二氯甲烷 → Ethyl-4-[[(1,1-dimethylethoxy)carbonyl]amino]-4,5-dihydro-2-thiophenecarboxylate

HRID 463518笔记

反应方程式

HRID 463518 反应方程式
[CH3:1][C:2]([CH3:19])([O:4][C:5]([NH:7][CH:8]1[CH2:12][S:11][CH:10]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH:9]1O)=[O:6])[CH3:3].C(Cl)Cl.CCN(CC)CC.S(Cl)(C)(=O)=O>CCOCC>[CH2:16]([O:15][C:13]([C:10]1[S:11][CH2:12][CH:8]([NH:7][C:5]([O:4][C:2]([CH3:1])([CH3:19])[CH3:3])=[O:6])[CH:9]=1)=[O:14])[CH3:17]

参与物

6

反应物 4

HCID 6344二氯甲烷HCID 8471三乙胺HCID 31297甲基磺酰氯HCID 13467841Ethyl 4-[[(1,1-dimethylethoxy)carbonyl]amino]tetrahydro-3-hydroxy-2-thiophenecarboxylate

产物 1

HCID 13457813Ethyl-4-[[(1,1-dimethylethoxy)carbonyl]amino]-4,5-dihydro-2-thiophenecarboxylate

试剂、催化剂与溶剂 1

HCID 3283乙醚溶剂

实验过程

Into an ice cooled stirring solution containing the crude alcohol obtained in Step C, 75 ml of CH2Cl2, and 10.5 ml (74 mmole) of Et3N was added 2.9 ml (37 mmole) of mesyl chloride while maintaining the system under a positive argon atmosphere. The reaction was stirred an additional 5 minutes at 0° C. and then 3 hours at 25° C. The reaction was poured into a separatory funnel containing 200 ml Et2O and successively washed with 70 ml water, 1N HCl until the aqueous wash tested acidic; 15 ml water and 50 ml brine, and dried over MgSO4. Removal of the solvent at reduced pressure afforded 6.5 g of a brown oil which was purified by flash chromatography (eluting with 15% and then 20% EtOAc/Hexanes) to yield 3.97 g of product. This material exhibited the following optical rotation [α]Damb =+122.8° at a concentration of 0.5M in ethanol. The highest rotation observed for the R enantiomer under similar conditions was -128.1°.

后处理

  1. temperaturewhile maintaining the system under a positive argon atmosphere
  2. stirringThe reaction was stirred an additional 5 minutes at 0° C.
  3. custom3 hours
  4. customat 25° C
  5. additionThe reaction was poured into a separatory funnel
  6. washsuccessively washed with 70 ml water, 1N HCl until the
  7. washaqueous wash
  8. dry with material15 ml water and 50 ml brine, and dried over MgSO4
  9. customRemoval of the solvent at reduced pressure

来源与证据

ORD记录
ord-868b080bf48f480b9a5da727d5631379
来源数据集
uspto-grants-1985_05
专利号
US04520028

反应笔记

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