I.VDUSTRIIL A-VD ESGINEERI-VG CHEMISTRY
June. 1927
739
The Oil from Port Orford Cedar W o o d ' By F. H. Thurber and L. J. Roll ORI~CON STATECOLLEGE, CORVALLIS, ORE.
A
S ANALYSIS and some observations on the prop-
of this process approximately 1.5 grains of a gummy mass reerties of Port Orford cedar wood oil (Chamaecyparis mained in the distillation flask and a total of 1905 cc. of oil lumoniana (Murr.) Parlatore) were made by Schorgere2 were recovered. Some of the distillate was lost because of The sample that he analyzed was four years old and was (1) the volatility of the warm oil as it came from the conobtained from selected resinous pieces of wood. It perhaps denser, ( 2 ) its slight solubility in the large amount of water was not a representative sample, and this may account for obtained from the condensed steam, and (3) the small amounts the wide variation between the present writers' results and of the oil adhering to the apparatus used in separating the those of Schorger. However, contrary to the statement oil from the water. in Schorger's paper, it should be noted that, although the After the distillation the oil had a slight cloudiness due oil has sollie physiological effect as a diuretic, its action is to its water content, but a water-white product resulted not noticeable enough to prevent continuous operation on after the cloudy oil had stood over anhydrous sodium sulthis kind of timber in the lumber mills. fate for a day. The last traces of water were removed from T h i s oil 1s now being the oil by heating it to 150" C. for a few minutes in a manufactured on a commercial scale at the Western flask connected with a conThe oil from Port Orford cedar wood was distilled White Cedar Lumber Conidenser. The dry oil had a with steam, then dried, and carefully fractionated. pany's Mi11 a t hlarshfield, volume of 1871 cc. It was Each of the following fractions, obtained from the disOre. Port Orford cedar is carefully fractionated in the tillate, is named from the chief component which it native only to northwestern apparatus which is inencontained: d-a-pinene, 45.7 per cent; d-limonene, California and southwesttioned below. 3.2 per cent; d-borneol, 26 per cent; d-cadinene, 21 ern Oregon. The lumber FIRSTFRACTIONATIOXper cent; I-cadinol, 3.9 per cent. from the 111111 IS used in the There is some decomposiThe following compounds were isolated and purified: manufacture of storage battion of the ester, bornyl (1) d-a-pinene (probably isomeric with d-a-pinene isotery separators and in conacetate, which is present in lated from American turpentine oil) ; (2) d-borneol; struction work of various the oil when it is heated to (3) d-cadinene. types in nhich the timber a temperature higher than may be subjected to the ac180" C. For this reason tion of bacteria or to the ravthe distillation was carried ages of termites. The dust from the saws is con\-eyed to out a t atmospheric pressure until the temperature of the large vats arranged for steam distillation The vats are 6 vapor reached 178" C. At that point the source of heat was feet in dialiieter and are constructed of wooden st'aves 2 remoyed, the pressure reduced to 14 mm., and the fractioninches thick and 16 feet high, Steam under a boiler pressure ation completed at reduced pressure. A column stillhead of 110 pounds is passed through the sawdust for 60 minut'es. patterned after the one described by Loveless3 was used in By this procedure a yield of approximately 1.6 per cent of the fractionation. oil is obtained from the wood. The temperature remains From the results of preliminary distillations it was expected con.stant (100" C.) throughout the distillation, and the pres- that the oil could be separated into four rather sharply desure in t'he vats, noted by means of a steam gage rarely ex- fined fractions-namely, pinene, b. p., 155-159" C.; d-limceeds one pound. onene, b. p., 170-178" C.; borneol and