PINE TREE SUGAR. By HARVEY W. WILEY.
Pine tree sugar is derived from :in exudation from the Piiizis Inmberfinun. T h e resin or sap of the tree collects in cavitieti made with an ax or by fire, and on drying forms masses of impure sugar. These crude samples have a very sweet taste and a somewhat peculiar one, due to the resin which they contain, b u t would at once be pronounced sugar from the taste alone. P)iiLu.s Inmbertiann occurs i i i tlic Oregon Cascade and Coast ranges, from the head of the JIackenzie River and the valley of the lioque River, south aloiig the western flank of the California Sierras, through the C‘oast ranges to the Santa Lucia Moun tains and i n the San Bernardino and Cuyamaca Mountains. It is a large tree 46 to 92 metres high, 3 to 7 metres in diameter. It is most common and reaches its greatest development upon the Sierras of Central and Kortliern California, between 1,000and 8,000 fcet elevation. I n Oregon it descends to 1,000 feet. In 1SS; some members of the Geological Survey collected a small quantity of this exudation from the sugar pines and this was sent to me by Mr. 11. 11. ’iVilso~i.* The quantity of material was sufficient for a preliminary study, which showed that it was a sugar haviiig a specific rotatory power of about 65, unacted on by Fehling solution either before or after treatment with hydrochloric acid, and possessing a compositioii which was represented approximately by the formula C, II,, 06.t I n searching through the literature 011 this subject I found that pine tree sugar had been examined by Berthclot and described in ‘(Annales de Chimie,” ~
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“Received Feb. 6, 1888. Esaiiimed 3Iarc11, 1889. +Means of three combustion\. C=41.21$. H=7.4$$,
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229
PINE TREE SUGAR.
3d series, Vol. 46, 1856, p. 76. Following is an abstract of Berthelot's paper :
'' M. Boursier de la Riviere, consular agent of France in California, in 1856 took with him to France a s'accharine substance produced by the Pinus Znnzbertiann. This material was given to 11. Berthelot for analysis. M. Boursier collected this substance from cavities near the base of trees. The exudation from t h e tree is a t first resinous and semi-liquid. I t gradually becomes dry and forms irregular masses, consisting mostly of sugar. The natives of the country eat it: Pure pinite is prepared by dissolving the crude sugar in water, filtering through animal boneblack, and lettvitig to spontaneous evaporation. Several weeks are required for the formation of the proper crystals. These were re-crystallized twice, and the pure pinite obtained subjected to analysis. The analysis gave the following percentages of carbon and hydrogen : Carbon - - - - - - - - - - .- - - - - - - - - - - - - - - - - .- - - - - - - _ _ --43.4$ Hydrogen. - - - - - _ _ - - - - ._ __ . - -. - - - _ _ - - - - ?'A$
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The second combustion gave : Carbon - - - - .- - - - - - - - - - - .- . - - - - - - - - - - - - - - - - - - - 43.5$ Hydrogen - - - - - - - - . - - - . - - - - - - - - - - - - - - - - - . - - 7.W ~
These numbers led to the formula C, H,, 0,or C,, H,, O,, in which the percentages of carbon and hydrogen completed are as follows : Carbon - - - - - - - - - - - - - - - .- - - - - - - - - - - - - - - - - - - - - - -43.9% Hydrogen - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 7.2% ~
T h e combustion of pinite is very difficult. It is necesEary t o mix i t intimately with oxide of copper and to end the combustion in a long current of oxygen a t a temperature near that of the fusion of the glass. Treated with ammoniacal lead acetate, pinite afforded a substance which, on analysis, gave the following nttnibers : Carbon - - - - - - - - - - - - - - - .- - - - - - - - - - - - - - - - - - - - - - -12.5% Hydrogen _ _ _ _ _ _ _ _ _ ___________________ _ _ _ _ _ _ _ _ 2.1% . PbO-- _ _ _ _ _ _ _ -72.59:
