10-18-01 03:11
No 226196
And as 2,4-DNP is a mitochondrial poison as well as an explosive, but still not psychoactive, it is beyond the scope of this board.
Wait!
Oh how curious - i was thinking about posting this topic just today but then decided it's not so hot, but now that this has been brought up...
What do you think of this:
a) Start w/, say, TNT 
- well, dinitrotoluene, dinitroxylene or whatever you can make at home w/nitric acid (i'm not sure, but people like PrimoPyro
should know this)
b) reduce to tri- or di-amine with SnCl2 (proc. available at Orgsyn) or w/iron turnings (a la Cheapskate)
c) Diazotization, followed by methanolysis will (at least, theoretically) afford m-di- or tri-methoxytoluene
d) Oxidize to benzaldehyde with MnO2 or Na2S2O8 (i'm afraid though that this rxn will bee stericaly hindered, no?)
Well i'm prepared to hear that this won't work but - hey, isn't it seductive - 2,4,6 or 2,3,6 ald's - with nothing toxic, expensive or otherwise nonkitchen!
Antoncho
(Hive Bee)
10-18-01 04:04
No 226203
DNT would be made by the same process as DNP, but with toluene substituted for benzene - I see no problems with that. You need mercuric nitrate as well as nitric acid I believe (maybe not necessary - might just be there for yields - anybee?)
Jeez, this reminds me of the "You know you've been thinking about drug chemistry too much when..." thread - when someone (can't recall who...) says something about trying to convince the judge he was making drugs instead of bio weapons.
OK, I got side-tracked there, what I was trying to say was this:
If your lab gets busted, and you happen to have TNT lying around, you're going to get a whole bunch of terrorism charges (possession of explosives, conspiracy to make explosives, conspiracy to commit terrorism or whatever the US/European equivalents of Class 3 Terrorism are) laid on over and above the others. Especially if you also happen to have DNP (a detonating compound for TNT) lying around.
Right now, you do NOT want to be called a terrorist.
Bee warned....
But still, anyone who dreams this, post your yields
(Hive Bee)
10-18-01 05:37
No 226216
Hmm, interesting, I thought about similar possibilities about two months ago, but figured Id be laughed at for posting such a possibility.........
Well, to address a few points:
1.TNT/TNP/TNX can all be made easily at home, much easier than drugs, with simple mixtures of nitric and sulfuric acids. Both acids must be concentrated. Even though the nitric is the active partaker in the nitrating reaction of the aromatic, there is usually more sulfuric acid used than nitric in the mixture. This is because the mechanism for nitration is through loss of water, forming a nitro group instead of a nitrate. Concentrated nitric acid is ~67% and thus contains too much water to be used alone. Sulfuric acid promotes dehydration, and an excess eliminates the hindrance of the excess water in HNO3.
SWIPP has made TNP/TNT/TNX b4 in a garage
By the way, DNP is not used as a detonator for TNT. TNP is the booster phase of the detonation sequence, acting as a power amplifyer. The detonator is DDNP, Diazo-dinitro-phenol, usually as a heavy metal salt, like lead, to assist in its instability. This, by the way, would also be of interest (DDNP) as it is similar, and more substituted.
I have synthesized DDNP as well, but I can tell you right now: I will contribute all I know in these threads, but in the current times, I will not post writeups on the synthesis of any explosives, even if TNT was proven to be a useable drug precursor, I will not post it, so dont ask in the threads for synthesis. Find it yourself or PM me and MAYBE I will tell you. Just figured Id get it out of the way early......
2.The configuration for TNT is 2,4,6-trinitro-1-methylbenzene. Replace the nitro groups with your alkoxy of choice and the methyl with the alkylamine of choice, and you have the configuration of your drug. I have never seen any drugs in these configurations. Im not saying they dont exist, Im merely asking "will this pose a problem psychoactively?"
3.SWIPP never used Hg(NO3)2 in his aromatic nitrations, just the standard H2SO4/HNO3 mixture. Never heard if using it, dont know a thing about it. Id be willing to try it if it will raise yields though.
