Vibrating_Lights (Hive Bee)
03-10-02 05:15
No 279922
      Possible DOB from DMMDA  Bookmark   

Basicly i want to know if there is a way to remove the 3,4 Methelenedioxy from the dmmda molocule. Leaving 2,5DMA just a short bromination step from DOB. Possibly this must be done before amination if nescesary.  Convert the aipole into 2,5 dimethoxyallybenzene.  Isomerize.  then either nitrosaturate to make the nitropropene,  do a wacker on the ally benzene, or try a peracid epoxidation.  All followed by the regular reduction routes to the amine.?????
VL_
 
 
 
 
    PrimoPyro
(Hive Prodigy)
03-10-02 05:20
No 279923
      Re: Possible DOB from DMMDA  Bookmark   

You cannot tear a methylenedioxy ring off the molecule without destroying the entire benzene ring. I am sorry.

                                                   PrimoPyro

Vivent Longtemps La Ruche!
 
 
 
 
    Vibrating_Lights
(Hive Bee)
03-10-02 12:58
No 280065
      Re: Possible DOB from DMMDA  Bookmark   

Would it be possible then to remove the O from the 4methoxy on asarone yeilding 4methyl-2,5dimethoxy suitable for DOM production?  or possibly selectivly cleave the whole 4 methoxy to leave 2,5dimethoxy?  what are the conditions for selective cleaving.  Perhaps a haphazard attempt could be made to destroy the methoxy with acid then seperate via fractional distillation.  Mabye VL_needs to sleep.crazy
 
 
 
 
    Antoncho
(Official Hive Translator)
03-10-02 13:43
No 280078
      Re: Possible DOB from DMMDA  Bookmark   

No, that's impossible. Sorrysmile

Antoncho

P.S. Isn't it true that DOB sucks by all means? From the data i gathered from Russian sources, it does.
 
 
 
 
    Vibrating_Lights
(Hive Bee)
03-10-02 13:50
No 280081
      Re: Possible DOB from DMMDA  Bookmark   

Dob is awesom.  DOM was the desired amine though.
Vl_
 
 
 
 
    Rhodium
(Chief Bee)
03-10-02 16:54
No 280124
      Re: Possible DOB from DMMDA  Bookmark   

Yes, DOB is really great, with the exception of the very long "tail" of stimulation. 
 
 
 
 
    Vibrating_Lights
(Hive Bee)
03-10-02 21:38
No 280204
      Re: Possible DOB from DMMDA  Bookmark   

With the exception of the very long "tail" of stimulation.  in swims experience the tail of stimulation was plesent and filled with visuals.  I remember getting home from a club while we had some dob and the spotts on the leperd skin bed cover each flowed independant of each other in each it own unique pattern.  it was amazing.  I could charchterize it as a cornocoupia of visuals followed by some minor depersonalization. No real body load to speak of.  the club was so visualistic that i thought i wasn't tripping......  then i walked outside..Oh my god.. can you go from thinking that youre sober one minute then walking outside and having the desert horizon look like an ocean flowing with waves and all  with the sun coming over the horizon at 4oclock in the morning.  yes the sun does come up at four there. 
someone needs to flood the planet with that great substance.
VL_wink
 
 
 
 
    Antoncho
(Official Hive Translator)
03-11-02 07:27
No 280486
      Re: Possible DOB from DMMDA  Bookmark   

Thank you very much for the positive input, guys! I appreciate it.

Antoncho
 
 
 
 
    Osmium
(Stoni's sexual toy)
03-12-02 13:26
No 281226
      Re: Possible DOB from DMMDA  Bookmark   

> Would it be possible then to remove the O from the
> 4methoxy on asarone yeilding 4methyl-2,5dimethoxy
> suitable for DOM production?  or possibly selectivly
> cleave the whole 4 methoxy to leave 2,5dimethoxy?

There is an obscure old ref from 1937 by some Indian researchers who claim that selenium dioxide converts asarone to 2,5-dimethoxypropenylbenzene. I have no idea how that is supposed to happen and I haven't seen any other refs detailing such a reaction, so I'm not sure if this really works or not.

I'm not fat just horizontally disproportionate.
 
 
 
 
    Vibrating_Lights
(Hive Bee)
03-13-02 06:38
No 281787
      Re: Possible DOB from DMMDA  Bookmark   

Os if you can find the time to dig up that ref or point in the right direction VL_ has a friend who is dying to try it.
VL_
 
 
 
 
    Niels_Bohr
(Stranger)
03-18-02 04:19
No 284139
      Re: Possible DOB from DMMDA
(Rated as: excellent)
 Bookmark   

Ah - hello fellow bees!  After a long hiatus, I'm back smile.

