My PhD dissertation - Institut Fresnel

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94 13 C NMR: δ = 40.8 (d, J = 3 Hz), 23.8 (d, J = 16 Hz), 23.7 (d, J = 14 Hz), 23.7 (d, J = 4 Hz), 23.6 (d, J = 3 Hz), 7.5 (d, J = 53 Hz) ppm. 31 P NMR: δ = 31.7 ppm. C10H24IP (302.18) calcd. C 39.75% H 8.01% found C 39.72% H 8.02%. Di-tert-butyldimethylphosphonium iodide (28b): Analogously prepared from di-tert-butylmethylphosphine (26c; 1.9 g, 12 mmol) and iodomethane (0.7 mL, 1.7 g, 12 mmol); white needles (from diethyl ether); m.p. > 320 °C (ref. [164] m.p. 338 - 346 °C); yield: 3.57 g (99%). 1 H NMR: δ = 2.13 (d, J = 11.8 Hz, 6 H), 1.48 (d, J = 15.3 Hz, 18 H) ppm. 13 C NMR: δ = 27.2, 26.1 (d, J = 4 Hz), 29.7 (d, J = 11 Hz) ppm. 31 P NMR: δ = 50.0 ppm. Dibutyldi-tert-butylphosphonium bromide (28c): Analogously prepared from butyldi-tert-butylphosphine (26a; 1.7 g, 8.4 mmol) and butyl bromide (2.3 mL, 2.9 g, 21 mmol); white prisms (from ethyl acetate); m.p. 105 - 106 °C; yield: 2.79 g (98%). 1 H NMR: δ = 2.52 (symm. m, 4 H), 1.7 (m, 4 H), 1.65 (symm. m, 4 H), 1.55 (d, J = 14.4 Hz, 18 H), 1.00 (t, J = 7.0 Hz, 6 H) ppm. 13 C NMR: δ = 35.0 (d, J = 37 Hz), 28.2, 26.1 (d, J = 6 Hz), 24.8 (d, J = 14 Hz), 17.8 (d, J = 40 Hz), 13.7 ppm. 31 P NMR: δ = 47.6 ppm. C16H36BrP (339.33) calcd. C 56.63% H 10.69% Tributylneopentylphosphonium iodide (28d) found C 56.08% H 10.56%. [ ] 232 : Butyl iodide (1.9 mL, 3.1 g, 17 mmol) was quickly added to a solution of dibutylneopentylphosphine (26d; 2.4 g, 11 mmol) in
95 hexanes (15 mL) and the reaction mixture was heated to reflux for 12 h. At 25 °C, the precipitate was filtered under inert atmosphere and recrystallized from ethyl acetate to afford white needles; m.p. 173 - 175 °C; yield: 4.40 g (98%). 1 H NMR: δ = 2.55 (d, J = 13.4 Hz, 2 H), 2.5 (m, 6 H), 1.6 (m, 12 H), 1.23 (s, 9 H), 0.99 (t, J = 7.0 Hz, 9 H) ppm. 13 C NMR: δ = 33.3 (d, J = 42 Hz), 32.3 (d, J = 5 Hz), 31.8 (d, J = 7 Hz), 24.1 (d, J = 5 Hz), 24.0 (d, J = 15 Hz), 21.2 (d, J = 46 Hz), 13.5 ppm. 31 P NMR: δ = 34.9 ppm. Butyltriethylphosphonium iodide (28e) [167] : Analogously prepared from triethylphosphine (3.1 g, 26 mmol) and butyl iodide (4.3 mL, 7.0 g, 39 mmol); white needles (from ethyl acetate); m.p. 194 - 196 °C; yield: 7.44 g (96%). 1 H NMR: δ = 2.53 (dq, J = 13.0, 7.7 Hz, 6 H), 1.6 (m, 6 H), 1.33 (dt, J = 18.0, 7.7 Hz, 9 H), 0.99 (t, J = 7.2 Hz, 3 H) ppm. 13 C NMR: δ = 24.0 (d, J = 15 Hz), 23.7 (d, J = 5 Hz), 18.2 (d, J = 47 Hz), 13.5, 12.7 (d, J = 49 Hz), 6.3 (d, J = 6 Hz) ppm. 31 P NMR: δ = 41.1 ppm. 3.4 Alkaline Decomposition of Phosphonium Salts General procedure: The phosphonium salt (1.0 mmol) was suspended in butanol (5 .0 mL) and a 6.0 M aqueous potassium hydroxide solution (1.0 mL) was added. Tributylphosphine oxide or triisopropylphosphine oxide (1 mmol), depending on the expected reaction products, was immediately added as internal standard. The reaction mixture was then heated at 110 °C 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 mL). After the gas evolution ceased, cyclohexane (20 mL) was added 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.
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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
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 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 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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