Author Topic: Short Questions Thread (Read 10820 times)

Wizard X · « **Reply #880 on:** May 15, 2011, 06:18:16 AM »

Quote from: no1uno on May 15, 2011, 05:39:32 AM

I'm working on an equation for a process - if the by-product of a reaction is Aluminium triethoxide in ethanol, then the addition of dry sodium carbonate should give sodium ethoxide and insoluble aluminium carbonate, shouldn't it?

Aluminum triethoxide: This product is pure liquid when just boil over. Then it develops to white solid. It decomposes when encountered water. It is hygroscopic. It is lightly soluble in dimethylbenzene, chlorobenzene and other high boiling point solvents. The melting point is 140°C and the boiling point is 200°C. It is used as reducing agent of aldehydes and ketones.Used as polymerized catalyst. This product should be sealed in a dry place.

Super dry ethanol, sodium carbonate, and sodium hydroxide.

no1uno · « **Reply #881 on:** May 15, 2011, 08:50:24 AM »

Yeah, tis what I was wondering - the ethoxide won't decompose the aluminium carbonate?

Adrenaline · « **Reply #882 on:** May 17, 2011, 06:01:04 PM »

Hey guys,

I have a problem.

I can´t get my amphetamine to crystallize.
I made it via the Nitrostyrene and Al/Hg-Reduction. After all Al had reacted I basified, extracted with three portions CH₂Cl₂ and distilled of the methylene chloride. I now had a few ml of a red oily liquid. (I reduced 3,5g P2NP)
I dissolved this oil in about 10ml of Acetone and started to add concentrated sulfuric acid. After the first drops of acid I got a white precipitate which unfortunately redissolved. I thought this was because I added to much acid so I basified again, extracted with methylene chloride and distilled.
This time I dissolved the obtained red oil in 10ml of IPA. After the addition of a few drops of sulfuric acid nothing happened.
I am confused. Maybe I screwed up reduction? What do you think? Any advise how to get the sulfate out of solution?

lugh · « **Reply #883 on:** May 17, 2011, 07:19:40 PM »

It's much harder to crystallize a small amount of an impure freebase than it is to crystallize larger quantities of pure free base

Amphetamine salts are soluble in methyl benzyl ketones so those impurities are probably the problem

It's best to do an acid base extraction followed by fractional vacuum distillation if one wants the job of crystallization to be easy

Some advice from the Hive:

sunlight
(Hive Bee)
04-09-01 04:50
No 183054
Re: How would correctly crystallize w. H2SO4 ?

A very easy way is to take your extractions of the base in ether or toluene, then add IPA/H2SO4 1:10 v/v slowly while swuirling, and check pH till 5-6, let cool, filter and wash with acetone a few times to remove the little excess of H2SO4 (it would decompose your salt with the time). That's all.
If you get a red layer at the bottom (some watter, salt and H2SO4) you need to add acetone to put all in solution and release your crystals.

The end results from the effort applied

Shake · « **Reply #884 on:** May 18, 2011, 02:07:07 AM »

try it in a smaller container, with some acetone, in the the freezer, the acetone should mix well with the MBK but wont dissolve your crystals.. so diluting that remaining, unreacted MBK with acetone, in the freezer in a narroow, test tube like dish, will help your xtals precipitate out..

Evilblaze · « **Reply #885 on:** May 22, 2011, 12:27:39 AM »

I would like to have 2 questions, mainly about two chemical what is really simmilar to MDA/MDMA, the only difference that they are NOT 1-phenyl-propyl-2-amines, they are 1-phenyl-propyl-1-amines. I found some data about them in the "Designer Drug Directory" -by Karel Valter and Philippe Arrizabalaga.

