تفاعل #3212

معادلة التفاعل

dimethyl 4,7-dichloroquinoline-2,3-dicarboxylate

sodium formate

water

→

solid

المردود 134.8%

Dimethyl 7-chloroquinoline-2,3-dicarboxylate

المردود 134.8%

المذيبات

dimethylformamide

ظروف التفاعل

المعالجة

1. 1
   درجة الحرارةwas heated at 90°-95° C. for 7 hr
2. 2
   أخرىwas degassed
3. 3
   workup.ADDITIONan additional quantity of tetrakis(triphenylphosphine)palladium(0) (0.92 g, 0.80 mM) was added
4. 4
   درجة الحرارةthe reaction mixture again heated at 90°-95° C. for 6 hr
5. 5
   أخرىThe cooled reaction mixture
6. 6
   استخلاصthe resulting mixture extracted with ethyl acetate
7. 7
   تجفيفThe combined extracts were dried (MgSO4)
8. 8
   ترشيحfiltered
9. 9
   تركيزconcentrated

الإجراء التجريبي

A stirred mixture of dimethyl 4,7-dichloroquinoline-2,3-dicarboxylate (5.00 g, 15.9 mM), sodium formate (1.63 g, 23.9 mM) and tetrakis(triphenylphosphine)palladium(0) (0.92 g, 0.80 mM) in anhydrous dimethylformamide (75 mL) under a nitrogen atmosphere was heated at 90°-95° C. for 7 hr. No reaction occurred so the reaction mixture was degassed and an additional quantity of tetrakis(triphenylphosphine)palladium(0) (0.92 g, 0.80 mM) was added and the reaction mixture again heated at 90°-95° C. for 6 hr. The cooled reaction mixture was poured into water and the resulting mixture extracted with ethyl acetate. The combined extracts were dried (MgSO4), filtered and concentrated to leave an gummy solid (6.0 g). Trituration of this residue with ethyl acetate and subsequent filtration separated a crystalline solid which was shown to be dimethyl 7-chloro-4-hydroxyquinoline-2,3-dicarboxylate. The filtrate was concentrated and the residue was flash chromatographed over silica gel (eluant: hexane/ethyl acetate, 3/2) to provide the title diester (1.13 g, 25.4%) as a light yellow crystalline solid; MS(CI): 280 (M+H).

المصدر