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T H E J O U R N A L OF I N D U S T R I A L A N D . E N G I N E E R I N G C H E M I S T R Y
cooled t h e pitch under slight pressure, t o avoid t h e formation of voids. T h e slow cooling always caused a marked increase i n apparent specific gravity with t h e harder pitches, while with soft pitches t h e difference is negligible. T h e writer hopes t h a t this paper on t h e homely subject of specific gravity will be useful i n some measure t o workers in general, a n d can s t a t e t h a t , i n his experience, t h e methods recommended here are rapid, convenient, a n d sufficiently accurate, RESEARCH DEPARTMEKT, BARRETT MANUFACTURING Co. 17 BATTERY PLACE. NET%' YORK CITY
OILS OF THE CONIFERAE: IV. THE LEAF AND TWIG OILS OF DIGGER PINE, LODGEPOLE PINE, AND RED FIR By A. W. SCHORCER Received November 2, 1914
It is well known a t t h e present time t h a t t h e oleoresins of t h e digger pine ( P i n u s s a b i n i a n a ) a n d Jeffrey pine ( P i n u s jejveyi) yield oils consisting almost entirely of n-heptane. Examination of t h e leaf a n d twig oil of t h e digger pine has revealed t h e very interesting fact t h a t heptane was present in t h e sample t o t h e extent of only about 3 per cent, t h e remainder of t h e oil consisting of aromatic bodies which are principally terpenes. It m a y be assumed with safety t h a t this small percentage of heptane was derived from t h e small twigs during distillation, since t h e latter were n o t separated from t h e leaves. T h e phytochemical processes taking place in t h e leaves a n d in t h e woody portions of t h e tree are, accordingly, entirely different, since t h e oil from t h e former consists of aromatic compounds a n d t h e oil from t h e latter of aliphatic derivatives. Anisic acid was obtained b y oxidation of certain fractions of t h e oils from digger and lodgepole pines. Lack of material prevented obtaining conclusive evidence a s t o t h e parent substance from which t h e anisic acid was derived, a n d for t h e same reason t h e presence of borneol a n d certain terpenes can n o t be shown with absolute certainty. T h e d a t a obtained, however, should be of i m p o r t a n t assistance t o t h e chemist who is fortunate enough t o obtain material for further investigation. LEAF A N D T W I G OIL OF DIGGER PINE
(Pinus s a b i n i a n a , DOUGL.) T h e physical a n d chemical constants of t h e oils are given in Table I. T h e sample of 238 grams gave t h e following fractions: I O O ~ - I ~ 6~ . 0~ ,per cent; 152'-160', 10.0 per c e n t ; 1 6 0 ~ - 1 7 0 ~5, 2 . 0 per cent; 1 7 0 ~ - 1 8 8 ~ 1, 5 . 0 per c e n t ; 1 8 8 " - 2 3 5 ~ , 8.5 per c e n t ; 235'-2goo, 2.3 per c e n t ; residue, 6 . 0 per cent. HEPTANE-The lower boiling portions of t h e oil were fractionally distilled a n d repeatedly t r e a t e d with concentrated sulfuric acid. B y this t r e a t m e n t 7.2 grams ( 3 . 0 per cent) of oil were finally obtained, having t h e specific gravity 0.7013 at I 5 ' a n d boiling between 9 8 . 5 a n d 101'. P u r e n-heptane boils at 98.4' a n d has a specific gravity a t I ~ of O 0.6880.
V O ~ 7. , NO. I
ff-PINENE-The fraction boiling a t 156-157 ' h a d 0 . 8 6 1 8 a n d ( ~ ~ 2 -26.24'. 0 0 A good yield of pinene nitrosochloride was obtained. T h e nitrosochloride was thoroughly washed with methyl alcohol a n d dissolved i n a small a m o u n t of hot chloroform. T h e crop d150
PHYSICAL AND CHEMICAL CONSTANTS OF THE LEAFAND TWIGOILS Ester No. Optical after Per cent Sp. p. Ref. :nd. rotation Acid Ester acetylayield Sample 15 15 aD200 No. No. tion of oil DIGGERPINE: 2493 0.8566 1.4670 -20.93' 2.05 11.98 37.16 0,102 2494 0.8543 1.4708 -38.36' 1.91 9.48 29.84 0.085 2496 0.8517 1.4671 -30.75' 1.47 6.77 25.86 0.078 LODGEPOLE PINE: 2495 0.8690 1.4831 -17.84' 0.90 32.30 0.234 6.02 RED FIR: 2529 0.8665 1.4861 -16.70' 0.75 0,154 9.93 36.22 TABLEI-THE
of crystals obtained on cooling, after washing with alcohol, melted a t 104-10j '. From t h e chloroform mother liquor a further a m o u n t of crystals was obtained on addition of methyl alcohol. These crystals after washing with methyl alcohol melted a t I D j '. T h e nitrolpiperidine derivative melted a t I I 7 '. T h e t o t a l a-pinene fractions amounted t o 58 t o 59 per cent. T h e relatively small a m o u n t of oil boiling between 160-1 7 0 ' was examined for @-pinene with negative results. LIMoNErz-The t o t a l limonene fractions amounted t o about 24 per cent. T h e fraction boiling a t 1701 7 5 ' a n d having 0LD21° -40.79' gave negative results for phellandrene. Sylvestrene was apparently a b s e n t since t h e dihydrochloride obtained melted a t 49-50'. T h e fraction boiling at 1 7 5 - 1 7 7 ' yielded a tetrabromide melting a t 1 0 4 ', t h e melting point of limonene tetrabromide. E S T E R FRACTION-The portion boiling at 206-23 j ' was saponified a n d distilled with steam. T h e recovered oil was t h e n oxidized with a saturated solution of potassium permanganate a n d again distilled with steam. Only a few drops of oil having t h e odor of camphor were obtained. O n acidifying t h e oxidation liquor a n acid was obtained t h a t crystallized from h o t water in t h i n needles a n d sublimed readily, giving crystals melting a t 183-184'. A portion of t h e acid weighing 0.1637 g. required 10.62 cc. of N / I O N a O H for neutralization, giving a neutralization equivalent of 1 5 4 . 2 . T h e properties of t h e acid showed i t
OCH3
t h e latter melting t o be anisic acid, CaH4
