March 1953
INDUSTRIAL AND ENGINEERING CHEMISTRY
A line is drawn t o join the point representing 16' C. with the value of L,/L, to intersect the first reference line. L,/L, may be found directly from the slope of a vapor pressure plot as previously drawn (8),and p: may be taken from a nomogram previously presented. From here a line joins p,O = 0.365 to obtain a point of intersection on the second reference line. From this point of intersection a line is drawn through V, = 74.0 on the molal volume line to obtain diffusion coefficient of 2.80 X 10-6 on the diffusion coefficient line. This compares with an experimental value of 2.97 X 10-6 sq. cm. per second. Another example may be cited for diffusion of caffeine in water. T o predict the diffusion coefficient of caffeine in water a t 10" C., the molal volume of caffeine is determined from its structural formula; this is equal to 232.6. The point of 10"C. on the temperature scale constructed for water on the second reference line ' is connected with 7 , = 232.6 and the line produced to obtain the value of the diffusion coefficient on the diffusion coefficient sq. cm. per second is read off, soale. A value of 0.40 X which is close to the experimental value of 0.41 X 10-6 sq. cm. per second. However, the nomograph is based on Equation 14, and the limitations of that equation should be borne in mind when the nomograph is used.
-4
D, D: Ed
= diffusion coefficient in water, sq. cm. per second
= diffusion coefficient in water a t 20" C sq. cm. per second = energy of activation for diffusion, calo;:es per gram-mole
Ed. = energy of activation in any solvent, calories per gram-mole Ea, = energy of activation in water, calories per gram-mole Ey = energy of activation for viscosity, calories per gram-mole E,, = energy of activation for viscosity in water, calories per gram-mole K , C, C', k = constants L = latent heat of vaporization, calories per gram-mole L, = latent heat of vaporization of any solvent, calories per gram-mole L, = latent heat of vaporization of water, calories per grammole P = vapor pressure of a liquid R = gas constant, calories per gram-mole X O K. T = absolute temperature, K. p = viscosity, centipoises p? = viscosity of any solvent at 20" C., centipoises p, = viscosity of water, centipoises V , = molal volume of the diffusing substances, ml. per grammole LITERATURE CITED
CONCLUSIONS
The method presented in this paper can be conveniently used
to obtain straight-line correlation of diffusion coefficients in
dilute solutions. For diffusion in water, it is suggested that a plot of diffusion coefficients against viscosity rather than against vapor pressure of water be used to obtain better straight-line correlation. The slopes of these straight lines are related to the energy of activation for diffusion. Equation 9 or Figure 4 can be used to obtain diffusion coefficients in water. To estimate diffuaion coefficients in solvents other than water Equation 14 or Figure 5 may be used. The use of the nomograph in Figure 6 facilitates the prediction of such data. The correlation is based on experimental data from widely varying sources, and some indicated assumptions. I t is to be used, therefore, with some reserve, especially with ionizing solutes; but it will often be most helpful for the many materials for which no experimental data are available. ACKNOWLEDGMENT
The help of Paul Maurer with the manuscript and figures is gratefully acknowledged. NOMENCLATURE
D D. D:
593
= diffusion coefficient, sq. cm. per second = diffusion coefficient in any solvent, sq. cm. per second = diffusion coefficient in any solvent a t 20' C., sq. cm. per
second
(1) Arnold, J. H., IND.ENQ.CHEM.,22, 1091 (1930). Arnold, J. H., J . Am. Chem. Soc., 52, 3937 (1930). Bradley, R. S., J.Chem. Soc., 1934,1910. Braune, H., 2. physilc. Chem., 110, 147 (1924). Gilliland, E. R., IND. ENG.CHEM.,26, 681 (1934). (6) Glasstone, S., Laidler, K., and Eyring, H., "Theory of Rate Processes," p. 522, New York, McGraw-Hill Book Co., 1941.