This post caught my eye, and I found the reference:
JCS (1937) p.1338  -Asarone, Rao & Subramaniam

excerpt:
(a) Action of Selenium Dioxide on -Asarone - A mixture of -asarone (70 g) alcohol (100 ml) and selenium dioxide (10 g) was heated on the water-bath for hour.  The filtered solution was poured into water, the oil dissolved in ether, and the dried etheral extract evaporated; the residue partly crystallized, and distillation gave asarone (60 g).

(b) A mixture of -asarone (20g), alcohol (50 ml) and selenium dioxide (5 g) was boiled for 5 hours.  The product isloated by ether in the usual manner gave an oil, which on distillation under 8 mm gave two fractions: (i) bp 140-145, d30/30 1.052, n20/d 1.5451; (ii) bp 145-150.  From the former, a picrate was prepared, crystallizing from alcohol in orange-red feathery leaflets, mp 87.  Decomposition of the picrate with alkali gave 2,5-dimethoxypropenylbenzene, bp 128-129/4 mm., d30/30 1.041, n30/d 1.5548.  The nitrosite, mp 118, was a pale yellow powder.
 
 
 
 
    Rhodium
(Chief Bee)
03-18-02 05:37
No 284163
      Re: Possible DOB from DMMDA  Bookmark   

What is the intermediate which is able to form a picrate?
 
 
 
 
    PrimoPyro
(Hive Prodigy)
03-18-02 05:41
No 284164
      Re: Possible DOB from DMMDA  Bookmark   

I was wondering the same thing Rhodium.

And what is beta asarone? (Im sure Im the only one who doesnt know this one though.)

                                                   PrimoPyro

Vivent Longtemps La Ruche!
 
 
 
 
    terbium
(Old P2P Cook)
03-18-02 06:34
No 284174
      Re: Possible DOB from DMMDA  Bookmark   

What is the intermediate which is able to form a picrate?
Eh? They say that it was the picrate of 2,5-dimethoxypropenylbenzene.
 
 
 
 
    terbium
(Old P2P Cook)
03-18-02 06:37
No 284175
      Re: Possible DOB from DMMDA  Bookmark   

And what is beta asarone?
The cis isomer. You really need to get yourself a Merck Index.
 
 
 
 
    Niels_Bohr
(Stranger)
03-18-02 06:51
No 284180
      Re: Possible DOB from DMMDA  Bookmark   

It is C11H14O2,C6H3O7N3  This must be the picrate salt of 2,5-dimethoxypropenylbenzene.

The article also states:

Asarone     mp 62-63  bp 167-168/12 mm    nD20 = 1.5683
-Asarone  mp  ----     bp 162-163/12 mm    nD20 = 1.5552
 
 
 
 
    PrimoPyro
(Hive Prodigy)
03-18-02 06:52
No 284184
      Re: Possible DOB from DMMDA  Bookmark   

Yes you're right, but how come Im the only one here who get's chastized for asking questions like this? Everyone else just gets an answer, I get this, "You should do this, or do that" crap all the time from everyone. laugh

If I didn't have a sense of humor I'd call double standards. tongue

                                                    PrimoPyro

Vivent Longtemps La Ruche!
 
 
 
 
    Rhodium
(Chief Bee)
03-18-02 18:36
No 284354
      Re: Possible DOB from DMMDA  Bookmark   

PP: We know you can do better, and we know that you will have actual use of a Merck in the future. We are trying to help you become a professional by forcing you to aquire the literature you need - if you just get the small answers the others get, you will not grow as fast as you can wink

Terbium: How could a propenylbenzene form a picrate salt?
 
 
 
 
    Osmium
(Stoni's sexual toy)
03-18-02 18:49
No 284358
      Re: Possible DOB from DMMDA  Bookmark   

> How could a propenylbenzene form a picrate salt?

It's not really a salt (as in M+X-), but an addition compound/complex.
Picric acid can form solid derivatives with all kinds of substances (especially aromatics). In the older literature sometimes trinitrobenzene derivatives are mentioned, this is the same principle.

I'm not fat just horizontally disproportionate.
 
 
 
 
    Vibrating_Lights
(Hive Addict)
03-19-02 02:13
No 284524
      Re: Possible DOB from DMMDA  Bookmark   

IN excerpt (A)  the product is givin as Asarone.  Is that a typo.  And in excerpt B  there is two distillation fractions. do these correspond to the cis & trans isomers of the formed 2,5 Dimethoxypropenalbenzene.
Also is the picrite to be prepared by refluxing (powder)picric acid and rxn product in MeOh similar to forming an oxime but without base. What is the purpose of forming a picrite when it is just decomposed by the base.
Now that that is done with how might one add a Me to the 4 position.wink
VL_
 
 
 
 
    terbium
(Old P2P Cook)
03-19-02 06:25
No 284662
      Re: Possible DOB from DMMDA  Bookmark   

Picric acid forms crytalline derivatives with amines, many phenolic ethers and some aromatic hydrocarbons. Taking the melting point of picric acid derivatives was one common means of qualitative organic analysis back in the days before instrumental analysis.

