Author Topic: Short Question Thread 2.0  (Read 5707 times)

carl_nnabis

  • Subordinate Wasp
  • ***
  • Posts: 245
Re: Short Question Thread 2.0
« Reply #100 on: July 11, 2012, 08:17:00 AM »
phew.... everything went fine  :)
picked it up this morning, there wasnt even pressure on the bottle
"It's like the drug trip I saw when I was on that drug trip!"

Shake

  • Dominant Queen
  • ****
  • Posts: 276
Re: Short Question Thread 2.0
« Reply #101 on: July 11, 2012, 04:06:12 PM »
little less info carl and we will still get the point man ;)

wasabi

  • Larvae
  • *
  • Posts: 22
Re: Short Question Thread 2.0
« Reply #102 on: July 12, 2012, 06:53:35 PM »
Answered myself.
« Last Edit: December 29, 2012, 02:10:30 PM by wasabi »

Electro´S

  • Pupae
  • **
  • Posts: 95
Re: Short Question Thread 2.0
« Reply #103 on: July 15, 2012, 01:51:46 AM »
I´M lost again. :'(
I had discovered recently the Nitroalcohol route to Phenylpropanolamine. (BzCOH +EtNO2 +Et3NH2=> Zn-HCOOH)
And I know than HI/RP will work.
But, Are any other routes to reduce the aminoalcohol to the aminoalkane?
Thanks for your time.

carl_nnabis

  • Subordinate Wasp
  • ***
  • Posts: 245
Re: Short Question Thread 2.0
« Reply #104 on: July 15, 2012, 02:22:03 AM »
dont worry i can help in this matter, use Zn/Hcl in alcohol, and if you desire an excess of 1R,2S enantiomer drip the acid slow in that it gets not too hot. after the zinc is consumed, reflux it 2-4 hours, extract with dichlormethane.
much fun, dont store that nitroalcohol its not  stable, reduction is really that simple  ;)
sorry misunderstood you again, use an ester of norephedrine than CTH reduction maybe? i like pyramids process very much i will use it maybe soon
« Last Edit: July 15, 2012, 02:25:36 AM by carl_nnabis »
"It's like the drug trip I saw when I was on that drug trip!"

fishinabottle

  • Subordinate Wasp
  • ***
  • Posts: 129
Re: Short Question Thread 2.0
« Reply #105 on: July 15, 2012, 10:01:23 AM »
I´M lost again. :'(
I had discovered recently the Nitroalcohol route to Phenylpropanolamine. (BzCOH +EtNO2 +Et3NH2=> Zn-HCOOH)
And I know than HI/RP will work.
But, Are any other routes to reduce the aminoalcohol to the aminoalkane?
Thanks for your time.
- Formation of the nitric acid ester followed by catalytic hydrogenation with hydrogen preloaded Pd on BaSO4. That should be the most practical hydrogenation pathway.

-The spanish claim that Al/Hg under pressure does the trick, whats not so far out. Don´t know anything about conditions etc. though, would be up to experimentation, one might suspect acidic environment.

carl_nnabis

  • Subordinate Wasp
  • ***
  • Posts: 245
Re: Short Question Thread 2.0
« Reply #106 on: July 15, 2012, 11:35:28 AM »
jep, i dont know but i have a feeling that a tosylester will work here to give good, maybe quantitative in a CTH?
"It's like the drug trip I saw when I was on that drug trip!"

fishinabottle

  • Subordinate Wasp
  • ***
  • Posts: 129
Re: Short Question Thread 2.0
« Reply #107 on: July 15, 2012, 02:41:36 PM »
jep, i dont know but i have a feeling that a tosylester will work here to give good, maybe quantitative in a CTH?
Sadly reactions are rarely driven to completion by feelings....  8)

lugh

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 876
Re: Short Question Thread 2.0
« Reply #108 on: July 15, 2012, 03:12:10 PM »
Quote
But, Are any other routes to reduce the aminoalcohol to the aminoalkane?

