Author Topic: A chemistry archive (Read 1287 times)

nk40ouvm · « **Reply #20 on:** April 21, 2011, 06:44:08 AM »

Thanks for uploading the split .rar form to 4shared. It downloaded fine for me. I never did open the .isz file.

First, congratulations. This is a good collection. I am most familiar with the Hive/Rhodium collections so that's where I looked most closely; Shroomery and whatnot I'm not so familiar with.

There are some duplicate files in this collection, but many of the dupes it makes sense to keep because they're referenced from different contexts. There are other duplicates that can just be dropped and will save some space, but not many. Only about a dozen I found.

I never ran any of the Java code or Windows executables included in this archive. I don't know if leaving the security tools included is a good idea. Anyone cautious enough to use computer security tools probably doesn't want to use computer security tools provided by a stranger as part of a giant drug archive.

Another relatively minor issue: you have a few hundred megabytes of books that are stored in .rar and .zip files (mostly rar) inside the .iso. Compressing each of those books separately may reduce the single file's size slightly but it will slightly hurt the compression ratio for the whole .iso, because the compressor you use on the .iso then can't effectively combine contexts across the different books. The other problem is it's a minor annoyance to open the .rar and then open the book inside instead of opening the book directly.

I ran into path problems in some of the HTML files, including top level indexes. The URL path separator is always /, forward slash. The back slash character, \, will work only by coincidence, and only on Windows. I tried browsing it on Linux and a lot of links were broken for me. I don't know if you did that yourself or if the parts of the archive already came that way, but it should be fixed. I can fix it up myself if necessary.

I am going to cross-check the Rhodium files in more detail later. I think I have a few (but not a lot) files that were missed. I can provide copies of the extra files to integrate, assuming that our mysterious archivist can visit this forum.

hypnos · « **Reply #21 on:** April 29, 2011, 11:40:04 AM »

How about some "introductory stuff about your self" in the "introductions,,for a start.....
YES!!!! IT IS THE INTERNET....but too many fuckwit hackers out there,,,I've had my share of 'unwillingly uploading" from those sites....and do it no more;,,certainly just coz someone puts a 1000 word Please.kinda makes me even more wary.....maybe you're CIA hoping to get access to

Sedit asked for a bit of "providence" which you havent provided-- its your ninth post and you are Flogging SOME OTHER DUDES SHIT??? smells strange to me...

NeilPatrickHarris · « **Reply #22 on:** April 29, 2011, 12:15:16 PM »

i haven't downloaded it yet but am curious if the psychonaut mirror is the new one i made from 3 months ago? because i'm aware the first mirror i made over a year ago got a lot of downloads but had a few problems such as the language changing (due to the crawler hitting the language preference links and trying to mirror those). the one i made 3 months ago not only has all of 2010's content but i fixed that language problem and a few other things.

the hyperlab mirror - is that the one that can be found on wetdreams or is it the small selective translated mirror that i made or is it a new mirror altogether?

hypnos · « **Reply #23 on:** May 03, 2011, 08:57:29 AM »

Yes PSE (neat) I WAS hasty in my comment-however I was Backin Sedit's POV beecause he "IS (one of) The Protectors" that without people of his ilk, this site wouldnt bee here for you to share your stuff/ask your questions....that said,,I feel OK "to your 'friend' sharing his love" now thanx to the courtesy of a few members.... so,, "welcome Stranger"

nk40ouvm · « **Reply #24 on:** May 04, 2011, 01:06:41 AM »

0 ['mp/rhod/pdf/srn1.arylation-2.pdf', 'mp/rhod/pdf/srn1.arylation-5.pdf']
1 ['mp/rhod/pdf/srn1.arylation-1.pdf', 'mp/rhod/pdf/srn1.arylation-4.pdf']
2 ['mp/rhod/djvu/hahn-doublet.djvu', 'mp/rhod/djvu/hahn.djvu']
3 ['mp/rhod/pdf/aromatic.aldehyde.synthesis.pdf', 'mp/rhod/pdf/chem.rev.38.227-254.1946.pdf']
4 ['mp/rhod/pdf/nitro.alkene.derivatives.pdf', 'mp/rhod/pdf/nitrostyrenes.fe-hcl.pdf']
5 ['mp/rhod/pdf/cth.ra-ni.benzylalcohol.deoxygenation.pdf', 'mp/rhod/pdf/ephedrine-rani-1.pdf']
6 ['mp/rhod/pdf/current.mitsunobu.chemistry.tour.pdf', 'mp/rhod/pdf/mitsunobu.pdf']
7 ['mp/rhod/pdf/alpha-ethylstyrene-0.pdf', 'mp/rhod/pdf/alpha-ethylstyrene-4.pdf']
8 ['mp/rhod/pdf/phenyl-2-alkenes.aldol-grob-1.pdf', 'mp/rhod/pdf/phenyl-2-alkenes.aldol-grob.pdf']
9 ['mp/rhod/pdf/srn1.arylation-3.pdf', 'mp/rhod/pdf/srn1.arylation-6.pdf']
10 ['mp/rhod/djvu/tiffenau.djvu', 'mp/rhod/djvu/tiffeneau.djvu']
11 ['mp/rhod/pdf/bentley-2.pdf', 'mp/rhod/pdf/ethorphine-2.pdf']
12 ['mp/rhod/pdf/nmr.amphetamines.pdf', 'mp/rhod/pdf/nmr.mda.mdea.mdma.meth.ephedrine.pdf']
13 ['mp/rhod/pdf/h2o2.terminal.epoxidation-2.pdf', 'mp/rhod/pdf/terminal.epoxidation.pdf']

You can ignore the 'mp/' prefix, it's just my ISO mount point. You only need to keep one of the files on each line.

nk40ouvm · « **Reply #25 on:** May 04, 2011, 01:26:21 AM »

The character \ should never appear in a URL. It will work only by accident, and only on Windows systems.
Some examples of bad URLs with \ in them:

In the top-level YouTopia.html:

Acacia DMT Extraction
Cacti Growing
Cannabis Growing
Coca Growing
Legal Highs
Mescaline Extraction

and many others. Some links are fine, and I can see no pattern in good vs. bad links.

