04-06-03 02:59
No 424287
After 3 failed trials with dmso route i decided to distill my own hbr in micro scale.
70 gramms NaBr
30 Ml draincleaner 75%
150 ml dH2O
I ended with the 2 times distilled fraction 124-128 celsius of Hbr 50 ml. end discarded the rest.
I purified my parsley leaf oil with the yudexk method (thank Hypo , many thanks Organikum)and I performed also a Freezing extraction too.From 10 ml oil I ended with 5 ml very strong purfumed supposed myristicine.
I cooled down the Hbr to minus 5 , I suspended my oil in ethylalcol and mixed with vigorous handstirring the two substances in a flask in a wather-acetone bad.
Immediatley the mixtur was green with undefined layer and after 10 minutes was divided in two layer a dark green
(the oil) and a clear .
After 1 Hour costantley shacking in the water-acetone-bad with a temperatur of 1 grad celsius the solution is in two layer a green yellow (the oil) and a yellow.
After two Hours hte layer are a dark yellow green(the oil) and a very clear.
After 12 Hours the oil layer is brown-green.
Am I this Time in the right way?
What colour have bromo-myristicine?
Thanks
(Hive Addict)
04-06-03 05:04
No 424299
how did you perform freezing extraction?
according to beilstein, the melting point of myristicin is -30°C: Post 322503 (hypo: "bps and mps of various propenyl and allylbenzenes", Methods Discourse)
maybe you have an apiole rich oil?
can you do melting point tests? once we know what's in your essential oil, i can try
to look up data for your bromo compound...
(Stranger)
04-06-03 05:22
No 424302
how did you perform freezing extraction?
I got a professional deep freezer (bis minus 25).My reference says myristicine mp is "unter -20"
HUNNIUS Pharmazeutisches Wörterbuch 7. Aufl., S. 953 (Walter de Gruyter, Berlin New York 1993)
according to beilstein, the melting point of myristicin is -30°C: hypo: "bps and mps of various propenyl and allylbenzenes" (Methods Discourse)
maybe you have an apiole rich oil?
I don´t now if apiole is present in my oil.I got two type:
Parsley leaf oil Rich of myristicine
Parsley seed oil Rich of apiole
The flavour is very different.
"Als natürlicher Bestandteil des etherischen Öls der Gartenpetersilie, Petroselinum crispum (MILL.) NYM. ex A.W. HILL. Es gibt bei dieser Pflanze verschiedene "chemische Rassen", und zwar eine Myristicin-Rasse mit bis zu 77% Myristicingehalt (Apiolanteil: 0-3%), weiterhin eine Apiol-Rasse mit ca. 58 bis 80% Apiol (Myristicinanteil 9-30%) sowie eine Allyltetramethoxybenzol-Rasse mit 50 bis 60% ATMOB, die nur Spuren von Petersilienapiol enthält. Die Daten beziehen sich auf das aus den reifen Früchten wasserdampfdestillierte Öl, vgl. Tab.1. Apiol und Myristicin sind für die spasmolytische (krampflösende), mild diuretische und stark uteruserregende Wirkung von Petersilienfrüchten verantwortlich. Der Substanz wird eine allergene Wirkung zugeschrieben."
I´m sorry but I can´t perform an exact mp test because I got no thermomether bis - 25 but I´m sure that my pars leaf oil is rich of myristicine and that my seed oil is rich of apiole because I know the dealer.
(Hive Addict)
04-06-03 06:08
No 424307
sounds good.
if i don't forget, i'll try to get boiling and melting points of the Br-derivate of myristicin tomorrow.
there's a huge old thread about safrole bromination with HBr. have you read it?
(do you know that aqueous HBr is supposed to work?)
(Stranger)
04-06-03 06:14
No 424308
And if it will function I will change my name from cavos to
dr.stranamore in honor to dr.starngelove.
thanks hypo
molte grazie
(Hive Addict)
04-06-03 06:41
No 424309
safrole and HBr gives about 500 hits
https://www.the-hive.ws/forum/dosearchx.
you really should read some of those, they have interesting pointers and hints.
there were some scary things about polymerisation in alcohol. but i didn't look
closer - see for yourself...
(Stranger)
04-06-03 13:15
No 424374
At least 500 thread.
but I can´t find useful notice about bromomyristicine.
I don´t now in usa but here in europe is very difficult to obtain good sassafras oil.what have I to do to become acces on beilstein crossfire?
(Hive Addict)
04-06-03 13:29
No 424378
> but I can´t find useful notice about bromomyristicine.
but the things said about bromo-safrole will be true for bromo-myristicin too,
because they are very similar! (just a methoxy more)
the thing is that if i read that right, then bromination in alcohol does not work
well! (a bee in the know - correct me please!)
