So, because actually nobody wrote to this thead, then I will do it.

Here is a report on the DOH synthesis from 2,5-dimethoxy.benzaldehyde:

We started from 5g of 2,5 dimethoxy benzaldehyde.

The used amounts were:
5g dimethoxy-benzaldehyde (0,03 mol)
2,7g nitroethane (0,036 mol)
0,22g sec-butylamine (0,003 mol)
15ml toluene

This was refluxed for 8 hours, yielding a black liquid:


This was washed several times with water to give something like this (the DP2NP at the bottom) :


The crystallined stuff looked really bad, but who cares? After the reduction everything will look nice:


Yield:5,6g (0,025 mol, if it would be pure, than it would be 80% yield what is too good to belive, so we have an Xg of pure stuff and an Yg of black tar:)

The reduction:

5,6g of the previously prepared compound was dissolved in 75ml IPA and 95ml of GAA. 9,5g of previously amalgamated aluminium foil was slowly added to the reaction mix between 50-60 Celsius.
When the reaction ended 350ml 30% NaOH was added to the mix and the DOH freebase was obtained.
The sulfate salt was made from it:

Yield: 3,35g (0,017 mol, overall there was an 56% yield:)

Melting point was okay, it is pure

yep I thought it was a nice thread also, and the pics and explanations were nice.......that said, i think the 'primary' problem is the 2,5 dimethoxy benzaldehyde.--aahh how exactly was this compound precured? Did you make it or? I would be most interested in "how it came to be..?"

 I believe the lack of this substance is the reason you had no response to an otherwise most interesting idea,, and then,made it even better,with an excellent 'concise and relevant'  practical synth and write up

   Now all we need from you is a good bioassay,,

 nonetheless GO SHARD!!! evilmon

A few methods for making 2,5 dimethoxy benzaldehyde from hydroquinone.




Hydroquinone is an easily obtained chemical for almost everyone. To start the synthesis 2,5 dimethoxy benzaldehyde (from now DMBA) from this OTC chemical looks a good idea.
Let’s see the basics:
The hydroquinone is a dihydroxy benzene, it has two –OH groups attracted to the benzene ring, it is a double phenol. It is really reactive, it could be easily oxidized into a black tar what is not good for anything, so we should use not so hard reagents.
The first step in the synthesis of the DMBA is to turn the hydroquinone to 1,4 dimethoxy benzaldehyde. It is an “easy” methylation what could be done in several ways. In lab they usually use dimethyl sulfate (1, 2) or trimethyl phosphate for the methylation of phenols. These reagents are not so cheap and not so friendly, so it is not the best idea to work with them without a “normal” lab.
Another way is to use alkyl halides, here methyl bromide (3) or methyl iodide. These are also not so friendly reagents, but they have a much better yield in methylating phenols.
And there is a third way to methylate hydroquinone, this is the cheapest way also: to use concentrated sulfuric acid or phosphoric acid and methanol. The yields are not so high, but the reagents are really cheap (and does not require carcinogen chemicals), but actually I have no idea where is my reference for this reaction.

The second and the last step to obtain DMBA from hydroquionone is the formylation. This can be done by several ways.
The first and the most toxic way would be to use carbon-monoxide, hydrogen chloride and aluminum chloride. This is the industrial way and this is enough from it. It is not an acceptable synthesis for a home lab.
The second alternative is the Duff reaction(4) what is simple and it requires almost nothing special, just a little hexamine and sulfuric acid. This is a really OTC synthesis and acceptable for almost everyone.
The third formilation reaction is the Reimer–Tiemann reaction what is a really dirty and low yielding aldehyde synthesis.  If anyone is interested in it, look up the 4,755,613 US patent.
The fourth way is a really good yielding and a little bit dangerous formylation reaction, the Gattermann aldehyde synthesis (5). It requires zinc cyanide what is not a really friendly stuff, but not so harmless (it is not soluble in water, like the sodium cyanide). 
And the to step way: at first the halomethylation of the 1,4 dimethoxy benzene  with paraformaldehyde and hydrochloric (6) or hydrobromic acid (7) and then react the halomethylated compounds with hexamine(8 ) or with DMSO and sodium hydrogencarbonate(9) to form the dimethoxy benzaldehyde in high yields.


1 /1,4 dimethoxy benzene from hydroquinone and dimethyl sulfate/:

In a round-bottomed flask equipped with magnetic stirring was added 250 mL of H2O, and 45 mL of 25% NaOH. 15 grams of hydroquinone was then added followed by 26mL of dimethyl sulfate. The flask was stirred at room temperature and after 15 minutes it was obviously no longer basic judging from the light color and flakes of hydroquinone floating around. At this point more 25% NaOH soln was added. In fact, he admits that too much base was added at this point which really hurt the yield in this reaction by slowing it down considerably. Anyhow, after another hour white crystals began to form out of the dark mixture and it took on the familiar smell of p-dimethoxybenzene. Stirring was continued for another 6 hrs, after which he became impatient and proceeded to vacuum filter the crystals on a buchner funnel and wash them with H2O. Yield: 11 grams (58%).

2 /2,5 dimethoxy toluene from toluhydroquinone and dimethyl sulfate/

Into 1 L H2O that was being stirred magnetically, there was added, in sequence, 62 g toluhydroquinone, 160 mL 25% NaOH, and 126 g dimethyl sulfate. After about 2 h, the reaction mixture was no longer basic, and another 40 mL of the 25% NaOH was added. Even with stirring for a few additional days, the reaction mixture remained basic. It was quenched in 2.5 L H2O, extracted with 3x100 mL CH2Cl2 and the pooled extracts stripped of solvent under vacuum. The remaining 56.4 g of amber oil was distilled at about 70 °C at 0.5 mm/Hg to yield 49.0 g of 2,5-dimethoxytoluene as a white liquid.

