&lug.,I 9 I 4
T H E J O U R N A L O F I N D U S T R l i l L -4 N D E LVGIX E E RI N G CH E M I S T R Y
THE, OIL OF PORT ORFORD CEDAR WOOD AND SOME OBSERVATIONS ON ~-LY-PINENE By A . \V. SCHORCER Received M a y 4, 1914
The Port Orford cedar [ C h a m a e c y p a r i s lazisoniana (Murr.) P a r l a t o r e ] occupies a very restricted range. I t is found along the Pacific coastal region from Coos Bay in southwestern Oregon t o t h e hlad River in northwestern California. The wood contains an oil having a strong, pleasant odor, and a pronounced physiological action on the kidneys. Owing t o t,he effect ,of the inhale? vapors upon the workmen, mills cutting Port Orford cedar do not operate continuously on this species. Selec'ied "resinous'' pieces of wood on steam distillation yielded I O per cent of oil having d160 0.891, i i D 1 j o 1.4;i. On distillation, a blood-red residue remained in the distilling flask. (The distiller of this oil mas physiologically affected in the usual way.) The oil when it reached t h e author was f o u r years old and had been stored in a tightly stoppered ambercolored bottle. The constants were redetermined $1-ith the following results: dls 0.9061, nD150 1.4806. The oil was rectified b y shaking with I O per cent Na2CO3 solution and distilling with steam over soda solution. B y this treatmer-t the oil lost 16.4 per cent b y volume. I n t h e subsequent examinations of the oil no physiological effects were noted and n o red resiclae o n distillation. I t is possible t h a t the cause of hoth phenomena was destroyed b y aging. EXPERIMENTAL
The rectified o;l had the following constants: d l s o 0 . 8 9 0 j ; ? i D l j o 1.4758; 0 D 2 j o +39,60°; acid no. 0.30; ester no. 32.8; ester no. after acetylation ; ~ . j ; . The ester numbers before a n d after acetylation are equivalent t o 11.48per cent bornyl acetate and 10.90 per cent of free borneol. The oil distilled as follows: Ijj-157", 60.5 per cent; 1j7-17oo, 3 per cent; 170ISO", 4 per cent; 100-130" a t 15 mm., 2 0 . 5 per cent; 130-160' a t r j inm.. ;per cent; 160-190' a t ~j m m . , I per cent. When distilled a t normal pressure decomposition took place above 180' with t h e splitting off of acetic acid. 0-PIKESE-Prelinlinary examination of the a-pinene €ractions indicated t h a t this terpene was present in an exceptionally pure state for a natural product. By fractionation over sodium 6 j per cent of the a pinene fraction mas obtained in a pure state. The carefully determined constants were as follows: B. p. I j6.0-156.1 ( 7 6 0 m m . ) ; dlbo 0.8631; nDls0 1.4684; j I . j 2 '. The molecular respecific rotation [cy J, fraction was found t o be Ll, = 43.88; calculated for C I O H j~ ==, ~ 43. j q . The highest previously recorded for specific rotations for a-pinene are: [a], f 4 8 . 4 ' d-a-pinene from Grecian turpentine oi1;I [ a ] D 1 9 ° -48.63 " for I-0-pinene from silver-top stringy-bark e uc a1y p t us oil ( Et i c a I y pt ZIS I a ev o p i n e a ) . Ten grams of the a-pinene fraction did not yield a trace of crystalline pinene nitrosochloride. One hundred grams of the terpene were then oxidized with
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Vrzes, Bd1. SOL. chim., (41 6 (1909), 932. Smith, Jour. a n d PYOCRoyal SOL..N. S. W,, 31 (1898). 195.
