Carbon Dioxide → Upb5G360MA

HRID 1951022ノート

反応式

HRID 1951022 の反応式
[CH3:1][NH2:2].Cl.CN.[OH-].[Na+].C(=O)=O.[O:11]1[CH2:16][CH2:15][C:14](=O)[CH2:13][CH2:12]1.[N:18]1[O:19][N:20]=[C:21]2[CH:26]=[C:25]([C:27](Cl)=[O:28])[CH:24]=[CH:23][C:22]=12>CO.C(Cl)(Cl)Cl.[Pd].C(N(CC)CC)C>[CH3:1][N:2]([CH:14]1[CH2:15][CH2:16][O:11][CH2:12][CH2:13]1)[C:27]([C:25]1[CH:24]=[CH:23][C:22]2=[N:18][O:19][N:20]=[C:21]2[CH:26]=1)=[O:28]

参加物

11

反応物 6

HCID 280Carbon DioxideHCID 6329MethylamineHCID 14798Sodium HydroxideHCID 121599Tetrahydro-4H-pyran-4-oneHCID 27354532,1,3-Benzoxadiazole-5-carbonyl chlorideHCID 6364545Methylamine hydrochloride

生成物 1

HCID 25104045Upb5G360MA

試薬・触媒・溶媒 4

HCID 23938Palladium触媒HCID 887Methanol溶媒HCID 6212Chloroform溶媒HCID 8471Triethylamine溶媒

実験手順

Methylamine, generated by heating a mixture of methylamine hydrochloride (10 g) and sodium hydroxide pellets (18 g), was condensed (dry ice trap) into a solution of tetrahydro-4H-pyran-4-one (1.0 g, 10 mmol) in methanol (50 ml). 10% Pd on C (350 mg) was added and the mixture was hydrogenated at room temperature for 7 hours. The solids were filtered off and the filtrate concentrated under vacuum. The residue was dissolved in chloroform (70 ml) and triethylamine (2 ml) and a solution of [2,1,3]-benzoxadiazole-5-carbonylchloride (500 mg, 2.73 mmol) in chloroform (10 ml) was added slowly. After stirring the reaction mixture for 30 minutes, the organic phase was extracted with 100 ml of water and sulfuric acid (→pH 2) and the aqueous phase re-extracted with chloroform (100 ml), dried over magnesium sulfate, and concentrated under vacuum to give an oil. The crude product was purified by silica gel chromatography eluting ethyl acetate/hexane (75:25) and chloroform/acetone (85:15) to give the title product as a white solid after crystallization from ethyl acetate. Mp=160-2° C., LC-MS, MH+=262; 1H NMR (300 MHz, CDCl3, 2 rotamers) δ 7.93 (d, 1H, J=9.0 Hz); 7.84 (s, 1H); 7.42 (d, 1H, J=9.0 Hz); 4.90-4.70 and 4.20-3.10 (m+m, 5H); 2.927 (s, 3H); 2.1-1.5 ppm (m, 4H).

後処理

  1. temperatureby heating
  2. filtrationThe solids were filtered off
  3. concentrationthe filtrate concentrated under vacuum
  4. dissolutionThe residue was dissolved in chloroform (70 ml)
  5. extractionthe organic phase was extracted with 100 ml of water and sulfuric acid (→pH 2)
  6. extractionthe aqueous phase re-extracted with chloroform (100 ml)
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated under vacuum
  9. customto give an oil
  10. customThe crude product was purified by silica gel chromatography
  11. washeluting ethyl acetate/hexane (75:25) and chloroform/acetone (85:15)

出典と根拠

ORDレコード
ord-fa2f450e9cb74c6e9a524663bddbe8a0
出典データセット
uspto-grants-2013_03
特許番号
US08404682B2

反応ノート

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