3 /1,4 dimethoxy benzene from hydroquinone and methyl bromide/:

110g hydroquinone (1mol)
450ml methanol
150g KOH (2.7 mol)

412g NaBr (4mol)
300ml water
250ml methanol (5mol)
230ml H2SO4 (4mol)

In a 1L RBF flask equipped with a dropping funnel and set up for distillation, methanol and sulfuric acid were slowly mixed together with cooling, and dropped onto a boiling (saturated) solution of sodium bromide over the course of two hours. The water/methanol/HBr (very little formed) vapors were condensed into a sealed flask, and the methyl bromide was collected with a plastic tube connected to the vacuum adapter, which led directly into a solution of hydroquinone in methanol. The methyl bromide was first slowly released to displace the oxygen in the flask, and potassium hydroxide (flake) then quickly added with *good* stirring while cooling the flask on ice bath. Methyl bromide was then generated (controlled by rate of MeOH/H2SO4 addition) more rapidly and driven through the solution until the supply was exhausted (2 hours), with vigorous stirring.

The solution first turns brownish (oxidation of hydroquinone) with a yellow tint (phenoxide of 4-methoxyphenol) and eventually a large mass of whitish crystals form (potassium bromide).
The potassium bromide was filtered (the solution is completely neutral at the end), washed with methanol and dried. 250g was recovered (79% recovery).
About half the methanol was then evaporated (~200ml) and the remains were quenched with 1.5L water and cooled to 5*C. The precipitated clear/white crystals were then filtered, washed a few times with warm water, vacuum filtered and dried.

Yield: 114g (83% yield)
The obtained DMB melts at 54-56*C.

4 /dimethoxymethylthiobenzaldehyde from dimethoxymethylthiobenzene by duff reaction/:

To 25 mmol of the dimethoxymethylthiobenzene (MW 184, 4.6 g) in 30 ml GAA there is added 50 mmol HMTA (hexamine, urotropine, hexamethylenetetramine) (MW 140, 7 g). The mixture is placed in a 100°C bath. At that temperature, with good magnetic stirring, there is added dropwise over one hour 100 mmol H2SO4 (MW 98, d 1.84, 95%, 5.5 ml) dissolved in 20 ml GAA. No reaction had yet occured at half the addition beside some precipitation of white salt (HPLC indicate starting conversion to the HMTA adduct and alot of starting product). 5 min after the end of addition the starting product had disapeared and the HMTA addition compound was majoritarly present but also there were aldehyde and some benzylamine. Addition time can be reduced to 5 min probably and then all stirred 30 min I bet, it is very quick. The mixture is stirred with a air condensor through the night at 100°C. After the night HPLC indicated 50% benzaldehyde 50% amine and no more HMTA adduct. It was intense yellow with a white ppt. Ammonium acetate (15 g, MM 77, 200 mmol) was then added to the hot mixture and it was cooked for two hours more. The mixture was less yellow than before. HPLC showed complete disapearance of the amine and only the aldehyde. The all mixture was poured in 200 ml of 1% aqueous HCl, the all was refluxed for ten minutes then cooled to RT and treated cautiously with 50% NaOH solution with stirring until pH 8 (~1 mol). The ppt solid formed became whiter. After cooling to 0°C it was filtered, washed with water (300 ml) and dried to yield the aldehyde. Yield : 4.8 g (MW 212 23 mmol) = 92%

5 /2,5 dimethoxy benzaldehyde from 1,4 dimethoxy benzene with zinc cyanide/

A mixture of 1,4- dimethoxybenzene (150 g.; 1.1 moles), anhydrous zinc cyanide (202 g.; 1.7 moles), and 450 ml. of dry benzene was cooled externally to 6 C. Hydrogen chloride gas was added with stirring until the mixture was saturated. Anhydrous granular aluminum chloride (220 g.; 1.65 moles) was then added, and the mixture was stirred and allowed to warm slowly to about 25 C. The temperature of the mixture was then raised slowly to 45-47 C., and additional hydrogen chloride was passed into the reaction with stirring at such a rate that substantially no escape of hydrogen chloride from the reaction vessel could be detected until the total amount of hydrogen chloride added was 40 g. Two and one-half liters of 3 normal hydrochloric acid was then added and the mixture was refluxed for 30 minutes. After cooling, the benzene layer was separated. The aqueous layer was extracted with four 300-ml. portions of ethyl acetate. The combined benzene layer and ethyl acetate extracts were dried and evaporated. The residue was distilled to give 160 g. (89% yield) of 2,5- dimethoxybenzaldehyde in the form of white solid with a faint yellow tint; m.p. 49 C.

6 /chloromethylation of 1,4 dimethoxybenzene with paraformaldehyde and hydrochloric acid/

37g 1,4-dimethoxybenzene (0.268mol),
50ml dichloromethane,
140ml 31% HCl,
8g paraformaldehyde (.267mol)
In a 500ml flask set on a small water bath, 1,4-dimethoxybenzene was dissolved in 50ml of dichloromethane, 140ml of 31% HCl added, and the solution saturated with HCl. Paraformaldehyde was then added, the solution further saturated for five minutes or so (the total amount of gas generated was from 50ml 31% HCl dripped onto 50ml H2SO4). The reaction flask was stoppered to prevent loss of HCl, and the reaction was stirred for an additional eight hours; at this point the organic layer was separated, transferred to a 1L flask, and largely evaporated under vacuum. Once the bulk of the liquid had evaporated (the remains were still liquid when vacuum was removed), the next reaction was performed immediately.

