The Literature of Wood Naval Stores - ACS Publications - American

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The Literature of Wood Naval Stores H E R M A N SKOLNIK, H E R M A N I. ENOS, JR., and F R A N K H . G A R D N E R , JR. 1

Research Center, Hercules Powder Co., W i l m i n g t o n , D e l . 19899

Aside

from

the

technical

sheets of industry,

sales bulletins

naval stores. The literature out the general significant

in tracing

literature

Patent

the

industrial

erature was selected to provide portant

primary

chemistry

of

most important

literature

naval

development

of the best secondary

of

and The

wood

the

documents cited

lit-

the reader with the most im-

products.

literature,

literature

sig-

chemistry

of wood naval stores and of

stores

primary

particularly

This paper reviews

and developments.

data wood

through-

is

rosin and terpenes,

discoveries

on

is found

literature

of wood naval stores and of the

of naval stores products, the principal

literature

of this industry

literature.

naval stores and its products. nificant

and product

there is no specific

is

To

complement

a general

the the

bibliography

included.

It took the experience, knowledge, and efforts of H o m e r T . Yaryan to begin the history of the wood naval stores industry (108, 113). Yaryan had perfected a process to extract linseed oil from flaxseed with a petroleum fraction. In 1906, he adapted this process to the extraction of rosin from waste pine wood and stumps. In 1910, after several unprofitable starts, the Yaryan N a v a l Stores C o . plant at Gulfport, M i s s , began regular operations. A second plant was built at Brunswick, G a , i n 1911 (80). T h e plant at Brunswick, G a , and one at Hattiesburg, Miss. (1920) are the centers of Hercules wood naval stores production. The Newport C o . (now H e y d e n Newport C h e m i c a l Corp.) entered wood naval stores through plants at Bay Minette, A l a . (1913) and Pensacola, F l a . ( 1 9 1 6 ) ; the M a c k i e Pine Products Co. at Covington, L a . ( 1 9 1 8 ) ; the Continental Turpentine and Rosin Corp. at L a u r e l , Miss. ( 1 9 2 1 ) ; A c m e Products C o . at D e Q u i n c y , L a . ( 1 9 2 2 ) ; Dixie Pine Products C o . at Hattiesburg, Miss. ( 1 9 2 8 ) ; more recently, Crosby Chemicals, Inc., at Picayune, Miss. (1937) and D e R i d d e r , L a . ( 1 9 4 6 ) ; and 1

Hercules Powder C o , Hattiesburg, Miss. 349 Smith; Literature of Chemical Technology Advances in Chemistry; American Chemical Society: Washington, DC, 1968.

350

LITERATURE

OF CHEMICAL TECHNOLOGY

Gulf N a v a l Stores C o . at Gulfport, Miss. (1946) and Andalusia, A l a . (1953) (74, 92). In 1957 G u l f N a v a l Stores built a plant at Arcadia, F l a . and subsequently closed their Gulfport, Miss, operation.


From the Stumps to Chips Stumps, w h i c h constitute the feed for the wood naval stores plants, are found i n the vast cut-over lands of Mississippi, Georgia, and Florida. A gasoline or naphtha extract of a typical virgin longleaf pine stump, w h i c h has remained i n the ground eight to 10 years after felling of the tree to weather off or rot away bark and sapwood, analyzes 1 8 % water, 5 % terpene oils, 2 2 % rosin, and about 4 % of a gasoline-insoluble resin. Harvesting the stump, during the early years, depended upon mule-power and dynamite. W i t h the advance of the motor age, mechanical stump pullers were designed to travel easily over the cut-over land and remove the whole stump (28, 73, 75, 82, 84, 97). Between 1920 and 1930, attempts were made to purify wood rosin by three approaches: distillation, extraction, and adsorption (24, 50, 54, 96). The most successful process was the selective solvent refining of F F wood rosin with furfural and w h i c h produced rosin of a l l color grades (48,49). This process is now operated commercially on a continuous basis (49, 58). Another commercial process for refining wood rosin uses fullers earth for adsorbing the color bodies from a naphtha solution of the F F wood rosin (78). Although the earlier processes involved a steam distillation prior to extracting wood chips, the patent literature is relatively large on directly extracting unsteamed chips—the process w h i c h has been used for many years. According to a recent patent (20), the use of ketone solvents i n extracting wood chips increases the efficiency of this step. The Constituents

and Composition

of Rosin

The literature on the composition of stump wood is relatively meager. Bottini (JO) thoroughly studied the composition of stumps as a function of tree and stump age. Other important studies are those of Dupont (25), Tolkachev (102), Schmidt-Nielsen and Refsnes (94), and Goldblatt and Burgdahl (36). The literature on the constituents and chemistry of rosin is voluminous. It was recognized as early as 1827 (105) that rosin is a mixture of resin acids. T h e name abietic acid was introduced i n 1826 by Baup (5) for the resin he isolated from Pinus Abies. U n t i l very recently, the literature has been dominated by confusion, errors, and misleading generalities. The difficulty i n many studies was the inability to differentiate between a mixture and a single component. Readers of the literature written prior to about 1935 should be alert to this situation. The major contributors who elucidated the structures of rosin components were: A . Tschirch, whose most important contribution was consolidating the literature as w e l l as his early work on isolating different acids from American gum rosin (103).