> what have I to do to become acces on beilstein crossfire?
try a university library (you'll find the location etc. on the internet) -
if they don't have online access, you'll have to resort to the paper
version. (which personally i've never had a look at)
(Stranger)
04-06-03 13:47
No 424381
Well,
I think I used the wrong word.
When I say
"suspend my oil in ethylalcol" I did´nt mind I used the alchol as medium.Only that I washed the flask with the oil
with a littlebit alchol maybe 2 ml.I hope that will not fuck my bromination.
(Stranger)
04-06-03 13:49
No 424382
Now the oil color is green-brown,
have I also to wait for a beatiful red-purple or wine colored oil layer as for safrole?
(Chief Bee)
04-06-03 15:20
No 424402
The precise colors need not be the same for you as it is in the case of bromosafrole.
(Stranger)
04-07-03 00:38
No 424488
I suspectded this Chief.
Can you tell me where can I find information or how can I be sure the bromination is complete?
I asked the TFSE. Imponent result. I readed all I find, from
dr.Strangelove to HBR bubble bubble trough Halosafrole.txt etc, but about Myristicine I found only the famous Chem_guy report:
Here's that helpful shit:
From "Analysis of
1-(3-methoxy-4,5-methylenedioxyphenyl)-2
Synthesized from Nutmeg Oil and 3-methoxy-4,5-Methylenedioxybenzaldhyde"
The Journal of Chromatgraphic Science, Vol. 34, January 1996.
The Nutmeg oil is a methanol extract.
(Quotation)
"BROMINATION REACTIONS
A suspension of nutmeg oil in 48% HBr was stirred vigorously at room
tempature for 7 days. The reaction was then quenched with the addition
of crushed ice and extracted with ether. The ether extracts were
combined, washed with water, and evaporated to dryness under reduced
presure , and the resultant product oil was analyzed directly by GC-MS.
AMINATION REACTIONS
The crude bromination product was disolved in methanol containing
methylamine and stirred for several days. The reaction mixture was
evaporated to dryness, and the resultant oil was disolved in 10% HCl.
The aqueous acid solution was washed with ether and then made basic
(pH 12) by the addition of NaOH pellets. The aqueous base solution was
extracted with ether, then the combined ether extracts were evaporated
to dryness under reduced pressure. The resulting oil was analyzed
directly. "
I know that is an old argument and that this method lead to low yeld, but I find it super for due his semplicity for first time chemiker.At least now I Know how to make good stinky HBr.
If I can from 5 ml empyrically purified oil become 2 ml MDA I´ll be the happiest guy in KAKANIEN and I´ll be ready for the next difficult steps as ritter,leukart etc.Help please.
Ubi major minor cessat
(Hive Addict)
04-07-03 01:20
No 424494
> how can I be sure the bromination is complete?
weigh increase. can you compute the theoretical weigh increase?
> I´ll be ready for the next difficult steps as ritter,leukart
try the buffered peracid methods. especially chromic's peracetic,
which is 100% OTC.
(i hadn't time to go to the library yet
)
(Stranger)
04-07-03 02:34
No 424504
I´m sorry, can you explain me what is that?
start klar for Buffered peracetic, with exept of DCM (any good european source?) but I think Ether work too. The only great problem is the reduction.I read and read the amalgam preparation I got already mercuri and 75% h2so4 for the AL/HG preparation but no conical flask. And I got no Sodium bohr.....
Also I´m looking for a suitable reduction method for newbee.
(Hive Addict)
04-07-03 02:48
No 424506
ok...
(but please check the math, it's early and i'm not really awake yet)
1 mol of myristicin weighs 192.2g
1 mol of bromo-myristicin weighs 273.1g
so out of 5g myristicin you should get 5/192.2*273.1 = 7.1g bromo-myristicin.
(if you want to know why, please refer to any standard chemistry text)
when bubbling HBr, you could simply bubble until the weight increased by 2.1g.
with your method, you will have to do the workup and if you don't have 2g weigh
increase, you'll know that you will have to do longer next time.
(of course this will only work, if you had pure myristicin to start with)
(Stranger)
04-07-03 03:10
No 424512
I did´nt wheigt the oil, I used only ml scale. But if I understand right there is an 40% wheigt increase and we can say a volume incrase too by a bromination.
I used 5 ml "purified" myristicine the brominatede product should be above 5 ml right? The reference says 70% will brominate also if I get a 20-30 % volume increase and I have also 6-6,5 ml can I say the shit is a bromcompound.
Right?
Now after 36 hours the color is brown with a littlebit green reflex.
(Hive Addict)
04-07-03 07:21
No 424532
"bromo-myristicin" melting point: 49.5-50°C
source: Chem.Pharm.Bull;42;3;1994
no boiling point given.
if you can get that journal, i would recommend to do so, maybe they
have some purification information. (or maybe not...)