bornyl acetate, b. p., The experiments here described were undertaken with 100-122" C. a t 14 mm.; and cadinene, b. p., 132-138' C. two objects in view: (1) to obtain a more accurate analysis at 14 mm. On the whole, the expected results were obtained; of the oil than is now available in the literature; ( 2 ) to iso- however, the d-limonene fraction was not definitely defined late and purify some of the more common compounds that and a fraction with a boiling point higher than that of cadare commercially important. Both of these objects u-ere inene was found to be present. After a number of distilattained. lations fourteen fractions were obtained, the boiling points The crude oil has the following physical corist'ants: color, and other physical constants of which are given in Table I. light brown; t)he odor differs from that of cedar oil produced T a b l e I-First Fractionation of Port Orford C e d a r 0 1 1 in the eastern part of the United States, being somewhat' similar to the odor of a mixture of pinene and borneol; d:o, 0.8913; n?, 1.4760; CY]^,, +46.68; acid value, 0.19; ester Crude oil 1871 100 1,4760 -46 68 0 8911 value, 19.3; ester ralue after acetylation, 88.3. The ester 1 742 155-1 59 39.65 1.4644 +52.98 0 8581 2 52 159-161 2 78 1.4O62 f ~ 6 18 . 0 8376 d u e s before and after acetylation are equivalent to 5.1 3 161-167 63 3.36 1,4664 +58.45 0 8604 4 167-178 44 1.4704 2.35 per cent of bornyl acetate and 20.4 per cent of free borneol. 4-60.81 0 8618 5 78-100 3 36 63 1.4748 +51.87 0 8928 These values are taken up in detail under the discussion of 123 6 100-1 10 6.66 1.4764 + 4 , .99 0 9376 7 267 110-118 14.24 1.4742 +53.55 0 9307 borneol in the lat'ter part of the paper. 8 29 118-122 1.55 1.4733 0 91.50 +25.15 Fractionation of Port Orford Cedar Oil
STEAM DISTILLATION-Kineteen hundred and seventy cubic centimeters of crude oil were distilled with steam over 10 per cent sodium carbonate solution; after the completion 1
Received February 14, 1927. THISJOURNAL, 6, 631 (1914).
9
58 122-132 3.10 1.4848 f21.77 0 266 14.20 132-136 1.5025 -I-40.97 0 24 136-145 1.28 1 5058 4-34.62 0 12 13 145-156 0 69 1 5058 fl6.57 0 13 155-170 17 0 91 1 5108 -10.54 0 14 170-180 38 2 03 1.307s 0 15 Losses 72 .. 3 x4 The first four fractions were fractionated a t 760 mm. and the 14 mm. pressure. 10 11
_-
3
THISJ O U R N A L , 18, 826 (1926).
91.22
9178 9367 9436 9717 9581
rest a t
Curve 1 in Figure I is made up from the boiling pointpercentage composition data given in Table I. Curve 2, Figure I, was made up from data obtained by noting the boiling point range for each 10 cc. of distillate collected when a previously dried 250-cc. sample of the crude oil was distilled a t atmospheric pressure. The same breaks are distinguishable in both curves, but in curve 1 the breaks are much more abrupt because of the careful fractionation carried out.
FRACTIONATION OVER SoDIuM-The four fractions mentioned above are all clearly defined on the curve, with the exception of d-limonene. Since the break in the curve was not definite in the section in which this compound should occur, it was thought that the distillate obtained in fractions 2 to 5 might be composed of a mixture, possibly of pinene, d-limonene, and borneol. For this reason a second distillation was made by combining fractions 2 to 5 and distilling the mixture over sodium to remove the borneol. The remaining components of the mixture were then readily separated by fractional distillation, as is shown in Table 11. Table 11-Fractionation over Sodium (Total volume, 222 cc.; fractions 2 t o 5, Table I) FRACTION
1 2 8 4 5
1-01. 19, KO.6
INDUSTRIAL A X D ENGINEERING C H E M I S T R Y
740
FRAC-
BOILINQPOINT VOLUME
* c.
155-159 159-167 167-178 78-100 (14 mm.) 100-122 (14 mm.)
cc.
80 9 34 15 5
TION
6 7
S 9
BOILINGPOINT VOLUME
= c.
cc.
122-132 (14 mm.) 3 132-145 (14 mm.) 27 145-170 (14 mm.) 3 Combined with so- 46 dium (detd. by diff.)
