40 Report of.Schimmel § Co. 1921. 



stitution of this oil, and as it has been suggested by one journal 1 ) that there may be one 

 or several isomerides of santalol in the alcoholic constituents, we have been attempting 

 to clear up the question whether santalol or the sesquiterpene alcohols related to this 

 compound really form the essential constituents of this oil. We had a large bulk of 

 material from a reliable source in London at our disposal for this examination, namely 

 600 g. of a material of the following constants: — d 15 o 0.9720; [«] D -f 4° 9'; n D20O 1.50900; 

 insoluble in 10 vol. 70 percent, alcohol, soluble in 1.5 vol. and more 80 percent, alcohol; 

 acid v. 1.5; ester v. 16.2 = 6.4 per cent, estersantalol ; ester v. after acetylation 165.2 

 = 74.1 per cent, total santalol. 



The oil was by twofold fractionation separated into the following fractions: — 

 1. b.p. (70 to) 100 to 135° (6 mm.) 135 g. 



2. 



»> 



135 „ 145° 



56 g. 





3. 



» 



145 „ 150° 



92 g. (disc 0.9851 ; 



[«] D + 4°26 f ) 



4. 



n 



150 „ 153° 



116 g. (d 15 o 0.9824; 



[«] D + 7°18') 



5. 



»» 



153 „ 160° 



141 g. (d 15 o 0.9825; 



[«] D + 7°52') 



6. 



» 



160 „ 182° , 



27 g. 





7. 



t) 



residue 



10 g. 





The fractions 2 to 5 all possessed a faint odour like mint with a more or less 

 distinct suggestion of santalol. We were, however, not able to convert one of these 

 alcoholic fractions into the phthalic ester by the usual method (heating for one 

 hour of the benzene solution with phthalic acid anhydride on the water bath). 

 We also failed to esterify the fractions boiling between 145 and 150° (6 mm.) with 

 benzoylchloride and pyridine and likewise the subsequent fraction 4 (as sodium com- 

 pound) in petrol ether with phthalic acid anhydride. On the other hand we obtained 

 from the last-mentioned fraction, by boiling with acetic acid anhydride on the sand 

 bath, easily the acetate: — b. p. 156 to 158° (5 mm.), sap. v. 216.2 = appr. 100 percent. 

 Ci 5 H 23 OCOCH3, which in its odour bore a strong resemblance to the acetic ester 

 of santalol. The phthalic ester, however, was prepared from the fractions mentioned by 

 heating for four or six hours on an oil bath, and in one case, at the end of this 

 research, by heating for the same period on a water bath at 80°. About 50 per cent, 

 of these fractions did not take part in the reaction. A solid phthalic ester acid was not 

 obtained. The alcohol fractions which the saponification of the esters yielded had the 

 following constants 2 ) : — 



Fraction 5 (ca. 140°, 6 hours). d 15 o 0.9898; [«] D + 9°16'; n D20O 1.51470; b.p. 146 

 to 149° (4 to 5 mm.); 



fraction 3 (ca. 135°, 3 to 4 hours). di 5 o 0.9843; |>] D — 3° 18'; n D20 o 1.51184; 

 b.p. 149 to 152 (6 mm); 



fraction 4 (ca. 80°, 3 hours). d 15 o 0.9767; [«] D + 6°18'; b.p. 141 to 143° (3 to 4 mm.). 



All the preparations had a faint odour of santalol and did not react with phenyl- 

 and «-naphthyl-wocyanate, in analogy to santalol. The results of a combustion test of 

 the preparation from fraction 3 agreed with the formula C15H24O: — 



(1) 0.2369 g. of substance: 0.7092 g. C0 2 , 0.2306 g. H 2 0; found C 81.65 p.c, H 10.81 p.c. 



(2) 0.2112 g. of substance: 0.6344 g. C0 2 , 0.2068 g. H 2 0; found C 81.81 p.c, H 10.88 p.c. 



Calculated for Ci 5 H 24 0: 81.82 p.c. C, 10.91 p.c. H. 

 When formic acid was added to the alcohol, water was split off on heating. 



x ) Americ. Perfumer 15 (1920), 284. — 2 ) We add for comparison the constants of santalol from East 

 Indian oil: — d 15 o 0.9761 ; [«] D — 17°44'; n D2 oo 1.50790; b.p. 138 to 140° (4mm.). 