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W h e n c e it is coiiclndcd that pinite is isomeric with aiihydrotis mannite i ~ n d 1mscsscs tlich sanic caomposition and formula 3s querci tc. T h e specific gravity of pinite was found to beequal to 1.52. I’initc is dextro-gyratory. a j = j S ” . (i. ‘l’reated with strong hydrochloric acid iznd heated to 100“ for I 0 minutes its rotatory power is not appreciabljr a1tered. I’initt: tloes not ferment, either before or aftcr treatment, with liydrocliloric w i d . l’initc does n o t reduce P’chling soliltion.” ‘l’lic difference between tlic behavior of tho sample ex:iiniiic.d by Bertliclot itnd c:tlled 1)y him pinite. and the samplt? sene to m e w;ts of siicli :i rn:t,rked nature tlirit I determined to secure, if possible, :I larger ciuantity of the material in order to make a more t ~ i o r o u g study ~i of its properties. ’J’hc? chief differcnccs, as will be noticed. iwre i i i the specific rotatory power. :tiid the prceiitage composition. The sibniplo examined by 13erthelot liwcl a much lower specific rotittot’? po~vcrt!iaii tlic otie es:imiiied l ~ yme and had the corn position of the ordinnrp g1ucost.s ; my s:tniplc~liatl a mncli higlier rotatory power :ind the composition of :L heptaglucose. l h r i n g tlic Summcr of 1SS!), therefore, I made :trr:~ngements with tlie 1)irector of the Geological Survey to (1nil)loy one of his men in C’alifornia for two weeks i n collcctiiip siirnples of this sug;$rt aiicl, as a result of this work, I received, i l l the A u t u m n of 188‘3, about fifty pounds of a very good article of c r ~ t l esugar. After tlie wception of this sample i n niy laboratory. but beforti I had commeiiced to work on it, 3f. Rlaquenno piiblislied a paper on ‘ ( A S e w SIIFLVVith an .iromatic Xiicleus,” which he mined Retrr p i i i iie iind which he claimed m i ~ sobtained from the I’L’?LUS i‘an&rtiu,/u growing in Sebraska. 11:asmuch as this tree does not grow in Sehraska, 11. Maqnciilie w;ts evidently mistaken in rcgard
to t h e origin of t h e sugar. I.Ie found the specific rotatory power pei,centage composition of the sugar, which he called Hettr piiiito, the same as I found it for the pinite obtained from California. 11. 1Iaquenne's pa1)er anticipated in a large degree the work which I had proposed to clo on this sample and it is of such interest that the following abstract of it is given : alii1
* ;'At present only two sugars :\re known derived from benzine, yiz., inosite and quercite, both of which are changed by the actioii of hydrodic acid into definite aromatic componnds. The relations of inosite and benzine are more intimate than those of quercite, since by oxidation this latter substance gives a fatty derivative, trioxyglutaric acid, instead of quinones or phenols. Ilet,r p i ) /L h is another of these aromatic sugars derived, according to Jlaquenne, from the Pinus Z a m k d i a u n from Sebraska (?). Beta y i i d e melts a t IdG" to lSY", and is strongly dcxtrogyrous. I t s specific rotatory power is (a,) = 6 j 0 .SI. (Uerthelot, pinitc (a) j = 5s' .G). These characters are exactly those of sennite. Betrr p i u i f e and sennite are probably identical. The analysis of Beta p ; ) L i f e gives aformula between C, I€,, 0, and C, H,, 0,. Heated for some minutes to boiling with hydroiodic acid it is decomposed with disengagement of methyl. It represents, therefore, a methylic ether like tho sugars of caoutchouc discovered by Girard, and without doubt isomeric with bornesite. If the residue be eraporated to a sirup and alcohol added, there is iroduced without agitation a crystalline precipitate, which, to the microscope is shown to be made u p of small tecraliedra. This new sugar, purified by a second crystallization from weak alcohol, melts a t 246". I t is very soluble in water, almost insoluble in alcohol (strong), wholly insoluble in ether. I t s composition corresponds exactly to t h e glucoses. I t s molor.nlar weight appears to be the same as the glucoses, as determined by Raoult's method. Heated in the sand bath to complete decomposition with nitric acid, rutilant vapors are set free and a white residue is left which, in contact with a solution of sodium carbonate in weak alcohol, precipitates immediately crystals of a black reddish color of sodium rhodizonate. It is X'
