dormouse
(Member)
04-21-00 03:10
No 108433
      boosting psilocin's octane numbers -drone 342
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Author  Topic:   boosting psilocin's octane numbers 
drone 342
Member   posted 07-16-98 04:47 PM          
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Being the enormous fan of psilocin and psilocybin that I am, I've given a lot of thought to taking a good thing, and running amok with it.
As everybody knows, the thing that makes psilocin so active is its acidity on the 4-position (the hydroxy group). This is at least what the cnsensus seems to be. What about boosting the pKa there? Starting from 2-halo-6-nitrotoluenes (available through several companies at reasonable prices) and diethyl oxalate, you can make 4-haloindole through the intermediate (2-chloro-6-nitrophenyl) pyruvic acid. Going from there, it can be substituted to make the hydroxy, the thiol, the peroxy, or the carboxylate of indole. From there, its just a couple steps from being something crazy I have a funny suspicion that DET- or DMT-4-carboxylic acid would be pretty nifty.

drone #342


spiceboy
Member   posted 07-17-98 10:53 AM          
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Hey. While I agree with you in principle, that is a little technical. I am going to ask you to call on your theory now. Tell me why some sick fucker couldnt (or could) make DMT from melatonin?
waiting patiently.


drone 342
Member   posted 07-17-98 01:46 PM          
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You can't make DMT from melatonin, but you can make 5-MeO. Melatonin is N-acetyl-5-hydroxy-tryptamine. Deacetylating it is cake (just a swish in some base for awahile will do it), then it is easily alkylated with methylamine.
Not only can it be used to make 5-MeODMT, it could also be useful to make 5-MeODET, 5-MeODiPT, etc...By first methylating the hydroxy with MeI, perhaps the Acetyl could act as a protecting group -- making the amine less nucleophilic by withdrawing electrons from its lone pair. Then deacetylation, followed by N-alkylation. I'm not guarunteeing this last bit, but I will guaruntee you that you can make 5-MeODMT.
-drone #342


monkey
unregistered   posted 07-17-98 06:32 PM           
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All right, you've raised my curiosity. WRT this swishing and alkylating: times, temps, ID of base, lit ref?
rgds,
monkey


assholium
Member   posted 07-18-98 03:52 AM          
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Drone,
you fucked up ^) -
but take it easy.

>You can't make DMT from melatonin, but you can make 5-MeO. Melatonin >is N-acetyl-5-hydroxy-tryptamine. Deacetylating it is cake (just a >swish in some base for awahile will do it), then it is easily >alkylated with methylamine.

melatonin - N-acetyl-5-MeO-tryptamine. And if you have a dream convert it to some N,N-dialkylated tryptamine, - this is simple 2-step one-pot synth. Just reduce melatonine with LAH, and then BEFORE usial hydrolysis add some ethylacetate and reflux this mixture another 6-8 hrs. After decomp. of unreacted LAH with water - you get N,N-diethyl-5-MeO-tryp. yields near 45-50%. Need refs and experimental details?

PS. ...add some ethylpropionate instead of ethylacetate - and you get N,N-ethylpropyl derivative, from ethylisopropionate - N,N-ethylisopropyl. Very fun compounds. BTW, ethylisopropionate i made by reduction of ethylmetacrylate with NaBH4/NiCl2 in ethanolic media. Another idea - using ethylmetacrylate directly in LAH reduction of melatonine. I guess, this will be N,N-ethylmetallyl derivative. Weird and mad-power compound. Never tried it... Huh, chemists! anybody!!! is this stuff (N,N-ethylmetallyl) desribed in TIHKAL? or not?


 
Lump
unregistered   posted 07-18-98 08:53 AM           
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Okay - I'll bite: What is the simplest (most OTC) method of producing N,N DMT from tryptophan? I can't wait for Rhodium's FAQ any longer.... ;>
Details please...my readers expect my protagonist to ponder every step at length...


 
assholium
Member   posted 07-18-98 01:32 PM          
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>from ethylisopropionate - N,N-ethylisopropyl
Sounds crazy. Like "isoformiate". I mean "ethylisobutyrate - N,N-ethylisobutyl" possibly, who knows?


drone 342
Member   posted 07-20-98 10:54 AM          
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Damb! Assholium, you nailed me there! What was I THINKING!?!?! Obviously, methylamine is not used.
N-alkylation is done properly at ambient temperature by disolving PTC in CH2Cl2, and adding finely-ground NaOH or KOH. This is stirred for a half an hour or so, then your amine is added (in this case, tryptamine). After another 0.5 h, add your alkyl halide, and let stir overnight. The next day, filter the solution, wash the filtrate, then combine the washing with the rest of the solution, wash with H2O, then dry with MgSO4, then evaporate off the solvent. Yields are in the high 90's.