4.If you get busted period, you're going to jail for a loooooooooong time. Yes, your sentence will be bigger if you have explosives onhand. So, DONT have them onhand. And while you're at it, dont have drugs on hand either. Use them as soon as you make them, theoretically speaking of course.
PrimoPyro
<----------------------Isnt called PRIMOpyro for nothing....
I collect synthetic drug precursers. Aren't you jealous? Member: C_F and pyrotek FanClubs
(Stoni's sexual toy)
10-18-01 07:56
No 226263
You can't make TNT easily in the garage. And most certainly not when using crappy azeotropic HNO3.
trinitrophenol is possible, but unless you have pure m-xylol TNX won't happen either, you'll produce a wild oily mixture.
DNP from benzene with Hg salts? Yes I've seen that procedure. Ewwww.
(Hive Bee)
10-18-01 08:09
No 226269
Sandmeyer on more than one aminogroup per. molekule is almost imposible, you get a lot of product. Why not just brominat and then sub. the bromine with methoxy ??
(And i think that talking abouth explosives in these times is a bad ider)
(Official Hive Translator)
10-18-01 10:49
No 226314
Hmm... Wait a minute... What about this then? (the 3rd hit on Google
)from http://home.inreach.com/eagleye/science/
Preparation: Mix 294 grams of concentrated sulfuric acid,(d.1.84) with a glass rod to 147 grams of nitric acid (d. 1.42), into a 600cc beaker. While the mixture is being cooled, using running water to maintain a temperature between 30 deg. to 40 deg. centigrade, add 100 grams of toluene. Stir using a electric mixer. Use a glass rod that has had both ends covered with rubber hose. Using a dropping funnel this procedure usually takes about 60 to 90 minutes. After the liquid has been stired then let the mixture set overnight.
Stage 2: In a separatory funnel remove the brown oil that has accumulated on the top of the acid, and discard the spent acid for use later in an appropriate container. Now mix 109 grams of sulfuric acid (d.1.84) with 50 grams of the mononitrated toluene from stage 1 while cooling using running water. Set this aside for now.
Next mix 54,5 grams each of nitric acid(d. 1.42) and sulfuric acid(d. 1.84) together in a 250cc beaker. Now take the beaker with the mixture of sulfuric acid and mononitrated toluene and heated to 50deg. centigrade. The mixed acid is then slowly added, the heat of the mixture will rise quickly, so keep the temperature down using a running water bath. The temperature should be between 90 and 100 deg. centigrade. Stir using a glass rod and stir it by hand, this will take about an hour to add all the acid tothe mixture. After the acid is add the mixture is stired for 2 more hours, while the temperature is held at 100 deg. centigrade. Let stand for the night.
Stage 3: The two layers will seperate on standing, the upper layer is the dinitrotoluene,and is easy to separated, or if one likes, which is the way I do it , is to leave it in the spent acid. After having heated the mixture to about 90 deg. centigrade, I add 143 grams of fuming sulfuric acid to the mixture(mixture to acid). I then mix 72.5 gram each of fuming sulfuric acid with fuming nitric acid (d. 1.50) together ,and while stiring I add this 175 grams of mixted acid drop by drop to the mixture of dinitrotoluene and fuming sulfuric acid. Using good agitation the mixture after awhile will need to have external heat added to it to maintain a temperature of 100 to 115 deg. centigrade. This will take about 2 hours. Let stand over night, then melt using boiling water wash the tnt till there is no sign of acid in the boiling water bath. The TNT will be tan to brown in color and when heated will give off little black parachutes of soot. It will smell like rifle pwder, (rifle pwder contain a small amount of tnt anyway). When the tnt is heated and then caustic soda is added the mixture bursts into flames. Tnt will disolve nitrocellulose and when mixed with Ammonium nitrate will produce a British explosive know as Amatol, which is comprised of 80% ammonium nitrate and 20% tnt.