49.5-50°C doesn't mean that you will be able to crystallise
all of it or even parts, but it is worth a try. if you manage to
get some pure crystalls, at least you can verify the identity
of your product by doing a melting point test.
> Right?
wrong. halo-compounds tend to be heavier (i.e. more dense). you won't get the
full volume increase.
(Stranger)
04-07-03 07:59
No 424535
Aslo I could extract the oil layer with the separatory funnel keeping the rest in the flask.
Then I could wash with 5% naoh and put the compound in cold water 10 Celsius and if solidify it´s good if not one time more in the flask with the hbr.Cold this be a workup?
(Distinctive Doe)
04-07-03 20:14
No 424658
But if I understand right there is an 40% wheigt increase and we can say a volume incrase too by a bromination.
A weight increase doesn't necessarily mean a volume increase.
(Stranger)
04-08-03 00:48
No 424709
I have extracted the compound from the hbr mixture.
It´s colour is brown as the wall of the pink floyd, more viscous as the original one and solidify in cold water.The original washed oil did´nt became solid at the same temperature
I puted the compound in a mixure of 200 ml ethanol, 4 gram KI and 3 gramms hexamine.I refluxed for 30 minute and the mixture became turbinos. After 12 hour the mixture is yellow , very clear and at the bottom I can see more cristal.
I will waiting for 6 hours or I will reflux 3 hours to see what happen and then I will proced as in the Pugsley workup.
(Stranger)
04-08-03 05:31
No 424738
-i decided to try the reflux.
I refluxed it and then i added the hcl.Ammonium cloride formed and discarded.I cristallised yellow needls, i trayed approx 30 mg, it´s smell like salt with a littlebit bitter aroma and the flavour is like gummy.
I decid to wash the product with 10% naoh in dH2O.I save the organic layer and dry it.It´s come back the same oil colored like the pink floyd wall 1 ml. .fuck delepine.
Next try will be dillapiole in hbr and reflux or bomb with methilamine and parallel dillapiole+koh and reduction with something.
ciao
cavos
(Hive Addict)
04-09-03 05:01
No 425063
you really should start to clean your intermediate products. we
have no idea why this failed: we don't even know whether you
really had myristicin (maybe the impurities crystallised on freezing!),
to start with!
if you really got an amine (you did an A/B, right) and used the
impurities in the oil, then god nows what you've got.
> or bomb with methilamine
that will give the N-methyl derivate, which is afaik more or less inactive.
(Stranger)
04-09-03 11:45
No 425154
I got foundamental 2 problem:
the first one
no magnetic stirrer
the second one
no fraction dist. column.
This year quarter I buyed a elettric plate and finally puted my old butan-propan camping plate in pension.
The next quarter I will buy a frac.dist.col.
My next step is following parallel game:
distillation of nabr to become hbr,hbr gasing hbr with phosph.acid,finkelstein swap (or alternat.gas ala judexk with nai red phosp) and
methylamine bomb.
isomerisation, peracid oxidation,and reduction with al/hg.
-you and the other old beeangels could help me in the following problem:
where can I find o.t.c. in the good old pacifist socialdemocratic europe DCM and PTC (De,At)?
Nec recida recedi.
(Hive Addict)
04-10-03 04:29
No 425367
> no magnetic stirrer
that sucks. you will have to work with overhead stirring.
but used magnetic stirrers can be had pretty cheap.
> no fraction dist. column.
before you buy a fractionating column: be sure to buy a vacuum pump.
that's much more important.
a column can be had for $10-$20. you don't need a fancy vigreux thing,
go with a simple hempel column. any glassblower can make one for cheap.
> isomerisation, peracid oxidation,and reduction with al/hg.
attention, that will give the n-methyl derivate! better do the oxime
thing and then reduction with al/hg.
(Stranger)
04-10-03 05:03
No 425372
Right, thanks.
Today I have become my delivery of NaI and NaBr.
I got some dmso analitical grade (100 Ml).
I don´t know what to do with this shit and I thinked I could try iodination throug HI in situ.How many NaI should I use for 100 Ml DMSO and 5 or 10 ml Dillseed oil?
(Hive Bee)
04-11-03 16:42
No 425844
Use phosphoric acid instead sulfuric acid to make HI, sulfuric acid will oxidize HI to I2.
Also, your dillseed oil will contain at most 40% dillapiole if it's the Indian variety (anethum sowa) so you really need to distill it. I doubt that using the essential oil will work.
http://www.ealasaid.com/fan/lorrelibrary
(Hive Bee)
04-13-03 11:47
No 426378
This is not easy to get to work in my experience. I attempted it a couple of times, but gave up in favour of making the nitrostyrene and then reducing.
Without some proper lab equpt. like scales, distillation apparatus, you will probably end up wasting countless hours and never knowing where you went wrong.
Good luck!