ii0
ISDUSTRIAL AND ENGINEERING CHEMISTRY
Phot. Znd., 24, 503 (1926); Madge, British Patent 340,024 (1931); Newman, U. S. Patent 1,783,973 (1930). (176) EFFECTOF PH ON LATEX: Fullerton, Rubber Research Inst. Malaya. Quart.J.,2, 156 (1930); van Harpen, Arch. Rubbercultuur, 11, 487 (1927); 12, 432 (1928); 13 61 (1929); de Vries and BeumBe-Nieuwland, Ibid., 10, 503 (1926); 11, 518 (1927); 12, 683 (1928). (177) GELLISG OF LATEX: Anode Rubber Co., British Patent 291,339 (1929); Beckmann, U. S.Patent 1,745,657 (1930); Dunlop Rubber Co., British Patent 326,210 (1930); Gabor, British Patent 319,801 (1929); Hayes, Madge, and Jennings, British Patents 329,381 and 330,536 (1930); McGavack, British Patent 298,628 (1929); and U. S.Patent 1,762,729 (1930); Teague, U. S.Patent 1,772,647 (1930). (178) LATEXIN ARTIFICIAL LEATHER:.4nonymoue, Gummi-Ztg., 45, 152 (1930); Anonymous, India Rubber J . , 77, 833 (1929); Christmas, U. S. Patent 1,724,906 (1929); Dal-ies, British Patent 306,994 (1929); Ferretti, Austrian Patent 111,535 (1929); U. 9. Patent 1,719,802 (1929). (179) LATEXIN PAPER: Blomberg, U. S. Patent 1,720,716 (1929); Kaye, French Patent 536,936 (1929); Ross-Wright, British Patent 286,661 (1928); Ruderman, U. S.Patent 1,723,581 (1929) ; (180) LATEXIN RUBBER FLOORING:Cresson, U. S. Patent 1,614,348
VOl. 24, No. 7
(1927); Loomis, U. S.Patent 1,682,530 (1928); U. S.Patent 1,765,748 (1930).
Teague,
(181) LATEXIN SHOESOLES: Anonymous, India Rubber J., 79, 302 (1930); Anonymous, India Rubber World, 83, No. 3, 57 (1930); Anonymous, Rubber Age ( N . Y . ) , 28, 24 (1930); SOC. financihre des caoutchoucs, British Patent 301,900 (1929); Wescott, British Patent 272,187 (1928); U. S. Patent 1,702,225 (1929). (182) PRESERVATIVES FOR LATEX: I. G. Farbenindustrie, A.-G., British Patents 271,836 (1927), and 289,022, 294,412, and 300,394 (1923); German Patent 503,645 (1930) ; Jury and Smith, U. S.Patent 1,619,938(1927); McGavack and Shive, U. S. Patents 1,699,368 and 1,699,369 (1929); Somer a n d Walker, British Patent 318,717 (1930). (183) THICKENIXQOF LATEX: Hauser, British Patent 342,469 (1931); Sutton, U. S. Patent 1,770,092 (1930); Teague, U. S. Patent 1,634,124 (1927); Wescott, British Patent 301,077 (1923). (184) VULCANIZATION OF LATEX: Cadwell, U. S. Patents 1,641,573 (1927), and 1,680,857 and 1,680,858 (1928); Schidrowitz, Kautschuk, 3, 202 (1927); U. S. Patent 1,682,857 (1928); Wilhelmi, Netherlands Patent 15,635 (1927). RECEIVED February 1, 1932.
Isolation of Symmetrical Xylenol from Crude-Tar Acids E. B. KESTER,Pittsburgh Experiment Station, U. S. Bureau of Mines, Pittsburgh, Pa.
