QUEBRACHITOL

INDUSTRIAL AND ENGINEERING CHEMISTRY

January 1951

c

b

(40) Hessen, R., and Schuch, K. A. (to Aug. Nowack A,-G.), I b X , 433,666 (Aug. 17, 1934). (41) Honel, H. (to Beck, Koller & Co.), Ibid., 467,081 (June 9, 1937). (42) Honel, H. (to Beck, Koller & Co.), U. S. Patent 1,800,295 (April 14, 1931). (43) Ibid., 2,049,447 (Aug. 4, 1936). (44) Honel, H., Ehrenfeld, J., and Reichhold, O., Brit. Patent 417,122 (Sept. 24,1934). (45) Howroyd, McArthur and Co., Ger. Patent 638,218 (Nov. 12, 1936). (46) Hunn, J. V. (to Sherwin-Williams Co.), U. S. Patent 2,330,217 (Sept. 28, 1943). (47) Kamm, O., “Qualitative Organic Analysis,” 2nd ed., p. 9, New York, John Wiley t Sons, 1932. (48) Kulas, C., and Pauling, C., U. S. Patent 1,609,367 (Dec. 7, 1926). (49) Lauter, F. (to Sealkote Corp.), Ibid., 2,101,948 (Deo. 14, 1937). (50) Mattiello, J. J., ed., “Proteotive and Decorative Coatings, Vol. I, p. 318, New York, John Wiley & Sons, 1941. (51) Miller, G. W. (to Bakelite Corp.), U. S. Patent 1,717,614 (June 18, 1929). (52) Mnookin, N. M., Ibid., 2,139,418 (Dec. 6, 1938). (53) Moss, W. H. (to Celanese Corp.), Ibid., 1,743,680 (Jan. 14,1930). (54) Muller, R. (to Bakelite Corp.), Ibid., 2,272,154-5 (Feb. 3, 1942). ( 6 5 ) Murdock, F. M. (to Fiberloid Corp.), Ibid., 2,037,585 (April 14, 1936). (56) Norton, A. J. (to Pennsylvania Coal Products Co.), Ibid., 2,414,417 (Jan. 14. 1947). (57):Novotny, E. E., and Romieux, C. J., Ibid., 1,738,310 (Dec. 3, 1929). Oste;sGtter, A. (to Pollopas, Ltd.), Ibid., 1,892,848 (Jan. 3, 1933). Petroff, G., Ibid., 1,693,461 (Nov. 27, 1928). Petrov, G. S., Russ. Patent 39,116 (Oct. 31, 1934). Rosenblum, I., U. S. Patent 2,131,757 (Oct. 4, 1938). IbicE., 2,175,215 (Oct. 10, 1939). Rossi, L. M. (to Bakelite Corp.), Ibid., 1,613,724 (Jan. 11, 1927). Rust, J, B. (to Ellis-Foster Co.),Ibid., 2,141,198 (Dec. 27, 1938).

141

Ibid., 2$155,907 (April 25, 1939). Scheiferwerke Ausdauer A.-G., Ger. Patent 529,323 (March 11, 1927).

Seebabh, F. (to Bakelite Corp.), U. S Patents 1,681,368-9 (Aug. 21, 1928).

Ibid., 1,891,455 (Dec. 20, 1932). Ibid., 1,998,098 (April 16, 1935). Sherburne, A. J. (to Canadian General Electric Co.), Can. Patent 390,308 (July 30, 1940). SociBt6 Franpaise Beckacite, French Patent 803,399 (Sept. 23, 1936).

Stewart, C. (to General Electric Co.), U. 8. Patent 1,896,842 (Feb. 7,1933).

Swain, R. C., and Adams, P. (to American Cyanamid Co.), Ibid., 2,331,744 (Oct. 12, 1943). Swallen, L. C. (to Monsanto Chemieal Co.), Ibid., 2,231,860 (Feb. 11,1941). Tarasov, K. I., Russ. Patent 56,405 (Jan. 31, 1940). Turkington. V. H. (to Bakelite Corn), U. S. Patent 1.660.403 (Febr28, 1928). Ihid., 2,006,189 (June 25, 1935)

Turkington, V. H., and Allen, I., Jr., IND.ENO.CHEM.,33, 966 11941).

