Benzylacetylene → HCID 21467975, 화합물

HRID 54249

반응식

HRID 54249 반응식
[NH2:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5](I)=[C:4]([CH3:10])[N:3]=1.[C:11]1([CH2:17][C:18]#[CH:19])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I.C(N(CC)CC)C>[NH2:1][C:2]1[N:7]=[C:6]([NH2:8])[C:5]([C:19]#[C:18][CH2:17][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[C:4]([CH3:10])[N:3]=1

참가 물질

6

반응물 2

HCID 575753BenzylacetyleneHCID 158557925-Iodo-6-methylpyrimidine-2,4-diamine

생성물 1

HCID 21467975HCID 21467975, 화합물수율 39.3%

시약·촉매·용매 3

HCID 83717Copper iodide촉매HCID 178418476HCID 178418476, 화합물촉매HCID 8471Triethylamine용매

실험 절차

A reaction vessel containing 0.8 gram (0.0032 mole) of 2,4-diamino-5-iodo-6-methylpyrimidine, 0.5 mL (0.0042 mole) of 3-phenyl-1-propyne, 0.2 gram (catalyst) of bis(triphenylphosphine)palladium(II) chloride, 0.05 gram (catalyst) of copper iodide, and 8 mL of triethylamine is evacuated and refilled with dry nitrogen gas three times. The reaction mixture is then stirred at ambient temperature for about 60 hours. After this time, the reaction mixture is diluted with 100 mL of water. The mixture is then extracted with three 75 mL portions of ethyl acetate. The combined extracts are washed with three 75 mL portions of an aqueous 5% lithium chloride solution. The organic layer is dried with sodium sulfate and filtered. The filtrate is concentrated under reduced pressure to a residue. The residue is subjected to column chromatography on silica gel, using 5-15% methanol methylene chloride mixtures as eluants. The appropriate product-containing fractions are combined and concentrated under reduced pressure, yielding 0.3 gram of 2,4-diamino-6-methyl-5-(3-phenyl-1-propynyl)pyrimidine. The NMR spectrum is consistent with the proposed structure. Other fractions containing less pure product are combined and concentrated under reduced pressure to a residue. This residue is subjected to column chromatography on neutral alumina, using 2.5-10% methanol in methylene chloride mixtures as eluants. The product-containing fractions are combined and concentrated under reduced pressure, yielding an additional 0.2 gram of 2,4-diamino-6-methyl-5-(3-phenyl-1-propynyl)pyrimidine. The NMR spectrum is consistent with the proposed structure. The two solids are combined, yielding about 0.5 gram of 2,4-diamino-6-methyl-5-(3-phenyl-1-propynyl)pyrimidine, mp 145°-149° C.

후처리

  1. customis evacuated
  2. additionrefilled with dry nitrogen gas three times
  3. additionAfter this time, the reaction mixture is diluted with 100 mL of water
  4. extractionThe mixture is then extracted with three 75 mL portions of ethyl acetate
  5. washThe combined extracts are washed with three 75 mL portions of an aqueous 5% lithium chloride solution
  6. dry with materialThe organic layer is dried with sodium sulfate
  7. filtrationfiltered
  8. concentrationThe filtrate is concentrated under reduced pressure to a residue
  9. additionThe appropriate product-containing fractions
  10. concentrationconcentrated under reduced pressure

출처 및 근거

ORD 기록
ord-73d1ac58b4634afba5883509639a5d88
출처 데이터셋
uspto-grants-1997_04
특허 번호
US05622954

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