dormouse (Member)
04-19-00 07:12
No 122785
      Oxidative mechanism of epinephrine -> andrenochrome -rev drone  Bookmark   


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Author  Topic:   Oxidative mechanism of epinephrine -> andrenochrome 
rev drone
Hive Bee   posted 01-24-1999 06:02 PM           
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Anybody who's read "Fear and Loathing in Las Vegas" with their eyes open has wondered about that andrenochrome scene. What is that stuff? Where do I get that stuff? etc.
Well, andrenochrome is 3-hydroxy-1-methyl-5,6-indoline-dione -- made by the oxidation of epinephrine (andrenalin). Now I can see where the hydrogens were abstracted from, and I can generally speculate about the mechnism, but does anyone have the definative word on electron-pushing for this little chemical anomaly?

Also, does anyone have experience with this stuff? Johnny Depp sure made it look kewl, and being the young, impressionable lad that I am, I'd sure like to know if it is "all that" or not.

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-the good reverend drone


Beagle
Hive Bee   posted 01-25-1999 09:36 AM           
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I have no experience with this compound, but of course I am very interested in it. Here are the original refs, in case anyone is willing to follow up on it.
The original paper, in which Hoffer obtained "profound psychomimetic symptoms" from as little as 0.5 mg S.C. or I.V.:
J. Mental Sci. 100, 29, '54

Later papers where negative results or possible slight effects were obtained by dosages up to 25mg:
Am. J. Psychiat. 111, 603, '55
ibid 115, 162, '58
ibid 116, 454, '59
Lancet ii, 308, '58

I believe that the ultimate athority of Shulgin refered to adrenochrome as "a facinating red herring" in Tihkal. And I really hate to argue with Him. I believe that the original, positive reports were based on experiments with one mentally unstable woman. This was covered in Hoffer and Osmonds The Hallucinogens, I believe. Other reviews are :
Hormones, Brain Function and Behavior, p181 1957.
Psychotropic Drugs p.10, 1957

Opinions that adrenochrome is not active:
Lancet, I 1287, 1960.

In Nature 191, 245, 61 it was pointed out that adrenochrome may have significance as a hallucinogen, since it is an in vitro glutamic acid decarboxylase and cholinesterase inhibitor.

It has also been described as having a wide range of other physiological activites, as reviewed in
Pharmacol. Rev. 1, 1, 49
Fortschr. Chem. Org. Naturstoffe. 14, 217, 57

Of course, most of this work was done under conditions that would be considered primitive today, and there is not absolute certainty that all research groups were working with the same compound. Originally, adrenochrome was prepared by oxidation of adrenalin with catechol oxidase or silver oxide. The chemistry of its preparation is reviewed in Chem. Rev. 59, 181, 59.

Additionally, adrenochrome semicarbazone has been claimed to have hallucinogenic properties similar to the parent substance: Acta Chem. Scand. 12, 1231, 58. It certainly would be interesting to apply modern techniques to this mystery and settle it once and for all. Anyone looking for a research project?


 
rev drone
Hive Bee   posted 01-25-1999 10:04 AM           
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Many thanks for the extensive foray into andrenochrome you've offered. I have a few more andrenalin oxidations I can offer. I was told epinephrine was available OTC in a veterinary context, but otherwise is avaiable in bulk through several chemical companies. THe synthesis is a mere one-step reaction, so it looks like the makings of a fun weekend project. Off to the library I go...
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-the good reverend drone


Beagle
Hive Bee   posted 01-25-1999 11:00 AM           
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I would be glad to hear of any other epinephrine oxidations that you could offer.
Also, for another fun fictionalized account of adrenochrome in the vein of H.S. Thompson, see Blood of a Wig, from the book Red Dirt Marijuana and Other Stories, by Terry Southern.


rev drone
Hive Bee   posted 01-25-1999 01:06 PM           
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The folowing were taken from Beilstein
Reaction