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233 grams K M n 0 4 in I . j liters of water and j o o grams of ice in an ice bath. On completion of the oxidation 2 5.3 grams of oil were recovered by steam distillation. The recovered oil after standing a week deposited a few fan-shaped clusters of needles. This product was evidently pinol hydrate, since i t melted a t 144-145~ after one crystallization from water. After removal of the manganese sludge the oxidation liquor was evaporated t o one liter and extracted several times with ether. The pinonic acid precipitated by dilute sulfuric acid was extracted with chloroform and the solvent removed by distillation. The residue distilled between 18.5-190' a t 1 7 mm.? mainly between 18;188'. The distillate weighing 34.8 grams soon crystallized on standing and 16.6 grams of the crystalline keto-acid were obtained. The crystalline d-pinonic acid melted at 68-69', its semicarbazone a t 20320j'. The specific rotation of the acid [a], +92.69O was determined from a j.3; per cent chloroform solution. The semicarbazone of the liquid pinonic acid melted a t 2 0 3 " . DIPEKTENE-The fractions, b. p. I j;-180°, consisted mainly of dipentene. The portion, b. p. I;o-I~o", comprising the major portion of the oil had a rotation a D 2 J o jr.16'. PhellandGene was not detected and the dihydrochloride from this fraction melted a t 4849'. On bromination a tetrabromide melting a t 124" was obtained. The high rotation indicates the presence of active limonene. BoRKEoL-The free alcohol obtained by saponification of the fraction, b. p. 100-130°, a t I j mm. distilled between 205-230' and was collected in j O ' f r a c tions. By oxidation with acetic and chromic acids on the water b a t h camphor could be detected in each fraction. The oxidation products were oils with a strong camphor odor. On treatment with semicarbazide hydrochloride, crystalline semi-carbazones were obtained, melting a t 236-23;'. However, b y oxidizing t l e oil. b. p. 2oj--21 j"! YO^^^ +32.16, with saturated permanganate solution and distilling with steam, solid camphor collected in the receiver. .4n alcoholic solution of t h e camphor was d-rotatory. COBIBIA-ED A C I D S - T ~ ~combined acids were recovered from the ester saponification liquor by distillation with phosphoric acid. h small amount of oily material*appearing on t h e surface of t h e distillate was removed b y extraction with ether. The solvent was allowed t o evaporate spontaneously, the residue neutralized with caustic soda and extracted xvith ether, t o remove resinous matter. On addition of LigNOs solution a precipitate was obtained and analyzed as follows : 0.0814 gram sil\.er salt gave 0.0313 gram -%g = 38.45 per cent .4g. Silver caprinate, CgH19COOAg, requires 38.66 per cent Ag. The acids in the aqueous portion of the distillate were neutralized with caustic soda and precipitated with silver nitrate. T h e precipitates were found t o contain silver formate, as shown by the decomposition on a t tempting t o recrystallize them from hot water. T h e silver formate was accordingly destroyed by alternate
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T H E J O l l 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
heating a n d filtration of t h e aqueous solution until decomposition h a d ceased. T h e shiny leaflets of silver acetate finally obtained were analyzed as follows: 0.1245 gram silver salt gave 0 . 0 8 0 ~gram Ag = 64.42 per cent Ag. Silver acetate, CH3.COOAg, requires 64.64 per cent Ag. FREE ACIDS-The acids recovered from t h e liquors remaining after rectifying t h e oil with sodium carbonate solution a n d s t e a m distillation were treated a s above. T h e acid obtained from t h e other extract was precipitated in t w o fractions a n d their silver cont e n t determined: ( I ) 0.0621 g r a m silver salt gave 0.0241 gram Ag = 38.81 per cent Ag. 0.0836 g r a m silver salt gave 0.032 j gram (2) Ag = 38.87 per cent Ag. Both precipitates evidently consist of silver caprinate since this salt requires 38.66 per cent Ag. The aqueous portion was found t o consist of acetic a n d formic acids. I n this case t h e formic acid was destroyed b y heating t h e distillate with mercuric oxide. Analysis of t h e silver salt of t h e remaining acid follows: 0.1993 gram silver salt gave 0.1283 gram Ag = 64.38 per cent A.g. CADINENE-The fractions boiling above 130 ’ a t I j m m . contained cadinene. T h e portion, b. p. 2 7 0 2 8 0 ’ ~d: 0.9329, aD24014.69, yielded t h e characteristic cadinene dihydrochloride, m. p. I I 7-1 1 8 O . A 6.04 per cent ether solution of t h e dihydrochloride h a d t h e rotation -1.95’.
