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THE CHEMISTRY OF THE AMINOCHROMES

PART V. REARRANGEMENTS IN THE PRESENCE OF SODIUM HYDROXIDE AND ZINC ACETATE1* * 3 2

R. -4. HEACOCK G. L. R ~ A T T O K AND


The Psychiatvic Research U n i t , University Hospital, Saskatoon, Saskatchewan Received September 10, 1962
ABSTRACT The rates of rearrangement of several aminochromes have been measured in: (I) water, (2) aqueous sodium hydroxide, and (3) aqueous zinc acetate. The rates were found t o be first order with respect to aminochrome concentration in each reaction medium, and to zinc acetate concentration. However, no simple kinetic relationship between the rate of rearrangement and alkali concentration was detected. The rate increased very rapidly with increasing alkali concentration. Mechanisms for these rearrangements are suggested, based on the influence of substituents in the I-. 2-, and 3-positions of the aminochrome molecule on the kinetic and thermodvnamic features of the reaction.

INTRODUCTION

The ease with which ,the red solutions obtained on oxidation of the catecholamines could be decolorized was recognized long before the structures of the compounds involved were established (see ref. 1 for references). As a result of studies on the oxidatiosl of 3,4-dihydroxyphenylalanine (DOPA) carried out over 30 years ago, Raper proposed what was essentially the correct explanation of the changes that occurred, namely that the oxidation of DOPA (I : R1 = R3 = H ; Rs = COOH) resulted in the initial formation

i.e. derivative (11: R1 = R 3 = H ; of an an~inochrome,~ a 2,3-dihydroindole-5,6-quinone R z = COOH),t which subsequently underwent a spontaneous internal oxidationreduction process, forming the colorless 5,6-dihydroxyindole (111: R1 = R z = R 3 = H). The rate of decolorizatioi~of the intermediate pigment could be increased by the action of either base or acid. In the latter case, however, the rearrangement product was not 5,6-dihydroxyindole, but 5,6-dihydroxyindole-2-carboxylic acid (111; R1 = R 3 = H ; R 2 = COOH) (3). This general picture has subsequently been confirmed spectroscopically, manometrically, and paper chromatographically (4-6). Solutions of adrenaline (I: R1 = CH3; R Z = H ; Rs = OH) and certain related catecholamines with a hydroxyl group in the P-position that have usldergone oxidation in
' T h i s investigation was supported by grants from the Gooernment of Saskatchewan (Department of Public Health) and the Department of National Health and Welfare (Ottawa). 2Presented in part at the 45th Annual Conference of the Chemical Institute of Canada, Edmonton, Alberta, M a y , 1962. 3Part I V : Can. J. Chem. 3 8 , 5 1 6 (1960). *The term "aminochrome" as a geneval name for the highly colored cyclic oxidation products of the catecholamines was not introduced until 1951 by Sobotka and A u s t i n ( 2 ) . t T h e chemical and physical properties of these compounds suggest that the switterionic form of the molecule, as shown above, makes the major contribution to the aminochrome structure (cf. ref. 1).
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alkaline media exhibited a transient but intense yellow-green fluorescence (see ref. 1 for references). The fluorescent derivative of adrenaline was, in fact, 5,6-dihjdroxy-Nmethylindoxyl" (i.e, adrenolutin; IV), first isolated and characterized by Lund in 1949