Turkington, V. H., and Butler, W. H. (to Bakelite Corp.), U. S. Patent 2,017,877 (Oct. 22, 1935). Ibid., 2,173,346 (Sept. 19, 1939). Wakefield, H. F. [to Bakelite Corp.),Ibid., 1,756,267 (April 29, 1930).

Whitmore, F. C., “Organic Chemistry,” p. 375, New York, D. Van Nostrand Co., 1937. Wilder, G. H. (to Du Pont Viscoloid Co.), U. S. Patent 2,035,616 (March 31, 1936). Wilder, G. H. (to E. I. du Pont de Nernours C Co.), Ibid. 2,058,649 (Oct. 27, 1936). RECEIVED May 4, 1950. of Purdue University by

Abstracted from a thesis submitted to the faculty Brage Golding in partial fulfillment of the requirements for the degree of doctor of philosophy.

QUEBRACHITOL Cyclic Polyalcohol f r o m Natural Rubber Latex JAN VAN ALPHEY Rubber Foundation, Delft, Holland

T h e latex of the rubber tree, Heaea brasiliensis, contains a beautifully crystallizing sweet compound, quebrachitol or the monomethyl ether of 1-inositol, C.IHHO~, which, after

*

coagulation of the rubber, remains behind in the serum. As this serum is a waste product, thousands of tons of quebrachitol are lost each year. In this communication attention is drawn again to this compound. A review of the literature is given, the preparation is discussed, a new estimate of production costs is made, and experiments relating to possible technical application are described.

Quebrachitol itself is the monomethyl ether of Ginositol (34) (the line represents an OH group) :

It is not known which hydroxyl group of &inositol is etherified, but the formula of &inositol is known by its transformation upon oxidation into saccharic acid (and mucic acid) (38, 34).

Q

UEBRACHITOL (the name is derived from the fact that it WBS first discovered in quebracho bark, the bark of Aspidosperma qudvacho), CrHl,Oe, is the monomethyl ether of Ginositol. There are nine stereoisomeric forms of inositol, six of which are known. They all are cyclohexanehexols with the formula:

CHOH . CHOH C d H

‘cHcm.

‘CHOH

cdH

but the position of the OH groups in connection with the plane of the ring differs (38).

H HOOC

$

I

O H 1-inositol

H

H O

.$ O H H

H

.COOH I

O H

saccharic acid

OCCURRENCE IN NATURE

Quebrachitol was discovered by Tanret (38), who found it in quebracho bark (the bark of Aspidosperma quebracho), but the compound became of interest to rubber chemists when de Jong (2%’)discovered its presence in the serum of Hevea latex. Pickles and Whitfield (31) found it also in rubber sheet and in

142

INDUSTRIAL AND ENGINEERING CHEMISTRY

"fine hard Para" rubber, and Whitby, Dolid, and Yorston (41) isolated 2.80% resin from Hevea rubber, but this contained only a small amount of quebrachitol. Quebrachitol is also found in other plants: 0.4% in the leaves of Grevillea robusta ( 6 ) and of Hakea laurina R.Br. (?), in the flower buds of Artemesia afra Jacq. (19), 0.7% in the stems of Haplophyton cimicidum ( I S ) , in Acalypha indica (36), and in the dried leaves of Acer pseudoplatanus and Acer platanozdes (25'); it was also isolated from the red oil of Minnesota wild hemp ( I ) , from all Sapindaceae examined, and from numerous species of Aceraceae (33). For industrial preparation only the occurrence of quebiachitol in the serum of Hevea latex is of interest, and it is remarkable that few data are available about the percentage of quebrachitol in Hevea latex. De Vries (40) estimated a content of 1.5%, probably based on Gorter's report (ZO), who calculated from the rotation of the plane of polarization that the serum must contain 1.45%. Spoon (37) gave the value 1.35y0 for latex serum; from this Bruni (9) calculated that in 1924 15,000 to 20,000 tons of quebrachitol were lost. However, Rhodes (35) isolated 0.45% from a Malayan and McColm (67) 0.21% from a Sumatran latex. PREPARATION