Some alternatives are discussed in the attached article:

SYNTHESIS OF 2-AMINO-1-PHENYL-1-PROPANOL AND ITS METHYLATED DERIVATIVES

FRED W. HOOVER, HENRY B. HASS
J. Org. Chem., 1947, 12 (4), pp 506–509
DOI: 10.1021/jo01168a003
Publication Date: July 1947

which has been discussed in the past:

https://the-collective.ws/forum/index.php?topic=22992

The attached european patent discusses the preparation of the nitroalcohol 8)

« Last Edit: July 15, 2012, 06:49:56 PM by lugh »
Chemistry is our Covalent Bond

Electro´S

  • Pupae
  • **
  • Posts: 95
Re: Short Question Thread 2.0
« Reply #109 on: July 15, 2012, 08:30:39 PM »
Wow Thanks all for your time.
I´M going to spend a little more of time in my question, because my English...
The idea is start from benzaldehyde to PhenylPropanolAmine like rhodium archive for P-f-4 MAR and stop in the norephedrine. And maybe run condensation with Nitroethanol also (Nitrometane + formaldehyde)

Condensation:

10 g (80.6 mmol) of para-fluorobenzaldehyde (99%+ purity, 124.11 g/mole) was mixed with 15 mL’s of methanol in a 100 mL Erlenmeyer flask, and put in the fridge and refrigerated till the temperature was -10°C. Fortunately the benzaldehyde was soluble at these low temperatures, which means that the reaction can be conducted as originally intended. In a separate beaker, 7.3 g (96.7 mmol) of nitroethane (75 g/mole) was mixed with 8.14 g (80.6 mmol) of triethylamine (99%+ purity, 101 g/mol). This was also cooled to –10°C. Once the mixture was cooled satisfyingly, the contents from the beaker with nitroethane/triethylamine was poured into the Erlenmeyer flask with the fluoro-benzaldehyde. This was swirled a few times, and put back in the freezer. Once every 30 min’s it was taken out and swirled. The color of the mixture went from totally clear to yellowish over the course of the 2½ hours, which the reaction was allowed to run. Once the reaction was complete (2½ hours), the amine was quenched with an 1.1 equimolar amount of acetic acid, while the reaction mixture was still cool. It is very important to quench the reaction while it is still very cold, as the isomers will reach an equilibrium once the temperature rises, if there still is active catalyst present. Most of the solvent was stripped under vacuum, and the remains where dissolved in DCM and washed two times with water and once with brine. The DCM was stripped, leaving behind about 15 g of the crude nitroalcohol.
Zn/Formic acid reduction:

The nitroalcohol was reduced in the usual manner, by Zn/formic acid. This method was used, with the following amounts:

    15 g crude nitroalcohol
    100 mL methanol
    18.6 g Zinc Powder
    70 mL of formic acid

After filtering the reaction mixture, a slightly reddish liquid remained. Most of the solvent was stripped, and the remains where dissolved in 100 mL water and acidified with hydrochloric acid to pH 2 (for some reason it was almost neutral, even though a huge excess of formic acid was used; maybe the zinc ate most of it?). The mixture was nearly pink at this point. This was washed twice with DCM to give a very pale red-tinted solution. Upon basification of this mixture, a lot of inorganic salts precipitated. This has probably been some Zinc salts of some sort. The whole lot was extracted once with chloroform and twice with DCM. After the first chloroform extraction and addition of DCM, the whole lot was filtered to remove the inorganic salts. The combined organic phases where stripped of solvents and left 7.6 g of para-fluoro-norephedrine (42.5 mmol) freebase as a pale yellow liquid.


Until here all is fine, but now i need alternatives for the primary amine from the Aminoalcohol, HI/RP is not available but may be any know to run something similar with Phosphoric acid and Iodine Salts, or other reagents completely different.
All my doubts are, what can i do with norephedrine if my goal is amph???

