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m-Chloroperbenzoic acid → Methyl 8-[bis-(tert-butoxycarbonyl)amino]-6-hydroxy-5,6-dihydro-pyrazolo[5,1-a]isoquinoline-7-carboxylate

HRID 595106
ノート
印刷プレビュー

反応式

HRID 595106 の反応式
[C:1]([O:5][C:6]([N:8]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[C:9]1[C:14]([C:15]([O:17][CH3:18])=[O:16])=[C:13]([CH:19]=[CH2:20])[C:12]([C:21]2[NH:22][N:23]=[CH:24][CH:25]=2)=[CH:11][CH:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C[N+]1([O-])CC[O:37]CC1.ClC1C=CC=C(C(OO)=O)C=1>C(Cl)Cl.CC(C1C=C(C=N[C@@H]2[C@@H](N=CC3C([O-])=C(C(C)(C)C)C=C(C(C)(C)C)C=3)CCCC2)C([O-])=C(C(C)(C)C)C=1)(C)C.[Cl-].[Mn+3]>[C:29]([O:28][C:26]([N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])[C:9]1[CH:10]=[CH:11][C:12]2[C:21]3=[CH:25][CH:24]=[N:23][N:22]3[CH2:20][CH:19]([OH:37])[C:13]=2[C:14]=1[C:15]([O:17][CH3:18])=[O:16])=[O:27])([CH3:32])([CH3:31])[CH3:30]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 3

HCID 70297m-Chloroperbenzoic acidHCID 82029Methyl morpholine oxideHCID 86712817methyl 6-[bis-(tert-butoxycarbonyl)amino]-3-(2H-pyrazol-3-yl)-2-vinylbenzoate2 回

生成物 1

HCID 71005652Methyl 8-[bis-(tert-butoxycarbonyl)amino]-6-hydroxy-5,6-dihydro-pyrazolo[5,1-a]isoquinoline-7-carboxylate収率 11.7%

試薬・触媒・溶媒 2

HCID 10211480
(S,S)-[N,N'-Bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine]manganese(III) chloride
触媒
HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

To a cooled solution of methyl 6-[bis-(tert-butoxycarbonyl)amino]-3-(2H-pyrazol-3-yl)-2-vinylbenzoate (Intermediate 9, 2.4 g) in anhydrous DCM (100 mL) at 0° C. was added (S,S)-(+)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamino manganese (III) chloride (0.280 g) and N-methylmorpholine N-oxide (3.2 g). m-Chloroperbenzoic acid (3.8 g) was then added portionwise and the reaction mixture was stirred at 0° C. for 20 minutes. The resultant mixture was quenched by the addition of 2M aqueous sodium carbonate solution and the organic layer was separated, dried (MgSO4) and filtered. The filtrate was concentrated in vacuo and the residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and DCM with a gradient of 0-100%. The resultant material was repurified by chromatography on silica, eluting with a mixture of ethyl acetate and DCM with a gradient of 0-100% to give methyl 8-[bis-(tert-butoxycarbonyl)amino]-6-hydroxy-5,6-dihydro-pyrazolo[5,1-a]isoquinoline-7-carboxylate (0.290 g).

後処理

  1. customThe resultant mixture was quenched by the addition of 2M aqueous sodium carbonate solution
  2. customthe organic layer was separated
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated in vacuo
  6. customthe residue was purified by chromatography on silica
  7. washeluting with a mixture of ethyl acetate and DCM with a gradient of 0-100%
  8. customThe resultant material was repurified by chromatography on silica
  9. washeluting with a mixture of ethyl acetate and DCM with a gradient of 0-100%

出典と根拠

ORDレコード
ord-5426ed3f692e412ea4aa6a3a59f5736a
出典データセット
uspto-grants-2016_01
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09242997B2

反応ノート

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