(2) (3) (4) (5) (7)
International Critical Tables, New York, McGraw-Hill Book
Co., 1926. (8) Othmer, D. F., IND. ENG.CHEM.,32,841 (1940). (9) Ibid., 36, 669 (1944). (10) Othmer, D. F., and Conwell, J. W., Ibid., 37, 1112 (1945). (11) Othmer, D. F., and Gilmont, R., Ibid., 36, 858 (1944). (12) Othmer, D. F., Josefowitz, S., and Schmutzler, ,4.E., Ibid., 40, 286 (1948). (13) Ibid., pp. 883,886. (14)Othmer, D. F., and Luley, A. H., Ibid., 38, 408 (1946). (15) Othmer, D. F., and Sawyer, F. G., Ibid., 35,1269 (1943). (16) Othmer, D. F., and Ten Eyck, E. H., Ibid., 41,2897 (1949). (17) Othmer, D. F., and White, R. E., Ibid., 34, 952 (1942). (18) Rabinowitch, E., Trans. Faraday Soc., 33, 1225 (1937). (19) Wilke, C. R., Chem. Eng. Progr., 45, 218 (1949). RECEIVED for review December 17, 1951. ACCEPTED October 16, 1952. Previous articles in this series have appeared in INDUSTRIAL AND ENQINEERINQ CHEMISTRY during 1940, 1942, 1943, 1944, 1945, 1946, 1948, 1949, 1950, and 1951; Chem. & Met. Eng., 1940; Chimie et Industrie (Paris), 1948; Euclides ( M a d r i d ) , 1948; Sugar, 1948; and Petroleum Refiner, 1961 and 1952.
Pinitol from Sugar Pine Stump Wood ARTHUR B. ANDERSON Forest Products Laboratory, University of California, Berkeley, Calif.
A '
RECENT investigation indicated that the amount of pinitol is not uniform in the trunk of the sugar pine tree (Pinus lambertiana Doug].) ( 2 ) . The greatest quantity of this cyclitol, which is a monomethyl ether of d-inositol, CBHB. (OH)SOCHa, is found in the butt heartwood adjacent to the stump This portion of the tree yielded from 4.8 to 8.6% pinitol, whereas the average yield for the total heartwood in the tree was about 4.0%. This suggested that sugar pine stumps now left in the forest might contain sufficient quantities of pinitol to warrant their removal and subsequent processing for the recovery of this product. In addition, there is evidence that stump removal would make the areas more adaptable for reforestation by either natural propagation or tree planting methods. Certain species of stump wood are being harvested and processed for their extractive components. Old-growth southern pine stump wood has been used for over 40 years for the recovery of rosin, turpentine, and pine oil, which augments the naval stores supplied by the living tree (12). More recently, ponderosa
pine stump wood has been found to be a good source of rosin and volatile terpenes ( 1 ) and a commercial extraction plant has been installed to process ponderosa pine stumps (15). Sugar pine stump wood, on the other hand, is not rich in resinous components, for i t contains only 3.0 to 6.5% benzene-soluble material and hence is not suitable for rosin production. It was nearly a hundred years ago that Berthelot first described the chemical nature of a pine tree "sugar" obtained from the exudate of sugar pine (4). Wiley later identified this product as pinite, now called pinitol (17). This cyclitol is present in redwood heartwood (Sequoia aempervirensD. Don Endl.) (14)andit hasbeen found in the heartwood of five other pines belonging to the Haploxylon subgroup or soft, white five-needled pines (11). Pinitol also occurs in red spruce (Picea rubra) (8). The yields of pinitol from these sources are reported to vary from traces to 0.5%. Recently, it has been reported that redwood stumps contain 1.9 to 2.1% cyclitols-Le., pinitol plus sequoyitol (10). None of these sources appears to contain as much pinitol as
INDUSTRIAL AND ENGINEERING CHEMISTRY
594
sugar pine. The purpose of this preliminary laboratory investibe gation was t o determine the amount of pinit01 that expected upon extracting sugar pine stumps. METHOD OF SAMPLING
The practice of the StumP-wood Processing industries is to allow the stump to remain in the ground for about 10 years, which permits the bark and decay-susceptible sapwood to slough off, leaving intact the sound heartwood, which is rich in resinous components. The harvested stumps are shipped to the plant,
Vol. 45, No. 3
analysis (see Figure 1). A minimum of five stumps was sampled a t each site. Trained and experienced foresters collected the samples. The stumps were chosen at random to give, as nearly as possible, sampling which would be representative of the area,. These included stumps which had incipient heartwood decay and several which were rather highly decayed. The stumps selected had seasoned from 6 to 12 years and were taken from three widely separated sites in California. The samples were collected during the summer of 1951.