Vogel (3rd Ed.) lists the melting points of several dozen phenolic ether picrates including those of safrole, iso-safrole, anethole and veratrole.

As Osmium mentioned, trinitrobenzene and styphnic acid were also used for the same purpose.
 
 
 
 
    Rhodium
(Chief Bee)
03-19-02 07:02
No 284683
      Re: Possible DOB from DMMDA  Bookmark   

Styphnic - that's trinitrocresol, right?
 
 
 
 
    terbium
(Old P2P Cook)
03-19-02 07:07
No 284684
      Re: Possible DOB from DMMDA  Bookmark   

  Monograph number: 9026
  Title: Styphnic Acid. 
  CAS Registry number: [82-71-3]
  CA name(s): 2,4,6-Trinitro-1,3-benzenediol; 2,4,6-trinitroresorcinol;
  Additional name(s): 2,4-dihydroxy-1,3,5-trinitrobenzene. 
  Molecular formula: C6H3N3O8
  Molecular weight: 245.11
  Composition: C 29.40%, H 1.23%, N 17.14%, O 52.22%. 
  Literature references: May be prepd from natural sources, such as Pernambuco wood extract or quebracho extract by the action of nitric acid:  Einbeck, Jablonski, Ber. 54, 1086 (1921).  Prepd industrially by first sulfonating, then nitrating resorcinol:  Merz, Zetter, Ber. 12, 681, 2037 (1879); Datta, Varma, J. Am. Chem. Soc. 41, 2043 (1919).  Prepd by nitrating 2,4-dinitroresorcinol:  Kametani, Ogasawara, Chem. Pharm. Bull. 15, 893 (1967).
  Properties: Hexagonal yellow crystals from dil alc.  Astringent, but not bitter taste.  Solvated crystals from acetic acid.  Sublimes in high vacuum.  Becomes almost colorless upon vacuum sublimation, but turns deep yellow on contact with air.  When dry, mp 175.5 deg; also reported as mp 179-180 deg.  One gram dissolves in 156 ml water at 14 deg, in 88 ml water at 62 deg.  Freely sol in alcohol, ether.  Acid to litmus.  Dibasic acid.  Deflagrates on rapid heating.
  Melting point: 175.5; 179-180

  USE:  Has been used in the manuf of explosives. 
 
 
 
 
    Vibrating_Lights
(Hive Addict)
03-19-02 07:41
No 284694
      Re: Possible DOB from DMMDA  Bookmark   

So the forming of the picrite,in the ref, was just to provide further varification of the product and was not really nescesary to the synthesis.????
VL_
 
 
 
 
    Rhodium
(Chief Bee)
03-19-02 10:45
No 284742
      Re: Possible DOB from DMMDA  Bookmark   

Is this SeO2 demethoxylation a known reaction of some sort? Or is it an oddity?
 
 
 
 
    Niels_Bohr
(Stranger)
03-20-02 00:52
No 285046
      Re: Possible DOB from DMMDA  Bookmark   

VL_  Yes, picrate was for ID/analytical purposes.  If you check the archives, I posted an article here a while back on making picrate phenol ethers - "Compound ID for the Hack"

Rhodium: Maybe the reaction doesn't work...the mere fact that it was published in the journal, does not mean it is set in stone. 
 
 
 
 
    Vibrating_Lights
(Hive Addict)
03-20-02 04:40
No 285115
      DOB From asarone  Bookmark   

I guess we will have to find out.  Osmium mentioned it, you found it.  Now Vl needs to have it tested. can methyl iodide be used to remethylate the 4 position.
VL
 
 
 
 
    Rhodium
(Chief Bee)
03-20-02 19:55
No 285443
      Another SeO2/propenylbenzene rxn  Bookmark   

I forgot where I read it last night, but I found an article where a propenylbenzene was oxidized to the corresponding cinnamaldehyde during alcoholic reflux with SeO2 for a few hours, I wonder if that is a general side-reaction.
 
 
 
 
    Vibrating_Lights
(Hive Addict)
03-22-02 07:55
No 286272
      Dob from Aasarone  Bookmark   

That would be an acceptable side reaction.Mabyee with a longer reaction Asarone could be reduced all the way to 2,5 Dimethoxybenzaldahyde Then make the nitrostyrene and reduce it to the amine with Zinc/HCL.wink A 2-CB synth for chromic
VL_smile
 
 
 
 
    Vibrating_Lights
(Hive Addict)
03-22-02 08:16
No 286287
      How to work this rxn up  Bookmark   

Will the aldehyde side product be extracted from the mix with DCM. Will it be in solution in the alcohol. An the SnO2 It must be filtered after an initial H2O flooding correct. Swip was going to flood the mix with H2O, filter the SnO2 off then extract with DCM and distill. After the propenalbenzene comes over then could the 2,5 DMB side product be recrystalized from the distilling flask for later use. If it doesn't get extracted with the DCM then could the rxn mix be concentrated to recover the aldehyde.
VL_