7 /bromomethylation of 1,4 dimethoxy benzene with paraformaldehyde and hydrobromic acid/

6.9g 1,4-dimethoxybenzene (0.05mol)
1.5g paraformaldehyde (0.05mol)
6.2g sodium bromide (0.06mol)
20ml acetic acid
3ml water
6.8g 93% sulfuric acid in 5ml acetic acid (0.065mol)
In a 50ml flask, (1) was mixed with paraformaldehyde, sodium bromide, acetic acid/water, and a stirbar. Sulfuric/acetic acids were dripped in over the course of 45 minutes, and the solution left stirring for 14 hours overnight. The solution was then dumped into 200ml of cold water, the precipitate filtered, and washed twice more with water
A crude melting point showed that the material melted around 70-80*C (although it was hard to tell because it was still a little bit damp). The literature melting point is 69-70*C. The crude yield of the slightly damp material was 10.4g (so in practice, yield was somewhere around 80-90%).

8 /reaction of 2,5-dimethoxybenzyl bromide with hexamine/

10.4g crude 2,5-dimethoxybenzyl bromide (~0.045mol)
10.4g hexamine (0.09mol)
40ml 50% acetic acid
18ml 31% hydrochloric acid
The crude benzyl bromide was added to 40ml of 50% acetic acid, hexamine added, and the mixture refluxed for 2 hours on an oil bath. This time there was a lot of yellow, fluffy precipitate towards the end of the reaction. With continued heat and stirring, 18ml of hydrochloric acid was then added and the solution refluxed for an additional 5 minutes, at which point the heat was turned off and the solution allowed to cool while still on the bath (this solid took a while to dissolve, and even at the end, not entirely). The solution was then dumped into 300ml of cold water, and stuck in the freezer to further the cool. The precipitated solid was filtered and added to 30ml of isopropanol. To this was added 25ml of concentrated sodium bisulfite solution, and the solution stirred for 1.5 hours. The precipitated solids were filtered, washed with water, followed by isopropanol, and dissolved in 150ml of 10% NaOH solution, with stirring. After the adduct dissolved, the solution was placed into the freezer for 30 minutes, and subsequently dumped into 500ml of water. The precipitated aldehyde was filtered off and set aside to dry.
Yield: 3.8g 2,5-dimethoxybenzaldehyde (46% from 1,4-dimethoxybenzene)

9 /reaction of 2,5-dimethoxybenzyl bromide with DMSO and sodium hydrogencarbonate/

~8g 2,5-dimethoxybenzyl bromide (~0.036mol)
100ml DMSO
20g NaHCO3
In a 250ml flask, the above reactants were mixed and vigorously stirred while simultaneously being heated to ~115*C on an oilbath. The progress of the reaction was quite visible with a notable color change occuring (white/clear --> yellow) and the evolution of gas (dimethyl sulfide). After 30 minutes, the solution was removed from the bath, allowed to cool down for a brief period of time (15 minutes), and subsequently dumped into 1L of cold water. The resulting precipitate was filtered, washed twice with water, and allowed to dry. (4.6g yield - near quantitative from starting material.

I never ever tried any of these reactions, because I can buy 2,5 dimethoxy benzaldehyde from a chemical supplier, but I hope that these informations will help a bit for everyone who want to make any kind of DOX.
The recipes are mainly from the Sciencemadness board, some of them are from patents and there are some what I can't remember where did I get(:

Hope that they are useful!

-Evilblaze

Evilblaze, I would question the applicability of the Duff to this specific substrate. The 4-thio homologue is far more reactive. If you have another ref. where this reaction is successfully attempted on DMB, HQ, or p-MeO phenol though, I'd love to see it.

wow really nice thread

i did a translation on WD's from the hyperlab called DOI success,  if anyone is interested i can post it here also

great work

hope it does help vesp here yuz go

    
hyperlab DOI Success !

_mescalito

Old Junior Chemist
Oct 14 2003, 00:34
[Post = 4460]


(Rated as: excellent)
As you know, schizophrenics fall start sharpening. That's my aunt's some strange visions and dreams began ... about them and it will be in this topic. Dream about the shaman.
In round-bottom flask shaman placed 60 ml of 96% ethanol, 700 mg of 2,5-dimetoksiamfetamina sulfate and stirring until completely dissolved. After the shaman manipulation with weights and iodine there it was chock-full of 1.46 g iodine, and also stir until completely dissolved. Then 1.8 g of finely powdered silver sulfate. The mixture was stirred at room temperature for 14 h, and after the first two hours it was clear that iodine is spent, and spent well.
Then the mixture was filtered, the filter residue washed with a little ethanol and ethanol are combined, and driven off in a water bath in the atmosphere. It remains to dark brown (due to iodine) butter. There has been poured about 30 ml of distilled water, and poured alkali-to-face grams 3-4. The dark color disappeared, surfaced pinkish-yellow butter, poorly soluble in petroleyke (Incidentally, I think all of 2,5-dimethoxy-... poorly soluble in petroleyke, and in benzene-excellent). Butter was extracted with benzene three times in 10 ml, and vykisleniem hodgepodge of benzene that was allocated to 630 mg (61% of theory) of pale pink powders melting at 200-201 degrees.
And the shaman said his aunt, that bioassay is the next dream, it is unclear when - is a long process and responsible ...

2Munlayt: a procedure for iodination yuhimike take away the phrase "there is no doubt that this procedure will be as good (maybe better) to work in Equatorial Africa" So far, the maximum yield of 2c-i was 33%: (. All the reagents from the same cans ...