All the links in rhod/index.html have the wrong character in them.
So do all the links in Hive/index.html.
Weirdly, all links in Hyperlab/Hyperlab.html appear ok.

Sorry for this abbreviated report. I would need to make more sophisticated tools to catch all files with bad URLs, and a little more work to automatically fix them too instead of cleaning up by hand...

Wizard X · « **Reply #26 on:** May 12, 2011, 12:07:36 AM »

Quote from: The Lone Stranger on May 11, 2011, 11:30:00 AM

From "His lowness" as he calls himself ---->

"nk40ouvm . Did the things you sugested and ALL the file / slash corrections . So tool now not needed . Thanks anyway .

I wanna do a credits page in the next version wich wiil be ready in about 1 week . I`d like to put the names nk40ouvm , NeilPatrickHarris and Wizard X in it ? Is that OK ? If i dont get a reply to that question i`ll go ahead and put them in there . IF anyone has ANYTHING at all they want added to their part in the credit.html please let me know within a wek from NOW either by posting here or by sending "Strangeness" a PM .

Wizard X . The X Files that i have from bit torrent are from you . I`ve "fixed" them so that they are now in .html format with the pictures and charts in them . They look to me ...... as a dickhead ...... like some of them are a bit strange and maybe not finished ? I want to put them in the Ark is that OK with you ? Do you want me to put the name Wizard X on the entry .HTML ? I am still doing the final touches to it . It would be cool if you would look at them and tell me any corections additions that are needed . When i`ve finished it i`ll upload a copy so you can have a look . I`ll send you a PM with the download link .

The next version 4.1 has a LOAD of changes and corrections + some more PDFs in it . I`m still looking for more things to put in version 5 if anyone has anything / any ideas ?

AGAIN ...... Any offers \ ideas \ sugestions \ comments ?"

Fine by me!

Again, fine by me!

I'll proof read them as time permits?

NeilPatrickHarris · « **Reply #27 on:** May 13, 2011, 12:26:58 PM »

Quote from: The Lone Stranger on April 30, 2011, 01:34:42 PM

NeilPatrickHarris. "the hyperlab mirror - is that the one that can be found on wetdreams" . If you tell me where there i`ll have a look and tell you . "

I finally downloaded it and took a look, i'm impressed you did a good job. I wouldn't mind a shoutout for the Psychonaut mirror and Hyperlab though cuz i spent a long time working on those

translating hyperlab was much more of a PITA than psychonaut was for sure
BTW good job on cleaning up the hyperlab mirror, i know it's not a full mirror was very selective primarily to mdxx compounds but with a few other interesting threads too. You did a good job at sorting through them and creating that index. I also like that you fixed the psychonaut banner in the psychonaut mirror.

BTW it looks like you're missing the 1998-2000 hive archive from before the server crashed. i just uploaded it for you: h**p://www.megaupload.com/?d=VUW43VHJ

hypnos · « **Reply #28 on:** May 14, 2011, 05:21:26 PM »

As I've tried to make clear,,I am a relatively "new" member,to the ranks of the many 'visitors to cyberspace', and I am hooked with this site, and the HUGE amount I have learned,,just by, spending many hours reading and downloading files---to read later

Unfortunately for me, I havent been living anywhere that would allow me to have a "functional (ghetto) lab"....... alas, as SOON as I DO, my back shits itself on me so I am HIGHLY RESTRICTED in what I can and cant do--

And the WORST part is you Never know 'when' a bit of disc moves, and I have the equivalent of a an instant toothache type "FAAARK! Something just touched a Nerve" shooting pain,like someone just stabbed me, but over a MUCH larger area, and able to last, until I lie down for a while, after taking a cocktail of drugs to "deal with the pain"....and sometimes, it REALLY DOES HURT HEAPS!! I've HAD TO lie down in the front of a shop a few months ago,for about 5 mins until it calmed down enough for me to 'continue walking!'

I REALLY APPRECIATE what you guys are trying to do, and though I have virtually nothing to "offer" from an "innovative chemistry" pov

,; except my admiration to ALL the people who have contributed down through the years,....from the earliest "Chatrooms" through to the Hive, and its counterparts, which WERE the "Precursors required..." for something as good as the Vespiary, to "Rear its Frightening Head";

And "scare the shit out of those people who would "rather they didn't talk about such discombobulating topics,such as, "The Vespiary and its peers"--My God!! "They" want people to take a drug, that Actually "MAKES YOU HAPPY,

AND ABLE TO APPRECIATE THE LOVING SIDES OF PEOPLE,,they may 'otherwise, NEVER SEE!!

And,, particularly for those, 'Sheeples', who "Truly Believe, and Trust, our Govts, 'Are Acting, (yes,'Acting', with, Logie Award Winning, nomination 'quality' Bullshit and deceit, much of the time....), for the Good (No, the Sheeple actually "receive, a tiny amount "% wise", of What ' REALLY "Goes on,In the Govt's minds, and what 'goes through' the Govt's Hands.... ) of the Sheeple!?' Ha!!

But what REALLY impresses me , the way members are able to, and DO "help other members" help each other....

There ARE many VERY capable,clever,intelligent,Experienced! members in this forum,, and its Soooo Good to see people from ALL OVER THE WORLD, sharing their knowledge....

It just blows me away---I believe the internet can Educate People who wish to learn--AMAZINGLY!!
And I want to thank ALL the members mentioned, who have/and still are participating on this great project....

