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HRID1077588

反应详情

EQUATION

反应方程式

HRID 1077588 的结构方程式

REACTANTS

反应物

4
结构：CC(C)(C)OC(=O)OC(=O)OC(C)(C)C
HCID90495

Di-tert-butyl dicarbonate

C10H18O5

结构：[O]=[Cr](=[O])([O-])[O][Cr](=[O])(=[O])[O-].c1cc[nH+]cc1.c1cc[nH+]cc1
HCID2724130

Chromic acid (H2Cr2O7), compd. with pyridine (1:2)

C10H12Cr2N2O7

结构：CCCC[N+](CCCC)(CCCC)CCCC.[F-]
HCID2724141

Tetra-n-butylammonium fluoride

C16H36FN

结构：COC(=O)[C@H]1CC[C@H]2[C@@H]3CN=C4C[C@@H](O[Si](C(C)C)(C(C)C)C(C)C)CC[C@]4(C)[C@H]3CC[C@]12C
HCID10458265

未命名化合物

PRODUCTS

生成物

1
结构：COC(=O)[C@H]1CC[C@H]2[C@@H]3CN(C(C)(C)C)C4=CC(=O)CC[C@]4(C)[C@H]3CC[C@]12CC(=O)O
HCID86749035

未命名化合物

AUXILIARIES

试剂、催化剂与溶剂

3
结构：O
溶剂HCID962

Water

H2O

结构：c1ccncc1
溶剂HCID1049

Pyridine

C5H5N

2 次

结构：C1CCOC1
溶剂HCID8028

Tetrahydrofuran

C4H8O

PROCEDURE

实验过程

Crude 17β-carbomethoxy-3β-triisopropylsilyloxy-6-azaandrost-5-ene (66 g, 0.135 mol)is dissolved in pyridine (500 mL), treated with di-t-butyldicarbonate (150 g, 0.69 mol) and allowed to stir overnight. The pyridine is removed by rotary evaporation and tetrabutylammonium fluoride (500 mL, 1M, 0.5 mol) in tetrahydrofuran (THF) added carefully and the reaction heated to reflux for 5 min. The THF is removed by rotary evaporation, the residue dissolved in ethyl acetate (500 mL), washed cautiously with water, saturated aqueous NaCl, dried with MgSO4 and concentrated. This material is dissolved in DMF (500 mL), is treated with pyridinium dichromate (153 g, 0.41 mol) and allowed to stir overnight. The reaction is poured into water (700 mL) and extracted with ethyl acetate (2×500 mL). The combined extracts are washed with water, 5% aqueous CuSO4, saturated aqueous NaCl, dried over MgSO4, concentrated and flash chromatographed (0-60%, diethyl ether/hexanes) to give 17β-carbomethoxy-6-t-butylcarboxy-6-azaandrost-4-en-3-one as an off-white foam; yield: 37.5 g (64%); FAB mass spec. MH+ 432.

WORKUP

后处理

  1. additionadded carefully
  2. temperaturethe reaction heated
  3. temperatureto reflux for 5 min
  4. customThe THF is removed by rotary evaporation
  5. dissolutionthe residue dissolved in ethyl acetate (500 mL)
  6. washwashed cautiously with water, saturated aqueous NaCl
  7. dry with materialdried with MgSO4
  8. concentrationconcentrated
  9. dissolutionThis material is dissolved in DMF (500 mL)
  10. stirringto stir overnight
  11. extractionextracted with ethyl acetate (2×500 mL)
  12. washThe combined extracts are washed with water, 5% aqueous CuSO4, saturated aqueous NaCl
  13. dry with materialdried over MgSO4
  14. concentrationconcentrated
  15. customflash chromatographed (0-60%, diethyl ether/hexanes)