(The Archetypical "Good Guy")
04-06-04 18:09
No 499440
(Rated as: excellent)
After much work with the CTH reduction i finally managed to get a pretty decent yield in an easy way! This first succesfull substrate was para-fluoro-(phenyl-nitropropene), but many will follow shortly.
Here is how it goes:
BH4 reduction:
The following method was used: Post 450179 (Barium: "Improvement", Novel Discourse), but please note:
a) Barium made a typo, switching the amount of IPA and water in the writeup. Please correct this prior to trying it out.
b)After finished reduction, 80% acetic acid is used to quench the remaining borohydride. Simply drip it in till the mixture stops fizzing.
7.4 g pF-P2NP (40.9 mmole) was added portionwise to a suspension of 2.8 g KBH4(25% excess) in IPA/water exactly1 as Barium described. After five minutes everything was added, the whole suspension was allowed to stirr for 30 mins. At this time 80% acetic was added dropwise till the fizzing subsided. Non-iodized table salt was poured in untill no more dissolved and stirred heavily for a minute or two. This was filtered through a small funnel to remove the borates + salt, and rinsed with a little IPA. The filtrate separated into an upper alcoholic layer(slighty yellow), and a lower aqeous layer (clear). The aqeous layer was discarded. The IPA layer was used without further fuzz in the following reaction.
CTH reduction:
The following amounts where used. The amount of the nitropropane can simply be switched with the amount of nitropropene used, as the first reduction is so high yielding.
50 mmol nitroalkane
250 mmol potassium formate
750 mmol water
25-50 ml IPA (depending on how much is needed to get a nice solution)
10%w/w 5%Pd/C (catalyst to substrate)
The IPA layer from the previous reaction was topped of with +20% more to make it a little more dilute. 0.7 g of 5% Pd/C was added to the IPA layer and stirred heavily.
In another beaker 7 mL's of water was made into a slurry with 14 g's of dry KOH2. While stirring like a madman, 13.5 g 85% HCOOH was dripped in (caution: very exothermic). Do the math yourself on how much water to add. You get water from: the neutralization of the two acids, the water in the formic acid, the KOH and perhaps the Pd/C if you use prewetted.
The potassiumformate mixture was poured into the nitro/IPA flask in one portion. The whole lot is heated to 75oC while stirring. Evolution of hydrogen was noted around 50oC. A few mL's of 80% acetic acid was added now and then, when the mixture got too "lumpy" (4 mLs was used in total). After two hours the hydrogen evolution had subsided and the reaction was deemed over.
The black slurry was filtered twice through filter paper (first time alot of black sludge came through, but simply use the same filter as before as a "plug" for the second filtering). The filtercake was rinsed with a little IPA to get all the goodies with it. The final filtrate was almost colourless. After saving the filtrate, the filtercake was washed with water a few times and saved in the "used 5% Pd/C pile".
The almost-clear filtrate was saturated with table salt and filtered (the Pd/C filtercake can actually be re-used here and THEN cleared up with water). The lower aqeous layer was yet again discarded and the IPA stripped at atmospheric pressure.
The yellowish oil residue weigthed 6.5 grammes. This was dissolved in dilute hydrochloric acid and washed twice with 15 mL's DCM, giving a nearly colourless solution (perhaps a tint of green/yellow?). The aqeous layer was basified and extracted with 3*20 mL DCM. The DCM was dried with a tiny bit of MgSO4, filtered and stripped. This left 4.5 grammes of a clear oil (p-F-amphetamine). The yield the total reduction is 72% with very easy steps in between
.The p-F-amphetamine was dissolved in IPA, and precipitated with a precisely half molar amount of H2SO4 dissolved in IPA. This was added in a thin stream and when the whole mess was unstirrable it was filtered and the filtrate titrated with the acid again. Yield of the sulfate salt was quantitative (95%+), which is good enough for me
!Conclusion:
Yeah! With a little practice the reduction from the nitropropene to the amphetamine can be done in about five hours total. The yields are really good, and reaction conditions are mild. It does not seem to bother the reactions, that the same IPA is used throughout the scheme.
Pretty slick dare i say!
Notes:
1) Potiassium borohydride was used as it was the closest container. The sodium version works exactly the same (except the different molar weight of course).
2) If using the regular 15% water KOH, please compensate for the additional water in your calculations.
Nuke the whales!
(Hive Adickt)
04-07-04 00:59
No 499485
Hi Bandil Good to see someone keaping up the good work.
Looking forward to see some more writups of the CTH reaction.