To Quote Drone 1240

Quote

Yep but i aint into restricted . I think the info needs to be collected , stewed down and distributed to anyone and everyone who wants it . If they fuck up they fuck up same with matches

ITS THE INFO THATS THE IMPORTANT THING AND PUTTING IT ALL TOGETHER IN ONE SEARCHABLE FILE FOR THE FUTURE

I TOTALLY AGREE
Hypnos

Balkan Bonehead · « **Reply #29 on:** June 14, 2011, 02:33:53 AM »

Quote from: The Lone Stranger on June 03, 2011, 08:41:14 PM

Anyone got anything else to add ?

I found an online hive mirror, which may prove useful to some: parazite.fi/hiveboard/

I have archived copies of the hive, the older strike-era hive, and synthetikal saved to an external drive and indexed with google desktop. This makes it infinitely easier to find some tidbit of information, since it utilizes google's flexible search parameters, which would probably be absent from a "bundled" search utility.

Balkan Bonehead · « **Reply #30 on:** June 14, 2011, 10:31:51 AM »

Quote from: The Lone Stranger on June 14, 2011, 09:22:59 AM

Have you got a link to it all please ? Maybe a zip / rar downloadable file if there is / are no web adressess . .

I`m not sure about the "Big Brother google" bit though . I`ll pass it on to His lowness and see what he has to say .

Pardon, a link to all what?

I agree with the google privacy concerns, but I concluded that it wasn't much less secure a proposition than my ordinary internet habits, which include browsing sites like this. I limit google to indexing the external drive, so it does not know what is on C:/, for example.

Balkan Bonehead · « **Reply #31 on:** June 14, 2011, 02:52:35 PM »

Quote from: The Lone Stranger on June 14, 2011, 01:56:59 PM

"Pardon, a link to all what?"

Things you have or know where to get that might add to the Ark ......... hive things ......

Oh. Actually, I don't remember where I got the archives I mentioned, or whether they came bundled as one file or were separate files. I want to say sciencemadness or Madhatter's FTP, but I may have just found them from googling 'hive archive torrent' or something similar. Be aware that some of the hive archives floating around are incomplete.

NeilPatrickHarris · « **Reply #32 on:** June 14, 2011, 06:48:57 PM »

^ yes, it's my understanding that the admins removed a large portion of content towards the end of the hive for whatever reason. that's what i've been told anyway, not sure how true it is.

Balkan Bonehead · « **Reply #33 on:** June 14, 2011, 07:44:02 PM »

Quote from: The Lone Stranger on June 14, 2011, 06:46:36 PM

I`ve never seen or heard of a complete one

By 'complete', I meant that the archive contains all of the threads that are included in the mirror I linked, which covers the years 2001-2004, approximately, plus some supplementary files like pdfs, gifs, and djvus. In some versions, however, some of the htm files are gone, so the links in the forum indices are effectively broken. I think I know what you mean r.e. none of them being truly complete: there are alot of links in the threads themselves that point to a non-existent "DUMMY" folder. As to the whereabouts of those missing posts, I have no idea.

In addition to that one, however, there is another archive that includes a bunch of posts from about 1998 thru 2001, plus the short-lived synthetikal forum from 2005. I really wish I could remember where I got it from. I'll look around, or just zip and mount my copy if I cannot locate it. Maybe java can help, he seems to know where everything is.

hypnos · « **Reply #34 on:** June 15, 2011, 12:02:36 PM »

IMO that sound sound both understandable, and likely...

No doubt though, that "Somewhere in Cyberspace" ,, live some Pretty complete mirrors...
Now this is Only, an "Educated Guess" from what I've been told,, by those IBelieve ,,becoz after much "intercourse togther"(asexual), they 'have Never given me A Reason,,to doubt their sincerity,,,in what they both say, and DO!

Seek and Ye Shall Find hexamatey, in that I Believe

,,'Luck' has NOthing to DO with shit

"ones," Successes ,,and /or Failures,.. in Life,, Are The ways we learn about this Game of Life We do our 'Best, To survive/evolve(hopefully!) as best we know How",, and we Do this by 'thinking about "it'

That, it is, "The Consistent Application of The Mind",, 'upon 'What you want,' (aka as Praying...!) and esp, WHY do "You"( in the Plural sense-i.e Every/any body?) Pray for, That It IS You DO,,while going to sleep??

Take care hexamatey, good to see you around

Cheers Hyppy

OoBYCoO · « **Reply #35 on:** June 15, 2011, 05:31:47 PM »

Quote from: The Lone Stranger on April 02, 2011, 12:48:46 PM

I`m looking for FULL copys of "The Complete Book of Ecstacy" , and "Psychedelic Chemistry" by Michael Valentine Smith as the ones i have found are not complete . I`m also looking for copys of the entheogen review issued after 2005 . If you know where i can get them please let me know.

If he's still looking for those books...

The Entheogen Review:
Complete run (11 issues) of The Psychedelic Review [1963-1971] in CBR. Complete run (57 issues) of The Entheogen Review [1992-2008] in PDF. A full index and sample issue is also included.
Magnet link---> demonoid.me/files/downloadmagnet/2397335/37509710

Smith - Psychedelic Chemistry 2e HTML.rar:
Magnet link---> demonoid.me/files/downloadmagnet/1458473/22505826 (When you open the torrent file w/ your app uncheck all of the other books, unless you want them.)

The Complete Book of Ecstacy: Sorry couldn't find it.

OoBYCoO · « **Reply #36 on:** June 15, 2011, 08:26:39 PM »

That's weird. When I put the www. infront of those addresses it works fine. I'll PM you the links, but it'll be the same as you just putting www. in front of demonoid.me/files/downloadmagnet/2397335/37509710 and the other one.

Buddah · « **Reply #37 on:** June 29, 2011, 02:06:40 AM »

Quote from: The Lone Stranger on June 16, 2011, 08:46:33 AM

Can someone please get those two torrents and either upload them to a download site and post the adress ......OR ...... put .txt on the end of them , open them and copy the contents into a PM and post them to me please ?