After the first nitration of the toluene two products are formed, the first is ortho- mononitrated toluene ( boiling point of 223deg centigrade ). The second of course will be para- mononuitrated toluene. Keep in mind that it is the meta groups are the hardest to substitute as is the cast in the third stage of nitration. However during the nitration of mono- to dinitro. of the two groups only the ortho group yields the 2,4 and the 4,6 dinitrotoluene which after nitration for the third time yields 2,4,6 trinitrotoluene
OK, in Step 3 you need fuming H2SO4. But can't you get the same mixture of acids by heating NaNO3 in H2SO4? That's how they dinitrate dichlorobenzene - also very electron-deficient.
(also, can anyone comment on the last passage???
)And, still, if you do the 1st nitration, then sep. the isomers by steam-dist'n...
The p-nitroT one can later rearrange to toluhydroquinone - for DMBA (BTW - just like the paracetamol route, it's four-step) or DOM. then 2nd nitration, you'll get 2,6-dinitroT.
It then can bee reduced like in this ex.: (http://orgsyn.org/orgsyn/prep.asp?prep=C
In a 500-cc. three-necked flask, fitted with a reflux condenser and a mechanical stirrer (Note 1), are placed 45.5 g. (0.25 mole) of 2,4-dinitrotoluene (Note 2), 85 g. (1.5 moles) of iron (Note 3), and 100 cc. of 50 per cent (by weight) ethyl alcohol (Note 4). The mixture is heated to boiling on a water bath, the stirrer is started (Note 5), and a solution of 5.2 cc. (0.06 mole) of concentrated hydrochloric acid in 25 cc. of 50 per cent (by weight) ethyl alcohol is added slowly (Note 6). The mixture is refluxed for two hours after addition of the acid is complete. At the end of this time the apparatus is disconnected and the hot mixture is made just alkaline to litmus by the addition of the calculated amount of 15 per cent alcoholic potassium hydroxide solution (Note 7). Without allowing the mixture to cool, the iron is removed by filtration and the reaction flask is rinsed with two 50-cc. portions of 95 per cent ethyl alcohol; the same alcohol is used to wash the iron residue. To the filtrate is added 84 cc. of 6 N sulfuric acid; the normal sulfate of 2,4-diaminotoluene precipitates. The mixture is cooled to 25° and filtered by suction. The product is washed with two 25-cc. portions of 95 per cent ethyl alcohol, dried in the air for two hours (Note 8) and then dried to constant weight at 110°. The yield is 49 g. (89 per cent of the theoretical amount) of a product which melts with decomposition at 249–251° (Note 9).
A solution of 20 g. of 2,4-diaminotoluene sulfate in 200 cc. of water at 60° is cooled to 40° (Note 10), and made alkaline to litmus with saturated sodium hydroxide solution (Note 11). To this solution is added 15 g. of the sulfate, which is dissolved by raising the temperature of the mixture to 55°. The solution is cooled to 40° and made slightly alkaline to litmus with saturated sodium hydroxide solution. The mixture is then cooled to 30° and filtered by suction. The remainder of the diaminotoluene sulfate (14 g.) is then dissolved in the filtrate by heating the mixture to 55°. The solution is cooled to 40° and again made alkaline to litmus with saturated sodium hydroxide solution. The mixture is cooled to 25°, and the diaminotoluene crystals are collected on a Büchner funnel. The entire product is dried to constant weight in a desiccator over calcium chloride. The yield is 26.5 g. (95 per cent of the theoretical amount based on the diaminotoluene sulfate used) of a product melting at 97–98.5°.
The crude diaminotoluene (Note 12) is dissolved in eight times its weight of benzene (212 g.) at 70°, and the solution is filtered quickly through a hot Büchner funnel (Note 13) with moderate suction (Note 14). The filtrate is cooled to 25°, and the mother liquor is decanted from the brown crystals. The mother liquor is concentrated to a volume of 25 cc. by distillation under atmospheric pressure and then cooled to 25°. The mother liquor is decanted from the diaminotoluene, and the entire product is dried in the air. The yield is 22.5 g. (81 per cent of the theoretical amount based on the diaminotoluene sulfate used; 74 per cent based on the dinitrotoluene used) of a product which melts at 98° (Note 15).
