98 



BACON. 



point of 105°. Schreiner " found 130° to 131° as the melting point of 

 the a modification of a phellandrene nitrite. My work seems to show- 

 that if the phellandrene nitrite is ciystallized from cold solvents it is 

 very easy to isolate the body of the higher melting point. WaUach 

 heated his solvents, which probably accounts for the lower melting point. 

 The yield of phellandrene nitrite is very far from quantitative, hence it 

 is not possible by use of the nitrites to detennine whether a phellandrene 

 is pure or contains other terpenes. Moreover, I was able to obtain a 

 considerable yield of a phellandrene nitrite of a melting point of 121 ** 

 from a terpene which from its physical properties and its behavior on 

 oxidation, I believed to be practically pure /? phellandrene. The experi- 

 ments on the phellandrene nitrites follow: 



(A) Supposed a phellandrene. The united specimens B-5 were three times 

 distilled over sodium, in vacuo, and in the last distillation the terpene was collected 

 in three equal fractions to test its unformity. 



Boiling point at 12 mm. pressure. 



(1) 62 to 62.3 _- 



(2) 62. 3 to 62. 8 . 



(3) 62. 8 to 63. 5. 



Refractive 

 index, 



D 



.30° 



1. 4680 

 1. 4680 

 1.4683 



92.2 

 91.2 

 91.0 



Specific 

 gravity, 



30° 



4° 



0.8363 

 0.8364 

 0.8363 



The whole, once redistilled at ordinary pressure, had a boiling point of 172" 

 to 174°; specific gravity, ^ =0.8363 N 52! = 1.4681; A^=91°.4. This terpene 



corresponds very well in its physical properties with the best published data for 

 a phellandrene. 



( 1 ) 13.6 grams of this a phellandrene were added to 12 grams of sodium 

 nitrite (Kahlbaum fused) dissolved in a small amount of water, and while the 

 whole was immersed in a freezing mixture, with vigorous shaking, 12 grams of 

 cold glacial acetic acid were added drop by drop. There were obtained 6 grams 

 of crude phellandrene nitrite. This was purified by dissolving in cold chloroform 

 and precipitating by ether. It was then recrystallized once from cold acetic ether, 

 when 1.6 gram of a substance having a melting point of 120° to 121° was 

 obtained. 



(2) 13.6 grams a phellandrene obtained as in experiment (A) with 16 grams 

 of sodium nitrite and 16 grams of glacial acetic acid, gave 8 grams of crude 

 nitrite, which purified as above gave 2.2 grams of pure nitrite melting at 120°. 



(B) Fractions 2 and 8 of the Gumaca terpenes were united and twice distilled 

 over sodium, giving an oil of the following properties: Boiling point, 760 milli- 



30° 30° 



meters, 106° to 168°.2; specific gravity, -jj- =0.8354; N^^p 



<!0° 

 1.4658; A^=9r.2. 



4° """' "" D 



To judge from its boiling point, this terpene would be taken for /3 phellandrene 

 and it seems hardly possible that it could contain any quantity of a phellandrene, 

 yet it gives large quantities of the same nitrite as the a phellandrene. 



(1) 13.6 grams /3 phellandrene, 12 grams of sodium nitrite, 12 grams of glacial 

 acetic acid treated exactly as above gave 5 grams of crude nitrite which gave 1.2 

 grams of pure nitrite of a melting point of 121°, 



'Ckem. CentralU. (1901), 2, 544. 