Psychedelic_Magazines_Entheogen_Review_[1992_2008]_Psychedelic_Review_[1963_1971]_O-Demonoid.me-O

LSD_Psychedelics_Essential_Books_v3-((Demonoid.me))

lugh · « **Reply #38 on:** July 13, 2011, 10:12:09 AM »

The Lord of the Realms has done nothing but try to help the members of the swarm, it's not his fault that as time passes computer files become corrupted

People need to take measures to protect such data, by using file checking tools that are freely available

A copy downloaded last year is attached, please try not to fuck it up this time

lugh · « **Reply #39 on:** July 13, 2011, 12:22:03 PM »

Quote

LOL.....ROTFL........Ahhhhh ! Yooz bin a lurkin agin .......... First thanks for the download ...... BUT ..... did you open it and look at the first .doc file = XFile 1.doc ? Its exactly the same as the other 4 we downloaded = totaly fucked and light years away from a quality that his lowness will acept for his master work . He spent several weeks trying to repair the files and also trying to find a program that will open them without the squares instead of the print that should be there . Could it be that XP , microshit office and every single conversion program that we have both tried are broken ? Or is it the x-files ?

I wouldnt think of slagging the lord of the realms or his work ....... i aint slagging anything or anyone ....... this time ....... I`m just pointing ouit that all 5 copys are either totaly fucked or loads of proffesional sofware is fucked ......... or maybe its terrorist mckenna and the machine elves putting a curse on both of us , our composters and all that software ........ ?

Sorry beeing a thicko i`m just haveing to guess as i`m not and dont even think i`m infalable just because i used to post on the hive ............ .

Please look at the attached picture to see what we can see and then please tell us how to see the words that should be where the squares are ....... in all 5 downloads ..........

The text from the document in question:

DISCLAIMER : THE FOLLOWING INFORMATION IS FOR INFORMATIONAL PURPOSES OR ACADEMIC STUDY ONLY. CHECK YOUR LOCAL, STATE AND FEDERAL LAWS, AND PROCURE THE NECESSARY PERMITS BEFORE UNDERTAKING ANY OF THE REACTIONS DESCRIBED BELOW. WIZARD X SHALL NOT BE HELD LIABLE AND INDEMNIFIED FROM IMPEACHMENT FOR THE USE, MISUSE, INJURY, DEATH, IMPRISIONMENT OR FELLATION DUE TO THE APPLICATION OF THIS INFORMATION.

PERFACE

In this revised supplementary procedure of Festers hydrogenation I will dream of 70% - 90% yields. Dreaming of 90% greater yields using this method is pure BS as medium to high hydrogen pressure is needed. There is however, only one method that I know that gives 100% yield at one normal hydrogen atmosphere ( 1Atm ) pressure, at 10 deg C, for 20 hours hydrogenation. The catalyst however, is very very difficult to make.

The greater efficiency in this revised supplementary procedure is due to cell design and hydrogen adsorbtion.

Look at all JPG files.

ELECTROCHEMICAL THEORY

Festers procedure is really a catalytic hydrogenation (hydrogenolysis) reduction with H2 produced insitu via electrolysis of water. The H2 and the Eph acetic ester are adsorbed onto the Pd metal surface where the reduction takes place. A sealed cell stops oxygen from being dissolved into the electrolyte as O2 is 27 times more soluble in the electrolyte than H2 at 20 deg C. If the Pd/C will catalytically reduce the Eph acetic ester and H2 which are adsorbed onto the Pd metal surface, then it surely will catalytically reduce the dissolved O2 with H2 to give water.
(2H2 + O2 ===> 2H2O) Thus O2 competes with the Eph acetic ester and O2 is reduced much more easy.

Electrochemical reduction (no catalysts)

Ph = C6H5- , ECR = electrochemical reduction

R = -COCH3, -COC6H5, -CO2Et or H

Ph-(HCOH)-CH(-NHCH3)-CH3 === ECR ===>> NO reduction reaction

Ph-(HCOR)-CN === ECR (2e) ===>> Ph-CH2-CN + HOR reduction reaction

Ph-(HCOR)-COOH === ECR (2e) ===>> Ph-CH2-COOH + HOR reduction reaction

Ph-(HCOR)-CO-CH3 === ECR (2e) ===>> Ph-CH2-CO-CH3 + HOR reduction reaction

Ph-(HCOR)-CO-CH3 == ECR(4e)==>> Ph-CH2-(HCOH)-CH3 + HOR reduction reaction

R1 = -COC6H5, -COCH3 best leaving groups.

-CO2Et or H poor leaving groups.

Ph-(COR1)(-COOH)-CH(-NHCH3)-CH3 ========== ECR (2e) =============>>

Ph-(HC-COOH)-CH(-NHCH3)-CH3 + HOR1 reduction reaction

Ph-(HC-COOH)-CH(-NHCH3)-CH3 === decarboxylation ===>> Ph-CH2-CH(-NHCH3)-CH3

Carbon-Oxygen bonds may be cleaved, electrohydrogenolysis (H2 cleaverage) in protic media (acidic solutions pH1 - pH3) when adjacent to one or more powerfully activating groups such as the carbonyl or cyano functions. The carbonyl or cyano functions activate a benzylic carboanion to be formed which reacts with a H+ from the acidic medium. The acidic medium helps protonate the oxygen on the carbon-oxygen benzylic bond helping to induce the benzylic carboanion.

Ac = -COCH3

Ph-(HCOR1)-CH(-NAc-CH3)-CH3 ==== ECR, 12-20 Volts, 4A === (2e) =======>>

Ph-CH2-CH(-NAc-CH3)-CH3 + HOR1, reduction reaction gives poor yield due to dimerization and alcohol formation with no activating group. Even though the reaction requires theoretically, 2 electrons, the amount is much greater, 5-7 fold. Simply you are forcing a benzylic carboanion to be formed which reacts with a H+ from the acidic medium. The acidic medium helps protonate the oxygen on the carbon-oxygen benzylic bond helping to induce the benzylic carboanion.