Smith; Literature of Chemical Technology Advances in Chemistry; American Chemical Society: Washington, DC, 1968.

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A . Vesterberg, who b y fractional crystallization of the sodium salts of gum rosin, was able to isolate levopimaric and pimaric acids (1887) (107). G . Dupont, who isolated the first relatively pure abietic acid by means of its 3:1 salt a n d reported the instability (isomerization) of the acid com ponents (26).


F . Balas, who d i d considerable work on the amine salt separation of resin acids, but was unsuccessful i n applying the technique (3). L . Ruzicka (86), who proved the structure of abietic acid first proposed by Fieser and C a m p b e l l . H e also d i d considerable work on proving the struc ture of levopimaric a n d pimaric acids. W . Sandermann, who d i d considerable work on proof of structure and studied biochemical origins b y radioactive tracer work ( 9 0 ) . S. Palkin and Ε. E . Fleck, who improved the isolation of abietic acid a n d first obtained dehydroabietic acid and prepared lactones (77). L . F . Fieser and W . P . C a m p b e l l ( 3 0 ) , who isolated pure dehydroabietic acid, a n d proposed the correct structure for abietic acid. G . C . Harris, who developed the amine salt method for isolating pure resin acids, isolated two new resin acids, neoabietic and isopimaric, b y combining the amine salt method with the Diels-Alder addition reaction of maleic a n hydride w i t h resin acids a n d ultraviolet spectra, and completed the structure proof of pimaric acid (still inconclusive from Ruzicka's w o r k ) , a n d isolated and characterized isopimaric acid (40, 41). Harris classified the acids into abietic-type a n d pimaric-type, as shown i n Figure 1. D . H . R. Barton (4) and W . J . K l y n e ( 5 7 ) , who established that the A - B ring union i n the di terpenoids is the same as i n tri terpenoids a n d steroids. G . Stork (100), who recently announced the first successful total synthesis of ^/-dehydroabietic acid. T w o new acids, palustric acid and caribeic acid, have been isolated re cently from gum rosin. T h e structure of palustric acid and its presence i n wood rosin have been established by R. V . Lawrence and co-workers at the N a v a l Stores Laboratory, U . S . Department of Agriculture (62, 63). Hampton ( 3 9 ) , who isolated a n d partially characterized caribeic acid, was unable to find it i n wood rosin and suggested that it is the factor responsible for the lesser tendency of gum rosin to crystallize. In recent years much attention has been given to stereochemistry of the pimaric acids b y E . O . Edwards (27) and R. E . Ireland (52), and to their role i n biogenesis of the di terpenoids by E . Wenkert (110). Also there have been excellent articles on applying new instrumental methods of analysis to resin acids: gas l i q u i d partition chromatography by J . A . H u d y (47), infra-red b y E . A . Cherches (18) a n d b y P . Kajanne (55), mass spectrometry by H . H . Brunn (13) and C . A . Genge (35), and nuclear magnetic resonance b y J. C . W . Chien (19). The current practice of most investigators and journals i n writing and numbering the diterpenoid ring structure is illustrated i n Figure 2 for abietic acid. T h e numbering is that of the phenanthrene ring system (see " T h e R i n g Index"), a n d the method of projection w i t h the ring I to the lower left is con-


352

LITERATURE O F CHEMICAL

Abietic Type

TECHNOLOGY

Pimaric-Type

CH=CH

C00H

Î00H

Abietic Acid

Levopimaric Acid


X

X

C00H

Palustric Acid

Ϊ00Η Isopimaric

CH=CH

Neoabietic Acid Figure 1.

Dehydroabietic Dihydroabietic Acid Acid Structural formulas

2

2

Pimaric Acid

of resin acids

(C $H COOH) 1

29

sistent w i t h the most commonly used method of projecting the structural formulas of the polyterpenoids and the steroids. I n the older literature, carbon atoms 4a, 4b, 8a, and 10a were numbered 12, 13, 14, and 11, respectively. T h e composition of the neutral fraction of rosin is not completely known. However, various investigators have isolated resin and fatty acid esters from the saponifiable portion of wood rosin. F r o m the unsaponifiable portion 3,5dimethoxystilbene (21), the aldehyde of isopimaric acid, and a trace of 1,8terpin (as terpin hydrate) have been isolated (40). Grades of wood rosin vary from X through W W ( water-white ), W G (water glass), Ν, Μ, Κ, I, H , G , F , E , a n d D w i t h increasing color. T h e official U . S . color standards are based on the work of Brice (11) and are speci fied i n terms of the 1931 Commission Internationale de l'Eclairage colorimetric coordinate system. A printed color chart was developed b y Hercules Power Company (44). Chemical

Properties of Rosin and Resin

Acids

The reactivity of resin acids essentially lies i n the carboxylic acid group and i n the double bonds. The literature on reactions of rosin and its component resin acids is vast and has been complicated b y the fact that rosin is a mixture of the several resin acids. Isomerization is particularly important inasmuch as i t occurs during the processing of rosin and increases its stability. Isomerization is carried out b y heating or by subjecting rosin to an acid medium. The maleic anhydride adduct of rosin is possible because this isomerization of the double bonds i n abietic acid occurs easily giving levopimaric acid at equilibrium (53, 59, 63, 85, 87, 88).



