반응 #1005554

ord-6d668e3188bc41deb95a1ddd13988844

반응 방정식

C[C@]12C=CC(=O)C=C1CC[C@H]1[C@@H]3C[C@@H](O)[C@](O)(C(=O)CCl)[C@@]3(C)C[C@H](O)[C@@]12F
21-chloro-9-fluoro-11β,16α,17-trihydroxypregna-1,4diene-3,20-dione
C=C(C)C=[N+]=[N-]
2-methyl-3-diazo-1-propene
→
C=C(C)CO[C@@H]1C[C@H]2[C@@H]3CCC4=CC(=O)C=C[C@]4(C)[C@@]3(F)[C@@H](O)C[C@]2(C)[C@@]1(O)C(=O)CCl
21-chloro-9-fluoro-11β,17 -dihydroxy-16α-[(2-methyl-2-propenyl)oxy]pregna-1,4-diene-3,20-dione

반응물

C[C@]12C=CC(=O)C=C1CC[C@H]1[C@@H]3C[C@@H](O)[C@](O)(C(=O)CCl)[C@@]3(C)C[C@H](O)[C@@]12F
21-chloro-9-fluoro-11β,16α,17-trihydroxypregna-1,4diene-3,20-dione
C=C(C)C=[N+]=[N-]
2-methyl-3-diazo-1-propene
—
N-(2-methyl-2-propenyl)-ethyl carbamate

시약

없음

용매

CO
methanol
CCOCC
ether

반응 조건

온도
0°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    기타The solvent is removed in vacuo
  2. 2
    workup.DISSOLUTIONthe residue is dissolved in chloroform
  3. 3
    기타chromatographed on an 80 g -silica gel column
  4. 4
    세척Elution with chloroform
  5. 5
    기타gives TLC pure material which
  6. 6
    기타crystallizes from acetone-hexane

실험 절차

A solution of 2-methyl-3-diazo-1-propene in 150 ml of ether (prepared from 0.1 mole of N-(2-methyl-2-propenyl)-ethyl carbamate by the method of J. L. Brewbaker and H. Hart, J. Am. Chem., Soc., 91, 711 (1969)) is diluted with 50 ml of methanol and cooled to 0°C. A total of 7 g of 21-chloro-9-fluoro-11β,16α,17-trihydroxypregna-1,4diene-3,20-dione, 16,17-cycloborate is added in portions until nitrogen evolution ceases. The solvent is removed in vacuo and the residue is dissolved in chloroform and chromatographed on an 80 g -silica gel column. Elution with chloroform gives TLC pure material which crystallizes from acetone-hexane to give 5.4 g of 21-chloro-9-fluoro-11β,17 -dihydroxy-16α-[(2-methyl-2-propenyl)oxy]pregna-1,4-diene-3,20-dione, melting point 238°-240°C.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US03971772uspto-grants-1976_07