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_Assholium

Old Junior Chemist
Oct 14 2003, 02:41
[Post = 4461]


(Rated as: good idea!)
Congratulations (IMG: images / icons_yellow / smile.gif)

've found this funny ssylochku:
Horiuchi, C. Akira; Haga, Akinori; Satoh, Yasuo J., Bull.Chem.Soc.Jpn. 1986, 59:8:2459-2462
A Convenient Procedure for Iodination of Electron-rich Aromatic Compounds using Iodine-Copper (II) Acetate

magazine could not get it, but the idea of this simple procedure can be obtained from Synthesis 1981,4:312-314, where they iodiruyut ketones in the alpha position:

2-Iodo-5a-cholestan-3-one (Cool:
A mixture of 5-cholestan-3-one (1, 800 mg, 2.07 mmol), iodine (578 mg, 2.28 mmol) and copper (II) acetate (454 mg, 2.28 mmol) in acetic acid (50 ml) is stirred at 60 ° C for 6 h. The precipitated copper (l) iodide is removed by filtration, the filtrate is poured into water (50 ml), and extracted with ether (3 x 100 ml). The ethereal solution is washed with a sodium hydrogen carbonate solution (6 x 30 ml) and with water (3 x 30 ml), then dried with sodium sulfate and evaporated. Crystallization of the re sidue from ethanol gives 2a-iodo-5a-cholestan-3-one (Cool; yield: 743 mg (70%); mp 132-133 ° C (Lit.1, m.p. 125-127 ° C).

It turns out that all it takes for the young chemist schastya - a vinegar, iodine, yes copper acetate. And iodized a complete victory over the mind (IMG: images / icons_yellow / laugh.gif)

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_azole

Old Junior Chemist
Oct 15 2003, 18:20
[Post = 4462]


(Rated as: good read)
I put in brifkeys Giperlaba article that I found Assholium, and earlier by the same authors (reference [6]) one. Djvu file. Translate the time no, sorry.

CAHoriuchi, A. Haga, JYSatoh, Novel Regioselective Iodination of Estradiol 17?-Acetate, Bull. Chem. Soc. Jpn., 59, 2459-2462 (1986).
CAHoriuchi, JYSatoh, A Convenient Procedure for Iodination of Electron-rich Aromatic Compounds using Iodine - Copper (II) Acetate, ibid., 57, 2691-2692 (1984).

http://briefcase.yahoo.com/
Login: hyperlab_storage
Password: yukhimik
File: iodination_bcsj.djvu

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_MoonLight

Old Junior Chemist
Oct 16 2003, 08:43
[Post = 4463]


This short article so the article is!
Thanks to young chemists antiquity!

Articles excellent - especially the second. However, yields could be better, especially in the case of anisole (69%) - but in the case of our substrates, they promise to be at least 80%, judging by their greater activation.

Now - would not it be mnogouvazh. Asolo or More somebody so good to find a few more options on the same subject (taken from an article number 2) - basically the same thing, but it is not used copper acetate, but much more affordable halide:

Baird, Jr; Surrindge, JOC, 35, 3436 (1970)
Sugita, Idei, Ishibashi, Takegami, Chem. Lett., 1982, 1481



In general, how difficult it is - get anhydrous copper acetate? Data on the pace. dehydration can not find ... Comes to mind dissolving copper oxide in excess ledyanki and banish azeotrope with water, and then the very acid - to obtain a saturated p-ra, which is cooled to give crystals.

But we are, of course, do not - enough to make a solution of acetate in ledyanke and use it as is. The only question - whether the dehydrated Cu (CH3COO) 2 in such circumstances, and whether it is necessary at all if it comes to that.

One thread of Euro-thread can say?


Moonlight

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_Chemister

Old Junior Chemist
Oct 16 2003, 09:23
[Post = 4464]


and where the actual article
I think someone erased (IMG: images / icons_yellow / crazy.gif). Or I have glitches.

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_azole

Old Junior Chemist
Oct 17 2003, 01:05
[Post = 4465]


(Rated as: good read)
http://briefcase.yahoo.com/
Login: hyperlab_storage
Password: yukhimik
Files:
        Iodination_ChemLett.djvu

T. Sugita, M. Idei, Y. Ishibashi, Y. Takegami, Aromatic Iodination with Aluminum and Copper (II) Chlorides and Iodine, Chem. Lett., 1982, 1481-1484.

        Iodination_JOC.djvu

WCBaird, JHSurridge, Halogenation with Copper (II) Halides. The Synthesis of Aryl Iodides, J. Org. Chem., 35 (10), 3436-3442 (1970).

   After the Sign In link must go to Your Briefcase address: http://briefcase.yahoo.com/hyperlab_storage, then see the files placed in the root directory (Chemister, they are all there).

   In general, how difficult it is - get anhydrous copper acetate? <...> Only question - whether the dehydrated Cu (CH3COO) 2 in such circumstances, and whether it is necessary at all if it comes to that.

   IMHO, if the reaction is carried out without the addition of Lewis acids, the small amount of water can not hurt. Preparation of Cu (OAc) 2.H2O see Karyakin, Angels, "Pure Chemicals, s.239 (there have Chemister'a). There the sulphate and soda prepare basic carbonate of copper, dissolved in GAA, evaporated and crystallized. They write that above 100 ° it loses its crystallization water; in anhydrous mp 115 ° (catalog ***).

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_mescalito

Old Junior Chemist
Oct 27 2003, 21:00
[Post = 4466]


bioassay
... DPI happened on two biological objects.

The first object swallowed 5 mg orally and noted the great euphoric and visual beauty compared with dobom, and a little more active. At the time of action - as well as ext.
The second object is swallowed 4 mg, and said not a good fizuhu - pain in the liver. And he says that he prefers ext:)

Here there are different opinions ... can be completed:)

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Erny

Earnest Bee
Oct 29 2006, 22:05
[Post = 505810]


Meanwhile, studies of small doses of the title substance revealed their value and interesting:). 1 mg of DPI was one of the best Faix imitations of MDMA-like substances. It's not like the DSS, or Dom or Don at the same intensity effects. Vizualki there are few, mainly in the significant increase in brightness of colors. Physiology is also virtually no. There is something of a small amount of mushrooms in this state, and the outputs (very nice for biotestera) of TMA-2. DPI was passed this morning at about 9. Acted naturally, all day, and only the night effects are substantially diminished. At 12 am biotester decided that it was time to sleep, perhaps he would have fallen asleep, and just like that, but just in case helped himself one milligramme clonazepam:).

