反应 #336833

ord-b4a48c91ee8a41a2a219c1a5dd170780

反应方程式

Cl
hydrochloric acid
CCOC(=O)CC(=O)C(=O)OCC.[Na]
diethyl oxalacetate sodium salt
[Na+].[OH-]
sodium hydroxide
Cl.N=C(N)C1CC1
cyclopropanecarboximidamide monohydrochloride
O=C(O)c1cc(=O)[nH]c(C2CC2)n1
title compound
收率 46.6%
O=C(O)c1cc(=O)[nH]c(C2CC2)n1
2-cyclopropyl-1,6-dihydro-6-oxo-4-pyrimidinecarboxylic acid
收率 46.6%

反应条件

温度
30°CELSIUS
详细条件
See reaction.notes.procedure_details.

后处理

  1. 1
    其他remained at 25-30° C.
  2. 2
    温度Then the stirred mixture was heated for an additional 30 min at 35° C
  3. 3
    温度The orange solution was heated to 50° C. over 30 minutes
  4. 4
    温度The reaction mixture was cooled to 35° C.
  5. 5
    其他(resulting in foaming) over 30 minutes at 30-40° C. until the pH was about 1.5-2.5
  6. 6
    浓缩The mixture was concentrated with a rotary evaporator at 35-40° C.
  7. 7
    其他to remove alcohols
  8. 8
    其他crystallization of the product
  9. 9
    温度After the mixture was cooled to 0° C. the solid
  10. 10
    过滤was collected by filtration
  11. 11
    洗涤The solid washed with water (2×60 mL)
  12. 12
    其他suction-dried
  13. 13
    其他dried in a vacuum-oven at 60° C.

实验过程

To a mixture of diethyl oxalacetate sodium salt (150 g, 714 mmol) in methanol (300 mL) and water (150 mL) warmed to 30° C. was added 50% aqueous sodium hydroxide (56 g, 700 mmol) in water (60 mL) over 30 minutes, over which time the temperature remained at 25-30° C. and the pH at 11-12. Then the stirred mixture was heated for an additional 30 min at 35° C. To this mixture was added cyclopropanecarboximidamide monohydrochloride (64 g, 530 mol) in portions over 15 minutes. The orange solution was heated to 50° C. over 30 minutes and held at that temperature for 3 h. The reaction mixture was cooled to 35° C., and concentrated hydrochloric acid (ca. 70 g, 0.7 mol) was added gradually (resulting in foaming) over 30 minutes at 30-40° C. until the pH was about 1.5-2.5. The mixture was concentrated with a rotary evaporator at 35-40° C. to remove alcohols, stirred for 3-4 h at 25° C. to complete crystallization of the product. After the mixture was cooled to 0° C. the solid was collected by filtration. The solid washed with water (2×60 mL), suction-dried, and then dried in a vacuum-oven at 60° C. to afford the title compound as a beige solid (ca. 60 g).

来源

DOI: 10.6084/m9.figshare.5104873.v1专利: US07863220B2uspto-grants-2011_01