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求助各位大神指导Boc哌嗪上亚硝基还原

Boc哌嗪上亚硝基还原

求助各位大神,我现在在做下面这个亚硝基还原,试了Fe/NH4Cl, Zn/AcOH, Zn/NH4Cl, Pd/C(4层气球和60psi),Ni, 保险粉/NaOH这些还原方法,结果都不理想。各位大神有做过类似的反应吗?给点建议呗

Boc哌嗪上亚硝基还原




回答:

  1. 换个原料试试,酮

  2. 可以试一试更温和的还原剂

  3. 是不是产品不稳定,做成草酸盐试一下。

  4. 亚硝基是自己做出来的,亚硝基的核磁和MS都是对的,往下做还原怎么做怎么不对

  5. 用醋酸和水作溶剂,加亚硝酸钠直接就能反应成亚硝基

  6. 楼主你的亚硝基用什么条件上的啊,我最近也做了一个类似,没做成功

  7. 我记得是用LiAlH4还原

  8. 1. To a solution of the compound obtained in the above step (1) (730 mg) in methanol (10 mL) was added zinc powder (1.1 g) at room temperature and thereto was added dropwise acetic acid (10 mL) under ice-cooling and the mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered and to the filtrate was added an aqueous sodium hydrogencarbonate solution to basify. After stirring, the mixture was extracted with chloroform. The organic layer was dried over sodium sulfate and filtered. The filtrate was concentrated in vacuo to obtain l-amino-4-tert- butoxycarbonylpiperazine (730 mg, yield: 100 percent) as a pale yellow oil.
    2. To a solution of 1 ,1 -dimethylethyl 4-nitroso-1 -piperazinecarboxylate (500 mg, 2.33 mmol) in THF (23 mL) at O0C was added dropwise a solution of LAH (5.8 mL, 5.8 mmol, 1 M in THF). The reaction mixture warmed to 25°C over 12h and was subsequently quenched by dropwise addition of a saturated solution of potassium sodium tartrate. The aqueous phase was extracted several times with DCM and the combined organic fractions were dried (Na2SO4) and concentrated at 250C yielding a yellow oil that was used without further purification (270 mg, 58percent): LCMS (ES) m/e 202 (M+H)+.

  9. 这两个条件我都试过了,生成的产品点做核磁都很像Boc哌嗪

  10. 试试用氯化亚锡还原

  11. tsonh2和胺直接制备

  12. 你确定用Pd/C 加氢也没有成功吗?反应吃氢明显吗?什么温度下做的?
    用Pd/C加氢是最温和的条件了

  13. Boc在酸性条件下容易掉,稍微控制不好条件就掉了

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