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arkhangel

in a nutshell
Aug 11 2007, 14:44
[Post = 512438]


C Good morning!

Nekozlyu well, very much wanted to try DOI.
And accordingly there were question for ...
Sorry for such silly questions, but both know how to ...

1. Need a silver sulphate. Accordingly, we find its mix of silver and sulfuric acid.
Prompt please correct me (for nekozlyuya) rassschital required number of initial reagents.
The reaction: 2Ag + 2H2SO4 = Ag2SO4 + SO2 + 2H20
Q: What is the mass of Ag and H2SO4 is needed to obtain 2gr. silver sulfate (Ag2SO4)

Decision:

M (Ag) = 108 m
M (H2SO4) = 98
Assume the molar mass Ag2SO4 for x
Ratio: 2 / 312 = x/98
x = 2 * 98/312 =
x = 0,628 g.mol but because in equation 2 moles H2SO4 then the mass of sulfuric acid needed to produce 2 oz. Ag2SO4 will 1.25gr.

Similarly
Assume the molar mass Ag2SO4 for x
Ratio: 2 / 312 = x/108
x = 2 * 108/312 = 0,69 g.mol but because in the equation Ag 2 moles, the mass of silver required to produce 2 oz. sulfate will 1.38gr.


2. Well, in general questions. Why is DOI is taken sulfate 2,5-DMA. It is very difficult zakristolizovat. Why not take the acetate or stupid reason?

3. Iodine crystalline. Does smysel buy reagent in a store or stupidly get it from the regular pharmacy.

4. Can ethanol replace the IRS?

5. Add please someone that knows about. Any perceived infa sincere and sensual.

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Erny

Earnest Bee
Aug 11 2007, 15:02
[Post = 512439]


Initially, the method grandfathers Sasha, from which it was copied, used silver sulphate. Therefore, the 2,5-DMA was taken in the form of sulphate, rather than hydrochloride, in order not to precipitate silver. Bare ground in this reaction strongly oxidized. The solubility of all this goodness in isopropanol is much lower than in ethanol, for this reason and for reasons of availability, used ethanol. Although better - methanol. The method of sulfate requires a very large amount of solvent and was relevant to the moment've done this with nitrate. UTFSE on yuzerneymu topikstartera.

You'd at least start cleaning agents learned to make a human being, DPI he wanted ...

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tetraedr

Praktiker
Aug 12 2007, 21:14
[Post = 512465]

Rated as: Good!
Sobstenno, DPI technique for high yield was tested Nekozlyuem based on the methodology for Ernie 2C-I (sm Erny - Iodized 2C-H with iodine with silver nitrate in methanol), I only made it available on the DPI and dootrabotal bit.


EXPERIMENTAL

1 - (2,5-dimethoxyphenyl)-2-aminopropan (Foil)
Amalgamiruyut 8 grams of foil with 0.5 g of mercurous nitrate, water is drained, add a solution of 4 g ref. propene, 25 g ? and 25 g of ethanol. There is an exothermic reaction, the foil is dissolved. The reaction takes place for 1-2 hours, then add a lot of ice, a solution of KOH. The product is extracted several times DCM, organic layers dried potash and carefully evaporated. Yield - 3.09 g (88% (MW 195.2)) - almost colorless oil, on standing solidifies.

1 - (2,5-dimethoxyphenyl)-2-aminopropan iodgidrat
1.60 g (MW 195.2) 1 - (2,5-dimethoxyphenyl)-2-aminopropana (obtained by the foil) as a base dissolved in 20 ml of methanol, cooled in the freezer and acidified with 10% nitric acid to slightly acid reaction (color of the solution must remain almost colorless). Then, the mass evaporated, co-evaporated with a mixture of toluene-IPA, washed 2 times MTB, dissolved in 5-7 ml of acetone and planted MTB. Blow is about to crystallize. Triturated with MTB, filtered, washed with MTB and dried. Yield - 1.91 g (90%, MW 258.2) nitrate in the form of white crystals.

DOI
The glass is ground thoroughly with 1.90 g (7.36 mmol, 1 eq) nitrate, 2,5-DMA and 1.25 g (1 equiv, MW 169.9) of silver nitrate and placed in a 100 ml flask, add 20 ml of methanol, the flask wrapped in aluminum foil, stirred 10 minutes (almost everything has to be dissolved), then dropwise within 10-15 minutes there is added a solution 1.87 g (1 equiv, MW 253.Cool powdered in advance (otherwise dissolve!) iodine in 50 ml of methanol (dissolved in parts!) . The mass is stirred an additional 1 hour, light-yellow silver iodide is filtered through a fine (S4) filter, the filtrate evaporated, stir in 100 ml of warm water (still poorly soluble), made alkaline KOH solution, a brown oily base is extracted with DCM, washed with water, dried carbonate potassium, evaporated, diluted with methanol, acidified to a weakly acid reaction HCl, evaporated, co-uparivavyut with a mixture of toluene-IPA, the remainder was ground with MTB, filtered, washed with MTB, and then with acetone. Yield - 2.02 g (77%, MW 357.6 (CH)) - crystals almost pure white. Mp. - About 200OS (Literary mp. 201OS).