An attempt was also made to separate fraction 9 (Table I) into its components by distillation over sodium. Some of the distillate came over above 132" C. at 14 mm., indicating the probable presence of cadinene, but the decomposition was so great that accurate results cannot be reported. After the redistribution of the distillate produced by the second fractionation, the curve shown in Figure I1 was constructed. I n making the curve, fraction 9, Table 11, was added to the borneol portion, b. p. 100-122" C. at 14 mm., since the sodium undoubtedly combined with the alcohol content of the oil. The breaks in this second curve are more definite than those shown in the curve in Figure I. They show the presence of five fairly well defined fractions. From the values given in Tables I and 11, these fractions may be seen to have the boiling points and percentage composition given in Table 111.
Analysis of P o r t Orford Cedar Oil
Analysis of each of these final fractions (Table 111) was now made. The chief components of each fraction were identified and also isolated and determined quantitatively whenever it was possible. The methods used and the results obtained are given below. ~ - ~ - P I K E(Fraction KE 1; b. p., 155-159" C.; volume 822 cc.)-The crude pinene fraction was purified by distillation over sodium; 64 per cent of the original 822 cc. came over at an almost constant boiling point (156-156.5' C.). This constant boiling fraction was considered to be a pure sample, It had the following physical constants; b. p., 156-156.5' C.; dm, 0.8584; n2:, 1.4608; [a]:, +53.01. The constants reported by Schorger2 were b. p., 156-156.1" C.; d l S , 0.8631; n v , 1.4684; [a]? , +51.52. (Short-scale thermometers were used in checking all melting points and boiling points reported.) The specific rotation of pinene obtained from this oil is of interest because it is higher than the specific rotation of any sample of pinene previously reported. This pinene does not form a trace of the inactive crystalline nitroso chloride compound. Since the formation of this derivative is a characteristic property of nearly all samples of d-a-pinene, it is probable that this product is a pure d-a-pinene isomeric with the ordinary form of a-pinene, which is isolated from American turpentine oil. That the compound was a da-pinene was determined by the preparation of pinene hydrochloride (m. p. 126-127" C.), by saturating the oil at a temperature of 5-15" C. with dry hydrochloric acid gas, and by the preparation of a-pinonic acid (m. p. 68" C,). The melting point reported in the literature for a-phonic acid (prepared from d-a-pinene) is 67-69" C. Method of Preparation. An emulsion of 50 grams of pinene in 300 cc of water was gradually added t o 120 grams of potassium permanganate contained in a liter of water. The mixture was cooled in a n ice bath and stirred continliously during the addition. After completion of the oxidation the manganese sludge was removed by filtration; the filtrate was saturated with carbon dioxide gas and distilled with steam t o remove unoxidized products. The liquid was evaporated in a current of carbon dioxide t o a volume of 400 cc. and was then extracted with two 50-cc. portions of ether. The pinonic acid was set free from the potassium salt by the addition of dilute sulfuric acid. After extraction with ether and recrystallization from petroleum ether, the acid melted a t 68' C.
No trace of pinonic acid was noted, which indicates that @-pineneis not a component of the oil. From these tests, and from the results obtained by fractional distillation, (Table 111), approximately 46 per cent of d-a-pinene is shown to be present in the oil. T a b l e 111-Final Fractionation of Port Orford Cedar Oil (Total volume, 1799 cc.; fractions 1 t o 14, Table I) PERCENTOF FRACTIONS FROM: TOTAL FRACTION BOILING POINT Table I Table I1 VOLUME VOLUMP:
c.
1 2 3 4 5
155-159 159-100 100-122 122-145 145-180
(14 mm.) (14 mm.) (14 mm.) (14 mm.)
cc
1 618
9-11 12-14
.
1 2-4 5and9 6-7 8
822 58 470 37s 71
45.7 3.2 26.1 21.0 3.9
~-LIMOSESE (Fraction 2; b. p., 159-178" C. and 78-100" C. (14 mm.); volume 58 cc.)-This fraction does not contain a high percentage of d-limonene, for a large amount of gummy residue remained in the flask after the distillation of the sample over sodium. I n this fractionation a small portion (b. p., 170-176" C.) was obtained which had a characteristic lemon-oil odor and formed a tetrabromide (m. p., 124" C.) when dissolved in glacial acetic acid and treated with bromine. I n this fraction, which makes up approximately 3 per cent of the original oil, d-limonene is shown to be present.
