Partial formulae

C2iff28 9 9 The C Hy partial formula is obtained by adding all CH units. 

It is suggested that in valeriodine the free hydroxyl group is at C or C , as in the above partial formula, and the esterified hydroxyl group at C , as is usual in this series (cf. hyoscyamine, p. 79). 

In 1931 Winterfeld and Kneuer, as a result of their observation that jS-lupinane can be obtained from lupanine, and the formation of 2-methyl-pyrrolidine by the oxidation of sparteine, combined these two features in a partial formula (II) for lupanine, which could be developed in various ways depending on the mode of attachment of the methylpyrrolidine residue. In view, however, of Ing s demonstration of the relationship of anagyrine, CJ5H20ON2, to Z-lupanine, CJ5H24ON2, and d-sparteine, C15H28N2, it was elearly neeessary to consider formul for lupanine derivable from the two alternati-ves, which Ing had proposed for anagyrine and which are shown below as (III) and (IV) with the formul for lupanine derived from them (V) by Ing and (VI) by Clemo and Raper. Sparteine would be represented by (V) or (VI) with the change CO CH2. 

A third form, w ooxyberberine (partial formula XII), was obtained by Pyman by the oxidation of berberineacetone (XIII) with permanganate in acetone solution. The steps in its formation are shown by... 

These formulae explain the scission products of the two alkaloids and the conversion of evodiamine into rutaecarpine, and were accepted by Asahina. A partial synthesis of rutaecarpine was effected by Asahina, Irie and Ohta, who prepared the o-nitrobenzoyl derivative of 3-)3-amino-ethylindole-2-carboxylic acid, and reduced this to the corresponding amine (partial formula I), which on warming with phosphorus oxychloride in carbon tetrachloride solution furnished rutaecarpine. This synthesis was completed in 1928 by the same authors by the preparation of 3-)S-amino-ethylindole-2-carboxylic acid by the action of alcoholic potassium hydroxide on 2-keto-2 3 4 5-tetrahydro-3-carboline. An equally simple synthesis was effected almost simultaneously by Asahina, Manske and Robinson, who condensed methyl anthranilate with 2-keto-2 3 4 5-tetrahydro-3-carboline (for notation, see p. 492) by the use of phosphorus trichloride (see partial formulae II). Ohta has also synthesised rutaecarpine by heating a mixture of 2-keto-2 3 4 5-tetrahydrocarboline with isatoic anhydride at 195° for 20 minutes. 

Cyanogen azide is a useful reagent for conversion of pyrrolidine enamines of 3-keto steroids to A-norsteroids. " Ring contractions can be carried out in the presence of 17j5-hydroxy, 17j -acetoxy, 20-keto groups and isolated double bonds. In a typical procedure, 17j -hydroxy-5a-androstan-3-one (partial formula 8) is converted into the enamine (9) by pyrrolidine in benzene... 

Molecular Weight, Molecular Formula, Partial Formula... 

A modification of the WiUgcrodt reaction that simplifies the procedure by obviating the necessity of a sealed tube 01 autoclave consists in refluxing the ketone with a high-boiling amine and sulfur (Schwenk, 1942). Morpholine, so named because of a relationship to an early erroneous partial formula suggested for morphine, is suitable and is made technically by dehydration of diethanolamine. The reaction is conducted in the absence of water, and the reaction product is not the amide but the thioamide this, however, undergoes hydrolysis in the same manner to the arylacetic acid. 

The structures of regioisomers, represented by the partial formulas 77 and 78 and formed by addition of organic azides to Bredt olefins, can be assigned unambiguously by lH- and 13C-NMR spectra. In structure 77 the proton a to the N=N double bond appears at lower field than the proton a to the /V-Ph group with approximately AS = 0.8 ppm. In the13C-NMR spectra a chemical... 

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