S
YMMETRICAL xylenol is a compound not a t present marketed in this country although it occurs in considerable quantities in both low- and high-temperature coal tars. It is easily isolated and purified and hence might become readily available if it were found to have industrial usefulness. It should be of particular interest to the synthetic-resin industry because of the two meta-alkyl substitutions. The compound is a white crystalline substance melting a t 63-64' C. and boiling at 220.2" C. under a pressure of 760 mm. When pure it will remain perfectly white for long periods. It enters readily into most of the reactions characteristic of phenols. To separate it from the tar acids, three methods are available that may be used singly or in combinations of the first with the second or third. SEPARATION OF XYLENOL FROM TARACIDS The first and simplest method consists in merely fractionating the acids carefuUy under a column and crystallizing the 217-222" C. cut from petroleum ether. A temperature several degrees below 0" C. is necessary for the best yields. This method, however, can be used only on tar acids that are relatively rich in the compound, as the solubility of the symmetrical xylenol in petroleum hydrocarbons, even at low temperatures, is greatly increased by the presence of other phenols. If the acid fraction is not rich in the compound, as evidenced by its refusing to crystallize when chilled either by itself or in petroleum ether solution, or if it is desired to recover additional quantities after recrystallization of the fraction from petroleum ether, use may be made of the insolubility of its sodium salt. The crude fraction is shaken with an equivalent of 25 per cent caustic soda. On cooling (which should be gradual for the formation of filterable crystals), a heavy crop of the sodium salt of symmetrical xylenol precipitates, which is further increased to almost quantitative proportions by
chilling the mass in an ice-salt mixture. The solid material is filtered and washed with 25 per cent caustic, which renders it almost pure white. The sodium salt is not oxidized easily by the air, is nonhygroscopic and nondeliquescent. If desired, it may be purified by recrystallization from water to which a small amount of caustic has been added, or from acetone. The crude material, however, will yield symmetrical xylenol in a fair degree of purity by merely dissolving it in water, and "springing" with mineral acid. A single recrystallization then from petroleum ether completely purifies it. Still another means by which symmetrical xylenol can be recovered from mixtures of the proper boiling point involves a modification of the method of Briickner (3) which makes use of the resistance of this compound to sulfonation and the relative ease of cleavage of its sulfonic acid. The fraction is heated 2 to 3 hours a t 103-105" C. with an equal weight of concentrated sulfuric acid. This treatment sulfonates the interfering phenols but affects only a portion of the symmetrical xylenol d i i c h is restored in the next operation. The charge is diluted with four volumes of water, refluxed one hour, and extracted repeatedly with ether. The ether solution is washed once or twice with water and distilled to dryness, the xylenol cut being taken when the thermometer starts to rise rapidly. As an alternative to the ether extraction, the diluted sulfonation mixture may be steam-distilled to remove the symmetrical xylenol. Care must be taken in this case that the dilute sulfuric solution does not concentrate, as it is easily possible to reach a cleavage point of some of the sulfonic acids of other phenols in solution. The resulting material by either method is reasonably pure symmetrical xylenol that will crystallize when chilled. It may be purified to a melting point of 63.2' C. by recrystallizing out of petroleum ether. This is the highest melting point obtained by this laboratory, although 64O, 64.5", and 68" C. have been reported. The sulfonation method, like the soda method, may be used subsequently to the straight-crystallization method to aug-
