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All 11 posts Subject: DOB starting from 4-br-2,5-dmeObz Please login to post Down

silenziox
(Hive Bee)
02-04-04 16:37
No 486336
User Picture       DOB starting from 4-br-2,5-dmeObz

The following will be conducted in few weeks as the timetable forbids, so to say.. The synth is following the writeup found at https://www.rhodium.ws/chemistry/mda.txt
I let you know the yields wink ... and all comments/suggestions are welcome!

STEP 1 (Makin' da nitroalkene)

Dissolve 500g (2.05mol, 245.07g/mol) of 4-bromo-2,5-dimethoxybenzaldehyde into 154g (2.05mol, 75.067g/mol, Density: 1.045) of nitroethane containing 33g of cyclohexylamine and let the mix stand for about 3 weeks... Then, crush your nitroalkene cake and wash it with about liter of freezer cold MeOH. Spread to dry...

Supposed YIELD: ABOUT 500-550g of 4-bromo-2,5-dimethoxyphenyl-2-nitropropene (288.095g/mol)

STEP 2 (Reducin' da above mentioned stuff with AlH3)...

To 250 g of LiAlH4 dissolved in 3,5 L of ice cold anhydrous THF or in 2L of anhydrous diethyl ether, add dropwise with cooling and stirring and to this, 48ml of 100% H2SO4 (keep under 0'C!). To the reducing solution, add 500-550 g of 4-Br-2,5-DiMeOP-2-NP (straight from the previous step) dissolved in 1 L of anhydrous THF or diethyl ether... The addition should take around 4 hours with proper cooling (keeping below 0'C) of the reaction mix...

Stir at room temperature for 48 hours... (NO REFLUX!) Check the completion of the reaction with TLC...

Then, add to the mix containing the now reduced compound, 1000 ml of IPA to decompose the residual AlH3... followed by 400 ml of ~20% aqueous NaOH... (100g NaOH)

Filter the solids (Al + Li salts) from the reaction mix and CAREFULLY wash the filter cake using first some THF and then with IPA...

Evaporate the solvents and (preferably distill the oil) gas the free base in anhydrous IPA with HCl or add 1:1/mol 85% phosphoric acid to get the monobasic phosphate.

Afterwork: Wash the salt with anhydrous Et2O and recrystallize from boiling IPA.

Holotna Pravda... Neskolko dnej iz zhizni siLENZiova   laugh

Novice
(Stranger)
02-04-04 19:46
No 486366
      Why H2SO4?

Won't the sulphuric acid destroy LiAlH₄ in a very explosive manner? Thus eliminating its reductive properties...

If IPA with its very weakly acidic O-hydrogen is used to destroy excess LiAlH₄ when the reduction is over, then concentrated sulphuric acid most definately should destroy the LiAlH₄ before addition of the substrate.

LiAlH₄ + 2 H₂SO₄ => Li^- + Al^3- + 3 H₂ + 2 SO4^2-

Correct me if I'm wrong.

[Post edited moments after posting; empirical formula of LiAlH₄ corrected :-]

indium
(Hive Bee)
02-04-04 21:37
No 486397
      The trick is to add just enough h2so4 to form...

The trick is to add just enough h2so4 to form the alane..

But 200gr of DOB is enough to send a moderately large city to la-la-land.

Rhodium
(Chief Bee)
02-05-04 00:15
No 486439
User Picture       LAH to Alane

2 LiAlH4 + H2SO4 -> H2(g) + Li2SO4(s) + 2 AlH3

^{The Hive - Clandestine Chemists Without Borders}

hest
(Hive Adickt)
02-05-04 12:39
No 486567
      Hoho

To 250 g of LiAlH4

Have fun.

Stick to NaBH4 and some sort of nitro red. (Al(Hg)-NH4COO/Pd/C-Zn/AcOOH ect.)

Lilienthal
(Moderator)
02-05-04 12:59
No 486571
User Picture       Addition in the cold is VERY dangerous!

Addition in the cold is VERY dangerous! It will most probably result in an uncontrollable exothermic reaction (= big fireball), especially on such a mega-scale. Only suicidal / killer personalities would try such a reaction without a scaling-up process from sub-gram amounts.

silenziox
(Hive Bee)
02-06-04 11:01
No 486870
User Picture       Mad Hatter in the Wonderland

Lili: Addition in the cold is VERY dangerous! It will most probably result in an uncontrollable exothermic reaction (= big fireball), especially on such a mega-scale.

Whaaat? What's the difference performing the reaction inside with ice-bath or doing it outside with snow cooling the reaction and keeping the temperatures below 0 degrees (stirring the solution vigorously, adding one drop at a time and waiting until the solution has cooled back to 0?

