138
HOWARD S. MASON
Anal. Calcd. for CmHiaOsNzSI : S, 6.26. 5.18.
Vol. 70
Found: S,
extractions with boiling dioxane followed by reprecipitation from the cooled solutions with water. 2-Amino-S-(N-P-quinolyl)-aminothiaxanthone-5-dioxide Anal. Calcd. for CisHlsOaNaS S, 7.99. Found: S, (IV).-A mixture of 0.32 g . (0.00062 mole) of XVI, 10 7.70*'8 ml. of concentrated ammonium hvdroxide< and a trace of Summarv copper powder was heated fifteen hours a t 205' in a sealed 2-Amino-8( ~ ~ ~ ~ p y r ~ ~ y ~ ) ~ a ~ ~ tube. Water (90 ml.) w a s added and the insoluble darkbrown solid filtered off. Upon heating this material three dioxide, 2-amino-8-(N-2-pyrimidyl)-aminothiaxtimes with 10 ml. of approximately 4 N hydrochloric acid, anthone-5-dioxide and 2-amino-8-(N-2-quinolYl)removing insoluble material by filtration, and reprecipitat- aminothiaxanthone-5-dioxidehave been syntheing from the cooled filtrate with ammonium hydroxide sized for study as possible new antibacterial agents. three impure brown-yellow fractions were obtained from ('*) *na1ysis by Dr. which 8 mg. (3%) of pure 2-amino-8-(N-2-quinolyl)aminothiaxanthone-5-dioxide was isolated by fractional BETHLEHEM, PENNA. RECEIVED JUNE 21, 1947
[CONTRIBUTION FROM
THE
OFFICEOF DERMATOLOGY, INDUSTRIAL HYGIENEDIVISION,BUREAU OF STATE SERVICES, U. S. PUBLIC HEALTH SERVICE]
The Allergenic Principles of Poison Ivy. VII. Absorption Spectra of 3-nPentadecylcatechol and Related Compounds1 BY HOWARD S. MASON In this study the absorption spectra of 3-n-pentadecylcatechol and a group of other substituted catechols, catechol derivatives and o-quinones have been determined. The feasibility of direct spectrophotometric assay of poison ivy allergens was also investigated.
Experimental Unless otherwise noted, all substances examined were analytically pure samples previously described'.
3-n-Pentadecyl-o-benzoquinone.-This compound was prepared and purified by following the procedure of Willstatterz for the preparation of o-benzoquinone. I t was recrystallized from a mixture of ether and hexane, from which it separated as oran5e rhomboids sintering and deThe colorless modification composing between 63-67 could also be obtained by following the procedure of WilLstatter and Muller' for the preparation of colorless o-benzoouinone. Anal. Calcd. for C21Hz402: C,79.2; H, 10.8. Found: C, 79.0;--H, 11.0. o-Benzoquinone .-This compound was readily prepared and recrystallized by the procedures of Willstatter' 4nd Goldschmidt.' The product consisted of b5ight red crystals melting and decomposing between 60-70 3-n-Pentadecylcatechol Diphenylmethylene Ether.This compound was synthesized by a general method already described'. It crystallized as white prisms from methanol and melted a t 42 '. Anal. Calcd. for C31H4401: C, 84.3; H, 9.16. Found: C, 84.0; H, 9.14. Spectral curves were determined with a Beckman quartz spectrophotometer. The solvent used was ethanol unless otherwise specified. The quartz cells employed were 10 mm. in thickness.
.
.
Results
250 270 290 310 330 Wave length, mp. Fig. 1.-Spectrum of 3-n-pentadecylcatechol in ethanol. The solution contained 0.102 mg. per ml. The measurements were made a t intervals of (1) zero days, (2) fourteen days, (3) thirty days and (4) ninety-one days. 510
230
(1) For the previous paper in this series, see Mason, THIS JOURNAL, 69, 2241 (1947).