Small samples of this easily crystallizing INTHE LABORATORY. compound can be prepared without difficulty. The serum of Hevea latex is partly evaporated, the proteins that separate are filtered, and the filtrate is evaporated to a sirupy mass. After some time crystals are formed, which are recrystallized from a small amount of water (after being decolorized with animal charcoal). The water can also be evaporated under reduced pressure (9) and the crystals can be recrystallized from acetone (26) or from acetic acid (34). If latex itself is used, the rubber is coagulated by pouring the latex into an excess of alcohol or by acidification with acetic acid, but it is necessary to dilute concentrated latex. It is also possible to precipitate the proteins from the watery solution by means of tannin ($4). A yield of 12 g r a m per kg. of serum is given in the literature ($4). As immediately after the war no fresh latex could be obtained, small samples of quebrachitol were readily prepared by extracting with alcohol the rubber powder pulvatex, a stock of which v a s in the laboratory of the Rubber Foundation. ON A TECHNICAL SCALE. According to Bruni (8),the serum is simply evaporated under reduced pressure. The Naugatuck Chemical Co. (68) dried the starting material by dispersion in hot air and extracted the powder 80 obtained during 15 to 20 minutes with boiling alcohol. The alcoholic solution was treated with decolorizing charcoal and evaporated, yielding 12 to 18% quebrachit~l(calculated on the dry starting material). The proteins can be salted out before dispersion. A more extensive description was given by the United States Rubber Co. (S9). The serum was treated with lime, heated to boiling, filtered, and concentrated to about one half its original volume, and the excess calcium was precipitated with carbon dioxide and filtered again. The filtrate was acidified to pH 3 to 4, passed through ion-exchange beds for removal of cations and anions, and evaporated a t reduced pressure. It is stated that the recovery of quebrachitol is nearly quantitative. Rhodes and Wiltshire (35) gave an extensive description of a preparation on a semitechnical scale. The serum was evaporated to one hundredth of its volume, the proteins were scummed, and the concentrate was cooled down to 0" C. The crystallization finished, the crystals were separated by centrifugation and recrystallized from water, decolorizing carbon being used. According to them, the cost of preparation of 1pound of quebrachitol in Malaya about 1931 would have been 85 cents (Straits dollars).

Vol. 43, No. 1

PROPERTIES

PHYSICAL PROPERTIES. Quebrachitol is a readily crystallizing colorless compound which melts a t about 192-193' C. (I) and which can be sublimed under a diminished pressure (13). Its boiling point in vacuum is about 210" (38) and [a]? is -81.2' (5% aqueous solution, I S ) . The crystals are monoclinic ( 3 )and contain two molecules in the elenientary cell, a 6.60, b 7.15, c 8.65 8.;p 90"; space group Ci d 1.54 (SO). The refractive index, 71, = 1.546, np = 1.552, n y = 1.572 ( I S ) . The crystal is piezoelectric (more than quartz) and on pressure the pointed end becomes positive (25). It is very soluble in water, 100 g r a m of the saturated solution containing 38 grams ( O O ) , 39 grams (12'), and 70 grams (looo)of quebrachitol (35). The solubility in boiling alcohol is relatively good, but it does not dissolve in ether (6, 58). It dissolves in acetic acid (34) and easily in pyridine (17). As it does not lower the surface tension of water, it is of no valuc as a wetting or spreading agent and it is useless for the prepamtion of emulsions of oleic acid, soybean oil, etc., in water (49). Furthermore, it is no antioxidant for rubber ( 2 ) . PHYSIOLOGICAL PROPERTIES. Quebrachitol has a sweet, taste (38). In man when administered by mouth it does not prevent hypoglycemia and does not raise the sugar content of the blood. I n experiments with rats it does not augment the glycogen content of the liver. I t is less sweet than cane sugar; to obtain the same grade of sweetness two or three times more are necesuary, but as this causes colic and diarrhea, its use as a sweetening agent is not recommended (26).

