Easterfield and McDowell. — Chemistry of the N.Z. Flora. 519 



lUnless the copper oxide was maintained at a very bright-red heat during 

 the analyses the results found were invariably too low (c/. the formula 

 CigHagO assigned in the preliminary note, loc. cit. ; also Dunstan and 

 Hem-y, J.C.S., Proc, 1896, p. 48). 



The molecular weight was determined by the cryoacopic method, using 

 glacial acetic acid as the solvent. The values found were 285 and 288. 

 The formula C20H30O requires a molecular weight of 286. No compound 

 of this formula is cited in chemical literature. 



Acetyl Totarol. 



Totarol can be recrystallized without change from acetic anhydride, but 

 upon prolonged boiling an acetyl compound results. Acetylation takes 

 place very rapidly and with considerable evolution of heat if a drop of 

 concentrated sulphuric acid be added to acetic anhydride in which finely 

 divided totarol is suspended. The compound is conveniently purified by 

 crystallization from alcohol, and melts at 123°-123-5°. The specific rotation 

 in light petroleum (4-per-cent. solution) [A]d = 44-6°. 



Calculated for Found 



C20H29O. C2H3O. I. ' II. 



C =8049 .. .. .. .. 80-14 80-15 



H = 9-75 . . ■ . . . . . . 9-96 9-92 



The substance is perceptibly hygroscopic. The molecular weight deter- 

 mined by hydrolysis with alcoholic potash gave the values 331-8, 328-7, 

 and 326-7. The calculated value for the above formula is 328. 



The totarol regenerated during hydrolysis had the same melting-point 

 and optical activity as the original totarol. 



The slow rate at which totarol undergoes acetylation suggests that it is 

 a tertiary alcohol. The same conclusion is to be drawn from the fact that 

 it yields no acid phthalic ester when the benzene solution is boiled with 

 phthalic anhydride, and that no acetyl ester results when totarol is heated 

 with glacial acetic acid in a sealed tube. 



Oxidation experiments also indicate that totarol is neither a primary 

 nor secondary alcohol. Chromic acid in glacial acetic-acid solution attacks 

 totarol very slowly at first ; subsequently the action becomes vigorous, 

 and much carbon dioxide is evolved. Unchanged totarol, but no oxidation 

 product, can be isolated after the reaction has ceased. Similarly no acid 

 or ketonic products could be isolated when totarol was oxidized with potas- 

 sium bichromate and dilute sulphuric acid, though the experiment was tried 

 at various temperatures. 



A neutral crystalline oxidation product, but no acid, results when 

 totarol dissolved in pure benzene or purified light petroleum is agitated for 

 some hours with decinormal permanganate solution. The yield is about 

 20 per cent, of the weight of the totarol taken. The substance is readily 

 purified by crystallization from ether, and when pure melts at 205°, at 

 which temperature sublimation commences. 



Calculated for 



^40^6003- 



C = 81-63 . . 

 H = 10-21 . . 



