反応 #302894

ord-321d369c111044e7b38ee4dee67f9574

反応方程式

Cc1cccc(CNC2=NCCS2)c1C
((2,3-dimethylphenyl)methyl)-1,3-thiazolin-2-ylamine
COC(=O)Cl
methyl chloroformate
[H-].[Na+]
sodium hydride
COC(=O)N(Cc1cccc(C)c1C)C1=NCCS1
N-((2,3-dimethylphenyl)methyl)methoxy-N-(1,3-thiazolin-2-yl)carboxamide
収率 45.7%

反応条件

詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    workup.ADDITIONwas added slowly
  2. 2
    温度The reaction mixture was heated to 60° C. where it
  3. 3
    workup.STIRRINGstirred for one hour
  4. 4
    抽出extracted with two 25 mL portions of ethyl acetate
  5. 5
    洗浄washed with 25 mL of water
  6. 6
    乾燥dried with sodium sulfate
  7. 7
    ろ過filtered
  8. 8
    濃縮The filtrate was concentrated under reduced pressure
  9. 9
    その他to leave a solid residue
  10. 10
    その他The residue was purified by column chromatography on silica gel
  11. 11
    洗浄eluting with hexanes:methylene chloride (1:1)
  12. 12
    濃縮concentrated under reduced pressure

実験手順

Under a dry nitrogen atmosphere, a solution of 0.25 gram (0.0011 mole) of ((2,3-dimethylphenyl)methyl)-1,3-thiazolin-2-ylamine dissolved in 10 mL of THF was added to a stirred suspension of 0.08 gram (0.0012 mole) of sodium hydride (60% suspension in oil). The mixture was stirred for 30 minutes, at which time a solution of 0.11 mL (0.0014 mole) of methyl chloroformate in 5 mL of THF was added slowly. The reaction mixture stirred at ambient temperature for about 18 hours. The reaction mixture was heated to 60° C. where it stirred for one hour. The reaction mixture was diluted with 25 mL of brine, then extracted with two 25 mL portions of ethyl acetate. The extracts were combined, washed with 25 mL of water, dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to leave a solid residue. Analysis of the residue by TLC indicated that two compounds were present. The residue was purified by column chromatography on silica gel, eluting with hexanes:methylene chloride (1:1). The appropriate fractions were combined and concentrated under reduced pressure to yield 0.05 gram of methyl 2-(1-aza-2-(2,3-dimethylphenyl)ethylidene)-1,3-thiazolidine-3-carboxylate (Compound C53) and 0.14 gram of N-((2,3-dimethylphenyl)methyl)methoxy-N-(1,3-thiazolin-2-yl)carboxamide (Compound D5). The NMR spectra were consistent with the proposed structures.

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US08193118B2uspto-grants-2012_06