Sulfuric Acid → Ethyl 2-picolinoylnicotinate

HRID 1054200Notes

Reaction equation

HRID 1054200 reaction equation
[CH3:1][C:2](O)(C1OC2C=C3OC=C(C4C=CC(O)=CC=4O)C(=O)C3=C(O)C=2C1)C.[CH3:28]/[C:29](/CO)=C\CC1C(O)=C2C(C3C4C=CC(O)=CC=4OC=3OC2=CC=1O)=O.[N:55]1[CH:60]=[CH:59][CH:58]=[C:57]2[C:61](=[O:65])[O:62][C:63](=[O:64])[C:56]=12.OS(O)(=O)=O.[N:71]1[CH:76]=[CH:75][CH:74]=[CH:73][C:72]=1[Li]>N1C=CC=C(C(OCC)=O)C=1C(OCC)=O.C(O)C>[N:71]1[CH:76]=[CH:75][CH:74]=[CH:73][C:72]=1[C:63]([C:56]1[N:55]=[CH:60][CH:59]=[CH:58][C:57]=1[C:61]([O:62][CH2:1][CH3:2])=[O:65])=[O:64].[N:71]1[CH:76]=[CH:75][CH:74]=[C:73]([C:61]([C:57]2[C:56]([C:63]([O:62][CH2:28][CH3:29])=[O:64])=[N:55][CH:60]=[CH:59][CH:58]=2)=[O:65])[CH:72]=1

Participants

9

Reactant 5

HCID 1118Sulfuric AcidHCID 69688Furo[3,4-b]pyridine-5,7-dioneHCID 632835Lupinisoflavone BHCID 1016132141,3,8-trihydroxy-2-[(E)-4-hydroxy-3-methylbut-2-enyl]-[1]benzofuro[2,3-b]chromen-11-oneHCID 178506720HCID 178506720, compound

Product 2

HCID 117925977Ethyl 2-picolinoylnicotinateHCID 117926477Ethyl 3-picolinoylpicolinate

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 108895172,3-Diethyl 2,3-pyridinedicarboxylateSolvent

Procedure

Each of the Rilyazines RL-1 through RL-4 may be synthesized according to the procedure of Scheme 1. Furo[3,4-b]pyridine-5,7-dione is reacted with ethanol in the presence of an acid, such as H2SO4, resulting in diethyl pyridine-2,3-dicarboxylate (1), which is then reacted with freshly-prepared pyridin-2-yl lithium to afford ethyl 2-picolinoylnicotinate (2) and ethyl 3-picolinoylpicolinate (3). Separation of the isomers (2) and (3) by chromatography and their reactions with cyclohexylhdrazine hydrochloride affords the ketone-Rilyazines RL-1 and RL-3, which may then be converted to the corresponding thione-Rilyazines RL-2 and RL-4 by reaction with Lawesson reagent.

Sources & evidence

ORD record
ord-bab5a582bc5c42f8a02b9386e882ad15
Source dataset
uspto-grants-2016_07
Patent number
US09394299B2

Reaction notes

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