Hydrogen Bromide → (R)-1-Bromo-1-(2-naphthyl)ethane

HRID 18846

反応式

HRID 18846 の反応式
[BrH:1].CN([C:5]1[C:10]2[C:11](N(C)C)=[CH:12][CH:13]=[CH:14][C:9]=2[CH:8]=[CH:7][CH:6]=1)C.[CH2:18](O)[CH3:19]>>[Br:1][C@@H:18]([C:6]1[CH:7]=[CH:8][C:9]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:5]=1)[CH3:19]

参加物

4

反応物 3

HCID 260Hydrogen BromideHCID 702EthanolHCID 88675Proton sponge

生成物 1

HCID 52420327(R)-1-Bromo-1-(2-naphthyl)ethane

実験手順

A 5 mm NMR tube was charged with 4.7 mg (0.010 mmol) of crystals of salt (S)-5. This readily dissolved in CDCl3 to 5 cm depth. NMR spectra (1H and 19F) showed 5 with a low level (7 mole %) of ethanol impurity. This was mixed with 2 mg of crystals of (R)-7a ([α]D≈+23°). Note that excess 5 is necessary to assure complete reaction of 7a, thus avoiding kinetic sorting at the end. NMR (1H and 19F) of this solution showed 5 and 7a in 1:0.82 mole ratio. After 30 min. at 20° C., the spectra showed 30% conversion of 7a cleanly to (S,S) and (S,R) diastereomers in ˜2.5:1 ratio. At 18 h, NMR showed 97% conversion to 3:1 mixture of the diastereomers (de≈50%). No more 7a was detected after an additional 24 h at 25° C. The final integration ratio of the two singlets at −69.42 and −69.28 ppm in the 19F NMR spectrum was 2.8 (de≧47%)* for the major (S,S)-6a and minor (S,R)-6a diastereomers. Proton NMR assignments for these are, respectively: 3.54 and 3.49 (q, CH3O, 5JHF=1.7 Hz), 1.76 and 1.71 (d, CH3CH, 3JHH=7 Hz), 4.89 and 4.91 (overlapping q, CH3CH) and 7.18-7.95 ppm (m, 12 aryl H, not resolved). Note that large crystals of the HBr salt of PROTON SPONGE (12-HBr) separated in the course of this reaction but did not interfere with NMR acquisitions and integrations.

後処理

  1. dissolutionThis readily dissolved in CDCl3 to 5 cm depth
  2. waitAt 18 h
  3. additionto 3:1 mixture of the diastereomers (de≈50%)
  4. customseparated in the course of this reaction

出典と根拠

ORDレコード
ord-d9ecdc9688a74aff99f67193d7b63e4b
出典データセット
uspto-grants-2010_06
特許番号
US07741513B2

関連ノート

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