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miamiechin

Junior Chemist
Sep 3 2007, 1:06
[Post = 512883]

Rated as: Excellent!
4C-DOI (1 - (4-iodo-2 ,5-dimethoxyphenyl) butan-2-amine, "COC1 = CC (CC (CC) N) = C (OC) C = C1I")

To the freebase of 4C-DMA (1 - (2,5-dimethoxyphenyl) butan-2-amine, "COC1 = CC (CC (N) CC) = C (C = C1) OC") 2.8 g, MW 209, 13 mmol dissolved in 50 mL of MeOH there was added:
14 mmol concentrated H2SO4, 750 uL (no precipitate was formed)
15 mmol iodine, MW 254, 3.8 g (it dissolved)
and finally 15 mmol Ag2SO4 MW 312, 4.7 g
The reaction mixture was left to stir at room temperature for five hours. After 2 hours the reaction is mostly done as indicated by the discolouration as well as the yellow precipitate that was formed.
Chromatography at the five hour point indicated total convertion of 4C-DMA into a less polar product.
The remaining iodine was quenched by addition of thiosulfate solution. The silver salts were then filtered by succion and the filter cake washed with some methanol.
The methanolic filtrate was concentrated in vacuo, the residue was taken up in acidic water and washed with dichloromethane to remove some yellow color and insolubles.
The aqueous phase was then basified to ph> 10 with caustic soda, the layer became purple.
After a celite filtration to get rid of the emultion, the aqueous layer was extracted three times with dichloromethane.
The combined dichloromethane washes were washed three times with distilled water and then concentrated and the residue azeotropically dried with acetonitrile.
The yield of 4C-DOI freebase was 3.7 g, MW 335, 11 mmole (82%)
This was dissolved in 25 ml of MeOH and methanolic HCl was then added to bring the pH to <3.
The MeOH was evaporated, the residue that remained was dissolved in more MeOH and evaporated again to get rid of excess HCl (2x).
The residue was then recristallised in MeOH/CH3CN.
After cooling in freezer, filtration, washes with CH3CN then Et2O and air drying there was obtained 3.4 g of 4C-DOI.HCl, MW 372, 9 mmol, 71% yield from 4C-DMA.

Analysis of 4C-DOI.HCl:
mp (acetonitrile) 220-221 ° C (lit (1).: 214-215 ° C)
ESI-MS: m / z = 377 (100%) (CH3CN adduct), 336 (65%), 277 (20%) (daughter of 336)
NMR 1-H (D2O): 0.91 (t, 3 H, CH3), 1.57 (m, 2 H, CH2), 2.74 (dd, 1 H, CH), 2.89 (dd, 1 H, CH), 3.36 ( m, 1 H, CH), 3.70 (s, 3 H, OCH3), 3.73 (s, 3 H, OCH3), 6.78, 7.35

References:
(1) Journal of Medicinal Chemistry (1977), 20 (12), 1543-6
(2) Journal of Medicinal Chemistry (1980), 23 (2), 154-62.

At 20 mg the compound is less euphoric than 4C-DOB, this is +1. It should be interesting to try it at 60-80 mg.

--------------------------------------------

4C-DOI (1 - (4-iodo-2 ,5-dimethoxyphenyl) butan-2-amine, "COC1 = CC (CC (CC) N) = C (OC) C = C1I")

By freebase Mr. direct 4C-DMA (1 - (2,5-dimethoxyphenyl) butan-2-amine, "COC1 = CC (CC (N) CC) = C (C = C1) OC") to the memory 2.8, MVTA 209 , 13 mmol dissolved in 50, mL MEOH there was added:
14 mmol concentrated H2SO4, 750 uL (no precipitate formed)
15 mmol iodine, MW 254, 3.8 g (it broke)
and finally 15 mmol Ag2SO4 MW 312, 4.7 g
A mixture of revocation was left to stir at room temperature for five hours. After the 2:00 tip for the most part is made, as indicated discolouration
as well as yellow cake, which was formed.
Chromatography in the five hour show nominal total convertion direct 4C-DMA to the memory of a less polar product.
The remaining iodine gasilo addition thiosulfate solutions. Silver salts and then filtered and the filter cake succion and washed with some methanol.
Methanolic filtrate was concentrated in vacuo, the remainder was raised in the acidic water and washed with dichloromethane, to move some yellow color and insolubles.
Aqueous phase was then basified to ph> 10 with caustic soda, the layer was purple.
After celite filtration rid emultion, the aqueous layer was extracted three times with dichloromethane.
Combinable dichloromethane wash was washed three times with distilled water and then concentrated and the residue azeotropically cos with acetonitrile.
Profit 4C-DOI freebase was 3.7 g, MW 335, 11 mmole (82%)
It was dissolved in 25 ml of MEOH and methanolic, HCl was then added to bring pH to <3.
MEOH was evaporated, the remainder, which remained dissolved in more MEOH and evaporated again freed from the additional HCl (2x).
The balance was then in recristallised MeOH/CH3CN.
After cooling in the freezer, filtration, washed with CH3CN and then Et2O and air drying there was obtained 3.4 g 4C-DOI.HCl, MW 372, 9
mmol, 71% yield from direct 4C-DMA to memory.

Analysis of 4C-DOI.HCl:
mp (acetonitrile) 220-221 ° C (lit (1).: 214-215 ° C)
ESI-MS: m / z = 377 (100%) (adduct CH3CN), 336 (65%), 277 (20%) (daughter of 336)
NMR 1-H (D2O): 0.91 (t, 3 H, CH3), 1.57 (m, 2 H, CH2), 2.74 (dd, 1 H, CH), 2.89 (dd, 1 H, CH), 3.36 (m, 1 H, CH), 3.
70 (s, 3 H, OCH3), 3.73 (s, 3 H, OCH3), 6.78, 7.35

Links:
(1) Journal of medicinal chemistry (1977), 20 (12), 1543-6
(2) Journal of medicinal chemistry (1980), 23 (2), 154-62.