(7, 8) and obtained by the alkaline rearrangement of the initially formed aminochrome (i.e. adrenochrome; 11: R1 = CH3;Rz = H ; R 3 = OH). Rearrangement of aminochromes t o 5,6-dihydroxyindole or 5,6-dihydroxyindoxyl derivatives is catalyzed by certain metallic ions, particularly Zn* and A13+ (9, 10). Although speculative mechanisms, notably those of Trautner and Bradley (11), Sobotka, Barsel, and Chanley (12), and Bu'Lock and Harley-R/Iason (13). have been advanced t o explain certain aspects of the manner by which the rearrangement of the aminochromes t o 5,6-dihydroxy-indole or -indoxy1 derivatives occurs, none is based 011 a systematic physico-organic chemical investigation. A number of reports of an essentially qualitative nature dealing with the stability of adrenochrome solutions has appeared in the literature, and these have been summarized previously (1). Zainbotti and lIoret studied the effects of pH and temperature on the stability of adrenochrome solutions in phosphate buffer polarographically and mano-metrically and reported that, in the relatively limited range studied, the decolnposition of adrenochroine follows first-order kinetics and that the rate of disappearance of aminochrome varied linearly with the pH a t 37" and exponentially with temperature a t pH = 7.38 (1-4-16). I t appeared to the authors that a systematic study of the kinetic and thermodynalnic features of the rearrangement of a number of different aminochromes would enable a more satisfactory explanation of the mechanisms of these reactions t o be formulated.
Aminoch~omes Adrenochrome (17), iV-isopropylnoradrenochrome (181, and adrenochrome methyl and ethyl ethers (18) were prepared as pure crystalline solids by the methods described in the literature. Holvever, in the cases of epinochrome, 2-methyladrenochrome, N-ethyl-2-methylnoradrenochrome, and noradrenochrome, where it was either not possible to isolate a pure sample of the aminochrome or where only limited quantities of the relevant catecholamines were available, the aminochrome was prepared in aqueous solution by oxidation of the appropriate catecholamine hydrochloride (25 mg in 3 ml water) with freshly prepared silver oxide (2X0.2 g) (finally filtering the oxidation mixture through a small Dowex-1 (Cl-) (200/400 mesh) resin bed t o ensure complete removal of colloidal and ionic silver (cf. ref. 17). The rates of rearrangement obtained for adrenochrome prepared in this way showed satisfactory agreement with those determined using crystalline adrenochrome. Solutions of noradrenochrome prepared in this manner were not entirely satisfactory, since the visible absorption spectra of these solutions frequently showed a shift in X,,,accompanied by a n increase in the intensity of absorption a t this wavelength. This phenomenon is possibly due to the relatibely slow cyclization of the initially formed "noradrenaline quinone" (i.e. 1-(a-hydroxy-0-aminoethy1)-3,4-benzoquinone) to noradrenochroine (cf. refs. 19, 20). However, it is not unreasonable to assume t h a t the rates obtained represent the relative order of reactivity of this con~pound. Kinetic ~Weasurements The rearrangements of the various atninochromes were studied in three reaction media: (a) water, (b) aqueous sodium hydroxide, (c) aqueous zinc acetate. T h e reactions were followed by measuring the decrease in absorbance a,t, ,A (ca. 480-495 m,u) with time using a Beckmann DK-2 spectrophotometer equipped with *Oftenfornzulated i n the enolic form, i.e. as 3,6,G-trilzydro?cy-N-1~zethylindole.

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a temperature-regulated cell holder. (The absorption maxima and minima of the an~inochro~nes are used given in Table I.) The initial concentrations of the reagents are given in Table 11. In all cases the solutions TABLE I Absorption spectra of some ami~lochromes water in (in the range 250-650 mM)

RI

Rg

R,

Absorption maxi~na (w)

Absorption mlnima (m~)

of the reagents were preheated to the reaction temperature in the cell holder. The reaction mixtures \rere prepared by the admixture of 2 ml of the aminochrome solution with 1 ml of the catalyst solution, care being taken to ensure rapid and complete mixing of the reagents. There was a good linear relationship between the aminochrome concentration an& the absorbance a t

