反応 #90764

反応方程式

2,5-dichloro-4-iodopyridine

2-aminobenzoic acid

DPEPhos

K3PO4

→

title compound

収率 73.0%

2-[(2,5-Dichloro-4-pyridinyl)amino]benzoic acid

収率 73.0%

反応条件

後処理

1. 1
   その他was degassed
2. 2
   workup.WAITleft
3. 3
   workup.ADDITIONAdded another 160 mg of Pd(OAc)2 to the mixture
4. 4
   温度heated to 120° C. for another 24 h
5. 5
   温度The mixture was cooled to room temperature
6. 6
   ろ過followed by filtration
7. 7
   洗浄washing with EtOAc
8. 8
   ろ過followed by filtration
9. 9
   その他collected solids could not
10. 10
    その他be dried completely
11. 11
    ろ過The resulting paste was filtered
12. 12
    洗浄washed with water and TBME
13. 13
    乾燥The solid was dried under vacuum over P2O5 for 2 days

実験手順

A mixture of 2,5-dichloro-4-iodopyridine (10 g, 36.5 mmol), 2-aminobenzoic acid (4.85 g, 35.4 mmol), DPEPhos [bis(2-diphenylphosphinophenyl)ether] (1.6 g, 2.97 mmol), palladium(II) acetate (160 mg, 0.713 mmol) and K3PO4 (20 g, 94 mmol) was degassed and heated at 120° C. (oil bath temp) for 20 h. After 20 h, LCMS showed there was 33% (relative to the desired product) starting material left. Added another 160 mg of Pd(OAc)2 to the mixture, and heated to 120° C. for another 24 h. LCMS showed conversion complete. The mixture was cooled to room temperature, followed by filtration, and washing with EtOAc. The solids were acidified to pH=7-8, followed by filtration. However, the mixture was a paste, and collected solids could not be dried completely. The solids (11 g) was acidified with 6N HCl to pH=1. The resulting paste was filtered, and washed with water and TBME. The solid was dried under vacuum over P2O5 for 2 days to give the title compound (7.32 g, 60.2% yield). MS: M(C12H8Cl2N2O2)=283.11, (M+H)+=283.8; 1H NMR (400 MHz, DMSO) ppm 13.6 (s, 1 H) 10.2 (s, 1 H) 8.3 (s, 1 H) 8.0 (d, 1 H) 7.6 (q, 2 H) 7.3 (s, 1 H) 7.2 (m, 1 H).

出典