At 20 mg euphoric blend of less than 4C-DOB, is one. It should be interesting to try it in 60-80 mg.

---------------------------------------


Peace, Miamiechin: lol:

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namgramk

The world of dream
Sep 6 2007, 20:44
[Post = 512988]


Nice to see some real chemistry here. : Heart:

And still more interesting is to learn something about human bioactivity of the 4C-series.

Somewhere in autumn 2003 someone;) reported 4C-DOB and 4C-DON to be recreationally active in 60-80 mg range, IIRC. The report soon disappeared for the obvious reason of not attracting attention of RC companies, but it was not forgotten.

A year later, someone who is not me:) synthesized 4C-DOPR.HCl, the most potent 4C-compound in improving avoidance response acquisition in the rat (4C-DOPR, namgramk, post 491664). There was not much biotesting, but from what had been done, one could see that the compound was not very promising. Threshold activity at 50 mg and +1 at 75 mg. Separate enantiomers (optical purity 90% or more) were biotested up to 44 mg (S-(+)-isomer) and 45 mg (R-(-)-isomer) and did not show any psychoactivity, which was a surprise.

Unfortunately, the substances were flushed down the sink during a paranoid outburst: (.

Apparently, the potency of 4C-compounds in humans does not correlate with the results of rat biotests. It may happen that the experiments in cats (DOM-like activity) are more relevant. If so, 4C-DOC and 4C-DOEt may be the most promising compounds of the series, and the lower potency of 4C-DOI is thus explained. I'm also very curious about the activity of 4C-MMDA-2, but these suggestions are more pertinent to the "unexplored substances" thread: Unknown substance, _MoonLight, post 4932.

I have a question concerning the writeup:
quote
The methanolic filtrate was concentrated in vacuo, the residue was taken up in acidic water and washed with dichloromethane to remove some yellow color and insolubles.

The hydrochloride of 4C-DOI is probably not very soluble in water, and still less soluble in dilute HCl. The sulfate must not be very soluble either. So, what acid was used in this synthesis, and what volume of water per gram of 4C-DOI was required to keep all the salt in a solution?

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Demonic

Old Junior Chemist
Sep 8 2007, 18:40
[Post = 513010]


quote
Apparently, the potency of 4C-compounds in humans does not correlate with the results of rat biotests. It may happen that the experiments in cats (DOM-like activity) are more relevant. If so, 4C-DOC and 4C-DOEt may be the most promising compounds of the series, and the lower potency of 4C-DOI is thus explained.

It is my subjective experience that the potency of the 4C's follows this direction: 4C-DON> 4C-DOB> 4C-DOC. Others also claim the same. The difference in potency between 4C-DON and 4C-DOB is very little and the two might be actually equipotent, but 4C-DOC is notably less potent. However, the potency is not as relevant as is the difference in subjective effects between these three (they were not of my own production and I only tried them a couple of times so I'm not competent for describing these differences) as well as the difference the 4C series has in comparison to the 2C and 3C compounds (the 4C's are more than just psychedelics). 4C-DOC is very smooth and I found 60mg to be a nice launch pad for combining it with 2C-B a couple of hours after it sets in. It combines without problems and it is nice in that when 2C-B is over one return not to the baseline but to the "4C line" (since it lasts> 10h, much more than the couple of hours of 2C-B).

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miamiechin

Junior Chemist
Sep 9 2007, 19:16
[Post = 513027]

Rated as: Thank you!
quote
namgramk:
I have a question concerning the writeup:
quote
The methanolic filtrate was concentrated in vacuo, the residue was taken up in acidic water and washed with dichloromethane to remove some yellow color and insolubles.

The hydrochloride of 4C-DOI is probably not very soluble in water, and still less soluble in dilute HCl. The sulfate must not be very soluble either. So, what acid was used in this synthesis, and what volume of water per gram of 4C-DOI was required to keep all the salt in a solution?


This was done using an excess of dilute sulfuric acid to make the hydrogenosulfate salt. The volume of the water phase was of more or less 100 ml, the washes were done with say 20 ml DCM. There was no solubility problem with those volumes. The few insolubles were some silver salt and oxide as well as some sulfur from the thiosulfate.

BTW during the celite filtration following basification, the freebase was of course already dissolved in dichloromethane (that is not clear in what i posted).

quote
Demonic:
it is my subjective experience that the potency of the 4C's follows this direction: 4C-DON> 4C-DOB> 4C-DOC. Others also claim the same. The difference in potency between 4C-DON and 4C-DOB is very little and the two might be actually equipotent, but 4C-DOC is notably less potent.


I agree with you on that point, except that my opinion is that 4C-DON is at least two times as potent as 4C-DOB, and its duration is very long. At 80 mg of the nitro compound (way too much!!) It takes at least 36h to come back to baseline. Altough 4C-DOB's plateau is not that long (6-8h) the compound never comes down until you go to sleep, and taking it several times a month makes long lasting changes in the daily mood, with insights taking places for days and persistant increase in color perception. Combos of the 4C-substances are interesting too, and quite active and long lasting especially 4C-DON/4C-DOB. 4C-DOC is clearly less active.

I never tried the 4C-DOPR nor 4C-DOET, it is interesting to known the potency do not correlate with animal testing ..

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MoonLight

Junior Chemist
Sep 9 2007, 20:56
[Post = 513030]


Oh!

It's just soooo nice seeing you here: friend:: up:: heart:

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miamiechin

Junior Chemist
Sep 10 2007, 1:31
[Post = 513040]


The synthesis of 4C-DMA.HCl is described here.

quote
Oh!

