THE ESSENTIAL OIL O F CINNAMOMUM OLIVER1 (BAIL.), ETC. 751

LXIV.-The Essential Oil o f Cinnanzomurn Olive?-i (Bail.) o r Brisbane Sussajm. By GEORGE WATSON HARGREAVES.

LAUTERER (Proc. Roy. SOC. Queensland, 1895, 11, i, 22) describes Cinnamomum Oliveri as a handsome tree with grey, rough bark, growing in the scrubs on the North Coast Railway, Queensland. The bark contains a layer o,f phylloderma on the outside, and just between the cells of this, oiI-ducts run along the bark.

Examinat ion of the Oil f rom the Bark.

The bark was distilled in a current of steam, 71 kilos. giving about 1700 C.C. of oil, which was filtered and dried over calcium chloride.

Fractional Distillation of the Oil.-The oil was subjected to frac- tional distillation under 30 mm. pressure. It was first collected in fractions over loo, and these refractionated, until finally the more important were collected in fractions over lo. It was thus found that the oil (1300 grains) can be roughly divided into four main portions, namely, (I) that boiling below 90° yielding 98 grams, (2) that boiling between 90° and 120° yielding 291 grams, (3) that boiling between 120° a.nd 135O yielding 326 grams, (4) that boiling between 135O and 155O yielding 533 grams.

Identification of Pinene, C,,H,,.-The fraction boiling a t 77-78O/30 mm. (n? 1*4655), which constituted roughly 12-15 per cent. of the oil, was identified as pinene, by analysis (Found, C= 88.0; H=11-8. Calc., C=88.2; H=11*8 per cent.), and by the preparation of the nitrosochloride melting a t 108O.

Identification of d-Camphor, C1,Hi,O.-From the fraction boil- ing between 90° and 120°/30 rnm. a white solid separated during distillation, a further quantity being obtaineld on cooling the liquid. This was dried and distilled, wheln i t boiled a t 204O. (Found, @= 78.4; H = 10.2.

The oxime was prepared and found to melt a t 119O. The white solid was therefore camphor.

It had D23 1.030 and n;; 1.5165.

Calc., C = 78-9 ; H = 10.5 per cent.)

This substance, which was present to the amount of absout 18-20 per c a t . of the oil, was shown t o be dextrorotatory when examined in alcoholic solution.

Identification of Safrole, CioH,,02.-The fraction boiling between 125O and 130°/30 mm. on cooling gave a white, crystalline deposit which, when collected and fractionally crystallisd, yielded a sub- stance melting at 8O, and having D18 1.09, n: 1.535. (Found, C=73.9; H=6-3. Calc., C=74.07; H=6-17 per cent.)

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752 HARGREAVES: THE ESSENTIAL OIL OF CINNAMOMUM

The1 a-nitrosite melted and decomposed a t 129-130O. These experiments establish the presence of safrole to the extent

of 25-27 per cent. of the oil. Identification of E'ugenyl Methyl Ether.-The fraction boiling

between 140° and 150°/30 mm. on refractionation yieldeld a fraction boiling between 146O and 147O (under atmospheric pressure a t 244O) having ng 1.5305. (Found, C = 74.1 ; H = 7.6. Calc., C = 74.1 ; H = 7.8 per cent.)

Oxidation of this substance with potassium permanganate gave an acid melting a t 179O ide'ntical with veratric acid. (Found, C=59*1; H=5.4. Calc., C=59.3; H = 5 * 5 per cent. Silver salt. Found, Ag = 36.9. Calc., Ag = 37.4 per cent.)

The tribromo-derivative, CGH,,Br(OMe),*C,H,Br, melt 77-78O.

This compound, theref ore, was clearly eugenyl melthyl ether, and constituted the main fraction, being about 40-43 per cent. of the oil.

Examination of tlbe Fraction Boilitzg above 150°/30 mm.-This fraction consisted of a dark brown oil which on redistillation gave a green oil. Since the chief product of oxidation with potassium permanganate was veratric acid, undoubtedly this fraction con- sisted mainly of eugenyl methyl ether and a trace of some ethereal substance, probably a decomposition product of eugenyl methyl ether.

Examination of the Oil from the Leaups.

The oil from the leaves was fractionated as described in the case of the oil from the bark.