(See the link for the additional details - lots of important ones.)
And then you only have to diazotize/methanolyse it and oxidize the CH3- to -CHO, which can bee done in a variety of ways, Na2S2O8 as well as Oxone(see Orgsyn) being, probably, the OTC'est.
Note that this is a 5-step process for producing a precursor either for DESOXY (active at 40-100 mg) or for TMA-5, well, in both cases i'm not sure about which way the substitution will take place - Osmium, do you know?
In any case, it'll bee smth. pretty uncommon, i guess.
Shall i emphasize again that it's very easy and very OTC
Comments of both complimentary and enflammatory
nature are very much welcome.Antoncho
[edit]: dear Hest! Can you, please, further comment on what you said?
AFAIUTFSE'd , Sandmeyer is Cu+X- replacement of diazogroup with X=halogen/cyanide. Does it apply here?
(Stoni's sexual toy)
10-18-01 15:17
No 226415
"Fuming H2SO4" is also known as oleum, or H2SO4 with 30% SO3. The 100% HNO3 can be prepared at home, but I doubt the oleum can. At least not easily. So no TNT at home. Why bother, as an explosive TNT sucks anyway.
About the rest of the reactions, well don't be too enthousiastic, first prove that you successfully did it, then we 'might' get interested.
5 steps to produce the precursor of a precursor doesn't sound that exiting to me right now. That will bee some expensive honey for sure.
(Hive Bee)
10-18-01 17:59
No 226537
Dear Antoncho, i just ment the diazotization. You'r right, it not a Sanmeyer.
I think this is a bit overkill
Just get the trimethoxy-something from the natrure (camilla, apples aso.)
(Official Hive Translator)
10-19-01 00:40
No 226684
Ok, ok, as i said i was prepared to hear that it wouldn't work. So please excuse my inappropriate enthusiasm if it is indeed inappropriate.
I guess i'll just conclude this topic w/ more info on these nitro reactions - may bee useful to some people one day, esp. those w/out a fume hood (i.e., no bromine, no DMS).
The 1st is a direct rearrangement/reduction of nitrotoluene to aminobenzaldehyde by Na polysulfide.
The 2nd is a reduction of nitroaldehyde to aminoaldehyde with ammoniac FeSO4.
The 3rd is a nitration of 3,4-diMeOaldehyde wiht nitric acid. This last one is also interesting because it kinda implies that benzaldehydes can bee methylated w/MeNO3 w/out appreciable damage to the aldehyde group. (Otto, how is it going? Any more trials plannned?
)p-AMINOBENZALDEHYDE
http://orgsyn.org/orgsyn/prep.asp?prep=c
To 600 ml. of distilled water in a 1-l. beaker are added 30 g. (0.125 mole) of crystalline sodium sulfide nonahydrate (Note 1), 15 g. (0.47 g. atom) of flowers of sulfur, and 27 g. (0.67 mole) of sodium hydroxide pellets. The mixture is heated on a steam bath for 15–20 minutes with occasional stirring and then poured into a 2-l. round-bottomed flask containing a hot solution of 50 g. (0.36 mole) of p-nitrotoluene (Note 2) in 300 ml. of 95% ethanol. A reflux condenser is attached, and the mixture is heated under reflux for 3 hours. The resulting clear but deep red solution is rapidly steam-distilled until about 1.5–2 l. of condensate has been collected (Note 3). The distillate should be clear when the distillation is stopped. The residue in the 2-l. flask should have a volume of 500–600 ml.; if less, it should be diluted to this volume with boiling water. The solution is rapidly chilled in an ice bath with occasional vigorous shaking and stirring to induce crystallization. After 2 hours in the ice bath the golden yellow crystals of p-aminobenzaldehyde are collected on a Buchner funnel and washed with 500 ml. of ice water to remove sodium hydroxide (Note 4). The product is immediately placed in a vacuum desiccator over solid potassium hydroxide pellets for 24 hours. The yield of p-aminobenzaldehyde, m.p. 68–70°, amounts to 18–22 g. (40–50%). The product contains some impurities but is pure enough for most purposes (Note 5). It should be stored in a sealed bottle (Note 6).