C. R., 109, 81 2.
th::s assnred f o i - tlie identification of tile salt that it is traiisforiiie~i i i i t o t e t ra o x yq u inon e II 11(11: r t h e it c t ion o f 11y d roc h 1or i c ac i t l :in ti that it gi.ies it red precipitate wit11 hariiini chloride. The p r o d u c t of tlie dedoubling of tlie Brtn pit(;/o by the l~xdroindiox i d is cert a i 111y :\I I a roni ;iti c (1 er i v ii t i ?,e. very 1I r o iia 111 y an add it ion 11r otl 11 t of bet~zincitself, and consequelit!! i l l 1 isomer of iiloeite. I t is 1lIYJposetl to desigiiiite it by the term ict ;,/o.site. It, noultl be interesting to snbmit the t r u e pinite to the wtion of hydroioclic :wid and to compare it, i n this respwt with f i e t i , Iliiiitc.. For this purpose Berthelot has kindly given n i t ' some of liis original matei.iir1. and I llare thus heen able to nuticc tliat tliis substance. is coiiverted, likc /{ern piiiite, wvheii it is boiieti with hydroiodic u.iJ, into a sugar wliich melts a t 5145" ant1 presents all the characters of Befn iiiosilv, k i n g couverted by nitric :xiti into rhoclizonic acid and into tetriioxyquirionc. There is prodncratl a t t h e same timix ;t lively effervescence. due without clonbt, to the escape of nirtt,liyl iodide. In general the two piiiites, and i ~ r o b a b l yscrinite, ;ire i n close relation with the aromatic series. They form ethers deriver1 from a new principle isomeric with the glucoses and which appexr to have the same formula as inosite." From a careful compai-ison of t h e work of 13erthelot :ind JIaqiieiiiie with the work which I 1mvc done on this sugar, I think it is evident a t once that there is only one variety of sugar, viz., pinite, and that Rertkelot, in t h e sample which he originally received, was mistaken in assigning it so low a specific rotatory power. I t will be noticed that in ii portion of Berthelot's original sample, which he sent t o Xaqueniie, the same characteristics \ v e x noticed, in so far as they were compared, and which are described by Macjueniie in the Beta piv,ife. There is, therefore, little cloubt of the fact that what Maquenne calls Beta I)i)z,itf: should simply be called pinitti and it is jmportant that this mistake of giving the same sngnr two different names should be rectified before it has found a permanent place in chemical literature. The method pursued by me i n purifying the crude product was BS follows : (,
The crude sugar contains a considerable quantity of resinous and coloring matter. I t s aqueous solution is almost black and has
PINE TREE SUGAR.
233
n pleasant piney odor. The crude sugar was finely powdered and treated with successive portions of boiling 95% alcohol until all the coloring matter soluble therein was removed. After renio;al of the alcohol the dry sugar was dissolved in water, making a coiicentrated solution. This solution was still highly colored. It was filtered through boneblack in a hot jacketed filter, by which process the greater part of the coloring matter was removed. The solution was nest treated with a slight excess of basic lead acetate, tho precipitate removed by filtration and the excess of lead removed with H, S. The filtered solution was then evaporated slowly over a steam bath until the crystallizing point was almost reacliec! and again filtered through hot boneblack. The solution thus obtained was alniost colorless. Two methods of procedure were followed both, of whidi yielded excellent results. First Metlmd-The clear solution was evaporated to the crystallizing point, quite a coloration resulting. I t was stirred while cooling and a fine mass of small crystals was thus obtained. The concentration should be such that the mass should have a paFtry consistence when crystallization is fully accomplished, which requires from two to four days. The crystalk are washed with 95$ alcohol on a filter until the filtrate shows no further color. The washing is then continued with absolute alcohol until the 05$ alcohol is all displaced. The final washings are with ether. The sugar is dried at a very gentle heat (not above 50') and then placed on filter paper over H, SO, until constant weight is obt ained. Srcoiit7 MellmZ.--The sirup is evaporated to near the point of crystallization and placed in a large jar of wliicli it does not occupy more than one-fourth. Tlie jar is placed on ice, and to the sirup, with constant stirring, three to three and one-half volumes of absolute alcohol are added. The thorough niisture of the alcohol with the sirup is finally conveniently accomplished by blowing through a tube or pipette. Tlie mixture is stirred from time to time to insnre small crystals. The deposition of sugar is complete in from ten to fifteen hours. The sugar is washed and dried as before.
