My PhD dissertation - Institut Fresnel

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R P N R 24a - 24d 30 HCl / DEE 4.8 M - 75 °C to 25 °C Cl R P R 25a - 25d Table 3. Dialkylchlorophosphines R2PCl. Product R = Yield 25a -C(CH3)3 79% [ ] 150 25b -C4H9 86% [147] 25c -C2H5 64% 25d -CH3 47% Mixed tertiary phosphines bearing two different alkyl groups were then prepared either from chlorophosphines 25a - 25d or from chlorodicyclohexylphosphine (25e) or Chlorodiisopropylphosphine (25f). The latter two chlorophosphines 25e and 25f were prepared according to a procedure described by W. Voskuil and J.F. Arens Treatment of these chlorophosphines with the suitable organometallic reagent afforded a series of mixed trialkyl phosphines 26a - 26k with moderate to good yields (Table 4). Cl R P R 25a - 25f R 'Li or R 'MgX DEE or THF, - 75 °C R ' [ ] 151 [ ] 152 R P R 26a - 26k [ ] 153 .
31 Table 4. Mixed tertiary alkylphosphines R2R'P. Substrate R = R'Li or R'MgX Product R' = Yield -C(CH3)3 (25a) LiC4H9 -C4H9 (26a) 83% -C(CH3)3 (25a) (CH3)2CHMgCl -CH(CH3)2 (26b) 52% -C(CH3)3 (25a) LiCH3 -CH3 (26c) 63% -C4H9 (25b) (CH3)3CCH2MgBr -CH2C(CH3)3 (26d) 65% -C4H9 (25b) LiC(CH3)3 -(CH3)3 (26e) 58% -C4H9 (25b) LiCH3 -CH3 (26f) 84% -C2H5 (25c) LiC4H9 -C4H9 (26g) 51% -CH3 (25d) LiC(CH3)3 -C(CH3)3 (26h) 67% -CH3 (25d) LiC4H9 -C4H9 (26i) 68% [38] -C6H11 (25e) LiC4H9 -C4H9 (26j) 82% -CH(CH3)2 (25f) LiCH3 -CH3 (26k) 69% The trialkyl phosphine oxides 27a - 27h were then prepared by simple oxidation of the corresponding tertiary phosphines 26a, 26b, 26d, 26e, 26g, and 26i - 26k with hydrogen peroxide in diethyl ether at 0 °C [ ] 154 [ ] 155 [ ] 156 [ ] 157 [ ] 158 [ ] 159 . These phosphine oxides were obtained in very good yield (75 to 93%) after distillation or sublimation in the case of solid compounds and served as authentic samples for NMR comparison with the crude products derived from phosphonium salt decompositions (Table 5). R' R P R 26a, b, d, e, g, i - k 30% H2O 2 DEE, 0 °C R O P R' R 27a - 27h
Page 1: Various Facets of Organophosphorus
Page 5: III Remerciements Je tiens à remer
Page 9: 3.3.6 Relevance of the Data Assesse
Page 13: VII Literature References 115 Compo
Page 17: IX Version Abrégée Les composés
Page 21 and 22: 1 Introduction 1 The present thesis
Page 23 and 24: 3 research groups in the field are
Page 25 and 26: 5 However, this mechanism suffers f
Page 27: 7 At first, a double bromine/lithiu
Page 30 and 31: 10 Although the most frequently emp
Page 32 and 33: 12 The preparation of the latter ph
Page 34 and 35: protected to its dioxolane derivati
Page 36 and 37: N (S)-14 1) NBS, THF, - 75 °C 2) -
Page 39 and 40: 3 Alkaline Decomposition of Phospho
Page 41 and 42: 3.2 Alkyl Carbanions Stabilities in
Page 43 and 44: 3.3.1 Mechanistic Discussion on the
Page 45 and 46: 25 The assumption reported by these
Page 47 and 48: 27 However, in the eventuality of a
Page 49: 29 To prepare tertiary phosphines b
Page 53 and 54: 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 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 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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My PhD dissertation - Institut Fresnel

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