Thanks again

« Last Edit: July 15, 2012, 08:33:12 PM by Electro´S »

lugh

  • Global Moderator
  • Foundress Queen
  • *****
  • Posts: 876
Re: Short Question Thread 2.0
« Reply #110 on: July 15, 2012, 08:40:44 PM »
Quote
Until here all is fine, but now i need alternatives for the primary amine from the Aminoalcohol

The applicable section from March's Advanced Organic Chemistry concerning the reduction of nitro groups to amines is attached  8)
Chemistry is our Covalent Bond

Gypsy

  • Larvae
  • *
  • Posts: 33
Re: Short Question Thread 2.0
« Reply #111 on: July 16, 2012, 07:35:09 AM »
Alright from trying the procedure a few times over, getting varied results.
Ive tabulated my previous experiments and I ended up with this.
Im getting a pretty even yield using this:
20grams piperonal,17ml nitroethane, 6.4g ammonium acetate anhydrous, in 45ml GAA. This is stir at room temp until everything is dissolved and once a slight discoloring observed, it is set up for a gentle reflux for two hours. Solution is a dark red/brown. This is left to cool to room temperature and is then poured into 1500ml dh20 with enough ice to just cover the surface with stirring (total time ends around the 3h mark). Yellow chunks precipitate. I receive an average of 23 grams from this, about 17-18g after recrystallizing with methanol. From that I've been using the mercury/aluminium amalgam to reduce the nitropropene. Every batch where the reduction hasn't worked its always been when I have used thick tin foil, and I would end up with much of it unused. I now use Reynolds thin tin foil. Its allot to shove down the neck of your flask mid reaction though. but hustle through that shit! gloves, goggles and respirators! I aim for my reduction to be finished by the second hour. I've only ever had to use a damp towel once, and that was out of carelessness. Anyway, two liter flask, and a leibig condenser, and a nice chunky stir bar (I use a 70mm bar and don't ever really have a problem here).
I used 200ml GAA, 350ml methanol, 15gram nitroproene and an extra 30ml to wash the beaker and the funnel after the solution has been poured into the flask. 0.75g mercuric chloride dissolved in 20ml hot water. 35g foil, cut into small squares (2cm x 2cm) and lightly blenderized. I have never tried pre-amalgamating the foil, I don't know if this would increase yields perhaps? I've only ever had the reaction peter out upon addition of thick foil. after-which I basify it strongly, slowly, and with moderate cooling, with a 750ml ice cold solution of 35% NaOH. I then extract with 1000ml toluene, distill this off until an oil remains. I dissolve this in a 5% HCl solution. Aqueous layer turns skin-peach. Some undissolved crap at the bottom is dissolved and removed with 100ml DCM, as a deep red brown layer. solution is basified again, and again extracted I personally use toluene here. dry it over calcium chloride, leaving a clear lager colored solvent, which is then gassed. Yields me about 6g of white/off-white MDA HCl consistently. mp is only ever within 10 degrees of the stated mp of 185c.
What am I overlooking or doing wrong?
And what is the consensus on al powder? too fine? could this be made into an amalgam slurry that could slowly be added into the reaction mix, at a slow enough pace, or is it just totally going to get away from me and paint the ceiling?
got some rad photos too.
« Last Edit: July 16, 2012, 08:21:31 AM by Gypsy »

Electro´S

  • Pupae
  • **
  • Posts: 95
Re: Short Question Thread 2.0
« Reply #112 on: July 16, 2012, 09:46:38 AM »
2GYPSY.

Hi mate, i nerver saw  piperonal but i had study benzaldehyde a lot in the same way than you.
Al/Hg for nitropropenes is hard to run fine. The best yield was observed when the amalgam was made in 1 minute and without standar glassware, just a wet towell in the hole of the bucket.
I had filtered the Al sludge and when the reaction is refrigerated with glassware or cold water bath, the colour of the liquid is allways red likes "Nitropropene polimerish", but if the reaction is kept free it self just with a wet towel in the top of the bucket, the filtrated is clear yellow like amphetamines.
For this reason i´m crazy looking anwsers for alternatives like the oxime or norephedrine to amph. I´m sure than Reducing Nitropropenes with Al/Hg is not the good way to work with nitroalkenes.