(Heavyweight Chempion(eer))
04-07-04 04:11
No 499503
My son! *sniffle*
(The Archetypical "Good Guy")
04-07-04 04:36
No 499505
Rhodium>
Would you like a HTML'ized version?
Nuke the whales!
(The Archetypical "Good Guy")
04-07-04 09:03
No 499530
Just got a whopping 86% overall yield, with 2,5-dimethoxynitropropene to 2,5-DMA
Where is the damn bromine!?!?!?
This method absolutely rocks!!
Nuke the whales!
(Chief Bee)
04-07-04 09:43
No 499536
Would you like a HTML'ized version?
Yes please! Include your latest success with 2,5-DMA, as well as (a corrected version of) Barium's original procedure (as I prefer to avoid having any links to Hive postings from the documents at my site).
The Hive - Clandestine Chemists Without Borders
(The Archetypical "Good Guy")
04-07-04 09:50
No 499538
Ill get to it!
As i am currently bioassaying the first success
with nice results, i will not have it ready in a few days!
Nuke the whales!
(Hive Bee)
04-14-04 06:04
No 500784
According to GC/MS-analysis, the product is definately > 98% pure. The last 2 % may very well be remains from the analysis done on the equipment just before.
Bioassays: SWIM has tested the compound a few times already.
On first occation (after seeing the results on other "test-pilots" who had ingested the compound a few hours before in different doses), 125 mg of the sulfate was insufflated. Slightly bad, long-lasting nose-burn; somewhat inbetween snorting meth and 2C-B. The setting was a small party, with a bunch of good friends around. After 40 minutes there was no doubt about having left baseline. A warm, fuzzy feeling in the body, elevated mood, and definately some degree of stimulation. However, the degree of stimulation seemed to be less than if the same amount of "regular" amphetamine sulphate had been ingested. SWIM had no real feeling of empathogenic effects - but just a good time! 50 mg more was insufflated ~2 hours later, but didn't really seem to add to the effects. 7 hours after first ingestion, reaching sleep was no problem.
A few days later, 100 mg was insufflated in a quiet setting at home. Didn't really help getting things done (writing papers, cleaning etc.) like normal amphs, but just induced a sort of "relaxed-stimulated", content state of mind.
IMO this compound is no new "blockbuster"
; the effects - apart from the stimulation - are quite subtle, but still rather fascinating. And if anything, the potency as a stimulant is lower than that for amphetamine. In the amounts tested, no "crash" on comedown has been experienced, and I don't think neurotoxicity is a big concern about this compound, so it might be worth trying out for people interested in novel stimulants.
To fathom Hell or soar angelic
Just take a pinch of psychedelic
(Hive Bee)
04-14-04 10:35
No 500818
I think you may like to change your dosage in order to get this compound to work well. I read the advice on Rhodium's site before bioassaying 4-FA. The first few times I tried it I took between 90-135mg. I must say I wondered what all the fuss was about as some people have claimed that this compound is really good (pHarmacist for one).
More recently I have found out how to make it work and this is achieved as follows:
1) Don't snort it. The effects are less intense/pleasurable for some reason.
2) Take 200mg all in one dose in a gelcap.
3) Don't try to redose as it is wearing off - It won't help.
4) If you have some benzodiazepines or other muscle relaxants, use them when you are finished as muscular tension has a tendency to develop on the comedown.
I have found that this makes for a really good social drug, with empathy, stimulation and relaxation combined (sounds weird I know). It combines well with moderate amounts of alcohol.
(Hive Bee)
04-14-04 22:24
No 500909
I pretty much agree fully with Starlight. Snorting 4F-A isn't very spectacular; definitely take it orally, and take at least 150mg. I found 150mg of the HCl salt produced pretty decent effects; since you're using the sulfate salt there I think you'll definitely need more than 150mg to achieve a good high. Out of the people that I now know who did it, all took 150mg of the HCl salt orally, and the described results varied a bit. Two people suggested that while it was fun, they simply weren't as fucked up as they would have liked to have been, while 4 people (myself being one of those 4) were VERY pleasently surprised with the effects at 150mg and considered them pretty much sufficient. One of those four (not me) said, "You could have lied to me in a club and said that this was some really good E, and I would have taken it and later said, 'hey you were right, that WAS some really good E'" Granted, the effects are pretty distinguishable and longer-lasting then those of MDMA, this is simply to illustrate how pleased some people have been.
Main point (directed at Prometheuz): Take MORE and take it ORALLY.