This was written from them:

Quote

Substance Number 4 in Chapter 2.1.2
lUPAC Name: l-Benzo[l,3]dioxol-5-yl-propylamine
Synonyms: 1 -(3,4-Methylenedioxyphenyl)-1 -propanamine
a-Ethyl-(3,4-methylenedioxy)benzylamine
l-Amino-l-(3,4-methylenedioxyphenyl)propane

MF: C10H13NO2
MW: 179.218
CA Registry Number: [127292-42-6]
CA Chemical Name: l,3-Benzodioxole-5-methanamine-a-ethyl-
Category: Psychotomimetic phenethylamine
Street Names: ALPHA
Abuse: Limited
Type of action: Entactogen, euphoriant, psychotomimetic
Human active dose: 100-150 mg
Duration of action: 2-4 hours
Toxic manifestations: Not reported
Toxicity: Not reported

Interestingly, this benzylamine possesses MDMA-like effects in man but
lacks its powerful anorectic activity [1]. It may be easily prepared from
readily available and uncontrolled precursors [2]. This reference also
describes the synthesis and identification of this drug by MS and HPLC. A
seizure of this substance by Dutch authorities has been reported [3].

References:
[1] Shulgin, A.T. and Shulgin, A.: PIHKAL, Transform Press, Inc., P.O.Box
13675, Berkeley, CA, p.718, (1991)
[2] DeRuiter, J.; Clark, C.R.; Noggle, F.T.: J. Chromatogr. Sci., 28, p.l29,
(1990)
[3] King, L.A. et al.: Forensic Sci. Int., 77, p.l41, (1996)

Quote

Substance Number 5 in Chapter 2.1.2
lUPAC Name: (l-Benzo[l,3]dioxol-5-yl-propyl)-methyl-amine
Synonyms: N-Methyl-l-(3,4-methylenedioxyphenyl)-l-propanamine
Ethyl-a-N-methyl-3,4-methylenedioxybenzylamine
l-(Methylamino)-l-(3,4-methylenedioxyphenyl)propane

MF:C11H15N02
MW: 193.245
CA Registry Number: [127292-43-7]
CA Chemical Name: l,3-Benzodioxole-5-methanamine, a-ethyl-N-methyl-
Category: Psychotomimetic phenethylamine
Street Names: MALPHA
Abuse: Limited
Type of action: Entactogen, euphoriant, psychotomimetic
Human active dose: 60-100 mg
Duration of action: 4-6 hours
Toxic manifestations: Not reported
Toxicity: Not reported

Similar to its N-desmethyl analogue, ALPHA, described above, this
benzylamine also possesses MDMA-like effects in man and lacks its powerful
anorectic activity [1]. It may be easily prepared from readily available
precursors [2]. This reference also describes the identification of this drug by
MS and HPLC.

References:
[1] Shulgin, A.T. and Shulgin, A.: PIHKAL, Transform Press, Inc., P.O.Box
13675, Berkeley, CA, p.718, (1991)
[2] DeRuiter, J.; Clark, C.R.; Noggle, F.T.: J. Chromatogr. Sci., 28, p.l29,
(1990)

In the PIHKAL:

Quote

The benzylamine counterpart (as if one were to move the amine function from the beta-carbon to the alpha-carbon of the three carbon chain of the amphetamine molecule) is alpha-ethyl-3,4-methylenedioxybenzylamine or 1-amino-1-(3,4-methylenedioxyphenyl)propane, ALPHA. The hydrochloride salt has a mp of 199-201 °C. At low threshold levels (10 milligram area) there were eyes-closed "dreams" with some body tingling. The compound was not anorexic at any dose (up to 140 milligrams) and was reported to produce a pleasant, positive feeling. It is very short-lived (about 3 hours). The N-methyl homologue is alpha-ethyl-N-methyl-3,4-methylenedioxybenzylamine or 1-methylamino-1-(3,4-methylenedioxy-phenyl)propane, M-ALPHA. It is similar in action, but is perhaps twice as potent (a plus one or plus two dose is 60 milligrams) and of twice the duration.

I couldn't get the references references(DeRuiter, J.; Clark, C.R.; Noggle, F.T.: J. Chromatogr. Sci., 28, p.l29,
(1990)), but both of them looks pretty interesting.

And long ago there was an article posted by Java "1-Phenylethylamines: a new series of illicit drugs?" at: http://127.0.0.1/talk/index.php/topic,568.msg7202.html#msg7202

Have anyone heard from these? Have these ever been tried by someone?