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Stores

Because it is unsaturated, rosin is highly susceptible to air oxidation, the products being dark i n color and insoluble i n oils and solvents. This property prevented wood rosin's entry into fields for which its other properties indicated potential usefulness. The hydrogénation of rosin, the literature of w h i c h is largely confined to patents, led to a product quite resistant to oxidation. It is quite apparent from the early literature that the hydrogénation proceeded smoothly and quickly to saturate one double bond; considerably more vigorous conditions and more effective catalysts were necessary to hydrogenate the second double bond (12, 16, 72, 88, 96). A commercial hydrogenated rosin, "Staybelite," differs from rosin i n having about 3 % as against 5 0 % of abietictype acids and 6 0 % as against 6% dihydroabietic acids. Rosin ester hydrogénation is likewise confined mostly to the patent literature and follows the processes described for hydrogenating rosin. Disproportionation of rosin also renders it less susceptible to oxidation by air. Although this reaction has been known for some time, it has been only relatively recently that commercial disprôportionated products, such as "Resin 7 3 1 " (Hercules), " G o r i t e " (Dixie Pine Products), " G a l e x " ( G . and A . L a b oratories), and " N i l o x Resin" ( N e w p o r t ) , have been available. Dehydroabietic acid is the main component of disprôportionated rosin, and its preparation and characterization has been the subject of several studies (30, 34, 42). The abietic-type acids i n rosin can be stabilized towards oxidation by polymerization. Since G r i i n and Winkler's (37) description of this process w h i c h used sulfuric acid, many patents have been issued involving many types of catalysts under varying conditions and with further treatment, such as hydrogénation and esterification. Oxonation of rosin and resin acids to yield rosin carbinols and hydroxymethyl resin acids was reported i n 1952 (61). The physical and chemical properties of commercial rosins and modified rosins are described i n technical trade bulletins and booklets such as those of Hercules Powder C o . The sodium salt of rosin has been used extensively for many years i n sizing paper (2), and its patent literature is quite extensive. L i m e d rosin, or calcium resinate, known since 1884 ( 5 6 ) , has found important use i n the protective coating industry as a varnish resin. Other heavy metal salts have been similarly applied.

/ CH \

CH

3

Ϊ00Η

Figure 2. Numbering of the diterpenoid ring struc ture of abietic acid



354

LITERATURE


Since M a l y (66) first announced i n 1865 the esterification of rosin, practi cally every conceivable ester has been prepared. M a n y have become commer cially important, for example, the glycerol ester of rosin ( 9 1 ) , known as ester gum, and the pentaerythritol ester of rosin (6). A significant commercial development was the continuous rosin esterification process to give alkyl rosin esters i n high conversion ( 1 5 ) . Results of a recent study of the mechanism of resin acid esterification were reported i n 1957 ( 9 8 ) . The carboxylic function i n rosin and rosin esters has been hydrogenated to the alcohol (60). In the process, the double bonds are partially hydrogen ated, and the product obtained is essentially hydroabietyl alcohol. T h e early literature, however, called the product abietyl alcohol ( 8 9 ) . Rosin has been converted to the nitrile ( 8 3 ) , w h i c h , i n turn, is readily hydrogenated to the amine. Both of these products are relatively new commer cially. Decarboxyation of rosin, accompanied by dehydrogenation, to give retene as the major product has been known since 1887 (1, 89, 107). Decarboxy lation to rosin o i l has been reported by H u m p h r e y ( 5 7 ) , Vassilev (106), and Whitmore and Crooks (111), i n which the main products were decarboxylated resin acids. Hydroxyethylation of rosin to produce an emulsion-breaking composition has been described by Moeller (71). T h e dark-colored, gasoline-insoluble fraction from the extraction of stump w o o d has found many uses. However, the literature on its composition and chemistry is limited to trade bulletins and patents. Constituents

of Turpentine

and Terpene Oils

W o o d turpentine is not the total terpene hydrocarbons from the wood extract. It is a distillation fraction enriched i n the lower-boiling terpene hydro carbons and is approximately 8 0 % α-pinene. The remainder consists of 5 % camphene and other bicyclics, and 1 5 % monocyclics including dipentene, p-menthane and p-cymene (76). Table I outlines the components of w o o d terpene oils (3-carene and heptane are found i n significant quantities only in Table I.

Components of Wood Terpene Oils

A. Turpentine

B. Pine O i l

1. Bicyclic terpenes a. a-Pinene b. Camphene c. 3-Carene

1. Bicyclic terpenoids a. Borneol b. α-Fenchyl alcohol c. Fenchone

2. Monocyclic terpenes a. Dipentene b. a-Terpinene c. Terpinolene

2. Monocyclic terpenoids a. a-Terpineol b. 0-Terpineol c. Terpin hydrate d. 1,8-Cineole

3. Miscellaneous hydrocarbons a. p-Cymene b. p-Menthane c. Heptane

3. Miscellaneous derivatives a. Estragole



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western stump w o o d ) . The extraction of one ton of chips yields on the average about 85-90 pounds of crude oils, of w h i c h about 50 pounds is turpentine (45,49). The greatest use of turpentine used to be as a thinner and solvent for paints, varnishes, and enamels. However, now the greatest demand for turpen tine is as a chemical for the synthesis of camphor, pine oil, terpineol, terpene resins, insecticides, and many other products. However, instead of using tur pentine for these chemical conversions, a distillation fraction enriched i n the desired constituent is used: for example, α-pinene, or dipentene. T h e fact that distillation fractions enriched i n dipentene are by no means pure often has not been recognized i n publications. Chemical Properties of Terpene