I
DISTRIBUTION OF COLD WATER EXTRACT
d composite portion of the x)ower saw cuttings from each sample was ground in a Wiley mill to pass a 2-mm. screen. This ground material was used to determine the amount of cold watersoluble extractives present a t each of the three stump levels sampled. It had previously been determined that all of the recoverable pinitol could be removed by cold water extraction. Subsequent hot water extraction of the cold water-extracted residue did not yield additional pinitol. Hence, the quantity of cold -water extract vould be indicative of the amount of pinitol, together with other water-soluble components, present. These data are reported in Table I. The greatest quantity of water-solubles in well seasoned stumps is found a t the top, with a decided decrease to\Yard the bottom. This was rather surprising, as previous analyses of freshly cut sugar pine butt heartwood indicated about 8 to 1070 watersoluble content, while the top portion of the seasoned stumps revealed nearly twice that amount of water-solubles to be present. Fresh stuma heartwood which had seasoned one Year was then sampled, and the amount of mater-soluble component determined. These results are reported in Table I1 These stumps have less water-solubles a t the top, but, greater amounts in the middle and bottom than the well seasoned stump wood, and the total amount of cold water extract is comparable t.0 the amounts found in the older stumps. This suggests that the heavy deposition of water-solubles a t and near thc top of the well seasoned stumps is brought about by the gradual upward movement of water, together with the water-soluble components, as the stump slowly dries during the weathering or seasoning process. Y
I
Figure 1. Method of Sampling Sugar Pine Stump chipped, and extracted with a suitable solvent, such as petroleum hydrocarbons, to recover the extractives. The majority of the stumps used in this investigation were, likewise, well seasoned, for the heartwood of sugar pine is the richest source of pinitol, Unlike old-growth southern pine and ponderosa pine stumps, the heartwood of sugar pine stumps may show evidences of deterioration due to decay after several years’ exposure. This apparent greater susceptibility of sugar pine stump heartwood to decay i s probably due to its low resin and terpene content. Because the distribution of extractives is not uniform, a method of stump sampling had to be devised which would provide representative material. After several attempts, the following pro. cedure was found satisfactory. The sapwood, if still intact, was removed from the stump and discarded. Then a horizontal power saw cut was made several inches from the top of the stump to the pith and the cuttings were allowed to collect on a tarpaulin, after which they were transferred to a container. This was repeated a t the middle and bottom portion of each stump, giving three separate samples for
DISTRIBUTION AND AMOUNT O F PlNlTOL
The aniount of pinitol present in each of the stumpwood samples was conveniently determined by water extraction of sawdust in a continuous-infusion extraction apparatus, shown in Figure 2.