Sedit · « **Reply #886 on:** May 23, 2011, 02:34:19 AM »

Condensation of Benzaldahyde with Nitromethane yeilds the nitrostyrene. Much of the time reduction is performed using NaBH₄ to yeild the nitroalkane or more powerful methods to yeild an amine.

Is there any simple means to reduce just the double bound leaving the Nitrogroup intack other then Sodium Borohydride?

Will the henry reaction performed with the resulting nitro product and formaldahyde stablize the double bond by isomerization or will it remain terminal after dehydration?

Wizard X · « **Reply #887 on:** May 23, 2011, 03:29:01 AM »

Quote from: Sedit on May 23, 2011, 02:34:19 AM

Condensation of Benzaldahyde with Nitromethane yeilds the nitrostyrene. Much of the time reduction is performed using NaBH₄ to yeild the nitroalkane or more powerful methods to yeild an amine.

Is there any simple means to reduce just the double bound leaving the Nitrogroup intack other then Sodium Borohydride?

Yeast. http://www.erowid.org/archive/rhodium/pdf/yeast.nitrostyrene.reduction.pdf

Partial Catalytic Transfer Hydrogenation. http://www.erowid.org/archive/rhodium/chemistry/2cb.beaker.html

Controlled (Partial) Electrochemical Reduction.

Tsathoggua · « **Reply #888 on:** May 23, 2011, 03:30:00 AM »

No reason not to use LAH in anhydrous THF (dry using Na foil or wire, added in small portions at a time, after first using a suitable conventional dessicant, I would reccomend either using N2 or Ar to do that part, although not needed for the reduction itself apparently assuming the LAH is only handled in air most quickly due to loss of yield, and everything kept pretty dry. And of course to exclude O2, as THF is prone to forming peroxides and quite possibly hydroperoxides, which are extremely sensitive, pretty powerful friction and/or shock sensitive explosives which can go off especially if they form as solid deposits on screw threaded tubs. I for one would not fancy being anywhere near an explosion right in/over a container full of diethyl ether, THF, dioxane etc. Diisopropyl ether is apparently particularly quick to form explosive peroxides on oxidation.

Shulgin uses LAH extensively in PIHKAL to reduce nitroalkenes to the the 1-phenyl-2-aminopropane (for the amphetamine) or using EtNO2 rather than MeNO2 to yield the nitroalkene appropriate in either case for the benzaldehyde substrate. Plain benzaldehyde and EtNO2 after reduction of the nitroalkene would of course, yield amphetamine).

IIRC I read tell somewhere that alpha-methylbenzylamines in some cases are fairly potent MAO-a inhibitors, which would be most dangerous with a serotonin releaser or adrenergic drug, causing serotonin syndrome, a hypertensive crisis, or both, 5HT syndrome, is hideously unpleasant and can be fatal. someone very dear to me had a sudden, unpredictable rxn
to sumatriptan and an SSRI which she had taken (SSRI) longterm and the triptan for migraines as needed, she went through hell, collapsed more or less immobile, in absolute misery, she thought she was going to die. By the time she was able to seek help, she had improved in state, and didn't bother, being so fiercely independent, and hating dependence on any medication whatsoever.

This is advice from somebody more experienced than I, about LAH, I am soon to perform a LAH reduction

Sedit · « **Reply #889 on:** May 23, 2011, 03:39:40 AM »

There are many reasons to not use LAH. Main one and the killer is the fact that it forms the amine and that is unwanted. Consider condensing BnO with MeNO₂. Partial reduction to yeild the nitroalkane and then condensation with Formaldahyde would yeild the nitro alcohol. Im curious if when this is dehydrated given the position of the alcohol if it will undergo isomerization to the more stable form which would be the same product you would get from condensing BnO with Nitroethane.

A better means may be to condense CHO with MeNO₂ followed with dehydration and reduction of the double bond since it would increase yeilds condensing Nitroethane with the more valuble BnO however I fear partial reduction would be much harder to control on such a simple substate.

