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Potassium Phosphate, Tribasic → 4-[5-({6,6-Dimethyl-4H,6H,7H-pyrazolo[3,2-c][1,4]oxazin-2-yl}amino)-1-methyl-6-oxo-1,6-dihydropyridin-3-yl]-2-{4,4-dimethyl-9-oxo-7-thia-10,11-diazatricyclo[6.4.0.02,6]dodeca-1(8),2(6),11-trien-10-yl}pyridine-3-carb aldehyde

HRID 1412118
ノート
印刷プレビュー

反応式

HRID 1412118 の反応式
[CH3:1][C:2]1([CH3:29])[O:7][CH2:6][C:5]2=[CH:8][C:9]([NH:11][C:12]3[C:13](=[O:28])[N:14]([CH3:27])[CH:15]=[C:16](B4OC(C)(C)C(C)(C)O4)[CH:17]=3)=[N:10][N:4]2[CH2:3]1.Cl[C:31]1[CH:36]=[CH:35][N:34]=[C:33]([N:37]2[N:48]=[CH:47][C:46]3[C:45]4[CH2:44][C:43]([CH3:50])([CH3:49])[CH2:42][C:41]=4[S:40][C:39]=3[C:38]2=[O:51])[C:32]=1[CH:52]=[O:53].[O-]P([O-])([O-])=O.[K+].[K+].[K+].C([O-])(=O)C.[Na+]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(#N)C.O>[CH3:29][C:2]1([CH3:1])[O:7][CH2:6][C:5]2=[CH:8][C:9]([NH:11][C:12]3[C:13](=[O:28])[N:14]([CH3:27])[CH:15]=[C:16]([C:31]4[CH:36]=[CH:35][N:34]=[C:33]([N:37]5[N:48]=[CH:47][C:46]6[C:45]7[CH2:44][C:43]([CH3:49])([CH3:50])[CH2:42][C:41]=7[S:40][C:39]=6[C:38]5=[O:51])[C:32]=4[CH:52]=[O:53])[CH:17]=3)=[N:10][N:4]2[CH2:3]1
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

8

反応物 4

HCID 62657Potassium Phosphate, TribasicHCID 517045Sodium AcetateHCID 866845164-Chloro-2-{4,4-dimethyl-9-oxo-7-thia-10,11-diazatricyclo[6.4.0.02,6]dodeca-1(8),2(6),11-trien-10-yl}pyridine-3-carbaldehydeHCID 866846053-(6,6-Dimethyl-6,7-dihydro-4H-pyrazolo[5,1-c][1,4]oxazin-2-ylamino)-1-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2(1H)-one

生成物 1

HCID 86684606
4-[5-({6,6-Dimethyl-4H,6H,7H-pyrazolo[3,2-c][1,4]oxazin-2-yl}amino)-1-methyl-6-oxo-1,6-dihydropyridin-3-yl]-2-{4,4-dimethyl-9-oxo-7-thia-10,11-diazatricyclo[6.4.0.02,6]dodeca-1(8),2(6),11-trien-10-yl}pyridine-3-carb aldehyde
収率 33.5%

試薬・触媒・溶媒 3

HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 962Water溶媒HCID 6342Acetonitrile溶媒

反応条件

温度
95 °C

実験手順

A 50-mL single-neck round-bottomed flask equipped with a magnetic stirrer and a reflux condenser was charged with 335b (240 mg, 0.60 mmol), 4-chloro-2-{4,4-dimethyl-9-oxo-7-thia-10,11-diazatricyclo[6.4.0.02,6]dodeca-1(8),2(6),11-trien-10-yl}pyridine-3-carbaldehyde 282i (107.7 mg, 0.30 mmol), Pd(dppf)Cl2 (24.5 mg, 0.030 mmol), K3PO4 (127.2 mg, 0.60 mmol), sodium acetate (49.2 mg, 0.60 mmol), water (0.5 mL), and acetonitrile (10 mL). After three cycles of vacuum/nitrogen flush, the mixture was heated at 95° C. for 1 h. It was then cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure and the resulting residue was purified by silica-gel column chromatography eluting with 30:1 dichloromethane/methanol to afford 335c as a brown solid (60 mg, 22%, two steps). MS-ESI: [M+H]+ 598.2.

後処理

  1. customA 50-mL single-neck round-bottomed flask equipped with a magnetic stirrer and a reflux condenser
  2. customAfter three cycles of vacuum/nitrogen flush
  3. temperatureIt was then cooled to room temperature
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated under reduced pressure
  6. customthe resulting residue was purified by silica-gel column chromatography
  7. washeluting with 30:1 dichloromethane/methanol

出典と根拠

ORDレコード
ord-5b9bd380b1b54117bb4ec0bc7e43e58f
出典データセット
uspto-grants-2014_12
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08921353B2

反応ノート

読み込み中…

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