-

CHEMICAL REACTIONS \ ~ I T HII\'ORGANIC CONPOUNDS.Quebrachitol is not

changed bv warming with dilute hydrochloric or sulfuric acid. By treatment with water under a high pressure a t a high temperature the methyl group is partly split off (14). With concentrated hydriodic a d solution the methyl group is completely removed and Ginositol is formed (66). Oxidation with concentrated nitric acid gives leuconic acid

/co-co

co \

4H20

I

co-co

a compound that decomposes a t 160" (the pentoxime melts at 172"), and by reduction is transformed into croconic acid (9, 1 4 ) :

/I

COH-CO

co I \

I

1

I

COH-CO

A patent (11) describes the preparation of the pentanitrate by treatment with concentrated nitric and concentrated sulfuric acids a t 10" to 25"; only its explosiveness is mentioned. The hexaphosphoric ester of mesoinositol is phytin, the compound in vhich the green plant stores its phosphorus. In this connection Contardi (14) mentions quebrachitol pentaphosphoric acid, [cY]D - 23.28", and its barium salt, C,H90z1P~Ba6.5H20. Bruni's (9) directions are as follows: One mole of quebrachitol and 5 moles of crystallized phosphoric acid are heated at 130" to 150" C. and a pressure of 5 cm. until the theoretical amount of water has distilled, a sirupy mass remaining behind. According to him, Contardi isolated calcium and magnesium salts of this quebrachitol pentaphosphoric acid from the seeds of Hevea and prepared those salts by evaporating the serum of Hevea latex, heating the residue with phosphoric acid, and neutmlizing with bases (8). He states that the calcium and magnesium salts, have a physiological effect analogous to that of phytin. Quebrachitol reduces ammoniacal solutions of silver oxide (38) and the carbon obtained from it by treatment with zinc chloride anti

INDUSTRIAL AND ENGINEERING CHEMISTRY

January 1951

143

TABLE I. PREPARATION OF QUEBRACHITOL FROM LATEXSERUM I

I1

215 liters of serum from undiluted latex

308 liters of serum

71

Sirupa Treatment chary

950 grams of crude product

Sirup"

from diluted latex

111 204 liters of serum from diluted latex

7.25 kg. of sirup Treatment charc?

5.10 kg. of sirup 2 Treatment h cham?

71

1490 grams of crude product

1

5.4 kg. of sirup

2 X treatment with charcoal,

ypor\

Q l 9 grams

2022 grams

of crystals

of sirup

Humidity 4.34% h1.p. 189-1910 c.

/\

3313 grams of crystals a

Quantity not determined.

hydrochloric acid a t 200' C. shows the x-ray picture of graphite (23).

WITH ORGANIC COMPOUNDS. It is stated by Tanret (58) that quebrachitol is not precipitated by basic lead acetate but (if the solution is not dilute) is precipitated by ammoniacal lead acetate. Contardi ( 1 5 ) obtained with formaldehyde a sirup that does riot crystallize, which splits off formaldehyde with ammonia. The following esters are known: The pentsacetyl ester has a melting point of 96-97', [ a ] D 25.1', and is soluble in chloroform and to a small extent in alcohol ( 1 , 9, 31). The isovaleric ester is a liquid, the laurinic ester has a melting point of 32' and the palmitic ester a melting point of 58' (24). The f i s t is prepared with acetic anhydride and sodium acetate, and the others with the acid chloride.

-

d

-

Sirup"

TECHNICAL APPLICATIONS

Some patents are known in which a use of quebrachitol is indicated. Bruni (8) prepared salts of phosphoric acid esters of quebrachitol, the physiological action of which was comparable with that of phytin. The pentanitrate is used as a component of explosives-for example, in a mixture with cellulose nitrate, glycol dinitrate, or nitroglycerol (11). Canadian Industries, Ltd. ( I O ) , prepared a mixed explosive by nitration of a mixture of quebrachitol and polyalcohols. Imperial Chemical Industries, Ltd., has patents concerning the preparation of drying oils (12). Resins are obtained by condensing quebrachitol with phthalic anhydride alone or in the presence of linseed oil, or fatty acids with or without tung oil. Semidrying oils rare prepared by heating 19.4 parts of quebrachitol and 150 parts of linolic acid for 6 hours a t 240" to 250", carbon dioxide being led through. Then the low boiling fractions are distilled at a pressure of 10 to 20 mm. and the residue is dissolved in the common solvents (alcohol,

turpentine). No indications are found in the literature that quebrachitol is really used in technical products. POSSIBLE TECHNICAL USE O F QUEBRACHITOL