Electro´S

  • Pupae
  • **
  • Posts: 95
Re: Short Question Thread 2.0
« Reply #113 on: July 16, 2012, 09:56:02 AM »
2Electro S
Condensation could be done more OTC (cat. Al(OH)3, Al2O3)

Thanks reckless, but at the moment chemicals are no hard to get for me (if iknow what is exactly what i need).

My problem now is the OH group in the norephedrine. will Al/Hg in methanol make the work like the ketone????
Or with electrolisys????  Or Zinc/ammonium formate???

Gypsy

  • Larvae
  • *
  • Posts: 33
Re: Short Question Thread 2.0
« Reply #114 on: July 16, 2012, 10:50:05 AM »
thanks for the reply. Is my problem perhaps that I have been using water to dissolve my mercuric chloride?
A bucket seems so ghetto.
http://www.erowid.org/archive/rhodium/clandestine/bucket/index.html <-- like such?
is it simply for the extra head room to enable dumping the entire lot of al in at once? makes me nervous.
« Last Edit: July 16, 2012, 10:55:43 AM by Gypsy »

Electro´S

  • Pupae
  • **
  • Posts: 95
Re: Short Question Thread 2.0
« Reply #115 on: July 16, 2012, 10:52:56 PM »
thanks for the reply. Is my problem perhaps that I have been using water to dissolve my mercuric chloride?
A bucket seems so ghetto.
http://www.erowid.org/archive/rhodium/clandestine/bucket/index.html <-- like such?
is it simply for the extra head room to enable dumping the entire lot of al in at once? makes me nervous.

In one this one
« Last Edit: July 16, 2012, 10:54:53 PM by Electro´S »

Tsathoggua

  • Autistic sociopath
  • Foundress Queen
  • *****
  • Posts: 662
Re: Short Question Thread 2.0
« Reply #116 on: July 17, 2012, 06:58:44 AM »
When making kompot, or something like it (plan is to end up with a full spectrum isolate from pods, and finally make the dipropionyl ester of the morphine content), does one add acid to the preliminary extraction to help solubilize the alkaloids? IIRC they are present in the plant as meconate salts, so should this be needed at all?

Also, will a MeOH extraction pull the goods without too much issue?
Nomen mihi Legio est, quia multi sumus

I'm hyperbolic, hypergolic, viral, chiral. So motherfucking twisted my laevo is on the right side.

Electro´S

  • Pupae
  • **
  • Posts: 95
Re: Short Question Thread 2.0
« Reply #117 on: July 17, 2012, 11:32:40 AM »
Extracting morphine from Raw Opium water should be the best solvent, and don´t acification is required.
How you try to isolate the M from the pods? I never saw a good extraction from pod before, i´m courious becaouse Ton of pods grow wild around me, and collect the raw meterial is a hard work.

bubble

  • Larvae
  • *
  • Posts: 22
Re: Short Question Thread 2.0
« Reply #118 on: July 17, 2012, 12:20:18 PM »
the use of methanol to extract the goods from poppy pods is the wrong way because methanol will extract to many resins, oils etc. methanol should be used by extracting morphine and codeine from raw opium because there is a limited amount of resins in there.

To extract the goods from poppy pods i use water which is acidified to a ph of 3-5 to get the hydrochloride which is way better soluble in water than the meconates. because meconic acid and meconates are not that soluble in water. I started an extraction today and the whole poppy powder wells so much that 350g soaked up nearly 2 liter of water and got a realy hard cement like consistence. I will post in a few days some results.

Gypsy

  • Larvae
  • *
  • Posts: 33
Re: Short Question Thread 2.0
« Reply #119 on: July 17, 2012, 12:48:27 PM »
Cool, I'll go see what they've got going at the local hardware store. Will report back once tests have been done!