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

HRID 463518노트

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HRID 463518 반응식
[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]

참가 물질

6

반응물 4

HCID 6344DichloromethaneHCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 13467841Ethyl 4-[[(1,1-dimethylethoxy)carbonyl]amino]tetrahydro-3-hydroxy-2-thiophenecarboxylate

생성물 1

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

시약·촉매·용매 1

HCID 3283Diethyl Ether용매

실험 절차

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°.

후처리

  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

출처 및 근거

ORD 기록
ord-868b080bf48f480b9a5da727d5631379
출처 데이터셋
uspto-grants-1985_05
특허 번호
US04520028

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