Of course, decarboxylation of amino acids (like tryptophan into tryptamine) are best done by heating in a high-boiling solvent with just a tiny dash of ketone.

Sorry about the melatonin mix-up. Still I have to say, my way's better.  Who on "Bob"'s blue Earth wants to work with LAH, when they can do without it? Amide hydrolysis is a snap, then alkylation goes smoothly.

Still, I have to admit, your way looks like the way to do it if you're into "mixed" alkylated tryptamines. Of course, I'm going to need to see some ref's, notes, and whatever other lit you have on this.

If this really is as slick as you say, it could be made even more useful. By hydrolyzing melatonin like I said, then reacting 5-MeO tryptamine with propionic anhydride (check out the synth I slapped together at Rhodium's page for that), or acetic formic anhydride (nomenclature?). Then, 5MeO-methylpropyltryptamine and many other tryptamines become possible.

Of course,yet another variation that could be done would be exhaustively aminating with MeI to form the quaternary salt, then reacting it with piperidine, morpholine, or other cyclic amines for some serious wierdness.

Anyways, you also fucked up.  You said:

"Sounds crazy. Like 'isoformiate'. I mean 'ethylisobutyrate - N,N-ethylisobutyl' possibly, who knows?"

"Isoformiate"? That sounds like some whacked-out stuff; what kind of structure would THAT have? Also, while isobutyric acid exists, "isobutyl" as an alkyl substituent does not exist, or at least its bad nomenclature (I don't even know what you mean by it.) There is n-butyl-, sec-butyl-, and tert-butyl alkanes, but not isobutyl.

-drone #342


drone 342
Member   posted 07-20-98 10:56 AM          
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Assholium,
Thanks for calling me on that one; we have to keep pushing our standards higher, and a little friendly correction is always good.

-drone #342


assholium
Member   posted 07-23-98 12:09 PM          
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>Thanks for calling me on that one; we have to >keep pushing our standards higher, and a >little friendly correction is always good.
Believe me, Drone, I'm completely friendly bee. Especially when stoned  ))

Well. Closer to lovely tryptamines chemistry.
HCA 49, f.3, No.132-133 p.1199 (1966): Roland Stauffer,
Synthese de nouvelles tryptamines substituees

[fashinating article, folks. sorry i have'nt scanner, so...]

N-methyl-indolyl-3-glyoxylamide (VI) Dans une solution de 100 g d'indole dans 2,5 l d'ether seche sur CaH2, on introduit goutte a goutte en une heure, avec une forte agitation 100 ml de chlorure d'oxalyle, la temperature etant maintenue au-dessous de 20C. Le chlorure l'acide indolyl-3-glyoxylique commence a crisstaliser apres l'introduction d'un tiers du chlorure d'oxalyle. L'introduction terminee, on agite encore une heure, puis filtre le chlorure (145 g, seche a l'air). Introduit par petites quantites a la fois dans 500 ml de methylamine aqueuse entre 0 et 10C, ce chlorure fournit 125 g (73%) d'amide VI, F. 222-223, aiguilles blanches (ethanol).

N-methyltryptamine (IV) 30 g d'amide VI places dans le cartouche d'un appareil Soxhlet sont extraits pendant 6 joirs par 2,5 l d'ether sec contenant 30 g de LiAlH4 en suspension. La decomposition est effectuee a froid par 100 ml de THF contenant 20% d'eau, puis par 100 ml d'eau. Apres filtration des hydroxydes et concentration du filtrat sous 12 Torr, on obtient 25 g d'une huile jaine qu'on distille sous vide (Eb. 150-155/ 0,2 Torr). Le distillat, dissous dans 75 ml de benzene, fornuit 18 g (71%) de IV en prismes blancs, F. 89C.

Benzyloxy-5-N,N-methylethyltryptamine (II) par reduction alcoylante de la benzyloxy-5-N-formyltryptamine (VII). Une solution de 35 g de VII dans 150 ml de THF est introduite goutte a goutte dans une suspension de 20 g de LiALH4 dans 400 ml de THF. Apres un reflux de 12 h, on ajoute lentement 35 ml d'acetate d'ethyle, prolonge le reflux 2 h encore et decompose par l'eau et NaOH a 15% comme ci-dessus. On obtent 20 g (42%) de II, isole comme oxalate, F.165C.

