DL-Phenylalanine--->PEA--->Dl-amphetamine?

java · Consumer

ahgreich
(Newbee)
09-18-03 00:34
No 459698




on it like a houn' daawk - but ah hav' uh quesion
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swymk has performed the first part of this a couple of times - amino in THF add I2 and NaBh4 - rxn is very tame, nothing shocking. However, chmcl ignorance hinders one from knowing the best / simplest post rxn workup of the alchie, as one would hate to proceed to the next rdxn rxn carrying phunkadangeroushithertounknowns.
Any suggestions for that workup and the ratios and workup for the alcohol rdxn?

Rhodium
(Chief Bee)
09-18-03 06:46
No 459750




Phenylalaninol, exact procedure
(Rated as: excellent)
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It's all there - you even have exact procedures for the reduction of phenylalanine to phenylalaninol.
This procedure is taken from J. Org. Chem. 58, 3568-3571 (1993) (https://www.rhodium.ws/pdf/borohydride-iodine.pdf)

L-Phenylalaninol (2d). Iodine Procedure.

2d was prepared from 82.60g (500 mmol) L-phenylalanine (1d) by the same procedure. The crude material was recrystallized from toluene to yield 72% of 2d as colorless crystals: mp 90-92?C (lit.11 92-94?C).

With "the same procedure" they mean to copy the directions given for the preceding compound, L-tert-Leucinol, only adjusting the amounts. If you start with 12.55g L-phenylalanine you can use the exact amounts given below, if you want to use their 500 mmol scale you have to scale up the amounts below by 6.58 (500 mmol/76 mmol=6.5 Cool

.

L-tert-Leucinol (2a).

A 1-L three-neck round-bottom flask was fitted with amagnetic stirbar, a reflux condenser, and an addition funnel. The flask was charged with 6.92g (183 mmol) sodium borohydride and 200 mL of THF (predried over sodium). L-tert-Leucine (1a) (10.00g, 76 mmol) was added in one portion. The remaining neck was sealed with a septum and an argon line attached, and the flask was cooled to 0?C in an ice bath. A solution of 19.30g (76 mmol) of iodine dissolved in 50 mL of THF was poured into the addition funnel and added slowly and dropwise over 30 min resulting in vigorous evolution of hydrogen. After addition of the iodine was complete and gas evolution had ceased, the flask was heated to reflux for 18 h and then cooled to room temperature, and methanol was added cautiously until the mixture became clear. After stirring 30 min, the solvent was removed by rotary evaporation leaving a white paste which was dissolved by addition of 150 mL of 20% aqueous KOH. The solution was stirred for 4 h and extracted with 3x150 mL of methylene chloride. The organic extracts were dried over sodium sulfate and concentrated in vacuo, affording a white semisolid (100%) which was bulb-to-bulb distilled to yield 7.53 g (84% of 2a as a white solid: mp 30?C, bp 90?C/0.2 mmHg (lit.10 117-120?C/57 mmHg).

java
(Hive Bee)
10-01-03 16:06
No 462134




RE: Benzylic vs. aliphatic alcohols
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Rhodium: Please clarify why ephedrine can be a benzylic alcohol ,when the OH is attached to the C1carbon from the benzene ring and in the case of Phenylalinol where the OH is attached to the C3 carbon, is considered an aliphatic alcohol.

My reasons for getting a clear picture is because of your recent posting ....Post 462116 (Rhodium: "NaBH4 Deoxygenation of Benzyl Ketones/Alcohols", Novel Discourse), and it's application,
If benzylic alcohol then the reducing the ephedrine /pseudoephedrine to ---- using the NaBO4/trifluroactic acid......as in the article Reduction of Monobenzylic Alcohols With Sodium Borohydride/Trifluoroacetic Acid
CF Nutaitis, JE Bernardo.
Synth Commun 20, 487 (1990) (https://www.rhodium.ws/djvu/nutaitis.djvu) (retrieved by lugh)

If by using NaBO4/I,in H2SO4 as in the article ....J. Org. Chem. 58, 3568-3571 (1993) (https://www.rhodium.ws/pdf/borohydride-iodine.pdf%29after reducing Phenylalanine to the alcohol phenylalinol then.......one could remove the THF and reload with additonal NaBO4/Trifluoroacetic Acid and finish reducing the amino acid to its corresponding alkane ,hence amphetamine if the procedure can also be applied to the aliphatic alcohol , but then in either case the article sheds light on the possible reduction of Ephedrine/pseudoephedrine to ---- and the unclear application to aliphatic alcohols as phenylalinol happens to be..........java

We're all in this world together,
http://www.chiapaslink.ukgateway.net/

Rhodium
(Chief Bee)
10-03-03 10:54
No 462406




benzylic/aliphatic alcohols
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Please clarify why ephedrine can be a benzylic alcohol ,when the OH is attached to the C1carbon from the benzene ring and in the case of Phenylalinol where the OH is attached to the C3 carbon, is considered an aliphatic alcohol.

