Ally1 aryl ethers which have no strongly electron attracting substitueuts undergo a charge-induced [3s, 3s] sigmatropic rearrangement in the prescence of 0.7 mole boron trichloride in chlorobenzene at low temperature, to give after hydrolysis the corresponding 0-ally1 phenols (Tables 1 and 2). The charge induction causes an increase in the reaction rate relative to the thermal Claisen rcarrangement of N 1O1O. With the exception of sllyl 3-methoxyphenyl ether (5). m-substituted allyl aryl ethers show similar behaviour (with respect to the composition of the product mixture) t o that observed in the thermal rearrangement (Table 3). The rearrangement of allyl aryl cthcrs wnth an alkyl group in the o-position, in the presencc of boron trichloride, yields a mixture of 0-and p-ally1 phenols, where more p-product is present than in the corresponding 1)

Die Umwandlung von Aryl-allyl-kthern in C-Allylphenole laisst sich nicht nur durch Erhitzen (CLAIsEN-Umlagerung), sondern vereinzelten Beobachtungen nach auch durch LEwIs-Sauren bei tieferen Temperaturen erzielen. Guajakol-allylather gibt mit BF3,2 CH,COOH bei 76" 38% Eugenol neben Guajakol, 6-Allyleugenol und delll Allylather von Allylguajakol oder Eugenoll).

Sunzlv2avy. The course of the reactions involved in the process of dcgradation of strychnine (1 ) to WIEALND-GUMLICH aldehyde (WGA) (2), first performed by WIELAND, KAZIRO & GUMLICH, has been elucidated. 23-Isonitrosostrychnine hydrochloride (9 a) upon treatment with thionyl chloride undergoes a fragmentation (2nd order BECKMANN rearrangement), thus furnishing N(a)-cyanoformyl-WGA hydrochloride ( l 4 a ) . On heating in an acidic medium, the latter compound is transformed -at least partially via the cyclic urethane 15 -into WCA (2), which is an important keyintermediate in the syntheses of strychnine and curare alkaloids. Thc compound 2 can now be obtaincd in high purity and good yield.A corresponding degradation has been rcalized with quaternary analogues (27 -f 3) as well as with 10-chlorostrychnine (58 -f 62).10-Chlorostrychnine (58) was prepared by chlorination of strychninc with chlorine in conc. hydrochloric acid a e :ording to LEUCHS & STEINBORN. A s by-products of the reaction, 10,15-dichlorostrychnine (59) and 10,15,19-trichlorostrychnine (60) could be identified.Starting from WGA a series of derivatives have been prepared. Special mcntion is made of the two cpimeric methyl cthers 18 and 19. The absolute configuration at the centre 17 of WGA and of these two substances h a s been cstablished by optical comparisons of 3 cpiineric pairs.The methyl ether 18, by-product P B D, is obtained if methanol is used in working up the BECK-RIANN rearrangement products of 23-isonitrosostrychnine hydrochloride (9a).X second by-product, (A)), results by working up under alkaline conditions. This compound has the structure 44 with invcrtcd configuration at centre 16. Degradation of 44 under controlled conditions leads either to WG-diol (42) or to 16-epi-WG-diol (51).Rcsidcs ( ( A ) and aBs a series of by-products and intermediates (16, 17, 11 a, 22, 23, 24 and 25)could l x detected in the course of the process ot strychnine degradation. Der WGA nimmt unter den Alkaloidcn der Strychnin-Gruppe eine zentrale Stellung ein. Unter dcm Namen Caracurin VII wurde er aus den siidamerikan. Strychnaceen S. toxifera und S. subcordata isoliert2). In der ersteren ist auch sein N(b)-Methosalz 3 = Alkaloid A-8 = Hemitoxiferin

Rei der Untcrsuchung der revcrsiblen p -C~~~s~x -U m l a g e r u n g am 2,6-Dimethyl- 4-[~-~4C,I-allyl-phenyl-allylather wurde bcobachtct, dass nach 24stiindigem Erhitzenauf 168" im zuriickgewonncnen Ather die Radioaktivitat nicht nur auf den 0-und C-Allylrest glcichmassig verteilt war, sondcrn dass die Aktivitat der y-C-Atome der beiden Allylreste urn etwa 37k abgenornmen, dafiir diejcnige der u-C-Atome um den gleichen Betrag zugenommcn hatte3

Es wurde mit Hilfe von radioaktiv indizierten Verbindungen gezeigt, dass die ortho‐Claisen‐Umlagerung von 2,4‐disubstituierten Phenylallyläthern – im Gegensatz zu in 2‐Stellung monosubstituierten Phenylallyläthern – einheitlich verläuft.