II. CHEMISTRY 



475 



prepared by condensing /3-oxocarboxylic acid esters and /3-diketones with 

 aldehydes and ammonia (Hantzsch's method). ^^ jS-PicoHne is commonly 

 recovered from coal tar. 



c. From Quinoline 



Quinoline can be oxidized to 2 , 3-pyridinedicarboxylic acid (quinolinic 

 acid) with heat^*'"'^*'^ or with acids. ^^' ^^^' ^"^ For example, quinoline plus 

 H2SO4, HXO3, and HgO (as a catalyst) when heated to 300° gives an 88.4 % 

 yield of nicotinic acid which can be recovered as the copper salt.^"^ Se02 is 

 also an effective catalyst in converting quinoline to nicotinic acid in high 



yiel(J.107, 108 



[O] 



Quinoline 

 d. From Pyridine 



-COOH 



^^/-COOH 

 Quinolinic acid 



/\ 



heat or 

 acid 



-COOH 



Nicotinic acid 



Pyridine may be sulfonated with fuming sulfuric acid, yielding the 

 3-sulfonic acid. When the sodium salt of this compound is distilled with 

 potassium cyanide, 3-cyanopyridine is formed. ^"^ This compound may then 

 be hydrolyzed to nicotinic acid. An alternative procedure is to brominate 

 pyridme in the 3 position and treat with cuprous cyanide to yield 3-cyano- 

 pyridine."*' 



V\ 



-Br 



+ CU2(CX)2 



pyridme 



— CN 



HCl 



^n/ 



-COOH 



\N/ 



'3 V. von Richter, The Chemistry of the Carbon Compounds, Vol. IV, p. 198. Elsevier 



Publishing Co., New York, 1946. 

 "OS. Hoogewerff and W. A. van Dorp, Ann. 204, 117 (1880); 207, 219, 226 (1881); 

 Rec. trav. chim. 1, 122 (1882). 



01 R. Camps, Arch. Pharm. 240, 353, 359 (1902). 



02 H. Weidel and J. Herzig, Monatsh. Chem. 1, 16 (1880). 

 »3 F. B. Ahrens and R. Gorkow, Ber. 37, 2063 (1904). 



0^ S. Hoogewerff and W. A. van Dorp, Ber. 14, 974 (1881). 



05 H. Weidel and J. Herzig, Monatsh. Chem. 6, 982 (1885). 



06 M. S. Larrison, U. S. Pat. 2,475,969 (July 12, 1949). 



07 M. B. Mueller, U. S. Pat. 2,436,660 (February, 1948). 



08 F. Porter, M. Bumpers, and J. N. Crosby, U. S. Pat. 2,513,251 (July 27, 1950). 



09 O. Fischer, Ber. 15, 63 (1882). 



10 S. M. McElvain and M. A. Goese, J. Am. Chem. Soc. 63, 2283 (1941). 