‘l’lie sugar t h u s obtaiiied is ;L 11:ire white powder. ‘I’ gritins of it occupy R voiurriv of 11i.:; L:v.: ~vhe1icc~its aOso1ute specific gritvity is 1..j33$. 1 t i specific 1,ot:ttijry 1)owt’r. i n v:ti,xiiig ~on~ciitriitioii, is shown 11.v t,lic. f o l l ~ \ \iig i t1at:t : .
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From the above it is noticed that tlic rotatory p o w r appears to be inilependent of t h e concentration m d is almost exactly G5 :IS it mean of all the ?esulte.* Distilled with snlphuric acid, according to the rnetliocl used for the productioii of furiura,rnide only a trace of this substance was noticed. Oxitliaed with nitric acid some pt!culiar reactions were observed its follow.^ : When thc oxidation was carried o n in t h e usual may aiid stopped itt it curtain time, large qu:tiiti t i e s of white rlloclozonic acid are proclucetl. Treated with strong iiitric iicitl i n iiii olieii dish, lioweyer, :mil evaporated to dryness, ;L pecuiiiir tiirry mass is produced, of which the b:trium salt forms a reddish bron.ii niiiss the coriipositiori of which has not been accurately cletc!rmiiied. From the work of JI:iyuciiiic, airi>;itlyqiioted, it is prob:tble t h t this substance rimy be hariuni rhoclizoiintc. 111 addition t o this a yellowish substance w:is noticed i i i small quantities, which is p ~ 0 1 ) ably due to the forniittiori or picric o r croconiciicid. ‘l’re;itetl with phenylhydrazin in the usual way, l~iiiitt.gircs 110 osomne ; piiiitc treated with it solutioii of barium Iiytli~itc:solution produces :in a m oq3lious precipitate, :t pilit of wliicli o n &taii(Ii~ig beccmes crystnl-. line. T h e s:ttne is triic wlicli trcatetl w i t h citiciiirii a n d stroiitiuni hydrates. Attempts t o form t h e po1yt)asic silts Iinvu Lecti o111.v partially successful. .
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*Incrensing tciuperature appcars to diniiriisli tlie rotatory ~ O W C J I . .A solution vliich at 5’ gave an s n p i l a r deviation of 14; 32’ ~:I.VI> at 82 OII~Y 13’ ob’. Allo\ying for the expansion of the sollltion the rcruIing shoulct have been neni,ly 14”.
PINE T R E E SCGAH.
235
The scparation of pinite into two bodies by Maqueiine, as indicated in the abstract of the paper given, has been followed by him by a study of these separate bodies, of which the following is an abstract : *"The Beta islosite produced by heating Betapiitite to 120" with an excess of hydroiodic acid, as stated in a previous communication, yields a molecule of methyl iodide and a molecule of Beta iuosite. Saturated hydroiodic acid, in the presence of a little red phosphorous, easiIy reduces the Beta inosite a t 160' to 170". There are formed some brown products of a tarry nature and also a substance having the odor of phenol which remains dissolved in the liquid acid. For thc determination of this last bcdy, ;t is converted by the action of iodine, and of potassium in excess, into an insoluble iodine derivative. The body thus obtained is yellow, crystallizable in alcohol or chloroform, in fine needlcs, fusible a t 159", soluble in alkalies and insoluble in water and dilute acids. Under the influence of boiling nitric acid, this body is transformed into picric acid, easily recognized by its bitter taste and the characteristic aspect of its potassium salt. I t is therefore identical with the phenol iodide which before has been obtained from inosite. This result, in addition to the production of quinones in the oxidation of Beta inosite, shows that this substance has the formula C, HI, O,, characteristic of ordinary inosite. The study of its ethereal combinations proves that it possesses also with iriosite the function of an hexatomic alcohol. Moreover, Beta inosite is without action on Fehling solution and upon t h e phenylhydrazin acetate, which excludes from it8 molecule the presence of aldhydic or acetonic carbonyls. The method of preparing hexacetyl-beta-inosite and hexabenzoyl-beta-inosite is also given. Rotatory Power.-Beta inosite is strongly right handed. A 106 solntion cxarnined in a 220 mm. tube gave a deviation of 14O.3 which corresponds to the formula (a)D=650. I t is remarkable t h a t the rotatmy power is very sensibly the same as that which has been found for Betapinite. In general Beta inosite possessesall the chemical properties of the inosite derived from muscles or from leaves. It constitutes, therefore, as that does, an addition product froiit *C.