Hydrocarbons

The following discussion pin-points the reactions of terpene hydrocarbons which have arisen at least i n part from research on products from the wood naval stores industry. The bicyclic terpenes, particularly «-pinene and camphene, are very i m portant commercially. Their uniqueness lies i n their ready conversion to mono cyclic terpenes and i n their rearrangement reactions. A typical example is the conversion of α-pinene to camphene and other bicyclic and monocyclic terpenes (43, 69). Camphene readily adds acids to form isoborneol esters, for example, the formate, w h i c h is readily converted to isoborneol. M a n y patents have been issued for preparing camphor, and a plant for its manufacture has been i n pro duction since 1932 (38). Camphene is an intermediate i n the production of two commercially important insecticides: Thanite (isobornyl thiocyanoacetate) and toxaphene (chlorinated camphene) (8, 14). Derivatives of pinene w h i c h have been of interest recently are pinic and pinonic acids (33, 99). Terpene-derived resins are produced by reaction of terpene hydrocarbon* or alcohols w i t h phenol i n the presence of acid catalysts, followed by reaction of the substituted phenol w i t h formaldehyde (104). Polymerization of terpenes by metal coordinate catalyst systems has been described recently (68). Terpenes react with sulfur to form complex sulfurized compounds, w h i c h have found wide use as extreme-pressure lubricant additives (46, 109). A i r oxidation of terpenes and terpene derivatives yields hydroperoxides (32, 93, 101, 112). p-Menthane hydroperoxide is produced commercially by this process (29). U n d e r some oxidation conditions hydroperoxides are not isolated, but are only intermediates providing other oxidation products. F o r example, the oxidation of terpinolene i n aqueous dispersion gives three isomeric triols ( 9 ) . T h e menthadienes, for example, dipentene, can be dehydrogenated to p-cymene or disprôportionated to a mixture of p-cymene and p-menthane. The p-cymene can be air oxidized to the hydroperoxide (65) and converted to 8-hydroxycymene (64, 65) or p-cresol (31).


356

LITERATURE

OF CHEMICAL

TECHNOLOGY

The cracking of dipentene yields isoprene (7, 22, 24). The menthadienes, for example, terpinene, terpinolene, react w i t h maleic anhydride to give valuable adducts (23, 38, 79).


Pine Oil and Terpene

Alcohols

The most distinctive product of wood naval stores is pine o i l , w h i c h is not found i n the exudation of living pines. Pickett and Schantz (81) reported the components of pine oil to consist of terpene hydrocarbons, «-terpineol, borneol, fenchyl alcohol, and terpene ethers. T h e constituents of pine o i l , that is, the alcohols, ketones, and ethers, have an extensive literature of organic chemistry. The chief commercial source of cyclic terpene alcohols is pine o i l . A n efficient distillation of pine o i l yields commercial «-terpineol. Pine o i l , a n d also α-terpineol, has become so valuable that it has been supplemented b y a syn thetic pine o i l , prepared b y the hydration of α-pinene i n the presence of acids ( 9 5 ) . Dehydration of 1,8-terpin with acid catalysts (90) yields a mixture of α, β, and γ-terpineols known as "terpineol extra" or "prime terpineol." 1,8Terpin hydrate is obtained from the crude oils recovered by steaming the residual rosin after distilling the more volatile terpenes a n d terpenoids (67). It is also produced synthetically b y the hydration of or pinene. The literature on the uses and applications of pine o i l a n d terpineol is large. A summary report of past and current practices a n d recommendations for the future i n writing structural formulas and i n numbering a n d naming the monoterpenes was prepared by M . W . Grafflin for the American Chemical Society's Nomenclature Committee and published as A D V A N C E S I N C H E M I S T R Y S E R I E S N O . 14.

Summary The literature of wood naval stores begins with the Yaryan patents and is dominated mostly b y the industrial developments and research of a relatively few American companies and by the publications of T h e N a v a l Stores Station, U . S. Department of Agriculture. T h e literature has borrowed heavily from and contributed generously to the general literature of organic chemistry and chemical engineering. Principal discoveries and developments i n w o o d naval stores have been related to their significant and critical literature. I n addition to specific documentation of these discoveries and developments, a bibliography of the general naval stores literature is included. Chemists new to the chemistry of terpenes and resin acids may gain an excellent background b y consulting the references marked w i t h an asterisk i n the bibliography of this paper. Literature

Cited

(1) Aktiengesellschaft für Chemishe Industrie, Ger. Patent 43,802 (Sept. 15, 1887); Chem. Zentr. 1888, 1372. (2) Bacon, W. N., Brit. Patent 28,886/190 (Dec. 18, 1906).