Anyways I'll be using argon/nitrogen blanket for preventing the possible flames to get enough oxygen to burn...

What comes to the usage of ether in the synth, that might be not so good idea, as it really has to be 110% anhydrous.. If it isn't, the fuckup is imminent.

Lili: Only suicidal / killer personalities would try such a reaction without a scaling-up process from sub-gram amounts.

Yes! My motives are to conquer the world! Nothing will stop me from my 1000-year reign!! I guess it's time for changing my title? wink

indium:But 200gr of DOB is enough to send a moderately large city to la-la-land.

I'm expecting around 400g yield from this wink

I liked my idea to make the synth even more mega-scale, couple of kilos of the benzaldehyde, but I unfortunately broke my rotavap during the distillation of the nitropropene mad

(200g is quite low scale anyways, how'd they do amphetamine in the big scale anyways?)

Holotna Pravda... Neskolko dnej iz zhizni siLENZiova   laugh

hest
(Hive Adickt)
02-06-04 11:26
No 486872
      Re: but I unfortunately broke my rotavap ...

but I unfortunately broke my rotavap during the distillation of the nitropropene

Ohh and now I'm rely trust your post-

Bandil
(The Archetypical "Good Guy")
02-06-04 11:45
No 486874
      I'm assuming that he is referring to the ...

I'm assuming that he is referring to the removal of the solvent using a rotovap, and not distillation of the NP smile

Drugs = Fun; Drugs <> Money

silenziox
(Hive Bee)
02-06-04 16:38
No 486904
User Picture       Thanks Bandil... Always tell I'm distilling...

Thanks Bandil... Why do I always tell I'm distilling the nitrocompound smile (watch out for the PM) wink

Wont the NaBH4 dehalogenate the compound? That is the main reason I'd do the reduction with alane (thanks for rhodium about this info) smile

Holotna Pravda... Neskolko dnej iz zhizni siLENZiova   laugh

Nicodem
(Hive Bee)
02-07-04 11:07
No 487065
      Wont the NaBH4 dehalogenate the compound?

Wont the NaBH4 dehalogenate the compound? That is the main reason I'd do the reduction with alane

No, the NaBH4 don't dehalogenate the arylbromides. It takes a 'stronger' hydride carier like LiAlH4 in aprotic solvents to dehalogenate it.

“The real drug-problem is that we need more and better drugs.” – J. Ott

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	All 11 posts		Subject: DOB starting from 4-br-2,5-dmeObz		Please login to post		Down


		silenziox (Hive Bee) 02-04-04 16:37 No 486336				DOB starting from 4-br-2,5-dmeObz
						The following will be conducted in few weeks as the timetable forbids, so to say.. The synth is following the writeup found at https://www.rhodium.ws/chemistry/mda.txt I let you know the yields ... and all comments/suggestions are welcome! STEP 1 (Makin' da nitroalkene) Dissolve 500g (2.05mol, 245.07g/mol) of 4-bromo-2,5-dimethoxybenzaldehyde into 154g (2.05mol, 75.067g/mol, Density: 1.045) of nitroethane containing 33g of cyclohexylamine and let the mix stand for about 3 weeks... Then, crush your nitroalkene cake and wash it with about liter of freezer cold MeOH. Spread to dry... Supposed YIELD: ABOUT 500-550g of 4-bromo-2,5-dimethoxyphenyl-2-nitropropene (288.095g/mol) STEP 2 (Reducin' da above mentioned stuff with AlH3)... To 250 g of LiAlH4 dissolved in 3,5 L of ice cold anhydrous THF or in 2L of anhydrous diethyl ether, add dropwise with cooling and stirring and to this, 48ml of 100% H2SO4 (keep under 0'C!). To the reducing solution, add 500-550 g of 4-Br-2,5-DiMeOP-2-NP (straight from the previous step) dissolved in 1 L of anhydrous THF or diethyl ether... The addition should take around 4 hours with proper cooling (keeping below 0'C) of the reaction mix... Stir at room temperature for 48 hours... (NO REFLUX!) Check the completion of the reaction with TLC... Then, add to the mix containing the now reduced compound, 1000 ml of IPA to decompose the residual AlH3... followed by 400 ml of ~20% aqueous NaOH... (100g NaOH) Filter the solids (Al + Li salts) from the reaction mix and CAREFULLY wash the filter cake using first some THF and then with IPA... Evaporate the solvents and (preferably distill the oil) gas the free base in anhydrous IPA with HCl or add 1:1/mol 85% phosphoric acid to get the monobasic phosphate. Afterwork: Wash the salt with anhydrous Et2O and recrystallize from boiling IPA. Holotna Pravda... Neskolko dnej iz zhizni siLENZiova