COMPARISON WITH ANALOGOUS COMPOUNDS.Quebrachitol contains an inactive methoxy group and five secondary alcohol groups. A priori no special properties can be expected and it must be compared with other water-soluble polyalcohols, the most important of which are glycerol, glycol, mannitol, sorbitol, ,pentaerythritol, and inositol. As it contains only secondary alcohol groups, i t should react somewhat more slowly than glycerol, glycol, or pentaerythritol, but its reaction velocity should be comparable with that of mannitol, sorbitol, and inositol, and the high temperature resistance of products made from it should be somewhat better than that of mannitol and sorbitol. Its competitor in every respect will be inositol; almost every outlet of inositol will be an outlet for quebrachitol and vice versa. In this connection it is important t h a t mesoinositol can be prepared cheaply in large quantities from calcium phytate, the precipitate made by adding lime to starch factory steep water, the dilute acid solution in which corn had been soaked in manufacturing starch (4, 5, 21, 38). From this it follows that inositol can be prepared on a technical scale, but whether this is done, and what the price and the technical uses are, is not known to the author [Gibbons and Gordon ( I S ) ] PREPARATION. G. J. v.d. Bie of the Indonesian Institute of Rubber Research, Buitenzorg, Java, kindly furnished an amount of quebrachitol prepared from rubber serum according to the method of Rhodes and Wiltshire ( 5 5 ) and gave the following description: At first coagulation serum of a n undiluted latex was used. The

INDUSTRIAL AND ENGINEERING CHEMISTRY

144

serum was evaporated to 10% of its original volume and the proteins were removed. The filtrate was treated with decolorizing carbon. At first charcoal, treated with dilute acetic acid, and afterwards a mixture of 1 part of active carbon and 2 parts of charcoal were used. As the crystallization from undiluted latex gave more difficulties than from diluted latex, for the following experiments diluted latex was used. The centrifugation of the sirups in a drum centrifuge took much time. Table I shows that 215 liters of undiluted latex serum gave 1650 grams of a crude product (0.8%), and 512 liters of a diluted serum eqiuivalent to 340 liters of undiluted serum gave 3573 grams of crude quebrachitol (1.3%). The yield of pure quebrachitol from 555 liters of latex serum was somewhat more than 2000 g r a m or 0.36%. Rhodes and Wiltshire give a yield of 0.2% from 1000 gallons of diluted latex, but they do not mention the dilution of their latex. ESTIMATED COSTSOF PREPARATION. For an approximate calculation of cost price, figures are based on a plant with a capacity of 1000 kg. of dry rubber per day. Required are 3000 liters of estate latex of 33'3,ruhber content, containing 45 kg. of quebrachitol (based on 1.5% quebrachitol content). The latex will be diluted to a 20% rubber-containing fluid or a total of 5000 liters, containing 45 kg. of quebra.chito1. The coagulun~(1000 kg. dry), however, binds 100% serum (1000 liters). Therefore 3000 liters of serum containing 3/5 X 45 = 27 kg. of quebrachitol are left. The maximum solubility of quebrachitol in rrater a t 20' to 30' C. is 40%. Therefore an installation is required capable of concentrating 3000 liters of serum of 0.9% quebrachitol content to a 40% quebrachitol solution, thereby evaporating 2930 kg. of water. In order to obtain a sufficient,ly large heating surface it will be necessary to use a flame tube vessel. Because such a vessel is hard to clean between the flame tubes, it is advisable to concentrate to not more than IO%, maintaining the fluid level well above the tubes. The total capacity above the tubes must therefore be figured a t minimum of 3000 liters and a total content of 6000liters. The lO%solution obtained thereby can be further concentrated to 40% in open containers by means of furnace gases. The following working method is suggested. An 11-day working period is scheduled. The first day the evaporator is filled with 6000 liters of serum and evaporates 3000 liters, leaving 3000 liters containing 54 kg. of quebrachitol. Every day 3000 liters of serum are added to this concentrate and 3000 liters of water are evaporated. After the 10th day there will be left 3000 liters of concentrate containing 54 (9 X 27) = 297kg. of quebrachitol or approximately 10%. The next 24 hours are used to draw and clean the evaporator and the 3000 liters of new serum are kept in store. This gives 6000 liters of serum for the next day's filling. This procedure requires an evaporating capacity of 125 liters per hour in the tube evaporator or a t a normal water temperature of 20' C. 75,000 calories. The practice has shown that in order to produce the necessary heat, approximately 900 kg. = 2 to 3 stapel meters (an Indonesian measure) of wood are required. At the end of an 11-day cycle there are 3000 liters of a 10% concentrate, which must be further evaporated in the next 11 days until 750 liters of a 40y0 concentrate (containing approximately 300 kg. of quebrachitol) are left. In order to effect this further concentration a flat open container, 1.5 X 0.8 X 2.5 meters is built in, in the smoke channel. The fluid is left in these vessels until 750 liters remain. One evaporating vessel should be sufficient to reach the 40% concentration within 10 days, depending upon the chimney temperature. It may be necessary to add a second vessel. The costs for an 11-day cycle are estimated as follows (florins):