Reaction ID 352748
Reactant BRN 2368277 4-((R)-1-hydroxy-2-methylamino-ethyl)-benzene-1,2-diol
Product BRN 84667 (R)-3-hydroxy-1-methyl-indoline-5,6-dione
-------------------------

Reaction Details 1 of 7

Reaction Classification Preparation
Reagent silver oxide
methanol
Ref. 1 1053607; Journal; Ellis; JPETAB; J.Pharmacol.Exp.Ther.; 79; 1943; 364,368;
Ref. 2 1053608; Journal; Veer; RTCPA3; Recl.Trav.Chim.Pays-Bas; 61; 1942; 638,643;
-------------------------

Reaction Details 2 of 7

Reaction Classification Preparation
Reagent silver oxide
ethanol
Ref. 1 1053607; Journal; Ellis; JPETAB; J.Pharmacol.Exp.Ther.; 79; 1943; 364,368;
Ref. 2 1053608; Journal; Veer; RTCPA3; Recl.Trav.Chim.Pays-Bas; 61; 1942; 638,643;
-------------------------

Reaction Details 3 of 7

Reaction Classification Preparation
Reagent silver oxide
methanol
formic acid
Ref. 1 1053583; Journal; Heacock et al.; CJCHAG; Can.J.Chem.; 36; 1958; 853,855;
Ref. 2 1053605; Journal; Sobotka; Austin; JACSAT; J.Amer.Chem.Soc.; 73; 1951; 3077;
Ref. 3 1053598; Journal; Harley-Mason; JCSOA9; J.Chem.Soc.; 1950; 1276,1279;
Ref. 4 1053586; Journal; Ingle et al.; JPHAA3; J.Am.Pharm.Assoc.; 37; 1948; 375;
Ref. 5 1053606; Journal; MacCarthy; CHIEAN; Chim.Ind.(Paris); 55; 1946; 435;
-------------------------

Reaction Details 4 of 7

Reaction Classification Preparation
Reagent oxygen
Other conditions in Gegenwart von Katalysatoren
Ref. 1 1053600; Journal; Green et al.; JBCHA3; J.Biol.Chem.; 220; 1956; 237;
Ref. 2 1053601; Journal; Chaix et al.; BBACAQ; Biochim.Biophys.Acta; 5; 1950; 472,473;
Ref. 3 1053602; Journal; Drevon; Stupfel; C.r.Soc.Biol.; 143; 1949; 271;
Ref. 4 1053603; Journal; Blaschko; Schlossmann; J.Physiol.London; 98; 1940; 130-140;
Ref. 5 1053604; Journal; Green; Richter; BIJOAK; Biochem.J.; 31; 1937; 598,609;
-------------------------

Reaction Details 5 of 7

Reaction Classification Preparation
Reagent iron (2+)
hydrogen peroxide
Ref. 1 1053598; Journal; Harley-Mason; JCSOA9; J.Chem.Soc.; 1950; 1276,1279;
Ref. 2 1053599; Journal; Mazur et al.; JBCHA3; J.Biol.Chem.; 220; 1956; 227;
-------------------------

Reaction Details 6 of 7

Reaction Classification Preparation
Reagent iron (2+)
sodium peroxo disulfate
Ref. 1 1053598; Journal; Harley-Mason; JCSOA9; J.Chem.Soc.; 1950; 1276,1279;
Ref. 2 1053599; Journal; Mazur et al.; JBCHA3; J.Biol.Chem.; 220; 1956; 227;
-------------------------

Reaction Details 7 of 7

Reaction Classification Preparation
Reagent water
iodic acid
Ref. 1 1053597; Journal; Correia; Alves; Anais Fac.Farm.Porto; 14; 1954; 101,109;
Ref. 2 1053596; Journal; Macciotta; GCITA9; Gazz.Chim.Ital.; 81; 1951; 485,488;

