Acetic Anhydride → 6-[acetoxy-(5-methoxy-7,8-dihydro-6H-3,4,8b-triaza-as-indacen-2-yl)-methyl]-6-bromo-7-oxo-4-thia-1-aza-bicyclo[3.2.0]hept-2-ene-2-carboxylic acid 4-nitro-benzyl ester

HRID 638889노트

반응식

HRID 638889 반응식
[CH3:1][O:2][C:3]1[C:14]2[CH2:13][CH2:12][CH2:11][C:10]=2[N:9]2[C:5](=[N:6][C:7]([CH:15]=[O:16])=[CH:8]2)[N:4]=1.[Br-].[Mg+2].[Br-].[N+:20]([C:23]1[CH:41]=[CH:40][C:26]([CH2:27][O:28][C:29]([C:31]2[N:32]3[CH:35]([S:36][CH:37]=2)[CH:34]([Br:38])[C:33]3=[O:39])=[O:30])=[CH:25][CH:24]=1)([O-:22])=[O:21].[C:42](OC(=O)C)(=[O:44])[CH3:43]>C(OCC)(=O)C.C(N(CC)CC)C.C1COCC1.C(#N)C>[N+:20]([C:23]1[CH:41]=[CH:40][C:26]([CH2:27][O:28][C:29]([C:31]2[N:32]3[CH:35]([S:36][CH:37]=2)[C:34]([CH:15]([O:16][C:42](=[O:44])[CH3:43])[C:7]2[N:6]=[C:5]4[N:9]([C:10]5[CH2:11][CH2:12][CH2:13][C:14]=5[C:3]([O:2][CH3:1])=[N:4]4)[CH:8]=2)([Br:38])[C:33]3=[O:39])=[O:30])=[CH:25][CH:24]=1)([O-:22])=[O:21]

참가 물질

9

반응물 4

HCID 7918Acetic AnhydrideHCID 82241Magnesium BromideHCID 222245485-methoxy-7,8-dihydro-6H-3,4,8b-triaza-as-indacene-2-carbaldehydeHCID 684433356-Bromo-7-oxo-4-thia-1-aza-bicyclo[3.2.0]hept-2-ene-2-carboxylic acid 4-nitro-benzyl ester

생성물 1

HCID 687056406-[acetoxy-(5-methoxy-7,8-dihydro-6H-3,4,8b-triaza-as-indacen-2-yl)-methyl]-6-bromo-7-oxo-4-thia-1-aza-bicyclo[3.2.0]hept-2-ene-2-carboxylic acid 4-nitro-benzyl ester수율 93%

시약·촉매·용매 4

HCID 6342Acetonitrile용매HCID 8028Tetrahydrofuran용매HCID 8471Triethylamine용매HCID 8857Ethyl Acetate용매

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온도
23 °C

실험 절차

A 30 ml acetonitrile solution of 5-methoxy-7,8-dihydro-6H-3,4,8b-triaza-as-indacene-2-carbaldehyde (660 mg, 3 mmol) was added 1.03 gram of magnesium bromide etherate. The mixture was stirred at 23° C. for half an hour. Then a 30 ml dry THF solution of the 6-Bromo-7-oxo-4-thia-1-aza-bicyclo[3.2.0]hept-2-ene-2-carboxylic acid 4-nitro-benzyl ester (1.155 gram, 1 eq.) was injected within a minute and the reaction mixture was then cooled to −20° C. Triethylamine (0.7 ml, eq.) was then injected and the reaction mixture was stirred for five hours at −20° C. Then acetic anhydride (0.377 ml, eq.) was injected and the reaction mixture was left at zero degree for 18 hours. The reaction media was then diluted with 400 ml ethyl acetate and washed with 100 ml 5% citric acid, 100 ml saturated sodium bicarbonate, and 100 ml brine. The organic layer was then dried over magnesium sulfate, filtered and concentrated. Flash column chromatography using 20% ethyl acetate in hexane gave 1.8 gram product. (93% Yield); MP: 118.7˜119.1° C.; MS: 645.9 (M+H)

후처리

  1. temperaturethe reaction mixture was then cooled to −20° C
  2. stirringthe reaction mixture was stirred for five hours at −20° C
  3. customThe reaction media
  4. washwashed with 100 ml 5% citric acid, 100 ml saturated sodium bicarbonate, and 100 ml brine
  5. dry with materialThe organic layer was then dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated

출처 및 근거

ORD 기록
ord-205591e7b7214d698c3323c341a71100
출처 데이터셋
uspto-grants-2010_04
특허 번호
US07691842B2

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