The fractions of lower boiling point were found to contain about 25 per cent. of a mixture of two terpenes, pinene, and another terpene with a slightly highelr boiling point, which gave a nitrosib. (The quantity of nitrosite obtained was too small t o purify for the purpose of a meflting-point determination.) This terpene was dextrorotatory, and had ngo 1.4719. It appeared in the fraction boiling between 75O and 80°/30 mm., and was probably phellan- drene, but the quantity of substance available was too small for further investigation,

The pinene was again identified by means of its nitrosochloride, which in this case was found tlo melt and decompose a t 103O, whereas that from the bark oil melted a t 1 0 8 O . There has been some discussion on this variation of melting point, Schimmel & Co. (Ge.sch@tsber., April, 1901) holding that it was 1OSo, and not 103O, as usually stated. Howeve'r, the fact that decomposition takeis place in one case points t o the possibility of a lower melting point being registered.

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OLIVERI (BAIL.) OR BRISBANE SASSAFRAS. 753

The fraction next above the terpenes contained a very high percentage (approx. 60) of d-camphor.

The higher fractions contained a t least two substances in very small quantities, one apparently being a phenol, which was obtained by extracting the fraction boiling above 150°/30 mm. with sodium hydroxide solution and ether. About 2 C.C. of this phenol were obtained. This compound, itself golden in colour, gave a green coloration with ferric chloride in alcohol :

0.1352 gave 0.3557 C‘O, and 0.1045 H,O. Consideration of these results leads one to expect a phenol of the

formula C,oH,,O,. The residue after extraction of the phenol furnished a small

quantity of a green substance boiling a t 2 6 3 O , which gave no pro- iiouiiced coloration with ferric chloridel in alcohol.

C=71.8 ; H=8-6.

A second combustion confirmed this formula.

Su In niury.

It may be seen tha t the oils from the bark and from the leaves of CIz‘izua rnomutn Oliveri contain similar substances in the lower fractions, bu t differ in the higher ones, no safrole or eugenyl methyl ether being found in that from the leaves.

Thus the oil from the bark contains four distinct substances in approximately the following proportioiis :

Pinene ............................. 12-15 per cent. &Camphor ........................ 18-20 ,, Safrole ............................ 25-27 ,, Eugenyl methyl ether . . . . . . . . . 40-45 ,,

The oil from the leavw contains: .......................... 25 1 ,

Pinene.. 1 Phellandrene ( 1 ) . . . . . . . . . . . . J &Camphor 60 8 ,

Phenols and other substances.. . 16 # #

........................

R. T. Baker (PTOC. Liizn. SOC. A7.S.HT., 1897, ii, 275), in his paper on “The Cinnaniomunis of New South Wales, with a Special Research on the Oil of the Bark of C. Oliueri (Bail.),” gives sonie- what incomplete results of a chemical analysis by H. G. Smith, no reference being made to the four main constituents of the oil. H e suspects the presence of traces of eugenol, cinnamaldehyde, and cineole, none of which could be detected by the1 author of the present paper. All Smith’s results, however, were based on colour reactions or odour; no analyses were carried out, nor were any derivatives prepared.

H e also states t ha t none of the terpenes of low boiling point is present, whetreas the present work has shown the presence of pinene to the extent of 12-15 per cent.

VOL. CIX. I 1

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754 REACTION O F T H E ALKYL NITRITES WITH PYRIDINE, ETC.

Again, no ment,ion is made by Smith of camphor, although he speaks of a stearoptsene (which was not isolated) crystallising a t - 1 2 O . This was probably a mixture of camphor and safrole, for the present' author, using liquid ammonia as rsfrigerant, succe,eded in fractionally crystallising these two substances, and by means o f . subsequent analyses and preparat'ion of derivatives their com- positions were ascertaineld. It is interesting to n o t e t ha t Margaret E. Scott (T., 1912, 101, 1612) examined the essential oil of the leaves of another sassafras, which, however, is of a different order and species, A t h e n o s p e r ~ n a rnosclbatum (Australian sassafras, native of Victoria), and obtained the following re'sults :

Eugenyl methyl ether . . . . . . . . . 50-60 per cent. Pinene . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15-20 $,

Camphor. ........................... 15- 20 ,, Safrole ................................. 5-10 ,,

These four substances are identical with those found in the oil from the bark of Ciii?uinioniw?n OZiueri, but not with those from the leaves.

The author's thanks are due to Professor B. D. S k l e f o r kind assistance t,liroughout the course of this research.

CHEMIUAL LABORATORY, UNIVERSITY OF QCJEENSLAND,

BRISBANE. [Received, March, 7th, 1916:.

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