pickle11 (Stranger)
11-28-02 13:34
No 384303
      nitrating 3-iodo-PMA  Bookmark   

would there be any danger in nitrating 3-iodo-PMA? I know NI3 is very explosive.   I am not enough of a chemist to know if anything dangerous would be formed.  My guess is 3-iodo,4-methoxy,5-nitroamphetamine would be the product.  Any chance it would be any good?
 
 
 
 
    Rhodium
(Chief Bee)
11-28-02 13:40
No 384305
      NI 3 won't form, so that is irrelevant.  Bookmark   

NI3 won't form, so that is irrelevant. There would be no other dangers than the usual ones, like the corrosive nature of the nitric acid. I don't think the yields will be especially good though, the starting material not being especially activated. I wouldn't expect the product to be very interesting either.
 
 
 
 
    pickle11
(Stranger)
11-28-02 13:47
No 384308
      better chance?  Bookmark   

if you made an amphetamine from eugenol, and put it into a birch, I would think you would get 3-methoxyamphetamine.  Would nitration or iodination of that be easier or yield a more promising product?
 
 
 
 
    Rhodium
(Chief Bee)
11-28-02 14:27
No 384314
      What are you trying to achieve?  Bookmark   

What are you trying to achieve?
 
 
 
 
    pickle11
(Stranger)
11-28-02 15:09
No 384317
      something useful to do with anethole and eugenol.  Bookmark   

something useful to do with anethole and eugenol.  So cheap and easy to get.
 
 
 
 
    GC_MS
(Hive Bee)
11-28-02 15:37
No 384319
      TFSE  Bookmark   

TFSE contains information about synthesizing halo-PM(M)A derivatives. Even bioassayed...

Ave Hive, synthetisandi te salutant!
 
 
 
 
    Rhodium
(Chief Bee)
11-28-02 16:31
No 384323
      Eugenol to something useful  Bookmark   

What about Post 381882 (GC_MS: "Eugenol -> elemicin and myristicin", Novel Discourse) if you are interested in TMA/Mescaline or MMDA-2?

Can't you make use of anything in ../rhodium/chemistry /eugenol.mdma.html either?

If you alkylate Eugenol with ethyl- or allyl-bromide, you get precursors for compounds said to be Mood Enhancers at ~300mg. UTFSE for details. 
 
 
 
 
    pickle11
(Stranger)
11-30-02 09:05
No 384844
      3C-AL from eugenol?  Bookmark   

The Problem for me is getting those chemicals.  Your site has stuff on vanillin that looks easy enough.  I dont kow the physics of whether it would work to substitue isoeugenol.  It would be best if 3-methoxy-4-hydroxyamphetamine could be used as the starting point (none of the ethylated benzene would be wasted in oxone oxidation).  Here is what I was wondering:

In this article, from rhodiums page, vanillin is iodinated:
../rhodium/chemistry /iodovanillin.html
-----------------------------------------------------------
5-Iodovanillin (JCS 3740-3741 (1958))
12.6g Iodine was added in 4 portions during 30 min to a rapidly stirred suspension of 7.5g vanillin in 200mL H2O containing 5g NaHCO3 and 10g KI. Stirring was continued for 3h and the mixture left overnight. The filtered product was washed with dilute Na2S2O3 and H2O and dried at 45C (11.8g, mp 175C). Crystallised from EtOH(aq), it had mp 180C.
------------------------------------------------------------
vanillin mol wt. 152.14
isoeugenol mol wt. 164.20
eugenol amphetamine mol wt. 181.22
so i would guess:
5-iodo-isoeugenol (or eugenol amphetamine)
12.6g Iodine was added in 4 portions during 30 min to a rapidly stirred suspension of 8.09g isoeugenol (or 13.4g eugenol amphetamine) in 200mL H2O containing 5g NaHCO3 and 10g KI. Stirring was continued for 3h and the mixture left overnight.

