My PhD dissertation - Institut Fresnel

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88 13 C NMR: δ = 32.9 (d, J = 12 Hz), 27.6 (d, J = 14 Hz), 24.4 (d, J = 11 Hz), 14.3 (d, J = 16 Hz), 11.9 (d, J = 13 Hz), 12.9 ppm. 31 P NMR: δ = 54.0 ppm. tert-Butyldimethylphosphine (26h) [156] : Analogously prepared from chlorodimethylphosphine (25d; 24 g, 0.25 mol) and tert-butyllithium (0.25 mol) in pentane (0.16 L); colorless liquid; b.p. 38 - 39 °C/140 Torr; yield: 19.7 g (67%). 1 H NMR: δ = 0.81 (d, J = 4.7 Hz, 6 H), 1.03 (d, J = 10.7 Hz, 9 H) ppm. 13 C NMR: δ = 26.5 (d, J = 10.6 Hz), 26.4 (d, J = 13.3 Hz), 9.5 (d, J = 19.8 Hz) ppm. 31 P NMR: δ = -28.7 ppm. Butyldimethylphosphine (26i): Analogously prepared from chlorodimethylphosphine (25d; 14 g, 0.15 mol) and butyllithium (0.15 mol) in hexane (0.10 L); colorless liquid; b.p. 45 - 48 °C/31 Torr (ref. [38] b.p. 56 - 60 °C/72 Torr); yield: 19.7 g (68%). 1 H NMR: δ = 1.3 - 0.9 (m, 9 H), 0.83 (d, J = 3.7 Hz, 6H) ppm. 13 C NMR: δ = 32.9 (d, J = 12.1 Hz), 27.6 (d, J = 13.7 Hz), 24.4 (d, J = 11.3 Hz), 14.3 (d, J = 16.0 Hz), 12.9 ppm. 31 P NMR: δ = -53.5 ppm. Butyldicyclohexylphosphine (26j): Analogously prepared from Chlorodicyclohexylphosphine (25e; 24 g, 0.11 mol) and butyllithium (0.11 mol) in hexane (68 mL); colorless liquid; b.p. 107 - 108 °C/0.39 Torr; yield: 20.8 g (82%). 13 C NMR: δ = 33.3 (d, J = 12 Hz), 30.7 (d, J = 18 Hz), 30.4 (d, J = 14 Hz), 29.1 (d, J = 8 Hz), 27.4 (d, J = 10 Hz), 27.3 (d, J = 6 Hz), 26.6, 24.6 (d, J = 12 Hz), 21.0 (d, J = 16 Hz), 13.9 ppm. 31 P NMR: δ = -1.3 ppm.
89 C16H31P (254.39) calcd. C 75.54% H 12.28% found C 75.52% H 12.26%. Methyldiisopropylphosphine (26k): Prepared following the procedure described by A.H. Cowley and J.L. Mills [158] starting from chlorodiisopropylphosphine (25f; 12 g, 80 mmol) and methyllithium (80 mmol) in diethyl ether (66 mL); colorless liquid; b.p. 47 - 48 °C/63 Torr (ref. [158] b.p. 150 - 151 °C); yield: 7.24 g (69%). 3.2 Trialkylphosphine Oxides Butyldi-tert-butylphosphine oxide (27a): Analogously prepared from butyldi-tert- butylphosphine (26a; 8.5 g, 42 mmol) and 30% hydrogen peroxide solution (10 mL); [ ] colorless liquid; b.p. 78 - 79 °C/0.5 Torr (ref. 231 b.p. 73 °C/0.025 Torr); yield: 7.96 g (87%). 1 H NMR: δ = 1.7 (m, 4 H), 1.4 (m, 2 H), 1.26 (d, J = 12.8 Hz, 18 H), 0.94 (t, J = 7.4 Hz, 3 H) ppm. 13 C NMR: δ = 35.7 (d, J = 59 Hz), 26.7, 25.3 (d, J = 5 Hz), 24.9 (d, J = 12 Hz), 21.5 (d, J = 57 Hz), 13.7 ppm. 31 P NMR: δ = 62.4 ppm. C12H270P (218.32) calcd. C 66.02% H 12.47% found C 65.95% H 12.34%. Di-tert-butylisopropylphosphine oxide (27b): Analogously prepared from di-tert-butylisopropylphosphine (26b; 3.2 g, 17 mmol) and 30% hydrogen peroxide solution (5 mL); white needles after sublimation; m.p. 64 - 66 °C (ref. [231] b.p. 63 - 65 °C); yield: 3.05 g (88%). 1 H NMR: δ = 2.37 (symm. m, 1 H), 1.41 (d, J = 17 Hz, 18 H), 1.32 (d, J = 13 Hz, 6 H) 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
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 106 and 107: 84 apparatus. The solution was adde
Page 108 and 109: 86 Di-tert-butylisopropylphosphine
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:
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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