Hydrochloric Acid → Ethyl 4-(2-azidoethoxy)-3-oxobutanoate

HRID 462457ノート

反応式

HRID 462457 の反応式
[N:1]([CH2:4][CH2:5][OH:6])=[N+:2]=[N-:3].[H-].[Na+].Cl[CH2:10][C:11](=[O:18])[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14].Cl>O1CCCC1.C(O)C.O>[N:1]([CH2:4][CH2:5][O:6][CH2:10][C:11](=[O:18])[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])=[N+:2]=[N-:3]

参加物

8

反応物 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 69484Ethyl 4-chloroacetoacetateHCID 1231182-Azidoethanol

生成物 1

HCID 13663141Ethyl 4-(2-azidoethoxy)-3-oxobutanoate

試薬・触媒・溶媒 3

HCID 702Ethanol溶媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒3 回

実験手順

A solution of 2-azidoethanol (160 g) in tetrahydrofuran (300 ml) was added over 40 minutes to a suspension of sodium hydride (114 g; 80% dispersion in oil) in tetrahydrofuran (500 ml). The mixture was stirred at room temperature for 1 hour and the ice-cooled solution treated with a solution of ethyl 4-chloroacetoacetate (276 g) in tetrahydrofuran (250 ml) dropwise over 2 hours. The mixture was stirred at room temperature for 16 hours, diluted with ethanol (150 ml), and the pH adjusted to 6-7 with 4M hydrochloric acid. Sufficient water was added to dissolve the solid present and the layers were separated. The organic layer was evaporated and the residue diluted with water (600 ml) and evaporated. The residue was then partitioned between ethyl acetate and water and the aqueous layer extracted twice with ethyl acetate. The combined ethyl acetate extracts were dried (MgSO4) and evaporated to give ethyl 4-(2-azidoethoxy)acetoacetate as a brown oil which was shown by g.l.c. to be 73% pure. A mixture of this crude product and ammonium acetate (92.3 g) in ethanol (600 ml) was heated under reflux for 1 hour, allowed to cool to room temperature and treated with methyl 2-(2-chlorobenzylidene)acetoacetate (286.6 g). The mixture was heated under reflux for 5.5 hours and then evaporated. The residue was stirred with methanol (1.5 l) for 16 hours and the resulting solid collected, washed twice with methanol, dried and recrystallised from methanol to give the title compound (78 g), m.p. 145°-146°.

後処理

  1. stirringThe mixture was stirred at room temperature for 16 hours
  2. dissolutionto dissolve the solid present
  3. customthe layers were separated
  4. customThe organic layer was evaporated
  5. additionthe residue diluted with water (600 ml)
  6. customevaporated
  7. customThe residue was then partitioned between ethyl acetate and water
  8. extractionthe aqueous layer extracted twice with ethyl acetate
  9. dry with materialThe combined ethyl acetate extracts were dried (MgSO4)
  10. customevaporated

出典と根拠

ORDレコード
ord-33c1d2feb02f4985a46bd74c0619fa8c
出典データセット
uspto-grants-1985_05
特許番号
US04515799

反応ノート

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