The filtered product was washed with dilute Na2S2O3 and H2O and dried at 45C (Something else would probably be necessary)
yielding 5-iodo-isoeugenol (mol wt. 291.1) (or 3-methoxy-4,5-dihydroxyamphetamine (mol wt. 308.12))
 
then another article says
../rhodium/chemistry /345-tmb.html
-----------------------------------------------------------
3,5-Dimethoxy-4-Hydroxybenzaldehyde (Syringaldehyde)
In a two-necked round-bottomed flask equipped with a Claisen, and a thermomether into the solution, is dissolved 4.9g Na in 100mL dry methanol. After distilling off 30ml methanol, a solution of 17,9g bromovanilin and 3g Cu(I)Br in 50mL DMF is added in one portion. The distillation is continued until the reaction mixture reaches 100C (takes app. 1-1.5 h. total methanol distilled off is 80mL). The reaction mixture is poured into 200mL 3M HCL/ice, extracted with 2*75mL EtOAc, the EtOAc is washed with 2*50mL water, dried with MgSO4 and evaporated. Mp.108C (rec. from ethanol) TLC Rf 0,35 EtOAc:P 1:1
------------------------------------------------------------
 If you substitute iodoisoeugenol or iodo eugenol amphetamine for bromovanillin:
3,5dimethoxy-4-hydroxypropenylbenzene (or 3,5DM-4OHA)
In a two-necked round-bottomed flask equipped with a Claisen, and a thermomether into the solution, is dissolved 4.9g Na in 100mL dry methanol. After distilling off 30ml methanol, a solution of 22.4g 5-iodo-isoeugenol (or 23.7g 3-methoxy-4hydroxy-5-iodo amphetamine) and 3g Cu(I)Br in 50mL DMF is added in one portion. The distillation is continued until the reaction mixture reaches 100C (takes app. 1-1.5 h. total methanol distilled off is 80mL). The reaction mixture is poured into 200mL 3M HCL/ice, extracted with 2*75mL EtOAc, the EtOAc is washed with 2*50mL water, dried with MgSO4 and evaporated.

this could then be reacted with allyl bromide to yield 3C-AL
http://www.erowid.org/library/books_online/pihkal/pihkal002.shtml

1. I know in pihkal it said that 34dma was difficult to brominate would eugenol amphetamine be hard to iodinate.

2.  In step 2 could an equimolar amount of lithium (1.47g) be used instead of Na(4.9g)

3.  Should Cu(I)I be used instead of Cu(I)Br

4.  If nothing else, could 3-methoxy-4-ethoxy be formed by ethoxylating the amphetamine, or do you have to do that as a phenylpropanoid.
 
 
 
 
    Rhodium
(Chief Bee)
11-30-02 10:33
No 384860
      reply  Bookmark   

First I must say that you are a great role-model for all the other newbees here, in that you are asking your questions in a very structured form, making it very easy to reply clearly, and you are also linking to all the reactions you are asking about, so that the ones who answer doesn't have to use the search engine themselves, just to be able to review what is being discussed. Also, the questions you are asking are valid, and not obvious things found everywhere in the archives or so. 

1. I know in pihkal it said that 34dma was difficult to brominate would eugenol amphetamine be hard to iodinate.

No, "eugenol-amphetamine" has a free OH group on the ring, which makes it exceptionally easy to iodinate. Also, you can be completely sure that the iodine will end up next to the OH in the 5-position. See Post 285579 (foxy2: "3,5-diiodo-4-methoxyphenethylamine", Chemistry Discourse) - in that article they iodinate tyramine (4-hydroxyphenethylamine) with KI3 which is a relatively weak iodination reagent.

2. In step 2 could an equimolar amount of lithium (1.47g) be used instead of Na(4.9g)

Yes. The purpose of the alkali metal is only to generate a methanolic solution of methoxide ions, it doesn't matter which cation is used. There were even some discussions here 1-2 years ago about using magnesium methoxide, formed by refluxing magnesium metal in methanol with a catalytic amount of iodine.

3.  Should Cu(I)I be used instead of Cu(I)Br

I believe they are interchangeable in this case. If one of them would be more effective, it would be CuI, but I don't think that effect is noticeable in practice, and definitely doesn't warrant the higher cost of CuI.

4. If nothing else, could 3-methoxy-4-ethoxy be formed by ethoxylating the amphetamine, or do you have to do that as a phenylpropanoid.

To be able to alkylate a hydroxy-amphetamine, you would have to protect the nitrogen against alkylation too, and that is cumbersome to do if you have an alternative way of doing it - so yes, definitely do the alkylation reaction [i]first[/b] on the phenylpropanoid.
 
