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Methanol → Ethyl 4-allyl-1-[5-[7-bromo-2-(ethylcarbamoylamino)-1,3-benzothiazol-5-yl]pyrimidin-2-yl]piperidine-4-carboxylate

HRID 712295
ノート
印刷プレビュー

反応式

HRID 712295 の反応式
[Br:1][C:2]1[C:10]2[S:9][C:8]([NH:11][C:12]([NH:14][CH2:15][CH3:16])=[O:13])=[N:7][C:6]=2[CH:5]=[C:4](I)[CH:3]=1.[CH2:18]([C:21]1([C:42]([O:44][CH2:45][CH3:46])=[O:43])[CH2:26][CH2:25][N:24]([C:27]2[N:32]=[CH:31][C:30](B3OC(C)(C)C(C)(C)O3)=[CH:29][N:28]=2)[CH2:23][CH2:22]1)[CH:19]=[CH2:20].CO.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(Cl)Cl>[CH2:18]([C:21]1([C:42]([O:44][CH2:45][CH3:46])=[O:43])[CH2:22][CH2:23][N:24]([C:27]2[N:28]=[CH:29][C:30]([C:4]3[CH:3]=[C:2]([Br:1])[C:10]4[S:9][C:8]([NH:11][C:12](=[O:13])[NH:14][CH2:15][CH3:16])=[N:7][C:6]=4[CH:5]=3)=[CH:31][N:32]=2)[CH2:25][CH2:26]1)[CH:19]=[CH2:20]
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

9

反応物 4

HCID 887MethanolHCID 62657Potassium Phosphate, TribasicHCID 578137231-(7-Bromo-5-iodobenzo[d]thiazol-2-yl)-3-ethylureaHCID 66976919Ethyl 4-allyl-1-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidin-2-yl)piperidine-4-carboxylate

生成物 1

HCID 86664009Ethyl 4-allyl-1-[5-[7-bromo-2-(ethylcarbamoylamino)-1,3-benzothiazol-5-yl]pyrimidin-2-yl]piperidine-4-carboxylate
収率 27%

試薬・触媒・溶媒 4

HCID 178418397HCID 178418397、化合物触媒HCID 6344Dichloromethane溶媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
80 °C

実験手順

To a solution of 1-(7-bromo-5-iodobenzothiazol-2-yl)-3-ethylurea (0.55 g, 1.29 mmol) and ethyl 4-allyl-1-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidin-2-yl)piperidine-4-carboxylate (0.79 g, 1.97 mmol) in 1,4-dioxane:MeOH (30:20 mL) was added potassium phosphate (0.41 g, 1.97 mmol) at rt and the mixture degassed for 15-20 min by purging N2 followed by addition of tetrakis(triphenylphosphine)palladium(0) (0.15 g, 0.13 mmol). The reaction mixture was again degassed for another 15-20 min then heated up to 80° C. for 5 h. After completion of reaction (by TLC), the reaction mixture was cooled to rt, diluted with EtOAc (500 mL) and passed through celite. The filtrate was evaporated and the crude residue was purified over 100-200 M silica-gel using 1.50% MeOH: DCM to obtain the desired product as a beige solid (0.20 g, 27% yield). 1H NMR (DMSO-d6): δ 1.09 (t, J=7.20 Hz, 3H), 1.21 (t, J=6.80 Hz, 3H), 1.47 (m, 2H), 2.05 (m, 2H), 2.29 (m, 2H), 3.18 (m, 2H), 3.21 (q, J=7.20, 2H), 4.17 (q, J=6.80 Hz, 2H), 4.46 (m, 2H), 5.05 (m, 2H), 5.72 (m, 1H) 6.74 (br s, 1H), 7.69 (s, 1H), 7.87 (s, 1H); 8.77 (s, 2H) and 10.90 (br s, 1H).

後処理

  1. customthe mixture degassed for 15-20 min
  2. customby purging N2
  3. customThe reaction mixture was again degassed for another 15-20 min
  4. customAfter completion of reaction (by TLC)
  5. temperaturethe reaction mixture was cooled to rt
  6. customThe filtrate was evaporated
  7. customthe crude residue was purified over 100-200 M silica-gel

出典と根拠

ORDレコード
ord-c6b56068507a4de092cffa9d98f5007e
出典データセット
uspto-grants-2015_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09181234B2

反応ノート

読み込み中…

このページの内容参加物反応条件実験手順後処理出典と根拠反応ノート