Hydrochloric Acid → Methyl 6-chloro-2,2-dimethylchroman-8-carboxylate

HRID 402802ノート

反応式

HRID 402802 の反応式
[CH3:1][C:2]1([CH3:16])[CH2:11][CH2:10][C:9]2[C:4](=[C:5]([C:12]([O:14][CH3:15])=[O:13])[CH:6]=[CH:7][CH:8]=2)[O:3]1.Cl.C1C(=O)N([Cl:25])C(=O)C1.S([O-])([O-])(=O)=S.[Na+].[Na+].[OH-].[Na+]>ClCCl.CO.O>[Cl:25][C:7]1[CH:8]=[C:9]2[C:4](=[C:5]([C:12]([O:14][CH3:15])=[O:13])[CH:6]=1)[O:3][C:2]([CH3:16])([CH3:1])[CH2:11][CH2:10]2

参加物

9

反応物 5

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 24477Sodium ThiosulfateHCID 31398ChlorosuccinimideHCID 66765741Methyl 2,2-dimethylchroman-8-carboxylate

生成物 1

HCID 66765164Methyl 6-chloro-2,2-dimethylchroman-8-carboxylate

試薬・触媒・溶媒 3

HCID 887Methanol溶媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒2 回

反応条件

温度
10 °C

実験手順

To a solution of methyl 2,2-dimethyl-3,4-dihydro-2H-chromene-8-carboxylate (330 mg, 1.50 mmol) in dichloromethane (3.74 mL) and methanol (3.74 mL) was added concentrated HCl (61.5 μL, 0.75 mmol) at 10° C. NCS (206 mg, 1.54 mmol) as added portion-wise. The solution was stirred for 1 hour at 8-12° C. The solution was then poured into a mixture of water (5.00 mL), saturated aqueous sodium thiosulfate (5.00 mL), 1 N aqueous NaOH (5.00 mL) and dichloromethane (30.0 mL). The mixture was stirred for 15 minutes at room temperature and the two phases were separated. The organic phase was acidified to pH<2 with 1 N aqueous HCl. The mixture was then extracted with dichloromethane (10.0 mL, 2×). The combined organic layers were dried over Na2SO4, filtered and concentrated under vacuum. The crude residue was purified by silica gel chromatography eluting with 0-15% EtOAc/hexanes to give the desired product as a colorless oil.

後処理

  1. stirringThe mixture was stirred for 15 minutes at room temperature
  2. customthe two phases were separated
  3. extractionThe mixture was then extracted with dichloromethane (10.0 mL, 2×)
  4. dry with materialThe combined organic layers were dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under vacuum
  7. customThe crude residue was purified by silica gel chromatography
  8. washeluting with 0-15% EtOAc/hexanes

出典と根拠

ORDレコード
ord-a20f0fe3bbda415b8f40a4c89e217936
出典データセット
uspto-grants-2014_06
特許番号
US08742110B2

反応ノート

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