R.,Vol. 109, p. 968.
benzine, a derivative from hesametliylene CRHIP. It differs from inosite physically by a. much greater solubilit!, by its higher melting point, by its crystallizing form, and LJ its ethers, which do not resemble any corresponding com1,inatioiia of inosite : and iiii:~Ilj. by its action on polarized liglit. The latter property would seen1 to indicate that a nioleculc of h ’ p f / / ; U U S / ‘ / P is assyniniet.rica1 i i i its constitntion, which may possibly i ~ edue to its coiitaiiiing two oxhydryls attached to thc same :Ltoni of carbon. Befa i ’ i m i t e is distinguished from the product recently obtained by ‘l’::miiet in t h e action of liydroiodic acid 011 quebrachite by its point of fusion-it is :t little higher. vi%., ’7.1’7 in place of 238 ;--by its crystallizing form, which is mucli less marked ; by its rotatory po~vei.,~vliicliis to the riglit, wiiilch the inositeof Tamret is strongly lcf t I1 an il c.d. E r f n i m s i t e is itlso different from the matczodamlose of (iirard, the rotatory power of wiiich is very small, viz., 6’. As 2t result of these researches, it follows that pinite constitutes the monometl~ylineof Befrc I’iiosite and that its formula is C7 R,, 0,. This iniportant principle is, therefore, ail isomer of bornesite and of quebracliite, that is t o say, it is it body absolutely distinguished in its composition and its chemical function from quercite.” Girard lias shown, however, that t h e B(,fupi?ii/i and tlic Beto iiioxife described by Maquenne, arc identical with the sugar obtained by him from caoutchouc and which lit! calls matezite ; and that the Hetci i/iositr is identical mitli another sugar called matezodambose. The abstract of t h e work of’ i;jrard showing these analogies follows ; *‘( Giritrd has abstracted from the juice of the c:ioutcliouc of Madagascar, a sugar which lie lias named matezite. Treating this substance by hydroiodic acid in a concentrated state, and at t h e boiling temperature, it is broken u p into the iodide of methyl and it sugar isomeric with the glucoses, namely, matezodambose. Shortly after, there was found in commerce, under the name of pinite, a sugar extracted from the l ’ i u z ~ s Zawberlicriiu which Maquenne calls Befa yinite to distinguish it from the pinite of Berthelot. When this sugar is treated with IiydroIodic acid it is “c‘. R. Vol. 110, p. 46.
AXALYSIS OF A PEKOE CEYLON TEA.
23'7
broken u p into methyl iodide and into a sugar which resembles inosite, which is cadled Beta iizosite. Struck with the analogies of this substance with the caoutchouc sugar, Combes has identified Beta piwite and matezite as the same sugar, and Befa inosite and niatezodamzite as the same sugar." The following is a table of the physical constitnts of the various substances : JIelting point- - - - - Hotatory power- - - - -
Matezite. B. Pinite. Matezodanibose. B. Inosite. 187" 186O.5 246" 24G" 650 . VI 6G0 G7".(i 6V.4
The rotatory powers are determined by solutions containing 2$ of the material. From what precedes, it is evident that Beta pinite and Beta iiiosifeare not new chemical compounds. I t is seen from the above data that we have in this exudation of the Piiizis Zawbe,~tiam a chemical body of the most remarkable and interesting properties. It is evident that the study of these properties has only been well commenced, and with the large quantities of material wliicli are now a t my disposal I hope at a subsequent time to add something more to our knowledge concerning it.
ANALYSIS OF A . P E K O E CEYLON TEA.
BY JOSEPH F. GEISLER This sample of tea would be considered a curiosity by most people, inasmuch as its appearance is so different from that of the usual varieties of teas met with in commerce. It is a fine Pekoe Ceylon Tea, and its appearance shows it to consist of a mixture of small dark and yellow leaves, the latter predominating. These small leaves are tightly rolled into coils varying from 2 to & inch in length, the greater portion being about inch long, with an average diameter of about J2 inch. T.he small, light, yellowish colored coils are completely dovered with hair, giving some a silvery appearance.