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SUMMARY
The rectified oil has approximately t h e following composition: d-a-pinene 60-6 I per c e n t ; dipentene 6-7 per cent; free Z-borneol 11 per c e n t ; ester as bornyl acetate 1 1 . 5 per c e n t ; cadinene 6-7 per cent; losses 5 per cent. T h e combined borneol occurs mainly a s bornyl acetate, but also evidently as t h e esters of formic a n d caprinic acids. I n t h e old oil, formic, acetic, a n d caprinic acids occur i n t h e free state. FOREST PRODUCTS LABORATORY FOREST S E R V I C E , U. S.DEPARTMENT O F AGRICULTURE (In Cooperation with the University of Wisconsin) MADISON
THE RELATION BETWEEN ALUMINUM SULFATE AND COLOR IN MECHANICAL FILTRATION’ By FRANK E HALE
Vol. 6 , No. 8
proportions, t h e ratio varying with t h e chemical character of t h e color i n different waters. This theory is i n keeping with t h e fact t h a t practically all organic coloring m a t t e r extracted from wood or vegetable growth combines with almost a n y hydrate, e . g., t i n , bismuth, aluminum, chromium, iron, etc. Recently, a t G r a n d Rapids, Mich., i n t h e softening of water, i t has been found t h a t excellent decolorization is obtained b y means of a n excess of magnesium hydrate.‘ ’
THE REACTION BETWEEK A L U M I N U J l SULFATE AND THE ALKALINITY
It is usually s t a t e d t h a t this reaction results in t h e formation of aluminum hydrate, Al(OH),. I n elementary courses i n chemistry i t is t a u g h t t h a t t h e reaction between aluminum salts a n d sodium carbonate results i n t h e cold i n t h e precipitation of basic aluminum carbonate, which only upon boiling changes completely t o t h e hydrate. This is undoubtedly t h e reaction occurring in water between aluminum sulfate a n d calcium bicarbonate. Indeed, judging from t h e a m o u n t of alkalinity reacting with one grain per gallon of basic aluminum sulfate a n d from t h e a m o u n t of carbonic acid set free, there is good reason t o believe t h a t t h e precipitate formed is a basic sulfate-carbonate. T h e usual aluminum sulfate employed is a basic salt containing about 18 per cent alumina (A1203). T h e analyses of seventeen samples, representing several years, of t h e aluminum sulfate used a t t h e Brooklyn filters were as follows: Percentages AlzQl sot Average. . . . . . . . . . . . . . . . . . . . . . . . . . Minimum.. . . . . . . . . . . . . . . . . . . . . . . Maximum... . . . . . . . . . . . . . . . . . . . . .
IS.2 16.6 20.6
39.3 35.9 41.4
T h e sulfate varied from a few per cent t o twenty per cent below t h e a m o u n t theoretically required b y t h e alumina t o form a neutral salt. T h e average deficiency was 11 per cent. This average salt m a y be expressed b y t h e formula A12(S04)8.A1(S04)(OH), b u t I prefer t h e doubled formula zAlz(S04)s.A12(SOI)Z(OH)B,since when written graphically i t better explains t h e probable reactions with t h e alkalinity. Theoretically a n aluminum sulfate containing I 8 per cent alumina requires 9 p . p . m. calcium carbonate t o react completely, t h u s : P. p. m. alkalinity = 300/102 X 1 7 . 1 X 18/100 = 9 in which 300 is the molecular weight of 3CaC03 102 is the molecular weight of A1208 17.1 is the p. p. m. equivalent of 1 grain per gallon 18 is t h e per cent of alumina
T h e older literature. especially t h e English, frequently speaks of t h e humic acid of swamp waters, particularly i n connection with t h e solution of lead b y drinking water. I n recent years t h e tendency has been t o consider free acidity due t o carbonic acid a n d t o be rather skeptical of t h e existence of free organic acid i n water. T h e experiments described in this paper seem t o prove t h a t free organic acid i n water is no m y t h , b u t actually exists as a property of t h e coloring m a t t e r , a n d i n all probability t h e removal of color b y t h e action of aluminum sulfate depends upon t h i s acid property. T h e acid coloring m a t t e r combines with t h e base, aluminum h y d r a t e , a n d i n definite
B u t i t is not t h e alumina t h a t combines with t h e alkaiinity. It is t h e sulfate. As t h e sulfate is 11 per cent short in t h e average aluminum sulfate t h e maxim u m alkalinity t h a t can react with t h e average coagulant is 8.3 p. p. m . I t will vary with t h e actual composition a n d is also governed b y other conditions such as a low or a high alkalinity, a n d a low or a high turbidity. With a high alkalinity t h e figures approach t h e upper limit b u t with a low alkalinity t h e y fall short, even a s low as j.5; i n fact figures have been published as low as 3.4, using alum containing 18 t o 2 2 per cent alumina. T h e following table gives some of t h e figures found i n practice:
S ,Cincinnati, April
1 “Report of Committee on Water Supplies,” A m . Jour. Pub. H e a l t h , 3 (1913). 1335.
1 Presented at the 49th Meeting of the A 6-10, 1914.
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