July,-193%
INDUSTRIAL AND ENGINEERING CHEMISTRY
ment the initial yield if the petroleum ether is first distilled off. Of the two, the soda method is productive of somewhat better yields. The following are the more important literature references dealing Kith symmetrical xylenol and its derivatives. BIBLIOGRaPHY
OCCURREICE. PREPARATION. AND PROPERTIES Baeyer,.A., and Piccard, J., Investigations on Dimethyl Pyrone, Ann., 407, 332-69 (1915). Behal, -I., and Choay, E., Qualitative Examination of Phenols Contained in Officinal Beech and Oak Creosotes, Bull. ioc. chim., [3] 11, 702 (1894). Bruckner, H., Cleavage of Phenolsulfonic Bcids and Purification of Phenols by Sulfonic ilcid Separation Method, 2. anal. C‘hem., 75, 289-92 (1928). Bruckner, H., Coal-Tar Phenols, Erdd t i . Teer, 4, 562-4, 580-3, 598-602 (1928). Carlinfanti, E., and Germain, A., The Xylenol from Dehydroacetic Acid, Atti. accal’. Lincei, 19, 11, 234-9 (1911). Fromm, E., and Eckard, H., Lignite Primary Tar, Ber., 56B, 948-53 (1923). Gatterman, L., “Practical Methods of Organic Chemistry,” 3d Am. trans. from 11th German ed., p. 204, Macmillan, 1923. Knovenagel, E.. Synthesis of Phenols by Means of .Icetoacetic Ester, Ber., 26, 1951-2 (1893). Knovenagel, E., l,j-Diketones, Ann., 281, 25-126 (1894). Nolting, A., and Forel, S.,Six Isomeric Xylidines, Ber., 18,266881 (1885). Raschig, F., Process for Production of 1,3-Dirnethyl-5-hydroxybenzene from Tar Oils, German Patent 2.54,716 (March 1, 1912). Ruhemann, S.,Studies on Cyclic Ketones, J . Chem. Soc., 101, 1729-39 (1912). Schneider, E. J., and Shohan, J. B., Xylenols and Higher Phenols That Have Been Found in Primary Tars, U. S.Bur. Mines, R e p t . Investigations 2968 (January, 1930). Schulze, K. E., Ber., 20, 409-14 (1887). Schiite, F., Buschman, R7., and Wissebach, H., Primary Tar, Ber., 56, 1967 (1923). Thol, A, sum-m-Xylidine and the Corresponding Xylenol, Ber., 18, 359-62 (1885). Vorllinder, D., Polymorphism of Liquids, Ber., 40, 4527-37 (1908). DERIVATIVES (18) Anselmino, O., Some Derivatives of Phenol Bromides, Ber., 35, 144-50 (1902). (19) Auwers, K . v., Lederer-Manasse Synthesis of Phenol Alcohols, Ber., 40, 2524-37 (1907). (20) Auwers, K. v., Aceto Derivatives of sum-m-Xylenol, Ber., 48, 90-3 (1915). (21) .iluwers, K. v., Formation of Flavonols from Benzylidenecoumaranones, Ber., 49, 809-18 (1916). (22) Auwers, K. v., and Borsche, E., sum-m-Xylenol, Ber., 48, 1698-1716 (1915). (23) Auwers, K. v., and Borsche, E., Formation of Mono- and Disazo Compounds from Phenols and Phenol Ethers, Ibid., 48, 1716-30 (1915). (24) Auwers, K. v., and Doll, R., Chromanones and Coumaranones from sum-m-Xylenol and Ring Formation from Unsaturated Ketones, Ann., 421, 86-108 (1920). (25) Auwers, K. v., and Dombrowski, A., Some Oxybenzylpiperidinea and Dibromo-p-oxypseudocumyl Aniline, Ann., 344, 280-99 (1906). (26) Auwers, K. v., and Michaelis, F., Formation of Mono- and Disazo Compounds from Phenols and Phenol Ethers, Ber., 47, 1275-97 (1914). (27) Auwers, K. v., Murbe, E., Sauerwein, K., Deines, G., and Schornstein, J., Formation of Quinonimides and Phenoxazones from o-Aniinophenols, Portsnhr. Chem. P h z i k . physik. Chem., 18 (2), 37-77 (1924). (28) Auwers, K. v,, and Srhutte, H., Coumaranones from sym-mXylenol, Bnn., 421, 59-85 (1920). (29) Badische Anilin- und Sodafabrik, Process for Preparation of Condensation Products from Aromatic Hydroxysulfonic Acids, German Patent, 300,567 (1917). (30) Blanksma, J. J., Trinitro-syrn-xylenol, Rec. trao. chim., 20, 4 2 2 4 (1902). (31) Bruckner, H., Phenols from Anthracite Tar, Z. angew. Chem., 41, 1043-6, 1062-6 (1929). (32) Cederberg, K. H., Acetylation of Trinitro-m-xylenol, Swedish Patent 56,955 (July 23, 1924). (33) Fischer, O., and Cammerlohrer, M. v., Isorosinduline. The Isorosindone Reaction, Ber., 34, 940-9 (1901).
