So I hit the books this weekend just trying to learn some more O. Chem. Was wondering if I could run a reaction schema by some of the greater wisdom here . If anyone knows a better way without Pd/C, LiAlH,(the literature routes) or the mess I have concocted, maybe they could share? I know ''weed is so abundant'', etc. This doesn't hault my interest...

The main step I don't know if it's viable or not is the decarboxylation. I read a paper saying reflux in DMSO failed, and those nitro groups look pretty scary! Though I did read a paper saying fermented Maize(corn?) made the reaction which is interesting but a little insane for a hypothetical thought experiment, no?{edit: ref attached}

The grignard has a -H2O meaning without water, not saying H2O hehehe.

Also that bromination should hit primarily Meta correct, because of the two nitro electron withdrawing groups?

The SnCl2 might not work but it does work on similar substrates.

Yes I've seen them, frankly they look very hard and each step uses either a watched or hard to acquire chemical. Except one publication I have found but it starts so bare bones it's futile and still uses a watched chemical or two.

You are absolutely right I got a little too excited towards the end there with the grignard and all hahaha. Good call on the wurtz-fittig.

The problem with nitrating after decarboxylation is the carboxyl group is meta-directing and removable(seemingly ideal?), and if that's the case then why even start from benzoic acid? Double nitration looks straight forward: hxxp://www.orgsyn.org/orgsyn/prep.asp?prep=cv3p0337 . 6 weeks wait is a little extreme but patience is greater than NOx fume exposure.

Yes picric acid is quite scary and very sensitive. Although I know 3,5-dinitrobenzoic acid is/was used in photography and wiki says its a corrosion inhibitor and a reagent. An MSDS lists it's melting point at 166*C(wiki says 200*C+) with no mention of an autoignition temperature anywhere, claiming to be stable at normal conditions? So it's not quite picric acid, but the warning is heeded.

Maybe a better route would be to immediately reduce the nitro groups at standard conditions to amino groups, reduce the carboxylic acid to the alcohol?, halogenate, then wurtz fittig(with shorter chain alkyl halide, n-butyl alcohol)? hmm I should think before I speak, I'll give it another shot tomorrow. Start fresh. Thank you for your input though, your an excellent help enkidu.

Also I would like to apologize for posting this, I know noob posts aren't appreciated and would understand if this went to the vacuous posts completely.

Although Diophosphorus Tetraiodide sounds far from OTC.. in my travels i found a decarboxylative bromination paper.. take a look at it, these refs are how i learn my chem so whether it helps or not its good to look at

The hard to obtain reagents sometimes make the whole thing not worth it

Those dinitro groups are pretty scary like enkidu said, when trinitro toluene (TNT) is only 1 more nitro group 

Looks like you could make DNP though pretty easy, 2,4 dinitrophenol although a little explosive, and used as a detonator for TNT, really sheds the Kgs from those hard to lose areas serious.

no wait.. you couldnt make DNP. the above is 3,5 not 2,4 my bad.

Edit

the paper gives Vinyl bromides. so there is my post out the window

The problem with nitrating after decarboxylation is the carboxyl group is meta-directing and removable(seemingly ideal?), and if that's the case then why even start from benzoic acid? Double nitration looks straight forward: hxxp://www.orgsyn.org/orgsyn/prep.asp?prep=cv3p0337 . 6 weeks wait is a little extreme but patience is greater than NOx fume exposure.

Benzoic acid is cheaply available. The decarboxylation is really messy, so you probably want to do that first. Once you have benzene, the first nitration (think NH4NO3 or KNO3 + H2SO4 for the first nitration, at least) will give nitrobenzene and the second will give 1,3-dinitrobenzene because the nitro group is meta directing.

Yes picric acid is quite scary and very sensitive. Although I know 3,5-dinitrobenzoic acid is/was used in photography and wiki says its a corrosion inhibitor and a reagent. An MSDS lists it's melting point at 166*C(wiki says 200*C+) with no mention of an autoignition temperature anywhere, claiming to be stable at normal conditions? So it's not quite picric acid, but the warning is heeded.