Total cost per 1 kg. of quebrachitol is 278/297 = 0.94, or, including centrifuging, f. 1 per kg. Any sugar mill in Java may be willing to do the centrifuging a t the end of a campaign. Refining costs cannot yet be estimated. I t is doubtful whether a t a selling price of f. 2 per kg. (or U. S. 0.37 to 0.38 cent per pound) the manufacturingof quebrachitol on an industrial scale will be a paying proposition (taking into consideration freight, overhead, packaging, profit, etc.). The prices were calculated before the devaluation of the florin.

A new calculation indicates that a cost price of 1.3 (Indonesian florins) per kg. does not change the selling price, which remaina U. S. 0.37 to 0.38 cent per pound.

TECHNICAL CONSIDERATIONS. -4t the moment it is n.ot probable that low-molecular derivatives of quebrachitol will find a large market. It has the properties of a polyalcohol, and derivatives of polyalcohols such as mannitol do not find much use. If the price became less than that of glycerol it could replace this compund to some extent. In the la.cquer industry polyalcohols are used for the preparation of synthctic resins of the following typcs : Esterified colophony, modified with phenolic or maleic acid resins. Phthalic acid resins modified with vegetable oils. Plastified urea or phenolic resins. The alcohols commonly used are glycerol and pentaerythritol. Sorbitol, for example, never was used on a large scale, RS it is not stable a t the temperatures of 240.' to 280' C. used with the technical methods described above. As quebrachitol seems to be stable a t higher temperatures, it might be used for the preparation of these lacquers, but the reaction velocity of the secondary hydroxyl groups would be expected to be somewhat low. Thr following experiments were madc: ESTERIFICATION WITH COLOPHONY. Colophony (acid value 170, softening point 73" C. j was heated with the theoretical amount of quebrachitol (12%) and with an excess under the conditions used for the eaterification of glycerol (stirring, carlmu dioxide atmosphere ). Reaction Time _ and _ ~Teinperature ~_____ Hours C. @

12% 1

+

5

11 11

si+4: +E

I

Labor

2 men a t f. 2 per day, 11 days

Firemen in total Control a n d administration 30 meters of fire wood a t f . 3 per meter Depreciation a n d interest, f . 2000 per year Total cost of 297 kg. of quebrachite

22 36 60 90 70

%

Vol. 43, No. 9

Acid V d u e

QUEBRACHITOL

240 240 240 240 260 240

127

280

55

65

60

63

260

Color of reaction product, medium dark 20% 3 3

'ioftening

1 2

QUEBRACHITOL

270 270 240

62

point 99' C., color dark

290 290

5 290 Dark product 17%

QUEBRACHITOL

1 5 5

++'105

250 260 250 270

250 270

i- 1%

43

136 70 59

IATHIUM hiAPHTHENATE

126 62

31 27

The color of the product was nearly as light as the color of the glycerol ester of colo h o w prepared under the same circumstances. When the tteoretical amount of glycerol (calculated from the acid value) was added and the mixture was again heated for 2 hours at, 250" C., the acid value became as low as 9, but the resin was dark, turbid, and somewhat sticky.

