GIFT OF 
 
 3^98 
 
THE ESSENTIAL OIL OP 
 SEQUOIA SBMPERVIRENS 
 
 A thesis submitted, in partial satisfac- 
 tion of the requirements for the degree 
 
 of 
 Master of Science 
 
 at the 
 
 University of California 
 by 
 
 HAYWARD 1/JKRRIAM SEVERANCE 
 
 Berkeley, Cal. 
 April 1912 
 
 (7 
 
IVk, 
 
 Wu_. 
 
THE ESSENTIAL OIL OF SEQUOIA 
 SEIIPERVIKEHS 
 
 No work has "been done on this oil, so far as 
 in own, with the exception of that of B. H. Eowrori, 
 California ! 02, whose results were presented in a 
 thesis for the "bachelor's degree April 1902. So 
 far as he was able to ascertain "no attempts have 
 teen made up to this time (1902) to investigate 
 this oil." Ho mention of it has "been found, in the 
 literature since that date. 
 
 The Sequoia genus comprises only two surviv- 
 ing species; (1) the Eigtree, Sequoia gigantea Dec. 
 (Washing ton! ana, Y'ellingtoniaria) growing only on the 
 western slope of the Sierra Nevada in California; 
 (2) the Kedwood, Sequoia, semp^rvirens, growing only 
 in a narrow "belt along the Calif ornian coasfc. The essen- 
 ti- 1 oil of the Eigtree was described by Lunge and 
 Steinkauler in 1880 (Eerichte, XIII, 1656 b, XIV 
 2202 b) . They obtained the oil from small trees grow- 
 ing in Zurich, Switzerland, Their results are dis- 
 
 897057 
 
cussed "below. This work, quoted "by Gildemeister 
 
 and Hoffman, is the only one found on the oil of the 
 
 Big tree. 
 
 The trees used in this work (Redwood) were 
 all young growth, largely stump sprouts of 10 to 
 20 years, a,nd were cut in cut over forest near 
 Fort Eragg, I'endocino co., Cal. the last w=ek in 
 February 1912. A previous shipment cut during a. 
 personal visit to the woods was lost in transit. 
 The weather conditions here (and in general along 
 the coast) are a temperature of about 50 F and a 
 moist atmosphere most of the time. During the 
 two days spent at Fort Eragg a light rain fell 
 almost continuously. This may have been pertly 
 to blame for the rapid loss of the oil from the 
 trees after cutting end during storage in the 
 
 basement of ithe Chemistry Building at Berkeley. 
 
 -^ . 
 
 Apparatus --The oi^ was extracted in a steam 
 still, shown in attached print. The still is of 
 copper, the upper part having a perforated bot- 
 tom on which the material extracted rests. The 
 lower part contains a steam coil attached to the 
 University Lea ting system. Vater is poured in the 
 lower part, heated by the coil, the steam generated 
 

passing upward, through the holes in the plate on 
 which the material rests. In starting a run the 
 water was also heated by a Bunsen burner un- 
 til water "began to come through the condenser, 
 after which the steam coil furnished heat enough 
 to keep a small stream of water dripping from 
 the outlet. 
 
 The four joints of the apparatus; (l) "be- 
 tween the top of the still and the head, (2) "be- 
 tween the two parts of the still, (5') "between 
 head and cross piece and (4) "between croespiece 
 and condenser, were all packed with gaskets cut 
 from asbestos reinforced with fine wire mesh 
 ("gas engine packing 11 ), "between brass collars 
 tightened "by "brass screws. The lower side of each 
 ring was coated with white lead and the upper 
 with graphite. This did away with the necessity 
 of cutting fresh rings after each run. 
 
 At the start of each run the still was 
 f illed. with w-.'ter to about one inch in the gauge 
 glass. The water which distilled over was with- 
 drawn from under the oil "by a siphon and returned 
 to the still. The oil floated on the water in 
 the receiving bottle and was withdrawn from time 
 to time with a pipette. In some cases a slight 
 

 
4 
 
 additional amount of oil separated from the milky 
 water in the large "bottle after standing overnight 
 at the conclusion of a run and was also withdrawn. 
 The oil was immediately transferred to a flask, 
 kept tightly corked in the dark in a "basement room. 
 
 Yield--The oil as it came over had a golden 
 Bellow color and the ocior of the fresh leaves. It 
 was nearly clear "but a turbidity developed on 
 standing. 
 
 It was impossible to make a satisfactory, deter- 
 mination of the yield owing to several circumstances. 
 The first of these was a delay of a week--ten days 
 after cutting--bef ore the still was available. The 
 first run was interrupted "by a leak in the still 
 p.tound the heating coil, causing another delay. The 
 solubility of the oil in water caused a consid- 
 erable loss, especially on the first run. 
 
 The first run was started Harch 7. Subsequent 
 rugis were made L'arch 20, 22, 26, 27, s.nd 29, and 
 April 12. The rapid decline in yield -showed that 
 this was obviously and unfair test. The odor from 
 the trees which was very pronounced e.t frist, de- 
 clined proportionately to the yield and appeared 
 to concentrate lower down in the branchrs. _s the 
 
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 v r ij iii--.^e^jf a 10 v^X 
 
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 Xli^Q dlid" fii 2L6: I t - . v 
 
 :. 1 .-^. 
 
