Sodium Chloride → 3-(4-Methoxyphenyl)-6,8-dimethyl-1-[(phenylmetoxy)methyl]-5-(phenylmethyl)-2,4-dithia-6,8-diazabicyclo[3.2.2]nonane-7,9-dione

HRID 1483183

反応式

HRID 1483183 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH:9]2[S:15][CH:14]3[C:16](=[O:19])[N:17]([CH3:18])[C:11]([CH2:22][C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)([C:12](=[O:21])[N:13]3[CH3:20])[S:10]2)=[CH:5][CH:4]=1.Cl[CH2:30][O:31][C:32]1C=CC=CC=1.C([Li])CCC.[CH3:43][CH2:44][CH2:45][CH2:46][CH2:47][CH3:48].[Na+].[Cl-]>C1COCC1>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([CH:9]2[S:10][C:11]3([CH2:22][C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)[C:12](=[O:21])[N:13]([CH3:20])[C:14]([CH2:30][O:31][CH2:32][C:45]4[CH:44]=[CH:43][CH:48]=[CH:47][CH:46]=4)([C:16](=[O:19])[N:17]3[CH3:18])[S:15]2)=[CH:7][CH:8]=1

参加物

7

反応物 5

HCID 5234Sodium ChlorideHCID 8058HexaneHCID 81201(Chloromethoxy)benzeneHCID 900047513-(4-Methoxyphenyl)-6,8-dimethyl-1-(phenylmethyl)2,4-dithia-6, 8-diazabicyclo[3.2.2]nonane-7,9-dioneHCID 178418339Butyllithium

生成物 1

HCID 1183410493-(4-Methoxyphenyl)-6,8-dimethyl-1-[(phenylmetoxy)methyl]-5-(phenylmethyl)-2,4-dithia-6,8-diazabicyclo[3.2.2]nonane-7,9-dione

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

Crystalline 26 (144 mg, 0.35 mmol, 1 eq) and phenyl chloromethyl ether (500 μL, 455 mg, 1.75 mmol, 5 eq., 60% reagent only) was dissolved in anhydrous THF (40 mL). The solution was cooled to −78° C. and to the stirred mixture 1.54 M n-butyllithium in hexane (1.16 mL, 1.8 mmol, 1.5 eq) was added dropwise over a period of 5 min. After the mixture was stirred for 10 min at −78° C. the resulting red, cloudy solution was allowed to warm to room temperature and was stirred. Saturated NaCl solution was added into the reaction mixture and the red solution was extracted with dichloromethane. The organic phase was washed with water twice, dried under MgSO4 and concentrated under vacuum. The syrup was separated on column (hexane-ethylacetate, 8-2, Rf 0.4) to give 114 mg of 27 as a glass-like solid (62%). 1H NMR (CDCl3, TMS, ppm) δ: 7.35 (m, 5H), 7.28 (d, J=8.8 Hz, 2H), 6.86 (d, J=8.7 Hz, 2H), 5.02 (s, 1H), 4.72 (d, J=11.7 Hz, 1H), 4.58 (d, J=12.0 Hz, 1H), 4.51 (d, J=10.8 Hz, 1H), 4.20 (d, J=16.5 Hz, 1H), 3.78 (s, 3H), 3.74 (d, J=10.5 Hz, 1H), 3.25 (d, J=16.9 Hz, 1H), 3.19 (s, 3H), 3.15 (s, 3H). FAB-MS: Calcd. for C29H30N2O4S2: 534.1. Found [M+H]+: 535.0.

後処理

  1. additionwas added dropwise over a period of 5 min
  2. temperatureto warm to room temperature
  3. stirringwas stirred
  4. extractionthe red solution was extracted with dichloromethane
  5. washThe organic phase was washed with water twice
  6. customdried under MgSO4
  7. concentrationconcentrated under vacuum
  8. customThe syrup was separated on column (hexane-ethylacetate, 8-2, Rf 0.4)

出典と根拠

ORDレコード
ord-fe941e5bca5d4cfe91d3a9abefafba82
出典データセット
uspto-grants-2016_08
特許番号
US09416145B2

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