Fifty grams of power saw shavings, as received, were put into the glass tube (32 mm. in inside diameter X 70 em.) containing a cotton plug a t the bottom to act as a filter. The one-holed rubber stopper containing the glass tubing was connected to the 1000-mI. 2-necked flask by rubber tubing having a capillary tube (1.5 mm.) as effluent inlet into the flask. Distilled water (about 500 ml.) was added to the extractor tube until the OF COLDWLTER EXTRACT IN SEASONED S T U ~ IWOOD P TABLE I. DISTRIBUTION shavings were covered with water, and Cold Water Extract, %, just overflowed into the flask. Then Year Years Heart Dry Basis 150 ml. of water were added to the flask, Stump Tree Stump Diam., Site No. Felled Seasoned Inches Top Middle Bottom Av. boiling started at a rate of about 10 ml. Msrtell, Calif. 1-M 1941 10 40 14.8 6.6 4.6 8.7 per minute, and the condensate allowed 2-M 1941 10 54 13.8 6.3 5.1 8.7 to collect a t the top of the extractor tube 3-M 1941 10 72 11 07 .. 05 containing the sample. The continuous 4-M 1945 6 24 31 04 .. 88 182 .. 23 97 .. 15 flow of aqueous effluent, containing the 5-M 1944 7 36 22.6 7.1 5.9 11.9 6-M 1944 7 72 10.5 4.8 . 5.1 6.8 water-soluble components, collected in Av. 1 7 . 7 7.5 6.2 10.5 the flask. Stirling City 1-S 1939 12 32 14.4 7.9 5.9 9.4 The extraction was carried out for 3 Calif. 2-S 1939 12 37 18.5 8.8 4.0 10.4 hours, after which the concentrated 12 48 15.1 9.1 3-5 1939 5.2 9.8 aqueous extract was transferred to an 23.3 8.7 3.2 11.7 4-5 1939 12 39 5-8 1939 12 27 16.2 9.0 4.2 9.8 evaporating dish, placed on a steam bath, Av. 1 7 . 5 8.7 4.5 10.2 and allowed to come to a heavy sirup, Susanville, 111-2 1941 10 29 23.6 11.5 6.8 13.0 which, in many instances, began to Calif. 111-3 1941 10 26 15.1 9.6 6.2 10.3 crystallize. Tenmilliliters of acetone were 14.8 25.7 12.4 6.2 1945 6 41 11-1 added to the warm sirup and stirred, 13.9 11.2 9.5 6 80 21.0 11-2 1945 111-3 1945 6 36 14.1 6.9 6.6 9.2 and the precipitate, which readily formed, Av. 1 9 . 9 10.3 7.0 12.4 was set aside for 1 hour. Theproduct was filt.ered with suction onto a tared,
INDUSTRIAL AND ENGINEERING CHEMISTRY
March 1953
595
As indicated by the amount of watersolubles in Table I, the largest quantity (HEARTWOOD) of pinitol occurs a t the top portion of Year Years Heart Cold Water Dry Basie Extract, %, well seasoned stumps, with decided deStump Tree Stump Diam., Site No. Felled Seasoned Inohes Top Middle Bottom Av. creases in pinitol content toward the Stirling City, Calif. 7-9 1950 1. 40 12.7 10.4 9.3 10.8 bottom. Surprisingly large amounts of 1950 1 38 12.3 11.3 9.4 11.0 8-9 pinitol were recovered from the top por1 35 12.1 11.9 1950 7.9 10.6 9-s Av. 12.4 11.2 8.9 10.8 tions, the average being 15.4 t o 17.2%, while the lower part of the stump contained from 3.2 t o 4.5% pinitol. The average yields for the whole stump sintered-glass funnel and washed with 10 ml. Of acetone, leavamounted to 8.3 to 9.8% or 166 t o 196 pounds of pinit01 per ing a light tan-gray solid material. This was dried in a 60" C. ton of stump wood (dry basis). vacuum oven, cooled in a desiccator, and weighed, and the Some of the stumps-Le., 3-S, 5-S, and 11-3 (Table 111)amount of crude pinitol determined. Other solvents, such as absolute ethanol, absolute methanol, and glacial acetic acid, were although slightly decayed, showed DO material drop in pinitol tried as precipitating agents, but acetone was found $0 be the yield. This is likewise true in the case of stumps 1-M and 5-M, best medium for quantitative recoveries of pinitol. which were slightly disintegrated owing to advanced stages of decay. Izowever, a more extensive analysis of decayed stump The amount of pure pinitol present in the precipitates averaged wood would be necessary to ascertain whether such stumps would about 85%, if based on methoxyl content, contain as much pinitol as sound stump wood. assuming the absence of other methoxylThe heartwood of several relatively fresh stumps was extracted containing components. Theory for to determine the amount of pinitol present. These stumps had pinitol