N-Methyltryptamine et N,N-methylethyltryptamine (I) 45 g d'amide VI sont extraits dans un appareil Soxhlet par 2.5 l d'ether sec, contenant 45 g de LiALH4 en suspension. L'extraction se fait en 6 joirs. Apres refroidissement a 15C on ajoute lentement 100 ml d'acetate d'ethyle, puis prolonge le reflux de 2 h. On decompose par l'eau et NaOH a 15% comme precendemment, filtre les hydroxydes et concentre les filtrats sous 12 Torr. On obtient ainsi une huile qui presente une fluorescence violette et distille entre 160 et 168 sous 0.2 Torr. Dissoute dans 100 ml de methanol et additionnee de 15 g d'acide oxalique anhydre, elle fournit une premiere fraction d'oxalate correspondant a l'oxalate de N-menthyltryptamine (IV) soit 13 g, prismes incolores, F. 178-180.
Le filtrat est aditionne de 50 ml d'ether et refroidi a -10C. Il fournit une deuxieme fraction d'oxalate, qui, recristallisee dans le methanol, pese 15 g. Il s'agit de l'oxalate de N,N-methylethyltryptamine (I), aiquilles blanches, F. 120.

[hhhuuuhhh... Drone, two beers from you  )]

OK.

>N-alkylation is done properly at ambient >temperature by disolving PTC in CH2Cl2, and >adding finely-ground NaOH or KOH. This is

OOppss! PTC - phase transfer catalysis, isn't it? How to dissolve PTC in CH2Cl2? Some witchcraft? Ouch... phase tranfer catalyst, yes?

>stirred for a half an hour or so, then your >amine is added (in this case, tryptamine). >After another 0.5 h, add your alkyl halide, >and let stir overnight. The next day,
>filter the solution, wash the filtrate, then >combine the washing with the rest of the >solution, wash with H2O, then dry with >MgSO4, then evaporate off the solvent. >Yields are in the high 90's.

... and you have sec, tert, and quat. amine salt from initial amine. And don't forget, indole moiety have own nitrogen too!

This is very interesting item - transformation tryptamine to DMT. Wanna some refs, Drone? 


Draeno
unregistered   posted 07-23-98 07:08 PM           
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Ok, I am kinda new around here so please don't flame me too hard for this one. I saw the French stuff and ran it through a translator 'cause I thought it might be interesting. This is the best I could get:


N-methyl-indolyl-3-glyoxylamide (VI) In a solution of 100 g of [indole] in 2.5 l of dry ether on CaH2, one introduces drop has drop in an hour, with a strong agitation 100 [ml] of chloride of [oxalyle], the temperature being maintained beneath of 20C.

The chloride the acid indolyl-3-glyoxylique begins be <2 Qnt> <3 Noun> old{Adv} [crisstaliser] after the introduction of a third of chloride of [oxalyle].

The ended introduction, one agitates an hour again, then filters the chloride (145 g, dry looks). Introduces by small quantities at a time in 500 [ml] of aqueous [methylamine] between 0 and 10C, this chloride provided 125 g (73%) of VI [amide], F. 222-223, white needles ([ethanol]). [N] N-methyltryptamine (IV) 30 g of VI [amide] places in the cartridge of a Soxhlet device is excerpts for 6 [joirs] by 2.5 l of dry ether containing 30 g of LiAlH4 in abeyance.

The decomposition is done is cold by 100 [ml] of THF containing 20% of water, then by 100 [ml] of water. After filtration of the [hydroxydes] and concentration of [filtrat] under 12 Torr, one gets 25 g of an oil [jaine] that one distills under emptiness (Eb. 150-155/ 0.2 Torr). The [distillat], dissolves in 75 [ml] of benzene, [fornuit] 18 g (71%) of IV in white prisms, F. 89C.

