Sodium Carbonate → HCID 86715476、化合物

HRID 2284568

反応式

HRID 2284568 の反応式
[Cl:1][C:2]1[C:7]([C:8]2[CH:9]=[C:10]3[C:14](=[CH:15][CH:16]=2)[NH:13]N=C3)=[CH:6][CH:5]=[CH:4][N:3]=1.BrC1C=CC2N=[CH:23][S:24]C=2C=1.ClC1C(B2OC(C)(C)C(C)(C)O2)=CC=CN=1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.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>[Cl:1][C:2]1[C:7]([C:8]2[CH:16]=[CH:15][C:14]3[N:13]=[CH:23][S:24][C:10]=3[CH:9]=2)=[CH:6][CH:5]=[CH:4][N:3]=1

参加物

7

反応物 4

HCID 10340Sodium CarbonateHCID 27951716-Bromo-1,3-benzothiazoleHCID 120670602-Chloropyridine-3-boronic acid pinacol esterHCID 867154695-(2-chloropyridin-3-yl)-1H-indazole

生成物 1

HCID 86715476HCID 86715476、化合物収率 82%

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 312751,4-Dioxane溶媒

実験手順

6-(2-Chloropyridin-3-yl)benzo[d]thiazole was prepared analogous to 5-(2-chloropyridin-3-yl)-1H-indazole by heating the mixture of 6-bromobenzo[d]thiazole (2.0 g, 9.3 mmol), 2-chloro-3-pyridine boronic acid pinacol ester (2.7 g, 11.2 mmol), Pd(PPh3)4 (500 mg, 0.43 mmol) and 2M aq.Na2CO3 (14 mL, 28 mmol) in 1,4-dioxane (100 mL). The reaction mixture was concentrated at the completion of the reaction (12 h) and diluted with CH2Cl2 (200 mL/100 mL). Mixed organic layers were stirred with MgSO4 and Celite® for 30 min. The slurry was suction filtered and concentrated by rotary evaporator under vacuum. The crude concentrate was dissolved in CH2Cl2, adsorbed on silica gel and dried. The dry powder thus obtained was purified by silica gel flash column chromatography (Combiflash® companion System® with RediSep® silica gel column 40 g, 30-70% EtOAC/hexanes eluting solvent gradient). 6-(2-chloropyridin-3-yl)benzo[d]thiazole (1.9 g, 82%) was obtained as a white solid upon concentration of the product fractions. 1H NMR (DMSO-d6): δ 9.46 (s, 1H), 8.46 (dd, 1H, J=1.7 and 4.7 Hz), 8.30 (d, 1H, J=1.4 Hz), 8.17 (d, 1H, J=8.2 Hz), 7.96 (dd, 1H, J=1.7 and 7.6 Hz), 7.63 (dd, 1H, J=1.4 and 8.5 Hz), 7.53 (dd, 1H, J=4.7 and 7.6 Hz). LCMS: rt 6.71 min (A), purity 99%, MS (m/e) 247.

後処理

  1. temperatureby heating
  2. concentrationThe reaction mixture was concentrated at the completion of the reaction (12 h)
  3. additiondiluted with CH2Cl2 (200 mL/100 mL)
  4. filtrationfiltered
  5. concentrationconcentrated by rotary evaporator under vacuum
  6. concentrationThe crude concentrate
  7. dissolutionwas dissolved in CH2Cl2
  8. customdried
  9. customThe dry powder thus obtained
  10. customwas purified by silica gel flash column chromatography (Combiflash® companion System® with RediSep® silica gel column 40 g, 30-70% EtOAC/hexanes eluting solvent gradient)

出典と根拠

ORDレコード
ord-5e6e6ed1d3aa44749b7fcc00763e63c1
出典データセット
uspto-grants-2015_09
特許番号
US09145433B2

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