IN MOST CASES THE REACTION PROCEEDS VIA H2 CLEAVERAGE BETWEEN THE O-R , OR THE O-R1 FORMING THE ALCOHOL IF NO ACTIVATING FUNCTION GROUP IS ADJACENT

CONTENTS

1 Power Supplies

2 Current Regulator

3 Tests : [ 1 ] Ester test
[ 2 ] Polarity test

4 Catalyst : 30 % Palladium on Carbon

5 Cell Dividers

6 Cell Design

7 Cell Resistance

8 Multiple Parallel Cell Arrangement

9 Revised Supplementary Procedure

POWER SUPPLIES

The power supply is important, but not crucial. Have two power packs that step-down from the mains :
( 1 ) 12 Volt, 1.5 - 2 Amps and ( 2 ) 12 - 15 Volts, voltage regulated if possible with 500 mAoutput.
Power pack 1 is used to pre-treat or anodize the Pd ingot, and nothing more. Power pack 2 is used in the main electrocatalytic hydrogenation. Simply there is no need to try and lower the current from Power pack 1 down to a useful level. Power packs are cheap and easy. I have included circuit diagrams LM2941.jpg and LM317.jpg for those who want to build a regulated variable power supply.

CURRENT REGULATOR
Look at file D_1 Figure 1.

This circuit is optional, but it does two things, regulate the current and fix the voltage.The Zener diode, fixes the voltage and the current regulated by the transistor BC 640 or MJ2955. The wire wound variable resistor determines or sets the regulated amount of current, sent through the ammeter. The transistor BC 640 can handle up to 1 Amp at its collector, but use no more than 500 mA. Transistor get very hot. The MJ2955 can handle up to 15 Amp at its collector, but use no more than 10 A, with a large heatsink. I have included a circuit diagram for a high current output variable voltage regulator, Icop.jpg

TESTS

ESTER TEST : Hydroxamic acid test for esters.
By comparing the colour of two samples produced before the hydrogenation and after, you can determine the amount of ester reduced ( hydrogenated ).

Pre - test : To 1 drop of the Ephedrine acetic ester mixture in a small test tube before the hydrogenation, add 1ml of 95% ethanol and 1ml of 1N HCl. Then add 1 drops of 5 % iron ( III ) chloride solution. If a violet , blue , red or orange colour develops, then the test below can not be used as something ( contamination ) else is reacting with the iron ( III ) chloride.

[ 1 ] Place 3 drops of the Ephedrine acetic ester in a small test tube before the hydrogenation. Place another 3 drops in a second small test tube after the electrocatalytic hydrogenation is complete. Now add to both test tubes 3 drops of a saturated solution of Hydroxylamine hydrochloride in methanol ( or 1ml of a 6 % solution of Hydroxylamine hydrochloride in methanol to both test tubes ).
[ 2 ] Add to both test tubes 6 drops of saturated Potassium hydroxide in methanol solution, or until distinctly alkaline to litmus. Remember add to both test tubes equal amounts. Heat the mixture gentle just to boil, the cool to room temperature.
[ 3 ] Acidify both test tubes with equal amounts of dilute HCl ( 2N ) and then add to both test tubes 2 drops of 5 % iron ( III ) chloride solution. A reddish ( burgundy ) or violet ( magenta ) colour will indicated the presents of ester.
Sample taken before hydrogenation is the control, assuming 100% Ephedrine converted into the acetic ester.
The second test tube having the sample after the electrocatalytic hydrogenation will indicate the amount of ester not hydrogenated.

POLARITY TEST

Look at file D_1 Figure 3.

Some power supplies have the current flowing from positive + to negative - And so, errors can occur when wiring up the cell. To ensure that this does not happen follow this polarity test procedure. When current flows in the A lead ( anode, long lead ) of a Light Emitting Diode, and out the K lead ( cathode, short lead ) it glows. If it is reversed it does not. Solder a 560 ohm resistor on the A lead ( anode, long lead ) making sure not to over heat the lead. The A lead with resistor connects (wired ) to the positive + terminal of the power supply, and the K lead connects (wired ) to the Pd ingot. Now, connect (wired ) the Pb electrode to the negative - terminal. By touching the two electrodes together ( make sure clean oxide free surface ), if the LED glows then the current polarity is correct. The current is flowing from positive + to negative - .This means the positive + terminal is the cathode and reduction occurs, and the negative - terminal is the anode where oxidation occurs.

If the LED does not glow, then reverse the wires at the terminals. Make sure at all times good connection is made.

REMEMBER ! ONCE YOU HAVE DETERMINED THE POLARITIES OF THE ELECTRODES, REMOVE THE LED TESTER FROM THE CELL CIRCUIT.

CATALYST : 30 % PALLADIUM ON CARBON

Palladium is the superior catalyst in this reaction. Platinum is the second, but can also attack the aromatic ring of the Ephedrine.

30 % Palladium on Carbon preparation. Prepare a solution of 8.25 grams of palladium chloride, or 9.93 grams of palladium chloride dihydrate in 5 mls of concentrated hydrochloric acid ( HCl ) and dilute with 50 mls of distilled water. Cool the solution in an ice-salt bath and add 50 mls of 40 % formaldehyde solution and 11 grams of acid-washed activated charcoal. ( Any of the commercial forms of activated charcoal, "Norit or Darco", may be employed ; the carbon should be heated on a steam bath with 10 % nitric acid for 2-3 hours, and then washed free of acid with distilled water and dried at 100 deg C before use. )

Stir the mixture mechanically and add a solution of 50 grams of potassium hydroxide in 50 mls of water, keeping the temperature below 5 deg C. When the addition is complete, raise the temperature to 60 deg C for 15 minutes. Wash the catalyst thoroughly by decantation with distilled water and finally with 1N acetic acid. Collect on a suction filter and wash with distilled water until free from chlorides and alkali. Dry at 100 deg C, and store in a desiccator.