Reaction

Reaction ID 2106910
Reactant BRN 2212160 4-(1-hydroxy-2-methylamino-ethyl)-benzene-1,2-diol
Product BRN 84665 3-hydroxy-1-methyl-2,3-dihydro-indole-5,6-dione
-------------------------

Reaction Details 1 of 2

Reaction Classification Chemical behaviour
Reagent VOCl2, O2
Solvent H2O
Temperature 25 C
Other conditions dependence of rate constant on pH, adrenaline concentration, VOCl2 concentration; ionic strength: 0.100 mol dm%-3& (KNO3)
Subject studied Rate constant
Ref. 1 5731416; Journal; Jameson, Reginald F.; Kiss, Tamas; JCDTBI; J.Chem.Soc.Dalton Trans.; EN; 1986; 1833-1838;
-------------------------

Reaction Details 2 of 2

Reaction Classification Chemical behaviour
Other conditions disproportionation during electrooxidation of title compound at carbon-fiber microelectrodes at physiological pH
Subject studied Rate constant
Mechanism
Ref. 1 5925724; Journal; Ciolkowski, Edward L.; Maness, Karolyn M.; Cahill, Paula S.; Wightman, R. Mark; Evans, Dennis H.; et al.; ANCHAM; Anal.Chem.; EN; 66; 21; 1994; 3611-3617;Reaction

Reaction ID 2106911
Reactant BRN 2212160 4-(1-hydroxy-2-methylamino-ethyl)-benzene-1,2-diol
Product BRN 84665 3-hydroxy-1-methyl-2,3-dihydro-indole-5,6-dione
161691 1-methyl-indole-3,5,6-triol
-------------------------

Reaction Details

Reaction Classification Chemical behaviour
Solvent D2O
Time 350 min
Temperature 24.9 C
Other conditions Irradiation
other sensitizers: methylene blue, rose bengal, fluoresceine, superoxide dismutase; other inhibitors: 1,3-diphenylisobenzofuran, 1,4-diazobicyclo<2,2,2>octane, KN3, NaN3; other solvent: H2O.
Subject studied Rate constant
Mechanism
Ref. 1 5689294; Journal; Kruk, I.; ZPCLAH; Z.Phys.Chem.(Leipzig); EN; 268; 3; 1987; 607-613;Reaction

Reaction ID 2106912
Reactant BRN 2212160 4-(1-hydroxy-2-methylamino-ethyl)-benzene-1,2-diol
Product BRN 84665 3-hydroxy-1-methyl-2,3-dihydro-indole-5,6-dione
2806381 C9H11NO3
-------------------------

Reaction Details

Reaction Classification Chemical behaviour
Other conditions Irradiation
laser induced oxidation at pH5 at various electrodes; half life of 0-quinone
Subject studied Product distribution
Ref. 1 5562583; Journal; Skully, Joan P.; McCreery, Richard L.; ANCHAM; Anal.Chem.; EN; 52; 12; 1980; 1885-1889;

Reaction

Reaction ID 2173865
Reactant BRN 2806381 C9H11NO3
Product BRN 84665 3-hydroxy-1-methyl-2,3-dihydro-indole-5,6-dione
-------------------------

Reaction Details

Reaction Classification Chemical behaviour
Other conditions the half life
Subject studied Rate constant
Ref. 1 5562583; Journal; Skully, Joan P.; McCreery, Richard L.; ANCHAM; Anal.Chem.; EN; 52; 12; 1980; 1885-1889;

Reaction

Reaction ID 2199350
Reactant BRN 3201122 (+-)-1-<3,4-dihydroxy-phenyl>-2-methylamino-ethanol
Product BRN 5741691 C9H9NO3
-------------------------

