987
N0TI.X
TABLE 1 3,4,6-TRl.~LHOXYBENZOICACIDSAND ESTERS,
/ RO Analvses. % Compound
R'
R C& CGHKCH~ n-CaH? n-C,Hr n-C4HB n-C4H9 n-C~H1t
Calcd.
Found
Hydrogen Calcd. Found
58 70 64 61 67 68 70
58 70 65 60 67 68 69
8 G 8 8 8 9 9
Carbon
M.P. or B.P.,
CGH,,CINa CaHiSClN'
H C,H,KCISa
H CHI CH8
"C.
128- 130 153-155 89-91 125-126 68 5-70 190-195/1 mm. 203-205/1 mm.
52 87 84 16 43 15 01
59 51 06 82 45 37 71
27 65 16 87 94 15 71
8 6 8 8 9 9 9
22 92 12 98 01 42 58
3.5)* and p-anisidine phosphate spray,j reyealed the presence of glucose, fructose, maltose, maltotriose, and other more slowly moving components.6 Inasmuch as the material arose from aphids it was expected that one of the components might be melezitose' but none was present. The maltose component was separated by sheet paper chromatography using Whatman N o . 3 paper and the above pyridine-ethyl acetate-water solvent in the usual D E P A R T M E X T O F CHEJIlSTRY U N I V E R S l T Y O F >1ISSOURI way and extracted from the appropriate segments COLUVBLI, 1 f O . of the paper with water. Removal of the solvent in oucuo produced a colorless sirup which crystallized when dissolved in the minimum quantity of water and treated with ethanol to incipient turIsolation of Maltose from Honeydew on Alsike bidity. The crystalline product proved to be maltose, melting point and mixed melting point 118(Trifolium hybridum) Seeds' 123O, [a]: 126' in water (c, 0.5). The maltose was further characterized by reduction with sodium F. SLIITHAXD H. C. SRIVASTAVA borohydride* to nialtitol which was tranformed by Received January 28, 1951 means of sodium acetate and acetic anhydride into the crystalline n ~ n a c e t a t e , ~melting ,'~ point and Recently Sorthrup King and Company, Min- mixed melting point 82-83'. neapolis, drew our attention to the presence of a Paper chromatography has show1 in other exsticky substance on alsike (Trifolium hybridum) periments that the honey dew exuded by the leaves seeds harvested in Idaho. The material, a type of of a young peach tree (ilrnygdalus s p . ) contained honey dew arising from infestation of the plants by glucose, fructose, and sucrose; that from the leaves aphids, Z'herioathis maculata (Buckton), was ob- of a House Balsam (Impatiens sultani) contained tained by washing the seeds with mater, filtering, (4) E. F. McFarren, K. Brand, and H. R. Rutkomslti, and concentrating the brownish yellow filtrate in Chem., 23, 1146 (1951). vacuo t o a sirup. This sirup reduced Fehling solution Anal. (5) S. hlukherjee and H. C. Srivastava, iVature, 169, and gave a positive nIolisch test. Paper chromato- 330 (1952). graphic analysis, using three different solvents; 1(6) C. J. P. Il-olf and W.H. Ewart, Arch. Biochem. and hutanol:ethanol:water, (4 :1:5);2 1-propano1:water Biophys., 58, 365 (1956); R. H. Hackman and Trikojue, : pyridine:water (2.5:l.O:- Biochem. J., 51, 653 (1952). a ~ e o t r o p e ;ethylacetate ~ mole) of the ester and 0.9 mole of sodium ethoxide, in 1 1. of absolute ethanol was stirred and heated to reflux. A solution of 181.2 g. (1.2 moles) of n-amyl bromide in 100 ml. of alcohol was added dropwise, and the reaction mixture was heated for 10 hr. It was TTTorked up in a fashion similar to that described in the preceding experiment. Distillation of the residue which remained after concentration of the ether solution yielded 48.5 g. (417,) of the ester; b.p. 203205"/1 mm., n'," 1.4971.
+
(1) Paper No. 3789 of the Scientific Journal Series, Minnesota Agricultnral Experiment Station. ( 2 ) S. S'l. Partridge, Nature, 158, 270 (1946). ( 3 ) F. Smith and H. C. Srivastava, J . Am. Chem. Sac., 78, 1404 (1956).
(7) C. S. Hudson and S. F. Sherwood, J . Am. Chem. Soc., 42, 116 (1920). (8) M. Abdel-Akher, J. K. Hamilton, and F. Smith. J . Am. Chem. Soc., 73, 4691 (1951). (9) M. L. Wolfrom and T. S. Gardner, J . Am. Chem. SOC., 62, 2553 (1940). (10) P. Karrer and J., Bjichi, Helv. Chim. Acta, 20, 86 (1937).