This makes plenty of catalyst ( approx 12 grams ) for many runs, as only half a gram is needed for each run. The catalyst used in that run is filtered and used again, and again until that first half a grams becomes non-active. Usually, 10-15 runs per half a grams.

CELL DIVIDERS

Look at file D_1 Figure 2. The green colour denotes the porous diaphragm or membrane.

Figure 2 a : filter paper extraction thimbles, used in Soxhlet extraction apparatus.

Figure 2 b : plastic tube ( PVC, Plexiglass, Acrylic, ect ) or glass tube with a disc of Whatmans acid-hardened filter paper or Whatmans glass-fiber filter paper, glued with epoxy glue or the plastic made soft with a solvent. Make sure you create a good seal between the plastic tube and the filter paper disc. Acrylic plastic tube placed vertically on a chloroform soaked filter paper disc and held there, with pressure, until the solvent dries works well. Place the chloroform soaked filter paper disc on a sheet of glass , not plastic.

Figure 2 c : same as above, with the plastic tube material or glass tube, but the material used in the porous diaphragm or membrane can be made of ( 1 ) Fiberfrax ( ceramic fiber ) paper or finely woven cloth, ( 2 ) Fiberglass (glass fiber ) paper or finely woven cloth, ( 3 ) Carbonfiber ( graphite fiber ) paper or finely woven cloth,
( 4 ) Asbestos ( asbestos fiber ) paper or finely woven cloth. The porous diaphragm or membrane properties can be improved by impregnating the paper or cloth with a methylcellulose gel. The gel is formed by impregnating the paper or cloth with a hot solution of methylcellulose in dimethylformamide solvent and allowing it to cool.

Figure 2 d : extraction thimbles as used in the Soxhlet extraction apparatus can be purchased as glass walled tubes with sintered glass porous frits. Use a fine porous frit.

Finally, potassium hydrogen sulphate (KHSO4)or potassium sulphate(K2SO4) agar gel salt bridge or plugs can be used, but with great care.
To make the salt agar gel the procedure is : heat 100mls of distilled water in a 250 ml Erlenmeyer flask just to boil and then place on a steam bath. Add 3.5 grams of agar powder, stir, and continue to heat until a uniform suspension is formed. Then, add 34 grams of potassium hydrogen sulphate ( KHSO4 ) and stir until it goes into solution. Cool the mixture to about 40 deg C, this will not allow the agar to gel, but keeps it liquid for use. The agar gels at room temperature. When making a agar gel salt bridge using a U shaped tube, try not to get air bubbles in the gelled agar, keep it uniform.
Finally, plugs of this salt agar gel can be made by adding the liquid gel mixture to Figure 2b & 2c type cell dividers.

Also, you can stretch the condom, as used in Festers procedure over a plastic tube ( PVC, Plexiglass, Acrylic, ect )
to obtain a more permeable membrane.

CELL DESIGN
Look at file D_1 C1 to C5

Keep the temperature of the electrolyte between 20 to 25 deg C.

C 1: You can purchase cell divided apparatus with a sintered glass frit.

C 2 : Make the cell divider 2 / 3 the diameter of the glass container ( beaker ), this will keep cell resistance low.

C 3 : Same setup as in C 2 , but the cathode is a copper foil plated with Pd , and wrapped around the cell divider with gas venting spacers inbetween the cell divider wall and copper foil. Remember the current density is for the entire copper foil area , and only expose the Pd plated area to the electrolyte. The copper foil ( clean from oxides and grease, oil etc) can be plated by placing it in a concentrated solution of palladium chloride PdCl 2 ,or it an be done at the cathode in the concentrated solution of palladium chloride electrochemically.

C 4 : Straight forward , look at the diagram.

C 5 : Use a glass walled , fine sintered glass frit cell divider. A large rubber bung with holes ( red colour ) through the top allowing the cell divider and electrodes into the cell. The cell must be absolutely sealed and air tight so no hydrogen gas escapes. A pressure equalization system is setup so the hydrogen pressure does not build up too great and explode the cell. This is done by filling a large test-tube , 2 / 3 with glycerine and immersing a glass tube almost to the bottom. See the diagram. The cathode can be suspended by using a copper wire through a glass tube, and making contact with the Pd ingot fixed to it by drilling a small hole in the Pd ingot and crimpping the copper wire in the hole and finally sealing the end by melting the glass . Seal all exposed copper wire with epoxy resin.

CELL RESISTANCE

Each electrolytic cell constructed with different materials , cell dividers , and electrolytes has an internal resistance that is different. Using Ohms Law V = IR, you can determine the maximum resistance at a particular voltage and current. If V = 12 volts and I = 0.3 amps, then 40 ohms is the maximum cell resistance. This means if you calculate the cell resistance by connecting a multimeter set at volts, on the Pd and Pb electrodes while beginning the electrocatalytic hydrogenation and determine the voltage between the electrodes. The majority of cell resistance is between the electrodes. Then determine the current flow and use (V/I = R), resistance is determined. Resistance of the cell is not constant. If it is greater than 40 ohms then a 0.3 amp current will not flow at that voltage AND heat is generated.

REMEMBER : THE GREATER THE CELL RESISTANCE IS THE LESS CURRENT FLOWS AND MORE HEAT IS GENERATED.

MULTIPLE PARALLEL CELL ARRANGEMENT

Multiple parallel cell arrangement can be performed from a single power source ( power pack or other ) by connection the cells in PARALLEL. This lowers the resistance. DO NOT CONNECT IN SERIES.