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5 
 
 trees "began to dry, tlie pleasant aromatic odor dis- 
 appeared, except on "breaking a twig 1-2" or more 
 in diameter, and another quite different one took 
 its place. There was no change in the oil except 
 possible slight darkening. (Owing to its being 
 spread out in a thin layer it was impossible to 
 determine this. 
 
 Blanches were cut off the trees as needed, 
 up to 8, diameter of about -J-" and including all 
 of the growth of the last year. The terpene odor 
 was strongest in the tops of the trees, especially 
 the new growth of the main trunk. 
 
 The still was packed tightly on the first run 
 with 7000 grams. The other runs were made on 
 smaller quantities up to 4600g. with the idea of 
 hastening the time of extraction. This appeared 
 to be complete in two to three hours in all cases 
 except the first. Y-Trien this work is resumed a 
 quantitative determination of the yield from 
 fresh foliage will "be made. 
 
 Purification of the oil--In this way about 
 150cc of oil were collected (not including the 
 oil dissolved in the water). This was rectified 
 . v distillation with steam, the oil coming over 
 being collected fractionally in four portions 
 of about 25cc each. The water was removed by a 
 
6 
 
 separating fuunel and the oil dried "by sodium 
 sulphate. The first fraction after "being so 
 treated was clear and colorless, with the same 
 odor as that of the original oil but more del- 
 icate evidently a terpene hydrocarbon. The se- 
 cond fraction had a light yellow green tinge, 
 the two following a deeper color. After four 
 fractions had "been collected, the oil ceased to 
 co-iie over with the water and distillation was 
 stopped. 
 
 Fractionation--The first fraction was dis- 
 tilled again from a 20cc flask. (There was not 
 enough to use a Hempel column.) The oil distilled 
 almost completely at 157--160. With about Ice re- 
 maining the thermometer rose above 162 and the 
 residue turned greenish yellow. The flame was re- 
 moved at this point. Ho carbonization or decom- 
 position was evident from the appearance or odor 
 of the residue. 
 
 The second, third, and fourth fractions 
 from the steam distillation were distilled a- 
 gain. The distillate was collected as the first 
 fraction to 160, the second to 1650. The tem- 
 perature then rose rapidly to 190 at which 
 most of the remainder passed over. This fraction 
 

 Je- 
 
7 
 
 evidently suffered some decomposition. At 198 
 no more passed over and the temperature dropped. 
 The residue (about 2cc) solidiifed on cooling. 
 This was dissolved with ether and placed in a 
 crystallizing dish. It failed to crystallize, 
 remaining as a yellow wax with slight odor. 
 
 The first fraction, constituting the 
 greater part of the oil, was distilled again 
 and constants determined as follows; 
 
 Boiling point 157 C (Stem exposed above 
 540) 
 
 Specific gravity (capillary pyvnometer) 
 
 d = 0.831 
 150 
 
 15 
 
 Refractive index (Abbe 1 ) n 1.473 
 
 18.5 
 
 Polarization (Schmidt & Haensch polar- 
 
 D 
 
 iscope, 10cm tube) (a) = 2440' 
 
 20 " 
 
 There was no action on the oil "by fresh- 
 ly cut sodium. The odor resembles that of the 
 entire oil but is not so strong and each dis- 
 tillation appeared to diminish it slightly. 
 

 
8 
 
 This suggests that the odor may come from a trace 
 of high boiling aldehyde or ester. 
 
 Ultimate analysis 0.3669g. of oil was burned 
 in a combustion analysis, resulting as follows: 
 
 Found Calculated for ^IQ^-IQ 
 
 C 87.085 88.20 
 
 H 11.73 11.80 
 
 The low yield of carbon is apparently a result 
 of the large quantity taken and of a slightly 
 rapid current of oxygen and air through the tube, 
 causing incomplete absorption of the COg. To 
 drive off all moisture in the tube it was heated 
 to the safe limit of the glass for an hour and 
 cooled with a slow stream of purified air pass- 
 ing through. 
 
 Comparison with terpene from Bigtree Lunge 
 and Steinkauler report as their first compound 
 form the oil of Sequoia washing t on iana a colorless 
 oil, b. p. 155, d 15 o 0.8522; vapor density (Vic- 
 tor :>yer in diphenyl amine) 69.67 ( C 10 H 16 ~ 68) 
 
 Rotation (Wild Polaristrobometer) (a).. 23.8 
 
 J 
 
 Found Calculated G-^E^e 
 
 C 86.09 87.90 88.20 
 
 12.68 1230 11.80 
 

 * 
 
 . 
 
 9 
 
 - 
 
 . 
 
