Bluetooth
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Phenylethylamines by alkylation of alpha nitroesters
I've found this in some Hive files on an old CD-Rom, so why don't post them!!!!
(this one was posted by lego from the hive).
Step 1: Bromomethylation of benzene
Monatshefte, 1950, 917-920
111,0 dry, finely powdered NaBr is suspended in 50,0 g benzene1, 50,0 ml glacial acetic acid and 27,0 g paraformaldehyde. The mixture is stirred and
heated to reflux at 80° C. Over a period of 3 h a mixture of 158,0 g sulfuric acid (d = 1,84 g/ml, 96%) and 80,0 ml glacial acetic acid is added. The
mixture is stirred for further 9 h at 80° C, then for 8 h at 80° C without stirring. The reaction mixture was allowed to cool to room temperature
and lots of water was added. The formed yellow oil was separated. The aqueous phase was extracted with benzene (feel free to use toluene or xylene),
the organic phase and the yellow oil were pooled, treated in usual manner with water, 5% sodium carbonate solution and again with water and dried.
After evaporation of solvent the oily residue was destilled at 11 torr (14,7 mbar). The boiling point was 82° C and 95,2 g pure benzylbromide were
obtained. Yield: 86,5% (based on benzene).
1 The authors use the same reagent system for the 1,4-bis-bromomethylation of benzene (32,3%), p-bromomethylation of toluene (87%) and bromobenzene
(35,2%) and alpha-bromomethylation of napthalene (81%). Other substituted benzenes like 1,4-dimethoxybenzene or 2,6-dimethoxyphenol should also work.
Although the yields show drastic differences this should bee no problem as all reagents are very cheap and the procedure can bee performed on a large
scale.
Step 2: Benzylbromide --> Methyl 2-Nitro-3-Phenylpropionate
Synth. Comm., 1987, 17(12), 1421-1429 (https://www.rhodium.ws/pdf/nitroacetate.ptc.alkylation.pdf)
Benzyl bromide (1a, 1.8 g1) was added to a stirring solution of methyl nitroacetate (2, 1.21 g) in dimethyl formamide (10 ml) containing benzyl
triethyl ammonium chloride2 (TEBA, 0.009 g) and anhydrous KHCO3 (0.5 g) at room temperature.
The reaction mixture was stirred at 60 °C for 16 hrs. DMF was removed under vacuum and the mixture was diluted with water and extracted with ether.
Drying and evaporation of the solvent furnished an oil which on vacuum distillation (110°-115 °C/3 mm) yielded pure (TLC) (3a, 1.49 g, Methyl
2-nitro-3-propionate).
In case of 3b and 3c purification was achieved by SiO2 chromatography using EtOAc : PhH (1:9) as eluents.
1 10,5 mmole of any other benzylbromide can bee substituted
Step 3: Decarboxylation
Method A:
JACS, 1955, 77, 5747-5748
3-(2-Nitroethyl)-indole (II). A solution of sodium hydroxide (32.0 g., 0.8 mole) in 64 ml. of water was added to 78.6 g. (0.30 mole) of ethyl
alpha-nitro-beta-(3-indole)-propionate ( I ) in 200 ml. of ethanol. The resulting solution was allowed to stand a t room temperature for 44 hours.
Solvent was removed under reduced pressure until the flask contained a mass of solid, semi-crystalline material. Ethanol (400 ml.) was added, the
mixture was slurried well and the solid was collected on a filter. It was washed with ethanol, then with ether and dried on the filter. The solid was
dissolved in 600 ml. of water, the solution was cooled in ice and acidified by slowly adding 20% hydrochloric acid until the pH was between 4 and 5 .
Crystalline material began to separate and the flask was cooled at 4° overnight. The light pink crystals were collected, washed with water and dried
under vacuum. The yield of 3-(2-nitroethyl)-indole was 47.4 g. (83.27,). Material of analytical purity was obtained from the "practical grade" product
described above by dissolving it in 200 ml. of ethanol, treating the solution with charcoal, filtering and adding 95 ml. of warm water to the warm
(60°) filtrate. The flask was allowed to cool slowly to room temperature and was then placed in the refrigerator for 2 days. The large, sparkling
plates were collected on a filter and washed with two 40 ml portions of 50% ethanol. The product, dried under vacuum, weighed 39.14 g. (68.5%) and
melted at 55.5-56.1°. Two months later the melting point of the same material was 68.3-69.2°. It was shown by analysis and infrared spectra that
these are dimorphic forms.
Method B:
J. Org. Chem., 1991, 56(16), 4990-4993
Nomenclature overkill (1.13 g, 3.08 mmol), sodium chloride (1.0 g, 17 mmol), and water (0.2 mL, 20 mmol) in dimethyl sulfoxide (15 mL) was heated at
150 °C for 4 h. The solvent was evaporated at reduced pressure, and the black residue was taken up in ethyl acetate and filtered through a small plug
of Celite. The filtrate was washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was evaporated to
leave a light brown solid. This solid was purified by silica gel chromatography using 1:1 hexanes-ethyl acetate as eluent to give the title compound
ae a white solid (0.66 g, 66%).
Edit by Chemoleo: Title
[Edited on 20-1-2009 by chemoleo]
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Sauron
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Just wondering. Exactly how many amphetamine cooking threads do you intend to open?
Sic gorgeamus a los subjectatus nunc.
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not_important
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Given that there a thread or two on the Hive. Rhodium's, and archives thereof, that many members likely have copies of such, and that much of this is
online, what is the point? Are you performing these experiments? Looking for help? Certainly you're not presenting new information, perhaps it might
be better to unplug your computer for a few days until the fever and accompanying delirium go away.
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chemoleo
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| Quote: | | and that much of this is online, what is the point |
This could be said for probably 80% of all threads here. So this is NOT a point.
Bluetooth, I suggest you remove the obvious 'drug' angle in the future, to receive a more welcoming response.
This forum is NOT the Hive, nor Wetdreams.
So please conform to the chemical angle we have here, or don't post.
PS thread title edited.
PS2 threads not obviously related to derivatives of the title's subject were left...for now.
[Edited on 20-1-2009 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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Ebao-lu
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Thanks for the bromomethylation procedure!
As for drug related chemistry, i think a-nitropropionic esters can be used as well, this is a good route for MDMA i suppose. Benzodioxol is easily
chloromethylated with HCl/CH2O.
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