Hydrochloric Acid → 3-Chloro-4-(methoxycarbonyl)benzoic acid

温度

45 °C

To a 2 L round-bottom flask, equipped with a mechanical stirrer, was charged 2-chloro-1,4-benzenedicarboxylic acid dimethyl ester (25.15 g, 0.11 mol), methanol (300 mL) and tetrahydrofuran (300 mL). Over 10 min, a solution of lithium hydroxide monohydrate (4.62 g, 0.11 mol) in water (200 mL) was added. After the reaction had proceeded at ambient temperature overnight, the solution was concentrated in vacuo to about 150 mL and then diluted with water (200 mL). The precipitated solid was filtered off and washed with water (2×20 mL) to give the recovered starting material, 2-chloro-1,4-benzenedicarboxylic acid dimethyl ester (1.8 g), as shiny platelets. The combined filtrates were stirred while 1N hydrochloric acid (112 mL, 0.112 mol) was added. The resulting solid was filtered off, washed with water (2×50 mL) and air dried. The solid was dissolved in methanol (300 mL) and warmed to about 45° C., then to the stirred solution, water was added to just before the cloud point. After the solution was left at room temperature overnight, the resulting colorless solid that had formed was filtered off, washed in turn with a cold mixture of methanol-water (1:2; 30 mL) and cold water (30 mL). The solid was recrystallized once more from methanol-water as described above and dried, to give 3-chloro-4-(methoxycarbonyl)benzoic acid (13.1 g, 55.5% yield) as colorless needles.

1. customTo a 2 L round-bottom flask, equipped with a mechanical stirrer
2. waitAfter the reaction had proceeded at ambient temperature overnight
3. concentrationthe solution was concentrated in vacuo to about 150 mL
4. additiondiluted with water (200 mL)
5. filtrationThe precipitated solid was filtered off
6. washwashed with water (2×20 mL)
7. customto give the recovered
8. additionwas added
9. filtrationThe resulting solid was filtered off
10. washwashed with water (2×50 mL) and air
11. customdried
12. dissolutionThe solid was dissolved in methanol (300 mL)
13. additionto the stirred solution, water was added to just before the cloud point
14. waitAfter the solution was left at room temperature overnight
15. customthe resulting colorless solid that had formed
16. filtrationwas filtered off
17. washwashed in turn with a cold mixture of methanol-water (1:2; 30 mL) and cold water (30 mL)
18. customThe solid was recrystallized once more from methanol-water
19. customdried

ORDレコード

ord-8914fcdd64034db6add750108a916f3e

出典データセット

uspto-grants-2003_02

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US06515124B2