Benzyloxy-5-N, [N] N-methylethyltryptamine (II) by reduction [alcoylante] of the benzyloxy-5-N-formyltryptamine (VII). A solution of 35 g of VII in 150 [ml] of THF is introduced drop has drop in an abeyance of 20 g of LiALH4 in 400 [ml] of THF. After an ebb of 12h, one adds 35 [ml] of acetate of [ethyle] slowly, prolongs the ebb 2 h again and decomposes by the water and NaOH has 15% like above. One [obtent] 20 g (42%) of II, isolates like [oxalate], F.165C. [N] N-Methyltryptamine and N, [N] N-methylethyltryptamine (I) 45 g of VI [amide] is excerpts in a device Soxhlet by 2.5 l of dry ether, containing 45 g of LiALH4 in abeyance. The extraction makes in 6 [joirs]. After cooling has 15C one adds 100 [ml] of acetate of [ethyle] slowly, then prolongs the ebb of 2 h. One decomposes by the water and NaOH has 15% like [precendemment], filters the [hydroxydes] and concentrates the [filtrats] under 12 Torr. One gets an oil who presents a thus fluorescence violet and distills between 160 and 168 under 0.2 Torr. Dissolved in 100 [ml] of [methanol] and added of 15 g of acid [oxalique anhydre], she provided a first fraction of [oxalate] correspondent has the [oxalate] of [N] N-menthyltryptamine (IV) is 13 g, colorless prisms, F. 178-180.The [filtrat] is [aditionne] of 50 [ml] of ether and cooled has- 10C. He provided a second fraction of [oxalate], who, [recristallisee] in the [methanol], weighed 15 g. He was about the [oxalate] of N, [N] N-methylethyltryptamine (I), white [aiquilles], F. 120.

If this was rude of please let me know. If it wasn't rude, could you please e.mail me some synth's and ref's for tryptamines? I would appreciate it

hecuba@uclink4.berkeley.edu


<>
 
ICEKAT
Member   posted 07-23-98 08:49 PM          
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Wow, that was not rude at all. Maybe helped many like myself. Thanks!
ICEKAT


 
drone 342
Member   posted 07-24-98 09:27 AM          
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Assholium,
I see what your concerns, and to tell you the truth, I can't explain it entirely either. However, PTC does mean phase transfer catalyst (I use benzyltriethylammonium chloride), and DCM is right. NaOH doesn't dissolve too well in DCM either, so you get a bit of a slurry.

I'm on vacation right now, and I'm away from my ref's, however, this is a common proceedure, and works like a charm. Actually, Sasha lists a variation on these methods in TiHKAL -- mine just happens to work better and is easier to perform than the ones he listed. As for your concerns about secondary and quaternary impurities, have no fear; the alkylation goes to completion, and the base keeps the reaction from going to exhaustive N-alkylation. This is why an excess of the alkyl halide is used.

The indole is NOT alkylated, and I'll tell you why. Indole is an aromatic polycyclic ring structure. The lone pair on the 1-position is NOT yer typical amine (i.e. not much of a nucleophile.) By donating that lone pair, it loses its aromaticity, and destabilizes. It doesn't do this without a good reason (if a worthwhile electron withdrawing group like an aldehyde were dangling on the 3-position, we got another story alltogether.) So, to make it short, the nitrogen in indole is not a basic amine. It doesn't do shit here.

I hope this disspells some of your fears and skepticism. I haven't steered anybody TOO wrong around here, and I intend to keep things that way. Sometimes the shit I pull out is wierd, but its been reviewed pretty closely before I say anything. I'm glad you're demanding good info.

-drone #342


drone 342
Member   posted 07-26-98 04:30 PM          
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Here's a crapload of info off Beilstein related to N,N dialylation methods that may be interesting in addition to the method I described. Its all N,N-dialkylation as related to phenethylamines, but the methods here will work for tryptamines as well. In addition, the conditions are similar enough to the conditions I described to grant my idea even more plausability.
phenylpropanolamine -> N,N-diethylphenylpropanolamine

Reaction
Reaction ID 2852902
Reactant BRN 505934 iodoethane 4292102 C9H13NO
Product BRN 4743622 C13H21NO
-------------------------

Reaction Details
Reaction Classification Preparation
Reagent K2CO3
Solvent ethanol
Yield 43. (BRN4743622)
Other conditions Heating
Ref. 1 5584063; Journal; Soai, Kenso; Yokoyama, Shuji; Hayasaka, Tomoiki; JOCEAH; J.Org.Chem.; EN; 56; 13; 1991; 4264-4268;

Reaction
Reaction ID 4685049
Reactant BRN 505934 iodoethane
2802895 (1S,2S)-2-amino-1-phenyl-propan-1-ol
Product BRN 7745428 C13H21NO
-------------------------

Reaction Details
Reaction Classification Preparation
Solvent methanol
Time 20 hour(s)
Yield 82. (BRN7745428)
Other conditions Heating
Ref. 1 6058763; Journal; Enders, Dieter; Zhu, Jiqun; Kramps, Laurenz; LIARFV; Liebigs Ann.,Recl.; EN; 6; 1997; 1101-1114;

phenethylamine -> N,N-dimethylphenethylamine

Reaction
Reaction ID 662929
Reactant BRN 507488 phenethylamine 1209228 formaldehyde
Product BRN 637106 dimethyl-phenethyl-amine
-------------------------

