Acetic Acid → 1-(Methoxymethyl)-6-phenylthiothymine

HRID 2210896노트

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HRID 2210896 반응식
C([N-][CH:5]([CH3:7])[CH3:6])(C)C.[Li+].[CH3:9][O:10][CH2:11][N:12]1[CH:20]=[C:18]([CH3:19])[C:16](=[O:17])[NH:15][C:13]1=O.C1([S:27]SC2C=CC=CC=2)C=CC=CC=1.C(O)(=O)C.O1C[CH2:42][CH2:41][CH2:40]1>C(OCC)(=O)C>[CH3:9][O:10][CH2:11][N:12]1[C:20]([C:6]2[CH:5]=[CH:7][CH:42]=[CH:41][CH:40]=2)=[C:18]([CH3:19])[C:16](=[O:17])[NH:15][C:13]1=[S:27]

참가 물질

7

반응물 5

HCID 176Acetic AcidHCID 8028Tetrahydrofuran4회HCID 13436Diphenyl disulfideHCID 2724682Lithium diisopropylamideHCID 150426441-(Methoxymethyl)thymine

생성물 1

HCID 540163721-(Methoxymethyl)-6-phenylthiothymine수율 73%

시약·촉매·용매 1

HCID 8857Ethyl Acetate용매

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온도
-70 °C

실험 절차

To 250 ml of methylene chloride, 25 g (0.20 mol) of thymine and 109 ml (0.44 mol) of bistrimethylsilylacetamide were added under a nitrogen flow, and stirred for 2.5 hours at room temperature. To this mixture, 24 g (0.30 mole) of chloromethyl methyl ether and 0.59 g (1.6 mmol) of tetrabutylammonium iodide were added and heated under reflux for 1.5 hours. Then, the reaction mixture was added with 400 ml of methanol and 100 ml of water slowly and concentrated under reduced pressure. The residue was crystallized from ethyl acetate to obtain 1-(methoxymethyl)-thymine. Then, 119 ml of lithium diisopropylamide (0.25 mol) solution in tetrahydrofuran (2.1M) was added to 335 ml of tetrahydrofuran under a nitrogen flow at -70° C., to which a suspension of 17.0 g (0.10 mol) 1-(methoxymethyl)thymine in 107 ml of tetrahydrofuran was added dropwise over 30 minutes. After stirring for 2.5 hours at -70° C., the reaction mixture was added with a solution of 43.6 g of diphenyl disulfide in 49 ml of tetrahydrofuran dropwise over 20 minutes and allowed to react for 20 minutes. The reaction mixture was added with 35 ml of acetic acid, brought to room temperature and then added with 1 l of ethyl acetate. The mixture was washed with water (100 ml×5) and saturated solution of sodium hydrogencarbonate (twice), dried on magnesium sulfate and concentrated under reduced pressure. The residue was crystallized from ethanol to obtain 20 g of the target compound (Yield: 73%).

후처리

  1. additionwas added dropwise over 30 minutes
  2. customto react for 20 minutes
  3. custombrought to room temperature
  4. washThe mixture was washed with water (100 ml×5) and saturated solution of sodium hydrogencarbonate (twice),
  5. customdried on magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was crystallized from ethanol

출처 및 근거

ORD 기록
ord-9025e083456c4fe890c080508c98be30
출처 데이터셋
uspto-grants-1995_10
특허 번호
US05461060

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