VOL. 4 (1950) CYCLIC PLANT ACIDS AND GLUCOSE 2O3 



SUMMARY 



The transformation of quinic acid into shikimic acid by means of the methylene derivatives 

 of these acids has been described. Thus the configuration of the carbon atoms 3,4 and 5 of quinic 

 acid has been shown to be the same as in shikimic acid, which had previously been configurationally 

 related to D-glucose. 



3-cyano-lobelanine has been synthesized from dihydroshikimic acid nitrile, benzoyl acetic acid, 

 and monomethyl amine under conditions sufficiently mild so that they might exist in plant or animal 

 organisms. 



RfiSUMfi 



Nous avons decrit la transformation de I'acide quinique en acide shikimique a I'aide des derives 

 methyMniques de ces acides. Nous avons montre ainsi que la configuration des atomes de carbone 

 3, 4 et 5 dans I'acide quinique est la meme que dans I'acide shikimique, dont la configuration avait 

 6t6 pr^cedemment reliee a celle du D-glucose. 



La 3-cyano-lobelanine a 6te synthetisee a partir du nitrile de I'acide dihydro-shikimique, de 

 I'acide benzoylacetique et de la monomethylamine sous des conditions suffisamment douces pour 

 exister dans I'organisme vegetal ou animal. 



ZUSAMMENFASSUNG 



Wir beschreiben die Umwandlung der Chinasaure in die Shikimasaure iiber die entsprechenden 

 Methylenderivate. Es wurde also gezeigt, dass die Konfiguration der Kohlenstoffatome 3, 4 und 5 

 in der Chinasaure dieselbe ist wie in der Shikimasaure, deren Konfiguration schon friiher auf die der 

 D-Glucose zuriickgefiihrt wurde. 



3-Cyanolobelanin wurde aus Dihydroshikimisaure-nitril, Benzoylessigsaure und Monomethyl- 

 amin unter milden Bedingungen synthetisiert, wie sie auch im pflanzlichen oder tierischen Organismus 

 vorkommen konnen. 



REFERENCES 



^ G. Dangschat, Naturwisenschaften ,30 (1942) 146; C. A., 37 (1943) 3408®. 



Th. Posternak, Helv. Chini. Acta, 25 (1942) 746. 



Confer also H. O. L. Fischer, Harvey Lectures, Ser. 40 (1945) 156-178. 



H. G. Fletcher Jr, Advances in Carbohydrate Chem., Vol. 3, Academic Press, Inc., New York 



1948. 

 2 H. O. L. Fischer and G. Dangschat, Ber., 65 (1932) 1009 and Helv. Chim. Acta, 17 (1934) 1200. 



* H. O. L. Fischer and G. Dangschat, Helv. Chim. Acta, 18 (1935) 1206. 

 ^ H. O. L. Fischer and G. Dangschat, Helv. Chim. Acta, 20 (1937) 705- 



* Max Bergmann et al., Ber., 55 (1922) 158; Ber., 56 (1922) 1052. 

 P. A. Levene and G. Mikeska, /. Biol. Chem., 88 (1930) 791. 



® Quinic acid occurs not only in the free state in the plant kingdom but also for example in chloro- 

 genic acid as a depside with caffeic acid. For the constitution of chlorogenic acid cf. H. O. L. Fischer 

 and G. Dangschat, Ber., 65 (1932) 1037. 



^ A preliminary notice on the same subject has been published in Die Naturwissenschaften, 26 

 (1938) 562. 



** gth Communication on Quinic Acid and derivatives, J.A.C.S., in press. 



* gth Communication on Quinic Acid and derivatives, J.A.C.S., in press. 

 '" gth Communication on Quinic Acid and derivatives, J.A.C.S., in press. 



^1 This relationship is also a confirmation of the assumption of the cis position of the hydroxyls 

 4 and 5 of quinic acid and shikimic acid which we have always made on the basic of the work of 

 Boeseken (cf. also Huckel, Theoretische Grundlagen der Chemie, i (65-66). 



^^ H. O. L. Fischer and G. Dangschat, Helv. Chim. Acta, 17 (1934) 1196. Cf. also shikimic acid 

 -^ aconitic acid, VIII, H. O. L. Fischer and G. Dangschat, Helv. Chim. Acta, 18 (1935) 1204. 



1^ Wl. Butkewitsch, Biochem. Z., 145 (1924) 442. 



!■* C. ScHOPF and G. Lehmann, Liebig's Ann., 518 (1935) 1-37. 



^* See gth Communication on Quinic Acid and derivatives, J.A.C.S., in press. 



^® H. O. L. Fischer and G. Dangschat, Ber., 65 (1932) 1020. The yield is increased if the processing 

 is performed two hours after action of the acetylation reagent. 



^' See gth Communication on Quinic Acid and derivatives, J.A.C.S., in press. 