Fresh solutions of 3-n-pentadecylcatechol in ethanol displayed maximum absorption a t 277 mp, log 6 = 3.28. On standing for several months absorption became more intense, the spectral curve shifting to slightly shorter wave lengths (Fig. 1). The effect of solvent upon the rate of this process was determined by following simultaneously the absorption spectra of identical concentrations of 3-n-pentadecylcatechol in ethanol, acetone and hexane. Over a period of forty-five days a t 21-24' the spectral changes took place most markedly in acetone and least markedly in hexane (Table I). Crude extracts of poison ivy also displayed (2) Willstlitter and Pfannenstiel, Bcr., 37, 4744 (1905). (3) Willstgtter and Miiller, ibid., 41, 2580 (1908). (4) Goldschmidt and Graef, i b i d . , 61, 1858 (1928).
~ ~ o
ABSORPTION SPECTRA OF 3-t2-PENTADECYLCATECHOL
Jan., 1948
ether and hexane. The spectral curve of 3-npentadecyl-o-benzoquinonein ethanol (Fig. 3B) developed a maximum a t 273 mp over a period of six days. In hexane solution this substance possessed an initial maximum a t 388 mp, log c = 3.36 (Fig. 3A). During a period of six days this specific absorption disappeared and only general absorption could be observed. The changing spectral curve of o-benzoquinone in ethanol (Fig. 4B) developed a maximum a t 282 mp in twenty-four hours. The chloroform solution displayed an initial maximum a t 368 mp, log c = 3.23 (Fig. 4A). In three days this shifted to 372 mp and a new maximum appeared a t 273 mp.
TABLE I SPECTRAL
3-n-PENTADECYL-
STABILITY OF SOLUTIONS OF CATECHOL
Density n t
Concn. mole/liter
Solvent
Density at 46 days (mp)
0 days (mp)
Ethanol 0.000156 0.300 (277) 0.384 (277) Acetone' .000156 .303 (277) .407 (275) Hexane' .000156 ,326 (273) .372 (272) Aliquots of the acetone solution were evaporated in vacuum a t room temperature. Spectral curves were determined with ethanolic solutions of the residues. b Determination upon hexane solution.
maximum absorption a t 277 mp, agd underwent optical transformations upon standing (Fig. 2). 1.4
1.2
I-
139
1
1.0 -
.-d :0.8 6
."6 0.1 -
0.6 -
A 1
i
i
1
1
1
,
8
121.8 0.4
/
1
1
,
,
,
:Q
-
-
,
-
1.4 -
1
0.2 210
I
I
I
i
J
I
I
250 270 290 310 330 Wave length, mp. Fig. 2.-Crude poison ivy extract containing 0.0542 mg. of resin per ml. of ethanol at (1) zero days, (2) eighteen days and (3) thirty-two days.
230
B
0.2
-
1
0
0.3 ............
Cl 0.5
0.3 1 ............-............... ',4. .............. .........-,:--,:,7.d ._._._-.-. A
.....................
