm. 13 C NMR: δ = 26.2 (d, J = 65 Hz), 24.2 (d, J = 14 Hz), 23.5 (d, J = 4 Hz), 19.8 (d, J = 66 Hz), 13.6, 5.7 (d, J = 5 Hz) ppm. 31 P NMR: δ = 58.1 ppm. Butyldimethylposphine oxide (27f): A 30% aqueous hydrogen peroxide solution (3.5 mL, 29 mmol) was added dropwise to a solution of butyldimethylphosphine (26i; 2.3 g, 19 mmol) in diethyl ether (38 mL) at 0 °C. After the exothermic reaction has ceased, phases were separated and the organic layers was washed with a saturated sodium sulfite solution (10 mL) and dried with sodium sulfate. Removal of the solvent and distillation of the residue afforded a colorless liquid; b.p. 81 - 82 °C/0.35 Torr (ref. [38] b.p. 70 - 73 °C/0.25 Torr; yield: 2.18 g (84%). 1 H NMR: δ = 1.7 (m, 2 H), 1.6 (m, 2 H), 1.48 (d, J = 12.3 Hz, 6 H), 1.45 (symm. m, 2 H), 0.95 (t, J = 7.2 Hz, 3 H) ppm. 13 C NMR: δ = 31.5 (d, J = 69 Hz), 24.1 (d, J = 20 Hz), 24.0, 16.1 (d, J = 68 Hz), 13.6 ppm. 31 P NMR: δ = 45.6 ppm. Butyldicyclohexylphosphine oxide (27g): Analogously prepared from butyldicyclohexylphosphine (26j; 2.7 g, 15 mmol) and 30% hydrogen peroxide solution (5 mL); white needles after sublimation; m.p. 57 - 59 °C; yield: 3.77 g (93%). 1 H NMR: δ = 2.0 (m, 3 H), 1.8 (m, 6 H), 1.7 (m, 3 H), 1.6 (m, 4 H), 1.4 (m, 6 H), 1.2 (m, 6 H), 0.93 (t, J = 7.3 Hz, 3 H) ppm. 13 C NMR: δ = 36.3 (d, J = 64 Hz), 26.6 (d, J = 3 Hz), 26.6 (d, J = 3 Hz), 26.0 (d, J = 1 Hz), 26.0 (d, J = 2 Hz), 25.7 (d, J = 3 Hz), 24.7 (d, J = 13 Hz), 24.1 (d, J = 4 Hz), 23.6 (d, J = 61 Hz), 13.7 ppm.
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
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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
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 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 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,
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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