o-AMINOBENZALDEHYDE
[Anthranilaldehyde]
http://orgsyn.org/orgsyn/prep.asp?prep=c
A 1-l. three-necked flask is employed as a reaction vessel from which the product can be steam-distilled immediately after completion of the reaction (Note 1). It is convenient to arrange the apparatus for the reaction and that for the steam distillation on the same steam bath, with provision for the rapid connection of the flask to the distillation assembly at the desired time. For use as a reaction vessel the flask is mounted on a steam bath and fitted with a mechanical stirrer and a reflux condenser; the third neck is closed by a cork.
In the steam-distillation assembly (Note 1) one of the small necks of the flask is fitted with a steam-inlet tube, connected through a water trap to a steam line; the other small neck is closed by a cork. The central neck is fitted to a Kjeldahl trap leading to a 50-cm. Allihn condenser set downward and connected in series to a 50-cm. Liebig condenser. The second condenser leads to a 500-ml. three-necked flask used as the receiver. The receiving flask is immersed in an ice bath and fitted with an Allihn reflux condenser.
When all the apparatus has been set up and tested the flask is connected to the reaction assembly, and 175 ml. of water, 105 g. (0.38 mole) of ferrous sulfate heptahydrate, 0.5 ml. of concentrated hydrochloric acid, and 6 g. (0.04 mole) of o-nitrobenzaldehyde (see p. 641) are introduced in the order given. The stirrer is then started, and the flask is heated by means of the steam bath. When the temperature of the mixture reaches 90°, 25 ml. of concentrated ammonium hydroxide is added in one portion, and at 2-minute intervals three 10-ml. portions of ammonium hydroxide are added. Stirring and heating are continued throughout. The total reaction time is 8–10 minutes.
Immediately after the addition of the last portion of ammonium hydroxide, the reflux condenser and stirrer are removed and the flask is connected to the steam-distillation assembly. The mixture is steam-distilled as rapidly as possible, and two 250-ml. fractions of distillate are collected during a period of 10–13 minutes (Note 2). The first fraction is saturated with sodium chloride, and the solution is stirred at 5° until precipitation appears to be complete. The solid is collected on a Buchner funnel and dried in the air. The product weighs 2.72–3.11 g. (57–65%) and melts at 38–39°. The second fraction of the distillate is saturated with sodium chloride and combined with the filtrate remaining from the first fraction. The combined solution is extracted with two 45-ml. portions of ether. The combined ether extract is filtered, dried over anhydrous sodium sulfate, and concentrated by distillation, finally under reduced pressure. The residue solidifies on cooling and weighs 0.6–1.0 g.; it can be purified by steam distillation from 40–50 ml. of saturated sodium chloride solution until 100 ml. of distillate is collected, saturation of the distillate with sodium chloride, cooling, and filtration. The pure product so obtained weighs 0.42–0.87 g. The total yield (Note 3) is 3.3–3.6 g. (69–75%).
6-NITROVERATRALDEHYDE
http://orgsyn.org/orgsyn/prep.asp?prep=c
The product of this reaction is quite sensitive to light, and the entire procedure should be carried out in semidarkness.
A wide-mouth 1-l. Erlenmeyer flask is supported inside a water bath of at least 2-l. capacity so that the bottom of the flask is not in contact with the bottom of the bath. The bath is filled with water at about 15° to cover at least half the height of the flask. The flask is fitted with a moderate-speed stainless-steel propeller-type stirrer, and 350 ml. of nitric acid (sp. gr. 1.4) at 20° is poured into it. Veratraldehyde is crushed at least as fine as rice grains and is slowly added in small portions to the acid. The rate of addition should be such that it requires about 1 hour to add all the aldehyde. It is helpful, although not usually necessary, to add two or three ice cubes to the bath at the start of the nitration. The internal temperature is checked from time to time and should be held between 18° and 22°. The mixture is stirred for 10 minutes after the addition of the last of the aldehyde.
