PHILIPPINE TERPENBS ANB ESSENTIAL OILS, III. 117 



1,350 cubic centimeters of oil were obtained. This was redistilled over sodium and 

 showed about the same relative percentage of heptane and hydropinene as the 

 nuts collected from Mount Mariveles at the same season. (Second lot above.) 

 The Benguet nut is considerably smaller and thinner than that from Mariveles."" 



AU the distillates up to 165° were now imited and carefully fractionated 

 ten timeSj the final result being as follows : 



Fraction 

 (degrees). Gthms. 



(1) 97-101 203 



(2) 101-120 12 



(3) 120-130 8 



(4) 130-140 7 



(5) 140-150 14 



(6) 150-160 600 



(7) Residue, a veiy resinous oil. 



Fraction No. 1 was shaken out twice with concentrated sulphuric acid and then 



distilled over sodium, giving 197 gTanis of an oil, boiling point, 97° to 98°; 



30° 30° 30° 



specific gravity,-— =0.6752; N^p— = 1.3840; A— ^=0. The odor is very pleasant, 



being very much like diphenyl methane. This oil is undoubtedly normal heptane. 

 125 grams of heptane were treated with 200 grams of bromine in the sunlight. 

 The influence of sunlight on the speed of bromination is very pronounced. It was 

 noted by counting the number of drops of bromine decolorized per minute, that 

 the reaction proceeded about six times as fast in direct sunlight as when the sun 

 was behind a cloud. The principal product of the reaction under these conditions 

 were m-heptyl bromide, boiling at 93° at 70 millimeters' pressure, 178° to 181° at 

 ordinary pressure. It gives jj^heptyl acetate when treated with fused sodium 

 acetate dissolved in glacial acetic acid. This is a liquid of pleasant odor, boiling 

 at 192°. 



Fraction No. 6 was distilled three times over sodium and then gave an oil 



of the following properties: Boiling point, 158° to 160°; specific gravity,^ — = 



orio orvo 4 



0.8252; N^ = 1.45S7; a5^=29°.6. The hydrochloride prepared from this oil 



had the following properties: Boiling point, 114° to 116° at 34 millimeters; 



specific gravity, ^=0.9343; n5^=I.4655; a2^ =+9°. The reaction of this 



chloride with magnesium according to Grignard was not very vigorous or complete 

 and therefore the corresponding hydrobromide was prepared and 50 grams 

 subjected to the Grignard reaction, which was quite violent. On treating the 

 product of the reaction with water and dilute acids, a hydrocarbon of the follow- 

 ing properties was obtained: Boiling point, 168° to 170°; specific gravity, 



'* In distilling resiniferous oils of the kind under discussion, it is often noted 

 that an emulsion is formed before the liquid has reached the boiling point, the 

 vapor and gas bubbles penetrate this emulsion with great difliculty; they have a 

 fibrous structure, are full of gas bubbles and are so persistent as to be well 

 worthy of note. One of these, while I was heating Pittosporum oil in a beaker, 

 was so persistent, that on emptying the contents into a Hirsch funnel, the oil 

 retained the form of the beaker, although on applying a vacuum, it filtered 

 practically clear, with only traces of water and dirt left on the filter paper. 

 These emulsions always disappear as soon as boiling becomes vigorous. 