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(3) Balas, F., Collection Czechoslov. Chem. Communs. 1, 306,352, 401 (1929); and earlier with Ruzicka. (4) Barton, D. H. R., J. Chem. Soc. 1948, 1197. (5) Baup, S., Ann. chim. phys. 31, 108 (1826). (6) Bent, L. N., Johnston, A. C. (to Hercules Powder Co.), U. S. Patent 1,820,265 (Aug. 25, 1931). (7) Bibb, C. H. (to Newport Industries, Inc.), U. S. Patent 2,386,537 (Oct. 9, 1945). (8) Borglin, J. N. (to Hercules Powder Co.), U.S. Patent 2,217,611-15 (Oct. 8, 1940). (9) Borglin, J. N., Lister, D. Α., Lorand, E. J., Reese, J. E., J. Am. Chem. Soc. 72, 4591, (1950); Lorand, E. J., and Reese, J. E., Ibid., 4595 (1950). (10) Bottini, O., Ricerca Sci. 10, 856 (1939); Chem. Abstr. 34, 4544 (1940). (11) Brice, Β. Α., J. Opt. Soc. Amer. 30, 152 (1940). (12) Brooks, B. T. (to Gulf Refining Co.), U.S. Patent 1,167,264 (Jan. 4, 1916). (13) Bruun, H. H., Ryhage, R., Stenhagen, E., Acta Chem. Scand. 12, 1355 (1958). (14) Buntin, G. (to Hercules Powder Co.), U. S. Patent 2,565,471 (Aug. 28, 1951). (15) Butts, D. C. (to Hercules Powder Co.), U.S. Patent 1,979,671 (Nov. 6, 1934). (16) Byrkit, R. J., Jr. (to Hercules Powder Co.), U. S. Patent 2,174,651 (Oct. 3, 1939). (17) Campbell, W. P., Todd, D., J. Am. Chem. Soc. 64, 928 (1942). (18) Cherches, Ε. Α., et al, I. Z. Vest Akad. Nauk. S.S.S.R., Ser. Fiz. 23, 1219 (1959). (19) Chien, J. C. W., J. Am. Chem. Soc. 82, 4762 (1960). (20) Cook, G. H., Jr. (to Hercules Powder Co.), U. S. Patent 2,757,170 (July 31, 1956). (21) Cox, R. F. B., J. Am. Chem. Soc. 62, 3512 (1940). (22) Davis, B. L., Goldblatt, L. Α., Palkin, S., Ind. Eng. Chem. 38, 53 (1946). (23) Diels, O., Alder, K., Ann. 460, 98 (1927). (24) Donk, M . G., U.S. Patent 1,219,413 (Mar. 13, 1917). (25) Dupont, G., Compt. rend. 172, 923, 1184, 1373 (1921); Bull. soc. chim. 29, 718, 727 (1921); 35, 394, 879, 890, 1209 (1924). (26) Dupont, G., Bull. inst. pin 1926, 517. (27) Edwards, Ο. E. et al., Can. J. Chem. 37, 760-74 (1959); J. Org. Chem. 27, 1930-1 (1962). (28) Edwards, W. J., U.S. Patent 2,295,458 (Sept. 8, 1942). (29) Farkas, Α., Stribley, A. F., Jr. (to Union Oil Co.), U. S. Patent 2,430,864-5 (Nov. 18, 1947). (30) Fieser, L. F., Campbell, W. P., J. Am. Chem. Soc. 60, 159, 2631 (1938); 61, 2528 (1939). (31) Filar, L. J., Taves, M . A. (to Hercules Powder Co.), U. S. Patent 2,663,735 (Dec. 22, 1953). (32) Fisher, G. S., Stinson, J. S., Ind. Eng. Chem. 47, 1368 (1955). (33) Fisher, G. S., Stinson, J. S., Ibid. 47, 1569 (1955). (34) Fleck, Ε. E., Palkin, S., U. S. Patent 2,239,555 (Apr. 22, 1941). (35) Genge, C. Α., Anal. Chem. 31, 1850 (1959). (36) Goldblatt, L. Α., Burgdahl, A. C., Ind. Eng. Chem. 44, 1634 (1952). (37) Grün, Α., Winkler, R., Chem. Umschau Gebiete Fette, Ole, Wachse u. Harze 26, 77 (1919). (38) Gubelmann, I., Elley, H. W., Ind. Eng. Chem. 26, 589 (1934). (39) Hampton, B. L., J. Org. Chem. 21, 918 (1956). (40) Harris, G. C., Sanderson, T. F., J. Am. Chem. Soc. 70, 334 (1948). (41) Harris, G. C., Sanderson, T. F., J. Am. Chem. Soc. 70, 3870 (1948). (42) Hasselstrom, T., Brennan, Ε. Α., Hopkins, S., Ibid. 63, 1759 (1941). (43) Henke, C. O., Etzel, G. (to Du Pont de Nemours, Ε. I. & Co.), U. S. Patent 1,901,746 (Mar. 14, 1933); 2,318,391 (May 4, 1943). (44) Hercules Chemist No. 19, 9 (1949). (45) Hightower, J. V., Chem. Eng. 54, 119 (1947). (46) Holt, L. C. (to Du Pont de Nemours, Ε. I. & Co.), U. S. Patent 2,443,823 (June 22, 1948). (47) Hudy, J. Α., Anal. Chem. 31, 1754 (1959). (48) Humphrey, I. W., Trans. Inst. Chem. Engrs. 9, 40 (1931). (49) Humphrey, I. W., Ind. Eng. Chem. 35, 1062 (1943).