June, 1927
ISDUSTRIAL A S D E,VGINEERING CHEMISTRY
BORNEOL (Fraction 3; b. p., 100-122" C. (14 mm.); volume 470 cc.)-Since borneol is a compound which crystallizes readily, it might be expected that a solid would separate from this fraction on refrigeration. However, a sample when cooled to - 15' C. did not yield a trace of solid material. Two other refrigeration experiments were tried. (1)
A nearly constant boiling point fraction (104-107" C.,
13 mm.) was refrigerated for a 2-hour period.
( 2 ) A sample of the oil (b. p., 104-107" C., 13 mm.) which had been previously saponified with alcoholic potash was also refrigerated.
I n both cases negative results were obtained. To isolate borneol it evidently is necessary to separate it from the liquid constituents of the oil. The isolation was finally accomplished by means of the preparation of the acid phthalate. The methods used in the preparation of the acid phthalate and in the separation of borneol are described briefly below, since borneol had never been isolated from Port Orford cedar oil up to the time of the carrying out of t.hese experiments. Three hundred grams of crude oil were hydrolyzed by refluxing for 1 hour with 25 grams of sodium hydroxide and 30 cc. of 80 per cent alcohol. The hydrolyzed product was washed with water, then dried, and the borneol present changed to the acid phthalate by heating the oil to 160" C. for 16 hours, with 100 grams of phthalic anhydride. After the heating period, the reaction product was poured into 150 cc. of water and a n excess of sodium carbonate added t o produce the soluble sodium salt of bornyl acid phthalate. The oil which had not reacted with phthalic anhydride formed a layer on top of the water. I t was separated from the water by decantation, the last traces of oil being removed by extraction of the water solution with petroleum ether. The insoluble phthalic acid ester was then obtained by acidifying the solution with 50 per cent sulfuric acid; bornyl acid phthalate separated as a n oily layer, which crystallized on cooling. A small portion of this product, after recrystallization from 50 per cent alcohol, melted a t 164" C.; melting point for bornyl acid phthalate reported in the literature, 164.5" C. An excess of 20 per cent sodium hydroxide was added to the remainder of the ester and the borneol, which soon separated in the form of an oil, was removed by steam distillation.
After two recrystallizations from petroleum ether, 18 grams of borneol with the following physical constants were obtained: m. p., 201 O C., m. p. after sublimation, 201 " C.; [a]?, +32.6, in 10 per cent alcohol solution, in a 1-dc. tube, +3.26. Constants reported for d-borneol in the literature m. p., 203-204" C.; [ c x ] ~ , ,+37.6-39.5.4 After the petroleum ether was removed by evaporation, 15 grams of a liquid which would not crystallize, b. p., 98-129' C. (13 mm.), were obtained. The major portion of this product distilled between 104-107° C. (13 mm.) That this is a pure alcohol with a molecular weight equal to that of borneol is shown from the acetylation values given in Table IV.
A part of the borneol present in the oil was destroyed during the fractionation. For this reason a second portion of the crude oil was dried and distilled to obtain. a new sample for use in the quantitative estimation of borneol. The method outlined below, which is essentially the one described by Martin,5 was used in the determination of borneol and borneol acet'ate: Five cubic centimeters of the oil were heated with an excess (15 cc.) of acetic anhydride t o 145-150" C. for 3 hours. The acetylated oil was then washed with water and 10 per cent sodium carbonate solution t o free it from acid. After careful drying, a weighed portion was saponified by refluxing it for one-half hour with alcoholic potassium hydroxide solution. Saponification values before and after acetylation are given in Table IV.
'
Parry, "The Chemistry of Essential Oils and Artificial Perfumes," 3rd ed., Vol. 11, p. 134. 6 J . pharm. chim., [7] I S , 168 (1921).
741
Table IV-Saponification
Values ALCOHOL 0 . 2 5 4 0 CALCD. A S BORNYL N HCI BORNEOLACETATE CADINOL cc. Per cent Per cent Per cent
0.4140 SAMPLEAi KOH Gram cc.
SKBSTAXCE
Acetylated crude oil 1.3900 Unacetylated crude oil 1.0140 Liquid alcohol from phthalic acid ester 1.3000 Acetylated cadinol fraction 1.1400
10
7.65
26.0
...