And yes, I further agree with Starlight that redosing later only served to prolong the potentially obnoxious (although still not too bad) effects experienced during comedown, as opposed to promoting additional nice effects. This compound is a one-shot deal.
-SpicyBrown
(Hive Bee)
04-19-04 09:56
No 501625
Well, I VERY reluctantly
decided to follow the advice in the two posts above; increase the dosage, and take it orally.~200 mg was ingested in a gelcap in a large party-setting. I was rather worn out from lack of sleep and excess of partying the last couple of days, and wasn't really in the mood for too much social interaction. About 1 hour after ingestion, that had certainly changed. The come-up was very relaxed and mellow. I wouldn't describe the state of mind reached as really "euphoric", but definately extremely enjoyable. On those who took the substance (we were a few on the same dose - seems like the others experienced about the same effects at just about the same level), it wasn't very obvious to notice they were "under the influence". Unlike MDMA there was no sudden change in the state of mind, it all came very smooth and nicely. Nice level of stimulation and empathogenic effects, and a very pleasant "clean" feeling in the mind - no real intoxication. No bodily discomfort was experienced. Only minor jaw-clenching, and a bit of physical restlessnes. Baseline was reached ~T+7 hours. No effects that couldn't be attributed to alcohol-intake at the party was noticed the day after.
Thanks to Starlight and Spicey for giving advice about how to get the desired effects from this drug. Actually, it may well end up being one of my favorite substances for large parties, where it is not acceptable to be too obviously fucked-up.
To fathom Hell or soar angelic
Just take a pinch of psychedelic
(The Archetypical "Good Guy")
04-21-04 10:29
No 502085
There - the final HTML work is done and shipped off. Hopefully it will be online soon
Nuke the whales!
(Hive Bee)
05-06-04 19:56
No 505490
Do the math yourself on how much water to add. You get water from: the neutralization of the two acids, the water in the formic acid, the KOH and perhaps the Pd/C if you use prewetted
Accounting the 7 grams of water used in preparing the potassium formate solution (388 mmole), the water from the neutralisation (250 mmole), and the water from 13,5 grams of a 85 g formic acid / 100 g solution (112 mmole) ( <- which would be logical since it contains 250 mmol formic acid), we have exactly 750 mmol water
I wonder, is there any particular reason why an water to formate ratio of 3 is prefered? In the patent Patent US4792625, it seems that the reaction goes (initially) faster at a ratio of 2,66.
I 'm sorry to bother you with a question about this futiliy, since the reaction works most beautifully. Probably the formate to water ratio doesn't matter that much (cfr.: Post 384333 (Barium: "Dare I say quantitative yield", Novel Discourse)).
Great work !!!
.
(The Archetypical "Good Guy")
05-06-04 20:30
No 505498
I wonder, is there any particular reason why an water to formate ratio of 3 is prefered? In the patent Patent US384333, it seems that the reaction goes (initially) faster at a ratio of 2,66.
The ratio 2.5-3 has in my experienced proven to be the best yielding one. To much water definately fucks up the reaction! The water to formate ratio is very important to get right - otherwise yields and reaction times will go to heck...
bad boy - now i gotta sleep!!
Nuke the whales!
(Hive Bee)
05-07-04 07:08
No 505586
After sleeping with the patent under my pillow & clearing the THC out of my head, I realised that the reaction consumes in fact 150 mmole of water.
50 mmol nitroalkane
250 mmol potassium formate
750 mmol water
250 HCOOK + 250 H2O --> 250 H2 + 250 KHCO3
50 -NO2 + 150 H2 --> 50 -NH2 + 100 H2O
________________________________________
50 -NO2 + 250 HCOOK + 150 H2O --> 100 H2 + 50 -NH2 + 250 KHCO3
I guess this more or less explains the rate of the reactions of Patent US4792625. Theoretically, the minimum water to formate ratio would be 150 / 250 (which would consume all the water from the medium).
The ratio 2.5-3 has in my experienced proven to be the best yielding one. To much water definately fucks up the reaction!
Then, the reaction not only consumes water ..., too much produces a hangover
. Thank you for clarifying this point, Bandil.The more I think about this reaction, the more I 'm impressed with this CTH.
EDIT: I screwed up the ref. to the patent in my previous post due to the partying (it has been corrected now <-- the screw-up was that I made a US patent out of Barium 's post
).Now I have to iron it (the patent, not the pillow
)
(Hive Adickt)
05-24-04 08:41
No 509263
Bandil wrote
There - the final HTML work is done and shipped off. Hopefully it will be online soon
I'm still looking forvard to read it.