Reaction Details 1 of 5
Reaction Classification Preparation
Reagent formic acid
Ref. 1 1913639; Journal; Icke; Wisegarver; Alles; ORSYAT; Org.Synth.; 25; 1945; 89;
-------------------------

Reaction Details 2 of 5

Reaction Classification Preparation
Reagent 88percent HCOOH
Other conditions 1.) 0 deg C, 1 h, 2.) 90 deg C, 4 h
Ref. 1 5812809; Journal; Ding, Charles Z.; Lu, Xingliang; Nishimura, Kuniko; Silverman, Richard B.; JMCMAR; J.Med.Chem.; EN; 36; 12; 1993; 1711-1715;
-------------------------

Reaction Details 3 of 5

Reaction Classification Preparation
Reagent 90percent HCOOH
Other conditions Heating
Ref. 1 5556382; Journal; Brine, G. A.; Boldt, K. G.; Huang, P.-T.; Sawyer, D. K.; Carroll, F. I.; JHTCAD; J.Heterocycl.Chem.; EN; 26; 1989; 677-686;
-------------------------

Reaction Details 4 of 5

Reaction Classification Preparation
Reagent 1.) ZnCl2, 2.) NaBH4
Other conditions 1.) CH2Cl2, RT, 1 h, 2.) CH2Cl2, 11 h
Note 1 Yield given. Multistep reaction
Ref. 1 5972853; Journal; Bhattacharyya, Sukanta; SYNCAV; Synth.Commun.; EN; 25; 14; 1995; 2061-2070;
-------------------------

Reaction Details 5 of 5

Reaction Classification Preparation
Reagent 98percent HCOOH
Time 6 hour(s)
Other conditions Heating
Ref. 1 6055343; Journal; Riddell, Frank G.; Rogerson, Martin; JCPKBH; J.Chem.Soc.Perkin Trans.2; EN; 2; 1997; 249-256;

amphetamine -> dimethylamphetamine

Reaction
Reaction ID 97323
Reactant BRN 1209228 formaldehyde 2205872 (S)-1-methyl-2-phenyl-ethylamine
Product BRN 2690504 dimethyl-<(S)-1-methyl-2-phenyl-ethyl>-amine
-------------------------

Reaction Details 1 of 2
Reaction Classification Preparation
Reagent formic acid
Ref. 1 1956519; Journal; Parham et al.; JACSAT; J.Amer.Chem.Soc.; 74; 1952; 5646;
-------------------------

Reaction Details 2 of 2
Reaction Classification Preparation
Reagent HCO2H
Ref. 1 292452; Journal; Schaeffer,J.C. et al.; JPMSAE; J.Pharm.Sci.; EN; 65; 1976; 122-126;

Reaction
Reaction ID 97865
Reactant BRN 1209228 formaldehyde 3195619 (+-)-1-methyl-2-phenyl-ethylamine
Product BRN 3196960 (+-)-dimethyl-<1-methyl-2-phenyl-ethyl>-amine
-------------------------

Reaction Details
Reaction Classification Preparation
Reagent formic acid
water
Ref. 1 1956522; Journal; Simon; ZOKHA4; Zh.Obshch.Khim.; 28; 1958; 2586;engl.Ausg.S.2619;

Reaction ID 664571
Reactant BRN 507867 1-methyl-2-phenyl-ethylamine
1209228 formaldehyde
Product BRN 1938312 dimethyl-<1-methyl-2-phenyl-ethyl>-amine
-------------------------

Reaction Details 1 of 4
Reaction Classification Preparation
Reagent aqueous ethanol
Raney nickel
sodium acetate
Other conditions Hydrogenation
Ref. 1 1934259; Journal; Woodruff; Lambooy; Burt; JACSAT; J.Amer.Chem.Soc.; 62; 1940; 922;
-------------------------

Reaction Details 2 of 4
Reaction Classification Preparation
Reagent HCO2H, aq. HCl
Ref. 1 274538; Journal; Babayan,A.T. et al.; JOCYA9; J.Org.Chem.USSR (Engl.Transl.); EN; 2; 1966; 1939-1945; ZORKAE; Zh.Org.Khim.; RU; 2; 1966; 1974-1983;
-------------------------

Reaction Details 3 of 4
Reaction Classification Preparation
Reagent formic acid
Time 24 hour(s)
Yield 91. (BRN1938312)
Other conditions Heating
Ref. 1 5559447; Journal; Machkova, Zuzana; Zavada, Jiri; CCCCAK; Collect.Czech.Chem.Commun.; EN; 46; 4; 1981; 833-849;
-------------------------

