Disodium disulfite → Methyl 3-hydroxy-3-(hydroxymethyl)-2,3-dihydro-1-benzoxepin-7-carboxylate

HRID 1791048ノート

反応式

HRID 1791048 の反応式
CC[C@H]1[C@H]2C[C@H]([C@H](OC3C4C(=CC=CC=4)C(O[C@H](C4C=CN=C5C=4C=C(OC)C=C5)[C@@H]4N5C[C@H](CC)[C@@H](CC5)C4)=NN=3)C3C=CN=C4C=3C=C([O:22]C)C=C4)N(CC2)C1.CS(N)(=O)=O.C=C1C=[CH:70][C:69]2[CH:72]=[C:73]([C:76]([O:78][CH3:79])=[O:77])[CH:74]=[CH:75][C:68]=2[O:67]C1.S(OS([O-])=O)([O-])=O.[Na+].[Na+].[C:89]([OH:93])([CH3:92])([CH3:91])[CH3:90].O>ClCCl>[OH:93][C:89]1([CH2:92][OH:22])[CH:91]=[CH:70][C:69]2[CH:72]=[C:73]([C:76]([O:78][CH3:79])=[O:77])[CH:74]=[CH:75][C:68]=2[O:67][CH2:90]1

参加物

7

反応物 5

HCID 24346Disodium disulfiteHCID 72879MethanesulfonamideHCID 22042256HCID 22042256、化合物HCID 510036741-((1R)-((2R,4R,5S)-5-ethylquinuclidin-2-yl)(6-methoxyquinolin-4-yl)methoxy)-4-((1R)-((2R,4S,5R)-5-ethylquinuclidin-2-yl)(6-methoxyquinolin-4-yl)methoxy)phthalazineHCID 714019492-Methylpropan-2-ol--water (1/1)2 回

生成物 1

HCID 22042276Methyl 3-hydroxy-3-(hydroxymethyl)-2,3-dihydro-1-benzoxepin-7-carboxylate収率 100%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

21 g (7 equivalents) of AD-mix-α and 1.31 g (13.8 mmol) of methanesulfonamide dissolved in 75 ml of a 1/1 tert-butyl alcohol/water mixture are added at ambient temperature to 3 g (13.8 mmol) of methyl 3-methylene-2,3-dihydro-1-benzoxepin-7-carboxylate, prepared according to example 35, in suspension in 20 ml of a 1/1 tert-butyl alcohol/water mixture. The reaction medium is stirred for 4 days and is then treated with 2.6 g of sodium disulfite. The medium is reextracted with dichloromethane and the organic phases are washed with brine. After evaporating, the crude reaction product is purified by chromatography on silica gel (ethyl acetate/heptane 50/50) to give 3.2 g (100%) of methyl 3-hydroxy-3-(hydroxymethyl)-2,3-dihydro-1-benzoxepin-7-carboxylate in the form of a colorless honey; 1H NMR (300 MHz, CDCl3): 7.88 (d, J=2.4 Hz, 1H), 7.81 (dd, J=2.4 Hz and 8.4 Hz, 1H), 6.98 (d, J=8.4 Hz, 1H), 6.37 (d, J=12 Hz, 1H), 5.88 (d, J=12 Hz, 1H), 4.24 (dd, J=1.2 Hz and 11.7 Hz, 1H), 4.01 (d, J=11.7 Hz, 1H), 3.87 (s, 3H), 3.69 and 3.60 (2d, J=11.4 Hz, 2H).

後処理

  1. customprepared
  2. washthe organic phases are washed with brine
  3. customAfter evaporating
  4. customthe crude reaction product
  5. customis purified by chromatography on silica gel (ethyl acetate/heptane 50/50)

出典と根拠

ORDレコード
ord-2bc99a6f11a2488abd035af078d29166
出典データセット
uspto-grants-2006_07
特許番号
US07071340B2

反応ノート

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