Methanesulfonic Acid → Ethyl 5-methyl-4-oxo-2,3,7,8-tetrahydro-4H-1-benzothiopyran-6-carboxylate

HRID 613811노트

반응식

HRID 613811 반응식
[CH2:1]([O:3][C:4]([C:6]1[CH2:11][CH2:10][C:9]([S:12][CH2:13][CH2:14][C:15]([OH:17])=O)=[CH:8][C:7]=1[CH3:18])=[O:5])[CH3:2].CS(O)(=O)=O.FC(F)(F)C(OC(=O)C(F)(F)F)=O>C1(C)C=CC=CC=1>[CH3:18][C:7]1[C:8]2[C:15](=[O:17])[CH2:14][CH2:13][S:12][C:9]=2[CH2:10][CH2:11][C:6]=1[C:4]([O:3][CH2:1][CH3:2])=[O:5]

참가 물질

5

반응물 3

HCID 6395Methanesulfonic AcidHCID 9845Trifluoroacetic anhydrideHCID 11043831Ethyl-4-beta-carboxyethylthio-2-methyl-1,3-cyclohexadiene-1-carboxylate

생성물 1

HCID 10868786Ethyl 5-methyl-4-oxo-2,3,7,8-tetrahydro-4H-1-benzothiopyran-6-carboxylate수율 79.5%

시약·촉매·용매 1

HCID 1140Toluene용매

반응 조건

온도
20 °C

실험 절차

A mixture of ethyl-4-β-carboxyethylthio-2-methyl-1,3-cyclohexadiene-1-carboxylate (121.3 g, 0.449 mole) in toluene is stirred at 20° C., treated sequentially with 5.0 ml methanesulfonic acid and portionwise over a 5 minute period with trifluoroacetic anhydride (94.3 g, 0.449 mole) and allowed to stir at ambient temperatures for 18 hours. The resultant reaction mixture is quenched with a 1:1 mixture of ethyl acetate and water and stirred for 15 minutes. The phases are separated. The organic phase is washed with water and concentrated in vacuo to give a residue. Crystallization of the residue from isopropanol/heptane affords the title product as a yellow solid, 90.1 g, (79.5% yield), mp 99°-100° C., identified by 1HNMR and mass spectral analyses.

후처리

  1. stirringto stir at ambient temperatures for 18 hours
  2. customThe resultant reaction mixture
  3. customis quenched with a 1:1 mixture of ethyl acetate and water
  4. stirringstirred for 15 minutes
  5. customThe phases are separated
  6. washThe organic phase is washed with water
  7. concentrationconcentrated in vacuo
  8. customto give a residue
  9. customCrystallization of the residue from isopropanol/heptane

출처 및 근거

ORD 기록
ord-018684c72cea4fbf84c379506e2e8857
출처 데이터셋
uspto-grants-1999_12
특허 번호
US06008402

반응 노트

불러오는 중…