Both ephedrine and phenylalaninol are aliphatic alcohols, but as ephedrine has its OH group on the C1 carbon, it is a benzylic aliphatic alcohol, and is thus easier to reduce than other "plain" aliphatic alcohols.

Alcohols with its OH group sitting next to a benzene ring are all benzylic alcohols, per definition.

tpower9s2003
(Hive Bee)
10-23-03 20:59
No 466440




An interesting possibility with hydrazine?
(Rated as: dangerous)
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Like PFED+I2+P, SWIT now thinks (or desperately hopes hes not wrong for once) he mightve found a reasonably rudimentary rxn possibility with the use of Borax, I2, Hydrazine, and D,DL-Phenylalanine.

Borax when hydrated with H2(g), as stated by engineers supporting Sodium Borohydride powered cars, forms NaBH4. Simplified equation with Hydrazine hydrate and Borax anhydrous.
2Na2B4O7 + 7N2H4 ---> 4NaBH4 + 4N2(g) + 4BH3

Borax decahydrate, solid with BP 320?C and MP is 75?C and doesn't sublime, so oven-dried 100<t<320 (about 200-250 seems would be ok) then cooled to resolidification should result in the anhydrous. Heard microwaves work but unsure if it overheating/superheating would be problematic. Hydrazine sulfate recipe on chief's site then freebased into MeOH solution gives the hydrate. For 4 moles NaBH4, about 160mL of MeOH. Borax annhydrous slowly added to chilled N2H4/MeOH solution on ice/acetone bath should both obtain NaBH4/MeOH 100%m/v solution while also destroying the BH3. N2 released as gas. Swirled occasionally and doesn't seem it would need to be refluxed. Also, hence no additional cleaning!

As chief mentioned earlier, iodine with borohydride will reduce phenylalanine to phenylalaninol:
SWIT assumes this molar ratio is used= Phenylalanine : NaBH4 : I2 ; 1.5 : 4 : 2

Since Hydrazine can also be used for HI, and assuming this ratio= Phenylalaninol : HI ; 1.5 : 6, moles is 1.5N2H4 and 3I2. No f*ckin matchbooks.

Therefore rxn done all in same flask: overall molar ratios:
1.5 D or Dl Phenylalanine freebase (purchased pure)
5 Iodine (RG,LG or resublimed)
4 Sodium Borohydride/MeOH solution
>1.5 Hydrazine Sulfate (via OTC method posted on Rhodiums site)

NaBH4/MeOH solution first. Phenylalanine added then I2 very gradually added while solution chilled on ice/acetone bath. Swirled occasionally, allowed to come to room temp, and refluxed for a couple hrs with minimal heat. Re-chilled as before.

Hydrazine very slowly added. Brought to room temp unto long reflux of 24+hrs. Oil bath temp starting at room temp rising to 117-127?C.

Byproducts vs. I2+P rxns would lesser: N2(g) won't condense at given temps if its not all lost prior to inplacing condensor. BH3 would be taken care of by MeOH. Without any phosphorous, plastics, gaaks, etc in post fluid, could get pretty pure end yields with minimal cleaning. Post should be mostly HI(aq) vs. MeOH. NaOH to neutralize PH then safely boil off most of the MeOH. Continue to 13+ with NP to pull and AB as usual...

"True love" is a thrill
Add a methyl group or two
Get it in a pill!

Lucid_Dreamer
(Hive Bee)
10-23-03 23:09
No 466460




Is there a way to synthesize ...
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Is there a way to synthesize alpha-methyl-phenylalanine from either isomer of regular phenylalanine?

--Word on the street is, You Reap What You Sow

Rhodium
(Chief Bee)
10-24-03 09:46
No 466513




tpower9s2003: Do NOT try to perform all the...
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tpower9s2003: Do NOT try to perform all the reactions together. Hydrazine can decompose explosively in the presence of HI/I2 etc... See posts by WizardX on the topic of using hydrazine as a HI recycling agent.

Lucid_Dreamer: That has been discussed here before. You can probably find more with a more exhaustive search.

The general idea: Post 50982 (Lilienthal: "Re: PHE---->Amphetamin", Serious Chemistry)
More references: Post 122776 (dormouse: "Alkylation of amino acids under PTC conditions! -Labrat", Serious Chemistry)

WizardX
(Wizard Master)
10-24-03 20:41
No 466610




BH3 (aka B2H6)
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Diborane CAS 19287-45-7
B2H6 RTECS HQ9275000
Synonyms & Trade Names
Boroethane, Boron hydride, Diboron hexahydride DOT ID & Guide
1911 119
Exposure
Limits NIOSH REL: TWA 0.1 ppm (0.1 mg/m3)
OSHA PEL: TWA 0.1 ppm (0.1 mg/m3)
IDLH 15 ppm Conversion 1 ppm = 1.13 mg/m3
Physical Description
Colorless gas with a repulsive, sweet odor. [Note: Usually shipped in pressurized cylinders diluted with hydrogen, argon, nitrogen, or helium.]
MW: 27.7
BP: -135?F
FRZ: -265?F
Sol: Reacts