It's just soooo nice seeing you here: friend:: up:: heart:


I am glad to be here too: friend: it is nice to see you again! : Bee:

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arkhangel

in a nutshell
Oct 16 2007, 20:31
[Post = 513813]


quote (said: tetraedr)
1 - (2,5-dimethoxyphenyl)-2-aminopropan iodgidrat
1.60 g (MW 195.2) 1 - (2,5-dimethoxyphenyl)-2-aminopropana (obtained by the foil) as a base dissolved in 20 ml of methanol, cooled in the freezer and acidified with 10% nitric acid to slightly acid reaction (color of the solution must remain almost colorless). Then, the mass evaporated, co-evaporated with a mixture of toluene-IPA, washed 2 times MTB, dissolved in 5-7 ml of acetone and planted MTB. Blow is about to crystallize. Triturated with MTB, filtered, washed with MTB and dried. Yield - 1.91 g (90%, MW 258.2) nitrate in the form of white crystals.

DOI
The glass is ground thoroughly with 1.90 g (7.36 mmol, 1 eq) nitrate, 2,5-DMA and 1.25 g (1 equiv, MW 169.9) of silver nitrate and placed in a 100 ml flask, add 20 ml of methanol, the flask wrapped in aluminum foil, stirred 10 minutes (almost everything has to be dissolved), then dropwise within 10-15 minutes there is added a solution 1.87 g (1 equiv, MW 253.Cool powdered in advance (otherwise dissolve!) iodine in 50 ml of methanol (dissolved in parts!) . The mass is stirred an additional 1 hour, light-yellow silver iodide is filtered through a fine (S4) filter, the filtrate evaporated, stir in 100 ml of warm water (still poorly soluble), made alkaline KOH solution, a brown oily base is extracted with DCM, washed with water, dried carbonate potassium, evaporated, diluted with methanol, acidified to a weakly acid reaction HCl, evaporated, co-uparivavyut with a mixture of toluene-IPA, the remainder was ground with MTB, filtered, washed with MTB, and then with acetone. Yield - 2.02 g (77%, MW 357.6 (CH)) - crystals almost pure white. Mp. - About 200OS (Literary mp. 201OS).

Damn time of war - methanol horseradish get it. We'll have to somehow make the thread itself ...
Is it possible to replace the MTB benzene?

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tetraedr

Praktiker
Oct 20 2007, 09:34
[Post = 513890]


I think that the MTB can be replaced with acetone (I just wrote as he did), and methanol - abslyutnym ethanol - just take pridetstsa more.

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den1

Someone
Nov 22 2007, 13:21
[Post = 514708]


Sorry for the stupid question. What is MTB?

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namgramk

The world of dream
Nov 22 2007, 13:26
[Post = 514709]


quote (said: den1)
Sorry for the stupid question. What is MTB?

Solvent. Methyl tert-butyl ether.

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qwerty777

Someone
Aug 20, 2010, 20:03
[Post = 539121]


quote (said: tetraedr)
1 - (2,5-dimethoxyphenyl)-2-aminopropan iodgidrat
..... Then, the mass evaporated, co-evaporated with a mixture of toluene-IPA, washed 2 times MTB, dissolved in 5-7 ml of acetone and planted MTB. Blow is about to crystallize.

Ie nitrate 2,5-DMA is soluble in acetone?
Indeed SVIM evaporated salt solution, after acidification, souparil a couple of times with the IRS, put in the fridge to freeze, and then tried to wash the salt with acetone (obezv. CaCl2), but it had dissolved.
Why? Or SVIMa so much dirt in it?
And what it wash may be toluene?

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Erny

Earnest Bee
Aug 20 2010, 20:11
[Post = 539122]


I rubbed these nitrates with acetone without consequences, but for me, as I remember, most were white directly. Most likely, yes - the dirtier stuff, the better it dissolves into anything. Probably better to do clean-up before receiving nitrate.

I have no idea what would DSS and DPI mean, never heard of them.

Our last project in the few last days was to make DON, the nitro compound. The success: 0.
We used purificated DMA/DOH and the recipe what Shulgin wrote down in the PiHKAL. The only difference was, that we used smaller amounts (3g of 2,5-dimethoxy-amphetamine freebase as the starting material) and we stored in the sulfate form, so we made the freebase form first with NaOH and it was separated from the water layer.
The results: the freebase didn't dissolved in the glacial acetic acid, it just dissolved while we added the nitric acid. The Shulgin recipe was based on a molar ratio: 0,043 moles of the DOH and 0,3412 moles of nitric acid. So there was a high excess from the acid.
The reaction mixture didn't warmed up so much, almost extra heat was detected. After the puring on the NaOH and extraction with toluene nothing was isolated.
At the second run the the freebase was dissolved in dichloromethane and the nitric acid was added to this solution. There were two layers, one layer with the DCM and one with the water. On the top of the DCM layer a little brownish goo appeared and no other reaction occoured. So: DAMN IT.


If I am lucky, than I will get soon a synthesis of 4-nitro-2,5-dimethoxy-acetophenone from 2,5-dimethoxy-acetophenone. At that sythesis 75% nitric acid was used insted of the 50%. But the solvent was also glacial acetic acid.

If you have any idea or comment, than please wite it!

Thanks!

I like this thread alot.
Now how about making hydroquinone from paracetamol?
Pretty much 100% otc 2C-x series! And maybe also DOx.

so it would be a pretty much 100% OTC 2C-x series! And maybe also DOx. Plus 500grams of paracetamol is pretty cheap, and if it only involves another cheap reagent, such as H2SO4, it could be very cheap, no shipping or waiting.

I believe that has been discussed here already -- feel free to revive any thread or create your own on how to do it if it hasn't. I would like to know the best way - my method sucks.

I'm all for using the product of this for the 2-C's as they have manageable durations. The DOX's last forever!