is 15.98% methoxyl; found, 13.42 seasoned 1 year, and the results are reported in Table IV. It to 13.4770 methoxyl in crude product or 84 will be noted that the pinitol content is less a t the top than is to 86% as pinitol. The melting point of found in the more seasoned stumps, but greater in the center the crude varied from .164" to 172" C., and and bottom than in the older stumps. The average yields for the it had an average [CY]% 58.6 (concentrawhole stump wood are comparable. This further suggests that tion, 1.0% in water). The product conthe water-soluble pinitol gradually migrates upward along with tained some reducing substances, as it the water, as the stump seasons, reacted with Fehling's solution, and it also contained pentose-producing components, as distillation with 12% hydrochloric acid TABLEIV. PINITOL IN HEARTWOOD OF FRESH STUMPS produced a phloroglucide amounting to 2.5 (Stirling City, Calif.) to 3.0%, calculated as arabinose. PartiStump No. 7-5 8-S 9-8 Years stump seasoned 1 1 1 tion chromatography of the crude pinitol Heart diam., inohes 40 38 35 indicated the presence of a t least four Crude Pinitol, %, Dry Basis Av. other substances, one of which is known to TOP 11.4 10.4 10.6 10.8 Middle 9.3 9.6 10.4 9.7 be another cyclitol. These components Bottom 7.9 6.3 6.8 6.7 are under investigation and will be subAV. 9.5 8.7 8.9 9.0 sequently reported. The distribution and amount of crude Sugar pine sapwood contains from traces to about 0.5% pinitol-Le., 85% pinitol-recovered from pinitol. Therefore, if the whole stump, including the sapwood, Figure2. Conthe various stump-wood samples are retinuous Infuwere extracted, lower pinitol yields would be anticipated. Several ported in Table 111. sion Extracsuch stumps were sampled and extracted, and the cold water tion Apparaextract and pinitol yields are recorded in Table V. As indicated, tus the average yield w~195.3% pinitol, which is equivalent to about TABLE111. D I S T R I B ~ I OAND N AMOUNT O F PINITOL IN SEASONED 60% of the average yields Obtained from the stump heartwood. The.amounts of pinitol are likewise more evenly distributed in STUMPS Martell, these fresher stumps. StumpCalif. No. 1-M 2-M 3-M 4-M 5-M 6-M
TABLE 11. DISTRIBUTIONO F COLD WATER EXTRACT I N FRESH STUMP
WOOD
-
+
Years stump seasoned Heart diam., inches
TOP
Middle Bottom Av.
Stirling City, Calif. Stump No. Yearsstump seasoned Heart diam., inches %&e Bottom Av.
10 40
10 10 6 7 54 72 24 36 Crude Pinitol, %, Dry Basis13.4 12.5 14.0 26.7 19.8 5 . 0 4.9 6.4 8.9 4.6 3.0 3.9 5.4 5.5 3.5 7.1 8 . 6 13.7 9 . 3 7.1
7 72
7.8 1.5 2.6 4.0
LABORATORY SCALE EXTRACTION OF PINITOL 15.7 6.2 4.0
8.3
apparatus, as described previously, was used.
I-s
2-5 3-5 4-s 543 12 12 12 12 12 32 37 48 39 27 Crude Pinitol, %, Dry Basis 13.1 16.8 13.4 19.1 14.8 6.0 7.4 7 . 3 6.2 6.3 4.0 3.0 3.7 2.4 3.1 7.7 9.1 8.1 9.2 8.1
Susanville, Calif. Stump No. 111-2 111-3 11-1 11-2 11-3 Years stump seasoned 10 10 6 6 6 Heart diam., inches 29 26 41 50 36 Crude Pinitol, %, Dry Basis TOP 21.4 11.2 23.5 18.6 11.3 Middle 9 . 3 5 . 3 11.0 9.4 3.5 Bottom 4.5 3.2 4.3 7.2 3.5 Av. 11.7 6.5 12.9 11.7 6.1
It was of interest to determine the rate of pinitol removed from coarse sawdust, such as might be used in industrial extractions. For this purpose, the continuous-infusion extraction
16.4
6.6 3.2 8.4
17.2 7.7 4.6 9.8
The tube was replaced with a 4-liter glass ercolator. Six hundred grams of coarse stump-wood sawdust (tirough a 6-mm. screen) was put in the percolator chamber, 3600 ml. of waterwere added to cover the sawdust, 150 ml. of water were added to the distilling flask, and the rate of distillation t o the top of the extractor was adjusted to 10 ml. per minute. The distillation was interrupted a t 1-hour intervals, the concentrated effluent in the flask was transferred to an evaporating dish and evaporated to a sirup on a steam bath, and the crude pinitol was recovered and determined as before. The rate of pinitol removal (average of three runs) is recorded in Table VI. (Sawdust contained 8.2% pinitol dry basis, or 7.4% air-dry basis.)