Reaction Details 4 of 4
Reaction Classification Preparation
Reagent 98percent HCOOH
Solvent H2O
Time 6 hour(s)
Other conditions Heating
Ref. 1 6055343; Journal; Riddell, Frank G.; Rogerson, Martin; JCPKBH; J.Chem.Soc.Perkin Trans.2; EN; 2; 1997; 249-256;

Reaction ID 933349
Reactant BRN 1209228 formaldehyde 2205872 (S)-1-methyl-2-phenyl-ethylamine
Product BRN 3196959 dimethyl-<(R)-1-methyl-2-phenyl-ethyl>-amine
-------------------------

Reaction Details
Reaction Classification Preparation
Reagent H2
Catalyst Pd-C
Solvent methanol
H2O
Ref. 1 95046; Journal; Gacek,M.; Undheim,K.; ACBOCV; Acta Chem.Scand.Ser.B; EN; 29; 1975; 206-212;

Reaction
Reaction ID 1678863
Reactant BRN 1209228 formaldehyde
4291522 (S)-(+)-1-phenyl-2-aminopropane
Product BRN 4664159 C11H17N
-------------------------

Reaction Details 1 of 2
Reaction Classification Preparation
Reagent 90percent HCOOH
Other conditions Heating
Ref. 1 5556382; Journal; Brine, G. A.; Boldt, K. G.; Huang, P.-T.; Sawyer, D. K.; Carroll, F. I.; JHTCAD; J.Heterocycl.Chem.; EN; 26; 1989; 677-686;
-------------------------

Reaction Details 2 of 2
Reaction Classification Preparation
Reagent formic acid, water, NaOH
Time 8 hour(s)
Yield 63.5 (BRN4664159)
Temperature 100 ÝC
Other conditions Heating
Ref. 1 5611228; Journal; Blagg, Julian; Davies, Stephen G.; TETRAB; Tetrahedron; EN; 43; 19; 1987; 4463-4472;

Reaction
Reaction ID 1679550
Reactant BRN 1209228 formaldehyde 4666456 C9H12DN
Product BRN 4672245 C11H16DN
-------------------------

Reaction Details
Reaction Classification Preparation
Reagent formic acid
Time 24 hour(s)
Yield 98. (BRN4672245)
Other conditions Heating
Ref. 1 5559447; Journal; Machkova, Zuzana; Zavada, Jiri; CCCCAK; Collect.Czech.Chem.Commun.; EN; 46; 4; 1981; 833-849;

Reaction
Reaction ID 4686995
Reactant BRN 507867 1-methyl-2-phenyl-ethylamine
1209228 formaldehyde
Product BRN 7722181 C11H17N*BrH
-------------------------

Reaction Details
Reaction Classification Preparation
Reagent 1.) 98percent HCOOH, 2.) 48percent HBr
Other conditions 1.) H2O, reflux, 6 h, 2.) ethanol
Note 1 Multistep reaction
Ref. 1 6055343; Journal; Riddell, Frank G.; Rogerson, Martin; JCPKBH; J.Chem.Soc.Perkin Trans.2; EN; 2; 1997; 249-256;

In addition, here's some stuff pertaining to the alkylation of indoles on the 1-position. THis apparently only happens, as I said before, when the 3-position is either unsubstituted, or substituted with a reasonably effective electron withdrawing group.

indole -> 1-methylindole

Reaction
Reaction ID 1560530
Reactant BRN 107693 indole
969135 iodomethane
Product BRN 111026 1-methyl-indole
-------------------------

Reaction Details 1 of 8
Reaction Classification Preparation
Reagent 50percent NaH
Solvent dimethylsulfoxide
benzene
Time 8 hour(s)
Yield 86. (BRN111026)
Temperature 50 ÝC
Ref. 1 5725306; Journal; Courant, Jacqueline; Leblois, Danielle; Tandon, Manju; Robert-Piessard, Sylvie; le Baut, Guillaume; et al.; EJMCA5; Eur.J.Med.Chem.Chim.Ther.; FR; 24; 1989; 145-154;
-------------------------

Reaction Details 2 of 8
Reaction Classification Preparation
Reagent sodium hydride
Solvent dimethylsulfoxide
Yield 65. (BRN111026)
Ref. 1 5728463; Journal; Jackson, Anthony H.; Lynch, Patrick P.; JCPKBH; J.Chem.Soc.Perkin Trans.2; EN; 1987; 1483-1488;
-------------------------