...
10
14.95
...
5,2
...
6.55
99.75
...
...
19.9
...
28.3
20
10
10.8
It should be noted that the saponification values obtained on the crude oil include borneol, the secondary alcohol similar to borneol, and cadinol calculated as borneol. The values given in Table I V under cadinol are equivalent to 0.7 per cent of this compound when calculated as borneol content of the crude oil. The percentage of secondary alcohol present should then be decreased by this amount, which would leave 25.3 per cent of secondary alcohol, of which 5.2 per cent is present as the acetate and 20.1 per cent as free alcohol. The total percentage of borneol and of liquid secondary alcohol present in the oil may be calculated by assuming that the percentage of solid d-borneol in the alcohol, which was not isolated as the phthalate, is identical to that separated rom the alcohol, which was isolated. If this assumption is correct, then there is a total of 13.8 per cent solid d-borneol and 11.5 per cent of a liquid secondary alcohol similar to borneol present in the oil.
160 .
1
1
1
1
1
D/sttlletion Curve
i y
_I
constructed from data giuen in
IO
20
I
30
I I
40
50
60
70
80
90
J
IO0
Percentage o f D/idiI&te Figure I1
~-CADINENE (Fraction 4; b. p. 122-145" C. (14 mni.); volume 378 cc.)-To prove the presence of cadinene in this fraction, the pure product was prepared in the following manner: Two hundred grams of the oil, which had been dissolved in 400 cc. of dry ether and cooled in a n ice bath, were saturated with dry hydrochloric acid gas. The product which separated after recrystallization from alcohol yielded 30 grams of cadinene dihydrochloride, m. p. 118"C. The cadinene was set free from the hydrochloride by heating the product on a steam bath for 4 hours with 100 grams of glacial acetic acid and 30 grams of anhydroup sodium acetate. The reaction mixture was poured into water and the oil which separated was washed with sodium carbonate solution, dried over anhydrous sodium carbonate, and fractionated.
Fifteen grams of cadinene having the following physical constants were obtained: b. p., 272-274" C. (760 mm.); da, 0.9255; ny, 1.5065; [a]2,, +103.7. The constants for cadinene reported in the literature6 are as follows: b. p. 272-275' C. (760 mm.); d,, 0.9215; n ' : , 1.5065; [CY]? 105.5. e Parry,
op. csf. p. 73
I,VDUSTRIAL A S D E,VGINEERING CHEMISTRY
742
Cadinene is shown to be present in this fraction of the oil which makes up 21 per cent of the original sample. I-CADINOL(Fraction 5; b. p. 145-180” C. (14 mm.); volume 71 cc.)-Cadinol has been characterized by Semmler and Jonas.7 It is a sesquiterpene alcohol with a boiling point about 15” C. higher than that of cadinene. Practically all the alcohol in the cadinene fraction is cadinol, for this fraction did not react appreciably with phthalic 7
anhydride when heated with it to a temperature of 160” C. If borneol or other secondary alcohols were present, an appreciable reaction would have been obtained. The cadinol fraction possesses a negative specific rotation, CY]',^, 10.54, and makes up approximately 3.9 per cent of the total volume of the oil. As is shown in the table of saponification values, this fraction contains 28.3 per cent of alcohol calculated as cadinol. Note-Further laboratory.
Ber , 47, 2068 (1914).
T’ol. 19, No. 6
work on Port Orford cedar oil is now in progress in this
Effect of Partial Hydrolysis on the AlkaliSolubility of Wood’ By L. F. Hawley and W. G. Campbell2 U. S. FOREST PRODUCTS LABORATORY, MADISON,WIS.