358

LITERATURE


(50) Humphrey, I. W. (to Hercules Powder Co.), Can. Patent 284,987 (Nov. 20 1928); U. S. Patent 1,715,083 (May 28, 1929); 1,715,086 (May 28, 1929). (51) Humphrey, I. W. (to Hercules Powder Co.), U. S. Patent 1,852,244 (Apr. 5, 1932) (52) Ireland, R. E., et al., J. Org. Chem. 28, 6, 17, 23 (1963). (53) I. G. Farbenindustrie Akt.-Ges., Brit. Patent 355,281 (Aug. 12, 1931); U. S. Patent 2,039,243 (Apr. 28, 1936). (54) Kaiser, H. E., Hancock, R. S., Ind. Eng. Chem. 22, 446 (1930). (55) Kajanne, P., Honkanen, E., Paperi ja Puu 39, 171 (1957). (56) Kissel, Α., U. S. Patent 303,436 (Aug. 12, 1884). (57) Klyne, W., J. Chem. Soc. 1953, 3072. (58) Langmeier, Α., Hancock, R. S. (to Hercules Powder Co.), U. S. Patent 2,070,125 (Feb. 9, 1937). (59) Lawrence, R. V., Eckhardt, O. S., U. S. Patent 2,628,226 (Feb. 10, 1953). (60) Lazier, W. A. (to Du Pont de Nemours, Ε. I., & Co.), U. S. Patent 2,358,234-5 (Sept. 12, 1944). (61) Levering, D. R., Glasebrook, A. L., Ind. Eng. Chem. 50, 317 (1958). (62) Lawrence, R. V., et al., J. Am. Chem. Soc. 77, 2823 (1955);82, 1734 (1960). (63) Lawrence, R. V., et al., J. Am. Chem. Soc. 77, 6311 (1955); 78, 2015 (1956). (64) Lorand, E. J. (to Hercules Powder Co.), U. S. Patent 2,484,841 (Oct. 18, 1949); with Reese, J. E., 2,491,926 (Dec. 20, 1949). (65) Lorand, E. J., Reese, J. E. (to Hercules Powder Co.) U. S. Patent 2,548,435 (Apr. 10, 1951). (66) Maly, R. L., J. prakt. Chem. 96, 145 (1865). (67) Marchand, R., U. S. Patent 1,411,859 (Apr. 4, 1922). (68) Marvel, C. S., Kinder, P. E., J. Polymer Sci. 61, 311 (1962). (69) Meerwein, H., Ulffers, F., Erbe, R., Aichner, F., Klaphake, W. (to ScheringKahlbaum A. G.), U. S. Patent 1,985,792 (Dec. 25, 1934). (70) Meuly, W. C., U. S. Patent 2,088,030 (July 27, 1937). (71) Moeller, Α., U. S. Patent 2,307,058 (Jan. 5, 1943). (72) Montgomery, J. B., Hoffman, A. N., Glasebrook, A. L., Thigpen, J. I., Ind. Eng. Chem. 50, 313 (1958). (73) Murry, J. T., and Patterson, C. B., U. S. Patent 1,663,277 (Mar. 20, 1928). (74) Naval Stores Review was used as source material. (75) Ollsson, V., Swed. Patent 54,628 (May 23, 1923). (76) Palkin, S., Chadwick, T. C., Matlack, M . B., U. S. Dept. Agriculture, Technical Bull. 596 (Dec. 1937). (77) Palkin, S., Fleck, Ε. E., Sci. 85, 126 (1937); J. Am. Chem. Soc. 59, 1593 (1937); 60, 921, 2621 (1938); 61, 247, 1230 (1939). (78) Palmer, R. C., Chem. & Met. Eng. 41, 456 (1934). (79) Peterson, E. G. (to Hercules Powder Co.), U. S. Patent 1,993,025 (Mar. 5, 1935); 1,993,031 (Mar. 5, 1935). (80) Peterson, J. M., J. Chem. Educ. 16, 203, 317 (1939). (81) Pickett, Ο. Α., and Schantz, J. M., Ind. Eng. Chem. 26, 707 (1934). (82) Powelson, P. F. (to Hercules Powder Co.), U. S. Patent 2,302,801 (Nov. 24, 1942). (83) Putnam, S. T. (to Hercules Powder Co.), U. S. Patent 2,534,297 (Dec. 19, 1950). (84) Ramer, R. S. (to Hercules Powder Co.), U. S. Patent 2,233,821 (Mar. 4, 1941). (85) Ritchie, P. F., McBurney, L. F., J. Am. Chem. Soc. 71, 3736 (1949); 72, 1197 (1950). (86) Ruzicka, L. (a series of papers in Helv. Chim. Acta from 1922 on). (87) Ruzicka, L., Ankersmit, P. L., Frank, B., Helv. Chim. Acta 15, 1289 (1932). (88) Ruzicka, L., Bacon, R. G. R., Ibid. 20, 1542 (1937). (89) Ruzicka, L., Meyer, J., Ibid. 5, 581 (1922). (90) Sandermann, W., et al., Ber. 69, 2198, 2202 (1936); Fette u. Seifen 49, 578 (1942); Chem. Abstr. 37, 6669 (1943). Fette, Seifen, Anstrichmittel 59, 852 (1957). (91) Schaal, E., Brit. Patent 12,807 (Sept. 25, 1884); Ger. Patent 32,083 (July 31, 1885); U. S. Patent 335,485 (Feb. 2, 1886). (92) Schantz, J. M., Marvin, T., Ind. Eng. Chem. 31, 585 (1939). (93) Schenck, G. O., Eggert, H., Denk, W., Ann. 584, 177 (1953).