VP(62?F): 39.5 atm
IP: 11.38 eV
RGasD: 0.97

Fl.P: NA (Gas)
UEL: 88%
LEL: 0.8%

Flammable Gas
Incompatibilities & Reactivities
Water, halogenated compounds, aluminum, lithium, oxidized surfaces, acids [Note: Will ignite spontaneously in moist air at room temperature. Reacts with water to form hydrogen & boric acid.]
Measurement Methods
NIOSH 6006
Personal Protection & Sanitation
Skin: No recommendation
Eyes: No recommendation
Wash skin: No recommendation
Remove: No recommendation
Change: No recommendation

First Aid (See procedures)

Breathing: Respiratory support

Respirator Recommendations NIOSH/OSHA
Up to 1 ppm: (APF = 10) Any supplied-air respirator
Up to 2.5 ppm: (APF = 25) Any supplied-air respirator operated in a continuous-flow mode
Up to 5 ppm: (APF = 50) Any supplied-air respirator that has a tight-fitting facepiece and is operated in a continuous-flow mode/(APF = 50) Any self-contained breathing apparatus with a full facepiece/(APF = 50) Any supplied-air respirator with a full facepiece
Up to 15 ppm: (APF = 1000) Any supplied-air respirator operated in a pressure-demand or other positive-pressure mode
Emergency or planned entry into unknown concentrations or IDLH conditions: (APF = 10,000) Any self-contained breathing apparatus that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode/(APF = 10,000) Any supplied-air respirator that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained positive-pressure breathing apparatus
Escape: (APF = 50) Any air-purifying, full-facepiece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern/Any appropriate escape-type, self-contained breathing apparatus
Exposure Routes inhalation
Symptoms Chest tightness, precordial pain, shortness breath, nonproductive cough, nausea; headache, dizziness, chills, fever, lassitude (weakness, exhaustion), tremor, muscle fasciculation; in animals: liver, kidney damage; pulmonary edema; hemorrhage
Target Organs respiratory system, central nervous system, liver, kidneys

Scottydog
(Hive Addict)
04-09-04 03:31
No 499872




Formulation change?
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"Actually those pills contain "pure crystalline, free form" so what more could anyone ask for?"

Tpower are you still around? Actually anyone else that can answer this question would be really helpful. Swim wanted to avoid violating the sources rule so thought he would bring up this older thread since the source is already mentioned here.

Swim did an ingredients search on google and it says there is much more then just dl-phenylalanine in the pills. Here is what Swim came up with.

"Ingredients:
Serving Size 1 Capsule
Daily Value not established

DLPA (DL-Phenylalanine) 500 mg

Other Ingredients: Gelatin, Purified Water, Cellulose, MCT, Magnesium Stearate, Silica.

Safety Info:
No tablet binders, coatings or colorings. Free of the most common allergens such as fish, corn, soy, yeast, barley, rice, wheat, lactose (milk sugar) and all milk and egg products. No added flavorings, sugars, salt, artificial sweeteners, colorings or preservatives."

In reference to these "other" ingredients are these just the ingredients that are used to make the gelcaps? Gelatin I can understand, but MCT? Did a search and it is a fatty oil that comes from coconuts. *Is the powder in the capsules 100% pure DLPA or did they change their formulation?*

Refuse/Resist

LoW_JacK
04-13-04 19:41




OK now here comes an easy one....
(Rated as: UTFSE!)
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Rhodium
(Chief Bee)
04-13-04 19:52
No 500700




COOH groups are inert to HI/P reduction, so...
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COOH groups are inert to HI/P reduction, so nothing useful would happen.

The Hive - Clandestine Chemists Without Borders

DrLucifer
04-13-04 22:48




cooh group reduction
(Rated as: UTFSE!)
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elfspice
(Hive Bee)
04-14-04 01:44
No 500741




dl-phenylalanine in oz
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i've seen them around, in little plastic containers with yellow and green label with red (i can't recall if it was red now, i've not looked at one in a while) at virtually every healthfood store i've ever seen. the only caveat is they're tablets, although i've had some success separating the amino acids from the pills, i'm sure a more precise method could yield much cleaner material. It says on the side of the label 'DL Phenylalanine 500mg' or something like that.

LoW_JacK
(Hive Martyr)
04-14-04 02:29
No 500745




Hhahahahah!
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I knew it was a dumb fucking question but seeing as how I've had these DLPA-750 extra strength capsules, that were bought after a stint in a rehab where they were giving them to patients in for ---- abuse and advised me to pick some up to "replace the chemicals in my brain that the ---- has depleted from abuse".
Taking all that into consideration, the question was asked.
No offense to the karma fairy for not just looking for the answer myself. I just love it when my chemical hero's answer me in any fashion. Even to tell me to UTFSE.
Rhod's a god in my world. Jade is climbing up the 'keep it real' tree as well.

Enough off topic shit. Just had to explain my insolence.

Smack goes some more bad karma!