Reaction Details

Reaction Classification Preparation
Reagent K3Fe(CN)6
Solvent acetic acid
H2O
Time 5 min
Temperature 5 C
Ref. 1 5676615; Journal; Kato, Eishin; Oya, Masayuki; Uda, Kozo; Iso, Tadashi; Fujita, Tadashi; Iwao, Jun-Ichi; CPBTAL; Chem.Pharm.Bull.; EN; 29; 7; 1981; 1935-1941;

Reaction

Reaction ID 3658966
Reactant BRN 6685443 C9H11NO3
Product BRN 84667 (R)-3-hydroxy-1-methyl-indoline-5,6-dione
-------------------------

Reaction Details

Reaction Classification Chemical behaviour
Reagent Fe(NO3)3, KNO3
Solvent H2O
Temperature 25 C
Subject studied Rate constant
Ref. 1 5856275; Journal; Linert, Wolfgang; Herlinger, Erwin; Jameson, Reginald F.; JCPKBH; J.Chem.Soc.Perkin Trans.2; EN; 12; 1993; 2435-2439;

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-the good reverend drone


Beagle
Hive Bee   posted 01-25-1999 02:17 PM           
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I just checked Medline, and low and behold, there has been quite a bit of work done in recent years on the physiological significance of adrenochrome.
One article that I saw on the mechanism of this transformation was Biol Signals, 5(5):275-82 1996 Sep-Oct, where it was suggested that the transformation is an enzyme mediated one, and is dependant on H2O2 and O2-. NADH also apparently stimulates the production of adrenochrome, indicating involvement of NADH dehydrogenase.

I had no idea that this was still a current topic of research, but there were over 100 cites, just going back to 1986.


Beagle
Hive Bee   posted 01-26-1999 09:53 AM           
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Further searching of Medline has yielded the following papers relating to adrenochrome and mental function that may prove interesting. I don't have easy access to any of them. If anyone gets them and finds anything interesting, please post.
Molecular interactions in the phenomenology of the onset of mental illness.
Chem-Biol-Interact. 1973 Jul; 7(1): 1-9

[Chemical interaction between serotonin and adrenochrome. Contribution to the "short circuit" theory of the genesis of mental disease]
Riv-Neurol. 1971 May-Jun; 41(3): 182-7

Short circuit theory on the onset of mental illness.
Clin-Chim-Acta. 1970 Oct; 30(1): 5-11


Mobius
NewBee   posted 01-27-1999 09:01 AM           
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In the book 'Legal Highs' (Adam Gottlieb) I found this monograph concerning Adrenochrome Semicarbazone:
Material ...)

Usage: 100 mg is thoroughly dissolved in just enough alcohol, melted fat (butter), or vegetable oil and ingested. Because of its poor solubility in water these must be used to aid absorption.

Effects: Physical stimulation, feeling of well-being, slight reduction of thought processes.

Contraindications: None noted. Act as a systemic hemostatic preventing capilary bleeding during injury. Adrenochrome causes chemicaly induced schizophrenia. Its semicarbazone does not...

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NAMF
Hive Bee   posted 02-20-2000 04:02 PM           
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unless ya are a real pro I think ya would be finding a mixture of various relater type cat things from such a procedure as seems typicial however not all would be active in a single transport mechanism thats what proally makes ice so dang cool
 
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    DRJEKEYL
(Stranger)
06-29-02 22:33
No 327070
      adrenocrome  Bookmark   

I had orderd adrenochrome from a certain chemical company and i can tell you yhat its completely worthless except for me getting a headache and a stomachache with slight slurred speech and a general bad vibe and trouble sleeping but no neusea but i did the second time at about 80mg experience a wierd head rushing sensation that was very intense and disorenting  with some distortion of time i think but it did have a scopolamine/atropine type feeling of confusion that i was'nt expecting as i had plans but i ended up waking the next morning with 4 messages and a headache that could have been from the valium but overall nothing to stong at what i thought was a high dose and it lasting somewhat around 6-8 hours if it was'nt just in my head.

NOT ONE DRUG IS ACTIVE ITS ONLY THE BRAIN THAT IS