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Dimethylformamide dimethyl acetal → 4-(3,5-ditert-butyl-4-hydroxy-phenyl)-2-dimethylamino-N-methyl-pyrimidine-5-carboxamide

HRID 2039751
ノート
印刷プレビュー

反応式

HRID 2039751 の反応式
CO[C:3](=O)[CH2:4][C:5]([C:7]1[CH:12]=[C:11]([C:13]([CH3:16])([CH3:15])[CH3:14])[C:10]([OH:17])=[C:9]([C:18]([CH3:21])([CH3:20])[CH3:19])[CH:8]=1)=O.CO[CH:25]([O:29]C)[N:26]([CH3:28])C.S(O)(O)(=O)=O.[CH3:36][N:37]([CH3:41])[C:38]([NH2:40])=[NH:39].CC(C)([O-])C.[K+]>C(O)(C)(C)C.O.C(OCC)(=O)C.C1(C)C=CC=CC=1>[CH3:28][NH:26][C:25]([C:4]1[C:5]([C:7]2[CH:8]=[C:9]([C:18]([CH3:19])([CH3:20])[CH3:21])[C:10]([OH:17])=[C:11]([C:13]([CH3:16])([CH3:15])[CH3:14])[CH:12]=2)=[N:39][C:38]([N:37]([CH3:41])[CH3:36])=[N:40][CH:3]=1)=[O:29]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

9

反応物 4

HCID 78373Dimethylformamide dimethyl acetalHCID 220673Guanidine, 1,1-dimethyl-, sulfateHCID 23665647Potassium tert-butoxideHCID 866627073-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-3-oxo-propanoic acid methyl ester

生成物 1

HCID 1360590344-(3,5-ditert-butyl-4-hydroxy-phenyl)-2-dimethylamino-N-methyl-pyrimidine-5-carboxamide収率 45%

試薬・触媒・溶媒

4
HCID 962Water溶媒HCID 1140Toluene溶媒HCID 6386tert-Butanol溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
80 °C

実験手順

A 50-mL round bottom flask was charged with 3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-3-oxo-propanoic acid methyl ester (2.69 g, 8.8 .mmol) and toluene (18 mL). The mixture was warmed to give a solution, then N,N-dimethylformamide dimethyl acetal (1.46 mL, 11 mmol) was added while the solution was still hot. The mixture was stirred for 2.5 h then evaporated. The residue was taken up in 2-propanol (28 mL) and 1,1-dimethylguanidine sulfate (1.80 g, 6.6 mmol) was added. The mixture was stirred at room temperature and a 1 M solution of potassium tert. butoxide in tert. butanol (21 mL) was added and the mixture was immersed into a bath maintained at 80° C. and stirred for 4 hours then at 50° C. overnight. The mixture was allowed to cool to room temperature, and was equilibrated with ethyl acetate (80 mL) and water (60 mL). The organic layer was washed with water (2×25 mL), once with brine (20 mL) then dried with sodium sulfate and evaporated to a brown solid. This material was boiled in dichloromethane (200 mL) without dissolving all solids. The mixture was allowed to cool and was filtered. The brown filtrate was charged to a column of silica gel G (70-230 mesh) in dichloromethane and using 1:4, 1:2, 1:1 ethyl acetate-hexane and ethyl acetate as mobile phases. The product was eluted with ethyl acetate and crystallized partly in the receptacles. The appropriate fractions were evaporated and the residue dissolved in a boiling ethanol-acetone mixture. The solution was concentrated, the resulting suspension diluted with cyclohexane and refrigerated. The solids were washed with 1:2 ethyl acetate-hexane to leave the title compound as a white powder, 1.52 g, 45% yield. TLC (ethyl acetate) Rf 0.73, TLC (1:1 ethyl acetate-hexane) Rf 0.20; 1H-NMR (300 MHz, DMSO-d6) δ 1.38 (9H, s), 2.64 (3H, d, J=4.5 Hz), 3.15 (6H, s), 7.60 (2H, s), 8.15 (1H, br s), 8.22 (1H, s).

後処理

  1. temperatureThe mixture was warmed
  2. customto give a solution
  3. customthen evaporated
  4. stirringThe mixture was stirred at room temperature
  5. customthe mixture was immersed into a bath
  6. stirringstirred for 4 hours
  7. customat 50° C.
  8. customovernight
  9. temperatureto cool to room temperature
  10. washThe organic layer was washed with water (2×25 mL), once with brine (20 mL)
  11. dry with materialthen dried with sodium sulfate
  12. customevaporated to a brown solid
  13. dissolutionwithout dissolving all solids
  14. temperatureto cool
  15. filtrationwas filtered
  16. additionThe brown filtrate was charged to a column of silica gel G (70-230 mesh) in dichloromethane
  17. washThe product was eluted with ethyl acetate
  18. customcrystallized partly in the receptacles
  19. customThe appropriate fractions were evaporated
  20. dissolutionthe residue dissolved in a boiling ethanol-acetone mixture
  21. concentrationThe solution was concentrated
  22. additionthe resulting suspension diluted with cyclohexane
  23. washThe solids were washed with 1:2 ethyl acetate-hexane

出典と根拠

ORDレコード
ord-7ded1fb3e00545b781d402981fd63fab
出典データセット
uspto-grants-2013_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08580805B2

反応ノート

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