H. R. SNYDER, H. F. STROHMAYER AND R. A. MOONEY
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Vol. 80
direct relationship with the bond orientation in the range 831-833 c m - ' because of the Cdaround C6 and C7 atoms. Accordingly, this band methyl group. is independent of the stereoche1nical configuration. I n addition to the above results it is seen froin The absorptioll of the C-H out-of-plane bend- Fig. 2 that each pair of santonin isomers epimeric ing vibration of ethylenic bond between C1 and C r a t Cli shows some similar absorptions, for instance, a t 1370 and 900 cm.-'. These bands cannot be is very similar to that of corresponding steroids. satisfactorily utilized for the determination of lac4-Norsantonins (11) possess this absorption as a tone structure since this feature is not cOnlmOn doublet a t the exact position of "G-band" of A' '- among their derivati\,es. Adsfor the spectral dif3-ketosteroid,I3 but santonins themselves absorb ference bet\veen the Cl1-q)in1ers there was found (18) R N Jones, I' Herling and L Katzenellenbogen, T I r r s no 'ysternatic ]OLKN4L,
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The Insecticidal Principles of Haplophyton cimicidum. 111. The Nature of the Acidic Function of Haplophytinel BY H. li. SNYDER, H. F. STROHMAYER A N D R. -4. _ ~ I O O N E Y ~ RECEIVED FEBRUARY 10, 1958 0x1 the basis of spectral evidence, the acidic funetioii of haplophptine has been determined to be a phenolic hydroxyl group. A partial structure I is proposed as a working model for the alkaloid, and the preparation of 0-inethylhaplophytine is described.
Haplophytiiie, the main alkaloid of Huplophyton cimicidum, has the empirical formula CzjHa,O&. The alkaloid shows amphoteric properties. Earlier investigations3 indicated the presence of two basic nitrogen atoms. The nature of the acidic group, however, was not understood. The acidity could be due to the presence of one of these various groups: a carboxylic acid, a phenol, an enolizable ketone, an a- or y-pyridone, or an easily hydrolyzable lactone or lactam. A carboxylic acid group can be ruled out because unchanged haplophytine is recovered on evaporation of ammoniacal or barium hydroxide solutions of haplophytine. Chloroform removes the alkaloid from 0.2 S aqueous sodium hydroxide, while aqueous 1 X alkali extracts haplophytine from chloroform. On attempted titration of the alkaloid with 0.1 -Ir sodium hydroxide, with phenolphthalein as indicator, no alkali was consumed a t room temperature or under reflux.l However, haplophytine was shown to be soluble in the 0.1 sodium hydroxide. This result would make the prcsencc of a carboxylic acid, a lactone or a lactam doubtful. enolizable ketone can be ruled out on the ground that no carbonyl group is reduced on catalytic hydrogenation, as shown by the infrared spectrum of the reduction product.3 Furthermore, dihydrohaplophytine still contains the acidic group. The acidic properties can best be explained by the presence of a cryptophenolic hydroxyl group. in the case of certain other phenols, for example o-liyclroxyacetophenone,j vomicine6 and demethyl( 1 ) Grateful a c k n u r v l e d ~ ~ n e is n l made of the suijport of this research I,? a grant from the National Science Foundation (G 5 8 0 ) . ( 2 ) American Cyanamid C o . Fellow, 1957-1938. R o g e r s , H. K . Snyder and R. F. Fischer, Tms J O U K N A L , 74, ; H . K. Snydm, I
