반응 #82550

반응 방정식

3-methyl-3-(4-chlorophenyl)-1-trimethylstannyl-1-butene

lithium chloride

2,4-diamino-5-iodo-6-methylpyrimidine

→

2,4-diamino-6-methyl-5-[3-(4-chlorophenyl)-3-methyl-1-butenyl]pyrimidine

수율 60.0%

용매

N,N-dimethylformamide

N,N-dimethylformamide

반응 조건

후처리

1. 1
   기타This compound is prepared in a manner analogous to that of Step E of Example 6
2. 2
   온도the reaction mixture is cooled
3. 3
   여과The mixture is filtered
4. 4
   workup.ADDITIONthe filtrate is poured into 300 mL of water
5. 5
   추출The mixture then is extracted with two 200 mL portions of ethyl acetate
6. 6
   건조The combined extracts are dried with magnesium sulfate
7. 7
   여과filtered
8. 8
   농축The filtrate is concentrated under reduced pressure to a residue
9. 9
   농축concentrated under reduced pressure to a residue
10. 10
    농축concentrated under reduced pressure

실험 절차

This compound is prepared in a manner analogous to that of Step E of Example 6, using 4.8 grams (0.014 mole) of 3-methyl-3-(4-chlorophenyl)-1-trimethylstannyl-1-butene, 2.7 grams (0.011 mole) of 2,4-diamino-5-iodo-6-methylpyrimidine (prepared in Step B of Example 3), 2.8 grams (0.066 mole) of lithium chloride, 0.4 gram (5 mole %) of bis(triphenylphosphine)palladium(II) chloride, and about 0.05 gram (catalyst) of 2,6-di-tert-butyl-4-methylphenol in 25 mL of N,N-dimethylformamide. After heating at 65° C. for about 2.5 days, the reaction mixture is cooled and diluted with 100 mL of N,N-dimethylformamide. The mixture is filtered, and the filtrate is poured into 300 mL of water. The mixture then is extracted with two 200 mL portions of ethyl acetate. The combined extracts are dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure to a residue. The residue is adsorbed onto silica gel and subjected to column chromatography, using 10% methanol in methylene chloride as the eluant. The product-containing fractions are combined and concentrated under reduced pressure to a residue. NMR analysis of the residue indicates that it is impure product. The residue is subjected to column chromatography on basic alumina (activity II), using 2%, 4%, and 6% methanol in methylene chloride as eluants. The product-containing fractions are combined and concentrated under reduced pressure, yielding about 2.0 grams of 2,4-diamino-6-methyl-5-[3-(4-chlorophenyl)-3-methyl-1-butenyl]pyrimidine, mp 195°-200° C. The NMR spectrum is consistent with the proposed structure.

출처