Methyl 4-chloroacetoacetate → HCID 24279063, compound

HRID 1031433Notes

Reaction equation

HRID 1031433 reaction equation
[CH3:1][O:2][C:3](=[O:9])[CH2:4][C:5]([CH2:7]Cl)=O.[C:10]([NH:13][C:14]([NH2:16])=[S:15])(=[O:12])[CH3:11]>>[C:10]([NH:13][C:14]1[S:15][CH:7]=[C:5]([CH2:4][C:3]([O:2][CH3:1])=[O:9])[N:16]=1)(=[O:12])[CH3:11]

Participants

3

Reactant 2

HCID 36240Methyl 4-chloroacetoacetateHCID 2723593Acetylthiourea

Product 1

HCID 24279063HCID 24279063, compound

Procedure

Methyl-4-chloroacetoacetate (11.54ml), N-acetylthiourea (11.8g) and 4A molecular sieves (10g) were stirred in dry, distilled dimethylformamide (DMF) (50ml) at 50° C., for 23h. After this time the reaction appeared complete by t.1.c. The mixture was cooled and filtered through a dicalite pad. The residue was washed with DMF and tetrahydrofuran and the resultant filtrates diluted with water. This solution was washed five times with ethyl acetate; the organic washes were combined, dried, filtered and evaporated to give a yellow oil. This was triturated under water whereupon a white precipitate formed. This was cooled to complete and the resultant solid filtered off, washed with cold water and dried to give the desired product (14.63g) as a white crystalline solid, m.p. 122°-123° C. (from ethyl acetate-hexane); υ max (nujol) 3175 (w), 1740, 1655, 1560 and 1543cm-1 ; δ[(CD3)2SO, 60MHz]2.1 (3H, s). 3.6 (3H. s). 3.7 (2 H. s). and 6.9 (1H. s). (Found: C, 44.9; H, 4.7; N, 13.4; S, 15.3. C8H10N2O3S requires: C, 44.9; H, 4.7; N, 13.1; S, 15.0%). The mother liquors were concentrated to low volume and cooled to yield a second crop of the desired material (2.54g) which was slightly less pure by NMR.

Workup

  1. customin dry
  2. distillationdistilled dimethylformamide (DMF) (50ml) at 50° C.
  3. temperatureThe mixture was cooled
  4. filtrationfiltered through a dicalite pad
  5. washThe residue was washed with DMF and tetrahydrofuran
  6. additionthe resultant filtrates diluted with water
  7. washThis solution was washed five times with ethyl acetate
  8. customdried
  9. filtrationfiltered
  10. customevaporated
  11. customto give a yellow oil
  12. customThis was triturated under water whereupon a white precipitate
  13. customformed
  14. temperatureThis was cooled
  15. filtrationthe resultant solid filtered off
  16. washwashed with cold water
  17. customdried

Sources & evidence

ORD record
ord-aea3851323b34b9a85200536e8f8b837
Source dataset
uspto-grants-1990_09
Patent number
US04954489

Reaction notes

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