I was into pyro before long before I got into drugs. I've had some really effing close calls, so I'm just advising caution. If dinitrobenzoic acid is explosive at all (the more sensitive ring nitrated high explosives seem to have electron donating groups, like ~OH [picric acid] and ~Me [TNT]), it will require shock to be initiated. http://en.wikipedia.org/wiki/Explosive_material#Secondary_explosive

Additionally, look up the preparation of picric acid from salicylic acid. That preparation involves the replacement of the ~COOH with ~NO2, but IIRC the decarboxylation occurs after the second nitro group has been added.

Although Diophosphorus Tetraiodide sounds far from OTC.. in my travels i found a decarboxylative bromination paper..

Look up the Hunsdiecker rxn. I can't remember whether it works for aryl carboxylic acids.

Damn about the polymerization.

I looked into the salicylic acid -> picric acid and didn't find anything too particularly useful. My eyes are pretty untrained thats probably why.

Checked into the longer alkyl chain derivatives a while back while reading through Otto Snow's ''THC & Tropacocaines'', interesting stuff no doubt. Though I see no particular advantage to going longer or shorter, it seems it's hard just to get the positioning right.

Your right about the benzoic acid, but starting from benzene wouldn't one get the 2,4,6 or 1,3,5 trinitro? Or would the third nitration be haulted by the ring changes?

I can't really think of anything else except maybe starting from benzaldehyde, doing a grignard with 1-bromobutane, double nitration(long chain ketone should be electron withdrawing/direct meta due to resonance?), reducing the nitro's to amino's(Fe), reducing the ketone to the secondary alcohol(NaBH4), dehydrating the alcohol(p-TsOH/H2SO4), then hydrogenating the remaining double bond(if that's possible)...

If anyone else has any creative ideas I'd love to hear/see them. Struggling a bit to hit lift-off here.

edit: I'll think about the toluene route somehow read over that a few times.

I looked into the salicylic acid -> picric acid and didn't find anything too particularly useful.

Look for Rosco Bodine's posts on SM. The idea is asprin --> TNP.

Checked into the longer alkyl chain derivatives a while back while reading through Otto Snow's ''THC & Tropacocaines'', interesting stuff no doubt. Though I see no particular advantage to going longer or shorter, it seems it's hard just to get the positioning right.

I also meant to include unsaturated chains, since you can use different conditions for sp2 -- sp2 coupling. I'm no expert in coupling reactions.

Your right about the benzoic acid, but starting from benzene wouldn't one get the 2,4,6 or 1,3,5 trinitro? Or would the third nitration be haulted by the ring changes?

edit: I'll think about the toluene route somehow read over that a few times.

The first nitro group will be the easiest to add. The second will be much more difficult. Adding a third will require harsh conditions. From toluene, you'd nitrate (probably stepwise) to 2,4-dinitrotoluene, then oxidize the benzyl position to the carboxylic acid using dilute nitric acid, and then decarboxylate if you're not worried about explosions.

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3,5-dihydroxybenzoic acid is made in decent yields from benzoic acid. Methylate it to give 3,5-dimethoxybenzoic acid using known methods, then react it with n-butyl lithium to give 3,5-dimethoxyphenyl-1-pentanone, reduction/cleavage of which with HI would give 3,5-dihydroxy-1-pentylbenzene, aka olivetol.

Can you give me a ref for the HI reduction of a benzylic ketone? I wouldn't want to work with any alkyl lithium. Fuming sulfuric acid (98% + some dissolved oleum) isn't exactly child's play, either, though garage chemist posted a nice writeup. If you want to get to that ketone, why not just destructively distill the benzoic acid with pentanoic acid?

That post was deleted since it was redundant    The article had been already been uploaded, but without posting the citation:

http://127.0.0.1/talk/index.php/topic,1255.msg14118.html#msg14118

which makes it a lot easier to locate when using the search engine    On the Hive all one had to do generally is input the first page number in the article and one would know if it had already been posted