896
INDUSTRIAL AND ENGINEERING CHEMISTRY
(11) Naval Research Laboratory. "Properties of Carbide and Carbon Synthetic Polymer Fiuids of Interest in Luhricatiori and
Hydraulics," Rept. P-2273 (February 1944). (12) O'Rear, J. G., Slilitz, R. O., Spessard, D. R., and Zisinan, I\-,A , . "Development of the Hydrolube Soninflammahle Hydi,aulic Fluids," Saval Research IJahoratory, R w t . P-3020 L i p d 1947). (13) Pohl, H. A., "Viscosity Breakdown i n Oils," S a v a l Research Laboratory, Rept. P-2075 (May 1943). (14) Sullivan, 31. V., Wolfe, J. K., and Zisman. IT. -4.. I S U . ESG. CHEM.,39, 1807 (1947).
Vol. 43, No. 4
(15) Wachter, .I.,and Stillnian, S . . ( t o Shell Development C o . ) , I-. 5. Patent 2,419,327 (-4pril 22, 1947). (16) K a l k e r . K , E.. Harford, E. F.. and IVholey, J.. Jr.. "Hydrolube Fluids, the Development of I,csu Inflamrnable Hydraulic Fluids," confidential report of .\nimonia Department. E. I. d u Pont de Seniours & Co., Inc., F e b r u x y 1945. ,I;) ~ v ~ i ~ pesman, ~ , c;,, ..nibliographyof ~ - ~ ~ ~ -4irl ~ ~ ~ i f i ~ d cr:ift-Fire Literature." S a d . .idvisory ~ C J I I .ieronaut., ~ ~ . R~pi.RME9H03 i S n v . 10. 1049). (18) l \ ~ o l f e ,J. Ic i n XIethoxyl c-
2 .x %,1R 3 6 , 80
2l.til
3 4 , 2ti 115-droxyl
Groups in Tannin, X 'Total hydroxyl groiiris Phcnolic hydroxyl group: Aliphatic hydroxyl group* TABLE
VIII.
AXdLYSIS OF
Material PentosanGalactau Glucosan Mannan Uronic anhh h i d e Undetermined
in sugar content ( I O ) . This fact makes i t an "acid-producing tannin," probably comparable t o chestnut tannin extract.
no by Weight
37.8 20.8
TABLE T'I
Vol. 43, No. 4
22.9 13.? 9.0
CARBOHYDRATE JIATERIAI Vc b y KVeighr
22.6
25,3 32.4 9.2 2.1
8.2
Ponderosa pine bark that had been previously extracted with diethyl ether and ethyl alcohol was next extracted with water, by extracting the bark in 50-gram 1)ntches in the conventional laboratory tannin extraction apparatus ( 2 ) . The extracts from 500 grams of bark were combined and filtered before evaporation a t reduced preasure to a thick sirup. The concentrated estrnct was poured into a large volume of ethyl alcohol. Under these conditions the carbohydrate material was precipitated, and the tannin and other colored materials, not previously removed, remained in the ethyl alcohol. T h e precipitated material was cent,rifuged and then Fashed with alcohol. T h e final product was a light tan-colored material. A pentosan determination on the dry material demonstrated the presence of 22.8'% pentosan. T h e yield of mucic acid on treatment with nitric acid corresponded to 25.3% galactan ( 3 ) . T h e filtrate from the mucic acid determination, after neutralization with potassium carbonate followed by acidification Kith acetic acid, contained potassium acid saccharate. The white salt crystals m r e recrystallized from n.at,er and identificrttion n - 3 ~ made under tlie microscope as outlined by Hassid and McCready ( 5 ) . T h e saccharic acid derived from glucose accounted for 32.4% of the carbohydrate material. A uronic anhydride determination by rcfluxing tvith 127, hydrochloric acid showed only 2.1%present. .in aqueous solution of the carbohydrate material !vas hydrolyzid with 27, sulfuric acid to test for mannose. After neutralization of the hydrolyzate and filtration, the solution wyi~ concentrated under reduced pressure. Phenylhydrazine added to llie cold solution, which had been acidified with acetic acid. formed inannose phenylhydrazone upon standing i n the icebox. T h e recrystallized phenylhydrazone had a melting point of 196" C:. T h e analysis of the carbohydrate material from the water extract of the hark is suniinarized in Table VItII. LITERATURE ( : i m I )
Cltraviolet absorption curves for the methylated tanirins are shown in Figure 5. Masimurn absorption was a t 280 m p . The increase in methosyl groups Kith each method of methylation is given in Table 1-11, For t'he determination of the metlioxyl present in the tannin before methylation, the ethyl acet'atasoluble tannin \vas dissolved in boiling water to remove absorbed solvent and then dried in a vacuum desiccator over sulfuric acid. Assuming tha.t the diazomethane reacted with the acidic hydrosyl groups and the dimethyl sulfate methylated all of the hydroxyl groups present in the tannin molecule, then the total hydroxyl, phenolic, and aliphatic hydroxyl found a-ere 22.2, 13.2. and 9.070,respectively. Oxidation of the diniethyl sulfnte-rnethylate(i~t~lylate~1 tannin riith hot alkaline permanganate gave veratric acid, melting point 179" to 180" C., and a neutral equivalent, of 181. A m i z d melting point test, n-ith an authentic sample of veratric acid, showed no depression in melting point. Inasmuch as the veratric acid was derived from the catechol nucleus in t h r tniinin, this fact c1iarncterizc.s the tannin as the catechol type. Most vegetable tanning mat,erials are shipped in thc solid state. For this purpose the aqueous tan liquors are concentrated to about 50% total solid content,, preferably iii continuous long-tube vacuum evaporators, \There they are subjected t o low temperature for short periods of time, and then may be dried to a ponder in spray dryers or vacuum-drum dryers. When ponderosa pinc bark tan liquor w i t 5 evaporated and dried below 60" C., there was a negligible loss of' tannin through conversion t o insoluble phlobaphenes. T h e addition of sodium sulfite to the tan liquor before evaporation was found beneficial in preventing formation of insoluble matter. Ponderosa pine bark tannin estract is high
.Idtims, 11.J.. J. IND. Esu. CHLM.,7, 9 5 i (1915). Anierican Leather C h e m i s t s Association, Cincinnati, Ohio. "Xethods of S a m p l i n g and .%nalysis. P r o p o s e d M e t h o d s , " 1946. Bates, F.J., K a t l . Bur. S t a n d a r d s , Circ. C440 (1942)). Graham, H. M,, arid K u r t h , IC. F.. IXD.E x : . CHEY.,41, 409
(1949). Hassid, \V. Z.,and JIcCready, It. >I.. IND. Esc. CHEM.,ANAL. ED.,14, 683 (1942). Hawk, E'. B., Osrr, B . L., a n d S u m m e r s o n , I\'. H., "Practic.al Physiological C h e m i s t r y , " 12th e d . , Philadelphia, Ulakiston
c o : , 1947. IIeitluschka. il., and Ripper, J., Bw.,56, 1736 (1923). .Tanliesoil, G. 6.. "Vegetable F a t s a n d Oils," 2nd e d . . S e w Tork, R e i n h o l d Publishing Corp., 1943. K u r t h , E . F., J . Am. Chem. Soc., 72, 1685 (19501. I i u r t h , E. F., H u b b a r d . J. I