Goldmember · « **Reply #890 on:** May 23, 2011, 09:20:07 PM »

Any suggestions on the best conditions to chlorinate cinnamyl alcohol using HCL instead of thionyl chloride/PCl3 etc? No luck in hunting down an experimental procedure so far.
i

lugh · « **Reply #891 on:** May 23, 2011, 11:06:56 PM »

Quote

Any suggestions on the best conditions to chlorinate cinnamyl alcohol using HCL instead of thionyl chloride/PCl3 etc? No luck in hunting down an experimental procedure so far.i

You should bee able to use the same procedures that work with amino alcohols such as ephedrine, it's been posted that zinc chloride can catalyze that reaction

Sedit · « **Reply #892 on:** May 23, 2011, 11:33:43 PM »

Zinc chloride catalysed chlorination of a primary alcohol(EtOH) proceeds poorly and I would expect even lower results bordering nil on secondary alcohols. I would lean more towards some kind of catalysed Bromination reaction if any sort of yeilds are desired.

lugh · « **Reply #893 on:** May 24, 2011, 12:52:02 AM »

Yields aren't as good but it is feasible:

http://www.sciencemadness.org/talk/viewthread.php?tid=10358#pid123979

Tsathoggua · « **Reply #894 on:** May 24, 2011, 11:37:55 AM »

My bad sedit, I thought you were referring to a henry rxn between the nitro and the substrate intended to give the aminoalkane.

Sedit · « **Reply #895 on:** May 24, 2011, 03:02:42 PM »

Just considering the possibility of circumventing the need for Nitroethane by using commonly avalible materials.

Everything should work out fine by i'm a bit curious if the Pi bond formed thru dehydration of the terminal alcohol will yeild the terminal Alkene. I have a hunch that it would be unstable and isomerize to the next carbon over. I just don't know if it will or not.

If someone wished to however they could reduce the Nitrofunction leaving the alcohol and run an RP/I2 to yeild amphetamine. The henry reaction can be performed sterospecific so it would be one of the few ways to make a single isomer of amphetamine without resorting to Ephedrines.

Tsathoggua · « **Reply #896 on:** May 24, 2011, 04:48:51 PM »

Regarding the henry condensation, a base is used, the good doctor usually used ammonium acetate IIRC from PIHKAL, but I am curious, whilst I have some GAA on the way, or could easily form some conc propionic acid and lead dried NH3 gas into it to give the anhydrous propionic ammonium salt....pain in the bee-hind.

Can triethylenetetramine be used successfully ?

Sedit-In the henry rxn, what determines the stereochemistry of the target compound, in the case of amphetamines?

Sedit · « **Reply #897 on:** May 24, 2011, 07:15:09 PM »

Every step of the condensation is reversible so that when a chiral catalyst is employed it becomes possible to force a single isomer.

From my understanding the single pot using primary amines produces lower yeilds then condensation followed with dehydration.

Tsathoggua · « **Reply #898 on:** May 24, 2011, 07:24:54 PM »

Hm, no idea of the chirality of the TETA I have available....its the hardener of a two-part epoxy resin kit.

The intended targets are a both a phenethylamine and its alpha-methylated counterpart. chirality will be an issue only with the latter of course. Wouldn't surprise me if the TETA is racemic, or do those epoxy hardeners employ a non-racemic amine base?

Is there much of a difference in yield dependent upon the base used? obviously carbonate and alkali metal hydroxides are a bad idea, due to the potential explosive properties if the nitronate salt is allowed to form.

Sedit · « **Reply #899 on:** May 25, 2011, 01:44:13 AM »

The catalyst may be complex but Im sure there are simpler ones that can be had once the process is fully understood.

Author Topic: Short Questions Thread (Read 10820 times)

Wizard X

Re: Short Questions Thread - Aluminium ethoxide + sodium hydroxide =?

no1uno

Re: Short Questions Thread

Adrenaline

Re: Short Questions Thread

lugh

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Shake

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Evilblaze

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Sedit

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Wizard X

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Tsathoggua

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Sedit

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Goldmember

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lugh

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Sedit

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lugh

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Tsathoggua

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Sedit

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Tsathoggua

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Sedit

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Tsathoggua

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Sedit

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