 
 
 
    pickle11
(Stranger)
11-30-02 13:22
No 384877
      if it works  Bookmark   

Thanks for the encouragement Rhodium.  I am mostly interested in really OTC stuff that anybody can do. 
If this works it could also be a route to
3C-E
http://www.erowid.org/library/books_online/pihkal/pihkal.025.shtml

and 3C-BZ
http://www.erowid.org/library/books_online/pihkal/pihkal.021.shtml
which is made with benzyl cloride instead of allyl bromide.  It is described as more powerful than TMA and one user found 150mg to be identical in effect to 100micrograms of LSD
 
 
 
 
    catastrophe
(Hive Bee)
12-10-02 00:14
No 387921
      Re: 2. In step 2 could an equimolar amount of ...  Bookmark   


2. In step 2 could an equimolar amount of lithium (1.47g) be used instead of Na(4.9g)

Yes. The purpose of the alkali metal is only to generate a methanolic solution of methoxide ions, it doesn't matter which cation is used. There were even some discussions here 1-2 years ago about using magnesium methoxide, formed by refluxing magnesium metal in methanol with a catalytic amount of iodine.




Not too sure if lithium methoxide will work. SWIM had also conceived this before alkoxides became OTC thanks to Antoncho. Maybe Osmium?, stated that the reaction requires a high concentration of methoxide ion, ~ 5M, but the solubility of lithium and magnesium methoxides did not allow for such concentrations to be achieved. Albeit lithium methoxide is much more soluble than magnesium methoxide it might just work, but why bother? UTSE and find Antoncho's post in the novel discourse.

Rhodium, about the allyloxy and methallyloxy compounds, what method of reduction would you recommend, as these are unsaturated groups? Would hydrogenation kill it? How about zinc/HCl? Also, have you had a chance to taste them?

 
 
 
 
    moo
(Hive Bee)
12-10-02 00:54
No 387930
      If I recall correctly there were problems with ...  Bookmark   

If I recall correctly there were problems with that reaction using sodium methoxide generated with the MeOH/NaOH/CaO method because it was contaminated with hydroxide ions, UTFSE lead me to the thread starting with post Post 274828 (Natrix: "Vanillin", Chemistry Discourse), which seems to give an explanation for the failure.

I also found something that may have been left unnoticed, Post 236749 (foxy2: "This is even better.", Chemistry Discourse) with a procedure that might help eliminating the sodium hydroxide. It also leaves me confused because one should be doing this if using ethyl acetate in the reaction, which would imply that the reaction conditions should be really anhydrous.
 
 
 
 
    Rhodium
(Chief Bee)
12-10-02 01:01
No 387932
      I have not tasted the allyloxy/methallyloxy ...  Bookmark   

I have not tasted the allyloxy/methallyloxy compounds personally, unfortunately.

What reduction step are you referring to, when inquiring about the stability of the double bond? When asking if it would stand up to catalytic hydrogenation, that depends on a lot of factors, such as choice of catalyst, hydrogen pressure etc - and I'm no good at hydrogenation theory anyway.
 
 
 
 
    catastrophe
(Hive Bee)
12-11-02 20:21
No 388477
      Thanks for your responses  Bookmark   

Moo, Antoncho's post also mentioned a way of synthesizing the alkoxide using potassium carbonate in an excess of methanol or ethanol. Forget the CaO method, it's dirty anyways. Also, at the very end of the thread he mentions that a russian bee successfully performed the rxn. Swim will confirm, but maybe instead try sodium carbonate.

Yes, Rhodium, your dislike for hydrogenation and electrochemistry has become quite pronouced to swim! Could you possibly offer a theoretical discussion on what reactions might indeed reduce the double bond on the allyl group? Would Zn/HCl be a good method?
 
 
 
 
    Rhodium
(Chief Bee)
12-11-02 22:46
No 388528
      If you WANT to reduce the double bond, you should ...  Bookmark   

If you WANT to reduce the double bond, you should probably look into CoCl2/NaBH4 for example. Are you looking for a way of turning the allyloxy into a propoxy?
 
 
 
 
    catastrophe
(Hive Bee)
12-12-02 00:14
No 388563
      No, swim does not want to reduce the allyl group ...  Bookmark   

No, swim does not want to reduce the allyl group at all. Swim just wants a safe way of reducing the nitrostyrene without reducing the double bond on the allyl group. (sorry, the swim's previous post was a little confusing) A procedure utilizing hydrogenation would be most desirable, but it was believed that hydrogenation would also saturate the double bond in the allyl group. So then a reduction using Zn/HCl would be the next most desirable method. Again, sorry for the ambiguity. Any suggestion that you may have would really be appreciated Rhodium. Thanks.
 
 
 
 
    Osmium
(Stoni's sexual toy)
12-15-02 17:33
No 389691
      Allylethers are rearranged to the ...  Bookmark   

Allylethers are rearranged to the 'propenylethers' by Pd/C, this results in their cleavage.

I'm not fat just horizontally disproportionate.