x :* ,
The Reaction of Adrenochronze ;l[ethyl Ether with Zinc Acetate -4 saturated solution of zinc acetate (1.5 ml) was added to a solution of adrenochrome methyl ether (73 mg) in water- (2.2 ml). The reaction mixture was left to stand for 1 hour and the dark blue precipitate which formed was filtered off, washed with water and ether, and dried in air. T h e weight of the dry precipitate was 60.2 mg. The aqueous filtrate, which was initially yellow but which quickly became blue-green in color, gave, after standing for a n hour, on the addition of more zinc-acetate solutio~l(3 ml) a blue precipitate, which was filtered, washedwith water and ether, and dried in a k . T h e weight of this dry residue was 29.8 rng. The aqueous filtrate (30 ml) was extraeted with ether ( 3 x 1 0 ml). Concentration of the dried (XasSO*) ether extract afforded a white crystalline residue (5.5 mg-).A paper chromatographic examination of this residue indicated that i t was probably 5,6-dihydroxy-A-methylindole (i.e. 111: K1 = CH3; R 2 = R3 = H (cf. ref. 21)). Assuming t h a t this w a s i n fact the product, the expected yield of a complex composed of one zinc atom and one aminochrome unit would be 90.4 mg, and t h a t for 1:2 complex, 78.9 mg. The total weight of complex obtained was 85.7 mg. Analyses of several different samples of these products for carbon, hydrogen, nitrogen, and zinc were inconclusive. (Found: C, 47.57, 4'i.38, 43.20, 43.19, 42.52, 49.53, 51.06; H, 5.32, 4.08, 4.07, 3.83, 4.16, 4.61, 4.70; N, 5.96, 5.90, 4.07, 5.63; Zn, 12.57, 12.57Gjo.) The calculated composition of 1 : l zinc/aminochrome complex would be C, 46.41; H, 4.29; N, 5.42; Zn, 25.28%; and t h a t for a 1:2 zinc/an~inochromecomplex would be C, 53.16; H, 4.91; N,6.20; Zn, 14.47%. I t is therefore difficult to say whether the experimentally supports a 1 : l or a 1:2 complex. determined percentage composition of the con~plex I t is interesting to note t h a t the averages of the experimental values (i.e. C, 46.35; H , 4.69; N,5.39; Zn, 12.577;) fit the calculated composition of a hydrated 1:2 complex (4 molecules of water) (i.e. C:oHzeNnOlaZn requires C, 46.21; H, 5.04; X, 5.39; Zn, 12.587;). Since these products are insoluble in the usual reagents, it was not possible to purify them further by recrystallization. In view of the formation of insoluble precipitates in this case, the reaction was not followed spectroscopically beyond approximately 10% reaction, since clouding of the cell walls t h a t resulted would have given anomalous results.
RESULTS

The rearrangemeilts of adrenochrome and its inethyl ether were first order with respect conce~ltratioll all three reaction ~ n e d i a in (see Figs. 1, 2 , 3, and 4). 111the t o aminochro~ne

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4 + LOG [AMINoCHROME&.~

FIG. 1. Rearrangement of: adrenochrome ( A ) , a t 28.g0, and adrenochrome methyl ether ( 0 ) , a t 30.2', in water. First-order plots ( k l (for adrenochrome) = l.10X10-4 min-I; kl (for adrenochrome methyl min-I). ether) = 0.96X FIG. 2. Rearrangement of: adrenochrome ( A ) , a t 29.7', 4.5X10-5 N NaOH, and adrenochrome methyl ether ( O ) ,a t 42.6', 8.5X10-6 N NaOH, in the presence of sodium hydroxide. Order with respect to aininochrome concentration. (A = adrenochrome; A M E = adrenochrome methyl ether.)
4 L G [A] O

0.2

0.3

0.4

SLOPE: 0'95

0 0

SLOPE. 1.03

SLnl.D.95

0.9
LT

"
_I

+ N

3
0.6
0.8

1'0

1'2

4 + L G [ZA] O

FIG. 3. Rearrangement of adrenochrome in the presence of zinc acetate, a t 28.8'. Order in: adrenochrome ( A ) , zinc acetate 9.4X1OP4 Af, and zinc acetate (O), adrenochrome 2.0X10-4 M. (A4 adreno= chrome; ZA = zinc acetate.) FIG. 4. Rearrangement of adrenochrome methyl ether in the presence of zinc acetate, a t 42.6'. Order in: (AME = adrenochrome methyl ether; ZA = zinc adrenochroine methyl ether ( 0 ) and zinc acetate (0). acetate.)

presence of zinc acetate the rearrangements also obeyed first-order kinetics with respect t o zinc acetate. Rearrangements in the presence of sodium hydroxide, whilst being first order with respect to aminochrome concentration, did not show any simple dependency on

HEACOCK AND MATTOK: AMINOCHROMES


I

FIG. 5. Effect of sodium hydroxide concentration on the rate of rearrangement of: (A) adrenochrome, a t 29.7", initial concentration of adrenochrome 1.90X10-4 M, and (B) adrenochrome methyl ether, a t 42.6", initial concentration of adrenochrome methyl ether 1.91X10-4 AM.