As can be seen from Table VI, about 6 volumes of water per unit weight of sawdust removed approximately 97% of the total
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
596
Vol. 45, No. 3
APPLICATION OF RESULTS A N D AMOUKT O F COLD SVATER EXTRACT AND TABLE v. DISTRIBUTION WHOLESTUMPWOOD(SAPWOOD A N D HEARTWOOD)
PINITOL I N
Sugar pine is found largely in California and extends into southern Oregon. (Susanville) The average annual production of sugar Stunip No. SP-3 SP-6 SP-7 pine lumber in the United States for the Year tree felled 1950 1950 1948 Years stump seasoned 1 1 3 5-year period, 1945-49, was about 322,Stump diam., inches 25 36 40 000,000 board feet, of which approxiPer Cent, Dry Basis Average mately 263,500,000 board feet, or about HzO HzO €120 H20 sol. Pinitol sol. Pinitol sol. Pinitol sol. Pinitol 80% of the total., is oroduced in Cali6.3 8.8 6.2 7.9 5.5 4.0 8.7 6.1 TOP fornia ( 6 ) . Stump height will vary from 5.0 7.8 5.0 4.8 7.5 8.2 7.8 5.3 Middle 8.3 6.1 7.9 5.9 7.2 4.4 7.8 5.5 1 t o 3 or 4 feet and the diameter from 20 Bottom 5.2 7.8 5.3 5.7 7.8 8.3 7.4 5.1 Av. inches to 5 or 6 feet, Thus, sugar pine stumps will weigh from several TABLE VI. EXTRACTION OF PINITOL hundred pounds to well over a ton, Total time hours 1 2 3 4 5 6 7 8 contingent on size. It is evident that 3000 3600 4200 4870 1800 2400 600 1200 Total HzO'through extractor, ml. Total pinitql, grams 12.47 24.86 32.45 37.34 4 0 . 9 8 43.24 4 4 . 0 9 44.40 a good supply of stump wood is poten6.83 7.21 7.35 7.40 5.41 6.22 2.08 4.14 Yield, %, air-dry basis tially available for the commercial pro97.4 9 9 . 3 1 0 0 . 0 9 2 . 3 7 3 . 1 8 4 . 1 5 6 . 0 % of total yield 28.1 duction of pinitol. The onlv other cvclitol now conimercially available is meso- or inactive inositol, obtained from corn products steep liquor. -4 recent amount of pinitol present in the sawdust. This would indicate reappraisal of the amount of quebrachitol (a monomethyl that reduced sugar pine stump wood would readily lend itself ether of l-inositol) obtained from the latex of the rubber tree, to simple countercurrent or continuous extraction processes for Hevea bmsiliensis, suggests this as a commercial source for this the commercial recovery of this cyclitol. particular cyclitol (16). While a number of uses have been PURIFICATION O F PINITOL AND SOME DERIVATIVES proposed for the meso-inositol, some of these developments appear to have been curtailed, because of the relatively high production There are several ways in which pure pinitol can be produced cost, which is unlikely to be reduced until its production can be from the crude product divorced from steep water extraction (6). It is possible that One method used was to dissolve the crude material in 10 parts pinitol or its derivative could replace meso-inositol in some of of water, and add 5 parts of a saturated solution of barium the proposed uses. In any case, pilot plant studies and market hydroxide and 10 parts of ethanol to precipitate the gums. The research surveys are the next steps to determine the economic solution was centrifuged or filtered and the solution acidified to feasibility of the production of pinitJol from sugar pine stump Congo red with dilute sulfuric acid to remove excess