My PhD dissertation - Institut Fresnel

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84 apparatus. The solution was added continuously during removal of the solvent under atmospheric pressure, and the residual liquid was distilled under vacuum to afford a colorless liquid; b.p. 57 - 58 °C/12 Torr (ref. [150] b.p. 70 - 72 °C/13 Torr); yield: 28.5 g (79%). 1 H NMR: δ = 1.22 (d, J = 12.2 Hz, 18 H) ppm. 13 C NMR: δ = 27.8 (d, J = 17) ppm. 31 P NMR: δ = 149.6 ppm. Dibutylchlorophosphine (25b): Analogously prepared from dibutyl-N,N-diethylaminophosphine (24b; 43 g, 0.20 mol); colorless liquid; b.p. 60 - 61 °C/3.4 Torr (ref. [147] b.p. 91 - 92 °C/12 Torr); yield: 31.0 g (86%). 1 H NMR: δ = 1.5 (m, 2 H), 1.4 (m, 8 H), 1.2 (m, 2 H), 0.90 (t broad, J = 7.0 Hz, 6 H) ppm. 13 C NMR: δ = 36.9 (d, J = 28.5 Hz), 26.6 (d, J = 14.2 Hz), 23.7 (d, J = 11.7 Hz), 13.7 (d, J = 0.5 Hz) ppm. 31 P NMR: δ = 119.1 ppm Chlorodiethylphosphine (25c): Analogously prepared from diethyl-N,N-diethylaminophosphine (24c; 32 g, 0.20 mol); colorless liquid; b.p. 34 - 37 °C/40 Torr (ref. [151] b.p. 131 - 132 °C); yield: 15.9 g (64%). 1 H NMR: δ = 1.5 (m, 2 H), 1.2 (m, 2 H), 1.0 (m, 6 H) ppm. 13 C NMR: δ = 26.7 (d, J = 27.3 Hz), 8.4 (d, J = 12.7 Hz) ppm. 31 P NMR: δ = 118.0 ppm. Chlorodimethylphosphine (25d): Analogously prepared from dimethyl-N,N diethylaminophosphine (24d; 27 g, 0.20 mol); colorless liquid; b.p. 62 - 65 °C (ref. [152] b.p. 72 -75 °C); yield: 9.07 g (47%).
85 1 H NMR: δ = 0.97 (d, J = 6.1 Hz, 6 H) ppm. 13 C NMR: δ = 23.0 (d, J = 27.6 Hz) ppm. 31 P NMR: δ = 93.1 ppm. Chlorodicyclohexylphosphine (25e): Prepared following the procedure described by W. Voskuil and J.F. Arens [153] , starting from cyclohexyl chloride (35 mL, 35 g, 0.30 mol), magnesium (7.0 g, 0.30 mol) and phosphorus trichloride (26 mL, 41 g, 0.15 mol); colorless liquid; b.p. 100 - 102 °C/0.45 Torr (ref. [153] b.p. 85 - 87 °C/0.001 Torr); yield: 18.0 g (53%). Chlorodiisopropylphosphine (25f): Prepared following the procedure described by W. Voskuil and J.F. Arens [153] , starting from isopropyl chloride (27 mL, 23 g, 0.30 mol), magnesium (7.0 g, 0.30 mol) and phosphorus trichloride (13 mL, 21 g, 0.15 mol); colorless liquid; b.p. 55 - 57 °C/18 Torr (ref. [153] b.p. 46 - 47 °C/10 Torr); yield: 8.96 g (37%). 3.1.3 Trialkylphosphines Butyldi-tert-Butylphosphine (26a): Analogously prepared from chlorodi-tert- butylphosphine (25a; 22 g, 0.12 mol) and butyllithium (0.12 mol) in hexane (82 mL); [ ] colorless liquid; b.p. 75 - 76 °C/7.4 Torr (ref. 230 b.p. 88 - 90 °C/8 Torr); yield: 20.5 g (83%). 1 H NMR: δ = 1.5 - 1.2 (m, 6 H), 1.12 (d, J = 10.6 Hz, 18 H), 0.90 (t, J = 7.4 Hz, 3 H) ppm. 13 C NMR: δ = 32.8 (d, J = 24 Hz), 31.1 (d, J = 20 Hz), 29.6 (d, J = 13 Hz), 24.6 (d, J = 13 Hz), 20.7 (d, J = 19 Hz), 13.9 ppm. 31 P NMR: δ = 31.6 ppm. C12H27P (202.32) calcd. C 71.24% H 13.45% found C 70.90% H 13.41%.
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
Page 21 and 22:
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
Page 43 and 44:
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
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 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 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,
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:
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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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