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(94) Schmidt-Nielsen, S., and Refsnes, E., Kgl. Norske Videnskab. Selskabs Forh. 15, 79 (1942). (95) Sheffield, D. H. (to Hercules Powder Co.), U. S. Patent 2,060,597 (Nov. 10, 1936); 2,178,349 (Oct. 31, 1939). (96) Sherwood, C. M., Cole, R. K., U. S. Patent 1,505,438 (Aug. 19, 1924). (97) Shimer, Α. Α., U. S. Patent 1,776,089 (Sept. 16, 1930). (98) Smith, T. L., and Elliott, J. H., J. Am. Oil Chem. Soc. 35, 692 (1958). (99) Stinson, J. S., and Lawrence, R. V., J. Org. Chem. 19, 1047 (1954). (100) Stork, G., and Schulenberg, J. W., J. Am. Chem. Soc. 78, 250 (1956). (101) Suzuki, K., Sci. Papers Inst. Phys. Chem. Research (Tokyo) 26, 560; 30, 662; Chem. Zentr. 1935, II, 526; 1937,I,2612. (102) Tolkachev, A. K., Mitt. Kirov. forsttech. Akad. (U.S.S.R.) 1940, No. 58, 93. (103) Tschirch, Α., Balzer, Α., Arch. Pharm. 234, 289 (1896). (104) Turkington, V. H., Allen I., Jr., Ind. Eng. Chem. 33, 966 (1941). (105) Unverdorben, O., Ann. Physik. 11, 27,230,393 (1827). (106) Vassiliev, G. Α., Chimie & industrie 47, 542 (1942). (107) Vesterberg, Α., Ber. 19, 2167 (1886); 20, 3248 (1887); 36, 4200 (1903); 38, 4125 (1905); 40, 120 (1907). (108) Walker, G. (to H. T. Yaryan), U. S. Patent 922,369 (May 18, 1909). (109) Watson, R. W. (to Standard Oil Co. of Indiana), U. S. Patent 2,445,983 (July 27, 1948). (110) Wenkert, Ε., J. Am. Chem. Soc. 81, 688 (1959). (111) Whitmore, F. C., Crooks, Η. M., J. Am. Chem. Soc. 60, 2078 (1938). (112) Widmark, G., Blohm, S. G., Acta Chem. Scand. 11, 392 (1957). (113) Yaryan, H. T., U. S. Patent 915,400-2 (Mar. 16, 1909); 934,257 (Apr. 14, 1909); 964,728 (July 19, 1910); (to Yaryan Naval Stores Co.), 992,325 (May 16, 1911); 1,120,007 (Dec. 8, 1914).

BIBLIOGRAPHY Books Aschan, O., "Naphtenverbindungen, Terpene und Campherarten," W . de Gryter & Co., Berlin, 1929. "Beilsteins Handbuch der Organischen Chemie," Springer-Verlag, Berlin. Fieser, L . F . and Fieser, M . , "Steroids," Reinhold, New York, 1959. Fieser, L . F . and Fieser, M . , "Topics in Organic Chemistry," Reinhold, New York, 1963. Gamble, Thomas, "International Naval Stores Year Book for 1929-30," Gamble, Savannah, Ga., 1929. Gamble, Thomas, "Naval Stores; History, Production, Distribution and Consumption," Review Publishing and Printing Co., Savanna, Ga., 1921. Gilman, Henry, ed., "Organic Chemistry, A n Advanced Treatise," vol. I V , p. 581, Wiley, New York, 1953. Grignard, Victor, éd., "Traite de Chimie Organique," vol. I l l , X V I , Masson, Paris, 1935, 1949. Kirk, R. E . and Othmer, D . F., eds., "Encyclopedia of Chemical Technology," 1st ed., Interscience, New York, 1954-1963. n

"Oils, Essential," vol. 14, p. 178, 1967 (2nd ed.) "Rosin and Rosin Derivatives," vol. 11, p. 779, 1953 "Terpene Resins," vol. 13, p. 700, 1954. ^"Terpenes and Terpenoids," vol. 13, p. 705, 1954 "Monoterpenoids—Acyclic," vol. 13, p. 708, 1954 *"Monoterpenoids—Cyclic," vol. 13, p. 720, 1954 *"Diterpenoids," vol. 13, p. 752, 1954 •"Turpentine," vol. 14, p. 381, 1955 Josephy, E . and Radt, F., eds., "Elseviers Encyclopedia of Organic Chemistry," vol. 12A, 13, Elsevier, New York, 1946, 1948. Mattiello, J . J . , ed., "Protective and Decorative Coatings," vol. 1, Wiley, New York, 1941.