088 only sucrose n-hich crystallizes on the plants while the nectar from flowers of the Poinsettia (Poinsettia sp.) contained glucose, fructose, and sucrose.
m-ere sulfonic acid type resins. The conversion7 was a little lower when Amberlite In-112 wa? usrd. hut all other results were independent of the resin used. dcknowledgment. The authors thank n’orthriip The yields in these alkylations were essentially King and Co., Minneapolis for the alsike clover independent of the concentration of resin. seeds supplied through the courtesy of Mr. E. When phenol was alkylated with isobutylene 11%Iloty. ing a cation resin there 11-as generally no ortho isomer in the product. n E P A R T A l E X T O F -4GRICULTURALBIOCHEIIISTRY The presence of water was deleterious, a t least GAIVERRITY OF ~IISNESOTA ST. PAUL, NINS in the diisobutylene alkylatioii reactions, for when the resin was used after only air drying, no reaction occurred. The reaction required an oven-dried resin. Drying of the diisobutylene also increased the yield. The use of a cation exchange resin as catalyst Cation Exchange Resins as Catalysts in the has the particular advantage over a mineral acid Alkylation of Phenols catalyst that a t the conclusion of the reaction, a simple filtration of the molten reaction mixture BERNARD LOEVA S D JOHN T. hIASSENGALE leaves an acid-free solution ready for distillation. There is no chance of acid catalyzed rearrangement Received January 28, 1967 during the distillation, and the product is a, high purity p-alkylphenol. In addition, the use of resins Both anion and cation exchange resins have been as catalysts eliminates by-products formed by reacn-idely used as catalysts for reactions such as esteri- tion of the mineral acids with the phenol, and by fication, hydrolysis, and sucrose inversion1p2by-products due to polymerization or degradation reactions which involve only carbon-oxygen bonds. of the olefin. By comparison, reports of the use of resins (particAttempts to alkylate xylene and benzene using ularly cation exchange resins) as catalysts for re- a resin catalyst were unsuccessful actions in which carbon-carbon bonds are formed, are few-.Ion exchange resins are reported to catEXPERINEXTAL alyze cyanohydrin formation, aldol c o n d e n s a t i ~ n , ~ ? ~ and the various modifications of the Knoevenagelj Preparation of resin catalyst. The resins which are normand ;\lichae16 condensations. It seemed of interest ally purchased in the salt form n-ere converted to the acid by washing with 5% HzSOcuntil the wash m-ater gave a t o investigate other reactions which are normally form negative flame test for sodium. The resin was then thorcatalyzed by strong acids, to see whether cation oughly washed with distilled water until the wash mater exchange resins could be used in place of the usual was neutral, air dried for 24 hr., and then heated for 18 hr. in a vacuum oven a t 100-120”. Lewis acids. The resin may be washed with acetone and ether, follorrIt has been found that the sulfonic acid type catthe air drying, to remove traces of colored organic ion exchange resins are excellent catalysts for the ing impurities. This treatment has no effect on the catalytic alkylation of phenol with olefins such as iso- activity of the resin. The resins wei e all commercial materials: Amberlite butylene, diisobutylene, and nonene-1. The resins investigated were Amberlite In-112 IR-112 and 1R-120, 16 t o 50 mesh (Rohm & Haas), Permuand IR-120, Don-ex 50 X 12, and Permutite Q; all tite Q, approx. 20 to 60 mesh (Permutite Corp.), and (1) (a) S. Sussman in Ion Exchange-Theory and ApplicaF. C . Nachod, ed., Academic Press Inc., New York, N. Y., 1949, p. 265. ( b ) F. C. Nachod, I o n Exchange Catalysis, L.Farltas Memorial Volume, A. Farkas, E. P. Wigner, eds., Research Council of Israel, Jerusalem, 1952, p. 188. (2) ( a ) R. Kunin and R. J. RIeyers, Zon Exchange Resins, John n’iley and Sons, S e w Tork, N. Y , p. 137, 1950. { b ) F. X. RIcGarvey and R. Kunin in I o n Exchange Technology, F. C. Kachod and J. Schubert, eds., Academic Press Inc., Nm- York, N Y.,1949, p, 265. (3) C.J. Schmidle and R. C. Mansfield, Ind. Eng. Chem., 44, 1388 (1952). (4)P. Mastadi and G. V. Durr, Bull. SOC. chim. France, 2G8 (1955); Chek. Abstr., 50, 1668.’ (5) RI, J. Astle and TV. C. Gergel, J . Org. Chem., 21, 493 (19%). (6) E. D. Bergmann and R. Corett, J . Org. Chem., 21, 107 (1956). tion,
Doaex 50 X 12, 200-400 mesh (Dow Chemical). p-tert-Octylphenols (p-dtisobutylphenol or I,l,d,3-tetramethylbutylphenol). A typical preparation is given. Phenol (250 g., 2.6 moles), diisobutylene, (328 g., 219 moles), and 17.5 g. of Amherlite l.R-112, prepared as described above, wete heated together with vigorous stirring for 24 hr. a t 70-75
.
( 7 ) For greater ease in discussing the results of these experiments, the terms “conversion” and “yield” are employed. Percent conversion represents the percent of theoretical value based on the amount of (limiting) starting material charged to the reaction. Percent yield represents the percent of the theoretical value based on the amount of starting material used lip (or not recovered) during the reaction. (8) As used here, p-tert-octylphenol refers t o the alkyl group 1,1,3,3-tetramethylbutyl-,which results from the alkylation of phenols with diisobutylene (DIB). IIIB is a mixture of tp-o isomers, 2,4,4-trimethyl-l-pentene and 2,4,4trimethyl-2-pentene which are assumed to give identical alkylation products.