Reaction Details 3 of 8
Reaction Classification Preparation
Reagent KOH
Catalyst PEG methyl ether
Solvent toluene
Time 0.5 hour(s)
Yield 65. (BRN111026)
Other conditions Irradiation
Ref. 1 5552090; Journal; Davidson, R. Stephen; Patel, Ali M.; Safdar, Ali; Thornthwaite, David; TELEAY; Tetrahedron Lett.; EN; 24; 52; 1983; 5907-5910;
-------------------------

Reaction Details 4 of 8
Reaction Classification Preparation
Reagent Na/liquid NH3
Catalyst Fe(NO3)3*9H2O
Solvent diethyl ether
Yield 90. (BRN111026)
Ref. 1 5562811; Journal; Davis, Paul D.; Neckers, Douglas C.; JOCEAH; J.Org.Chem.; EN; 45; 3; 1980; 456-462;
-------------------------

Reaction Details 5 of 8
Reaction Classification Preparation
Reagent Thallium(I) ethoxide
Solvent benzene
Yield 60. (BRN111026)
Other conditions Heating
Ref. 1 5572646; Journal; Shafiee, A.; Sattari, S.; SYNTBF; Synthesis; EN; 5; 1981; 389-390;
-------------------------

Reaction Details 6 of 8
Reaction Classification Preparation
Reagent 1.) KOH
Other conditions 1.) acetone, 2.) room temp., 10 min
Note 1 Yield given. Multistep reaction
Ref. 1 5573640; Journal; Kikugawa, Yasuo; Miyake, Yuko; SYNTBF; Synthesis; EN; 6; 1981; 461-462;
-------------------------

Reaction Details 7 of 8
Reaction Classification Preparation
Reagent potassium tert-butoxide
Catalyst 18-crown-6
Solvent diethyl ether
Time 1 hour(s)
Yield 94. (BRN111026)
Other conditions Ambient temperature
Ref. 1 5576181; Journal; Guida, Wayne C.; Mathre, David J.; JOCEAH; J.Org.Chem.; EN; 45; 16; 1980; 3172-3176;
-------------------------

Reaction Details 8 of 8
Reaction Classification Chemical behaviour
Catalyst PEG methyl ether
Solvent toluene
Other conditions with or without ultrasound
Subject studied Product distribution
Ref. 1 5552090; Journal; Davidson, R. Stephen; Patel, Ali M.; Safdar, Ali; Thornthwaite, David; TELEAY; Tetrahedron Lett.; EN; 24; 52; 1983; 5907-5910;

indole-3-carboxaldehyde -> (1-methyl)indole-3-carboxaldehyde

Reaction
Reaction ID 77668
Reactant BRN 114117 indole-3-carbaldehyde
Product BRN 121302 1-methyl-indole-3-carbaldehyde
-------------------------

Reaction Details
Reaction Classification Preparation
Reagent tert-butyl alcohol
potassium tert-butylate
Other conditions unter Sickstoff und anschliessend mit Methyljodid.
Ref. 1 1040686; Journal; Wenkert et al.; JACSAT; J.Amer.Chem.Soc.; 81; 1959; 3763,3768;

Reaction
Reaction ID 1647439
Reactant BRN 114117 indole-3-carbaldehyde 969135 iodomethane
Product BRN 121302 1-methyl-indole-3-carbaldehyde
-------------------------

Reaction Details 1 of 6
Reaction Classification Preparation
Reagent NaH
Solvent tetrahydrofuran
Yield 80. (BRN121302)
Other conditions Ambient temperature
Ref. 1 5802602; Journal; Chapman, Robert F.; Phillips, Norman I. J.; Ward, Robert S.; HTCYAM; Heterocycles; EN; 24; 11; 1986; 3115-3128;
-------------------------

Reaction Details 2 of 6
Reaction Classification Preparation
Reagent K2CO3
Solvent acetone
Yield 65. (BRN121302)
Ref. 1 5627790; Journal; Moody, Christopher J.; Ward, John G.; JCPRB4; J.Chem.Soc.Perkin Trans.1; EN; 12; 1984; 2903-2909;
-------------------------

Reaction Details 3 of 6
Reaction Classification Preparation
Reagent NaOH, trimethylbenzylammonium chloride
Solvent H2O
Time 3 hour(s)
Yield 51.4 (BRN121302)
Temperature 35 - 40 ÝC
Ref. 1 5631275; Journal; Velezheva, V. S.; Yaroslavskii, I. S.; Kurkovskaya, L. N.; Suvorov, N. N.; JOCYA9; J.Org.Chem.USSR (Engl.Transl.); EN; 19; 7; 1983; 1367-1376; ZORKAE; Zh.Org.Khim.; RU; 19; 7; 1983; 1518-1529;
-------------------------