alkali concentration (see Fig. 5). The rate of rearrangement in the presence of sodium hydroxide increased rapidly with alkali concentration. With the exception of experiments which were carried out t o determine the order of the reaction, they were all performed with standardized zinc acetate and sodium hydroxide concentrations. The first-order rate constants were calculated by the method of initial slopes to avoid errors due t o any secondary reactions. The rates of rearrangement, a t 35', of some aminochromes are given ill Table 11. When the substituent on carbon atom 3 only is varied the sequence of reactivity is: H > OH > OCH3 > OCzHS. Further, when the substituent on the nitrogen atom only is varied the sequence of reactivity is i-C3H7> CH3 > H . Variation of the substituent on Cz from EI to C H 3 had little effect on the rate of reaction (see Table 11). These generalizations are true for rearrangements in water, alkali, and zinc acetate solution. An incidental observation is that OH- is about 10 times better a catalyst for the rearrangement than Zn2+ (on a molar basis). I t is also of interest to note that solutions of noradrenochrome are not as unstable as they are generally considered to be. The effect of temperature in the range 30-50' on the rates of some of these reactions was also investigated, and the thermodynamic functions (at 35') for these rearrangements are given in Table 111. In each of the three reaction media, the activation energy decreases as the rate of rearrangement increases. In general, the entropy term is fairly constant. However, with epinochrome, which carries two hydrogen atoms on C3, the entropy term is co~~sistently more favorable than for adrenochrome. Although this difference is small, it is probably significant.

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TABLE I1 Rearrangement of several amiriochromes in various reaction media (Rate constants a t 35') 0\~-_CHR3

CHRz

kl

X l o 4 (mill-l) in:

Aminochrome"

RI

Rz H H H H H H CHI CH,

R3 H OH OCH, OC,H, OH OH OH OH

Hz0
14.6 2.04 1.26 0.76 3.72 1.48 1 80 1 .S O

NaOH*
72.1 22.4 15.3 10.2 41.7 12.3 17.3 19.3

Zil(OAc)?*
126 13.4 10.4 9.77 19.5 11.9 16.3 18.8

Epinochrome CH 3 Adrenochrome CH3 CI-13 Adrenochrome methyl ether CHI Adrenochrome ethyl ether N-1soprop)-lnoradre~lochrome i-C3H7 H Noradrenochromet 2-Methyladrenochronle CHa A'-Ethyl-2-methyli~oradre~~ochrome C2Hs

*Initial concentrations of reagents: NaOH = 8.5OX10-5 M , Zn(0Ac)z = ?See experimental section dealing with preparation of aminochromes.

9.5OX10-4 .If, aminochrome = 2.05X10-4 M.

TABLE I11 Rearrangement of aminochrotnes in (i) water, (ii) aqueous sodium hydroxide, and (iii) aqueous zinc acetate (Thermod~ namic fu~lctionsa t 35')

Substituents RI R3

E,,,*
AS*?
AFc*

II'ater

NaOH (1.5X10-5 Jf) AS* AF*

Zn(0Xc)z (9 5 X

31)
-

E,,,

E,,,

AS*

AF*

*Eexpand AF'
?AS* in

e.u.

in

kcal/mole.
DISCUSSION

Reurrungements in Watev and Alkali T h e overall reaction consists of relnoval of protons from the 2- and 3-positions in the five-membered ring of the aminochrome molecule (11) and the addition of a proton to each of the Cg- and C6-carbonyl oxygen atoins on the o-benzoquinone ring. The primary t reaction center i l ~ u s therefore be either C2 or Ca. T h e following lines of evidence suggest t h a t the primary reaction center is, in fact, C3: (i) In the cases investigated, substituents in the 3-position had a marked effect on the reaction rates, whilst those in the 2-position e had little effect; (ii) the entropy term for epiilochrome (11: R1 = C H 3 ; R = R 3 = H) is slightly more favorable for rearrangement than for the other aminochromes. This would be expected if the rate-determining process is reinoval of a proton from carbon 3.