barium. The barium sulfate was removed by centrifuging, the solution wood. decolorized with charcoal, and the resulting clear solution partially concentrated under reduced pressure on a water bath. The concentrate was transferred to an evaporating dish and further conACKNOWLEDGMENT centrated to a heavy sirup, and glacial acetic acid was added to crvstallize the pinitol in the form of fine white crystals, melting Appreciation is expressed to the Diamond Match Co., Stirling p c h t 182-184" C. (All melting points, uncorrected, were taken City, Calif., Winton Lumber Co., Martell, Calif., Fruit Growers on a Fisher melting point block; microanalysis was by the hlicrochemical Laboratory, University of California.) SubsequentrecrysSupply Go., Susanville, Calif.. and Caldor Lumber Co., Diamond tallization from water and ethanol (9Oy0) produced a pure product, Spring, Calif., for collecting the stump samples used in this inwith 75% recovery, melting point 185-186" C., [ a ] $ z 66.1 vestigation. in water). Some previous values reported melting point 185 , [a]= 65.4 (14); melting point 184-185", [ a ] ~ 67.7 (7); melting point 186", [a]= 65.3 ( 9 ) . Analysis. Calculated for C&e(OH)h OCHa (194.2) carbon, LITERATURE CITED 43.29; hydrogen, 7.26; methoxyl, 15.98yO.Found: carbon, 43.08; hydrogen 7.32; methoxyl, 16.0570. (1) Anderson, A. B., IRD. ENG. CHEM.,39, 1664 (194i); Paper d-Inositol. P h t o l was demethylated with hvdriodic acid in Trade J . , 129, S o . 2, 35 (1949). the customary manner, yielding 96.47, d-inositol, melting point (2) Anderson, A. B., T a p p i , 35, No. 5 , 198 (May 1952). 246-247" C., 64.9 (lye in water) (melting point 246", (3) Anderson, A. B.. MacDonald, D. L., and Fisoher, H. 0. L., [ a ]3.~65) ( 1 7 ) . J . Am. Chem. SOC.,7 4 , 1479 (1952). Pentaacetyl Pinitol. The pentaacetyl derivative was prepared (4) Berthelot, M., Compt. rend., 41, 392 (1855). from acetic anhydride and anhydrous sodium acetate, yielding 797, of the acetylated product, melting point 98-99', (5) Bur. Census, Staff Report. 11.3 (1% in ethanol) (melting point 9 8 O , [ N ] D 8:s) ( I S ) . ( G ) Ckem. W e e k , 68, 26-7 (June 23, 1951). Diisopropylidene Pinitol. The recent preparation of the diace(7) Erdtman, H., Suensk Kern. Tidskr., 56, 2 (1944). tone compound of pinitol in good yield, melting point 104-105', ( 8 ) Gottlieb, S.,and Brauns, F. E., J . Am. Chem. SOC.,7 3 , 5880 [a]gz - 45.1 (1.9% in C.S.P. chloroform), has established the (1951). position of the methyl group in pinitol to be as follows (3): (9) Griffin, E. G., and Wilson, J. M., Ibid., 3 7 , 1569 (1915). (10) Lewis, H. F., T a p p i , 34, KO.9, 388 (1951). CHs CH, (11) Lindstedt, G., Acta Chem. Scand., 5, 129 (1951). (12) Palmer, R. C., IND.ENG.CHEM.,26, 703 (1934). (13) Pease, D. C., Reider, RII. J., and Elderfield, R. C., J . Org. Chem., OH OH I "
+
+ +
+
(170
+
+
+
>c< 9 0 I
I-)
/-\
+ ZCH&OCH,+ I
OH
5, 192-7 (1940).
1
1OCH
(14)
Sherrard, E. C., and Kurth, E. F., IND.ENG.CHEM.,20, 722
(15) (16) (17)
Timberman, 50, 105 (October 1950). Van Alphen, J., IND. E m . CHEM.,4 3 , 141 (1951). Wiley, H. W., J . Am. Chem. SOC.,1 3 , 228 (1891).
(1928).
I
1
0-C-CH, 1
CH3 Pinitol
Diacetonc Pinitol
RECEIVED for review February 19, 1952.
ACCEPTED Sovember 5 , 1952.