PARALLEL CELL ARRANGEMENT RESISTANCE FORMULA :
1 / R = ( 1 / R 1 ) + ( 1 / R 2 ) + ( 1 / R 3 )

R = the cell resistance

REVISED SUPPLEMENTARY PROCEDURE

THE 1998 FESTER FORMULA: SUPPLEMENTARY PROCEDURE

BY WIZARD X

Electrocatalytic Hydrogenation of Ephedrine, Pseudoephedrine and Phenylpropanolamine

Materials:

One (1) gram of purified ephedrine, pseudoephedrine or phenylpropanolamine.
One troy ounce ingot of palladium
Glacial acetic acid
Concentrated sulfuric acid
Sodium hydroxide
Anhydrous HCl gas source
pH-indicating paper
Toluene
Kling-Tite Naturalamb brand condoms or cell divider in Figure 2
Lead or graphite electrode 1/2-inch wide by 3-4 inches long
Six one-inch alligator clips
Several feet of 16 to 20 gauge insulated copper wire
Variable DC power supply
Ammeter capable of measuring up to 3 amps, with resoloution to 1/10 of an amp
Voltmeter (optional)
thermometer
Apparatus for Cell C 5 construction.

Procedure:

One gram of ephedrine, pseudoephedrine or PPA hydrochloride is placed in a large test-tube along with 9 mL of glacial acetic acid. The test tube is heated in a water bath until all the ephedrine (in this case)
hydrochloride is dissolved. Add 1 ml of concentrated HCl or 10 drops of concentrated sulfuric acid.

Mix it all together and LOOSELY stopper the end of the test tube to prevent steam from entering. Heat the water bath to just about boiling,(80-95 deg C) and use it to heat the test tube and its contents for 2 hours. If you see the once clear solution turn brown quickly over the coase of the 2 hour heating, then cease and cool. This forms the acetic ester of the ephedrine, pseudoephedrine or PPA used in the reaction. The solution should appear clear and water-like, completely homogenous. Save 3 drops in a small test tube for ester test. After heating, the reaction mixture can be kept stoppered as is for a few days, but it's best to use it immediately after it's cooked.

Next, mix up a solution of 10 mL of concentrated sulfuric acid in 200 mL of water. Take a 250 mL beaker, C 5 cell construction and place it on a magnetic stirrer. Have the cell C 5 constructed beaker, and place a piece of lead ( Pb ) 1/4 to 1/2 inch in diameter and a 4 inches long inside the cell divider. On the other side of the beaker, insert the one-ounce ingot of palladium cathode. Using alligator clips, to make contact with the ingot, via the copper wire and with the piece of lead. They are your two electrodes. Next, pour the dilute sulfuric acid solution into the cell divider so 1 / 2 to 2 / 3 full. Next , the dilute sulfuric acid solution is poured into the beaker so that the solution level is about 2 cm lower inside the beaker than the cell divider. The ingot of palladium should be completely immersed.
The surface of the palladium ingot should be very lightly sanded with very fine sandpaper prior to use and washed with methanol. This increases its surface area a little and exposes fresh, clean metal. The piece of lead should be scrubbed free of grease and dirt.
Measure the cell resistance with a multimeter set on volts, and determine the voltage between the electrodes.
A DC current meter (ammeter) should be put in series with the wiring.

The wires are first hooked up so that the palladium ingot is connected to the positive pole (oxidation) of the DC power supply, and the piece of lead to the negative (reduction). Use the polarity tester to get the polarities correct.
The typical one-ounce ingot will have a face with an area of about 6-7 square centimeters immersed in the solution. Only count the area on the side facing the lead piece. The back side doesn't count because significant current doesn't reach it. With this typical ingot apply about 1.5 - 2 amps for 30 seconds to one minute.
Oxygen will bubble freely from the ingot, and hydrogen from the piece of lead. Blackening will be noted on the edges of the ingot, where the current is most intense, and a lighter discoloration on the flat face of the ingot. This pre-treatment is called anodizing. It has been found that anodizing increases the ability of the palladium ingot to adsorb hydrogen when the wiring is turned around, and the ingot is made the cathode.

Next, redo the wiring so that the palladium ingot is attached to
the negative pole (reduction) of the DC power supply, and the piece of lead to the positive (oxidation). Use the polarity tester to get the polarities correct.
Add 1 / 3 to 1 / 2 grams of the 30 % Pd on carbon catalyst and start magnetic stirring immediately.
Apply a gentle vacuum to the outlet tube of the pressure equalization test tube so it sucks out the air in the reaction beaker.

Turn the juice back on and run between one and two amps of current for about 20 minutes. At first, the amount of hydrogen generated at the palladium ingot will appear small.This is because the Pd adsorbs hydrogen so well. After about five minutes of current passage, the whole surface of the ingot will freely bubble off hydrogen and the 30 % Pd on carbon catalyst is also adsorbing hydrogen. Stop the vacuum after 2 minutes of suction and disconnect from theoutlet tube.

After the 20 minute charging with hydrogen, add all of the ester reaction mixture from the large test tube with a syringe. Use two syringes so one plugs the addition port at all times , so the hydrogen gas doesn't escape. Adjust the current flow from the power supply so that a current of about 50 milliamps per square centimeter of palladium surface flows. If one has about six square centimeters of the ingot facing the piece of lead immersed in the solution, a current of about 300 milliamps is called for. This will result in some gassing off of hydrogen from the edges of the ingot, but over the rest of its surface the hydrogen will react before it bubbles off. The lead anode will form a brown layer of lead oxide, and will not dissolve at all in the sulfuric acid solution.
Some surface particles will be kicked off the lead when it's first charging, but they don't make it through the cell divider. The lead anode can be replace with a piece of platinum if desired, but lead is a lot cheaper. Graphite is another possibilty.

Keep the temperature of the cell electrolyte between 20 - 25 deg C.

Keep an eye on the current meter, as the current flow can change as the reaction progresses if you do not use the current regulator.
Keep the current flow around 300 mA ( 0.3 amp )for the size ingot given in this example. A Coulomb is a unit of charge equalling one amp-second.
C = A x s
96,500 C = 1 mole of electrons.

Continue at 300 milliamps until 3000 coulombs have passed through the solution. Let us use the 300 mA current to show an example of these calculations: At 300 milliamps, 3000 coulombs pass in 10,000
seconds, or two hours, 45 minutes.