771
Fromm, E., and Eckard, H., Lignite Primary Tar, Ber., 5SB, 948-53 (1923). Gatterman, L., Synthesis of Aromatic Aldehydes. 11. The Hydrocyanic Acid Method, Ann., 357, 362 (1907). Knecht, E., and Hibbert, E., sum-Trinitroxylenol, Ber., 37, 3477-9 (1904). Kohn, M., and Feldman, M. K., Preparation of 2,6-Dibromom-xyloquinone from sym-Xylenol, Monatsh., 49, 169-72 (1928). Megson, N. J. L., and Drummond, A. A., Formaldehyde Condensations with Phenol and Its Homologs, J. SOC.Chem. Ind. [K.S.], 49, 251-7T (1930). Meyer, K. H., and Elbers, W. E., Action of Nitric Acid on Phenols and Phenol Ethers, Ber., 54, 337-46 (1921). Noelting, E., sum-m-Xylenol Derivatives, Bull. soc. ind. Mu1house, 94, 648-9 (1926;. Xolting, E., and Forel, S., Six Isomeric Xylidines, Ber., 18, 2668-81 (1885). Raschig, F., Scientific and Technical Importance of Tar Phenols, 2. angew. Chem., 25, 193948 (1913). Raschig, F., Process for Preparation of 1,3-Dimethyl-5-hydroxybenzene-4-sulfonic Acid, German Patent 283,306 (Feb. 4, 1914). Rowe, F. M.,Bannister, S.H . , Seth, R. R., and Storey, R. C., Derivatives of m-Xylenols. I. Intermediate products from m-5-Xylenol. J. SOC.Chem. Ind. [N. S . ] , 49, 469T (1930). Schneider, E. J., and Shohan, J. B., 1,3-Dimethyl-5-phenoxyacetic Acid and 1,2-Dimethyl-3-phenoxyaceticAcid, U. S. Bur. Mines, Rept. Investigations 2969 (December, 1929). Simonis, H., and Herovici, L., 2,3,5,7-Tetramethyl Chromone, Ber., 50, 787-93 (1917). Smiles, S., and Le Rossignol, R., Sulphination of Phenolic Ethers and Influence of Substituents, J. Chem. Soc., 93,745-62 (1908). Stoermer, R., Syntheses in the Cuniaron Series, Ann., 312, 237-336 (1900). Stolle, R., and Knebel, E., New Method of Preparing Cumarandiones, Ber., 54, 1213-20 (1921). Thol, A., sum-m-Xylidine and the Corresponding Xylenol, Ber., 18, 359-62 (1885). VorlBnder, D., Polymorphism of Liquids, Ber., 40, 4527-37 (1907). MISCELL.4NEoCS (52) Auwers, K. v., Borsche, E., and Weller, R., Oxidation of mSubstituted o-Aminophenols, Be?., 54B, 1291-1316 (1921). (53) Blanksma, J. J., Influence of Methyl Group on Substitution in Benzene Kucleus, Rec. trav. chim., 21, 327-38 (1902). (54) Bruckner, H., Cleavage of Phenolsulfonic Acids and Purification of Phenols by Sulfonic Acid Separation Method, 2. anal. Chem., 75, 289-92 (1928). ( 5 5 ) Bruckner, H., Coal-Tar Phenols, Erddl u. Teer, 4, 562-4, 580-3, 598-602 (1928). (56) Duboc, T., and Palfray, L., Action of Tribromo-m-xylenol on Some Cases of Tuberculosis, Bull. acad. mid., [3] 102, 396-8 (1929). (57) Fichter, F., and Rinderspacher, M., Electrochemical Oxidation of Phenols: sum-Xylenol, Thymol, and Potassium Isoeugenol Sulfonate, Helv. Chirn. Acta, 10, 102-6 (1923). (58) Hailer, E., and Ungermann, E., Further Investigations on Killing the Typhus Bacilli in the Organism of the Dog. 111. Arb. h i s . Gesundh., 47, 3 0 3 4 6 (1914). (59) Lesser, R., and Gad, G., The Isomerism of &Naphthol Sulfide and Analogous Isomerisms of Aromatic +Hydroxy Sulfides, Ber., 56B, 963-78 (1923). (60) Muller, E., and Kraemer-Willenberg, H., Hydrogenating, Reducing, and Oxidizing Action of Hydrazine on Organic Compounds, Ber., 57B, 575-83 (1924). (61) Votocek, E., and Potmesil, R., Quantitative Determination of Phloroglucin and Resorcinol by Means of Furfural, Ber., 49, 1185-93 (1916). RECEIWDJanuary 29, 1932.
Published by permission of the Director,
U. S. Bureau of Mines. (Not subject to copyright.)
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