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"Naval Stores Review International Yearbook," H . L . Peace Publications, New Orleans, «

1 9 4 8

·


"Nomenclature for Terpene Hydrocarbons," A D V A N C E S I N C H E M I S T R Y SERIES N O . 14,

American Chemical Society, 1955. Patterson, A. M . , Capell, L . T., "The Ring Index," Reinhold, New York, 1960. 1st Suppl., 1963; 2nd Suppl., 1964. *Pinder, A . R., "The Chemistry of Terpenes," New York, Wiley & Sons, 1961. *Rodd, E. H , ed., "Chemistry of Carbon Compounds," vol. IIB, Chap. X I I - X V , Elsevier, New York, 1953. Sandermann, W., "Naturharze, Terpentinol und Tallol—Chemie und Techologie," Springer-Verlag, Berlin, 1960. Schimmel & Co., Inc., "Annual Report on Essential Oils, Aromatic Chemicals and Related Materials," Schimmel & Co., New York, 1892-. *Simonsen, J . L . , and Owens, L . N . , "The Terpenes," 3 vols., 2nd ed., University Press, Cambridge, 1947-52. Todd, Alexander, ed., "Perspectives in Organic Chemistry," p. 265, Interscience, New York, 1956. Thorpe, T. E . and Whiteley, Μ. Α., eds., "Thorpe's Dictionary of Applied Chemistry," 12 vols., 4th ed., Longmans, New York, 1937-56. Tschirch, Alexander and Stock, Erick, "Die Harze," 2 vols., 3rd éd., G. Borntraeger, Berlin, 1933-36. Tschirch, Α., "Die Harze und die Harzbehalten," 2 vols., G. Borntraeger, Leipzig, 1906. West, C. J . , ed., "Nature of the Chemical Components of Wood," Technical Associa tion Paper and Pulp Industry Monograph 6, New York, 1948. Wise, L . E . and Jahn, E . C , eds., "Wood Chemistry," Vol. I, Reinhold, New York, 1952.

Abstracts Chemical Abstracts, American Chemical Society, 1155 Sixteenth St., N . W., Washing ton, D. C. 20036, weekly. Year Section 1912 22. Petroleum, Asphalt, Coal Tar and Wood Products. 1915 22. Petroleum, Asphalt, and Wood Products. 1961 23. Cellulose, Lignin, Paper, and Other Wood Products. 1962 34. Terpenes. 49. Cellulose, Lignin, Paper, and Other Wood Products. 1963 40. Terpenes. 51. Cellulose, Lignin, Paper, and Other Wood Products. 1967 30. Terpenes. 43. Cellulose, Lignin, Paper, and Other Wood Products. Chemisches Zentralblatt, Akademie-Verlag G m b H , Leipziger Str. 3-4, Berlin W.8, Germany, weekly. Bulletins Hercules Power Co., Wilmington, Del. 19899. "Hercules Wood Rosins and Stabilized Rosins," Form No. 400-429-D, 1959 "Hercules Terpenes and Related Pine Chemicals," Form No. 400-514-A, 1960 "Hercules Vinsol Resin—Modifier of Pheolic Resins," Form No. 400-493-B, 1960 "Vinsol Resin, Properties and Uses," Form No. 400-567-A, 1961. Veitch, F. P. and Donk, M . G., Department of Agriculture, Bureau of Chemistry, Bulletin 144 (1911). Patents CL·ss—subclass Material 106—Compositions, Coating or Plastic Carbohydrate or derivative containing —200 W i t h natural resin or derivative



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162—Paper Making and Fiber Liberation Processes and Products Non-fiber additive —173 Hydrocarbons —180 Natural Resin 252—Compositions —367 Soaps (Alkali-Metal Salts of Water-Insoluble Fatty or Rosin Acids) —368 Products —369 Including saponification —370 With subsequent operations 260—Chemistry, Carbon Compounds —97 Natural Resins and Reaction Products —97.5 Tall oil and reaction products thereof —97.6 Separation of constituents of tall oil —97.7 Purification and recovery —98 Sulfur containing —99 Oxidized —99.5 Polymerized —100 Hydrogenated —101 Reaction products with terpenes and/or polycarboxylic anhydrides —102 Reaction products with ammonia, amido or amino compounds —103 Esters of natural resin acids —104 With polyhydric alcohol (e.g., ester gum) —105 Salts of natural resin acids —106 Pyrolytic or heat isomerized products (e.g., rosin oil) —107 Purification, preservation or recovery —108 Resins of pine origin —109 Oleoresin —110 Extraction from cut wood —Ill Treatment of pine origin Carbocyclic or Acyclic Esters and processes of making same —489 With terpenes Ketones —587 Terpene Hydroxy —631.5 Terpene derived Hydrocarbons —675.5 Cyclic terpenes RECEIVED March 26, 1964. Presented in part at the Joint Symposium on "Literature of Naval Stores," sponsored by the Division of Chemical Literature and the Division of Paint, Plastics, and Printing Ink Chemistry at the 131st Meeting of the American Chemical Society at Miami, April 10, 1957, and in part at the Forest Products Research Society, National Meeting, New Orleans, June 16-20, 1963.


The Literature of Wood Naval Stores - ACS Publications - American

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