Author Topic: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole... (Read 2846 times)

Oerlikon · « **Reply #180 on:** March 13, 2011, 03:41:28 AM »

My bad,we use word titration for few other things
in science and medicine apart from quantitative chemical analysis.

Depends on what you have available! Art of clandestine chemistry is using effectively what you have!
For example I don't have MgSO4 and NH4Cl at the moment but can get tons of cheap NaOH!
Unfortunately we don't use ammonia for the household so it isn't easy to find that either.

Sedit · « **Reply #181 on:** March 13, 2011, 03:59:12 AM »

Im sorry Oerlikon and even though I agree full force that we use what we can get I find it impossible that you don't have MgSO₄. Epsom salt is one of the few chemicals that I fear going into the dark ages. Its Dirt Dirt cheep.... like 3$ for a few pounds...

There is no way that NaOH is cheeper or more readily avalible then MgSO₄, not by a long shot.

I know for sure that you must have some sort of dehydrating reagent somewhere in your home(all of you) cheeper then NaOH.

fractal · « **Reply #182 on:** March 13, 2011, 04:13:20 AM »

Quote from: Oerlikon on March 13, 2011, 02:45:22 AM

We don't use SWIM here. It's agains the forum rules,it's logically pointless and self-insulting!

Good to know, not like every other drug chemistry forum on the internet uses it or anything

Bad habits die hard, I know from now on though.

Quote from: Oerlikon on March 13, 2011, 02:45:22 AM

And no,that is not good advice at all! Harming actually!
Water can't hold allmost ANY NH3 when strong base like NaOH is present in same solution.
Not adding water is also pointless and harming since hydrolysis of NaOH produces A LOT
of heat and "water that it makes on it's own" will become steam,ruining everything if
you don't have CaO or CaCl2 tube to catch it,which is not good since every known good
desicant catches NH3 too.

The cooling chamber condenses most of the formed steam and CaCl₂ or MgSO₄ will get rid of the rest of the water present even if it removes a bit of NH₃ in the process. It's completely possible to make anhydrous ammonia this way. I've made liters like this. Does waste a lot of NaOH though as sedit it said but never found that to be a problem because it cost $30/12lb, pretty cheap. Never tried it with saturated solutions before, just stated a method I know works decently

Quote from: Sedit on March 13, 2011, 02:45:22 AM

The most effective way, that I never tried mind you, I feel would be to drip a saturated solution of NaOH onto dry Nitrate. Pass this thru a drying tube/bottle to absorb all the water and feed it into NaCl/Ice chilled alcohol.

Yeah that does seem like it would work a lot better. I'll give it a go next time I need to generate some.

Sedit · « **Reply #183 on:** March 13, 2011, 05:24:24 AM »

CaCl2 complexes with amines.... Avoid at all cost. You will lose your ammonia as it sucks up water.

jon · « **Reply #184 on:** March 14, 2011, 08:21:36 PM »

Quote

Maybe mixing IPA,CaO and urea and distilling might do the trick!
Jon will say we are overcomplicating things but it's just fun to invent
new ways of doing the same thing

nope oerlikon it won't work your ammonia or methylamine will gas out as you distlll it.
this procedure is something i pulled out of j.a.c.s. i tend to trust them a lot more than the grapevine i did it sans the drying trap but i found it is'nt nessecary as it does'nt kick off much water if you do it in that order (add sat. naoh to ch3nh3+Cl-) because most of the heat is from the dissolution of the naoh.

Oerlikon · « **Reply #185 on:** March 14, 2011, 08:49:01 PM »

Yeah Sedit,it's hard to believe but I have only 50g or so of MgSO4 (some hydrate) and my source
doesn't have it for months! I bought p.a. grade Na2SO4 instead since it was cheap,that will do the trick even better I hope.

You won't believe what kind of things man can find in another culture/country/period that are forbiden or precious in another!
Explosives,drugs,guns,radioactive stuff,war gases,exotic and forbiden chemicals...you name it!

And finally,how the f..k did I forget that,it's logical!
I remembered what is the best as drying agent for NH3 or methylamine if you reall need it:
Dry NaOH!

Jon,problem is that I have glass funnel and NaOH allready violated it badly...
I hope that dissolving NaOH and adding saturated solution of AN will work good too!

jon · « **Reply #186 on:** March 14, 2011, 10:14:12 PM »

ammonium nitrate will frustrate you it crashes out in the funnel clogging it up.
you can get u-235?
polonium 210?

Oerlikon · « **Reply #187 on:** March 14, 2011, 10:55:49 PM »

LOL I worked with AN for years,it isn't that bad just don't oversaturate it!

I can get both of those!
But only in miniscula amounts

No,seriously you can get a bunch of Po 210 from old Russian trucks in ExSSSR states.
They used as aprt of ignition system,beat me if I know why!
Khazastan is notorious as being Russian nuclear waste site,search there.

Wizard X · « **Reply #188 on:** March 15, 2011, 01:19:04 AM »

Nucleophilic substitution of a halogenoalkane with ammonia or primary aliphatic amine (ammonolysis)

Secondary alkylhalide nucleophilic substitution

http://chemistry2.csudh.edu/rpendarvis/SN1Elim.html
http://www.docbrown.info/page06/OrgMechs2.htm
http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/alhalrx1.htm
http://en.wikipedia.org/wiki/Nucleophilic_substitution
http://www.el-fellah.com/amines1.htm
http://www.chemguide.co.uk/mechanisms/nucsub/ammonia.html

Nucleophilic substitution of a halogenoalkane with ammonia or primary aliphatic amine. http://www.docbrown.info/page06/OrgMechs2.htm#ammonia

http://en.wikipedia.org/wiki/Amine_alkylation
http://en.wikipedia.org/wiki/Amine

www.knockhardy.org.uk/sci_htm_files/08amine.pdf Why excess ammonia is used? Page 4.