The mixture is then poured into 4 l. of vigorously agitated cold water (Note 3) in a suitable opaque container. From this point onward the protection of the product from light is extremely important. The stirring is continued for a few minutes; then the batch is filtered through a 24-cm. Büchner funnel. The container and funnel are kept covered with an opaque sheet of some kind except while the transfer is being made. The cake is sucked down well and then returned to the crock and reslurried a few minutes with 2 l. of cold water. It is then refiltered, pressed out well with a spatula, and drained as well as possible.
The filter cake at this point is 60% to 80% water, and the material is sensitive to heat and to light. The drying, therefore, is difficult and slow, and the exact procedure will depend upon the equipment available. One satisfactory method is to set the Büchner funnel containing the wet material in a large forced-draft oven for 8 hours at 50°. The material, still very wet, is then easily spread on a tray and is placed in a dark but ventilated storeroom, where it is allowed to air-dry for 48 hours or until the weight of the product is less than about 90 g. The product now contains from 10% to 20% of water and is best recrystallized without more thorough drying.
The material is dissolved in 2 l. of boiling 95% ethanol. It is not necessary to filter this solution for the first crystallization. Upon standing overnight, the solution is solid with precipitate. This structure is easily broken up and is filtered on a large Büchner funnel. The mother liquor is concentrated to about 700 ml. and allowed to cool. The second crop of solid is added to the first and dried in a vacuum oven at 50° overnight. The dry material weighs 65–70 g., corresponding to a yield of 73–79%, and melts at 129–131°. It is sufficiently pure for most purposes. One additional crystallization from 1 l. of 95% ethanol gives 55–60 g. of pure material, melting at 132–133°.
Osmium :
a) As for the expense of so obtained honey - i bet you dollars to donuts it will cost you 10 times less - admittedly, only in terms of money investment as all the precursors are enormously cheap (which you can't say about bromine for instance).
c) in your phrase "then we 'might' get interested" by "we" you mean yourself and...exactly whom else?
Antoncho
(Stranger)
10-19-01 05:35
No 226745
hi antoncho,
very pleasing to read this interesting thread. concerning your question to MeONO2 the methylation on eugenol definitely works though yields still have to be established. i doubt that there will be problems with the benzaldehydes. eugenol seems to me more sensitive to oxidation than vanillin.
in the nitration of toluene you get a mixture of o- and p- isomers. separation of those isnt going to be easy (fractional destilation/crystallisation). the ratio of isomers can be influenced by means of nitration conditions.
w/ conc. H2SO4 and HNO3 (the normal 65% one) at room temperature one gets 60% o-nitrotoluene. using nitric acid alone one gets around 60% p-isomer.
to get pure 2,4 - DNT one must start from p-MNT. i did the nitration w/ HNO3 alone once. it can be done using the remainings of MeONO2 - production. this aqueous HNO3 is put together with an excess of toluene to reflux on my beloved dean&stark. water contained in the acid and liberated during reaction is carried off reaction vessel as azeotropic mixture. reaction is complete when no more water separates. the excess toluene is distilled off afterwards. the product (MNT) gives crystals of p-MNT (which are decanted or filtered off) upon standing.
i have a chemistry book here that says o- or p- MNT can be condensed with carbonylcompounds in presence of a base. an example is then given. reaction of o-MNT with oxalic diethylester in presence of sodium alkoxide gives o-nitrophenylpyruvic ester.
so if one uses ethylacetate as carbonyl compound, one would get o-nitrophenylacetone.
with 2,4-DNT the methylgroup should be even more active towards this reaction, giving 2,4-dinitropenylacetone.
arrising question: will the side-chain be stable to procedures converting the nitrogroups to whatever (simply removing would give P2P, also a product of interest)
otto