INDUSTRIAL AND ENGINEERING CHEMISTRY

January 1951

Acid . Value ___.

Without With 1% Reaction Time and Temperature lithium lithium Hours ' C. naphthenate naphthenate 16% QUEBRACHITOL GLYCEROL 4 230 139 139 4 230 i l l 240 44 26 4 230 $5 270 55 31 The necessary amount of glycerol (calculated from the acid value 10% excess) waa added. 1.6 270 49 35 1.5 270 4-6 250 14 7 Clear dark brown product with a softening point (Kraemer-Sarnow) of 105' C.

+

'

+

16%

QUEBRACHITOL,

+

GLYCEROL 0.5% LITHIUMNAPHTEEKATP Acid Value

6 270 10 270 Clear light product Theoretical amount of glycerol added 4

Clear, rather dark product 13 Clear, dark product

45

31

260

20

260

17

From these experiments it can be concluded that the esterification of colophony with quebrachitol is slower than with glycerol or pentaerythritol. AB for practical use a resin must be obtained with an acid value below 16, the product of the reaction must be further esterified with glycerol. A good esterification catalyst shortens the reaction time, but esterification of the residual carboxyl groups with glycerol remains necessary. The color of the resins is darker than that of pure glycerol colophony esters, but when prepared on a technical scale the color of the resins will be lighter than those prepared in the laboratory.

ESTERIFICATION WITH LINOLEIC ACIDAND WITH LINSEEDOIL.

Esterification with Linoleic Acid. A mixture of 100 parts of linoleic acid and 23 parts of quebrachitol was heated for 5 hours at 200' C. (stirring, carbon dioxide atmosphere). No reaction occurred. Now 1.5 parts of lithium naphthenate were added. After heating for 2 hours at 230" C . a clear dark brown oil was obtained (acid value 19). The theoretical amount of water plus 300/, had distilled over; this excess of water must have been formed by etherification. Again 2.3 parts of quebrachitol were added and the mixture was heated for 2 hours a t 230" C. The clear but intense dark brown li uid had an acid value of 12. Re-esterification with Linseej Oil. No reaction was obtained when 100 parts of linseed oil were heated with 14 parts of quebrachitol for 7 hours a t 200' C. and then 3 hours a t 250' C .

The esterification products of a polyalcohol with linoleic acid are intermediates in the production of phthalate resins modified with vegetable oils. I t will be a technical objection that the reaction product of quebrachitol with linoleic acid is very dark. PLASTICIZED UREARESINS. A preliminary experiment was made in which quebrachitol was condensed with a dibasic carboxylic acid and a condensation product of urea and formaldehyde at a maximum temperature of 160' C. The technical properties of the resin (velocity of drying on heating in a muffle oven, elasticity, hardness, and color of the film) are satisfactory, but somewhat less than those of the resins prepared with the usual alcohols. CONCLUSIONS

Quebrachitol, a beautifully crystallizing cyclic polyalcohol with the properties of mannitol, sorbitol, or inositol could be obtained In practically unlimited quantities from rubber serum a t a price of about f.2 per kg., or 37 to 38 cents a pound. Experiments showed that it can be used in the preparation of different lacquers. ACKNOWLEDGMENT

The author wishes to thank J. Rinse, Chemisch-Technisch Adviesbureau Dr. J. Rinse, W. Dorst, Haarlem, Holland, and F. T. Bokma for their cooperation in preparing this paper,