3000 coulombs per gram of feed material has been found to give good yields of a fine product, but by no means consider this number to be optimal. It may well be that a greater yield would be obtained by passing
more current. It may also be that pseudoephedrine and PPA differ from ephedrine in their ease of electrocatalytic hydrogenation. Apply no more than 3 hours at 300 milliamps of current.

During the course of the reduction, the colour slowly changes from its initially clear color to slightly tinted with yellow. Now that a hydrogen atmosphere is present the reaction mixture is not in contact with oxygen in the air. It's a byproduct of the reaction. In any case, it's a remarkably clean reaction.

When the desired amount of current has passed, the work-up and isolation of the product is very simple. Save another 3 drops in a second small test tube. The cell divider is rinsed off into the beaker and removed from the beaker , after pulling out the lead electrode first. The anode can be used over and over again.
The palladium cathode is then washed into the beaker and removed.
It too can be reused an INNUMERABLE number of times.
The process of anodizing the palladium will have to be repeated prior to each run. Some fresh metal may have to be exposed on occasion by very light sanding of the metal surface. An ingot of palladium should last for a lifetime.

The reaction mixture should be filtered into a sep funnel, so to collect the Pd/C catalyst and rinse both the catalyst and beaker with water. Add a 20 % NaOH solution should be added with shaking until the solution is strongly (13 + pH) alkaline to pH paper. The catalyts is dried at 100 deg C after being rinsed again with water. Store in desicator.

Extract with two 50 to 100 mL portions of toluene. This should be plenty for one-gram of product. The toluene extracts are pooled together and dried with anhydrous magnesium sulphate. Decant in a clean beaker and rinse with tolulene the anhydrous magnesium sulphate and decant in the same clean beaker.Then bubble with dry HCl to get the crystalline hydrochloride product. After rinsing them off with some fresh toluene or ether , they are spread out to dry.

The most pleasantly surprising finding is that crank produced by this method doesn't give one the body and soul-wrenching hangovers so typical of the product made by the iodine-red phosphorous method..
If one should wish to produce more than a gram or so at a time, a larger palladium cathode should be used. Linking together parallel more ingots of palladium would get pretty expensive, so a more economical alternative will be detailed. That alternative is electroplating some copper or brass screen with a thick coating of palladium.

The simplest way to get this section of screen electroplated with palladium is to go to the yellow pages, look under electroplaters and find one who plates palladium. Ask for a plate build-up of several thousandths of an inch, so that enough Pd is deposited to last a while.

The Pd plated screen would then be used exactly like the ingot. First it must be anodized, then charged up with hydrogen in exactly the same way. The sole difference is that the greater surface area of the
screen facing the condom-encased anode requires a correspondingly greater amount of current to be passed. Then, during the course of the reduction, again 50 milliamps per square centimeter of surface area facing the anode
is used. The total of 3000 or so coulombs per gram of feed material doesn't change by increasing the size of the electrode.

An alternative to this is plating the screen yourself, anodically dissolving a portion of the ingot to form a PdCl2 solution .

The lastest word from Fester is a couple of references from Indian journals on electroplating graphite electrodes with palladium, essentially giving a Pd black on C catalyst in the cell!

1) Krishnan, Electrochemica Acta, Vol 21, Pg 449-450 (1976)

On the Electrochemical Reduction of Benzyl Cyanide to Phenethylamine with
a Pd/C Electrode

2) Krishnan, Journal of Applied Chemistry, Vol 5, Pg 125-128 (1975)

The greater activity of Pd on C (over straight Pd) results in a shorter reaction time.

Water Electrolysis :

ANODE (Oxidation) : H2O ==>> 2(H+) + 2e + O2 E ox = -1.23 V Standard Electrode Potential

CATODE (Reduction) : 2H2O + 2e ==>> H2 + 2(OH-) E red = -0.83 V Standard Electrode Potential

E = E red + E ox So E = -0.83 + (-1.23) = -2.06 V This is the emf of the electrolysis.
Because -2.06 is negative the reaction is nonspontaneous, so a potential of 2.06 V is reqiured to start electrolysis.

Total Cell Voltage : E = E (back emf) + E (overvoltage) + E (iR ; cell resistance) + E (polarization)

E (back emf) is -2.06 V

E (overvoltage) is excess potential that must be applied over the reversible potential -2.06 V

Overvoltage of Hydrogen and Oxygen on Pt and Pd Electrodes.

Overvoltage , V
Current Density amps/cm2 H2 O2
0.001 0.024 0.72
0.01 0.068 0.85
0.1 0.29 1.28
1.0 0.68 1.49

Overvoltage can be minimized by keeping electrode area large and current density low.

E (iR ; cell resistance) Occurs mostly between the electrodes in the cell. Since strong acids are being used excellent
H+ concentration gives good conductance. However, R of the cell is not constant like metals or semiconductors.
In general V = I & C = I , where V is volts , I is current A , C is concentration in mol/dm3. Basically, as you increase volts you increase current & as you increase C (strong acids only) you increase I.
Now, if (2.06/0.3) = 6.87ohms, then you need another 2.06 V for the resistance, assuming the cell R is 6.87 ohms.
Cell resistance is not constant so R is always changing. To minimize R, have good stirring and high concentrations of acid.

E (polarization) this can be omitted. Concentration polarization can be minimized by good stirring and high concentrations and low current densities.

I passed a current of 0.31 A at 4.2 V (electrode potential ) using a sintered glass frit cell divider. Power voltage was 6.56 V. So, E = 2.06 + 2.06 + 0.29 = 4.41 V close.

His lowness needs to fix his computer(s) himself, instead of wasting the staff's valuable time and expensive bandwidth posting complaints about a local issue

The only person who can help his lowness is himself, the question is whether he is willing to do something about his computer problems or keep wasting everyone else's time

A clean reinstall would have solved this issue a few weeks ago

The end results from the effort applied

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