Potassium Phosphate, Tribasic → Ethyl 7-(2-(3-ethylureido)-7-(pyridin-2-yl)benzothiazol-5-yl)-2-methyl-3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1,4]oxazine-2-carboxylate

HRID 712316ノート

反応式

HRID 712316 の反応式
FC(F)(F)S(O[C:7]1[CH:8]=[C:9]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][N:23]=2)[C:10]2[S:14][C:13]([NH:15][C:16]([NH:18][CH2:19][CH3:20])=[O:17])=[N:12][C:11]=2[CH:21]=1)(=O)=O.[CH3:30][C:31]1([C:51]([O:53][CH2:54][CH3:55])=[O:52])[O:36][C:35]2[CH:37]=[C:38](B3OC(C)(C)C(C)(C)O3)[CH:39]=[N:40][C:34]=2[NH:33][C:32]1=[O:50].ClC1N2N=C(N)N=C2C=C(Cl)C=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.CCOC(C)=O>[CH2:19]([NH:18][C:16](=[O:17])[NH:15][C:13]1[S:14][C:10]2[C:9]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][N:23]=3)=[CH:8][C:7]([C:38]3[CH:39]=[N:40][C:34]4[NH:33][C:32](=[O:50])[C:31]([CH3:30])([C:51]([O:53][CH2:54][CH3:55])=[O:52])[O:36][C:35]=4[CH:37]=3)=[CH:21][C:11]=2[N:12]=1)[CH3:20]

参加物

7

反応物 4

HCID 62657Potassium Phosphate, TribasicHCID 594375625,7-Dichloro-[1,2,4]triazolo[1,5-A]pyridin-2-amineHCID 66977204ethyl 2-methyl-3-oxo-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydro-2H-pyrido[3,2-b][1,4]oxazine-2-carboxylateHCID 72724619HCID 72724619、化合物

生成物 1

HCID 86664029Ethyl 7-(2-(3-ethylureido)-7-(pyridin-2-yl)benzothiazol-5-yl)-2-methyl-3-oxo-3,4-dihydro-2H-pyrido[3,2-b][1,4]oxazine-2-carboxylate収率 42%

試薬・触媒・溶媒 2

HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
80 °C

実験手順

To the solution of 2-(3-ethylureido)-7-(pyridin-2-yl)benzothiazol-5-yl trifluoromethanesulfonate (0.5 g, 1.12 mmol) and ethyl 2-methyl-3-oxo-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydro-2H-pyrido[3,2-b][1,4]oxazine-2-carboxylate (0.4 g, 1.12 mmol) in 1,4-dioxane:MeOH (5:3 mL) was added potassium phosphate (0.36 g, 1.68 mmol) at rt and the mixture degassed for 15-20 min by purging N2 followed by the addition of dichloro(1,1-bis(diphenylphosphino)(ferrocene)palladium (II) (0.091 g, 0.11 mmol). The reaction was degassed for another 15-20 min then heated to 80° C. for 5 h. After completion of reaction (by TLC), the reaction was cooled to rt, diluted with EtOAc (500 mL), passed through celite, the filtrate concentrated under reduced pressure and the crude residue purified over 100-200 M silica-gel using eluent 2.3% MeOH: DCM to obtain the desired product as an off-white solid (0.25 g, 42%). 1H NMR (DMSO-d6): δ 1.06-1.13 (m, 6H), 1.77 (s, 3H), 3.21 (q, J=7.20, 2H), 4.14 (m, 2H), 6.87 (br s, 1H), 7.45 (m, 1H), 7.97-8.03 (m, 2H), 8.09 (s, 1H), 8.29 (s, 1H), 8.55 (s, 2H), 8.80 (d, J=4.0 Hz, 1H), 10.62 (br s, 1H) and 11.73 (br s, 1H). MS: 533.24 [M+H]+.

後処理

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

出典と根拠

ORDレコード
ord-cad16fdd0f1e4f62875d48f437be9442
出典データセット
uspto-grants-2015_11
特許番号
US09181234B2

反応ノート

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