145

BIBLIOGRAPHY

(1) Adams, R., Pease, D. C., and Clark, J. H., J . Am. Chem. SOC., 62,2194 (1940). (2) Altman, R. F. A., Rubber Chem. Technol., 21, 752, 757 (1948). (3) Angelis, Maria de, Atti SOC.ital. Sci. natur. Milano, 69, 39-41 (1930). (4) Bartow, E., and Walker, W. W., IND.ENG.CHEM.,30, 300 (1938). (5) Bartow, E., Walker, W. W., and Hoglan, F. A., U. S. Patent 2,112,533 (1938); Atti X congr. intern. chim., 4, 561-5 (1939). (6) Bourquelot, E., and Frichtenholz, A., Compt. rend., 155, 615 (1912). (7) Bourquelot, E., and Hbrissey, H., Ibid., 168, 414 (1919). (8) Bruni, G., Brit. Patent 216,982; Chem. Zentr., 1926, 11, 828. (9) Bruni, G., Indian Rubber J., 68, 110 (1924). (10) Burke, C. E., and MacGili, R. (to Canadian Industries), Can. Patent 326,147; Chem. Zentr., 1934, 11, 1406. (11) Burke, C. E., and MacGiil, R. (to E. I. du Pont de Nemours b Co.), U. 8. Patent 1,962,172 (1934); Chem. Zentr., 1935, I , 2121. (12) Burns, R., and Imperial Chemical Industries, LM., Brit. Patent 408,597 (1934); French Patent 770,421; Chem. Zentr., 1935. I, 1953. (13) Clark, E. P., J . Am. Chem. SOC.,58, 1009 (1936). (14) Contardi, A., Ann. chim. applicata, 14, 281 (1924); Chem. Zentr., 1925, I, 533. (15) Contardi, A., and Cicocca, B., Rend. kt. Zombardo sci., 69, 1057-66 (1936); Chem. Zentr., 1937, 11, 234.

Dangschat, Gerda, and Fischer, H. 0. L., Naturwissenschaften, 30, 146 (1942).

Dillen, L. R. van, Arch. Rubber cult. Nederland. Indie, 6, 263, 268 (1922).

Gibbons, J. P., and Gordon, K. M., IND.ENO. CHEM.,42, 1591 (1950).

Goodson, J. A., Biochem. J., 16, 489 (1922). Gorter, K., Arch. Rubbercult. Nederland. Indie, 1, 375 (1917). HogIan, F. A,, and Bartow, E., IND. ENQ. CHEM., 31, 749 (1939); J . Am. Chem. Soc., 62, 2397 (1940). Jong, A. W. K. de, Rec. trav. chim., 25, 48 (1906). Levi, G. R., and Baroni, A., 2. Krist., A93, 156 (1936). Levi, T. G., Gam. chim. ital., 59, 550 (1929). Lucas, R., Compt. rend., 178, 1890 (1924). MoCance, R. A,, and Lawrence, R, D., Biochem. J . , 27, 986 (1933).

MoColm, E. M., and Haefele, J. W., IND. ENG.C H E M .40, , 31112 (1948).

McGavack, J., and Rinmore, G. B. (to Naugatuck Chemical Co.), U. S. Patent 1,758,616 (May 13, 1930); Chena. Zentr., 1931, I, 172. Malmy, M., and Bouvet, P., J . pharm. chim., (9) 2, (133), 5 (1942); Chem. Zentr., 1942, 11,924. Patterson, A. L., and White, T. N., 2. Krist., 78, 86 (1931). Pickles, 9. S., and Whitfield, R. W., J . Chem. SOC.Proc., 27, 5 4 (1911).

Ploetz, T., Angew. Chem., 56, 231 (1943). Plouvier, V., Compt. rend., 224, 1842 (1947); 227, 85, 22.5 (1948).

Posternak, T., Helv. Chim. Acta, 19, 1007 (1936); 25, 746 (1942). Rhodes, E., and Wiltshire, J. L., J. Rubber Research Inst. Malaya, 3, 160 (1931). Rimington, C., and Roets, G. C. S., Onderstepoort J. Vet. Sci. Animal I d . , 9, 193 (1937); Chem. Zentr., 1938, 11, 3408. Spoon, W., Arch. Rubbercult. Nederland. Indie, 9, 937 (1925). Tanret, C., Compt. rend., 109, 908 (1889). U. S.Rubber Co., U. S.Patent 2,378,141 (1945); Brit. Patent 572,128 (1947).

Vries, 0.de, "Bereiding en Eigenschappen van Plantagerubber," p. 18, Batavia, Vereinigung "Centraal Rubberstation," 1919. Whitby, G. S., Dolid, J., and Yorston, F. W., J . Chem. SOC., 1926,1448.

Woodman, R. M., and Rhodes, E., J . Rubber Research Inst. Malaya, 4, 153 (1932). R E C I I V ~November D 7, 1949. Communication 111 of The Rubber Foundation, Delft, Holland.