		Novice (Stranger) 02-04-04 19:46 No 486366				Why H2SO4?
						Won't the sulphuric acid destroy LiAlH₄ in a very explosive manner? Thus eliminating its reductive properties... If IPA with its very weakly acidic O-hydrogen is used to destroy excess LiAlH₄ when the reduction is over, then concentrated sulphuric acid most definately should destroy the LiAlH₄ before addition of the substrate. LiAlH₄ + 2 H₂SO₄ => Li^- + Al^3- + 3 H₂ + 2 SO4^2- Correct me if I'm wrong. [Post edited moments after posting; empirical formula of LiAlH₄ corrected :-]



		indium (Hive Bee) 02-04-04 21:37 No 486397				The trick is to add just enough h2so4 to form...
						The trick is to add just enough h2so4 to form the alane.. But 200gr of DOB is enough to send a moderately large city to la-la-land.



		Rhodium (Chief Bee) 02-05-04 00:15 No 486439				LAH to Alane
						2 LiAlH4 + H2SO4 -> H2(g) + Li2SO4(s) + 2 AlH3 ^{The Hive - Clandestine Chemists Without Borders}



		hest (Hive Adickt) 02-05-04 12:39 No 486567				Hoho
						To 250 g of LiAlH4 Have fun. Stick to NaBH4 and some sort of nitro red. (Al(Hg)-NH4COO/Pd/C-Zn/AcOOH ect.)



		Lilienthal (Moderator) 02-05-04 12:59 No 486571				Addition in the cold is VERY dangerous!
						Addition in the cold is VERY dangerous! It will most probably result in an uncontrollable exothermic reaction (= big fireball), especially on such a mega-scale. Only suicidal / killer personalities would try such a reaction without a scaling-up process from sub-gram amounts.



		silenziox (Hive Bee) 02-06-04 11:01 No 486870				Mad Hatter in the Wonderland
						Lili: Addition in the cold is VERY dangerous! It will most probably result in an uncontrollable exothermic reaction (= big fireball), especially on such a mega-scale. Whaaat? What's the difference performing the reaction inside with ice-bath or doing it outside with snow cooling the reaction and keeping the temperatures below 0 degrees (stirring the solution vigorously, adding one drop at a time and waiting until the solution has cooled back to 0? Anyways I'll be using argon/nitrogen blanket for preventing the possible flames to get enough oxygen to burn... What comes to the usage of ether in the synth, that might be not so good idea, as it really has to be 110% anhydrous.. If it isn't, the fuckup is imminent. Lili: Only suicidal / killer personalities would try such a reaction without a scaling-up process from sub-gram amounts. Yes! My motives are to conquer the world! Nothing will stop me from my 1000-year reign!! I guess it's time for changing my title? indium:But 200gr of DOB is enough to send a moderately large city to la-la-land. I'm expecting around 400g yield from this I liked my idea to make the synth even more mega-scale, couple of kilos of the benzaldehyde, but I unfortunately broke my rotavap during the distillation of the nitropropene (200g is quite low scale anyways, how'd they do amphetamine in the big scale anyways?) Holotna Pravda... Neskolko dnej iz zhizni siLENZiova



		hest (Hive Adickt) 02-06-04 11:26 No 486872				Re: but I unfortunately broke my rotavap ...
						but I unfortunately broke my rotavap during the distillation of the nitropropene Ohh and now I'm rely trust your post-



		Bandil (The Archetypical "Good Guy") 02-06-04 11:45 No 486874				I'm assuming that he is referring to the ...
						I'm assuming that he is referring to the removal of the solvent using a rotovap, and not distillation of the NP Drugs = Fun; Drugs <> Money



		silenziox (Hive Bee) 02-06-04 16:38 No 486904				Thanks Bandil... Always tell I'm distilling...
						Thanks Bandil... Why do I always tell I'm distilling the nitrocompound (watch out for the PM) Wont the NaBH4 dehalogenate the compound? That is the main reason I'd do the reduction with alane (thanks for rhodium about this info) Holotna Pravda... Neskolko dnej iz zhizni siLENZiova



		Nicodem (Hive Bee) 02-07-04 11:07 No 487065				Wont the NaBH4 dehalogenate the compound?
						Wont the NaBH4 dehalogenate the compound? That is the main reason I'd do the reduction with alane No, the NaBH4 don't dehalogenate the arylbromides. It takes a 'stronger' hydride carier like LiAlH4 in aprotic solvents to dehalogenate it. “The real drug-problem is that we need more and better drugs.” – J. Ott

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