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The reaction in water is first order with respect t o aminochrome concentration. ('This is the case for a t least 40% reaction.) In aqueous alkali, the rearrangement is also first order with respect t o amillochrome; however, the order with respect t o sodium hydroxide concentration is not simple, indicating that alkali probably plays a multiple role in the reaction. The rate-controlling process would then be the loss of a proton from the three position, resulting in a transition state involving one aminochro~l~e molecule. The two carbonyl groups in o-quinonoid structures tend to promote electromeric changes in opposite directions, resulting in the high reactivity associated with these structures, which have a tendency to revert to structures in which the tension of the opposed electroineric effects has been relieved (22). The tendency of the Cs-carbonyl group to polarize effectively lowers the electron density on C3, by the series of electromeric changes as shown below, thus facilitating the removal of the proton from the 3-position. Electronattracting substitueilts a t C 3 will diminish the supply of electrons available for the

elertro~nericshifts, resulting in the polarizatioil of the C6-carbonyl group. The rate of rea_rra~lgemeilt will therefore decrease with an increase in electron-attracting capacity of the C3-substituent (R3), and this is, in fact, observed for the following series of co~npounds: epinochroine (R3 = H) > adrenochrome (R3 = OH) > adrenochrome methyl ether (R3 = OCHB) > adreilochrorne ethyl ether (Ra = OC2H5). The rate-determining stage is then followed by a second series of electronic shifts in the pyrrole moiety of the molecule, resulting in the loss of a proton from Cz a n d t h e formation of a fully aromatic structure. Electron-donating groups on the nitrogen atom will promote fnrther polarization of the CG-carbonyl group, resulting in an increase in t h e already high contribution of the zwitterionic form of the aminochrome molecule t o the ground-state resonance hybrid. This results in a raising of the ground-state free energy of the molecule. The observed sequence of reactivity for the N-substituted arninochromes is: N-i-C3H, > N-CH3 > N-H. This would be expected 011 the basis of the inductive effects of these groups. This effect is also probably associated with the observed shift towards longer wavelengths of the iilain absoi-ptioil peak (see Table I ) of the N-substituted aminochrornes with increasing electron-donating capacity of the N-substituent. The rapid increase in the rate of rearrangement of the aminochromes with increasing alkali co~lcentrationindicates that the catalyst does not play a single role in the reaction, but presumably assists several processes simultaneously. The hydroxyl ions will act as proton scavengers, and the presence of alkali will also tend to stabilize the enolate anion of the tra~lsition state. Furthermore, interaction of the hydroxyl ions with the quaternary nitrogen center will localize the positive charge of the zwitterionic system and thus destabilize the molecule by limiting the possibilities for resonance. f Rearrangements in the Puesence o Zinc Acetate Several of the observed kinetic features of these rearrangements are si~nilar o those in t the alkali-catalyzed and u~lcatalyzedrearrangements. The same sequence of reactivity for substituents in the I-, 2-, and 3-positions is observed. The thermodynamic aspects of