9 
 
 Addition of Bromine Two cc of hydrocarbon 
 were dissolved in four volumes of alcohol and 
 four of ether, the solution cooled by ice and 
 sqlt and bromine added drop "by drop. Complete 
 discoloration resulted, indicating unsaturation. 
 Bromine was added u#til a yellow color appeared. 
 On standing in ice a short time the color dis- 
 appeared and a few more dops of bromine were 
 added, shaking after each addition. When the 
 yellow color reappeared the tube was left in 
 ice until the ice melted but no crystals ap- 
 peared. The tube was then exposed to the air. 
 After approximately a third of the solution had 
 evaporated a layer with a slight yellow tint 
 appeared at the bottom. At room temperature this 
 was slightly turbid, but cleared on warming to 
 about 25. After three days the solvent was driv- 
 en off as much as possible by surrounding with 
 water which was gradually brought to boiling. 
 There still remained a volume of solvent approx- 
 imately that of the oil below. The upper layer 
 was pipetted off, some of the lower removed and 
 placed in a clean tube, a few drops of ligroin 
 added and the tube cooled and allowed to stand 
 24 hours. The oil again separated as a turbid 
 liouid, clearing on .-;entl^ warming. 
 
10 
 
 As the quantity of "brominated oil on hand 
 was not sufficient to attempt a purification by 
 distilling, it was transferred to a "boiling point 
 apparatus and the sulphuric acid "bath slowly 
 heated. The oil gradually darkened, indicating 
 a separation of "bromine. At 50 it was red 
 (the color of dilute ferric sulphocyanate) 
 and at 100 almost "black. At 157 o fumes of 
 bromine and hydrobromic acid came off co- 
 piously and the oil distilled into the reser- 
 voir above the air chamber. After cooling the 
 liquid remained black, slightly more viscous 
 and with a changed odor, but not one suggesting 
 carbonization. 
 
 Addition of Iodine About Ice of oil was 
 dissolved in an equal volume of absolute alcohol 
 and a saturated solution of iodine in alcohol 
 added drop by drop with shaking. No visible dis- 
 coloration followed. The mixture was allowed to 
 stand for two days and the excess aloohl was 
 then driven off by immersing the bottle in water 
 which was brought to a boil. The liquid which 
 remained had a color not quite as dark as ordin- 
 ary iodine tincture and a peculiar odor resem- 
 bling that of anethol. Owing to lack of ti.,-.e 
 work was discontinued at this point. _Ji attempt 
 
11 
 
 to form ;;n iodine addition compound will "be made 
 
 later. 
 
 Residue of the original oil The residue 
 which remained in the flask on the rectification 
 by distillation with steam was separated from the 
 water by a separating funnel and allowed to stand 
 ntil the emulsion layer and presumably impurities 
 carried over from the original distillation had 
 settled. This left a yellow oil, thicker than the 
 original oil s.s obtained from the still and with 
 nearly the same odor. This oil was filtered through 
 cotton, coming through perfectly clear. On heating 
 it was found to contain a large percentage of 
 water. Granulated calcium chloride was added and 
 the oil allowed to stand two days with occasion 1 
 shaking. A considerable amount of water separated 
 out below the oil. An attempt was then made to 
 distill the oil. This was a total failure under 
 
 Lospi-eric pressure. Decomposition (and prob- 
 ably formation of resins) occurred before any 
 vapor passed over. The quantity of unheated oil 
 on hand was not sufficient for a distillation 
 under reduced pressure and that is also deferred 
 

 
12 
 pending a new supply of foliage. 
 
 Products from the Bigtree As the only close- 
 ly allied botanical species, the Sequoia oils give 
 an indication of possible products to expect from 
 the redwood. Lunge and Steinkauler report the 
 following, "besides the hydrocarbon already re- 
 ferred to: 
 
 (2) A colorless oil turning yellow on long 
 keeping, odor reminding of peppermint. Boiling 
 point 227--230 , d 1.045, n about 60 
 
 (3) In very small amount a heavy yellow oil, 
 boiling point 280--290 . 
 
 (4) A solid body "Sequojen" with melting 
 point 105, boiling point 290-300. White leaf- 
 lets with weak bluish fluorescence. 
 
 This study was begun at the suggestion of 
 llr. Carl A. Kupfer, Forest Assistant, United 
 otates Forest Service, San Francisco, to whom 
 a indebted for kind assist ance at several 
 stages of the work. Acknowledgments are also 
 due to President -Johnson -nd other officers of 
 the Union Lumber Co., S?n Francisco, for assis- 
 
- 
 
 o e tf o.v 
 
 rto wo Ile 
 
 
 
 o 
 
 t ooei 
 
 -8i 
 
13 
 
 ance in securing material end to Dr. G. E. Burke 
 of the College of Chemistry, University of Cal- 
 ifornia for many suggestions and aids in the an- 
 is. To all of these, my most cordial thanks. 
 The work will "be continued. 
 
 Chemistry Building, University of California, 
 
 Berkeley, Cal. , 
 April, '1912. 
 
Sprout grovrbh from Bed ; od stunp. 
 Material of c" r used in this v/orl:. 
 :ioto by Forest Service 
 

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