Reaction Details 4 of 6
Reaction Classification Preparation
Reagent 1.) LiCN
Other conditions 1.) THF, room temp., 5 min, 2.) 25 deg C, 5 h
Note 1 Yield given. Multistep reaction
Ref. 1 5641638; Journal; Kurihara, Takushi; Fujimoto, Toshiro; Harusawa, Shinya; Yoneda, Ryuji; SYNTBF; Synthesis; EN; 4; 1987; 396-397;
-------------------------

Reaction Details 5 of 6
Reaction Classification Preparation
Reagent 1.) potassium hydroxide
Other conditions 1.) DMSO, 0.5 h; 2.) room temperature, 2 h
Note 1 Yield given. Multistep reaction
Ref. 1 5725079; Journal; Canoira, Laureano; Rodriguez, J. Gonzalo; Subirats, Juan B.; Escario, Jose-Antonio; Jimenez, Isabel; Martinez-Fernandez, Antonio R.; EJMCA5; Eur.J.Med.Chem.Chim.Ther.; EN; 24; 1989; 39-42;
-------------------------

Reaction Details 6 of 6
Reaction Classification Preparation
Reagent 50percent NaH
Solvent dimethylformamide
benzene
Time 8 hour(s)
Temperature 50 ÝC
Ref. 1 5725306; Journal; Courant, Jacqueline; Leblois, Danielle; Tandon, Manju; Robert-Piessard, Sylvie; le Baut, Guillaume; et al.; EJMCA5; Eur.J.Med.Chem.Chim.Ther.; FR; 24; 1989; 145-154;

In addition to all of this, there's also the entries in TiHKAL that are akin to both the methods I've described, as well as some of the articles listed here. Check under DMT, DET, and a couple others.

hope this all helps,

-drone #342


drone 342
Member   posted 07-30-98 08:54 PM          
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Hello? Anybody there? Any coments? Anybody at least look up the stuff in TiHKAL that I mentioned? That book has some pretty practical cooking tips if you look closely enough. Yes, I know that half of the damn thing is devoted to cooking, but I mean there's some reeeely substancial meat in there that goes beyond the typical awe-inspiring Shulgin shennanigans.
-drone #342


Piglet
Member   posted 07-31-98 06:45 AM          
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Unfortunatly, not all of us live within striking distance (get it!) of a good library, which is a great shame. If I could check out the references, I would love to comment. Could you send just a couple to OP's new page, maybe? I would love to rap!
Piglet 

P.S. the PPA synth via 2-bromo acetophenone. What would happen if you added Na2NCN at that point? Just a small idea that has been bugging me.


jimwig
Member   posted 07-31-98 07:49 AM          
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You guyz- all this and brains too.
I stand in the wings and marvel at the gymnastics you all perform with those molecules.

Someday. . . . . JW


drone 342
Member   posted 08-03-98 10:17 PM          
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Here's a review of a few tryptamine articles I've dug up from the droniam chem library.
"La decarboxylation thermique des acides alpha-amines. 1," Chateulus, Bull. Soc. Chim. France 1964, III, 2523-2542
In French, but is a good resource for anybody interested in the decarboxylation of tryptamine by heating with a ketone catalyst.

J. Chem Soc. Perkin Trans. 1, 1992
Describes decarboxylation by just heating the fuck out of it in diphenyl ether *sans* ketone.

Hashimoto, et al; "A NOVEL DECARBOXYLATION OF a-AMINO ACIDS. A FACILE METHOD OF DECARBOXYLATION BY THE USE OF 2-CYCLOHEXEN-1-ONE AS A CATALYST" Chem. Lett. 893-896, 1986
Same as the last article, but older, and in English. Yields are good, but their catalyst is more exotic than it has to be. Still, defiately worth getting.

"EFFICIENT SYNTHESIS OF TRYPTAMINE" Takano, et al; heterocycles, vol 6, no 8, (1977), 1167-1171
This is a great article. They try with different ketones and different molar ratios. This is definately one to get.

I still will go back and look for more articles regarding the alkylation, but like I said, its all in TiHKAL (and in me.)

-drone #342


Slappy
Moderator   posted 04-05-99 08:34 PM          
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Drone,
Have you made any progress on this either? The idea of 4-carboxy-DMT really intrigues me. Is there any way that you could build this from say, tryptamine?

-S


KrZ
Member   posted 04-11-99 01:25 PM          
--------------------------------------------------------------------------------
Drone; Do you have an email or any way I can contact you?
 
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