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the rearrangements are similar. However, there are some important differences. Firstly, there is a good first-order dependency with respect to the zinc acetate co~lcentration, whilst there is no simple relationship to alkali concentration. Secondly, rearrangement of the various aminochromes in the presence of sodium hydroxide leads to analogous products in every case. However, when zinc acetate is the catalyst, rearrangement of the aminochro~nes with R 3 = H or OH leads to the formation of the same products as with alkali, whereas when R 3 = 0-alkyl (i.e, the aminochrome ethers) these aminochromes react with zinc acetate solution to form an insoluble dark blue precipitate (cf. ref. 21), which forms relatively slowly. The composition of these precipitates is uncertain. Analysis of the product derived from adrenochrome methyl ether did not confirm either a 1 : l or 1:2 zinc/aminochrome compositioll but suggested a hydrated 1:2 complex. I t was in~possible to obtain a pure sample of this material, since it is probable that the product is contaminated with insoluble melanitic Inaterials which are formed a t the same time as the complex. Insoluble precipitates were never obtained initially in the cases where R 3 = H or OH. Bu'Lock and Harley-Allason have suggested, by analogy with the products formed during the oxidation of catechol in the presence of zinc acetate, that the rearrangement of aminochromes in the presence of zinc acetate proceeds via an intermediate co~nposedof one zinc unit and two aminochrome units (13). Our results do not rule out the formation of such a complex as the final product with the aminochrome ethers, but, the transition state for the zinc ion catalyzed rearrangement must, from the kinetic data, involve only one zinc ion and one aminochrome molecule. The birnolecular process required to form a 1:1 conlplex is more likely than the threebody collision necessary for the formation of the 1:2 complex proposed by Bu'Lock and Harley-Mason. Further, it is difficult to rationalize the pronounced effect of the C3substituent, in the case of the aminochrome ethers, on the solubility and stability of this complex. From the kinetic data, there will be a primary interaction between one Z1l2+ ion and one aminochrome molecule. Presumably, the zinc ion approaches the dicarbonyl function of the benzoquinone moiety. The polarization of the Cs-carbonyl group will assist this approach. The proximity of the ZnL+ion t o the Cs-carbonyl will induce polarization in this group, thus providing the driving force for the same electromeric shifts, resulting in the removal of the C3-proton,as proposed for the hydroxyl ion catalyzed rearrangement. T h e C2-proton is removed by the second series of shifts as described previously. The mechanisms of rearrangement of the amiilochromes in the presence of alkali or zinc acetate therefore differ mainly in the method by which the two catalysts bring about the same electronic changes in the aminochrome molecule. This is in accord with the fact that, apart from catalytic aspects, the same general kinetic features are observed for the two types of rearrangement.
ACKNOWLEDGMENTS

The authors wish to express their thanks to Burrough-Wellcome and Co. (Canada) Ltd., for a generous gift of epinine hydrochloride and to Mrs. B. D. Scott for the preparation of samples of 3,4-dihydroxyephedrine hydrochloride and N-ethyl-3,4-dihydroxynorephedrine hydrochloride.
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HEACOCK A S D MATTOK: AMISOCHROMES

4. H. S. MASON. J. Biol. Chem. 172, 83 (1947). 5. H. S. R~IASON C. \%'RIGHT. J . Biol. Chem. 180, 235 (1949). and and 6. S. BOUCHILLOUX A. KODTA. Bull. Soc. Chim. Biol. 42, 65 (1960). . 7. A. LEWD. Acta Pharmacol. ~ o x i c o l 5. 75 (1949). 8. A. 1 , ~ s ~Acta Pharmacol. Toxicol. 5: 121'11949). . P. FISCHER, G. DEROUAUX,. LAMBOT, H and^. LECOMTE. Bull. Soc. Chim. Belges, 59, '72 (1950). J . HARLEY-MASON J . D. BU'LOCK. Nature, 166, 1036 (1950). and E. M. TRAUTKER T. R. BRADLEY.Australian J . Biol. Sci. 4B, 303 (1951). and N. and H. SOBOTKA, BARSEL, J . D. CHANLEY. Fortschr. Chem. Org. Naturstoffe, 14, 217 (1957). and J . D. BU'LOCK J. HARLEY-MASON. Chem. Soc. 2248 (1951). J. V. ZAUBOTTI V. MORET. Arch. Sci. Biol. (Bologna). 33. 522 11949). and 1 ZA~IBOTTI and V. RIORET. Arch. Sci. Biol. (Boloina), 34, 272 (1950). ' . V.~ I O R E T Giorn. Biochim. 3, 210 (1954). . R. A. HEACOCK, NERENBERG, A. N. PAYZA. Can. J. Chem. 36, 853 (1958). C. and R. A. HEACOCK B. D. SCOTT. Can. J. Chem. 38, 516 (1960). and A. KODJA and S. BOUCHILLOCX. Compt. Rend. Soc. Biol. 153, 1407 (1959). Biochim. B i o ~ h ~Acta. 41. 345 11960). s. A. K o ~ r x S. BOCCHILLOUX. and 21. R. A. HEACOCK. Chem. Ind. (London), 752 (1'959). 22. J . R. JOHXSOW.I n Organic chemistry. Val. 11. Edited by H. Gilman. John \I7iley & Sons Inc., New York. 1957. p. 1922.