Ammonia solution, 2.0 M in isopropanol. http://www.sigmaaldrich.com/catalog/ProductDetail.do?lang=en&N4=392693|SIAL&N5=SEARCH_CONCAT_PNO|BRAND_KEY&F=SPEC
References Merck 14, 492.

Properties.

vapor pressure
20.22 psi ( 55 °C)
6.34 psi ( 20 °C)

concentration: 2.0 M in isopropanol
bp: 50 °C
density: 0.773 g/mL at 25 °C

jon · « **Reply #189 on:** March 17, 2011, 01:19:14 AM »

yeah you'll need a much higher concentration than that.

Wizard X · « **Reply #190 on:** March 17, 2011, 05:52:28 AM »

Quote from: jon on March 17, 2011, 01:19:14 AM

yeah you'll need a much higher concentration than that.

It was for reference only and a saturated alcoholic solution is always optimum.

This procedure below uses 18.2% w/w alcoholic methylamine. Also the "Dimerization of isosafrole" is to bring to attention that Hg salts, and others, can cause dimerization.

jon · « **Reply #191 on:** March 18, 2011, 05:55:30 AM »

right it's a beta-methylstyrene and styrenes are notorious for polymerization
that's why bromosafrole turns to gak when it's heated it splits out to isosafrole and that polymerizes.

Sulfuro · « **Reply #192 on:** March 19, 2011, 08:34:40 PM »

You all should buy the first edition of The Shulgin Index (2011). In it is a mammoth amount of references for the syntheses of many known (and unknown) compounds.

One of them is for MDA.

Page 166, second paragraph:

"From safrole (with HgCl2, AcOH and HBr) to 1-(3,4-methylenedioxyphenyl)-2-bromopropane; (with NH3, Cu2O) to MDA (Muszynski, 1961).

Muszynski reference, page 610:

Muszynski, I.E. (1961) Derivatives of amphetamine. Acta Polon. Pharm. 18: 471-478. (in Polish)

Another interesting Muszynski reference, found on the same page:

Muszynski, I.E. (1965) Synthesis of new compounds in the amphetamine group. Acta Polon. Pharm. 22(2): 103-109.

There may be a Chemical Abstracts citation for each of these somewhere. Anyone near a Chemistry library?

jon · « **Reply #193 on:** April 07, 2011, 04:19:03 AM »

you know i wonder but i'll never be for certain why is CuO2 in the mix?
i know copper compounds (not to be confused with the constabulary) complex ammonia and amines i'm just curious the overall scheme.
and yes i gave to shulgin's cause, he is in ill health after suffering a stroke.

akcom · « **Reply #194 on:** April 07, 2011, 04:59:11 AM »

If I had to guess I'd say Cu(NH3)x is the active species and there is a four membered ring transition state

Code: [Select]

?+   ?-
Cu----NH3
 |     |
Br----CR2
?-     ?+

probably generates Cu(Br2)- I didn't look at the paper, but if they have to use a large xs of NaOH to neutralize that might support the proposed mechanism

edit: I guess this forum doesn't like unicode characters. ?+ = partial positive

jon · « **Reply #195 on:** April 07, 2011, 05:33:40 AM »

that a very informative hypothesis there akcom.
so it would lower the Ea and likely increase yields?
i got to look that up sounds interesting.
if it's a room temp reaction that would minimize side reactions.

atara · « **Reply #196 on:** April 07, 2011, 05:51:33 AM »

Indeed; the transition state would be such that dialkylation (to a secondary amine with two methylenedioxyphenylisopropyl substituents) would be suppressed.

jon · « **Reply #197 on:** April 07, 2011, 06:36:00 AM »

that looks good.
less possible E2 side reactions too?
that's the ball buster in aminating bromosafrole but it only happens with heat which is why iodosafrole gives near quan. yields.
but it's not that simple, solvent effect is crucial there as isopropanol only worked consistently.
but that could cut out an expensive reagent i like it!
i see, the transition state looks like it would exclude other potential angles of attack

xxxxx · « **Reply #198 on:** April 08, 2011, 08:38:11 PM »

Hi everyone, I haven't had a lot of time to finish my experiments over the last few weeks. I still have a quantity of what I feel is pretty impure iodosafrole sitting in the freezer. After the unsuccessful attempts of creating NH3 in IPA and of synthing methylamine from hexamine, I have decided to acquire some nitromethane and make guaranteed pure monomethylamine from it?

Until then, would it be possible to carry out a Delphine reaction on the crude iodosafrole to hopefully get something from it? and good anybody provide me with a referance or writeup? I'll give it ago again anyways during the summer and hopefully make less mistakes! Thanks in advance!

fractal · « **Reply #199 on:** April 08, 2011, 09:45:22 PM »

Delepine only works on primary halides, iodosafrole is a secondary halide.

Author Topic: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole... (Read 2846 times)

Oerlikon

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

Sedit

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

fractal

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

Sedit

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

jon

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

Oerlikon

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

jon

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

Oerlikon

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

Wizard X

Ammonolysis

jon

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

Wizard X

Bromosafrole + 18.2% w/w alcoholic methylamine.

jon

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

Sulfuro

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

jon

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

akcom

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

jon

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

atara

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

jon

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

xxxxx

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...

fractal

Re: Yeee Haaah!! Jon's method DOES TOO work!! Bromosafrole...