0.1 -
1
60
1
1
1
1
1
1
1
1
1
1
1
1
~
300 20 40 60 80 4Oq Wave length, mp. Fig. 3.-A, 3-n-pentadecyl-o-benzoquinone in hexane, 0.044 mg. per ml. at (l), twenty-five minutes and (2) six days; B, in ethanol, 0.032 mg. per ml. at (1) twenty minutes and (2) six days. 80
_
1
\\
c
I
--____--------
I--
I
o-Benzoquinone and 3-n-pentadecyl-o-benzoquinone were unstable in ethanol, chloroform,
1
i
\
I
I
I
I
I
I
I
I
I
I
I
I
I
HOWARD S. : MASON
140 3-Bromocatechol diphenyl methylene ether 4-l-Butylcatechol diphenylmethylene ether I3 hihwanol diphenylmethylene ether6 2,3-Dirnethoxy-n-pentadecylbenzene . 2,3-Dime thoxy -n -pentadecen 1-ylbenzene
Vol. 70
bonded through hydrogen to the adjacent carbonyl g r o ~ p . ~The , ~ major shift of the spectral curves of o-benzoquinone and 3-n-pentadecyl-o287 (3.73) benzoquinone solutions, from initial absorption 280 (3.60) in the region of 868-388 mp to final absorption 271 (3.18),277 (3.16) between 273 and 282 mp indicates that in the solvents investigated benzenoid molecules forni 271 (3.07), 277 (3.05) from the quinones originally present. In the case of 3-n-pentadecyl-o-benzoquinone both the Discussion position and intensity of the final absorption are A d a m and co-workerss observed that substitu- consistent with the hypothesis that the changes tion of alkyl groups in the 4 position of catechol in the spectrum of aging solutions of 3-n-pentaderesulted in bathochromic spectral shifts of approx- cylcatechol are autoxidative and proceed through imately 5 mp. This phenomenon has been gen- the formation of the corresponding o-quinone. eralized by Jones’ as the B-effect, and it has been This in turn is transformed into a benzenoid rnoleshown that “the magnitude of the shift depends cule. In order to characterize this substance atupon the position of the substituent in the ring tempts a t isolation were made using o-benzoquisystem.” The absorption spectrum of 4-t-butyl- none as a starting material. From ethanolic solucatechol, determined in the present study, is con- tions only catechol and an intractable black polysistent with the observation of Adams6 However, mer were obtained. Upon zinc dust distillation, i t has been found that catechol, 3-n-propylcate- the polymer yielded biphenyl in small amounts. chol, and 3-n-pentadecylcatechol display principal Some of the absorption in the 273-282 mp region absorption (in ethanol) a t 277,276 and 277 mp, re- must therefore be due to the catechols themselves, spectively, and that the corresponding diphenyl- but no decision with respect to the structures of methylene ethers show principal absorption a t 283 the remaining solutes can yet be made. Acknowledgments.-I wish to acknowledge 251 and 281-281 inp. The B-effect therefore does not obtain when alkyl groups are attached to the the assistance of Mrs. Dorothy Peterson of the Industrial Hygiene Laboratory, National In3 position of catechol. The increase in intensity of absorption a t 277 stitute of Health, in the determination of some nip characteristic of solutions of 3-n-pentadecyl- of the spectral curves. I am indebted to catechol and the changes with time in the spec- hfr. Charles A. Kinser for the microchemical trum of solutions of crude poison ivy extracts limit analyses. the applicability of spectrophotometric assay of Summary the poison ivy allergens. However, the results in1. The spectral curves of 3-n-pentadecylcatrdicate that standard solutions of these allergens are best prepared, from the point of view of chemi- chol, related substituted catechols, catechol derivatives and o-quinones, have been determined. cal stability, in hydrocarbon solvents. 2. The effects upon absorption spectra of Goldschmidt and Graef4 have found that, in changes in structure and autoxidation of the catehexane, o-benzoquinone and 4-methyl-o-benzoquinone display principal maxima a t 363 and 365 chols, and of instability of quinonoid solutes, were inp, respectively. 3-n-Pentadecyl-o-benzoquinone observed. 3. The syntheses of 3-n-pentadecyl-o-benzoshows maximuni absorption in the same solvent quinone and 3-n-pentadecylcatechol diphenyla t 388 mp. The substitution of an alkyl group in the 3 position of o-benzoquinone thus results in a methylene ether are reported. bathochromic shift of unexpected magnitude, BETHESDA, MARYLAND RECEIVED JUNR 28, 1947 suggesting that the a-methylene group may he ( R ) Morton and Stubbs, J . Chcm. Soc., 1347 (1940). 287 (3.61)
(6) Adams, Cain and Wolff, THIS JOURNAL, 61, 732 (1940) (7) Jones, ibid., 67,2127 (1945).
(9) Cf.Marvel, Copley and eo-workers, c. g., THISJOURNAL, 61, 3109 (1940).