T HAS been pointed out by Bray3 that during the decay of wood by several different fungi the alkali-solubility of the residue rapidly increases. When the decay has resulted in a loss in weight of about 30 per cent, the alkalisolubility of the residue may amount to as much as 57 per cent. Bray did not determine how much of this alkalisolubility was due to lignin or how much to cellulose, but in certain cases, even if the assumption were made that the cellulose and all other constituents than lignin were completely alkali-soluble, yet more than half the lignin must have been soluble also.4 Since the hydrolysis of wood is similar to decay in that cellulose is removed with but little removal of the lignin, it was decided to determine whether hydrolysis increased the alkali-solubility and, if so, whether the increase was chiefly due to changes occurring in the cellulose or in the lignin. The wood chosen for the test was Sitka spruce in the form of 6&80 mesh sawdust. Its composition and its behavior under direct alkali treatment were first determined as a basis for comparing results obtained with hydrolyzed specimens. The analysis of the original wood is given in Table I, and in Table I1 is shown the composition of the residue left after treatment with one per cent caustic soda for one hour a t the water-bath temperature. Table I-Analysis of Original Wood (Results on basis of weight of original dry wood) Per cent Water-soluble 4.: Ether-soluble 0.I Alkali-soluble 12.0 Cellulose Lignin Methoxyl Total pentosans Pentosans not in cellulose
62,3 29.3 4.8 9 9 6.2
Table 11-Analysis
of Wood Residue after Treatment with 1 per cent NaOH for 1 Hour a t looo C . (Results on basis of weight of original d r y wood) Per c e n t Loss on alkali treatment 13.7 Cellulose 59 2 Lignin 2i.7 Methoxyl 4.3 Total pentosans 7.4 Pentosans not in cellulose 3.9
I n each of the tables there is given a figure unusual in records of wood analysis-viz., “pent’osans not in cellulose.” Received February 14, 1927. Commonwealth Fund Fellow. 8 Pafier Trade J.,78, No. 1 , 58 (1924). 1 Hawley and Wise, “The Chemistry of Wood,” p. 299, The Chemical Catalog Company, Inc., h-ew York, 1926. 1
2
Pentosans are determined on the total sample and then in the crude cellulose and are commonly recorded as “total pentosans” and “pentosans in cellulose.” I n the interpretation of the analytical data here presented, however, it was found that the value for the pentosans not in the cellulose was used frequently but the pentosans in cellulose not a t all. The values for the former were therefore computed and used in the tables. Experimental
In studying the alkali-solubility of the hydrolyzed wood, the general plan was to subject samples to different degrees of hydrolysis, analyze them, treat them with caustic soda, and analyze the residue. It has frequently been found, however, that on account of the difficulty of obtaining the same conditions throughout the mass, a chemical reaction which takes place with small quantities of wood, such as the sample for analysis, cannot be reproduced exactly when larger quantities are used. For this reason it was not attempted to hydrolyze enough wood so that the residue would be sufficient for an analysis, alkali treatment, and the further analysis of the residue. Instead, two samples were hydrolyzed under as nearly as possible the same conditions, one of which was used for intermediate analysis and the other for alkali treatment and final analysis. The analyses are shown in Tables I11 and IV. The loss in weight on hydrolysis as given in the second columns of these tables shows the relatively slight variation in the results obtained by the duplicate hydrolyses. Table 111-Analysis
of Wood Residue after Treatment for 6 Hours with HCl a t looo C. (All results expressed as percentages of weight of original wood) TOTALPENTOSANS CELLU- LIG- METH- PEXTO- NOT IN ACID Loss O N HYDROLYSIS CONCN. Detd. Calcd. LOSE NIN OXYL S.4NS CELLULOSE 0.05 6.0 12.5 55.6 28.9 4.6 7.5 5.1 28 7 4.7 6 4 4.2 13 9 55.3 0.25 10.0 1.5 17.6 23.9 49.0 26.7 4.7 4.4 3.5 22.9 27.4 46.2 8.0 26.4 4.2 3.4 2.1 15.0 36.2 42.5 32.7 26.3 4.3 0.9 0.6
Comparison of Results
I n Table I11 the values headed “calculated loss in weight” are obtained by adding together the losses in cellulose, lignin, and “pentosans not in cellulose” as determined from the analyses of the original wood (Table I) and of the residue after hydrolysis, t o which is also added the water-soluble in the original wood, on the assumption that this is all removed by hydrolysis. It is immediately noticeable that the calculated loss is always considerably higher than that
